Science, Faculty of
Earth, Ocean and Atmospheric Sciences, Department of
DSpace
UBCV
Stock, Elizabeth Denise
Doctor of Philosophy - PhD
University of British Columbia
Archean lode-gold deposits are a significant source of gold. However, exploration of this deposit type is hindered by their poorly understood genetic models and geochemical features. This project investigated the geochemical expression surrounding the Archean lode-gold Red Lake Gold Mines (RLGM) in the Superior Province, Canada. Mineral chemistry, whole rock and isotope geochemistry were used to establish how hydrothermal and metamorphic events influenced ore genesis. The RLGM is a basalt-hosted lode-gold deposit that formed from multiple superposed hydrothermal and metamorphic events. This study defined three significant superposed events which were important for gold mineralization. The first event was a widespread hybridized seafloor-magmatic event which caused reduction with FeO, MnO, K2O, SO3, SiO2, Rb, As and Cu enrichment. Seawater interaction created abundant micas-clays-chlorite-carbonate-FeMn oxides. Localized acidic magmatic fluids, in syn-volcanic faults, caused advanced argillic alteration. Subsequent peak-regional metamorphism created a widespread (>7km) occurrence of metamorphosed altered basalts. The micas-clays-chlorite-carbonate-FeMn oxides were metamorphosed to form Fe-biotite-Ti-magnetite±carbonate and Fe-chlorite-Fe-amphibole-FeMn-garnet-epidote/clinozoisite-magnetite-calcite-biotite assemblages. The metamorphosed argillic alteration created a quartz-muscovite-andalusite assemblage. Overprinting the widespread metamorphosed altered basalt was the significantly narrower (<1km), and structurally-controlled main vein and mineralization event. Abundant ankerite-calcite±quartz veins with replacement sulfide assemblages of pyrrhotite-pyrite-arsenopyrite-magnetite-gold-quartz-Mg-brown biotite were formed. The replacement ore-forming fluid enriched the basalt in CaO, MgO, SiO2, K2O, Ag, Au, Ni, Cu, Sb and Zn. Sulfides were created by sulfidation reactions between the host rock and ore-forming fluid. Redox differences during sulfidation reactions between the reduced wall rock and relatively oxidized fluid were identified as the main influence on gold precipitation. Carbon isotopes from the ankerite-calcite±quartz veins ranged from -4 to +4‰ δ13C which is consistent with a metamorphic origin by devolatilization reactions of pre-existing marine carbonates. Sulfur isotope from mineralized samples ranged from δ34SH2S 0–9‰. These are consistent with a magmatic source as well as metamorphic desulfidation of pre-existing sulfides (-7 to +6‰ 34S). The stable isotopes are most consisted with an evolved ore-forming fluid derived from a magmatic intrusion emplaced during regional-metamorphism. Therefore, gold mineralization at the RLGM was formed during ongoing, but post-peak regional metamorphism from an evolved magmatic source emplaced during a regional-contact metamorphic event.
THE MINERALOGICAL, GEOCHEMICAL AND ISOTOPE CHARACTERISTICS OF ALTERATION, MINERALIZATION AND METAMORPHISM OF THE RED LAKE GOLD MINES, ONTARIO by Elizabeth D. Stock MSci., Imperial College London, 2007 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Geological Sciences) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) September 2012 © Elizabeth D. Stock, 2012 ii Abstract Archean lode-gold deposits are a significant source of gold. However, exploration of this deposit type is hindered by their poorly understood genetic models and geochemical features. This project investigated the geochemical expression surrounding the Archean lode-gold Red Lake Gold Mines (RLGM) in the Superior Province, Canada. Mineral chemistry, whole rock and isotope geochemistry were used to establish how hydrothermal and metamorphic events influenced ore genesis. The RLGM is a basalt-hosted lode-gold deposit that formed from multiple superposed hydrothermal and metamorphic events. This study defined three significant superposed events which were important for gold mineralization. The first event was a widespread hybridized seafloor-magmatic event which caused reduction with FeO, MnO, K2O, SO3, SiO2, Rb, As and Cu enrichment. Seawater interaction created abundant micas-clays-chlorite-carbonate-FeMn oxides. Localized acidic magmatic fluids, in syn-volcanic faults, caused advanced argillic alteration. Subsequent peak-regional metamorphism created a widespread (>7km) occurrence of metamorphosed altered basalts. The micas-clays-chlorite-carbonate-FeMn oxides were metamorphosed to form Fe-biotite-Ti-magnetite±carbonate and Fe-chlorite-Fe-amphibole-FeMn- garnet-epidote/clinozoisite-magnetite-calcite-biotite assemblages. The metamorphosed argillic alteration created a quartz-muscovite-andalusite assemblage. Overprinting the widespread metamorphosed altered basalt was the significantly narrower (<1km), and structurally-controlled main vein and mineralization event. Abundant ankerite-calcite±quartz veins with replacement sulfide assemblages of pyrrhotite-pyrite- arsenopyrite-magnetite-gold-quartz-Mg-brown biotite were formed. The replacement ore- forming fluid enriched the basalt in CaO, MgO, SiO2, K2O, Ag, Au, Ni, Cu, Sb and Zn. Sulfides were created by sulfidation reactions between the host rock and ore-forming fluid. Redox differences during sulfidation reactions between the reduced wall rock and relatively oxidized fluid were identified as the main influence on gold precipitation. Carbon isotopes from the ankerite-calcite±quartz veins ranged from -4 to +4‰ δ13C which is consistent with a metamorphic origin by devolatilization reactions of pre-existing marine carbonates. Sulfur isotope from mineralized samples ranged from δ34SH2S 0–9‰. These are consistent with a magmatic source as well as metamorphic desulfidation of pre-existing sulfides (-7 to +6‰ 34S). The stable isotopes are most consisted with an evolved ore-forming fluid derived from a magmatic intrusion emplaced during regional-metamorphism. Therefore, gold mineralization at the RLGM was formed during ongoing, but post-peak regional metamorphism from an evolved magmatic source emplaced during a regional-contact metamorphic event. iii Preface This dissertation builds upon the larger-scale investigation of the collaborative MDRU- Goldcorp-NSERC-CRD project investigating the footprints of Archean lode-gold deposits. The collaborative MDRU-Goldcorp-NSERC-CRD project was initiated by Drs. F Bouzari and R Tosdal. This was a lithogeochemical study of the Red Lake mine and surrounding area through surface and subsurface sampling to identify pathfinder elements to ore. This project is a continuation of that study. Geological information from 27 drill holes, logged by Dr. Bouzari was used in the compilation of the lithological cross sections (Chapter 2). Samples from those 27 drill holes were also used for the geochemical analysis (Chapter 4). The drill holes used from Dr. Bouzari are clearly indicated in the thesis. Whole rock data from this study was supplemented with carefully selected samples from Dr. Bouzari’s research. The selection criteria are indicated within the thesis. In the data appendix samples from Dr. Bouzari are clearly indicated. All mineral chemistry, C and O isotope, SWIR and magnetic susceptibility data was collected by the author. Sulfur isotopes were collected as part of collaboration work with Dr. Janina Micko at the University of Tasmania. Sample selection, data processing and interpretation are the author’s. Data collection and interpretation was guided by the supervisorary committee (Drs. Greg Dipple, Farhad Bouzari and Dick Tosdal), but primary conclusions remain that of the author iv Table of contents Abstract ......................................................................................................................................... ii Preface .......................................................................................................................................... iii Table of contents ......................................................................................................................... iiv List of tables ................................................................................................................................ xii List of figures ............................................................................................................................ xivi List of abbreviations .............................................................................................................. xxiiiii Acknowledgements .................................................................................................................. xxvi Dedication ............................................................................................................................... xxviii Chapter 1: Introduction .............................................................................................................. 1 1.1 The importance of geological research in ore deposit exploration ..................................................... 1 1.2 Characteristics and previous studies of lode-gold deposits ................................................................ 1 1.2.1 Overview of footprint and pathfinder element studies in lode-gold deposits .............................. 4 1.2.2 Mineral chemistry studies in lode-gold deposits ......................................................................... 6 1.3 Introduction to the Red Lake Gold Mines .......................................................................................... 7 1.3.1 Previous Red Lake studies ........................................................................................................... 7 1.4 Project rationale and objectives ........................................................................................................ 11 1.5 Research approach ............................................................................................................................ 12 1.5.1 The RLGM cross sections and sample distribution ................................................................... 12 1.5.2 Mapped areas ............................................................................................................................. 17 1.5.3 Choice of geochemical methods ................................................................................................ 20 1.6 Overview of the dissertation ............................................................................................................. 21 Chapter 2: Geology of the Red Lake greenstone belt and Red Lake Gold Mines ................ 23 2.1 Introductation .................................................................................................................................... 23 2.2 Geological setting of the Red Lake greenstone belt ......................................................................... 23 2.2.1 Stratigraphy of the Red Lake greenstone belt ........................................................................... 24 2.2.2 Metamorphism and associated geological phenomena of the Red Lake greenstone belt .......... 24 2.2.2.1 Plutonism and associated metamorphism .......................................................................... 27 2.2.2.2 Regional deformation and associated metamorphism ........................................................ 28 2.2.2.2.1 D0 – pre-mineralization ............................................................................................... 28 v 2.2.2.2.2 D1 – pre-mineralization .............................................................................................. 28 2.2.2.2.3 D2 – syn-mineralization .............................................................................................. 29 2.2.2.2.4 D3 and D4 – post-mineralization ................................................................................. 29 2.2.2.3 Gold-mineralization and metamorphism in the Red Lake greenstone belt ........................ 31 2.3 Geology of the Red Lake Gold Mines .............................................................................................. 31 2.3.1 Mine stratigraphy ....................................................................................................................... 31 2.3.2 Structure of the RLGM .............................................................................................................. 32 2.3.2.1 Structural control on fluid flow and mineralization ........................................................... 33 2.3.3 Mineralization............................................................................................................................ 35 2.3.4 Metamorphic facies at the RLGM ............................................................................................. 37 2.3.5 Hydrothermal alteration ............................................................................................................. 38 2.3.5.1 Regional alteration footprint .............................................................................................. 38 2.3.5.2 Mine Scale Alteration ........................................................................................................ 39 2.3.6 Previously suggested genetic models for the RLGM ................................................................ 42 2.4 Critical unanswered questions .......................................................................................................... 43 Chapter 3: Superposed hydrothermal and metamorphic alteration at the lode-gold Red Lake Gold Mines ......................................................................................................................... 44 3.1 Introduction ....................................................................................................................................... 44 3.2 Characterization of hydrothermal and metamorphic origins of minerals ......................................... 46 3.3 Hydrothermal and metamorphic mineral assemblages ..................................................................... 47 3.3.1 Stage 1 – widespread regional metamorphic footprint with evidence of prior hydrothermal alteration ............................................................................................................................................. 48 3.3.1.1 Pervasive biotite-Ti-magnetite ± carbonate ....................................................................... 48 3.3.1.2 Early chlorite ...................................................................................................................... 51 3.3.1.2.1 Berlin blue chlorite ± sulfides ..................................................................................... 52 3.3.1.2.2 Brown chlorite ............................................................................................................ 52 3.3.1.3 Regional metamorphic greenschist-amphibolite facies and localized bleached zones ...... 54 3.3.1.3.1 Greenschist-amphibolite facies regional metamorphic assemblage ........................... 56 3.3.1.3.2 Aluminous-bleached assemblage (quartz-muscovite-andalusite ± chlorite ± biotite) 65 3.3.1.4 Plagioclase.......................................................................................................................... 68 3.3.1.5 Blue tourmaline .................................................................................................................. 68 3.3.1.6 Blue chlorite-muscovite ± carbonate ± quartz ................................................................... 69 3.3.2 Stage 2 – Main vein stage progressing to ore stage ................................................................... 70 3.3.2.1 Calcite-magnetite veins ...................................................................................................... 70 3.3.2.2 Ankerite-quartz veins with biotite selvages ....................................................................... 71 vi 3.3.2.3 Epidote-carbonate ± quartz veins ....................................................................................... 73 3.3.2.4 Chlorite veinlets ± magnetite ± ankerite ± blue tourmaline ............................................... 73 3.3.2.5 Ankerite-calcite veins and carbonate-quartz breccia .......................................................... 73 3.3.2.5.1 Cryptocrystalline to microcrystalline ankerite veins .................................................. 75 3.3.2.5.2 Medium to coarse ankerite veins ................................................................................ 75 3.3.2.5.3 Brecciation event ........................................................................................................ 75 3.3.2.5.4 Colloform-crustiform ankerite-calcite ± quartz veins ................................................. 76 3.3.2.5.5 Chlorite selvages to ankerite-calcite veins .................................................................. 77 3.3.2.6 Ankerite-calcite-quartz ± chlorite halos ............................................................................. 77 3.3.2.7 Quartz-ankerite vein ........................................................................................................... 79 3.3.2.8 En echelon quartz veins ..................................................................................................... 79 3.3.2.9 Initiation of the ore-stage sulfides-magnetite and associated alteration ............................. 82 3.3.2.10 Sphalerite ......................................................................................................................... 82 3.3.2.11 Pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold and pervasive quartz disseminated sulfide assemblage ......................................................................................................................... 84 3.3.2.12 Stibnite ± gold .................................................................................................................. 84 3.3.2.13 Quartz-molybdenite ± gold veins ..................................................................................... 84 3.3.2.14 Replacement pyrrhotite-pyrite-arsenopyrite-quartz ± gold .............................................. 86 3.3.2.15 Quartz-ankerite-brown biotite -pyrrhotite-gold veins ...................................................... 86 3.3.2.16 Arsenopyrite-pyrrhotite-quartz-pyrite-magnetite-gold-brown biotite alteration .............. 88 3.3.3 Stage 3 – Late hydrothermal alteration and minor metamorphism ........................................... 88 3.3.3.1 Late calcite ......................................................................................................................... 88 3.3.3.2 Remobilized gold (minor contact metamorphism) ............................................................. 90 3.3.3.3 Quartz-muscovite ± carbonate ± pyrite veins ..................................................................... 90 3.3.3.4 Quartz-tourmaline ± carbonate ± pyrite ............................................................................. 92 3.4 Spatial arrangement of alteration mineral assemblages .................................................................... 92 3.4.1 Distal footprint (> 5 km from ore) ............................................................................................. 94 3.4.2 Intermediate footprint (3–5 km from mineralization) ............................................................... 95 3.4.3 Mine and ore-scale footprint (0–3 km) ...................................................................................... 95 3.4.4 Regional metamorphic footprint ................................................................................................ 96 3.5 Interpretation and discussion ............................................................................................................ 99 3.5.1 Geological sequence of hydrothermal and metamorphic events at the RLGM ......................... 99 3.5.1.1 Early hydrothermal alteration of the host basalt ................................................................ 99 3.5.1.2 Initiation of M2 peak-regional metamorphism ................................................................. 102 3.5.1.3 Continued M2 peak-regional metamorphism ................................................................... 102 vii 3.5.1.4 Post-M2 hydrothermal alteration ...................................................................................... 103 3.5.2 Comparison of new observations with previous knowledge ................................................... 103 3.5.2.1 Comparison of pre-mineralization events ........................................................................ 103 3.5.2.2 Comparison of main vein and ore-forming stage ............................................................. 106 3.5.2.3 Comparison of post-mineralization events ....................................................................... 107 3.6 Future discussion topics .................................................................................................................. 108 3.7 Conclusions ..................................................................................................................................... 108 Chapter 4: Mineral chemistry and lithogeochemistry of the Red Lake Gold Mines ......... 110 4.1 Introduction ..................................................................................................................................... 110 4.2 Methodology ................................................................................................................................... 111 4.2.1 Petrography.............................................................................................................................. 111 4.2.2 Cathodoluminescence and acid testing for carbonate mineral identification .......................... 111 4.2.3 Scanning electron microscopy ................................................................................................. 112 4.2.4 Electron microprobe analysis .................................................................................................. 112 4.2.4.1 Chlorite ............................................................................................................................. 115 4.2.4.2 Biotite ............................................................................................................................... 116 4.2.4.3 Amphibole ........................................................................................................................ 117 4.2.4.4 Carbonate ......................................................................................................................... 118 4.2.4.5 Garnet ............................................................................................................................... 119 4.2.5 Lithogeochemistry (whole rock geochemistry) ....................................................................... 120 4.3 Mineral chemistry data ................................................................................................................... 122 4.3.1 Chlorite .................................................................................................................................... 122 4.3.2 Biotite ...................................................................................................................................... 131 4.3.3 Amphibole ............................................................................................................................... 140 4.3.4 Carbonate ................................................................................................................................. 150 4.3.5 Garnet ...................................................................................................................................... 156 4.4 Geothermometry ............................................................................................................................. 162 4.4.1 Carbonate thermometry ........................................................................................................... 165 4.4.2 Garnet-biotite thermometry ..................................................................................................... 166 4.4.3 Chlorite thermometry .............................................................................................................. 167 4.4.4 Geothermometry summary ...................................................................................................... 169 4.5 Whole rock geochemistry data........................................................................................................ 169 4.5.1 Identification of least altered basalt protolith .......................................................................... 169 4.5.2 Identification of altered basalt protolith .................................................................................. 170 4.5.3 Calculation of mass balances between alteration assemblages ............................................... 178 viii 4.5.4 Characterization of element variations for the key alteration assemblages ............................. 182 4.5.5 Ferric and ferrous iron variations ............................................................................................ 185 4.6 Chemical vectors, and footprints to mineralization ........................................................................ 194 4.6.1 Lithogeochemistry; pathfinder elements – vectors to ore ........................................................ 194 4.6.2 Mineral chemistry vectors ....................................................................................................... 200 4.7 Summary of the controls on composition and distribution of minerals .......................................... 202 4.8 Conclusions and future discussion .................................................................................................. 205 Chapter 5: Stable isotopes of Carbon, Oxygen and Sulfur from the Red Lake Gold Mines: implications for fluid sources ................................................................................................... 207 5.1 Introduction ..................................................................................................................................... 207 5.2 Stable isotopes from Archean lode-gold deposits ........................................................................... 207 5.3 Stable isotopes from the Red Lake Gold Mines ............................................................................. 208 5.4 Methodology ................................................................................................................................... 209 5.4.1 Carbon and oxygen isotopes .................................................................................................... 209 5.4.2 Sulfur isotopes ......................................................................................................................... 210 5.5 Results ............................................................................................................................................. 216 5.5.1 Carbon and oxygen isotopes .................................................................................................... 216 5.5.2 Sulfur isotopes ......................................................................................................................... 218 5.6 Suggested Fluid sources .................................................................................................................. 225 5.6.1 Origin of carbonate vein-forming fluid ................................................................................... 225 5.6.2 Source of the mineralizing (sulfur-bearing) fluid .................................................................... 232 5.6.3 Summary of implied fluid sources........................................................................................... 233 5.7 Explanation of isotope enrichment proximal to gold-mineralization ............................................. 234 5.8 Conclusions and suggestions for exploration ................................................................................. 235 Chapter 6: Environments of hydrothermal and metamorphic events: implications for ore genesis at the Red Lake Gold Mines. ...................................................................................... 237 6.1 Introduction ..................................................................................................................................... 237 6.2 The environment and nature of H1: early hydrothermal alteration in the RLGM ........................... 238 6.2.1 Evidence of early hydrothermal alteration from mineral assemblages, mineral chemistry and whole rock geochemistry .................................................................................................................. 238 6.2.2 Possible early hydrothermal environments .............................................................................. 240 6.2.2.1 Summary of a subseafloor system .................................................................................... 241 6.2.2.2 Summary of a low-sulfidation system .............................................................................. 242 6.2.2.3 Summary of a detachment fault system ........................................................................... 242 ix 6.2.3 The comparison of suggested possible hydrothermal environments with Red Lake observations………………………………………………………………………… ……………..246 6.2.4 Conclusion of the early hydrothermal environment at Red Lake ............................................ 251 6.3 Nature of H2: the ore-forming hydrothermal system ...................................................................... 254 6.4 Nature of H3: minor post-mineralization (syn-D3–D4) hydrothermal alteration ............................. 255 6.5 Genesis of the Red Lake Gold Mines ............................................................................................. 256 6.5.1 Previous genetic models of the RLGM and Archean lode-gold deposits ................................ 257 6.5.2 Gold precipitation mechanisms in Archean lode-gold systems ............................................... 259 6.5.3 Improved genetic model for gold deposition at the Red Lake Gold Mines ............................. 260 Chapter 7: Application of non-destructive, field-based techniques for exploration in the Red Lake area ........................................................................................................................... 269 7.1 Introduction ..................................................................................................................................... 269 7.2 Methodology ................................................................................................................................... 270 7.2.1 Shortwave infrared (SWIR) analysis ....................................................................................... 270 7.2.2 Magnetic susceptibility ............................................................................................................ 274 7.2.2.1 Core diameter corrections ................................................................................................ 277 7.2.2.2 Split core corrections ........................................................................................................ 277 7.2.3 A note on analytical techniques ............................................................................................... 278 7.3 Identification of minerals and chemical trends using the SWIR..................................................... 278 7.3.1 Chlorite .................................................................................................................................... 279 7.3.2 Biotite ...................................................................................................................................... 284 7.3.3 Carbonate ................................................................................................................................. 287 7.3.4 Amphibole ............................................................................................................................... 294 7.3.5 Comparison of SWIR and whole rock geochemistry trends ................................................... 296 7.3.6 Influencing factors on SWIR ................................................................................................... 299 7.4 Magnetic susceptibility ................................................................................................................... 301 7.4.1 Relationship between magnetic susceptibility, mineralization and alteration ......................... 302 7.4.2 Comparison of magnetic susceptibility and whole rock chemistry ......................................... 306 7.5 Conclusions and exploration implications for field-based exploration in the Red Lake area ......... 308 Chapter 8: Conclusions ............................................................................................................ 309 8.1 Introduction ..................................................................................................................................... 309 8.2 Mineral chemistry ........................................................................................................................... 309 8.2.1 Chlorite .................................................................................................................................... 310 8.2.2 Biotite ...................................................................................................................................... 311 x 8.2.3 Carbonate ................................................................................................................................. 312 8.2.4 Amphibole ............................................................................................................................... 312 8.2.5 Garnet ...................................................................................................................................... 313 8.2.6 Summary of the influences on mineral composition and distribution ..................................... 314 8.3 Evolution of the Red Lake Gold Mines .......................................................................................... 315 8.3.1 Relationship between early, pre-regional hydrothermal alteration and the main ore-formation event……………………………………………………………………………………………… .. 315 8.3.2 The vein and main mineralization hydrothermal event ........................................................... 317 8.3.3 Improvements to the RLGM genetic model ............................................................................ 318 8.4 Exploration implications ................................................................................................................. 319 8.4.1 Mineral chemistry vectors ...................................................................................................... 319 8.4.2 Isotopic compositional variations ............................................................................................ 322 8.4.3 Pathfinder elements within whole rock geochemistry ............................................................. 322 8.5 Suggestions for further investigations ............................................................................................ 324 References .................................................................................................................................. 325 Appendices ................................................................................................................................ 365 Appendix A For Chapter 1 .................................................................................................................... 365 A.1 Drill hole logs .......................................................................................................................... 365 A.2 Sample details of all samples used in this dissertation to obtain data ...................................... 421 A.3 Underground Map .................................................................................................................... 442 A.4 Regional geological map .......................................................................................................... 444 A.5 Carbonate mineral staining and ultraviolet methods and results .............................................. 446 Appendix B For Chapter 4 .................................................................................................................... 449 B.1 Electron microprobe errors ....................................................................................................... 449 B.2 Chlorite EMPA data ................................................................................................................. 450 B.3 Biotite EMPA data ................................................................................................................... 478 B.4 Amphibole EMPA data ............................................................................................................ 498 B.5 Carbonate EMPA data .............................................................................................................. 513 B.6 Garnet EMPA data ................................................................................................................... 537 B.7 Quality control for four acid digestion and lithium borate fusion geochemistry methods ....... 578 B.8 Four acid digestion whole rock geochemistry data .................................................................. 583 B.9 Lithium borate fusion data ....................................................................................................... 592 B.10 Carbonate mineral identification using cathodoluminescence, scanning electron microscopy and reactivity with acid ................................................................................................................... 594 xi B.11 Least altered samples and mass balance data ......................................................................... 598 Appendix C For Chapter 5 .................................................................................................................... 633 C.1 Quality control for carbon and oxygen isotope data ................................................................ 633 C.2 Quality control for sulfur isotope data ..................................................................................... 636 C.3 Carbon and oxygen isotope data .............................................................................................. 637 C.4 Sulfur isotope data .................................................................................................................... 640 Appendix D For Chapter 7 .................................................................................................................... 642 D.1 SWIR data ................................................................................................................................ 642 D.2 Magnetic susceptibility data ..................................................................................................... 671 xii List of tables Table 1.1 Summary of geochemical anomalies associated with gold mineralization in the Yilgarn Craton, Australia ............................................................................................................................. 6 Table 1.2 Number of samples used in terms of lithology and analytical method ........................ 14 Table 2.1 Summary of the main supracrustal assemblages in the RLGB .................................... 25 Table 2.2 Details of the ore zones mentioned in this dissertation: their location, vertical extent and mineralization style(s) ............................................................................................................ 37 Table 2.3 Summary of the main alteration assemblages observed at the RLGM ......................... 39 Table 4.1Standard operating information for EMPA ................................................................. 113 Table 4.2 Minerals investigated using electron microprobe with sample numbers and lithology .................................................................................................................................................... 113 Table 4.3 Representative chlorite EMPA ................................................................................... 123 Table 4.4 Representative Biotite EMPA .................................................................................... 133 Table 4.5 Representative Amphibole EMPA data ...................................................................... 142 Table 4.6 Representative carbonate EMPA ................................................................................ 151 Table 4.7 Representative garnet EMPA data .............................................................................. 157 Table 4.8 Previous peak-metamorphism P-T conditions ............................................................ 165 Table 4.9 Summary of temperature estimates derived from multiple calculation methods for garnet-biotite thermometry ......................................................................................................... 167 Table 4.10 Summary of calculated chlorite thermometry estimates .......................................... 168 Table 4.11 Least altered basalt samples from the RLGM .......................................................... 171 Table 4.12 Representative whole rock analysis .......................................................................... 175 Table 4.13 Eight alteration and vein assemblages, their mineralogy and paragenetic timing .... 180 Table 4.14 Summary of mass balance differences for mineral assemblages in paragenetic order .................................................................................................................................................... 184 Table 4.15 Representative basalt samples for Fe2+ and Fe3+ ...................................................... 189 Table 4.16 Summary of pathfinder elements at the RLGM ....................................................... 196 Table 5.1 Summary of carbon isotopic compositions (δ13CVPDB ‰)..................................... 217 Table 5.2 Summary of oxygen isotopic compositions (δ18OVSMOW ‰) ............................... 218 Table 5.3 Summary of sulfur isotopes with regard to mineral and relatively timing in relation to ore mineralization. ...................................................................................................................... 224 xiii Table 6.1 Summary and comparison of possible early hydrothermal environments at Red Lake .................................................................................................................................................... 244 Table 7.1 Investigated minerals and their distinguishing SWIR absorption features ................. 271 Table A.1 Complete sample details ............................................................................................ 422 Table B.1 Calculated error for each element and mineral for the EMPA data ........................... 449 Table B.2 Complete electron microprobe data for all samples probed for chlorite chemistry ... 451 Table B.3 Complete electron microprobe data for all samples probed for biotite chemistry ..... 479 Table B.4 Complete electron microprobe data for all samples probed for amphibole chemistry .................................................................................................................................................... 499 Table B.5 Complete electron microprobe data for all samples probed for carbonate chemistry .................................................................................................................................................... 514 Table B.6 Complete electron microprobe data for all samples probed for chlorite chemistry ... 538 Table B.7 Four acid digestion methodology whole rock geochemistry quality control ............. 579 Table B.8 Quality control for lithium borate fusion whole rock geochemistry .......................... 582 Table B.9 Complete four acid digestion whole rock geochemistry data for the RLGM and surrounding area along the cross sections .................................................................................. 584 Table B.10 Complete lithium borate fusion whole rock geochemistry data .............................. 593 Table B.11 Carbonate mineral identification using SEM-ED, CL and reactivity with acid ...... 594 Table B.12 Subset of representative samples for mass balance calculations ............................. 599 Table C.1 Duplicated samples assessed for carbon and oxygen isotopes collected at the University of British Columbia with calculated mean and standard deviation .......................... 633 Table C.2 Duplicated samples assessed for carbon and oxygen isotopes collected at the GNS Stable Isotope Laborator, New Zealand with calculated mean and standard deviation ............. 634 Table C.3 Assessment of dupllicated sulfur isotope samples for quality control ...................... 636 Table C.4 Carbon and oxygen isotope data ................................................................................ 638 Table C.5 Sulfur isotope data ..................................................................................................... 640 Table D.1Complete shortwave infrared data ............................................................................. 643 Table D.2 Complete magnetic susceptibility data ...................................................................... 671 xiv List of figures Figure 1.1 Sketches showing characteristics of lode-gold deposits.. ............................................. 2 Figure 1.2 Location of the Red Lake Gold Mines within the Uchi Subprovince, Superior Province, Canada (modified from Card and Ciesielski, 1986). ...................................................... 8 Figure 1.3 The Red Lake greenstone belt with the distribution of volcanic-clastic assemblages with the known mineral deposits (past and present) and mineralized occurrences indicated (modified from Sanborn-Barrie et al., 2001). ................................................................................. 9 Figure 1.4 Geological map of the area surrounding the RLGM. Information compiled from Pirie and Grant (1978); Thurston and Barlett (1981); Sanborn-Barrie et al. (2004); Bouzari (2009). . 15 Figure 1.5 Both cross sections, A) Campbell, B) Red Lake, with all the drill cores logged in this study and by Bouzari, (2007). ...................................................................................................... 16 Figure 1.6 Ore zones visited and samples for both mine complexes, with the area mapped indicated. A) Campbell complex, B) Red Lake complex ............................................................. 18 Figure 1.7 Location of all basalt samples used for whole rock geochemistry, mineral chemistry, shortwave infrared, magnetic susceptibility and petrographic analysis for the following PhD dissertation. A) Campbell complex, B) Red Lake complex ......................................................... 19 Figure 2.1 The distribution of metamorphic facies in mafic units only in the RLGB, modified from Thompson (2003). Ages of felsic intrusions from Corfu and Wallace, (1986), Corfu and Andrews, (1987), Noble, (1989) and Corfu and Stone, (1998). Past and current producing gold mines in the RLGB occur in the upper greenschist to lower amphibolite facies. ........................ 26 Figure 2.2 RLGB with indicated D2 structural corridors. Ore deposits of the RLGB are located within these strain corridors, each with a halo of highly altered rocks (carbonate-sericite-biotite). Modified from Pirie (1981), Andrews et al. (1986) and Hugon and Schwerdtner (1988). .......... 30 Figure 2.3 Red Lake complex 16 level mine stratigraphy. ........................................................... 33 Figure 2.4 Lithology along both cross sections. A) Campbell, B) Red Lake. Data obtained from re-logged drill cores in this study and by Bouzari, (2007). .......................................................... 34 Figure 3.1 Schematic conceptual cross section of the RLGM based on drill core observations showing spatial relationship of the alteration assemblages prior to late deformation. ................. 46 Figure 3.2 Paragenetic sequence of both hydrothermal and metamorphic mineral assemblages as defined and characterized in this study. Ages of plutons from Wallace et al. (1986) and Corfu and Andrews (1987) ..................................................................................................................... 49 xv Figure 3.3 Early biotite-Ti-magnetite ± carbonate alteration.. ..................................................... 50 Figure 3.4 Birefringent chlorite varieties ..................................................................................... 51 Figure 3.5 Examples of Berlin blue chlorite ± sulfide alteration. ................................................ 53 Figure 3.6 Examples of brown chlorite. ....................................................................................... 55 Figure 3.7 Examples of the greenschist assemblage. ................................................................... 58 Figure 3.8 Examples of transitional and amphibolite assemblage .............................................. 60 Figure 3.9 Amphibolite facies assemblages. ................................................................................ 62 Figure 3.10 Examples of garnet timing ........................................................................................ 64 Figure 3.11 Examples of garnet and quartz-muscovite-andalusite assemblage. .......................... 66 Figure 3.12 Examples of quartz-muscovite-andalusite ± chlorite ± biotite (bleached) assemblage. ................................................................................................................................... 67 Figure 3.13 Examples of plagioclase and blue tourmaline. .......................................................... 69 Figure 3.14 Acicular blue chlorite-muscovite ± carbonate ± quartz assemblage. ........................ 71 Figure 3.15 Examples of calcite-magnetite veins.. ...................................................................... 72 Figure 3.16 Examples of ankerite-calcite-biotite ± quartz and epidote-carbonate ± quartz veins. ...................................................................................................................................................... 74 Figure 3.17 Chlorite veinlets. ....................................................................................................... 76 Figure 3.18 Examples of ankerite-calcite veins ± chlorite selvages ............................................ 78 Figure 3.19 Examples of ankerite-calcite-quartz and quartz-ankerite veins. ............................... 80 Figure 3.20 Examples of en echelon quartz veins. ...................................................................... 81 Figure 3.21 Examples of sphalerite. ............................................................................................. 83 Figure 3.22 Examples of pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold, stibnite ± gold assemblages and quartz-molybdenum ± gold veins. .................................................................... 85 Figure 3.23 Quartz-ankerite-brown biotite-pyrrhotite-gold vein examples. ................................ 87 Figure 3.24 Examples of arsenopyrite-quartz-pyrrhotite-gold-brown biotite-quartz mineralization. .............................................................................................................................. 89 Figure 3.25 Examples of late calcite between ankerite and quartz, ankerite and ore-stage sulfide and ankerite vein and regional metamorphic assemblage. ........................................................... 91 Figure 3.26 Examples of quartz-muscovite and quartz-tourmaline veins. ................................... 93 Figure 3.27 Distribution of alteration assemblages compiled along both cross sections. A) Campbell, B) Red Lake ................................................................................................................ 97 xvi Figure 3.28 Summary of the recorded alteration mineral assemblage zonation surrounding the RLGM. .......................................................................................................................................... 98 Figure 3.29 The distribution of chlorite birefringence colours as seen in thin sections from basalt units of the RLGM. A) Campbell, B) Red Lake......................................................................... 100 Figure 3.30 Metamorphic facies as defined by thin section observations of basalt samples across the RLGM cross section. A) Campbell, B) Red Lake. Damer’s (1997) staurolite in and chloritoid out isograd lines are indicated on the Red Lake cross section. .................................................. 101 Figure 3.31 Schematic diagram showing the major geological phases of the RLGM’s development ................................................................................................................................ 104 Figure 3.32 The stages of hydrothermal mineral assemblages identified at the RLGM. ........... 105 Figure 4.1 Location of all samples selected for electron microprobe analysis showing which minerals were analyzed per sample. A) Campbell, B) Red Lake ............................................... 114 Figure 4.2 Location of basalt whole rock samples from this study and Bouzari (2009) which are used in the lithogeochemical study of the RLGM. A) Campbell complex, B) Red Lake complex. .................................................................................................................................................... 121 Figure 4.3 All chlorite EMPA XMg verses Si. ........................................................................... 127 Figure 4.4 Variation in chlorite chemistry relative to Fe/(Fe+Mg) apfu .................................... 128 Figure 4.5 Spatial distribution of the chlorite varieties along the A) Campbell complex and B) Red Lake complex for basalt samples only. ............................................................................... 129 Figure 4.6 Vertical distribution of chlorite chemistry with depth for basalt samples only. ....... 131 Figure 4.7 The comparison between chlorite Fe/(Fe+Mg) and whole rock Fe/(Fe+Mg) ........... 132 Figure 4.8 Biotite classification based on Deer et al., (2004) and Fabbrizio et al., (2006) ........ 134 Figure 4.9 Variations in biotite chemistry relative to F, Cr, Mn, Site and Cr for various alteration assemblages. ............................................................................................................................... 135 Figure 4.10 Comparison between whole rock XMg and Biotite XMg....................................... 136 Figure 4.11 Variation in biotite chemistry with depth in the mine complexes........................... 138 Figure 4.12 Variation in biotite chemistry with increasing distance from known ore zones of the RLGM ......................................................................................................................................... 139 Figure 4.13 Classification of amphibole EMPA data based on Leake et al. (1997) and Hawthorne and Oberti, (2007b). .................................................................................................................... 144 Figure 4.14 Variations in amphibole chemistry in relation to type and name. ........................... 145 Figure 4.15 Comparison of whole rock and amphibole EMPA Mg/(Mg+Fe) ratios ................. 146 xvii Figure 4.16 Variations in amphibole chemistry in relation to the main alteration assemblage affecting the host basalt and metamorphic grade. ...................................................................... 147 Figure 4.17 Variation of amphibole chemistry with lateral distance from ore. .......................... 148 Figure 4.18 Zonation of amphibole porphyroblasts. .................................................................. 149 Figure 4.19 Carbonate mineral identification. ............................................................................ 152 Figure 4.20 Variation in carbonate chemistry over the paragenetic sequence. .......................... 153 Figure 4.21 Distribution of carbonate mineral as defined by acid testing .................................. 154 Figure 4.22 Distribution of carbonate minerals identified using SEM-EDS and EMPA ........... 155 Figure 4.23 Variations of major cations of carbonate minerals with increasing distance from ore zones. .......................................................................................................................................... 156 Figure 4.24 Examples of rim-core-rim EMPA profiles of garnets in type 1 tholeiitic basalt, type 2 calc-alkaline basalt and argillite. ............................................................................................. 160 Figure 4.25 Variation of garnet chemistry with increasing distance from known ore zones of the RLGM versus metamorphic facies. ............................................................................................ 161 Figure 4.26 Variation in garnet chemistry at the mine site from shallow to depth. ................... 163 Figure 4.27 Variations of garnet chemistry in relation to the dominant alteration assemblage of the bulk rock. .............................................................................................................................. 164 Figure 4.28 Synchronous ankerite and calcite from sample ES09_AP_6A used for carbonate thermometry calculations............................................................................................................ 166 Figure 4.29 Chemical identification of ultramafic and basalt samples. ..................................... 172 Figure 4.30 Chemical divisions of basaltic units of the Balmer assemblage. ............................ 174 Figure 4.31 Comparison of pre-metamorphic altered Balmer basalt samples and sediment packages ...................................................................................................................................... 177 Figure 4.32 Element ratios of Zr/Al verses Ti/Al to isolate the most immobile element for mass balance calculations .................................................................................................................... 179 Figure 4.33 The paragenesis with the eight main alteration assemblages highlighted ............... 181 Figure 4.34 The mass balance differences – both trace and major elements –between the main mineral assemblages described at the RLGM, as defined in Table 4.13 .................................... 186 Figure 4.35 Theoretical trends for oxidation, reduction, addition of hematite, magnetite and ankerite. ...................................................................................................................................... 190 Figure 4.36 Variations in ferric and ferrous iron of basalt ......................................................... 192 xviii Figure 4.37 Locations of samples used for Fe2+/Fetotal ratios from this study and approximate locations of MacGeehan and Hodgson (1980) and MacGeehan et al., (1982) ........................... 193 Figure 4.38 Variation of element abundance derived from four acid digestion methods with increasing distance from mineralization at the RLGM ............................................................... 197 Figure 4.39 Summary of mineral chemistry trends exhibited by chlorite, biotite, amphibole, carbonate and garnet at the Red Lake Gold Mines. .................................................................... 201 Figure 4.40 Schematic diagram showing the major geological phases of the RLGM’s development with added chemical characteristic of H1 and H2 events. ..................................... 203 Figure 5.1 Location of all carbon and oxygen isotopes (derived from carbonate) along both cross sections. A) Campbell, B) Red Lake. ......................................................................................... 211 Figure 5.2 Examples of carbonate veins. .................................................................................... 212 Figure 5.3 Location of all sulfur isotope samples indicating the lithology and relative timing of sulfide. A) Campbell, B) Red Lake. ........................................................................................... 214 Figure 5.4 Examples of pre-, syn- and post-mineralization sulfides .......................................... 215 Figure 5.5 Summary plots for carbon and oxygen isotopes for each paragenetic stage of carbonate investigated. ............................................................................................................... 219 Figure 5.6 Distribution of carbon isotopes across the A) Campbell cross section and B) Red Lake cross section. ............................................................................................................................... 220 Figure 5.7 Distribution of oxygen isotopes across the A) Campbell complex and B) Red Lake complex. ..................................................................................................................................... 221 Figure 5.8 Comparison of carbon and oxygen isotopes from mineralized occurrence in the RLGB. ......................................................................................................................................... 222 Figure 5.9 Summary of sulfur isotopes....................................................................................... 223 Figure 5.10 Sulfur isotope halo derived from syn-mineralization sulfides demonstrated along (A) Campbell complex, (B) Red Lake complex. .............................................................................. 226 Figure 5.11 Variation of sulfur isotopes at the RLGM and surrounding area compared to prior research in the Red Lake deposits, similar Archean lode-gold deposits in Western Australia and Canada and natural sulfur isotope reservoirs. ............................................................................. 227 Figure 5.12 A) Comparison of C and O isotope data with common reservoirs. B) Effect of metamorphic devolatilization on residual carbonate and produced CO2-fluid on the carbon isotopic signature and the effect of Rayleigh fractionation ........................................................ 231 xix Figure 6.1 Schematic diagram showing the major geological phases of the RLGM’s development with added chemical characteristics of H1 and H2 events. Possible hydrothermal environment and fluid sources are also added. ....................................................................................................... 239 Figure 6.2 Summary of sketched of comparable hydrothermal systems responsible for the early, pre-regional metamorphism hydrothermal alteration at Red Lake. ............................................ 243 Figure 6.3 Examples of tourmaline bearing veins from the Buffalo deposits compared to a similar tourmaline-bearing vein in a lamprophyre dyke cutting ore at the RLGM. ................... 264 Figure 6.4 Sample of high grade ore from CBC stope 40_43-FV showing pyrite rimmed by pyrrhotite. Inset A (modified from Mikucki and Ridley, 1993) is a log ƒO2 vs. log aH2S plot indicating pyrite desulfurization reaction: pyrite (red dot) goes to pyrrhotite and magnetite. Inset B (modified from Halley (2007) and Cooke and Simmons (2000)) is a log ƒO2 vs. pH plot indicating that redox differences between fluid and rock can cause gold precipitation ............. 265 Figure 6.5 The solubility of gold as a function of temperatuere and H2S content modified from (Mikucki, 1998).. ........................................................................................................................ 268 Figure 7.1 Location all samples analyzed using the Analytical Spectral Device. A) Campbell, B) Red Lake. .................................................................................................................................... 273 Figure 7.2 Reference SWIR spectra for chlorite, carbonate, biotite and hornblende (amphibole).. .................................................................................................................................................... 274 Figure 7.3Location of all samples analyzed for magnetic susceptibility values. A) Campbell, B) Red Lake. .................................................................................................................................... 276 Figure 7.4 Examples of magnetic susceptility calibrations. A) Calibration graph for diameter 4.7 cm. B) Whole:split core conversion factor for core diameter 4.7 cm. Sus = magnetic susceptibility ............................................................................................................................... 278 Figure 7.5 Comparison of proposed SWIR chlorite composition classification and known chlorite composition and corresponding birefringence colour ................................................... 281 Figure 7.6 Comparison of SWIR spectra known to contain the diagnostic wavelength features (2250 and 2340 nm) versus estimated distance from ore ........................................................... 283 Figure 7.7 Comparison of biotite chemistry by EMPA and SWIR identification ...................... 288 Figure 7.8 Variation in diagnostic biotite absorption wavelength peaks at (A) 2250, (B) 2320 and (C) 2375 nm ................................................................................................................................ 287 Figure 7.9 Identification of carbonate chemistry though SWIR absorption features ................. 289 Figure 7.10 Direct comparison between EMPA and SWIR carbonate mineral composition .... 291 xxi Figure A.7 Graphical log for drill hole 30L1268. ...................................................................... 371 Figure A.8 Graphical log for drill hole 34L814. ........................................................................ 372 Figure A.9 Graphical log for drill hole 34L235 ......................................................................... 375 Figure A.10 Graphical log for drill hole 37L726. ...................................................................... 377 Figure A.11 Graphical log for drill hole BK05009 .................................................................... 378 Figure A.12 Graphical log for drill hole BK05010 .................................................................... 379 Figure A.13 Graphical log for drill hole BK05011. ................................................................... 380 Figure A.14 Graphical log for drill hole CR464......................................................................... 381 Figure A.15 Graphical log for drill hole CR466......................................................................... 382 Figure A.16 Graphical log for drill hole CR467......................................................................... 383 Figure A.17 Graphical log for drill hole CR468......................................................................... 384 Figure A.18 Graphical log for drill hole CR469......................................................................... 385 Figure A.19 Graphical log for drill hole CR4610....................................................................... 386 Figure A.20 Graphical log for drill hole CR4611....................................................................... 387 Figure A.21 Graphical log for drill hole CR4612....................................................................... 389 Figure A.22 Graphical log for drill hole CR4613....................................................................... 389 Figure A.23 Graphical log for drill hole D14981. ...................................................................... 390 Figure A.24 Graphical log for drill hole D15367. ...................................................................... 392 Figure A.25 Graphical log for drill hole D16355. ...................................................................... 393 Figure A.26 Graphical log for drill hole D21708. ...................................................................... 394 Figure A.27 Graphical log for drill hole D27343. ...................................................................... 397 Figure A.28 Graphical log for drill hole D27943 ....................................................................... 398 Figure A.29 Graphical log for drill hole DS11. .......................................................................... 402 Figure A.30 Graphical log for drill hole DS139. ........................................................................ 403 Figure A.31 Graphical log for drill hole DS172. ........................................................................ 404 Figure A.32 Graphical log for drill hole DS173. ........................................................................ 405 Figure A.33 Graphical log for drill hole DS174. ........................................................................ 406 Figure A.34 Graphical log for drill hole DS177. ........................................................................ 407 Figure A.35 Graphical log for drill hole DS180. ........................................................................ 409 Figure A.36 Graphical log for drill hole DS340. ........................................................................ 410 Figure A.37 Graphical log for drill hole DS615. ........................................................................ 411 Figure A.38 Graphical log for drill hole GC01080 .................................................................... 415 xxii Figure A.39 Graphical log for drill hole R87105. ...................................................................... 417 Figure A.40 Graphical log for drill hole R87106. ...................................................................... 418 Figure A.41 Graphical log for drill hole R87107. ...................................................................... 419 Figure A.42 Graphical log for drill hole R87108. ...................................................................... 420 Figure A.43 Geological map of stope 44-746-1 Sill................................................................... 442 Figure A.44 Accompanying annotated photographs for figure A.43 ......................................... 443 Figure A.45 Regional map of an outcrop near the Cochenous-Willans mine workinds. ........... 445 Figure A.46 Examples of carbonate staining of samples proximal to distal. ............................. 447 Figure A.47 Example of ultraviolet fluorescence of carbonate on a proximal sample A (D27943- 314) and a distal sample B (R87105-699.8).. ............................................................................. 448 Figure C.1 Graphical comparison of δ18C (VDP) data collected at the University of British Columbia (UBC) and at GNS Stable Isotope Laboratory, New Zealand. .................................. 634 Figure C.2 Graphical comparison of δ18O (smow) data collected at the University of British Columbia (UBC) and at GNS Stable Isotope Laboratory, New Zealand... ................................ 635 xxiii List of abbreviations RLGB Red Lake greenstone belt RLGM Red Lake Gold Mines CBC Campbell Complex RLC Red Lake Complex G Greenschist facies T Transitional facies A Amphibolite facies Min Mineralization Ab Albite Au Gold Amp Amphibole And Andalusite Ank Ankerite Anth Anthophyllite Aspy Arsenopyrite Bio Biotite Br. Bio Brown biotite Cal Calcite Carb Carbonate Cord Cordierite Chl Chlorite Chlt Chloritoid Cpy Chalcopyrite xxiv Czo Clinozoisite Dol Dolomite Epi Epidote Grt Garnet Hbl Hornblende Ilm ilmenite Kfs K-feldspar Mag magnetite Moly Molybdenite Mus Muscovite Plag Plagioclase feldspar P. carb Pervasive carbonate Py Pyrite Po Pyrrhotite Rut Rutile Ser Sericite Sph Sphalerite Stau Staurolite Stb Stibnite Sul Sulfide Ti-mag Ti-magnetite Tit Titanite Tour Tourmaline Qtz Quartz xxv ASD Analytical Spectral Device apfu Atoms per formula unit CL Cathodoluminescence EDS Electron Dispersion Analysis EMP Electron Microprobe EMPA Electron Microprobe Analysis LA-ICP-MS Laser Ablation-Induced Coupled Plasma-Mass Spectrometry ICP-AES Inductively Coupled Plasma-Atomic Emission Spectronometer ICP-MS Induced Coupled Plasma-Mass Spectrometry SEM Scanning Electron Microscope SWIR Shortwave Infrared TSG© The Spectral Geologist© XRD X-ray diffraction Pct Percent Tot Total δ13C ‰ delta 13C per mil δ18O ‰ delta 18O per mil δ34S ‰ delta 34S per mil VDPB Vienna Pee Dee Belemnite VSMOW Vienna Standard mean ocean water CDT Cañon Diablo Troilite oz/t Ounces per ton ppm Parts per million xx Figure 7.11 Distribution of reclassified carbonate SWIR spectra, dolomite < 1875 nm < calcite, along (A) the Campbell cross section and (B) Red Lake cross section.. .................................... 292 Figure 7.12 Distribution of reclassified carbonate SWIR spectra, dolomite < 2330 nm < calcite, along (A) the Campbell cross section and (B) Red Lake cross section ...................................... 293 Figure 7.13 Variation of diagnostic carbonate SWIR absorption features in relation to increasing distance from mineralization ...................................................................................................... 294 Figure 7.14 SWIR data that indicate a feature at both 2330 and 2400, implying a doublet diagnostic of amphibole spectra. ................................................................................................ 296 Figure 7.15 Distribution of the diagnostic amphibole SWIR absorption peaks, the 2300 and 2400 doublet, with increased distance from mineralization.. .............................................................. 297 Figure 7.16 The comparison of whole rock FeO and MgO with the SWIR 2250 nm feature. .. 299 Figure 7.17 The differences in spectral quality between dark basalt rocks and lighter basalt rocks, due to alteration.. ........................................................................................................................ 302 Figure 7.18 Relationship between percentage of magnetite and pyrrhotite in relation to whole rock sample magnetic susceptibilities ........................................................................................ 303 Figure 7.19 Relationship of magnetic susceptibility and gold grades in (A) ounces per ton, and (B) ppm. C and D represent down drill hole studies of drill holes in the Campbell and Red Lake complexes, to investigate if magnetic susceptibility can highlight areas of gold mineralization... .................................................................................................................................................... 304 Figure 7.20 Distribution of magnetic susceptibility values of basalt samples in relationship to ore zones along the A) Campbell and B) Red Lake cross section. ................................................... 305 Figure 7.21 Variation of magnetic susceptibility values between mineral assemblages. ........... 306 Figure 7.22 Comparison of whole rock molar Fe2+/Fetotal ratios and magnetic susceptibility. .. 307 Figure 8.1 Schematic diagram showing the major geological phases of the RLGM’s development, with inferred chemical characteristics of each hydrothermal event, proposed fluid sources from stable isotopic data and suggested hydrothermal environment/tectonic setting ... 316 Figure A.1 Complete key for all lithological units used in the drill core logs. .......................... 365 Figure A.2 Graphical log for drill hole 13L833. ........................................................................ 366 Figure A.3 Graphical log for drill hole 16L1067. ...................................................................... 367 Figure A.4 Graphical log for drill hole 19L020. ........................................................................ 368 Figure A.5 Graphical log for drill hole 19L457. ........................................................................ 369 Figure A.6 Graphical log for drill hole 30L1162. ...................................................................... 370 xxvi Acknowledgements This project was part of a larger NSERC (Natural Sciences and Engineering Research Council) funded research program into the footprints of Archean Lode-gold deposits co-ordinated by Drs. Bouzari and Tosdal, from the University of British Columbia. Thank you for the addition of my PhD and the opportunity to continue to learn. My sincere gratitude to Goldcorp Ltd. (the sponsoring company), the Society of Economic Geologists, the Geological Society of America and the Geological Society of London (specifically the Mineral Deposits Studies Group) for providing financial support to this project through scholarships and conference funding. I am indebted to so many people for making this project possible, particularly those at MDRU and at the Red Lake Gold Mines. My heartfelt thanks to all the staff at the Red Lake Gold Mines. There are probably very few people that did not end helping me in some way through computer issues, safety training, getting core boxes or tours of underground. Sadly there is not enough room to thank you each by name, but I know who you are. Thanks specifically to the production, mine exploration, regional exploration and core shack teams. My particular thanks to Lindsay May (best roommate ever!), Rob Penczak, Mark Epp, Chris Osowiy, Amy Newport and past employees Jim Rogers and Ken Williamson. Thanks to my supervisors/committee: Greg Dipple, Dick Tosdal and Farhad Bouzari; for hours of discussions, making time (a commodity that you rarely had), endless reviewing, guidance and suggestions for improving abstracts, posters, papers and of course, this thesis. Mati Raudsepp, Edith Czech, Jenny Lai and Elisabetta Pani – you guys are awesome! Without your help I would not have data. Thanks for answering probably thousands of questions regarding SEM, EMPA and XRD analysis. Arne Toma and Karie Smith, I am convinced that you keep MRDU running. Thank you for sorting computers/printers/posters and finances respectively. Shaun Barker, thanks for your help with getting carbon and oxygen isotopes, cathodoluminescence and general random questions about structure, mapping and lab issues. Ken Hickey, although we never shared much of my project, what I did ask/show you was always met with enthusiasm, encouragement and suggested ideas I would have loved to have tried if time allowed. Jeremy Vaughan and Trent Newkirk, thanks for being great office mates, for challenging me on more topics than our projects. Esther, Sara and Kathy thank you for your patience in reading, editing and making comments. You definitely helped in refining and improving this thesis. xxvii To my friends from other walks of life – thank you for helping me see geology is not everything. Thanks to my friends from UBC and home group (especially the Ross family) for your encouragement to keep going. Special thanks to Laura Estrada; you are a star! Thank you for your enthusiasm, encouragement and Jedi powers. Thanks to my family back in the UK and here in Canada. Mum, Dad, Ellie and Sarah, you are a constant source of support; I never would have been able to do this without you cheering me on. Bruce and Susanne for introducing me to the wonders of Northern Ontario, for feeding me and making summers significantly more interesting than just rocks. Finally, Daniel, thank you for being you. For your continued patience, something one day I’d like you to teach me. xxviii Dedication For my Grandfather, Dennis, who showed me the importance of having an education. For my parents, David and Yvette, who allowed me to pursue my dreams of learning across the northern hemisphere. For my husband, Daniel, for helping me get to the finish line. 1 Chapter 1: Introduction 1.1 The importance of geochemical research in ore deposit exploration Gold-rich, hydrothermal Archean lode-gold deposits (Cooke, 1946; Hagemann and Cas- sidy 2000; Robert et al., 2005) constitute approximately 20% of the world’s gold production (Roberts, 1987; Robert and Poulsen, 1997). This is a remarkably high statistic considering that their narrow mineralized zones and subtle geochemical footprint make Archean lode-gold depos- its particularly challenging exploration targets (Goldfarb et al., 2005). Detailed knowledge of the distal hydrothermal geochemical footprint is key to expanding the exploration target of this de- posit type. However, the geochemical footprint associated with lode-gold mineralization is poor- ly-understood, particularly with regard to how distal alteration relates to narrow ore zones. Geo- chemical investigations of known Archean lode-gold deposits have the potential to provide the crucial link between geological research and exploration targeting (Kelley et al., 2006). This pro- ject focused on a detailed documentation and characterization of the greater hydrothermal foot- print surrounding the Archean lode-gold system of the Red Lake Gold Mines (RLGM). This ge- ochemical study of the greater hydrothermal system provides useful information regarding ore genesis, fluid-rock interactions, and geochemical influences on gold mineralization. 1.2 Characteristics and previous studies of lode-gold deposits Lode-gold deposits are defined as epigenetic with structurally controlled vein or wall rock mineralization and associated alteration (Groves et al., 1998; Fig. 1.1). This deposit type has also been referred to as shear-zone-related, quartz-carbonate, mesothermal, greenstone- hosted, orogenic and metamorphic gold (Dubé and Gosselin, 2007 and references therein). Some of these names infer a specific ore genesis. For this project, the name lode-gold was chosen be- cause of its generalization and emphasis on the morphology of mineralization, with no specific inference regarding ore genesis. A brief summary of general lode-gold deposit features follows but the reader is referred to Colvine et al. (1988); Hodgson (1993); Kerrich and Cassidy (1994); Robert and Poulsen (1997); Eilu et al. (1997); Groves et al. (1998); Goldfarb et al. (1998); Groves et al. (2003); and Goldfarb et al. (2005) for more detailed information of specific aspects of lode-gold deposits. Lode-gold deposits are found in regionally metamorphic (granite-greenstone) terranes, hosted by a variety of rock types ranging from the mid-Archean to Quaternary (Groves et al., 2 Figure 1.1 Sketches showing characteristics of lode-gold deposits. A) Schematic and stylized representation of a lode-gold deposit formed in a compressional/transpres- sional regime showing narrow, structurally controlled gold mineralization. Dashed box indicates the close-up area shown in figure B. B) Schematic sketch showing a generic model (not to scale) of hypothetical primary geochemical dispersion and alteration halos enveloping lode-gold mineralization. Dashed lines indicate less common occurrences. CO2 = carbonation, K = sericitization, Ba, Rb, Si, Te, W, Y, etc. enrichment or depletion factors. Modified from Groves et al. (1998), Eilu and Groves (2001), and Goldfarb et al. (2005). 3 1998; Hagemann and Cassidy, 2000; Goldfarb et al., 2001, 2005). These deposits are formed at depth during compressional to transpressional deformation associated with convergent plate margin tectonics, e.g. accretionary and collisional orogenies, which can possibly be associated with plutonism (Sibson et al., 1988; Groves, 1993; Gebre-Mariam et al., 1995; Poulsen, 1996; Eilu et al., 1998; Groves et al., 1998; Cox, 2005). Lode-gold deposits are proposed to have formed over a large vertical extent, typically 5–15 km depth. Hence they are considerably more vertically extensive than other gold-only deposit types (Groves et al., 2003). Lode-gold deposits are structurally controlled (Boulter et al., 1987; Cox et al., 1995; Cox, 1999), with mineralization located in second or third order structures related to first order regional scale (transcrustal) de- formation zones (Eilu et al., 1998; Neumayr and Hagemann, 2002; Cox, 2005). Mineralization occurs late in the deformation history with lower stress regimes but highly over-pressured ore fluids focused along reactivated faults (Sibson et al., 1988; Elder and Cashman, 1992; Eilu et al., 1998). Gold mainly occurs within contractional faults and shear zones with complex anatomiz- ing geometry and conjugate arrays (Hodgson, 1993; Robert and Poulsen, 2001: Dubé and Gosselin, 2007). The ore-forming fluid is water-dominated and carbonic having a near neutral to slight alkaline pH with a low to moderate salinity (1–8 wt% NaCl), which transports gold as a reduced sulfide complex (Robert and Kelly, 1987; Powell et al., 1991; Gebre-Mariam et al., 1993; Ridley et al., 1996; Goldfarb et al 1997; Eilu et al., 1998). The fluid is formed by metamorphic or mag- matic processes (Burrows et al., 1986; Powell et al., 1991). Mineralogically, these deposits are dominated by quartz veins containing 3–5% sulfides and 5–15% carbonate minerals, with com- mon fuchsite, albite, chlorite and scheelite gangue minerals (Groves et al., 1998). Ore-forming fluid flow is broadly synchronous (syn- to post-) with peak-metamorphic conditions (Barnicoat et al., 1991; Neumayr et al., 1993; Smith, 1996; Witt et al., 1997; Knight et al., 2000). Lode-gold deposits can occur within sub-greenschist to rare granulite facies, however, greenschist to am- phibolite facies are the most common (Eilu et al., 1998). At greenschist-amphibolite conditions the controlling structures range from brittle to brittle–ductile to ductile, producing a variety of structural corridors and traps for mineralizing fluids (Cox et al., 1995; Phillips and Powell, 2010). The metamorphic grade, composition, and competence of the host rocks all influence the nature, distribution, and intensity of wall-rock alteration (Mikucki and Ridley, 1993; Dubé and Gosselin, 2007). The most commonly associated alteration assemblages are iron-carbonate, 4 potassic (either biotite in amphibolites facies, or sericite for greenschist facies), sodic, sulfidation and Ca-silicate (Eilu et al., 1998; Franklin, 1997; Dubé and Gosselin, 2007). At the deposit scale, particularly the ore zone scale (0–300 m); investigations have documented zoned alteration ex- pressions (Fig. 1.1). For greenschist-hosted deposits the proximal alteration is commonly serici- te-Fe-dolomite/ankerite-albite ± quartz ± pyrite, whereas distal alteration is calcite-chlorite- quartz-epidote-rutile and lacking sulfides (Colvine et al., 1988; Mikucki and Ridley, 1993; Rob- ert and Poulsen, 1997; Eilu et al., 1998; Goldfarb et al., 2005). For amphibolite metamorphosed deposits, the proximal alteration is calc-silicate (amphibole, garnet, diposide)-plagioclase-biotite- Fe-dolomite/ankerite-pyrrhotite-titanite and the distal alteration expressions contain amphibole (hornblende)-ilmenite ± biotite (Colvine et al., 1988; Knight et al., 1993; Eilu et al., 1998; Knight et al., 2000; Goldfarb et al., 2005). Distal alteration halos in greenschist facies extend lat- erally ≤ 2 km, whereas in amphibolite conditions a narrower halo of 0–100 m is recorded (Gold- farb et al., 2005). Compared to other hydrothermal systems, the far field alteration halos remain cryptic and poorly developed in Archean lode-gold deposits (Goldfarb et al., 2005). Several genetic Archean lode-gold models have been proposed, including magmatic volatile exsolution (Bateman, 1950; Burrows et al., 1986), syngenetic sea-floor (Hutchinson and Burlington, 1984), metamorphic crustal devolatilization (Philips and Groves, 1983; Philips et al., 1987; Cameron, 1988; Powell et al., 1991; Chi et al., 2009) and finally syn-orogenic (continental collision tectonics) seismic pumping and earthquakes (Sibson et al., 1988; Cox et al., 1995; Cox, 2005, Robert et al., 2005). More contemporary models bring in mantle activity as a thermal source for the devolatilization process (Haeussler et al., 1995; Murphy et al., 1999; Thompson and Newberry, 2000). In all cases, during orogenic tectonic events, multiple fluid sources are common, leading to a variety of settings eligible for lode-gold ore genesis (Goldfarb et al., 2005). 1.2.1 Overview of footprint and pathfinder element studies in lode-gold deposits To expand the exploration target for Archean lode-gold deposits previous research has investigated geochemical footprints, or alteration halos, which envelope mineralization to identi- fy pathfinder elements (Fig. 1.1; Eilu and Mikucki, 1998; Prendergast, 2007). A pathfinder ele- ment varies in concentration from proximal to distal occurrences and can be used to vector to- ward mineralization, e.g. the Sb abundance will increase nearer gold mineralization. Lode-gold deposits are conventionally thought to have an extensive vertical but limited lateral extent in 5 terms of fluid-rock interactions (Groves et al., 1998). This is documented as a narrow footprint of alteration halos that envelope mineralization (Ames et al., 1991; Knight et al., 1993; McCuaig et al., 1993; Cox et al., 1995; Robert and Poulsen, 1997; Bierlein et al., 2000; Ridley and Dia- mond, 2000). This definition has been challenged by the recent identification of geochemical features extending 4 km distally from gold mineralization in lode-gold deposits of the Yilgarn Craton, Western Australia (Perrault et al., 1984; Prendergast, 2007; Neumayr et al., 2008). The physicochemistry of this wide-ranging, lateral imprint is not fully understood; nonetheless, it is likely linked to mineralization on the smaller scale. The identification of zoned alteration assemblages enveloping lode-gold deposits, no matter how narrow, has challenged researchers to identify specific pathfinder elements which have the potential to provide vectors to ore over greater distances (> 2 km). Lode-gold ore zones are enriched in Au, Ag, As, B, Hg, Sb, W (± Rb, Se, Te, Bi, Pb) 103 to 104 times background. Other elements such as Ba, Cu, Pb, Ni and Zn are present at only 10-1 to 101 times background (Kerrich, 1983; Eilu et al., 1998). Regional studies have recognized that the pathfinder elements Au, As, B, Cu, and Sb are enriched up to 4 km laterally from ore (Boyle, 1979; Fyon and Crock- et, 1980; Kerrich, 1983; Perrault et al., 1984; Couture and Pilote, 1993). Studies of the Yilgarn deposits (Table 1.1) have identified features of the Archean lode- gold ore-forming system, which have aided exploration through the recognition of key attributes. The most promising discoveries are (1) the identification of wide-ranging (> 2 km) specific path- finder elements As, Sb, W, Bi, Mo, Y, and Te via bulk chemistry (lithogeochemistry); (2) the association of carbonate and sericite alteration with gold mineralization; and (3) the precipitation of gold at a redox interface. Recent investigations have considered both lithogeochemistry and stable isotope geo- chemistry to expand the footprint studies to approximately 10 km (Prendergast, 2007; Neumayr et al., 2008: Bouzari, 2009). The wide-ranging pathfinder elements for Archean lode-gold depos- its in Western Australia and the Superior Province of Canada include As, Bi, Sb, W, and Mo (Prendergast, 2007; Bouzari, 2009, Bouzari et al., 2009). The previous footprint study at the RLGM by Bouzari (2009) and the lithogeochemistry study by Prendergast (2007) at the St Ives gold camp (analogous age and geology to the Superior Craton (Robert et al., 2005)) represent the primary references and foundation for this PhD study. 6 Table 1.1 Summary of geochemical anomalies associated with gold mineralization in the Yilgarn Craton, Australia Author Deposit/Area Host Rock(s) Discoveries Eilu and Mikucki (1998) Bulletin  Tholeiitic metavol- canic basalts and dolerites  Inter-flow sedimen- tary rocks, felsics and intermediate dykes 1) Distal alteration of chlorite-calcite, intermediate alteration of calcite-dolomite, proximal alteration of sericite/dolomite-sericite 2) Targets defined by As and S extend ~150m dis- tally 3) Wider anomalies are Te, W, Sb, As, carbonation and potassic alteration Eilu and Groves (2001) Yilgarn Craton  Basalt  Dolerite  Komatiite  BIF or clastic sedi- mentary rocks  Felsic volcanics or intrusions 1) Dispersion halos of As, Au, Sb, Te and W 2) Carbonate and sericitic indices increase towards ore 3) Se or Y anomalies associated with gold mineral- ization Polito et al. (2001) Junction  Fe-rich tholeiitic sill of dolerite 1) CH4 bearing fluid inclusions are found exclu- sively at the margin of gold mineralization where the reduction of CO2 to CH4 occurred Robertson (2001) Harmony  Mafic and ultramafic flows  BIF and turbiditic sedimentary rocks 1) K, Rb and Ba, and Eu, Lu and Yb (phyllic alter- ation halo), increase in abundance near gold miner- alization 2) Au and W are the most significant indicators of mineralization Prendergast (2007) St Ives  Dolerite sills  Komatiitic and basal- tic rocks 1) Potassic and sodic alteration correlate with gold mineralization 2) Pathfinder elements – As, Sb, Bi, W and Mo linked to areas of gold mineralization 3) W is the most constrained pathfinder element Neumayr et al. (2008) St Ives  Mafic to ultramafic volcanics  Minor interflow sed- imentary rocks 1) Redox zonation around the deposit 2) Au found at the redox interface 1.2.2 Mineral chemistry studies in lode-gold deposits Mineral chemistry has been utilized in lode-gold deposits in order to distinguish fluid conditions, sources and transport distance, paragenetic stages, and thermobarometry estimates of mineralization or peak-metamorphism (Christie, 1986; Kontak and Smith, 1993; Mumin and Fleet, 1995; McClenaghan, 2005). Research has shown that the mineral chemistry composition is controlled by the wall rock, but more importantly that major element variations produce variable zonation patterns at the grain and deposit scale (Kontak and Smith, 1993; Uemoto et al., 2002). These documented zonation patterns can be used to aid exploration (McClenaghan, 2005), but also to understand ore genesis through interpretation of fluid sources, fluid-rock interactions and possible influences of external geological factors on mineralization, e.g. metamorphism (Damer, 1997). An integration of whole rock and mineral chemistry data, combined with paragenetic 7 studies is considered the best approach to fully understand the geological development, ore gene- sis and controlling factors on gold mineralization in lode-gold systems. 1.3 Introduction to the Red Lake Gold Mines The subject of this dissertation is the Archean RLGM, located in Balmertown, northwest- ern Ontario, approximately 275 km north of Thunder Bay (Fig. 1.2). The Red Lake area is a pro- lific gold camp that has contained several gold-producing mines from 1927 until present day, including the RLGM (Fig. 1.3; Penczak and Mason, 1997; Dubé et al., 2004; Sanborn-Barrie et al., 2001). The RLGM comprises two mine complexes, Campbell (CBC) and Red Lake (RLC). Mineralization at the RLGM is situated within the basalt unit of the Balmer assemblage of the Red Lake greenstone belt (RLGB) (Fig. 1.3; see Chapter 2). The RLGB has a history of explora- tion and mining which began in the 1920’s with early exploration and staking of gold showings across the belt. The future site of the RLGM was staked in 1944 by George W. Campbell and Colin A. Campbell, where visible gold was found in highly carbonate altered and silicified vol- canic rocks exposed in exploration trenches (Penczak, 1996). The Campbell and Dickenson (now Red Lake) mines were established in 1945 and 1948 respectively. These mines share one body, but were operated by different companies — Campbell by Placer Dome and Red Lake by Brews and White, then Goldcorp — until 2007 when Goldcorp purchased the Campbell mine, unifying the RLGM. The RLGM is Canada’s richest gold mine, with an estimated 40 Mt at 21 g/t (Bouzari et al., 2009). Due to Red Lake’s mining history, the productivity of the RLGM, and known gold showings in surface outcrops, exploration continues within this area. 1.3.1 Previous Red Lake studies The earliest studies of the Red Lake area were compiled by the Geological Survey of Canada and Ontario Department of Mines, through regional mapping and reconnaissance studies regarding mineral occurrences in the RLGB (e.g. Dowling, 1894; Horwood, 1945; Chisolm, 1951; Pirie and Grant, 1978; Berger and Helmstaedt, 1984). During the 1980’s to early 1990’s, regional studies of stratigraphy (Pirie, 1982; Wallace et al., 1986; Stott and Corfu, 1991), and U- Pb geochronology (Corfu and Wallace, 1986, Corfu and Andrews, 1987; Noble et al., 1989) were undertaken. Most recently, a belt scale metamorphic study (Thompson, 2003) and a review of stratigraphy, geochronology and regional mapping has been compiled (Sanborn-Barrie et al., 2000, 2001; Sanborn-Barrie et al., 2004). 8 Figure 1.2 Location of the Red Lake Gold mines within the Uchi Subprovince, Superior Province, Canada (modified from Card and Ciesielski, 1986). 9 Figure 1.3 The Red Lake greenstone belt with the distribution of volcanic-clastic assemblages with the known mineral deposits (past and present) and mineralized occurrences indicated (modified from Sanborn-Barrie et al., 2001). 10 Research at either or both of the mine complexes has focused on the structural under- standing, the environment of hydrothermal alteration, the distribution and geochemistry of al- teration assemblages and the peak-metamorphic conditions (Rigg, 1980; Hodgson et al., 1980; Hodgson and MacGeehan, 1981; Rigg and Helmstaedt, 1981; Andrews and Hugon 1985; Christie 1986; Mathieson, 1982; Mathieson and Hodgson, 1984; Rogers, 1992; Penczak, 1996; Damer, 1997; Zhang et al., 1997; Penczak and Mason, 1997, 1999; Tarnocai, 2000; Dubé et al., 2000; Dubé et al., 2001, 2002; Dubé et al., 2004; Cadieux et al., 2006). All these geological phe- nomena have the potential to influence gold-mineralization. Sulfur, carbon and oxygen isotopes have provided constraints on source reservoirs, and genetic models (Lavigne, 1983; Lavigne and Crocket, 1982; Crocket and Lavigne, 1984; Tarnocai, 2000). From isotopic studies the ore- forming fluid at Red Lake is suggested to be magmatic (Lavigne and Crocket, 1982; Crocket and Lavigne, 1984). The aforementioned studies have concentrated on the ore zone observations rather than the distal hydrothermal alteration. Regional investigations are less common, but have docu- mented a dolomite core associated with mineralization enveloped by distal calcite (MacGeehan et al., 1982; Andrews et al., 1986; Parker, 2000). Mineralization at the RLGM is also docu- mented to be surrounded by a 2 km-wide envelope of feldspar-destructive alteration (alumi- nosilicate bleached zone) (MacGeehan et al., 1982). Distal spilitic alteration containing albite is found farther than 5 km distally (MacGeehan et al., 1982; Bouzari, 2009). The feldspar- destructive alteration is considered to have occurred post-spilitic alteration during an overprint- ing acid fluid phase (Bouzari, 2009). This is due to the localization of feldspar-destructive altera- tion nearer mineralization, the accompanied loss of Na, Mg and Ca with gains in SiO2 and asso- ciation with aluminosilicate minerals (MacGeehan et al., 1982; Bouzari, 2009). Most recently, a preliminary investigation into mineral chemistry trends as identified using SWIR have indicated that chlorite becomes increasingly Fe-rich toward mineralization and muscovite becomes in- creasingly Fe-Mg rich, i.e., phengitic (Bouzari, 2009). These trends are demonstrated by basalt, ultramafic and diorite units of the Balmer assemblage (Bouzari, 2009). What is lacking from previous RLGM alteration studies is an integrated analysis of the greater km-scale hydrothermal system in terms of mineral chemistry, whole rock and isotopic variations from proximal to its most distal expression. An established alteration paragenesis, combined with geochemical data, can thoroughly aid in the understanding of the geochemical evolution and geological influences on such an ancient, gold-rich deposit. The new information 11 gathered can be applied to the general ore model, aiding in its development to better suit lode- gold systems globally. 1.4 Project rationale and objectives Despite detailed research on lode-gold systems, the understanding of the greater ore- forming hydrothermal system, alteration, fluid flow models, and physiochemical characteristics are the major unconsidered aspects. This lack of comprehensive understanding of the greater hy- drothermal system impacts exploration. This PhD project tackles the above mentioned issues in two ways: Firstly, in reference to advancing scientific understanding of ancient gold-rich hydrothermal systems, and secondly to enhance exploration efforts by characterizing an Archean lode-gold deposit laterally from its gold-rich core to its outermost physicochemical expression, up to 7 km laterally. The subject of study is the highest grade Archean lode-gold deposit in the world, the RLGM, located in north- western Ontario, Canada (Fig. 1.2). The RLGM has a known vertical extent of at least 3 km (which continues toward depth) with a subtle lateral hydrothermal footprint of greater than 7 km. The RLGM provides a unique view of the anatomy of one of the Earth’s oldest hydrothermal systems (Robert et al., 2005), including its evolution with depth and width. This work will build upon the geological and geochemical framework established by pre- vious investigations (see Chapter 2), and in particular, the larger-scale investigation of the col- laborative MDRU-Goldcorp-NSERC-CRD project assessing the footprints of Archean lode-gold deposits. This collaborative project was initiated by Drs. Richard Tosdal and Farhad Bouzari. They undertook an alteration and lithogeochemical study of the RLGM and surrounding area through surface and subsurface sampling to identify district alteration halos and pathfinder ele- ments to ore. This project is a continuation of that study to identify elements and minerals for the purpose of providing scientific information regarding the geochemical evolution and geological influences on the formation of the RLGM. The principle objectives of the PhD are to: (1) Document and characterize the alteration mineral assemblages from proximal to min- eralization up to 7 km distally; (2) Characterize major and trace element and isotopic compositions of common altera- tion minerals in order to provide a basis for their use in exploration targeting; 12 (3) Separate broadly syn-mineralization alteration from pre- and post-mineralization (hy- drothermal, metamorphic and/or metasomatic) events; (4) Assess the mineralogical expression of any metamorphic overprint and possible in- fluences of metamorphism on ore deposition; (5) Construct a physiochemical evolution model with regard to hydrothermal and meta- morphic events; (6) Compare mineral chemistry with whole rock geochemistry data in order to assess ap- plications of whole rock analysis, for the purpose of mapping alteration assemblages and mineral composition changes as they vary toward gold mineralization; and (7) Test the accuracy and reliability of non-destructive methods (magnetic susceptibility and Shortwave Infrared) with more precise destructive (e.g. electron microprobe) methods in the production of rapid data for exploration. The objectives are focused on the analysis of alteration minerals, with care taken to document the chemical and isotopic variations and physiochemical expressions. The combination of lithogeochemistry, mineral chemistry and stable isotope geochemistry provide a precise docu- mentation of specific element and/or isotopic variations within individual minerals and associat- ed hydrothermal stages. This information can better isolate the physiochemical characteristics responsible for the observed alteration halos surrounding the RLGM. 1.5 Research approach This PhD study (presented in the following chapters) used an integrated research ap- proach combining fieldwork and laboratory data. Ten months of fieldwork provided the founda- tion for the study with observations gathered primarily along two cross sections through the ac- tive mine complexes, with supplemental data from surface and underground mapping. Geologi- cal information was gathered principally from re-logged drill core with multiple representative samples taken for further laboratory analysis. The following section is dedicated to outlining the field methods, areas mapped, sample locations, and which geochemical methods were chosen and why to investigate the physiochemical evolution and genesis of the RLGM. 1.5.1 The RLGM cross sections and sample distribution The RLGM has been investigated along two parallel northeast-southwest trending cross sections transecting both the CBC and RLC (Fig. 1.4). This method of investigation was chosen to allow comparable observations of alteration and metamorphic assemblages at both mine com- 13 plexes. Cross sections allowed the analysis of alteration proximal to mineralization until the lim- its of the subtle distal footprints, therefore, allowing continuous observations of the greater hy- drothermal system. The Campbell section line is approximately 1 km from the old workings of the H.G. Young deposit which is also hosted in mafic volcanics (Lichtblau and Storey, 2009). This deposit was mined from 1960-1963, producing 55,244 troy ounces of gold with a grade of 0.192 oz/t (Lichtblau and Storey, 2009). In comparison, the RLGM as collectively produced 19,102,081 troy ounces since 1948 with an average grade of 0.684 oz/t (Lichtblau and Storey, 2009). The H.G. Young deposit produced < 1% of the gold and tonnage compared to the RLGM. The H.G. Young deposits’ mineralization occurs in quartz-fissure veins, with associated pyrite- pyrrhotite-arsenopyrite-scheelite ore minerals (Penczak, 1996). To date, no information has been published about the alteration. Due to the lack of knowledge regarding the alteration, the minor amount of gold compared to the RLGM, the similarity in host rock and mineralization styles, the influence of the H.G. Young alteration halo is correspondingly small and not important. The sections range from 6.5 km (CBC) to 7.5 km (RLC) laterally with a depth of 2.2 km at the mine (due to the underground workings) to approximately 500 m depth regionally (due to the limitation in drill hole lengths) (Fig. 1.5). Drill holes were selected at regular intervals in or- der to evenly cover the area (Fig. 1.5). Fewer holes available at the intermediate and distal scale required large gaps in data. Each drill hole was re-logged (see Appendix A.1), recording lithol- ogy, mineralization, alteration and vein types observed throughout the core. The cross sections were divided into three scales of investigation: mine (0–3 km), inter- mediate (3–5 km) and distal (> 5 km) (Fig. 1.5). These scales will be referred to throughout the following discussion to document variations in mineralogy, geochemistry and isotopes laterally from proximal to distal expressions. During field work, rock samples were taken consistently at 15–30 m spacing along drill core and at every visited underground stope. Representative samples of lithology, alteration as- semblages, mineralization styles and vein types were collected. Samples collected by Bouzari (2007) from the RLGM and surrounding area were also available for geochemical and mineral chemistry analysis. From this combined suite, 587 samples were chosen to investigate the miner- al chemistry, whole rock and isotope geochemistry variations at the RLGM. Table 1.2 provides details of the number of various lithology sampled. Table 1.2 also includes how many of the 587 samples were used in various methods to obtain chemical data. 14 Table 1.2 Number of samples used in terms of lithology and analytical method Lithology Total samples Number of samples analyzed per method Basalt 405 (4 = gabbro) Petrography = 210 samples Cathodoluminescence = 45 samples Scanning electron microscopy = 62 samples Electron microprobe = 29 samples Magnetic susceptibility = 296 samples Short-wave infrared = 131 Carbon and Oxygen isotopes = 43 samples Sulfur isotope = 48 samples Whole rock geochemistry by lithium borate fusion = 19 samples Whole rock geochemistry by 4-acid digestion = 141 samples (46 ES, 95 FB) Ultramafic 79 Petrography = 51 samples (30 BK, 6 PK, 15 UL) Electron microprobe = 1 sample (PK) Cathodoluminescence = 6 samples (2 BK, 4 UL) Scanning electron microscopy = 7 samples (1 BK, 6 UL) Magnetic susceptibility = 53 samples (34 BK, 1 PK, 18 UL) Short-wave infrared = 35 samples (8 BK, 15 PK, 12 UL) Carbon and Oxygen isotopes = 5 samples (UL) Sulfur isotope = 5 samples (4 BK, 1 UL) Whole rock geochemistry by lithium borate fusion = 2 samples Whole rock geochemistry by 4-acid digestion = 42 samples (7UL ES, 12BK 14PK 9UL FB) Felsic 26 (4 = QFP, 1 = MFP, 19 = rhyolite) Petrography = 13 samples (1 QFP, 1 MFP, 11 rhyolite) Electron microprobe = 3 samples Cathodoluminescence = 2 rhyolite samples Scanning electron microscopy = 3 rhyolite samples Magnetic susceptibility = 13 samples (2 QFP, 11 rhyolite) Short-wave infrared = 8 samples (1 QFP, 1 megaryst feldspar, 6 rhyolite) Carbon and Oxygen isotopes = 1 sample Sulfur isotope = 1 felsic tuff sample Whole rock geochemistry by lithium borate fusion = 1 sample Whole rock geochemistry by 4-acid digestion = 15 samples ( 1 MFP and 1 rhyolite ES, 4 QFP and 9 rhyolite FB) Diorite 18 Petrography = 14 samples Cathodoluminescence = 1 sample Scanning electron microscopy = 2 samples Electron microprobe = 2 samples Magnetic susceptibility = 11 samples Short-wave infrared = 5 samples Carbon and Oxygen isotopes = 1 sample Sulfur isotope = 1 sample Whole rock geochemistry by lithium borate fusion = 1 sample Whole rock geochemistry by 4-acid digestion = 13 samples (4 ES, 9 FB) Sedimentary unit 46 (9 = chert and 37 = argillite) Petrography = 12 samples (8 argillite, 4 chert) Scanning electron microscopy = 2 argillite samples Electron microprobe = 3 argillite samples Magnetic susceptibility = 9 samples (6 argillite, 3 chert) Short-wave infrared = 7 argillite samples Sulfur isotope = 10 samples (5 argillite, 3 chert, 2 cherty argillite) Whole rock geochemistry by lithium borate fusion = 1 argillite sample Whole rock geochemistry by 4-acid digestion = 19 argillite (3 ES, 17 FB), 8 chert (all FB) Lamprophyre 7 Petrography = 5 samples Cathodoluminescence = 1 sample Scanning electron microscopy = 1 sample Electron microprobe = 1 sample Magnetic susceptibility = 5 samples Short-wave infrared = 1 samples Sulfur isotope = 1 sample Whole rock geochemistry by lithium borate fusion = 1 sample Whole rock geochemistry by 4-acid digestion = 2 samples (1 ES, 1 FB) Abbreviations BK = basaltic komatiite, PK = peridotitic komatiite, UL = unclassified ultramafic, MFP = megacryst feldspar porphyry, QFP = Quartz-feldspar porphyry. 6 samples of overburden were also used from Bouzari (2009). 15 Figure 1.4 Geological map of the area surrounding the RLGM. Information compiled from Pirie and Grant (1978); Thurston and Barlett (1981); Sanborn-Barrie et al. (2004); Bouzari (2009). The investigated cross section lines are indicated. A-A’ the Campbell cross section. B-B’ the Red Lake cross section. All drill core collars (including the surface projection of underground cores) are indicated. 16 Figure 1.5 Both cross sections, A) Campbell, B) Red Lake, with all the drill cores logged in this study and by Bouzari, (2007). All the samples from both cross section are also displayed. For full sample details refer to Appendix A.2. 17 At underground stopes direct observations of the ore-scale alteration (0–15 m), different mineralization styles, vein types and the metamorphic grade from shallow to depth were com- piled. Figures 1.5 and 1.6 show the distribution of all drill hole and underground samples respec- tively used in this study. From this subset of investigated samples, 315 were chosen from the cross sections for petrographic analysis. Of those 315 samples, 245 samples had corresponding whole rock geochemistry data. Figure 1.7 shows the presence of all 405 basalt samples used in this thesis which is the bulk of the data and the specifically investigated lithology. Details of all samples collected in this study (lithology, locations, mineralogy, etc.) are provided in Appendix A.2. 1.5.2 Mapped areas Two mapped areas are available in the Appendix (A.3 and A.4). The areas mapped are an underground stope, 44-746-1 Sill, at 44 level in the RLC (Fig. 1.6 for location), and a surface outcrop near the Cochenour-Willans deposit (Figs. 1.3 and 1.4 for location). Due to active min- ing, the underground area could not be mapped in detail. However, observations, structural data and samples gathered have provided a source for supportive information regarding vein orienta- tions, vein types and alteration minerals associated with high grade veins, and to confirm major structural trends within the deposit (see Appendix A.3). Regional outcrops are sparse in the RLGB with < 1% exposure, most of which are artifi- cially created by drill platforms or exploration stripping. A regional outcrop has been mapped in detail on a 1.5 m (5 foot) scale (Appendix A.4). The outcrop is the up-dip projection from the underground Wilmar deposit, part of the recently reactivated Cochenour-Willans mine workings. The Wilmar mine was an extension of the Cochenour-Willans mine during its final years of op- eration. In total 203,256 tons were mined from Wilmar, with an average grade of 0.3 oz/t (Licht- blau and Storey, 2009). Mineralization styles are noted to be similar between Wilmar and the RLGM, with mineralized fault breccias, abundant ankerite veins and narrow quartz-filled frac- tures hosted by the Wilmar granodiorite or the Balmer assemblage basalt (Penczak, 1996). Simi- lar alteration (carbonatization, silicification, sericitization and chloritization) and metamorphic grade is also reported between the two areas (Penczak, 1996; Thompson, 2003). Through map- ping observations, a similarity in paragenetic relationships was also identified. Although a dif- ferent and smaller mineralizing system occurred to form the Wilmar deposit compared to the RLGM, the similarities in metamorphic grade, alteration, mineralization types, veins types and 18 Figure 1.6 Ore zones visited and samples for both mine complexes, with the area mapped indicated. A) Campbell complex, B) Red Lake complex. 19 Figure 1.7 Location of all basalt (n = 405) samples used for whole rock geochemistry, mineral chemistry, shortwave infrared, magnetic susceptibility and petrographic analyses for the following PhD dissertation. A) Campbell complex, B) Red Lake complex. 20 paragenetic relationships provide a similar reference when assessing the geochemical evolution of alteration in the Red Lake area. This outcrop was also selected to map in detail because it pro- vided an environment with ample time to assess vein textures, deformation phases and a thor- ough characterization of the vein paragenetic sequence, which were difficult to constrain at the mine due to narrow core intercepts and limited time at active stopes. Although mapping is not used extensively in this dissertation, the information gathered has aided significantly in further understanding the structural development, geological and geo- chemical evolution and the controls on gold-mineralization, so as to successfully fulfil the objec- tives of this dissertation. 1.5.3 Choice of geochemical methods Multiple geochemical tools were used to investigate the physiochemical evolution, ore genesis and pathfinder elements of the RLGM. Whole rock geochemistry, a tool already utilized in exploration of the Red Lake area, and Archean-lode gold deposits globally (Prendergast, 2007) was also used in this study. Alteration in the Red Lake area, particularly surrounding min- eralized areas is extremely intense (Pirie, 1981). As a result, protolith rock types are not easily recognized. Whole rock analysis enabled the characterization and chemical identification of highly altered host rocks. This consequently allowed the isolation of Balmer basalt samples which were preferentially chosen for detailed investigation as: (1) the Balmer basalt is the most abundant lithology in the RLGB (Hollings et al., 1999), (2) the Balmer basalt is the main host rock to gold-mineralization and (3) to ensure an isochemical reference with regard to metamor- phism and/or hydrothermal alteration. Comparison of least altered and altered whole rock sam- ples established the elemental gains and/or losses due to hydrothermal or metasomatic events. These data identified pathfinder elements and information regarding the nature of the hydro- thermal system. Analysis of specific minerals by scanning electron microscopy (SEM), electron micro- probe analysis (EMPA), shortwave infrared (SWIR), reactivity with HCl and cathodolumines- cence (CL) allowed the pin-pointing of geochemical trends to specific minerals, as well as ele- mental trends from proximal to distal expressions. The minerals chosen for chemical analysis were: amphibole, biotite, carbonate, chlorite and garnet. These minerals were chosen because (1) these are the most abundant minerals throughout the RLGM and RLGB, (2) they can be formed by hydrothermal and/or metamorphic processes, (3) thermobarometry calculations can be calcu- 21 lated from co-precipitated minerals, (4) all occur in multiple paragenetic stages of the deposit’s development (Chapter 3), and (5) all are easily recognized in hand sample and thin section. From mineral chemistry data, both physical and chemical information regarding metamorphism, hydrothermal alteration and fluid-rock interaction can be obtained. Stable isotopes of carbon, oxygen (from pre- to syn-mineralization carbonate) and sulfur (from pre-, syn- and post-mineralization sulfides) were gathered to provide physiochemical in- formation from the pre-, syn- and post-mineralization hydrothermal system, particularly its iso- topic signature, sources of fluids, conditions of ore-formation and influences on mineralization. Non-destructive methods were used to supplement the above data by the rapid, field- based collection of geochemical and geophysical information by SWIR and magnetic suscepti- bility. The field-based data was compared to more accurate geochemical methods. This compari- son provided an examination of the effectiveness of field-based techniques to identify mineral chemistry trends towards mineralization. Some tested techniques proved unsuccessful in identifying trends or minerals. These in- cluded chemical staining and ultraviolet fluorescence (UVF) of carbonate minerals. Both tech- niques assess the major cations present to identify the carbonate mineral. Neither technique was successful at identifying carbonate minerals due to the abundance of the Fe2+ cation in both cal- cite and ankerite at the RLGM and surrounding area. The Fe2+ cation dominated the fluorescence and staining reactions, hence only Fe-carbonate was identified regardless of scale. Appendix A.5 outlines the methodology and outcomes of carbonate staining and UVF. 1.6 Overview of the dissertation This PhD dissertation is presented in five chapters (Chapters 2 to 7) with a final 8th chap- ter dedicated to the conclusions. This dissertation is structured as a traditional thesis with each chapter building upon the previous data and discussions. Each chapter focuses on a specific area of investigation within this PhD study. Chapter 2 provides a literature review on the geology, hydrothermal alteration and metamorphism of the RLGB and RLGM. Chapter 3 outlines the characterization and definition of the mineral assemblages in and surrounding the RLGM complexes. This data is arranged and discussed in its paragenetic se- quence from oldest to youngest, highlighting the superposed nature of the mineral assemblages. A km scale mineral assemblage footprint surrounding the RLGM is documented, and the meta- 22 morphic isograd defined by mineral distribution. The established paragenesis provides a rigorous and well defined context for the following geochemical, mineral chemistry and isotope data. Chapter 4 outlines the laboratory methodology (field work details are provided above) and subsequent report of mineral chemistry and whole rock geochemistry data collected. Data is referenced to the paragenesis as outlined in Chapter 3, providing a context for which miner- als/mineral assemblages/veins were investigated and why. This data is discussed with regard to the effects of hydrothermal/metasomatic fluids on the host Balmer basalt composition and min- eral chemistry. Thermometry estimated from carbonate minerals, garnet-biotite and chlorite are also included. Chapter 5 discusses the stable isotope geochemistry particularly with regard to possible fluid sources. Potential exploration trends and the controls on stable isotope geochemistry will also be discussed. Chapter 6 discusses the possible environment(s) of the earliest recognizable hydrother- mal event to alter the Red Lake basalts. This early hydrothermal event occurred prior to peak- regional metamorphism. The chemical parameters of pre-, syn- and post-mineralization hydro- thermal events will be discussed also. The influence of pre-regional metamorphism on ore gene- sis, improvements to the genetic model and suggested gold precipitation mechanisms will also be included. Chapter 7 considers the application of non-destructive, field-based methods of geo- chemical and geophysical analysis. The identification of both minerals and mineral chemistry trends were investigated. The SWIR and magnetic susceptibility data is presented then compared and correlated with more precise and accurate geochemical methods (lithogeochemistry and electron microprobe). Finally, comments are made regarding the effectiveness of field-based tools for exploration. Chapter 8 contains the conclusions of this dissertation regarding the chemical evolution of the RLGM, ore genesis and recommendations for exploration and further academic work in the Red Lake area. 23 Chapter 2: Geology of the Red Lake greenstone belt and Red Lake Gold Mines 2.1 Introduction The subject of this study, the Red Lake Gold Mines (RLGM), is located within the Red Lake greenstone belt (RLGB) of the Uchi Subprovince, Superior Province Canada, approxi- mately 275 km northwest of Thunder Bay, Ontario (Fig. 1.2). This chapter provides the larger geological context of the RLGM and surrounding area. A synthesis of previous knowledge re- garding geological events, mineral assemblages and the current paragenetic sequence of altera- tion is included. This synthesis highlights some of the least understood aspects of this deposit that require further investigation. These least understood aspects are addressed in this study to improve the characterization and documentation of alteration assemblages, and to identify the influencing geological controls on gold mineralization at the RLGM. 2.2 Geological setting of the Red Lake greenstone belt The Superior Province, Canada is composed of several subprovinces, including the Uchi Subprovince (Fig. 1.2). The Uchi Subprovince is morphologically tabular, trending east-west, with semi-continuous ribbon-like regions of metavolcanic and metasedimentary rocks inter- woven between granitic bodies (Stott and Corfu, 1991). The Uchi Subprovince is bounded by the English River Subprovince, a high grade metasedimentary-plutonic belt to the south, and the Berens River Subprovince, a plutonic belt to the north (Stott and Corfu, 1991). The English River, Berens River and Uchi Subprovinces amalgamated during the 2713–2700 Ma Uchian phase of the Kenoran orogeny (Stott et al., 1989; Percival and Williams, 1989; Stott and Corfu, 1991). The Uchi Subprovince itself contains several greenstone belts, which in turn include nu- merous gold, iron ore, volcanic massive sulfide and magmatic copper-nickel deposits (Stott and Corfu, 1991; Percival, 2007). A particularly gold-rich area of the Uchi Subprovince is the RLGB. This area contains numerous gold occurrences with both past and presently producing mines, including the RLGM (Fig. 1.3). The RLGB is characterized by 300 Ma of almost continuous geological activity including deposition of diverse volcano-clastic stratigraphy, emplacement of granitoid batholiths, poly- phase deformation and metamorphism with gold-rich mineralization (Corfu and Andrews, 1987; 24 Sanborn-Barrie et al., 2000, 2001). Gold mineralization has been suggested as synchronous with the Uchian phase of the Kenoran orogen (Penczak, 1996). 2.2.1 Stratigraphy of the Red Lake greenstone belt Seven supracrustal assemblages compose the RLGB; these are defined by rock types, U- Pb geochronology and geochemical characteristics (Sanborn-Barrie et al., 2000, 2001; Sanborn- Barrie et al., 2004) (Fig. 1.3). All supracrustal assemblages (Mesoarchean and Neoarchean) have undergone subsequent metamorphism and hydrothermal alteration. Each assemblage’s stratigra- phy and relative ages are summarized in Table 2.1. Stratigraphic analysis of the RLGB assemblages has suggested a complex geodynamic evolution. Mesoarchean assemblages started with the deposition of the Balmer assemblage vol- canic sequence, which was suggested to have occurred at an island arc with mantle plume activ- ity (Tomlinson et al., 1998; Hollings et al., 1999; Sanborn-Barrie et al., 2001). After the Balmer the Ball assemblage was deposited. The Ball assemblage stratigraphy was interpreted as depos- ited in a shallow, marine, central–volcanic edifice with quiescence and stromatolite growth in an arc-like setting (Hollings et al., 1999; Sanborn-Barrie et al., 2001). The locally overlying Slate Bay assemblage clastic and conglomerate units contain Balmer- and Ball-age zircons (Corfu et al., 1998). This indicates an erosional event occurred after the deposition of the Ball assemblage. This erosional event caused a parallel unconformity between the Balmer and Bruce Channel as- semblages. Following deposition of the Slate Bay assemblage, the Bruce Channel sequence indi- cated further explosive, arc-like volcanism with later subsidence and deposition of clastic sedi- ments. The last Mesoarchean assemblage, the Trout Bay, represents back arc or oceanic plateau crust (Sanborn-Barrie et al., 2001). A regional angular unconformity then occurred, separating the Mesoarchean (Balmer and Bruce Channel assemblages) from the Neoarchean rocks of the Huston and Confederation assemblages. Volcanic rocks of both assemblages indicate arc-related volcanism and eruption of juvenile magma (Sanborn-Barrie et al., 2001). 2.2.2 Metamorphism and associated geological phenomena of the Red Lake greenstone belt Three recognizable episodes of metamorphism have affected the RLGB. The first, pre- peak metamorphic event (M1) was synchronous with early deformation, forming a foliation fab- ric. The second, peak-metamorphic event (M2) formed the dominant metamorphic facies throughout the RLGB. This peak-metamorphic event produced lower greenschist to upper am- 25 phibole facies known through mapping of mineral assemblages within mafic and sedimentary units (Durocher et al., 1991; Easton, 2000; Thompson, 2003). Figure 2.1 shows the distribution of peak-metamorphic mineral facies in the RLGB as defined by Thompson (2003). In the center of the belt, upper greenstone (or greenschist) facies are documented. Towards the limits of the RLGB, the metamorphic grade progressively increases to upper amphibolite facies. Peak- metamorphism can be constrained between 2734 to 2720 Ma, which is the range of pre- and syn- tectonic felsic intrusions across the RLGM (Corfu and Wallace 1986; Corfu and Andrews 1987; McMaster 1987; Noble 1989; Corfu and Stone 1998). The cause of peak-metamorphism has been intrinsically linked to either, plutonism and/or regional penetrative deformation (orogenic) events in the RLGB (Stott and Corfu, 1991; Easton, 2000; Dubé et al., 2004). However, debate remains over which geological phenomenon is more influential in the development of the peak- metamorphic facies. The third metamorphic event (M3) occurred as contact metamorphism at 2704-2699 Ma (Noble, 1989) associated with post-M2, plutonic emplacement. The M3 event was less intense than M2, therefore allowing the preservation of the greenschist-amphibolite facies pattern within the greenstone belt. Table 2.1 Summary of the main supracrustal assemblages in the RLGB Assemblage Description† Age (Ma)‡ Confederation (Volcanic sequence) 1. McNeely sequence: intermediate brecciated tuff and calc-alkaline felsic rocks. 2. Heyson sequence: tholetiic felsic rocks with pillowed mafic flows and quartz- feldspar crystalline tuff, and andesite basalt. 3. Graves sequence: tuffaceous conglomerate, andesite to dacite pyroclastics, and syn-volcanic diorite and tonalite. 2748 ± 7 2734 2731 ± 3 Huston Clastic detritus, with well-bedded argillite and turbiditic wacke. Marks an angular unconformity with a polymictic conglomerate. 2714 ± 19 Trout Bay Lower sequence of basalt with overlying intermediate tuffs and chert-magnetite iron-formation. Overlain by pillowed thoeiitic basalt capped by thin bedded ox- ide-facies iron-formation. 2853 ± 1 Bruce Channel Intermediate volcaniclastic rocks, overlain by upward grading chert-pebble con- glomerate, cross bedded wacke, siltstone, and quartz-magnetite iron-formation. 2894 ± 1.5 2891 ± 2 Slate Bay Clastic rocks (feldspathic wacke, with interbedded lithic wacke, argillite, lenticu- lar conglomerate, quartz arenite) and felsic volcanic. 2916 Ball Calc-alkaline sequence of basalt, andesite, dacite, and rhyolite intercalated with minor komatiite and komatiitic basalt flows, conglomerate, quartzite, and locally stromatolite bearing marble. 2940 ± 2 and 2925 ± 3 Balmer Submarine pillowed tholeiitic basalt, ultramafic komatiite, komatiitic basalt with minor felsic volcanics, iron formation and fine-grained clastic rocks. 2964 ±5 to 2992 ± 20 † Parker (2000); Rogers (1992); Sanborn-Barrie et al. (2000, 2001); Sanborn-Barrie et al. (2004) ‡ Corfu and Wal- lace, (1986); Corfu and Andrews (1987); Corfu et al. (1998) and Sanborn-Barrie et al. (2001). 26 Figure 2.1 The distribution of metamorphic facies in mafic units only in the RLGB, modified from Thompson (2003). Ages of felsic intrusions from Corfu and Wallace, (1986), Corfu and Andrews, (1987), Noble, (1989) and Corfu and Stone, (1998). Past and current producing gold mines in the RLGB occur in the upper greenschist to lower amphibolite facies. For abbreviations, refer to list of abbreviations. 27 2.2.2.1 Plutonism and associated metamorphism Felsic intrusions surround the greenstone belt (Figs. 1.3 and 2.1). Three generations are recognized: (1) The 2734–2731 Ma Little Vermillion Lake batholith and Douglas Lake pluton were emplaced towards the western side of the greenstone belt (Corfu and Andrews, 1987; Corfu and Stone, 1998). (2) Approximately 2720 Ma syn-tectonic Dome stock, McKenzie stock, Abino granodiorite (intruded into the Abino workings: Fig 1.3; Atkinson (1994)), Wilmar granodiorite (intruded into the Cochenour-Willans, Wilmar deposit workings; Fig. 1.3; Atkinson, (1994)), Howey diorite and Hammell Lake batholith were emplaced in the central to external northern regions of the greenstone belt (Corfu and Wallace, 1986; Corfu and Andrews, 1987; McMaster, 1987). The 2720 Ma intrusions exhibit hydrothermal alteration (carbonate ± sericite) and occa- sionally auriferous quartz-tourmaline veins (Atkinson, 1993, 1994; Pirie and Grant 1978; Pirie and Kita, 1979; Parker, 2000, 2001). (3) The 2704-2699 Ma multistage emplacement of the Killala-Baird Batholith, Walsh Lake and Cat Island plutons (Corfu and Wallace, 1986; Noble, 1989). The 2720 and 2700 Ma intrusions are possibly related to the Uchian phase of the Kenoran orogeny (Stott and Corfu, 1991; Stott et al., 1989; Percival and Williams, 1989). Several authors have attributed the metamorphic isograds, which appear concentrically around the external intrusions, to regional plutonism (Fig. 2.1; Thurston and Breaks, 1978; An- drews et al., 1986; Corfu and Andrews 1987; Corfu and Wallace, 1986; Damer, 1997; Durocher et al., 1991; Hugon and Schwerdtner, 1988; Menard and Pattison, 1998; Menard et al., 1999; Tarnocai, 2000). However, work by Thompson (2003) has suggested that some of the plutons were either too old or too young to be the principal heat source for explaining the regional metamorphic pattern. Plutons that overlap in time with the deposition of the Confederation as- semblage (Douglas Lake – 2734 Ma, Corfu and Stone (1998); Little Vermillion Lake – 2729 Ma, Corfu and Andrews (1987)) are too old to be a heat source for belt-scale metamorphic zones that cut across major structures in the belt (Thompson, 2003). In addition plutons which display car- bonate veins (post-M2 formation), such as the Dome stock, Howey diorite and McKenzie Island stock are also thought to be too old to have contributed to the heat source for (M2) peak-regional metamorphism (Parker, 2000; Thompson, 2003). Although localized contact metamorphism surely occurred, it is suggested that the supracrustal rocks of the RLGB were already undergoing peak-greenschist to amphibolite regional metamorphism when syn-tectonic intrusions occurred (Easton, 2000; Thompson, 2003). The youngest intrusions of the Walsh Lake pluton (2699 Ma; 28 Noble, 1989) and Killala-Baird batholith caused post-M2 contact metamorphism (Andrews et al., 1986; Thompson, 2003). This youngest intrusive event has been linked to retrograde chlorite which replaced garnet porphyroblasts (Menard and Pattison, 1998), the remobilization of gold (Dubé et al., 2004) and the cause of amphibolite facies (Damer, 1997). 2.2.2.2 Regional deformation and associated metamorphism Synchronous deformation and metamorphism is considered the best explanation of M1 and M2 metamorphism (Thompson, 2003; Dubé et al., 2004). The demonstration of foliation fab- rics with M1 and M2 metamorphic assemblages confirms synchronous deformation and meta- morphism. Five deformation phases are observed to have affected the RLGB; however, only three accompanying metamorphic events are distinguishable from foliation fabrics. The domi- nant deformation event throughout the RLGB is D2 (synchronous with M2). The earlier deforma- tion events of D0 and D1 are consequently not well preserved. However, evidence for each is ob- servable in some areas of the greenstone belt. 2.2.2.2.1 D0 – pre-mineralization D0 is an initial (pre-2748 Ma), non-penetrative deformation event which resulted in the tilting of the Mesoarchean rocks and formation of an angular unconformity with the overlying Neoarchean assemblages (Sanborn-Barrie et al., 2000, 2001). D0 deformation is rarely preserved as it is overprinted by younger deformation (D1 to D4). Where D0 deformation is visible, it is manifested by the overturning of the Balmer assemblage, as noted by the opposing facing pillow structures on either side of an angular unconformity in the Madsen area (Sanborn-Barrie et al., 2001). 2.2.2.2.2 D1 – pre-mineralization D1 penetrative deformation caused isoclinal folds (F1) with an associated foliation fabric (S1) (Dubé et al., 2004; Menard and Pattison, 1998; Sanborn-Barrie et al., 2001). The S1 foliation is northerly trending and axial planar to north-northeast trending F1 folds (Dubé et al., 2004). The D1 event coincides with the deposition of the Huston polymictic conglomerate, but predates the Graves sequence volcanism at approximately 2742-2733 Ma (Table 2.1; Sanborn et al., 2000, 2001; Dubé et al., 2004). Belt-wide D1 structures indicate a regional-scale, east-west trending shortening (in present day orientation) (Sanborn-Barrie et al., 2001). D1 may have been associat- 29 ed with a uniform low grade metamorphic event across the belt, due to the formation of S1 folia- tion (Menard and Pattison, 1998; Easton 2000; Thompson 2003; Dubé et al., 2004). The P-T conditions and tectonic setting of M1 is unknown. 2.2.2.2.3 D2 – syn-mineralization D2 deformation is dominantly preserved as east to northeast-striking penetrative brittle- ductile deformation, which produced folds (F2), associated foliation fabric and large scale faults (Menard and Pattison, 1998; Menard et al., 1999; Sanborn-Barrie et al., 2001; Dubé et al., 2004). F2 folds trend southeast, associated with a S2 foliation fabric with a L2 stretching lineation, both dipping southwest (Dubé et al., 2004). F2 re-folded F1 structures (Sanborn-Barrie et al., 2000), forming structural traps for mineralization (Dubé et al., 2002; Dubé et al., 2004). The main folia- tion throughout the RLGB is attributed to D2 with minimal crenulations of S1 observed (Rigg and Helmstaedt, 1981; Dubé et al., 2001; Sanborn-Barrie et al., 2001). Structural corridors of high D2 strain transect the RLGB (Fig. 2.2; Sanborn-Barrie et al., 2001). The corridor from Cochenour to Gullrock Lake contains several deposits and mineralized occurrences including the RLGM, Cochenour-Willans, HG Young, and McMarmac properties (Dubé et al., 2001; Fig. 2.2). This structural corridor strikes east-southeast and contains ductile foliation with stretching lineation fabrics (120°/75°N) as well as a mineral lineation plunging 45- 65° southwest which is coplanar with D2 fabrics (Sanborn-Barrie et al., 2001). It is widely agreed that syn-D2 metamorphism formed the peak-metamorphic facies (greenschist-amphibolite) of the RLGB. D2 has been linked to the Uchian phase of the Kenoran orogeny (Menard and Pattison, 1998; Penczak and Mason, 1997) and suggested as the possible creation mechanism of the ore-forming fluid (Chi et al., 2009). 2.2.2.2.4 D3 and D4 – post-mineralization D3 is a post-collisional strain event interpreted to have resulted from north–east regional shortening, which was significantly less intense than D2 deformation (Dubé et al., 2004). This could represent a late increment of the Uchian phase of the Kenoran orogen (Dubé et al., 2004). D3 is locally recorded in the RLGB as having occurred after 2700 ± 6 Ma, the maximum age of a younger unconformably overlying polymictic conglomerate of the English River assemblage (2696–2704 Ma), near the Madsen mine, which displays a penetrative foliation (S3) and amphi- bolite facies (Sanborn-Barrie et al., 2004). The preservation of an S3 foliation in post-D2 dykes 30 Figure 2.2 RLGB with indicated D2 structural corridors. Ore deposits of the RLGB are located within these strain corridors, each with a halo of highly altered rocks (car- bonate-sericite-biotite). Modified from Pirie (1981), Andrews et al. (1986) and Hugon and Schwerdtner (1988). 31 (cutting F2 folds) has been documented at the CBC by Penczak (1996), Zhang et al. (1997) and Tarnocai (2000). D3 strain remobilized gold into late fractures in lamprophyre dykes (which cut the preceding main gold event), producing the second mineralizing event in the Red Lake area (Dubé et al., 2001, 2004). Brittle D4 deformation is manifested as tourmaline filled, hairline faults known as “black line faults” (Rogers, 1992; Penczak and Mason, 1997, Tanrocai, 2000; Dubé et al., 2004). Late brittle structures caused by northeast–southwest shortening, identified by Zhang et al. (1997) in the Campbell complex (CBC), have also been attributed to D4 deformation (Menard and Patti- son, 1998; Menard et al., 1999). The black line faults are barren, 2–5 mm slip planes containing fine tourmaline-quartz which displace mineralization, feldspar porphyries, granodiorite and lam- prophyre dykes over several meters (Dubé et al., 2003, 2004). The lack of foliation with D4 de- formation signifies that synchronous metamorphism and deformation did not occur during this phase. 2.2.2.3 Gold-mineralization and metamorphism in the Red Lake greenstone belt Several past and currently producing mines occur near or on metamorphic isograds be- tween the greenschist and amphibolite facies in the RLGB (Fig. 2.1; Thompson, 2003). The RLGM itself is located on the low-grade side of the boundary of the greenschist to transitional facies (Fig. 2.1; Thompson, 2003). This association is consistent with Archean lode-gold depos- its in the Yilgarn Craton, which are also known to occur in transitional facies (Mikucki and Rob- erts, 2003). Consequently, transitional isograds between metamorphic facies zones are important areas for Archean lode-gold exploration. The metamorphic isograd, the relative timing of miner- alization to peak-metamorphism and the importance of metamorphism are key issues addressed in this dissertation. 2.3 Geology of the Red Lake Gold Mines 2.3.1 Mine stratigraphy The RLGM is composed of three supracrustal assemblages: the Balmer, Bruce Channel and an overlying polymictic conglomerate part of the Huston assemblage (Figs. 1.4, 2.3). This has been confirmed by re-logged drill core along the two investigated cross sections (Fig. 2.4). The Balmer assemblage consists of mostly basalt and ultramafic units (basaltic komatiite and peridotitic komatiite), with minor rhyolite and interbedded volcaniclastics (Fig. 2.4). Frequently, 32 Balmer assemblage rocks are intensively altered, causing challenging primary rock identification (Mathieson, 1982; Rogers, 1992). The Balmer basalt is an Fe(Mg)-tholeiitic basalt (Kusmirski and Crocket, 1980; MacGeehan and Hodgson, 1981) and is the main host rock to the mineraliza- tion (Rigg and Helmstaedt, 1981; Rogers, 1992; Dubé et al., 2001, 2002; Dubé et al., 2004). As- sociated with the Balmer assemblage is an early diorite intrusive called the Campbell Diorite. The Bruce Channel assemblage consists of well bedded argillite, wacke, chert and iron forma- tion, which occur in the northeast regions of the mine complexes (Fig. 2.4). Both the Balmer and Bruce Channel assemblages have been cut by quartz-feldspar porphyry dykes, followed by (melanocratic and later mesocratic) lamprophyre dykes (Dubé et al., 2004). 2.3.2 Structure of the RLGM The RLGM is situated in the hanging-wall (eastern) limb of a regional, southeast- plunging, north-northeast-trending F1 anticline (Rogers, 1992; Sanborn-Barrie et al., 2001; Dubé et al., 2003, 2004; Fig. 1.4). The majority of mine deformation is attributed to D2, but minor D1 deformation is preserved in the Huston conglomerate (MacGeehan and Hodgson, 1982; Zhang et al., 1997; Sanborn-Barrie, 2001; Dubé et al., 2001). Minor crenulations are also preserved in garnet porphyroblasts as S1 crenulated by D2 (Rigg, 1980; Rigg and Helmstaedt, 1981). D2 southeast-trending F2 folds have been transected by southeast-trending, steeply dip- ping, 70–80°south/southwest faults known as the Kovala, Red Lake, Dickenson and Campbell faults (Fig. 2.4; Penczak, 1996; Dubé et al., 2002). The faults slice stratigraphy producing alter- nating southeast-trending F2 antiforms and synforms, a manifestation due to opposite sinistral and dextral fault movement (Figs. 2.3 and 2.4; Mathieson, 1982; Penczak, 1996; Penczak and Mason, 1997; Dubé et al., 2001, 2002). 2.3.2.1 Structural control on fluid flow and mineralization Mineralization is primarily hosted and occurs in the vicinity of the main shear zones and fault structures at the RLGM. Carbonate-quartz veins and stringers of sulfides occur parallel to the fault plane with accompanying intense alteration along the main foliation throughout the RLGM (Fig. 2.3E; Penczak, 1996). It is thought that the main faults (the Dickenson, Campbell and Red Lake) acted as conduits for the ore-forming fluid (Andrews et al., 1986; Penczak, 1996; Penczak and Mason, 1997; Dubé et al., 2001, 2002). These faults are thought to have been active pre- to syn-mineralization, due to the parallel nature of mineralization and associated alteration 33 Figure 2.3 Red Lake complex 16 level mine stratigraphy. Mine floor plan geology amalgamated by K. Willamson (pers. comms., 2008). A) Fine-grained argillite, part of the Bruce Channel assemblage. B) Campbell fault deformation zone as manifested in the highly sheared peridotite komatiite unit. C) East South ‘C’ ore, replacement arsenopyrite style of mineralization with disseminated pyrite. D) Overlying conglomerate, part of the Huston, Confederation assemblage. Dashed lines outline chert, wacke and argillite clasts. E) Highly altered basalt with bleaching and fuchsite-sericite and disseminated sulfides (pyrite) parallel to the main foliation. 34 Figure 2.4. Lithology along both cross sections. A) Campbell, B) Red Lake. Data obtained from re-logged drill cores in this study and by Bouzari, (2007). 35 (Penczak, 1996). Carbonate veins, which were later replaced by quartz + gold, were focused into D2 high strain areas in basalt units, with the overlying ultramafic peridotitic komatiite and basal- tic komatiite acting as a less permeable barrier, controlling the fluid flow (Rigg and Helmstaedt, 1981; Penczak, 1996; Rogers, 1992; Dubé et al., 2001, 2002). 2.3.3 Mineralization The RLGM is a gold-only deposit with structurally-controlled mineralization. Ore zones are indicated by abundant sulfides of pyrite-pyrrhotite-arsenopyrite and accompanying magnet- ite, stibnite, molybdenite, quartz, brown biotite and gold (Rogers, 1992; Penczak, 1996; Tarnocai et al., 1997; Dubé et al., 2001, 2002, 2004; Twomey and McGibbon, 2002). Gold can be invisi- ble, associated with abundant pyrite (Tarnocai et al., 1997), or occur as free gold in quartz veins or fractures in lamprophyre dykes (Dubé et al., 2004). Several ore zones from both the Campbell complex (CBC) and Red Lake complex (RLC) will be mentioned in this dissertation. Figure 1.6 indicates the ore zones that were visited and sampled during field work for this dissertation. For details of other RLGM ore zones, refer to Lavigne (1983), Tarnocai et al. (1997), Dubé et al. (2001) and references therein. Table 2.2 briefly summarizes the location, vertical extent and mineralization styles of the ore zones visited for this dissertation. Ore zones typically consist of multiple mineralization styles (Table 2.2). Five mineral- ized styles are documented within the RLGM: (1) structurally-controlled sulfide-rich veins, mi- cro-stockwork sulfide veinlets, sulfide cemented breccias and replacement-style ore, e.g. the East South Campbell (ESC) ore zone in the RLC (Mathieson and Hodgson 1984; Penczak, 1996; Penczak and Mason, 1997, 1999); (2) banded carbonate-quartz/quartz-carbonate veins (Dubé et al., 2004); (3) magnetite-rich ore occasionally associated with the RLC ‘Main Zone’ and areas of the High Grade Zone (HGZ); (4) high-grade arsenopyrite-quartz rich rock characterized by the presence of multi-ounce zones which typify the RLC HGZ, e.g. Hanging wall 5 and South ‘C’ (Dubé et al., 2001; Mathieson and Hodgson, 1984). Stibnite and sphalerite commonly occur in high-grade zones (Penczak and Mason, 1997); and (5) visible gold can occur on its own coating and filling late fractures or with sulfides in fractions cutting silicification (Penczak, 1996; Penczak and Mason, 1997; Dubé et al., 2002). Visible gold increases in abundance with depth (Dubé et al., 2002). In the shallower mine levels, particularly the CBC, widespread disseminated pyrite-rich sulfides are documented (mineralization style 1). The sulfides are fine-grained, com- 36 posed of pyrite-pyrrhotite ± arsenopyrite with invisible gold forming low grade mineralization, approximately 0.20 oz/t to 0.30 oz/t (Rogers, 1992; Tarnocai et al., 1997). The disseminated py- rite-rich mineralization is associated with widespread quartz alteration. Banded carbonate (ankerite)-quartz veins can be replaced by quartz ± sulfides of pyrite- pyrrhotite-arsenopyrite ± stibnite ± gold (mineralization style 2). This style of mineralization oc- curs throughout the RLGM, but is most common at depth. Carbonate veins are commonly barren or contain low-grade mineralization associated with sphalerite (MacGeehan and Hodgson, 1982; Penczak and Mason, 1997; Tarnocai, 2000; Dubé et al., 2001, 2004). The replacement quartz ± sulfides are usually contained within the center of the ankerite vein. Quartz is typically micro- crystalline with accompanying fine- to coarse-grained sulfides. Gold is commonly visible within quartz-rich areas. The carbonate veins can also exhibit brown biotite + quartz altered halos (Dubé et al., 2001). Magnetite ore forms dark, fine bands mixed with Fe-dolomite-anthophyllite-grunerite and sulfides of pyrrhotite-arsenopyrite-ilmenite ± pyrite ± gold (mineralization style 3; Lavigne and Crocket, 1982; MacGeehan and Hodgson, 1982). These mineralized areas are often associat- ed with silicified host rocks (Lavigne and Crocket, 1982; Crocket and Lavigne, 1984). Magnet- ite-associated ore may have formed by metamorphic recrystallization and decarbonation of pri- mary sulfide-quartz, characteristic of mineralization style 1 (MacGeehan and Hodgson, 1982). With increased depth, the replacement style of mineralization becomes arsenopyrite- pyrrhotite rich and morphologically narrower, becoming structurally contained within fault zones (mineralization style 4; Rogers, 1992, Penczak, 1996). The gold grade also significantly increases with depth; the deepest mineralized zones contain the highest grades (average grade of 80.6 g/t Au: Dubé et al., 2004). At depth, mineralization is frequently associated with reddish- brown biotite + quartz and bleached alteration of aluminous minerals andesine-biotite-chlorite- quart-andalusite-staurolite-margarite ± chloritoid ± garnet ± epidote (Dubé et al., 2001; Cadieux et al., 2006). However, no direct spatial relationship exists between bleached and high-grade zones. Therefore, the bleached assemblage was not formed with the mineralization phase (Cadieux et al., 2006). Finally, the most spectacular gold occurs as remobilized mineralization in late lampro- phyre dykes (Dubé et al., 2004). This mineralization style consists of only gold, with no associ- ated alteration or sulfides (Dubé et al., 2004). The remobilized gold is present within lampro- 37 phyre dykes that cut previous arsenopyrite-pyrrhotite-pyrite ± gold mineralization (mineraliza- tion styles 1–4). This indicates that two stages of gold precipitation have occurred at the RLGM. A main mineralization stage composed of mineralization styles 1–4 occurred between 2722– 2712 ± 2 Ma (Corfu and Andrews., 1987; Penczak and Mason, 1997; Dubé et al., 2004). This was followed by younger remobilized gold (mineralization style 5) at ~2702 Ma (Dubé et al., 2004). These ages have been constrained from U-Pb geochronology of cross cutting quartz- feldspar and lamprophyre dykes (Dubé et al., 2004). This coincides with the proposed age of the Uchian phase of the Kenoran orogeny (Penczak and Mason, 1997) and D2 deformation, as sup- ported by cross cutting relationships of the gold-rich quartz and carbonate ± quartz veins (Dubé et al., 2001, 2002; Twomey and McGibbon, 2001). Table 2.2 Details of the ore zones mentioned in this dissertation: their location, vertical extent and mineralization style(s) Ore Zone Abbreviation Complex Vertical Extent† Mineralization style‡ East South Campbell ESC Red Lake ≈3000 feet Starting 2250 feet from sur- face 1, 3 and 4 High Grade Zone- both footwall and main zone HGZ Red Lake >3500 feet Starting ≈ 4500 feet beneath the surface 3, 4 and 5 L Zone LZ Campbell <2000 feet Starting 2100 feet from sur- face 1, 2 and very rarely 5 Deep Campbell DCB Campbell ≈ 2200 feet Starting 4000 feet from sur- face 4 and 5 †A. Newport and E.A.M. Rivera (pers. comms., 2011). ‡Rigg and Helmstaedt (1981); MacGeehan and Hodgson (1981); Rigg (1980); Hugon and Schwerdtner (1988); Rogers (1992); Penczak (1996); and this study. 2.3.4 Metamorphic facies at the RLGM Through documented mineral assemblages, the RLGM has undergone greenschist to am- phibolite metamorphism (Thurston and Breaks, 1978; Pirie, 1981; Mathieson, 1982; Mathieson and Hodgson 1984; Andrews et al., 1986; Christie, 1986; Tarnocai and Hattori, 1996; Easton, 2000; Thompson, 2003). Thermobarometry calculations estimated physical conditions of 2–4 kbars and 400–600°C, which corresponds to 7–14 km depth, assuming a lithostatic load and geo- 38 thermal gradient of 40–60°C/km and ρ = 2.85g/cm3 (Mathieson and Hodgson, 1984; Penczak and Mason, 1997; Tarnocai, 2000; Thompson, 2003). Debate remains, however, over the meta- morphic grade in each complex. It has been proposed that the metamorphic isograd occurs be- tween the two mine complexes, placing the CBC in the greenschist facies and the RLC in the amphibolite facies (Mathieson, 1982; Mathieson and Hodgson 1984; Andrews and Hugon, 1985; Andrews et al., 1986; Tarnocai et al., 1997). It has also been proposed that the greenschist- amphibole isograd cuts through each complex (Christie, 1986; Damer, 1997; Tarnocai et al., 1997; Tarnocai, 2000; Thompson, 2003; Cadieux et al., 2006). Consensus over this issue has yet to be reached. 2.3.5 Hydrothermal alteration Alteration in the RLGM reflects several superposed hydrothermal events (MacGeehan et al., 1982; MacGeehan and Hodgson, 1982; Mathieson, 1982; Mathieson and Hodgson, 1984; Menard and Pattison, 1998; Damer, 1997; Dubé et al., 2004). At least one hydrothermal event occurred prior to the peak of metamorphism (Christie, 1986; Damer, 1997; Durocher and Hugon, 1983; Kerrich et al., 1981; MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Penczak, 1996; Penczak and Mason, 1997, 1999; Thompson, 2003). Mathieson (1982) has argued that the pre-metamorphic hydrothermal alteration was so severe that the mafic rocks were of pelitic composition prior to metamorphism, thus explaining the presence of chloritoid, staurolite and andalusite in basalt, which are more common in metapelites (Penczak, 1996). The overprinting nature of the hydrothermal alteration causes a complex temporal and spatial arrangement with gold-mineralization. Previous alteration studies of the RLGM have focused either on a km-scale regional in- vestigation of the surrounding greenstone belt, concentrating on the distal expressions, or at the ore zone scale: 0–50 m wide. Both scales of investigation will be summarized below. 2.3.5.1 Regional alteration footprint Regional alteration envelopes are marked by an abundance of replacement quartz, car- bonate minerals, epidote, plagioclase, and chlorite, focused in areas of primary permeability (e.g. pillow rims, flow top breccia) (Pirie, 1981; MacGeehan et al., 1982). Footprint studies have doc- umented wide-ranging km-scale alteration halos (MacGeehan et al., 1982; Parker, 2000; Bouzari, 2007, 2008; Bouzari et al., 2009). Distal alteration consists of minor distal albite, perva- 39 sive biotite-carbonate, carbonate ± biotite veins, and pervasive chlorite-actinolite ± epidote ± chloritoid (Bouzari, 2007, 2008; Bouzari et al., 2009). The carbonate mineral varies from dolo- mite near ore to calcite distal to ore (MacGeehan et al., 1982; Andrews et al., 1986; Parker, 2000). Proximal to ore, the abundance of carbonate-quartz veins increases, and alteration assem- blages such as garnet-chlorite ± magnetite, carbonate-magnetite veins, bleached zones (quartz- muscovite ± andalusite) and sulfides become dominant (Parker, 2000; Bouzari, 2007, 2008; Bouzari et al., 2009). A 2 km wide envelope of ‘feldspar destructive’ alteration, a quartz- muscovite-chlorite-amphibole ± biotite ± garnet assemblage associated with gold, surrounds the RLGM (MacGeehan and Hodgson, 1981; MacGeehan et al., 1982). This alteration is enriched in As, Au and variable amounts of Si with corresponding depletion in Na, Ca, and variable Mg, Fe and K (MacGeehan et al., 1982). 2.3.5.2 Mine Scale Alteration The previously defined main alteration assemblages and geochemical characteristics (Ta- ble 2.3) have been documented compared to fresh, least altered basalt samples (Pirie, 1981; Penczak, 1996; Cadieux et al., 2006). For mass balance calculations (using Grant’s 1986 method) Al2O3 Cr, Ni, CO, and Zr were considered immobile (Cadieux et al., 2006). Table 2.3 Summary of the main alteration assemblages observed at the RLGM Alteration Mineralogy† Enriched Elements* Depleted Elements* Aluminosilicate bleached zones (feldspar destruction) Quartz-muscovite-biotite- chlorite-andalusite-staurolite ± garnet ± chloritoid ± margarite. SiO2, K2O Na2O, CaO, FeO, MgO, MnO, Y Garnet-magnetite ± chlorite Garnet-carbonate minerals- chlorite-biotite-amphibole- magnetite-pyrrhotite ± plagio- clase ± chloritoid ± andalusite ± staurolite ± epidote ± pyrite SiO2, FeO, MnO, K2O, S and CO2 CaO, Na2O Brown biotite- quartz ± carbonate Reddish brown biotite- amphibole-quartz-sulfides- carbonate minerals ± anorthite SiO2, CaO, K2O, S, CO2, andFe2O3 Na2O, Y Arsenopyrite- quartz-sulfides (replacement) Quartz-biotite-muscovite- amphibole-arsenopyrite- pyrrhotite-pyrite-quartz ± car- bonate minerals ± gold K2O, S, CO2, SiO2, As, Au and Fe2O3 Na2O, MnO, MgO, Y *Mass gains and losses derived from Cadieux et al., 2006 from using Grant’s (1986) †Observations compiled from, MacGeehan and Hodgson (1981, 1982); MacGeehan et al. (1982); Mathieson (1982); Mathieson and Hodgson (1984); Andrews (1984); Andrews and Hugon (1985); Andrews et al. (1986); Penczak (1996); Damer (1997); Penczak and Mason (1997, 1999); Dubé et al., (2000); Tarnocai (2000); Cadieux et al. (2006); Bouzari (2009) 40 Spatially associated with mineralization is the presence of aluminosilicate bleached zones throughout the deposit (Lavigne, 1983; Penczak, 1996; Penczak and Mason, 1997; Cadieux et al., 2006). Bleached zones contain quartz-andalusite-sericite-chloritoid-cordierite-margarite (Penczak and Mason, 1997). Aluminosilicate bleaching, or previously reported as feldspar de- struction, is characterized by the leaching of alkalis, particularly Na (Lavigne, 1983; Penczak, 1996; Damer, 1997). Bleached areas are zoned, with a proximal assemblage of quartz- andalusite-muscovite-chloritoid progressing to a garnetiferous assemblage (quartz-chlorite- garnet-chloritoid ± ankerite), and finally into quartz-ankerite-chlorite ± epidote up to 3 m from mineralization (Penczak, 1996; Penczak and Mason, 1999). The aluminous bleached zones are overprinted by the main vein stage, and therefore predate mineralization (Lavigne, 1983; Penc- zak, 1996; Cadieux et al., 2006). The garnet-magnetite ± chlorite assemblage demonstrated mass gains consistent with the mineralogy, but unexpected loss of CaO and Na2O due to the association of carbonate minerals ± plagioclase (Table 2.3). The unusual mass gains and losses for this alteration assemblage was proposed to have been the result of significant Si addition with loss of Mg, Ca, Na and K as well as the increase of Fe and Mn relative to the adjacent leaching of major cations in the aluminosili- cate bleached zone (Penczak and Mason, 1999). An alternative could have been the relative loss of amphibole compared to unaltered basalts. Compared to the unaltered basalt samples (Pirie, 1981; Cadieux et al. 2006) the minimal components of carbonate minerals and plagioclase in the altered rocks would have provided minimal influence on the bulk rock composition. As this as- semblage is considered metamorphosed hydrothermal alteration, comparison with fresh basalts as identified by Pirie (1981) and Cadieux et al. (2006) may have provided a false comparison. Rather, comparison with previously altered basalts possibly would provide more truthful repre- sentations of mass loss or gains for this assemblage. Syn-mineralization alteration of brown biotite-quartz is most commonly present at depths of, 0–150 m from mineralization. High grade carbonate-quartz veins exhibit reddish-brown bio- tite halos with disseminated pyrite ± carbonate veinlets which are replaced by arsenopyrite- muscovite ± pyrite ± pyrrhotite ± magnetite ± stibnite ± rutile mineralization (Dubé et al., 2001; 2002; Cadieux et al., 2006). The arsenopyrite-rich replacement zones are commonly enveloped by the biotite-carbonate alteration when replacing the host rock (Cadieux et al., 2006). Conse- 41 quently, the mineralogy between the arsenopyrite-rich and biotite-carbonate (Table 2.3) are simi- lar. A synthesis of alteration phases is presented below with vein and mineralization assem- blages in paragenetic sequence (oldest to youngest). This information is compiled from multiple publications, as each focused on a specific area of the RLGM rather than integrating observa- tions from the entire mine. 1. Pervasive chlorite-biotite-carbonate-amphibole and carbonate ± biotite veinlets (Mathi- eson and Hodgson, 1984; Tarnocai, 2000); 2. Locally overprinting bleached zones + quartz is accompanied by minor quartz- carbonate veining and brecciation (MacGeehan et al., 1982; Cadieux et al., 2006; Damer, 1997; Penczak, 1996; Tarnocai, 2000). Bleached areas are localized in primarily permeable structures (MacGeehan and Hodgson, 1982) and sporadically associated with garnet-chlorite ± magnetite (Penczak 1996); 3. Vein stage consisting of a. Carbonate breccias overprinted by carbonate-magnetite breccias which are cut by crustiform carbonate veins (Cadieux et al., 2006). Crustiform colloform dolomite to ankerite-quartz veins and cockade breccia infill (Penczak and Mason, 1997), b. Banded sphalerite and arsenopyrite (Penczak and Mason, 1997), c. Massive carbonate-quartz veins with (Mg-)chlorite halos (Penczak and Mason, 1997); 4. Syn-mineralization: a. Quartz-muscovite-biotite alteration, gold-replacement carbonate-quartz with bio- tite halos (Cadieux et al., 2006 ; mineralization style 2), b. Overprinting Au, As, Sb, Hg and Zn mineralization. Formation of replacement ore and breccia-hosted mineralization (Penczak and Mason, 1997; Tarnocai, 2000); 5. Narrow, quartz-rich replacement zones localized along borders of quartz-carbonate veins, possibly with gold (MacGeehan and Hodgson, 1982; Tarnocai, 2000); 6. Remobilized gold into lamprophyre dykes and late fractures (Dubé et al., 2004); 7. Veins and mineralization overprinted by quartz ± tourmaline veins and faults (Penczak and Mason, 1997; Dubé et al., 2004). 42 2.3.6 Previously suggested genetic models for the RLGM Despite several investigations into alteration assemblages and mineralization (particu- larly at the ore scale), debate remains over the ore genesis of the RLGM, particularly regarding timing (pre- or syn-metamorphism) and hydrothermal environment of formation. Pre- metamorphism mineralization has been proposed as either a syn-volcanic exhalative event with associated seafloor alteration (Crocket el at., 1980; Rigg, 1980; Kerrich et al., 1981; MacGeehan and Hodgson, 1982) or a near surface epithermal environment (Penczak, 1996; Damer, 1997; Penczak and Mason, 1997, 1999). The syn-volcanic timing of gold mineralization was proposed due to auriferous sediments and mafic volcanics (Crocket et al., 1980; Rigg, 1980) and relatively flat normalized REE patterns up to Sm-Gd, followed by an abrupt decline (Kerrich et al., 1981). This was interpreted as metasomatic fluid emanating onto the seafloor during a quiescent mafic submarine volcanic event (Kerrich et al., 1981). Pre-metamorphic epithermal mineralization was suggested due to zoned aluminosilicate-bearing alteration. This was interpreted to be originally zoned intermediate to advanced argillic alteration associated with mineralization which was sub- sequently metamorphosed to create the aluminosilicate-bearing assemblages now preserved at the CBC (Penczak and Mason, 1999). The most widely accepted genetic model is that gold mineralization occurred synchro- nously with D2 deformation and peak-(M2) regional metamorphism (MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Mathieson and Hodgson., 1984; Wilson et al., 1984; Andrews et al., 1986; Christie, 1986; Rogers, 1992; Tarnocai et al., 1997; Zhang et al., 1997; Twomey and McGibbon, 2001; Tarnocai, 2000; Dubé et al., 2004; Chi et al., 2009). This was concluded be- cause (1) high grade mineralization has occurred within and parallel to the main deformation structures (Zhang et al., 1997, Tarnocai, 2000; Dubé et al., 2001, 2004); (2) compositional zon- ing in carbonate and sulfide minerals are preserved (Tarnocai et al., 1997); (3) arsenopyrite min- eralization is recorded to be associated with metamorphic minerals, and was used to estimate metamorphic conditions (Mathieson and Hodgson, 1984); and (4) CO2-rich fluid inclusions from quartz-gold veins suggest metamorphic devolitization (Chi et al., 2009), however, the relation- ship between the studied fluids and the gold mineralization is uncertain. 43 2.4 Critical unanswered questions A consensus is yet to be reached regarding several issues needed to fully understand the RLGM. These include 1) the evaluation and contribution of the pre-metamorphic events in the gold endowment of the Red Lake camp; 2) the nature, conditions and influence of metamor- phism on the ore-formation; 3) the metamorphic grade preserved at the RLGM; and 4) ore gene- sis, as it is known that the RLGM formed due to several superposed hydrothermal events (Mathieson, 1982; Penczak, 1996; Damer, 1997). Consequently, the possibility of subsequent canalized deformation (D2) and associated gold-forming hydrothermal fluids within zones of pre-D2 altered basalts should also be considered as influential on the formation of the RLGM. Mineral deposits in Canada and Western Australia have been reported to occur in, or near to, metamorphic isograds (Hall, 1998; Mikucki and Roberts, 2003; Thompson, 2002). This common co-incidence has implications for alteration assemblages and ore genesis. Therefore, it is important to ascertain — through detailed petrography — whether the RLGM occurs within or near to a metamorphic isograd, and the grade of metamorphism. A hydrothermal event affected the host rocks at the RLGM prior to peak-metamorphism. However, the environment for this ear- ly hydrothermal event has not been defined, nor have estimated physiochemical conditions been postulated for this event. Furthermore, it is not fully understood if this pre-peak metamorphic hydrothermal event played a subsequent role in the mineralization event, e.g. did the prior hydro- thermal event provide critical ground preparation for subsequent ore-forming fluids or was the event co-incidental? Documentation of each stage of hydrothermal alteration can be used to con- struct a geochemical evolution of the RLGM from a barren to gold-rich system. Finally, was the ore genesis of the RLGM pre- or syn-peak metamorphism and deformation? These main issues will be addressed in the following PhD dissertation. Detailed petrog- raphy, whole rock, and isotope geochemistry will be used to provide more information on the ore-forming system. This new information can be utilized to better understand the formation of the gold-rich RLGM, with implications for Archean lode-gold deposits globally. 44 Chapter 3: Superposed hydrothermal and metamorphic alteration at the lode- gold Red Lake Gold Mines 3.1 Introduction Footprints of hydrothermal alteration associated with ore deposits have aided exploration and scientific understanding of the fluid pathways, fluid-rock interactions and genesis of the in- vestigated deposit. Lode-gold deposits are typically thought to have a narrow lateral extent and a considerable vertical extent in terms of their associated alteration (Groves et al., 1998). These parameters hinder exploration. Recent work investigating lode-gold deposits in the Yilgarn Cra- ton of Western Australia has indicated that this deposit type may be a narrow expression of a greater — several km-scale — hydrothermal system, which leaves only a subtle lateral imprint on the surrounding rock (Prendergast, 2007; Neumayr et al., 2008). The Red Lake Gold Mines (RLGM), an Archean lode-gold deposit in northwestern Ontario, Canada (Fig. 1.2), is analogous to the Yilgarn Craton in age and geology (Robert, 2005), also displays a complex arrangement of superposed hydrothermal alteration and metamorphic assemblages. The superposed alteration assemblages have caused confusion over the timing of mineralization, ore genesis and the identi- fication of a true associated footprint on a km-scale. The RLGM was chosen to investigate Ca- nadian examples of Archean lode-gold deposits similar to those in Western Australia, so as to examine whether they also have lateral hydrothermal footprints > 4 km distally. Previous RLGM research has considered both paragenetic and spatial relationships of al- teration assemblages to ore, providing details of timing and assemblage characterization (MacGeehan et al., 1982; Penczak, 1996; Damer, 1997; Parker, 2000; Dubé et al., 2004; Bouzari, 2007, 2009). Several superposed stages of hydrothermal alteration with synchronous deforma- tion and metamorphism have been documented in the RLGM and surrounding greenstone belt (Table 2.1; McGeehan et al., 1982; Mathieson and Hodgson, 1984; Parker, 2000; Sanborn-Barrie et al., 2001; Dubé et al., 2004). Debate remains over environments of hydrothermal alteration (particularly the early events), timing of the main gold event in relation to peak metamorphism and how many stages of alteration have occurred. Prior alteration studies at Red Lake have focused on two scales: the ore zone to mine scale (0 to 2 km distally: Penczak, 1996; Cadieux et al., 2006) and the regional scale (> 2 km dis- tally: Pirie, 1981; Parker, 2000). Lithogeochemistry studies have clearly demonstrated intense alteration surrounding the RLGM and other gold occurrences in the Red Lake greenstone belt (RLGB) (e.g. Pirie, 1981; Bouzari, 2009). The alteration is marked by an abundance of quartz, 45 carbonate, epidote, plagioclase and chlorite, which replaced original mineralogy in areas of pri- mary permeability (e.g. pillow rims) (Pirie, 1981; MacGeehan et al., 1982). The widest footprint has been recorded as a calcite halo enveloping a proximal dolomite/ferro-carbonate core that en- compasses mineralization (MacGeehan et al., 1982; Parker, 2000). Other wide-spread footprints include minor distal albite, pervasive biotite-carbonate, carbonate ± biotite veins and pervasive chlorite-amphibole ± epidote ± chloritoid (Andrews et al., 1986; Parker, 2000; Bouzari, 2007, 2008, 2009; Bouzari et al., 2009). With increased proximity to mineralization, the abundance of carbonate-quartz veins intensifies. Alteration assemblages such as garnet-chlorite ± magnetite, carbonate-magnetite veins, bleached zones of quartz-muscovite-andalusite and quartz associated with abundant sulfides also become marked (Penczak, 1996; Parker, 2000; Bouzari, 2007, 2008; Bouzari et al., 2009; Stock et al., 2010). The quartz-muscovite-andalusite assemblage has also been referred to as aluminosilicate bleaching (Penczak, 1996, Penczak and Mason, 1997, 1999, Bouzari, 2009). Mine scale alteration (Fig. 3.1) is dominated by various carbonate-quartz veins, a 1 km halo of quartz-muscovite-andalusite with smaller halos (< 400 m) of garnet-chlorite ± magnetite alteration. Narrow halos of quartz-brown biotite surround gold-rich zones containing pyrrhotite-pyrite-arsenopyrite ± stibnite ± molybdenite ± sphalerite (Dubé et al., 2001; Cadieux et al., 2006; Bouzari, 2009). In this study, alteration and metamorphic mineral assemblages have been documented and characterized along two cross sections through the Red Lake complexes (Figs. 1.4 and 2.4). Detailed information from drill core, surface outcrops and thin sections has provided a par- agenetic and spatial context for subsequent geochemical data (Chapters 4, 5 and 6). Cross section analysis has provided documentation of minerals as they vary from proximal to distal expres- sions. Mineralogical information has provided evidence of hydrothermal and metamorphic events, with implications for the geological evolution of the RLGM. The Balmer assemblage tholeiitic basalt was chosen as the constant protolith. All mineral assemblage characteristics and geochemical data have been obtained from this lithology. The Balmer basalt is the main host to gold-mineralization and the most abundant lithology (~50%) throughout the RLGB (Hollings et al., 1999; Sanborn-Barrie et al., 2000; Dubé et al., 2004). The Balmer assemblage is also similar to other host basalts elsewhere in the Superior Province and Western Australia, particularly those characterized by komatiite-basalt associations (Thurston and Chivers, 1990; Jackson and Fyon, 1991; Stott and Corfu, 1991; Williams et al., 1991; Xie et al., 1993; Robert et al., 2005). 46 This chapter has three purposes: (1) to characterize in detail the paragenesis of the RLGM; (2) to document the metamorphic and hydrothermal evolution of the RLGM; and (3) map footprints of the mineralization and associated alteration for use in current exploration methods. Throughout this chapter, the deformation and metamorphic events described in Chapter 2 are used. If required, the reader can refer to Chapter 2 for details. For all abbreviations in the following chapter, please refer to the list of abbreviations. Figure 3.1 Schematic conceptual cross section of the RLGM based on drill core observations showing spatial rela- tionship of the alteration assemblages prior to late deformation. Abbreviations: po = pyrrhotite, py = pyrite, sp = sphalerite, Fm = formation, int. = intermediate, BIF = banded iron formation (Modified from Bouzari, 2007). 3.2 Characterization of hydrothermal and metamorphic origins of minerals Several superposed geological events have affected the RLGB and RLGM. The most re- cent of these events has been a belt wide metamorphism. Consequently, all mineral assemblages (and lithology) have been metamorphosed. To understand the geological development of the RLGM, it is critical to see through this metamorphic overprint to distinguish and define precur- 47 sory hydrothermal events. Below are the criteria established to aid in seeing though the over- printing nature of metamorphic and hydrothermal events superposed at the RLGM. These crite- ria have also aided in defining the paragenetic timing of mineral assemblages. The criteria are as follows: I. Cross cutting relationships and textural events (i.e. Almeida et al., 2010) have been used to identify the relative ages of mineral assemblages. II. The development of a foliation by platy minerals (chlorite, biotite, muscovite) implies that synchronous metamorphism and deformation affected the mineral assemblage during growth. A crenulated foliation would indicate that an original synchronous metamorphic and deformation event (e.g. D1) was overprinted by another synchronous metamorphic and deformation event with a different stress orientation (e.g. D2). III. A zonation pattern demonstrated by mapped mineral assemblages of 0–7 km wide, and centered on the ore mineralization, suggests a hydrothermal origin. However, a metamor- phic zonation pattern is also present in the RLGB (Fig. 2.1). These two zonation patterns can be distinguished through detailed observations of mineral assemblages, as well as textural and cross cutting relationships. IV. The presence of high temperature metamorphic minerals stabilized by bulk chemical compositions atypical for basalt was used to infer chemical alteration before mineral growth. For example, Mn- Fe-rich garnets are unusual; however they are possible if the basalt composition is altered, modifying the rock chemistry, prior to metamorphic garnet growth (c.f. Harte and Graham, 1975). 3.3 Hydrothermal and metamorphic mineral assemblages The paragenetic sequence defined in this study is divided into three stages: (1) an early, pervasive, widespread event, including the regional metamorphic assemblage; (2) a localized, vein dominated event accumulating in the mineralization phase; and (3) a post-mineralization event consisting of tourmaline-bearing veins and gold-remobilization. All three events are con- sistent with previous published interpretations (see the synthesis of literature in Chapter 2, sec- tion 2.2.5.2). To ease the amalgamation of new observations into the current understanding of the RLGM, the paragenesis remains, where possible, tied into the geological stages as outlined by Dubé et al. (2004). The paragenetic sequence of alteration assemblages will be presented be- low from oldest to youngest (Fig. 3.2). 48 3.3.1 Stage 1 – widespread regional metamorphic footprint with evidence of prior hydrother- mal alteration 3.3.1.1 Pervasive biotite-Ti-magnetite ± carbonate This assemblage consists of biotite-Ti-magnetite ± carbonate. Intense, early biotite altera- tion produces a black colour in basalt (Fig. 3.3A). When biotite is associated with abundant car- bonate, a mottled brown colour is observed (Fig. 3.3B); however, this is a less frequent occur- rence. Biotite with abundant carbonate is commonly overprinted by later veins and pyrite (Fig. 3.3B). Typically, biotite is ~ 20 µm in size, elongated platy crystals, parallel to S2 foliation and associated with Ti-magnetite ± carbonate (Fig. 3.3C and D). Elongated Ti-magnetite crystals, ~10 µm, are preserved as inclusion trails in overprinting garnet (Fig. 3.3E and F). The carbonate is more sporadic in its occurrence, but equally fine (~10–30 µm) and intergrown with the biotite (Fig. 3.3D and E). Ti-bearing biotite, identified using EDS-SEM, is adjacent to areas of concen- trated Ti-magnetite. Biotite alteration ranges in abundance (1–20%), with an average abundance of < 5% of the sample. The biotite-Ti-magnetite ± carbonate assemblage is replaced by chlorite, overgrown by amphibole, garnet and cut by all vein types. The chlorite developed obliquely to the foliation displayed by the biotite assemblage. Fine to microcrystalline biotite, Ti-magnetite and carbonate (< 0.1 mm) are common inclusions in overprinting minerals (e.g. blue chlorite and porphyroblas- tic garnet and amphibole), which support an early paragenetic timing. The biotite assemblage depicts crenulated foliation trends (both D1 and D2), which are preserved as trails in, (Fig. 3.3E) or wrap around, garnet porphyroblasts (Fig. 3.3C). The alignment of biotite-Ti-magnetite ± car- bonate parallel to the S2 fabric suggests this is a metamorphosed assemblage derived from metamorphosed hydrothermal alteration. This assemblage could have developed during either or both, M1 or M2 metamorphic events. The metamorphic origin would suggest that the basalt was altered prior to metamorphism, with possible enrichment in K2O with abundant precursor clays and micas (see Chapter 6 for discussion). 49 Figure 3.2 Paragenetic sequence of both hydrothermal and metamorphic mineral assemblages as defined and charac- terized in this study. Ages of plutons from Wallace et al. (1986) and Corfu and Andrews (1987). For abbreviations, please refer to the list of abbreviations. 50 Figure 3.3 Early biotite-Ti-magnetite ± carbonate alteration. A) Hand sample BK05009-833.4; early black pervasive finely crystalline biotite alteration, replaced by later pervasive chlorite alteration of a green grey colour. B) Hand sample 34L814-195; biotite + abundant carbonate assemblage with replacement pyrite overprinted by ankerite- quartz veins. C) Thin section (plane polarized light) D39018-3050; early biotite-Ti-magnetite ± carbonate aligned into foliation trends curve around later syn-tectonic garnet porphyroblast. D) Thin section (plane polarized light) D39018-4848; early biotite ± carbonate overprinted by (grey) chlorite, amphibole and pyrrhotite. E) Thin section (reflected light) CR4612-360; garnet porphyroblast showing inclusions of early pyrite and pyrrhotite with crenulated Ti-magnetite trails (D2 affecting D1). F) Backscatter image of D39018-3562; showing inclusions of biotite-Ti- magnetite and carbonate in garnet. A second, later phase of anthophyllite-garnet-biotite is identified overprinting biotite-Ti-magnetite ± carbonate assemblage (see section 3.3.1.3.1). Refer to list of abbreviations for abbreviations. 51 3.3.1.2 Early chlorite Chlorite is easily distinguished in a hand sample due to a pervasive green colour, but is noticeably complex in its paragenesis when observed in a thin section. Different stages of chlo- rite are distinguished by texture, orientation, coeval associated minerals and particularly bire- fringence colour. Three distinct chlorite varieties are identified primarily by birefringence col- ours: berlin blue, brown and grey. Both berlin blue (Fig. 3.4A) and brown chlorites (Fig. 3.4B) replace the older biotite assemblage and are overprinted by garnet and amphibole. Grey chlorite is associated with amphibole (section 3.3.1.3) (Fig. 3.4C). Figure 3.4 Birefringent chlorite varieties. A) Thin section (cross polarized light) DS173-499; blue chlorite over- printed biotite alteration. Both biotite and chlorite are foliation aligned (with slight curvature), and cut by a garnet porphyroblast. B) Thin section (cross polarized light) D21708-2760; brown chlorite in the pressure shadow of gar- net. Brown chlorite has been overgrown by later coarse magnetite and amphibole. C) Thin section (cross polarized light) 37L482-2057; showing massive, foliation aligned, felt-like grey chlorite, associated with actinolite overprint- ing earlier biotite. For abbreviations, refer to list of abbreviations. 52 3.3.1.2.1 Berlin blue chlorite ± sulfides Berlin blue (hereafter blue) chlorite varies in abundance from 5–10% of the total rock at the mine scale, but decreases distally to only ~ 3%. This decrease in chlorite abundance is due to an increased abundance of porphyroblastic overgrowths of garnet-amphibole ± epi- dote/clinozoisite distally. Blue chlorite ranges in size from ≤ 10–200 µm, with the average size being 50–70 µm. Blue chlorite is present as fine-grained (50 µm), felt-like, platy crystals, which are commonly foliation aligned to the S2 fabric (Fig. 3.5A). Blue chlorite can also occur as acic- ular, tabular crystals subparallel to foliation (Fig. 3.5B). The acicular crystals are the coarsest occurrences of blue chlorite. The acicular chlorite overprints the biotite-Ti-magnetite ± carbon- ate. Felt-like chlorite also overprints the biotite-Ti-magnetite ± carbonate, but common replace- ment of the biotite is observed (Fig. 3.5C). Both blue chlorite textures replace prior biotite altera- tion, indicating a similar timing of development. At distances > 3 km from mineralization, blue chlorite is only present as inclusions contained in garnet or amphibole porphyroblasts. Blue chlo- rite inclusions in garnet are the only preservation of pervasive chlorite distally in the Red Lake area. Blue chlorite inclusions in garnet can be associated with early sulfides of pyrrhotite, pyrite and chalcopyrite (Fig. 3.5D). Blue chlorite rarely contains carbonate and Ti-magnetite inclu- sions, supporting a post-biotite assemblage formation (Fig. 3.5E). Blue chlorite is overprinted by both brown and grey chlorite, carbonate veins, quartz veins, amphibole ± epidote/clinozoisite, rare chloritoid and syn-mineralization replacement sulfides (Fig. 3.5F-H). The demonstration of the main S2 fabric by replacement chlorite (of the S2 aligned bio- tite) does not necessarily indicate a metamorphic origin. However, the overprinting blue chlorite varieties (e.g. acicular crystals) which also demonstrate the S2 fabric are consistent with a meta- morphic origin. As blue chlorite is preserved as inclusions in porphyroblasts, the metamorphic development of this chlorite phase is considered to be early, possibly at the onset of regional metamorphism. 3.3.1.2.2 Brown chlorite Dark to tan brown chlorite is the least abundant of the chlorite varieties. Brown chlorite composes approximately 2% of the total rock at the mine scale, and < 1% of the total rock at the intermediate to district scale. Brown chlorite ranges in size from 10–100 µm, with occasional berlin blue highlights to its cleavage planes (Fig. 3.4B). Brown chlorite is observed to gradation- ally change from birefringent blue to brown near garnet porphyroblasts (Fig. 3.6A). Brown chlo- rite is common in the pressure shadows of garnets as blocky, coarse (100-200µm) crystals (Fig. 53 54 Figure 3.5 Examples of Berlin blue chlorite ± sulfide alteration. A) Thin section (cross polarized light) DS358-1215; massive felt-like blue chlorite overprinting earlier biotite. Blue chlorite is overprinted by later amphibole/epidote. B) Thin section (cross polarized light) D39018-4848; bladed blue chlorite overprinted biotite, but later overprinted by amphibole and muscovite. C) Thin section (cross polarized light) GC01018-1372.7; Coarse blue chlorite crystals with biotite preserved along its cleavage planes. Both biotite and chlorite are overgrown by late, coarse quartz. D) Thin section (reflected light) D39018-4848; garnet porphyroblast with inclusions of early pyrite, pyrrhotite, chal- copyrite and blue chlorite. E) Thin section (cross polarized light) GC9510-350; quartz-rich basalt containing a single blue chlorite crystal with microcrystalline inclusions of carbonate. F) Thin section (cross polarized light) D14981- 1798; massive brown chlorite overprinted blue chlorite. Both chlorites overprinted by later quartz. G) Thin section (cross polarized light) 19L547-495; grey chlorite is observed to obliquely overgrow foliation aligned blue chlorite. H) Thin section (cross polarized light) CR4611-581.4; early (assumed felt-like) blue chlorite overprinted by coarse epidote, amphibole, clinozoisite, and quartz which have all been later preplaced by pyrrhotite and pyrite. For abbre- viations, refer to list of abbreviations. 3.4B). It can also be present in the matrix as tabular, fine, acicular crystals overgrown by younger muscovite, carbonate and grey chlorite-amphibole ± epidote (Fig. 3.6B and C). Brown chlorite postdates blue chlorite, as suggested by cross cutting relationships (Fig. 3.5G). Brown chlorite is overgrown by amphibole but not included in garnet porphyroblasts like blue chlorite (Fig. 3.6D). The brown chlorite is considered to have predated garnet and postdated blue chlo- rite, as the garnet sharply overgrows the brown chlorite. The demonstration of the S2 fabric by tabular, acicular brown chlorite indicates that this phase developed during regional metamor- phism (the synchronous D2-M2), but after the development of blue chlorite. The replacement of blue chlorite by brown biotite suggests continued prograde metamorphism (Spear, 1993). 3.3.1.3 Regional metamorphic greenschist-amphibolite facies and localized bleached zones The regional metamorphic assemblage has been defined by texture, scale and associated minerals. This has then been characterized as greenschist to amphibolite facies in terms of metamorphic grade. Prior to regional metamorphism, the Balmer basalt was intensively altered, causing heterogeneity in the basalt composition (Mathieson, 1982). Therefore, the metamorphic assemblages now present in the RLGM and surrounding areas are metamorphosed equivalents of precursor assemblages formed prior to peak-regional metamorphism. The pre-metamorphic hydrothermal alteration is demonstrated by the presence of chloritoid, staurolite and andalusite within the now present metamorphic assemblages (which are described below). These minerals are more commonly associated with metapelites rather than metabasalts. The unusual metamor- phic minerals are the result of metamorphosed altered basalts which were leached of alkalis with aluminium concentrated prior to regional metamorphism. The prior hydrothermal alteration is presumed to have created a precursor mineral assemblage composed of abundant clays, carbon- ate and chlorites. The heterogeneity in basalt composition at the time of regional metamorphism would have also created a variety of associated minerals. For example, in K2O rich basalts, gar- 55 Figure 3.6 Examples of brown chlorite. A) Thin section (cross polarized light) 19L547-495; massive textured blue chlorite grading into brown chlorite rimmed by garnet porphyroblasts. B) Thin section (cross polarized light) 34L235-1961; bladed brown chlorite overgrown by grey chlorite. Both are replaced by later carbonate, quartz and mica. C) Thin section (cross polarized light) DS173-499; grey chlorite-epidote overgrown by brown chlorite. D) Thin section (cross polarized light) D21708-2760; the matrix contains brown chlorite, but blue chlorite is present as inclusions in garnet. For abbreviations, refer to list of abbreviations. net-biotite may be the dominant assemblage. However, garnet-amphibole and epidote are consis- tently found and used to identify greenschist to amphibolite assemblages. The general mineral associations for greenschist to amphibolite facies are as follows: Greenschist: Grey chlorite-epidote ± clinozoisite-amphibole (non-calcic)-magnetite ± calcite ± biotite ±chloritoid. Amphibolite: Amphibole (calcic)-magnetite-garnet ± calcite ± plagioclase ± epidote ± clinozoi- site ± biotite ± staurolite ± cordierite ± sphalerite. These two assemblages are linked by the following reactions: Mg-chlorite + non-calcic amphibole  calcic amphibole (1) Chloritoid  Staurolite (Damer, 1997) (2) Mg-chlorite + epidote + clinozoisite  garnet (3) 56 The regional metamorphic assemblages suggested are based on typical greenschist-amphibolite facies mineralogy as outlined by Spear (1993) and Bucher and Frey (1994). These assemblages are metamorphic equivalents of precursor clays, chlorite, carbonate and possibly Fe-oxides. The metamorphic minerals are parallel to the main foliation trend, suggesting a syn-D2 formation. The bleached mineral assemblage (c.f. Penczak, 1996) has been reclassified based on ob- servations from this study. Bleached zones contain quartz-muscovite-andalusite ± chlorite ± bio- tite. The platy minerals, muscovite, chlorite and biotite, display the main S2 foliation, suggesting a metamorphic development during D2 deformation. The quartz-muscovite-andalusite assem- blage has been considered a metamorphosed equivalent of precursor clays of possible intermedi- ate to advanced argillic alteration (Penczak, 1996; Penczak and Mason, 1999). This is a different mineral assemblage compared to the greenschist-amphibolite facies which is assumed carbonate- clay-chlorites. The precursor mineral assemblage to the quartz-muscovite-andalusite assemblage would have been created by hydrothermal alteration of the basalt prior to regional metamor- phism (see Chapter 6 for full discussion). Although derived from different precursor mineral packages, the greenschist-amphibolite (chlorite-carbonate-clay?) and bleached assemblage (argillic alteration?) are considered to have formed during M2 regional metamorphism. The regional metamorphic and bleached assemblages are distinct in their mineralogy. Because of this, they are discussed separately below. Metamorphic mineral associations observed in this study support a regional metamorphic assemblage, which is consistent with greenschist-amphibolite facies conditions (Pirie and Grant 1978; Andrews and Wallace, 1983; Andrews et al., 1986; MacGeehan and Hodgson, 1980; Christie, 1986; Atkinson and Stone, 1993; Tarnocai, 2000; Thompson, 2003). 3.3.1.3.1 Greenschist-amphibolite facies regional metamorphic assemblage Greenschist facies: The greenschist facies is typified by the presence of grey birefringent chlorite, non-calcic amphibole (Fe2+-rich actinolite, anthophyllite and ottoliniite) and epidote/clinozoisite with minor magnetite, chloritoid and trace calcite and biotite. Grey chlorite is fine-grained (~ 20–30 µm) and either displays the main foliation or occurs as radiating crystals (Fig. 3.4C and 3.7A). Less common, coarse (100–200 µm) blades are also observed weakly aligned to the main foliation trend (Fig. 3.7B). Grey chlorite is associated with amphibole ± epidote/clinozoisite, and over- prints blue and brown chlorite and the early biotite-Ti-magnetite ± carbonate assemblage (Fig. 3.5H and 3.6C). 57 Epidote, and less commonly clinozoisite, form blocky, coarse (100–700 µm) crystals with poikiloblastic cores (quartz and carbonate inclusions) and inclusion-poor rims (Fig. 3.7C). Although no clear relationships have been observed for clinozoisite in this study, it is consis- tently associated with epidote, hence is considered part of the regional metamorphic assemblage. Both clinozoisite and epidote are weakly to moderately aligned to the main foliation. Rare metamorphic biotite comprises < 3% of the regional metamorphic assemblage and is coeval with anthophyllite and occasionally, though rarely, garnet (Fig. 3.3F). It is distin- guished from the biotite-Ti-magnetite ± carbonate assemblage by its association with anthophyl- lite (Fig. 3.3F). Regional metamorphic biotite is approximately 50 µm in size, forming either single crystals or aggregates. The presence of abundant biotite within basalts indicates pre- metamorphic alteration. Transitional facies: The transition from greenschist to amphibolite facies is a gradual boundary over several hundred meters, defined by reactions 1–3 above. The transitional facies is characterized by (1) the loss of grey chlorite and chloritoid; (2) a progressive decrease in epidote/clinozoisite abun- dance; (3) the appearance of garnet, staurolite and cordierite; (4) an increase in amphibole abun- dance; and (5) the amphibole type changing from non-calcic to calcic with increased metamor- phic grade. Chloritoid has been identified at depth in the Campbell complex (CBC). Chloritoid is medium-grained, 50–300 µm crystals, which overgrew blue chlorite and pervasive biotite (Fig. 3.7E). Chloritoid only composes < 0.1% of the greenschist assemblage. Magnetite forms cubic crystals 20–60 µm in size. It is common in pressure shadows associated with amphibole (Fig. 3.4B) or within grey chlorite rich areas (Fig. 3.7F). Cubic magnetite overgrew foliation aligned Ti-magnetite (Fig. 3.7F). Metamorphic, cubic magnetite comprises a minor abundance, < 5% of the total rock. Grey chlorite and associated amphibole ± epidote are all overprinted by carbonate- and quartz-bearing veins and ore stage sulfides. This study has identified both non-calcic (actinolite, (ferro-) anthophyllite, (ferro-) otto- liniite) and calcic (actinolite, (ferro-)tschermakite, magnesio-hornblende and ferro-hornblende) amphiboles in the transitional facies. This is known due to petrographic observations and elec- tron microprobe (EMP) data (see Chapter 4). Non-calcic amphiboles are a pleochroic yellow- green to green-brown colour in plane polarized light, with a fibrous aggregated habit ranging in 58 Figure 3.7 Examples of the greenschist assemblage. A) Thin section (cross polarized light) 37L482-2057; felt-like grey chlorite with associated amphibole with radiating chlorite crystals. B) Thin section (cross polarized light) D39018-3562; grey chlorite blades + amphibole replacing earlier biotite and carbonate. C) Thin section (plane po- larized light) CR4612-360; clinozoisite and epidote overprinted a quartz dominated matrix with pyrrhotite-pyrite- magnetite inclusion trails exhibiting foliation trends. Clinozoisite and epidote occur obliquely to foliation with poikiloblastic rich cores. D) Thin section (plane polarized light) BK05010-376; radiating actinolite crystals associ- ated with epidote and calcic amphibole. E) Thin section (cross polarized light) D33003-3210; Blue chlorite over- grown by randomly oriented chloritoid. F) Thin section (reflected light) 06L337-478; cubic metamorphic magnetite overprinted Ti-magnetite in grey chlorite rich area. For abbreviations, refer to list of abbreviations. size from 100–150 µm (Fig 3.8A). In transitional areas, the non-calcic and calcic amphibole can be intergrown, consistently foliation (S2) aligned, displaying coeval timing. Previous studies of both mine complexes have reported tschermakite, anthophyllite, grunerite and cummingtonite (Penczak, 1996; Damer, 1997; Cadieux et al., 2006). A zonation of amphibole with tremolite 59 cores to anthophyllite rims have also been reported (Menard and Pattison, 1998). Tremolite has not been identified in this study. This could be a result of the limited number of samples ana- lyzed with the electron microprobe. Amphiboles in the transitional facies were, however, ob- served to be zoned with non-calcic cores to calcic amphibole rims. Only calcic amphibole is pre- sent in the amphibolite facies, distally from mineralization and at depth in both mine complexes. Calcic amphibole becomes the dominant amphibole type in transitional facies rocks dis- tally from mineralization. Calcic amphiboles are blocky, prismatic, pleochroic blue-green to green in plane polarized light, and approximately 100–200 µm in size. At depth and distally, cal- cic amphiboles are abundant, ranging from 20–70% of the sample. Calcic amphibole is rarely poikiloblastic with inclusions of Ti-magnetite, carbonate and quartz (Fig. 3.8B). Calcic amphi- bole is associated with garnet porphyroblasts (Fig. 3.8C). Cordierite comprises < 1% of the regional metamorphic assemblage. Cordierite is found sporadically throughout the Red Lake area, but usually at the mine scale in transitional facies rocks. Typically, cordierite is pale blue-green to colourless, < 50 µm, and poikiloblastic, contain- ing inclusions of biotite, Ti-magnetite and carbonate. Cordierite is associated with amphibole in foliation aligned occurrences (Fig. 3.8D). Rare cordierite inclusions in garnet rims are observed (Fig. 3.8E). Staurolite has been identified at the district scale in a transitional rock composed of dominantly quartz and amphibole. Staurolite is coarse, 150–200 µm in size, with a sieve-like tex- ture. Inclusion trails of Ti-magnetite, biotite and quartz are preserved (Fig. 3.8F). No reaction relationships between staurolite and chloritoid were observed. Amphibolite facies: The amphibolite facies is dominated by the presence of calcic amphibole (tschermakite and magnesio-hornblende), garnet and magnetite, with less common staurolite, cordierite, car- bonate, biotite, fine-grained feldspar and sphalerite. Sphalerite associated with the amphibolite facies is rare and only observed in rocks > 5 km from mineralization. Sphalerite is dark red, contains no optical zoning, no observable fluid inclusions, and ranges in size from 10–150 µm. Sphalerite is associated with epidote and clino- zoisite, contained in garnet rims (Fig. 3.8G), or overgrew the older blue chlorite ± sulfides as- semblage (Fig. 3.8H). Very fine-grained, 10–30 µm, intergrown plagioclase-quartz can be seen associated with amphiboles, far from mineralization (Figs. 3.9A and B). Approximately 5–10% of distal amphi- 60 61 Figure 3.8 Examples of transitional and amphibolite assemblage. A) Thin section (plane polarized light) 37L482- 2057; fibrous non-calcic amphibole and calcic-amphibole associated with biotite and grey chlorite. B) Thin section (plane polarized light) 34L06-1235; associated amphibole, epidote and clinozoisite with inclusions of quartz and epidote overgrew earlier biotite alteration. C) Thin section (plane polarized light) D39018-3562; biotite + anthophyl- lite, with garnet and tschermakite hornblende. (LA-ICP-MS spots are seen in the garnet crystal). D) Thin section (plane polarized light) 34L235-196; rare cordierite with associated amphibole overprinting earlier chlorite replacing biotite. E) Backscatter image of DS177-1500.8; showing the intensity of the poikiloblastic nature of the garnet por- phyroblasts. Inclusions include quartz, carbonate (calcite, dolomite and ankerite), chlorite, plagioclase, biotite, Ti- magnetite and pyrrhotite. F) Thin section (cross polarized light) CR4610-947; synchronous staurolite-cordierite- quartz overprinting biotite. G) Thin section (cross polarized light) GC01018-1372.7; sphalerite as inclusions in gar- net rims. H) Thin section (plane polarized light) CR4611-581; sphalerite with associated quartz-carbonate-pyrite, overprinting epidote and clinozoisite. For abbreviations, refer to list of abbreviations. bolite facies rocks contain plagioclase. At the mine site, there is a distinct lack of plagioclase. This supports previously suggested ‘feldspar destruction’ hydrothermal alteration (MacGeehan et al., 1982). Plagioclase is most clearly identified using scanning electron microscopy or cold- cathodoluminescence (Figs. 3.9C and D). Cathodoluminescence displays a yellow-green colour for plagioclase, and combined with EDS, simple distinction of plagioclase from quartz is possi- ble. Distal calcite is intergrown with calcic amphibole, but is only a minor aspect of the am- phibolite facies. Calcite has been identified using cathodoluminescence. Two calcite types have been identified. These are differentiated by texture and cathodoluminescence colour. One is a bright red, the other a dull red (Fig. 3.9C and D). Overprinting ankerite veins, in comparison to the regional metamorphic calcite, appear black. The bright red calcite is fine-grained (10–50 µm) and aggregated in texture, surrounding dull red calcite in the center, which is coarser (100 µm). Garnet is present in Balmer assemblage basalt and diorite, and rarely in Bruce Channel assemblage argillite (Fig. 3.9 D-F). Garnets are 0.5–5 mm (average 1.5 mm) in size with ragged edges. They are typically poikiloblastic with inclusions varying in size from 10–100 µm (fig. 3.10A and B). Consistently, and regardless of the host lithology, the garnets are pink. Garnets contained in basalts are smaller and inclusion rich, as compared to garnets within argillite units (Fig. 3.10B). The difference may be due to increased metamorphic grade distally (refer to Fig. 2.1). Frequently, the garnet cores contain more inclusions than the rims (Fig. 3.10A). Garnet growth is interpreted to postdate biotite-Ti-magnetite ± carbonate and blue chlorite ± sulfides assemblages, as both are preserved as inclusions throughout the garnet (Fig. 3.8E and G). Inclu- sions of quartz and feldspar are considered remnant of the original basalt composition, and unaf- fected by early hydrothermal alteration or regional metamorphism. Titanium-magnetite ‘z- shaped’ inclusion trails in garnets are either linear (Fig. 3.3F) or crenulated (Fig. 3.3E). Garnet is consistently associated with amphibole, epidote and biotite. However, towards garnet rims, rare 62 63 Figure 3.9 Amphibolite facies assemblages. A) Thin section (plane polarized light) GC01018-85.3; amphibole with inclusions of chlorite, biotite surrounded by a plagioclase-quartz matrix. B) Thin section GC01018-85.3; backscatter image to show the relationship of intergrown plagioclase-quartz overgrown by amphibole. C) Thin section (plane polarized light) CR468-629; regional metamorphic assemblage of amphibole-calcite-garnet-plagioclase. D) Thin section CR468-629; cathodoluminescence image of C. Plagioclase is yellow blue, calcite displays two types, a dull and bright red colour. E) Hand sample DS172-123; garnet-biotite-amphibole and garnet-chlorite-amphibole assem- blages are seen in the same sample, cut by later epidote-quartz vein. F) Hand sample DS172-303.7; typical diorite containing quartz eyes and garnet porphyroblasts. G) Hand sample GC01018-691; argillite with abundant sulfides as indicated by the rusted areas, with coarse garnet porphyroblasts. For abbreviations, refer to list of abbreviations. amphibole, cordierite, sphalerite and magnetite inclusions are observed (Fig. 3.8E). The preser- vation of these minerals in garnet rims suggests a syn- to post-amphibole-cordierite-sphalerite growth (Figs. 3.8C and G). Due to prior hydrothermal alteration of the Balmer basalt, heterogeneity in the bulk rock composition at the time of peak metamorphism was expected. This has been confirmed by varia- tions noted in the metamorphic assemblage present. For example, the amphibolite facies can be garnet-biotite-amphibole-calcite or garnet-amphibole-epidote/clinozoisite-biotite-sphalerite- cordierite. The minerals, garnet and calcic amphiboles are consistent and were used to confirm amphibolite facies mineralogy. Carbonate veins with both biotite and chlorite selvages, carbonate-quartz, and carbonate- magnetite veins all cut garnet (Figs. 3.10C-F). Ore-stage pyrrhotite, pyrite and magnetite veins cut garnet (Fig. 3.10G). Pervasive quartz, typically associated with ore-stage mineralization, lo- cally replaces garnet (Fig. 3.11A). Garnet rotation is localized, as only approximately 5% of the garnet porphyroblasts observed in this study displayed curved inclusion trails (Fig. 3.11B). Gar- nets are aligned and elongated parallel to S2 foliation. Garnet growth is considered to be syn- metamorphic and possibly synchronous with D2 deformation. These observations are consistent with prior studies (Christie, 1986; Damer, 1997; Mathieson, 1982; Penczak and Mason, 1997). Penczak, (1996) and Penczak and Mason, (1999) suggest a link between the garnetiferous bearing assemblage (garnet-chlorite-magnetite) and bleached zones (quartz-muscovite- andalusite). Both were created during regional metamorphism from precursor minerals of pre- sumed clays, chlorite, mica and carbonate. Textural observations from this study show a garnet- chlorite ± magnetite assemblage interfingering with bleached zones which commonly contain a transitional boundary (Fig. 3.11C). In this transitional boundary, garnet porphyroblasts are rare and have ragged edges. In the center of intense bleached zones, no garnets occur (Figs. 3.11C and D). From these observations, two hypotheses are suggested. The first hypothesis is that the precursor mineral assemblage for the garnet-chlorite-magnetite alteration was overprinted by the precursor assemblage for the quartz-muscovite-andalusite alteration, e.g. chlorite-carbonate-clay 64 65 Figure 3.10 Examples of garnet timing. A) Thin section (plane polarized light) 19L547-495; inclusion rich poiki- loblastic core and inclusion poor rim hosted in basalt. Inclusions of biotite and quartz are present. Garnet cuts chlo- rite and biotite in the matrix. Chlorite and biotite demonstrate the main foliation. B) Thin section (cross polarized light) GC01018-691; garnet porphyroblast in biotite rich matrix in argillite. C) Thin section (plane polarized light) GC01018-85.3; carbonate vein cuts garnet porphyroblast associated epidote and amphibole. D) Thin section (cross polarized light) DS172-123; carbonate vein with blue chlorite selvage cut garnet porphyroblast. Dashed lines outline carbonate-chlorite veins. E) Thin section (plane polarized light) 34L006-25; carbonate-biotite vein cutting a garnet porphyroblast. F) Thin Section (reflected light) 19L547-495; showing calcite-magnetite vein cut garnet porphyro- blasts (indicated by the dash marks), with magnetite, pyrite and pyrrhotite as inclusions within the garnet. G) Back- scatter image 19L547-495; Possible folded garnet horizon with subsequent boudinage with magnetite-pyrrhotite filling the boudin necks. For abbreviations, refer to list of abbreviations. was overprinted by acidic fluids forming argillic alteration (c.f. Penczak, 1996). The overprinting acidic fluid would have stripped cations such as Fe, Mn, Mg and Ca, which are required to de- velop metamorphic garnet. Subsequent regional metamorphism would have then created alter- nating bands of garnetiferous and bleached alteration. The second hypothesis is that the garnetif- erous alteration formed first. This garnet-bearing alteration would then have been overprinted by acidic fluids (presumably metasomatic in origin). These fluids would have had to have been cor- rosive to garnet. As metamorphism continued the quartz-muscovite-andalusite assemblage would be formed. The first hypothesis is the simplest explanation, and is favoured. This suggested for- mation between garnet-chlorite ± magnetite and the bleached assemblage supports Penczak (1996). A full discussion of the precursor assemblages and their formation will follow in Chapter 6. 3.3.1.3.2 Aluminous-bleached assemblage (quartz-muscovite-andalusite ± chlorite ± biotite) Bleached zones are composed of quartz-muscovite-andalusite ± chlorite ± biotite (Fig. 3.12A, B and C). The matrix comprises muscovite ± chlorite ± biotite, which are all microcrys- talline, foliation aligned (to the S2 fabric) and occasionally wrap around coarser quartz and anda- lusite. Andalusite porphyroblasts are 10–150 µm with ragged edges, and have < 10% abundance in mafic rocks (Figs. 3.12 C). Locally intense quartz-muscovite-andalusite alteration has caused the basalt to appear like a rhyolite. Intensively quartz-muscovite-andalusite altered basalt is only distinguishable due to pillow structures (Fig. 3.12D). Severely quartz-muscovite-andalusite al- tered basalt has a buff pink to tan brown to light, steel grey colour (Fig. 3.12D-F). At the mine scale, quartz-muscovite-andalusite alteration is localized in foliation parallel lenses 10’s –100’s cm in length (Fig. 3.12F). Where less intense bleached zones are present, 0.5–1 cm elongated milky white foliation parallel ovals are observed. These are composed of microcrystalline quartz-muscovite. Bleached ovals characterize the rock in 5–8 cm bands with accompanying pervasive quartz (Fig. 3.12G). 66 A magnetic susceptibility study has indicated that both bleached and unaltered basalt are magnetic. These observations could be due to multiple stages of magnetite or partial destruction of the early biotite-Ti-magnetite-carbonate alteration in bleached areas, with preservation in the non-bleached areas. Petrographic observations support both hypotheses, with early magnetite (as part of the biotite-Ti-magnetite-carbonate and peak-metamorphic assemblage) partially broken down, and subsequent overprinting magnetite associated with ore stage mineralization. The quartz-muscovite-andalusite assemblage is considered synchronous with the metamorphic devel- opment of garnet-chlorite ± magnetite (Penczak, 1996). Quartz-carbonate veins cut the lenticular bleached zones (Fig. 3.12F), demonstrating that the bleached assemblage formed prior to the main vein and mineralization stage, supporting observations by Cadieux et al. (2006). Figure 3.11 Examples of garnet and quartz-muscovite-andalusite assemblage. A) Thin section (plane polarized light) CR467-86.3; intensive quartz destroying a garnet porphyroblast with associated hornblende and epidote. B) Thin section (reflected light) D39200-3241; garnet porphyroblast with replacement ore-stage pyrite-pyrrhotite-magnetite. The dashed line indicates the curved foliation. C) Hand sample D21708-2116.8; assemblage of garnet-chlorite- magnetite with quartz-muscovite-andalusite stripes. D) Drill core, CR468-418; garnet- chlorite ± magnetite altera- tion interfingering with quartz-muscovite-andalusite areas. For abbreviations, refer to list of abbreviations. 67 68 Figure 3.12 Examples of quartz-muscovite-andalusite ± chlorite ± biotite (bleached) assemblage. A) Thin section (cross polarized light) D39018-635; fine-grained quartz and minor andalusite surrounded by microcrystalline, folia- tion aligned mica in the matrix. B) Thin section (plane polarized light) D2252-75; microcrystalline quartz with mi- nor chlorite and biotite present. C) Drill core, 30L1268-399.1; abundant andalusite porphyroblasts with fine-grained quartz-muscovite altered basalt. D) Surface outcrop located at the ‘Marcus’ property, north of Cochenour (Fig. 1.3) showing highly altered pillow basalt. Pillow rims are chloritized, with bleached cores. E) Hand sample D39018-635; intense quartz-muscovite-andalusite pervasively altered basalt. F) Underground Red Lake Complex (RLC) 34 level 875 stope. Steel grey coloured intense quartz-muscovite-andalusite is localized to foliation parallel zones. Late en echelon quartz veins perpendicularly cut bleached zones. G) Drill core, DS615-1588.4; basalt with oval, foliation aligned bleached oval blebs and abundant pervasive quartz. For abbreviations, refer to list of abbreviations. 3.3.1.4 Plagioclase There is a distinct lack of feldspar at the mine scale. This has previously been reported as ‘feldspar destructive’ hydrothermal alteration (MacGeehan et al., 1982). Rare occurrences of lo- calized coarse plagioclase have been observed in this study, at least > 5 km distally from miner- alization. In hand sample, plagioclase alteration is difficult to distinguish, as it has a similar ap- pearance to pale, bleached (quartz-muscovite-andalusite ± chlorite ± biotite) alteration or quartz associated with ore stage mineralization (see section 3.3.2.14). Plagioclase alteration is present as minor, irregular occurrences of white, microcrystalline light grey masses overprinting biotite alteration (Fig. 3.13A). Coarse, single plagioclase crystals associated with quartz are observed microscopically to overprint amphibole + epidote (Fig. 3.13B). These single plagioclase occur- rences compose < 1% of the total rock. The only timing constraints are plagioclase overprinting biotite-Ti-magnetite ± carbonate assemblage and amphibole + epidote. This suggests syn- to post-regional metamorphic growth of plagioclase. However, timing relationships with veins and the mineralization event are unconstrained. 3.3.1.5 Blue tourmaline Rare occurrences (< 2% of the total rock) of blue-green tourmaline are documented. This early tourmaline phase was also observed in the Bruce Channel gold deposits (Marsden, 2012; Fig. 1.3). Typically, blue tourmaline is 50–100 µm and blocky, with rare zonation from a green core to blue rims (Fig. 3.13C). Blue tourmaline is not associated with quartz and does not occur in faults or veins. Consequently, this phase of tourmaline is distinct from the previously reported D4 post-mineralization, ‘black line fault’ tourmaline (Rogers, 1992; Penczak and Mason, 1997, Tarnocai, 2000; Dubé et al., 2004). Timing relations to the ore minerals, carbonate-quartz veins and many of the early alteration assemblages are ambiguous. Blue tourmaline overgrew horn- blende (hornblende inclusions are preserved) (Fig. 3.13C) biotite, blue chlorite, epidote and the 69 main foliation fabric (S2) (Fig. 3.13D and E). Therefore, blue tourmaline developed after the peak regional metamorphic event. The relation of blue tourmaline to veins and mineralization remains elusive. Tourmaline possibly originated in either magmatic-hydrothermal origins, re- lated to syn-tectonic plutons such as the Dome Stock or Cat Island pluton (2718 ± 1.1 Ma and 2699 Ma respectfully, Fig. 1.3) (Hinsberg et al., 2011), or from continued regional metamor- phism (Henry and Dutrow, 1996). Figure 3.13 Examples of plagioclase and blue tourmaline. A) Hand sample 37L726-784.8; plagioclase alteration overprinted biotite alteration. Rare carbonate mineral inclusions are observed in the plagioclase alteration. B) Thin section (cross polarized light) CR467-86.3; late coarse plagioclase overprinted epidote + clinozoisite + amphibole + carbonate assemblage. C) Thin section (plane polarized light) DS615-1095.1; blue amphibole overprinted horn- blende. The blue amphibole is zoned, with green cores and blue rims. D) Thin section (plane polarized light) D39018-4848; blue amphibole overgrew biotite + anthophyllite. E) Thin section (plane polarized light) DS172-123; blue tourmaline cuts chlorite and epidote. For abbreviations, refer to list of abbreviations. 3.3.1.6 Blue chlorite-muscovite ± carbonate ± quartz The blue chlorite-muscovite ± carbonate ± quartz assemblage is rare (< 0.5% of the total rock), though it is consistently observed to overgrow garnet rims (Fig. 3.14). Both chlorite and muscovite are acicular, 30–50 µm in length, and have no preferred orientation. Chlorite over- 70 growths can be differentiated from chlorite inclusions on the following basis: (1) older chlorite occurs as prismatic and blocky inclusions, whereas the younger chlorite is acicular; (2) older chlorite has twinning and cleavages present, whereas the younger acicular variety does not; and (3) the older chlorite is aligned in the foliation, whereas the late chlorite occurs without preferred orientation (Fig. 3.14A). Carbonate is often associated with chlorite and less so with quartz. Car- bonate and quartz are also observed to have overprinted garnet rims (Fig. 3.14B–D). Rounded quartz inclusions are also observed within garnet cores. Quartz inclusions are not part of this as- semblage as they occurred prior to garnet growth. Chlorite and muscovite can occur without as- sociated carbonate and quartz (Fig. 3.14D). Carbonate veins and veinlets cut both garnet and the chlorite-muscovite ± carbonate ± quartz assemblage (Fig. 3.14C). Therefore, the chlorite- muscovite ± carbonate ± quartz assemblage was formed prior to the main vein and mineraliza- tion event, but after garnet. 3.3.2 Stage 2 – Main vein stage progressing to ore stage All veins and mineralization are considered hydrothermal or metasomatic in origin, as they fill fractures or form veins. During this study multiple vein types were observed in drill core and underground stopes. However, these were poorly constrained temporally due to lack of cross cutting relationships, narrow core intercepts and a lack of sufficient time to comprehensively in- vestigate stopes. Consequently, an outcrop located at the Red Lake Airport, which corresponds to the up-dip projection from the old mine workings of the Wilmar deposit, Cochenour-Willans mine, has been mapped (Appendix A.4). Here, the vein paragenesis is better demonstrated and shares similar textures, compositions and temporal relationships with veins at the RLGM. Veins typically comprise carbonate (ankerite-calcite), with quartz replacement mineralization and oc- casional selvages of chlorite or biotite. Where the carbonate mineral has been identified with electron microprobe or scanning electron microscope analysis, the specific type has been stated. 3.3.2.1 Calcite-magnetite veins Calcite-magnetite veins account for approximately 3% of the total rock at the mine scale and < 1%, 2.5–3 km distally. Two types of carbonate-magnetite veins have been observed in this study. Type 1 are fine to medium-grained intergrowths of magnetite and carbonate, with rare coarse (< 0.5–1mm) pyrrhotite (Fig. 3.15A). Type 1 calcite-magnetite veins are moderately magnetic, grey coloured and readily effervesced with dilute HCl. Type 2 are alternating fine- grained (≈ 20–70 µm) bands of magnetite that line wider white calcite. Type 2 veins also effer- 71 vesce with dilute HCl (Fig. 3.15B). Type 2 calcite-magnetite veins are less common than type 1. Both types of calcite-magnetite veins have sharp linear boundaries with the surrounding wall rock. Timing relationships are limited, but ankerite-calcite-chlorite veins cut type 1 calcite- magnetite veins (Fig. 3.15C). No relative timing relationships are seen with type 2 banded cal- cite-magnetite veins. Due to the similarity in composition, it is thought both types of calcite- magnetite veins are coeval in timing. Figure 3.14 Acicular blue chlorite-muscovite ± carbonate ± quartz assemblage. A) Thin section (cross polarized light) 19L547-495; garnet broken down into chlorite-muscovite-carbonate. The garnet overgrew blue chlorite and amphibole in the matrix. B) Thin section (cross polarized light) 30L1268-25.7; garnet with acicular chlorite and muscovite overgrew garnet. Carbonate and quartz affected garnet rims only. C) Thin section (cross polarized light) 30L1268-25.7; garnet broken down into blue chlorite-muscovite-carbonate-quartz. Carbonate veinlet cut the garnet. D) Thin section (cross polarized light) 19L547-495; garnet overgrew early blue chlorite ± sulfide assemblage, but garnet is itself overgrown by acicular blue chlorite and muscovite. For abbreviations, refer to list of abbreviations. 3.3.2.2 Ankerite-quartz veins with biotite selvages Barren ankerite-quartz veins with biotite selvages are limited to the mine scale where they compose < 1% of the total rock. Ankerite is coarse-grained (500–700 µm) with a biotite selvage < 1mm wide (Fig. 3.16A). The accompanying quartz is also coarse, approximately 500 µm. Biotite is fine to microcrystalline, < 25 µm crystals, parallel to the vein edge. Ankerite veins 72 with biotite halos cut garnet (Fig. 3.10E), brown chlorite and the regional metamorphic assem- blage (Fig. 3.16B). Due to the scarcity of this vein type, the paragenetic timing is not well con- strained. Figure 3.15 Examples of calcite-magnetite veins. A) Drill core D27943-1779; type 1, calcite-magnetite ± pyrrhotite vein cut earlier biotitized basalt. Dashed lines indicate the edges of the calcite-magnetite ± pyrrhotite veins. B) Drill core (from Bouzari, 2007); type 2, rare layered/banded calcite-magnetite veins. C) Drill core, CR4613-1.3; garnet- chlorite-magnetite altered basalt, first cut by a type 1 calcite-magnetite vein, then by ankerite + chlorite halo vein. Dashed lines indicate the edge of calcite-magnetite veins. Dotted line indicates the edge of ankerite-chlorite selvage vein. For abbreviations, refer to list of abbreviations. 73 3.3.2.3 Epidote-carbonate ± quartz veins Epidote-carbonate ± quartz veins are observed < 5 km distally from mineralization. Epi- dote-carbonate ± quartz veins range between 1–3 cm in width, and are distinctive due to the yel- low-green colour of finely crystalline epidote. Veins are epidote-rich, with only minor, inter- mixed, fine-grained carbonate or quartz occurring in the vein center (Figs. 3.16C and D). Car- bonate or quartz is microcrystalline and white, with the epidote present as a fine-grained selvage or intergrown occurrences approximately 0.5 cm wide. The only timing relationship identified is that a carbonate-quartz vein cut an epidote-carbonate-replacement pyrite vein (Fig. 3.16E). The formation of this vein type could be via metasomatic fluids synchronous with regional metamor- phism (syn-D2), or from later hydrothermal activity unrelated to the regional metamorphism. 3.3.2.4 Chlorite veinlets ± magnetite ± ankerite ± blue tourmaline Chlorite veinlets are rare, affecting approximately 2% of the total rock along the cross sections. The linear veinlets are composed of finely crystalline (≤ 10 µm) chlorite of both a brown to blue birefringence colour. In rare instances, magnetite, ankerite and blue tourmaline can be associated with the chlorite veinlets (Fig. 3.17A-D). Chlorite veinlets cut the biotite-Ti- magnetite ± carbonate assemblage, and the regional metamorphic assemblage (chlorite- amphibole ± garnet etc., Fig. 3.17A and B). Temporal relationships between different birefrin- gent chlorite veinlets and other vein types are scarce. However, brown chlorite veinlets are cut by carbonate veins containing replacement syn-mineralization pyrrhotite (Fig. 3.17C). The few temporal relationships observed indicate that the chlorite veinlets are pre-carbonate veins and possibly syn-blue tourmaline. Similar to epidote-carbonate-quartz veins, a metasomatic origin is considered possible for chlorite veinlets. 3.3.2.5 Ankerite-calcite veins and carbonate-quartz breccia Ankerite-calcite veins demonstrate a variety of grain sizes and textures. Ankerite-calcite veins can be cryptocrystalline–microcrystalline to medium–coarse-grained, textured (commonly crustiform-colloform) and possibly have a chlorite selvage (Fig. 3.18A-G). Regardless of grain size or texture, each vein type is considered composed of ankerite or Fe-calcite (see Chapter 4). All these veins are weathered to a rust colour. Ankerite is the dominant carbonate type, with mi- nor co-precipitated calcite. Detailed mapping of the Cochenour-Willans outcrop (Appendix 74 75 Figure 3.16 Examples of ankerite-calcite-biotite ± quartz and epidote-carbonate ± quartz veins. A) Thin section (plane polarized light) D39018-43; ankerite-calcite-quartz vein with biotite halo. B) Thin section (cross polarized light) 34L006-25; ankerite-calcite-biotite vein cross cut brown chlorite. C) Drill core, R87105-560; epidote- carbonate vein cross cuts a recrystallized basalt showing coarse grains due to late M3 contact metamorphism (see Chapter 2). D) Drill core, CR4611-94.3; microcrystalline quartz vein with an extensive finely crystalline epidote halo. E) Drill core, BK05011-837; epidote - carbonate vein (with rare pyrite) cut by later carbonate-quartz vein. For abbreviations, refer to list of abbreviations. A.4) revealed that cryptocrystalline to microcrystalline ankerite was the earliest carbonate vein phase. This was followed by a medium to coarse-grained vein. Both veins were affected by a brecciation event, observed only at the mapped outcrop. However, cockade breccias have been documented at the CBC (Penczak, 1996). Finally, ductily deformed colloform-crustiform and medium to coarse-grained (demonstrating no texture) carbonate-quartz veins ± chlorite halos are observed. All these vein types are described below. 3.3.2.5.1 Cryptocrystalline to microcrystalline ankerite veins The cryptocrystalline to microcrystalline veins are composed of 5–20 µm ankerite crys- tals. In hand sample, the cryptocrystalline veins appear grey (Fig. 3.18A). This vein type is bar- ren, with no sulfides or oxides present. Cryptocrystalline ankerite veins were observed at the mapped outcrop only. However, crustiform textured ankerite veins (observed at both the mapped outcrop and the RLGM) cut the cryptocrystalline ankerite. 3.3.2.5.2 Medium to coarse ankerite veins Medium to coarse-grained ankerite veins are composed of milky white, 100-200 µm sized, anhedral crystals. This vein type clearly cuts the cryptocrystalline to microcrystalline ankerite veins in the mapped outcrop (Fig. 3.18A). This vein type also occurs at the RLGM. However, from the RLGM, no constrained cutting relationships were observed in this study. 3.3.2.5.3 Brecciation event Both the cryptocrystalline and medium-grained ankerite vein types demonstrate breccia- tion in all samples collected from the mapped outcrop. The brecciation event formed a stock- work with fine-grained intergrown quartz ± ankerite cement (Fig. 3.18A). It is unknown how the brecciation event observed at the mapped outcrop relates to the cockade breccias described at the CBC (Penczak, 1996). The brecciation of ankerite veins in the mapped outcrop was found to be extensive. The surrounding basalt host rock was not found to be brecciated. This is due to com- petency differences between the ankerite-calcite vein and the host basalt. 76 Figure 3.17 Chlorite veinlets. A) Thin section (cross polarized light) R87108-629; late chlorite (brown) veinlet which cut coarse magnetite, biotite + carbonate + Ti-magnetite and ankerite-quartz ± chlorite ± amphibole. B) Thin section (plane polarized light) D21708-2760; finely crystalline chlorite ± carbonate veinlet cut garnet, pyrrhotite and epidote-amphibole-chlorite (grey) assemblage. C) Thin section (cross polarized light) R87108-629; chlorite veinlet (overprinting epidote-chloritoid assemblage, and early pervasive carbonate) cut by later carbonate-pyrrhotite vein. D) Thin section (plane polarized light) D27943-2104; blue tourmaline contained in a cross cutting chlorite vein cut- ting pervasive carbonate alteration. For abbreviations, refer to list of abbreviations. 3.3.2.5.4 Colloform-crustiform ankerite-calcite ± quartz veins Colloform-crustiform ankerite veins are distinct due to their texture and coarse grains. Colloform-crustiform veins are ankerite dominated with minor (< 10%) quartz. The ankerite ranges from medium to coarse, and can have trigonal habits locally with fine ankerite in the inte- rior (Fig. 3.18C and D). This vein type ranges in width from 1–2 cm to 1 m (Fig. 3.18B–D). Quartz is microcrystalline and occurs in the vein center with fine ankerite. Calcite occurs as a very minor component of this vein type. Fine-grained calcite is co-precipitated with ankerite in the vein’s core. In rare cases, this vein type can be associated with a chlorite halo. Colloform- crustiform veins are commonly folded (Fig. 3.18C). When observed to cut cryptocrystalline ankerite, the dominant texture is crustiform (Fig. 3.18D). 77 3.3.2.5.5 Chlorite selvages to ankerite-calcite veins Medium to coarse-grained ankerite-calcite veins, as well as colloform-crustiform ankerite veins, have chlorite selvages. Chlorite selvages display the same range of birefringence as ob- served in matrix chlorite, namely, either blue, grey or brown chlorite (Figs. 3.18E–G). Pervasive and vein selvage chlorite are texturally distinctive. Pervasive chlorite has a grain shape preferred orientation that defines the main foliation. The chlorite selvage cuts the foliation obliquely to the plane. Coarse carbonate veins cut the regional metamorphic assemblage (Fig. 3.18E) and the brecciated cryptocrystalline to fine-grained carbonate veins (Fig. 3.18D). Carbonate veins with chlorite selvages are observed throughout at the mine-scale (≈ 5%), and are described proximal to ore veins (Penczak, 1996). Observations from this study have identified that ankerite-calcite veins decrease in abundance distally to < 1% of the total rock. 3.3.2.6 Ankerite-calcite-quartz ± chlorite halos Ankerite-calcite-quartz veins are the most abundant vein type along the cross sections, composing approximately 10–30% of the total rock. Ankerite-calcite-quartz veins occur as trigo- nal coarse ankerite or microcrystalline ankerite-calcite. These line sharp cutting veins contain microcrystalline, opaque, white quartz in the center (Fig. 3.19A and B). In hand sample and core, the carbonate and quartz are easily distinguishable. The carbonate minerals are fine to medium in size, a creamy, opaque white colour, but irregular in habit. In contrast, quartz is a milky white colour and microcrystalline. The ankerite-calcite-quartz veins cut the metamorphic minerals and fabric, however, are localized within faults and occur parallel to the main (S2) foliation. Chlorite selvages to ankerite-calcite-quartz veins are observed at the mine and at the air- port outcrop (Fig. 3.19C). Although a rare occurrence, the chlorite selvages to ankerite-calcite- quartz veins share the same characteristics as carbonate veins with chlorite selvages (Fig. 3.18E– G). Chlorite selvages are the same colour as the pervasive chlorite in the matrix. Ankerite-calcite-quartz veins cut carbonate-chlorite (Fig.3.19D) and carbonate-epidote veins (Fig. 3.16E), but have an unknown relationship to carbonate-biotite veins. The localized occurrence of these veins in D2 faults, and their parallel nature to the S2 foliation, would suggest that these veins are synchronous with D2 deformation, and possibly syn-peak metamorphism (c.f. Chi et al., 2002). Petrographic timing relationships suggest a metasomatic origin of the carbon- ate-quartz veins. 78 79 Figure 3.18 Examples of ankerite-calcite veins ± chlorite selvages. A) Hand sample ES09_AP_27 showing several phases of carbonate veins all brecciated then cut by quartz-tourmaline veins. B) Drill core, R87108-372.7; pervasive carbonate alteration cut by a coarse crustiform ankerite-calcite vein. C) Underground RLC 16 level wall; folded crustiform-colloform ankerite-calcite vein overprinted weakly quartz altered basalt. D) Regional outcrop, located at Red Lake Airport; cryptocrystalline to microcrystalline ankerite vein cut by coarse crustiform ankerite vein. E) Thin section (cross polarized light) GC04007-134; blue chlorite halo to an ankerite-calcite vein with replacement quartz cut a matrix composed of blue chlorite-quartz-plagioclase-biotite. F) Thin section (cross polarized light) DS360- 751; brown chlorite halo to carbonate vein cut earlier pervasive carbonate alteration. G) Thin section (cross polar- ized light) DS352-512; grey chlorite halo to ankerite-calcite vein cut pervasive carbonate and quartz. For abbrevia- tions, refer to list of abbreviations. 3.3.2.7 Quartz-ankerite vein Quartz-ankerite veins are dominantly found at depth in the RLGM. These veins consist of intergrown, abundant, microcrystalline quartz and coarse ankerite (Figs. 3.19E and F). These veins are often banded/layered with alternating microcrystalline ankerite and quartz. After the layered quartz-ankerite veins formed, subsequent fractures were infilled with remobilized fine- grained amphibole-chlorite from the surrounding host rock (Fig. 3.19F). Quartz-ankerite veins clearly cross cut carbonate-quartz veins (Fig. 3.19E). Similar to ankerite-calcite veins, the quartz-ankerite veins are typically parallel to the S2 foliation plane and localized into areas of D2 deformation. The ankerite-calcite-quartz and quartz-ankerite veins indicate typical fibrous crack seal veins. This would suggest a syn-metamorphic origin for both veins (supporting the above observations for ankerite-calcite-quartz veins). The main mineralization event post dates all the veins described above. This will be de- scribed in detail in sections 3.3.2.9 and following. The mineralization event replaced the wall rock and the veins described above. Ore-stage sulfides and oxides are frequently associated with abundant quartz and brown biotite alteration. Sulfides present in carbonate veins are replacement style, ore-stage mineralization. Before the mineralization assemblages are addressed, one final vein type is described: en echelon quartz veins, which are possibly syn-mineralization. 3.3.2.8 En echelon quartz veins En echelon quartz veins are white, microcrystalline (Figs. 3.12F and 3.20A) and ≤ 1–10’s cm wide. In the mapped outcrop, the en echelon veins are concentrated in the boudins and boudin necks of large ankerite veins (Fig. 3.20B). Commonly, the late quartz veins are barren, but rare sulfides (especially pyrite), oxides or gold mineralization — as at the Wilmar deposit (Rigg and Scherkus, 1983; this study) — can be present. In the mapped outcrop, the late quartz veins carry gold grade ≤ 678 ppb gold (Appendix A.4). These quartz veins obliquely cut the 80 Figure 3.19 Examples of ankerite-calcite-quartz and quartz-ankerite veins. A) Drill core, D33003-2004; chlorite altered basalt cut by ankerite-calcite-quartz veins. Trigonal ankerite crystals developing into the vein. The interior of the vein is microcrystalline quartz. B) Drill core, 37L726-53; ankerite-calcite-quartz vein cuts pervasive chlorite- carbonate alteration. Carbonate is irregular in habit, but still occurs on the outside of the vein and quartz in the inte- rior. C) Thin section (plane polarized light) ES09_AP_6A; ankerite-quartz vein with a grey chlorite halo. Yellow dashed lines outline the grey chlorite selvage. D) Thin section (plane polarized light) DS352-241; ankerite-chlorite vein cut by ankerite-quartz vein. E) Thin section (cross polarized light) D22203-1604; ankerite-quartz vein cut by quartz-ankerite vein. Yellow dashed lines outline the quartz-ankerite vein. Red dashed lines outline the ankerite- quartz vein. F) Underground stope, 35 level of the RLC. A layered/banded quartz-ankerite vein is cut by later chlo- rite-amphibole ladder structures. The host basalt displays quartz + brown biotite alteration. Dashed lines surround chlorite-amphibole ladders. For abbreviations, refer to list of abbreviations. 81 main ankerite vein. At the RLGM, only barren en echelon quartz veins are present at the mine. Here, the en echelon quartz veins cut the prior ankerite-calcite, ankerite-calcite-quartz and quartz-ankerite veins (Fig. 3.20B-D). These extensional quartz veins had to have begun during the ore stage and are syn-D2, but are oriented parallel to late D3 tourmaline-bearing quartz veins. Therefore, mineralized en echelon quartz veins in the RLGB could be late D2 to early D3 as well (c.f. Dubé et al., 2004). The focused quartz-only veins in boudin necks are due to lower stress and a difference in competency of the ankerite and surrounding basalt. En echelon quartz veins decrease in abundance distally from mineralization at the RLGM. Figure 3.20 Examples of en echelon quartz veins. A) Mapped outcrop, Cochenour; Boudinage carbonate vein, with late perpendicularly cross cutting microcrystalline quartz veins. Dashed line indicates curvature of the foliation in the host basalt. B) Underground CBC 25-51 East Sub (‘L’ ore zone) showing late obliquely cutting quartz veins concentrated in microcrystalline ankerite-calcite-quartz veins. Dashed lines outline quartz veins. C) Underground RLC 16 level drift wall; three vein types are observed (in chronological order): sheeted carbonate veins which are arranged in an open fold. Perpendicular to the sheeted carbonate veins are cross cutting ankerite-calcite-quartz veins. En echelon quartz veins cut both carbonate and ankerite-calcite-quartz veins. Dashed lines indicate folding of sheeted carbonate veins. D) Underground RLC, 35 Level drift wall; quartz-ankerite veins cut by a quartz vein. Red dashed lines outline quartz-ankerite veins. Black dashed lines outline cross cutting quartz vein. For abbreviations, refer to list of abbreviations. 82 3.3.2.9 Initiation of the ore-stage sulfides-magnetite and associated alteration Mineralization consists of abundant sulfides of pyrite, pyrrhotite, arsenopyrite, stibnite, sphalerite, molybdenite and gold, accompanied by magnetite, quartz and brown biotite. Ore- stage mineralization is present in all rock types, most commonly in basalt and less commonly in rhyolite and ultramafic units of the Balmer assemblage. The mineralization style is dominated by veins and/or replacement of the wall rock or ankerite-calcite-quartz veins. Ore zones are sulfide rich, containing > 10% (of the total rock) sulfides. Mineralization occurs parallel/subparallel to the foliation fabric. Ore-stage veins and replacement mineralization cross cut and overprinted the biotite-Ti- magnetite ± carbonate, regional metamorphic (greenschist-amphibole), quartz-muscovite- andalusite assemblages and all ankerite-calcite-quartz veins. The alignment of mineralization parallel to the main (S2) foliation and localization within D2 structures suggests a syn-D2 forma- tion (c.f. Penczak, 1996). The ore-stage minerals and associated alteration are discussed below. Mineralization at the RLGM is not considered to have been remobilized from an earlier mineralization event (e.g. formed prior to regional metamorphism). This was concluded from two observations. Firstly, the cross section of the RLGM does not represent a 2 km depth intact section of the oceanic crust. Rather, the area has been extensively transformed and deformed during various deformation events (see Chapter 2 for details of D0-D2 and Fig. 2.4 for mine-site D2 brittle-ductile deformation). Secondly, the mineralization at the RLGM is vertically exten- sive, documented over approximately 2.5 km and is hosted by the deformed Balmer assemblage rocks (Fig. 2.4). Mineralization is structurally-controlled within D2 faults, with associated nar- row halos of brown biotite-quartz. It is highly unlikely that this style of mineralization and geol- ogy retained the coherency of a seafloor hydrothermal system during synchronous deformation and amphibolite facies metamorphism (D2-M2). Therefore, the mineralization is considered to have been the result of hydrothermal fluids. 3.3.2.10 Sphalerite Sphalerite is minor in abundance compared to other sulfides such as pyrite, pyrrhotite, stibnite and arsenopyrite. Sphalerite has an abundance of 0.5–1% of the mine scale rocks. Sphalerite occurs in two varieties, which are differentiated by colour. One is yellow; the other is a reddish-brown in hand sample (Dubé et al., 2001). The difference between yellow and red sphalerite is due to Fe content variations, temperature differences and a reflection of the trace element chemistry (Kelley et al., 2004). During this investigation, only red sphalerite was identi- 83 fied. This could be due to the rarity of sphalerite associated with mineralization (Dubé et al., 2001) and having limited access to current working stopes. As no yellow sphalerite was ob- served, it will not be included further. Red sphalerite occurs as cement to brecciated ankerite- quartz veins (Fig. 3.21A) and as a replacement of ankerite-quartz veins (Fig. 3.21B). Red sphalerite is always massive, comprising fine to medium crystals. Timing relationships are sparse. However, sphalerite postdates ankerite-quartz veins. Syn-mineralization sphalerite occurs in ore-zones at depth, therefore exhibits a very narrow spatial association of approximately 5 m from ore. Figure 3.21 Examples of sphalerite. A) Drill core, D14981-987.3; brecciated ankerite-quartz vein with sphalerite cement. B) Underground RLC 44 level, 746-1 stope (active 26th June 2009); sphalerite replaced brecciated quartz- ankerite. Dashed lines outline massive replacement sphalerite mineralization. For abbreviations, refer to list of ab- breviations. 84 3.3.2.11 Pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold and pervasive quartz disseminated sulfide assemblage Ore-stage pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold are associated with pervasive quartz. This assemblage replaced the host rock, exploiting porous and permeable porphyroblastic minerals such as highly poikiloblastic garnet (Fig. 3.11B). This assemblage is commonly zoned, with a magnetite core overgrown by pyrrhotite, then rimmed by pyrite (Figs. 3.22A-C). This could have been caused by redox variations, pH or variations in sulfur and oxygen fugacities. The replacement pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold are fine- to medium-grained, anhedral, with grain shape preferred orientation parallel to the S2 foliation (Fig. 3.22D). Magnet- ite is abundant in some ore zones, e.g. the Main zone of the RLC, where it is massive and finely crystalline (< 50 µm) with associated pyrrhotite (Fig. 3.22E). ‘Invisible’ gold is associated with this massive disseminated sulfide assemblage, forming low grade, large tonnage mineralization (Tarnocai et al., 1997). 3.3.2.12 Stibnite ± gold Concentrations of stibnite are localized within middle to lower level ore zones. Stibnite is rare; it only composes ~1 % abundance of the mine-scale rocks. Stibnite replaces ankerite-quartz veins as massive, textured, coarse (1–3 mm), acicular, metallic-grey crystals (Fig. 3.22F). The associated gold is ‘invisible’, but concentrations of stibnite are associated with high gold values. Inclusions of the vein (quartz and ankerite) and quartz-muscovite-andalusite altered host basalt are present inside massive concentrations of stibnite. This indicates that stibnite mineralization occurred after the ankerite-quartz vein and quartz-muscovite-andalusite alteration. 3.3.2.13 Quartz-molybdenite ± gold veins Quartz-molybdenite ± gold veins contain opaque, microcrystalline and milky-white quartz, with finely crystalline, metallic-grey molybdenite. The molybdenite formed thin, < 2–3 mm wide, intermittent concentrations on the edges of the quartz (Fig. 3.22G). In rare cases, this vein type contains free gold (B. Kraft pers. comms., 2009). Quartz-molybdenite veins vary in width from 0.5–1 cm. This vein type is limited to the upper levels of the CBC. Quartz- molybdenite ± gold veins could also be present in the upper RLC, but no observations from this study can confirm this. No cross-cutting relationships were observed that establish the timing of these veins relative to other events. 85 86 Figure 3.22 Examples of pyrite-pyrrhotite-magnetite ± chalcopyrite ± gold, stibnite ± gold assemblages and quartz- molybdenum ± gold veins. A) Drill core, GC01018-759.7; coarse magnetite surrounded by pyrrhotite with late py- rite stringers. B) Thin section (reflected light) D39018-4848; massive pyrrhotite mineralization replacing carbonate (vein) with inclusions of rounded magnetite. C) Thin section (reflected light) 34L814-92; chalcopyrite and magnet- ite surrounded by pyrrhotite with pyrite rims. D) Underground CBC 18 Level stope 1812 (active 29th June 2009); massive disseminated sulfides with ‘invisible’ gold. Dashed line represents the main (D2) foliation trend. E) Hand sample, RL348651T from RLC 34 Level stope 865-1 (active 5th June 2009); magnetite ore. Black fine-grained mag- netite with associated pyrrhotite mineralization. F) Underground photograph of RLC Level 35, 826-1 stope (active 5th June 2009); A massively crystalline ankerite vein with replacement stibnite. Dashed lines outline the stibnite-rich ankerite vein. G) Hand sample, BK01_MB; molybdenite coating a microcrystalline quartz vein. H) Drill core, 34L171-202.3; (note: hole is not on the cross sections, instead intersecting the high grade zone in the RLC). Pyrite- pyrrhotite-arsenopyrite ± gold mineralization has replaced the host basalt. Red dashed lines outline arsenopyrite. Yellow dashed lines outline pyrite. For abbreviations, refer to list of abbreviations. 3.3.2.14 Replacement pyrrhotite-pyrite-arsenopyrite-quartz ± gold Pyrrhotite-pyrite-arsenopyrite-quartz ± gold mineralization is present throughout the de- posit. This is a common mineralization style, typically observed in high grade ore zones where it has replaced the host basalt (Fig. 3.22H) or prior ankerite-quartz veins. The pyrite, pyrrhotite and arsenopyrite range in size between 0.5–1 mm and are irregular in habit. Accompanying quartz is microcrystalline and intergrown with the sulfides. In shallower mine levels, the assemblage is pyrite-rich, with a wide dispersion halo centered on D2 faults. At depth, the mineralization is nar- rower, with a more localized occurrence within D2 faults. In deeper mine levels this assemblage becomes pyrrhotite rich. The dominance of pyrrhotite at depth could be related to increased metamorphic grade, higher temperatures and/or redox differences (see Chapter 6 for a full dis- cussion). Invisible gold is associated with this assemblage (c.f. Tarnocai et al., 1997). This min- eral assemblage is not associated with brown biotite, which is distinctive of higher grade mineral assemblages described in sections 3.3.2.15 and 3.3.2.16. No relative cutting relationships were observed with the pyrrhotite-pyrite-arsenopyrite-quartz ± gold assemblage to better constrain the paragenesis with magnetite abundant mineralization assemblage. 3.3.2.15 Quartz-ankerite-brown biotite-pyrrhotite-gold veins This vein is composed of a pyrrhotite-gold core surrounded by white quartz-ankerite with a brown biotite-quartz selvage (Fig. 3.23A and B). The ankerite is finely crystalline with re- placement microcrystalline quartz (Fig. 3.23C). The pyrrhotite mineralization is also fine- grained, with gold occurring as visible specks throughout the quartz-rich vein core (Fig. 3.23A and A1). Massive microcrystalline intergrowths of biotite + quartz replace the metamorphic as- semblage in the selvages to these veins (Fig. 3.23C and D). The biotite-quartz selvage ranges in 87 size from 3 to 100 cm. The vein selvage is distinguishable from the country rock by its distinc- tive brown colour. The selvage width is proportional to vein thickness. This vein type is parallel to the main faults and foliation trend (syn-D2) but re- placed/overprinted the regional metamorphic assemblage. This suggests a synchronous hydro- thermal and metamorphic origin (e.g. metasomatic) of the ore-forming fluid, possibly syn- to post-peak M2 metamorphism. Figure 3.23 Quartz-ankerite-brown biotite-pyrrhotite-gold vein examples. A) Underground CBC 39 level 2 sub (ac- tive 11th June 2009); planar quartz veins with accompanying brown biotite and quartz with disseminated pyrrhotite cross cut chlorite altered basalt. Yellow box indicates location of A1. Dashed red line indicates the boundary be- tween biotite-quartz-gold and the wall rock. A1) Underground CBC 39 level 2 sub (active 11th June 2009); inset of quartz vein showing free gold. B) Underground CBC 30 level, 256-1 stope (active 23rd June 2009); ore-vein show- ing quartz veins with replacement arsenopyrite + gold in the center, with distinctive brown biotite-quartz selvage. The red line indicates a small fault with 2 inches of displacement. White dashed lines outline boundaries of ore veins + biotite selvage. C) Thin section 34L235-944 brown biotite + quartz selvage to quartz-ankerite vein. Dashed line indicates boundary of biotite-quartz selvage and wall rock. D) Thin section (plane polarized light) 34L235-944; contact where brown-biotite replaces amphibole (part of the amphibolite facies). For abbreviations, refer to list of abbreviations. 88 Quartz-ankerite-brown biotite-pyrrhotite-gold veins are the most significant vein type due to the considerable gold grade of multiple 10’s of ounces per ton. This vein type occurs from the mid-levels of both complexes and continues to depth. This mineralized vein characterizes ore zones such as the RLC ‘High Grade Zone’ and the ‘DC Zone’ in the deep to middle CBC. 3.3.2.16 Arsenopyrite-pyrrhotite-quartz-pyrite-magnetite-gold-brown biotite alteration Arsenopyrite-pyrrhotite-quartz-pyrite-magnetite-gold-brown biotite alteration is common in high grade areas of both mine complexes. This mineral assemblage is characterized by a core of intergrown microcrystalline arsenopyrite and quartz, with visible coarse gold enveloped by brown biotite-quartz (Fig. 3.24A–E). Microscopically, arsenopyrite and pyrrhotite are the most abundant sulfides in this assemblage with minor magnetite occurring near the rims and free gold (Fig. 3.24F). The quartz can also be present as a < 1 cm wide microcrystalline vein, surrounded by arsenopyrite-quartz and brown biotite. Accompanying arsenopyrite are coarse (1–3 mm) ran- domly oriented pyrrhotite crystals. Pyrrhotite is visible as brassy, bronze crystals scattered throughout the arsenopyrite. Gold forms in areas of intense arsenopyrite-quartz mineralization (Fig. 3.24C). Surrounding the arsenopyrite-quartz core is a 2–4 cm wide selvage of brown bio- tite-quartz (Figs. 3.24D and E). No gold is found at the interface between arsenopyrite-quartz and brown biotite-quartz, nor at the selvage. This mineral assemblage has replaced the host rock in 30–50 cm wide zones (Figs. 3.24A and B). 3.3.3 Stage 3 – Late hydrothermal alteration and minor metamorphism Following stage 2, minor hydrothermal alteration and contact metamorphism occurred (Fig. 3.2). Stage 3 hydrothermal alteration and contact metamorphism formed late calcite, quartz-muscovite and quartz-tourmaline veins and tourmaline filled D3-D4 faults. Contact meta- morphism also caused remobilization of gold into post-ore lamprophyre dykes (Dubé et al., 2004). The post-mineralization hydrothermal and metasomatic events are described below. 3.3.3.1 Late calcite Late calcite is observed between coarser and prior ankerite, quartz and ore-stage sulfides (Figs. 3.25A-D). Late calcite is visible only using cathodoluminescence. When visible, late cal- cite is observed to form thin (< 10 µm) veinlets or cement between prior crystals (Fig. 3.25). Some calcite veinlets demonstrate textural differences and luminescence colours. Brighter red calcite occurs in veinlet cores with a deeper red coloured calcite at the vein edge (Fig. 3.25E and 89 90 Figure 3.24 Examples of arsenopyrite-quartz-pyrrhotite-gold-brown biotite-quartz mineralization. A) Drill core, 16L1067-267.9; ESC ore zone, with strong arsenopyrite-quartz with fine quartz veins, with earlier ‘shreds’ of early biotite-Ti-magnetite ± carbonate alteration. B) Underground stope, RLC 42 Level, 42-2 sub (active June 12th 2009); disseminated gold associated with replacement pyrrhotite (and minor pyrite) in strong arsenopyrite-quartz alteration. C) Underground stope, RLC 35 Level, 2-806 stope (active August 4th 2009); gold in quartz veins surrounded by arsenopyrite-quartz alteration. D) Underground stope, RLC 35 Level stope 806 (active August 4th 2009); thin quartz vein with large associated arsenopyrite and brown biotite halo. E) Underground stope, RLC 35 Level, stope 35-806; gold with quartz veinlet surrounded by strong brown biotite-quartz halo. Dashed lines outline the brown biotite- quartz halo. F) Thin section (reflected light) CB302561; abundant arsenopyrite-pyrrhotite mineralization with less abundant pyrite-magnetite and free gold associated with quartz and brown biotite. For abbreviations, refer to list of abbreviations. F). This could possibly suggest recrystallization from the prior regional metamorphic assemblage calcite (Fig. 3.9D). This is a minor alteration stage, with only 5% of samples investigated with cathodoluminescence (n = 64) observed to contain late calcite. Timing relationships indicate a post-mineralization formation due to (1) calcite between ankerite and replacement ore-stage sul- fides (Figs. 3.25C and D); and (2) calcite veinlets cutting ankerite veins and the regional meta- morphic amphibolite assemblage (Figs. 3.25E and F). 3.3.3.2 Remobilized gold (minor contact metamorphism) Lamprophyre dykes, although not a significant lithology, host younger remobilized gold in late fractures (Dubé et al., 2004). Lamprophyre dykes cut the main mineralization stage sul- fide-magnetite-brown biotite-quartz assemblage (see section 3.3.2 above). Gold, being relatively soft and easily malleable, can be readily mobilized at elevated temperatures. The influence of post-tectonic intrusions (e.g. Cat Island pluton) in the RLGB caused the remobilization (Dubé et al., 2004). This is the second gold forming event at the RLGM (Dubé et al. 2004). 3.3.3.3 Quartz-muscovite ± carbonate ± pyrite veins Quartz-muscovite ± carbonate ± pyrite veins cut basalt, ultramafic rocks and lampro- phyre dykes, indicating that they post date mineralization (Figs. 3.26A and B). This vein type is composed of microcrystalline, white quartz with coarse (≥ 0.7 mm), randomly oriented platy muscovite. Quartz-muscovite is rare, but occurs accompanied by finely crystalline carbonate and pyrite. Typically, in basalt only, quartz-muscovite veins occur (Fig. 3.26A). The associated min- erals of carbonate ± pyrite are restricted to veins hosted in lamprophyre dykes (Fig. 3.26B). In lamprophyre dykes, the quartz-muscovite ± carbonate ± pyrite veins have extensive pink sel- vages of microcrystalline intergrown K-feldspar-quartz. These selvages can be several cm in width, whereas the vein is < 1 cm wide (Fig. 3.26B). In contrast, the quartz-muscovite veins that 91 92 Figure 3.25 Examples of late calcite between ankerite and quartz (A-B), ankerite and ore-stage sulfide (C-D) and ankerite vein and regional metamorphic assemblage (E-F). A) Thin section (plane polarized light) D39018-43; a quartz-carbonate vein with trigonal dolomite crystals. B) Thin section (CL) D39018-43; corresponding cathodolu- minescence (CL) image for A, dolomite is cemented with minor calcite. C) Thin section (plane polarized light) 34L006-2;5 example of ankerite vein with replacement ore stage sulfide. D) Thin section (CL) corresponding ca- thodoluminescence image of C. Late calcite occurs in the boundary between ankerite-sulfide. E) Thin section (plane polarized light) 34L006-25; with late calcite veinlets cuts the ankerite vein and regional metamorphic assemblage. F) Corresponding CL image of E. For abbreviations refer, to list of abbreviations. cut the basalt have no alteration selvage. Quartz-muscovite veins compose 3% of the total rock where present. 3.3.3.4 Quartz-tourmaline ± carbonate ± pyrite Quartz-tourmaline veins are composed of microcrystalline and translucent quartz, with massive, fine-grained or coarse (3–7 mm), acicular tourmaline with rare carbonate and pyrite (Fig. 3.26C-G). Acicular, coarse, tourmaline crystals occur as randomly oriented, but isolated crystals within the quartz (Fig. 3.26E). The associated pyrite is disseminated (Fig. 3.26C–D). Cream-white to pink carbonate is coarse ≈ 0.5 cm and blocky (Fig. 3.26F). When quartz- tourmaline veins occur in lamprophyre dykes, bleached selvages are observed (Fig. 3.26D). These bleached selvages are composed of K-feldspar and quartz. Petrographically, the massive and acicular tourmaline is distinct from the blue tourmaline (Fig. 3.13). The vein associated tourmaline is tabular to acicular in habit, occurring as aggregated concentrations associated with quartz, with a pleochroic blue-green core with common brown rims (Fig. 3.26H). Quartz-tourmaline ± carbonate ± pyrite veins compose 2% of the total rock along the cross sections. This vein type cuts ore, and is associated with post-mineralization ‘black line faults’ (Chapter 2: Dubé et al., 2004). Tourmaline-bearing veins cut carbonate-quartz veins (Fig. 3.26C) and lamprophyre dykes (Fig. 3.26D). Formation of abundant tourmaline is possibly due to magmatic fluids (Hinsberg, 2011), or contact metamorphism (Henry and Dutrow, 1996). 3.4 Spatial arrangement of alteration mineral assemblages Observations of mineral assemblages compiled from drill core, underground samples and thin sections were mapped along both RLGM cross sections (Figs. 1.4, 2.4). Mineralogical in- formation was plotted along the cross sections using MapInfo® version 5.1 and the plugin Dis- cover® version 5. The distribution of minerals along these two cross sections indicates an altera- tion assemblage footprint surrounding the gold-rich mineralization (Fig. 3.27). From these data, a summary sketch of the alteration footprint has been compiled (Fig. 3.28). Mineral assemblages and abundances vary gradually along these two cross sections. Observations are divided into 93 94 Figure 3.26 Examples of quartz-muscovite and quartz-tourmaline veins. A) Drill core, CR4613-363.9; quartz- muscovite vein cutting basalt with no halo. Dashed lines outline quartz-muscovite vein. B) Drill core, CR4612- 273.2; lamprophyre dyke with a quartz-carbonate-muscovite-pyrite vein with an extensive bleached halo. Dashed lines outline the extent of the bleached (k-feldspar-quartz) selvage to the quartz-carbonate-tourmaline-pyrite vein. C) Drill core, 34L814-572.3; late tourmaline-quartz-pyrite vein cuts quartz-carbonate veins. D) Drill core, DS340- 488.3; a quartz-tourmaline-pyrite vein with minor bleached selvage. E) Drill core, 34L814-1446-4; quartz- tourmaline vein with acicular tourmaline crystals in microcrystalline quartz. F) Drill core, D21708-2484.3; pink carbonate (dolomite)-quartz-tourmaline (acicular crystals) vein cuts quartz-muscovite-andalusite altered basalt. G) Drill core, DS360-751, a massive tourmaline vein. H) Thin section (plane polarized light) ES09_AP_10B micro- scopic view of a quartz-tourmaline vein. For abbreviations, refer to list of abbreviations. three scales: mine (0–3 km from ore), intermediate (3–5 km from ore) and district (> 5 km from ore), to assess a mineralogical footprint. 3.4.1 Distal footprint (> 5 km from ore) Previous work has suggested that the hydrothermal assemblages envelope the RLGM in excess of 10 km laterally from ore (MacGeehan et al., 1982; Parker, 2000; Bouzari, 2009). Al- teration is extensive throughout the RLGB. Consequently, it is important to confirm that distal alteration assemblages are, in fact, halos to mineralization. All distal assemblages defined in this study are present proximal to ore zones up to at least 7.5 km away. The most distal assemblages from mineralization are the early paragenetic stages (Fig. 3.2). These assemblages are: biotite-Ti-magnetite-carbonate, blue chlorite ± sulfides, calcic- amphibole-garnet-epidote-clinozoisite (peak-metamorphic) sporadic quartz-muscovite- andalusite. The assemblages represent metamorphosed equivalents of precursor assemblages formed during pre-metamorphic hydrothermal alteration. Cutting these metamorphic assem- blages are minor ankerite-calcite-quartz/quartz-ankerite ± chlorite selvages and quartz veins. The most abundant assemblage is the amphibolite facies, which dominates distal basalt samples. The quartz-muscovite-andalusite assemblage is significantly less abundant distally, compared to within the mine. At distances > 5 km from mineralization, the most frequent chlorite observed is birefringent blue. The blue chlorite is preserved only as garnet inclusions. The documented veins (ankerite-calcite ± quartz, quartz-ankerite and quartz) are less abundant distally (< 5% of the total rock) compared to the mine-scale (approximately > 30% of the total rock). The wide-spread na- ture of the early alteration assemblages suggests the pre-metamorphic hydrothermal event which formed the precursor minerals to these metamorphic assemblages was wide-ranging and affected the Balmer basalt over several kilometers. 95 3.4.2 Intermediate footprint (3–5 km from mineralization) The intermediate scale footprint is harder to define, as compared to the distal and mine scales, because basalt units are less abundant. The dominant assemblage at this scale is the Bruce Channel, which is composed of abundant argillite, BIF, chert, and wacke, with less abundant ma- fic volcanics (Fig. 2.4). The Bruce Channel assemblage basalt was utilized in order to study the footprint as demonstrated in mappable mafic volcanic units, continuously along the cross sec- tions. The mineral assemblages described are present in the Bruce Channel and Balmer assem- blage basalts. Alteration at 3–5 km from mineralization is more intense than > 5 km distally. The altera- tion assemblages of biotite-Ti-magnetite ± carbonate, greenschist–amphibolite facies, pervasive brown chlorite, blue tourmaline and epidote-carbonate ± quartz veins are documented. Patchy, quartz-muscovite-andalusite altered basalt is observed in minor abundances as a buff, yellow- brown colour. This suggests that muscovite is becoming the main constituent of the bleached as- semblage. 3.4.3 Mine and ore-scale footprint (0–3 km) At the mine scale, the hydrothermal alteration is intense. All described and characterized mineral assemblages (section 3.3) are observed. Hydrothermal veins and mineralization have created a narrow footprint, < 2 km width, centered on major D2 structures, which were observed to overprint the widespread metamorphic assemblages. The bleached assemblage (quartz- muscovite-andalusite ± chlorite ± biotite) and brown biotite-quartz alteration are intense proxi- mal to ore zones. Bleached basalts display a sporadic surface expression that can be mapped up to approximately 1050 m laterally from the ore zones. This envelope narrows with depth to ap- proximately 700 m at lower levels of the deposit. This creates a funnel-shaped quartz-muscovite- andalusite alteration halo to the deposit (Fig. 3.28). While all chlorite varieties are present at the mine scale, the grey chlorite is the most abundant (Fig. 3.29). A very weak zonation of grey chlorite, proximal, and blue chlorite distal to mineralization was documented. Distal blue chlorite is preserved as inclusions in garnet porphy- roblasts, whereas grey chlorite is abundant in the matrix of multiple mine-scale samples. The complex distribution is due to several superposed chlorite phases (Fig. 3.2). The biotite-Ti- magnetite ± carbonate assemblage increases in abundance toward mineralization compared to distal expressions. Amphibole (both non-calcic and calcic types) is present at depth in both mine 96 complexes. Due to the intense hydrothermal alteration at the mine scale, ‘unusual’ metabasite minerals are present (staurolite, chloritoid and andalusite), predominantly at depth. Veins of all compositions, excluding epidote-carbonate ± quartz veins are present at the mine scale. The overall vein abundance dramatically increases from approximately 5% of the total rock distally to > 30% of the total rock at the mine. Ankerite-calcite, ankerite-calcite-quartz and quartz-ankerite veins are much thicker (1 cm to 2 m) at the mine site than elsewhere. Cal- cite-magnetite veins are more common at the mine scale than distally (3 to 0.5% respectively), with the highest concentration occurring 100–200 m laterally from ore. Chlorite selvages to ankerite-calcite and ankerite-calcite -quartz veins are frequently observed proximal to ore zones. This vein type extends outwards < 1 km from ore. Selvages to high grade ore veins are com- posed of brown biotite-quartz. This alteration creates a very narrow footprint < 50 m from min- eralization. Sulfide and oxide minerals observed in this study from most to least abundant are pyr- rhotite, pyrite, magnetite, arsenopyrite, stibnite, sphalerite and molybdenite. They are most abundant at the mine. Distribution of syn-mineralization sulfides-magnetite defines a narrow halo, as sulfide abundance increases significantly inward from approximately 150 m from ore zones. The syn-mineralization sulfide-magnetite halo is wider at shallower levels due to the na- ture of widespread disseminated ore. At depth, mineralization is narrower and fault-hosted. The dominant sulfide in the shallower mine levels is pyrite. With increasing depth in the mine, the dominant sulfide is pyrrhotite (Bouzari, 2009). 3.4.4 Regional metamorphic footprint The regional metamorphic assemblage is part of a larger, belt scale zonation, from lower greenschist in the center of the RLGB to upper amphibolite facies at its edge (Thompson, 2003; Fig. 2.1). The distribution of greenschist to amphibolite facies mineral assemblages have been compiled along both cross sections (Fig. 3.30). The RLGM is located at the greenschist to am- phibolite facies transition (Fig. 3.30). A transitional area was defined as the first appearance of amphibolite facies mineralogy, with the upper limit defined as where amphibolite facies assem- blages become dominant. Previous research has also identified an isograd occurring in the Red Lake Complex (Damer, 1997; Fig. 3.30). This isograd was characterized by the staurolite-in and chloritoid-out isograd (Damer, 1997). This newly defined isograd is steeper compared to Damer’s (1997). The mineral assemblage variations from greenschist to amphibolite are due to variations in the P-T conditions, and bulk rock chemistry variations. 97 Figure 3.27 Distribution of alteration assemblages compiled along both cross sections. A) Campbell, B) Red Lake 98 Figure 3.28 Summary of the recorded alteration mineral assemblage zonation surrounding the RLGM. For abbreviations, refer to list of abbreviations. 99 3.5 Interpretation and discussion The relative timing of hydrothermal alteration and metamorphism is important for under- standing the processes responsible for ore-forming fluids and ore genesis. Lode-gold ore-forming fluids could be metamorphic or hydrothermal in origin. Prior events possibly influenced ore deposition by the creation of a chemical or physical trap. With reference tools of only rock and petrography, it is difficult to discern unambiguously. However, relative timings and possible synchronous geological events can be identified, providing a foundation upon which to apply geochemical data (Fig. 3.31). Mineral assemblage observations from this study support multiple stages of hydrothermal and metamorphic overprints at the RLGM (see Chapters 1 and 2; Fig. 3.2). This sequence of events is important to understand, as there are implications for understanding the creation of such a gold-rich deposit. The documented and characterized mineral assemblages in this study have identified four main stages of overprinting hydrothermal and metamorphic events. These four stages are graphically represented in figures 3.31 and 3.32, and are discussed below. 3.5.1 Geological sequence of hydrothermal and metamorphic events at the RLGM 3.5.1.1 Early hydrothermal alteration of the host basalt Mineralogical information suggests that at least one barren, widespread hydrothermal event affected the Balmer basalt. This occurred prior to M2 peak-regional metamorphism. This event is represented in Figure 3.2 as H1*. The hydrothermal event could have been associated with D1 and M1 events. Evidence of this prior hydrothermal alteration event is implied by the early M2 metamorphic assemblages of biotite-Ti-magnetite ± carbonate, greenschist-amphibolite facies mineralogy and quartz-muscovite-andalusite. The presence of abundant biotite, muscovite, andalusite, chloritoid and staurolite all suggest that the Balmer basalt composition was signifi- cantly changed prior to regional metamorphism (c.f. Mathieson, 1982). The precursor mineral assemblage required to create the above-mentioned metamorphic assemblages was presumably rich in clays, mica, carbonate, and possibly chlorite and Fe-oxides. Different precursor mineral packages for quartz-muscovite-andalusite and garnet-chlorite-amphibole-biotite assemblages are suggested by the distinct mineralogy. It has been suggested previously that the precursor assem- blage for the quartz-muscovite-andalusite assemblage was advanced to intermediate argillic al- teration (Penczak, 1996). The early hydrothermal events could have implications for the 100 Figure 3.29 The distribution of chlorite birefringence colours as seen in thin sections from basalt units of the RLGM. A) Campbell, B) Red Lake. 101 Figure 3.30 Metamorphic facies as defined by thin section observations of basalt samples across the RLGM cross section. A) Campbell, B) Red Lake. Damer’s (1997) staurolite in and chloritoid out isograd lines are indicated on the Red Lake cross section. 102 subsequent gold-rich metasomatic event which formed the RLGM. For a full discussion of the early hydrothermal event(s) see Chapter 6. 3.5.1.2 Initiation of M2 peak-regional metamorphism At the start of M2 peak-regional metamorphism, the first metamorphic assemblage to be grown was the biotite-Ti-magnetite ± carbonate assemblage. This assemblage is foliation aligned to the main S2 foliation fabric, therefore, formed during synchronous D2 and M2 metamorphism. As M2 metamorphism continued, the main metamorphic assemblage of greenschist-amphibolite facies developed. This began with the formation of the foliation aligned blue chlorite ± sulfide assemblage. As prograde metamorphism continued, the blue chlorite was overprinted by brown chlorite. Both blue and brown chlorite were overprinted by the regional metamorphic and the quartz-muscovite-andalusite assemblage. Each of these assemblages define the S2 foliation, therefore, are considered metamorphic in origin. Menard and Pattison (1998) have suggested an M3 (contact) retrograde metamorphic event, due to splays of chlorite and epidote/clinozoisite ± calcite replacing garnet porphyroblasts. To date, this is the only publication to suggest a retrograde metamorphism in the Red Lake area. Observations in this study confirm the identification of acicular blue chlorite-muscovite ± car- bonate ± quartz, which has overgrown some, but not all, garnet rims. Only 5% of garnets are af- fected by this assemblage. The chlorite-muscovite ± carbonate ± quartz assemblage could be due to localized metasomatic fluids which caused the breakdown of garnets. It could also indicate a drop in P-T conditions (i.e. retrograde reactions) from the peak of regional metamorphism. It is possible that the timing of this assemblage is an issue of nomenclature, that Menard and Patti- son’s (1998) M3 event is the same as late M2 defined in this study. As the chlorite-muscovite ± carbonate ± quartz assemblage is cut by ankerite-calcite ± quartz veins, it implies this assem- blage formed during late M2, as suggested in this thesis. 3.5.1.3 Continued M2 peak-regional metamorphism After the formation of the pervasive biotite, greenschist-amphibole metamorphic facies, and quartz-muscovite-andalusite alteration, synchronous hydrothermal alteration, deformation and metamorphism occurred. D2 deformation created structural corridors which focused fluid flow at the mine site. This event commenced with the formation of a series of ankerite-calcite, ankerite-calcite-quartz and quartz-ankerite veins. These veins occur with a variety of associa- tions (magnetite, epidote, chlorite and biotite), which typically occur as selvages. Each vein type 103 was consistently observed to overprint the previously formed metamorphic assemblages (biotite- Ti-magnetite ± carbonate, greenschist-amphibolite and quartz-muscovite-andalusite assem- blages). Following the formation of structurally-controlled veins, the main mineralization event oc- curred. Mineralization is characterized by abundant sulfides-magnetite ± gold, accompanied by quartz and brown biotite. It is thought that synchronous hydrothermal alteration, deformation and metamorphism continued. Ore-forming fluids were focused into D2 structures. Sulfides formed parallel to the main S2 foliation trend. Consistent observations from this study were compiled demonstrating that the various carbonate minerals-quartz veins and mineralization event overprinted the earlier metamorphic assemblages. Therefore, the auriferous event at Red Lake was a narrower event superposed upon a metamorphosed altered sequence. 3.5.1.4 Post-M2 hydrothermal alteration After peak-metamorphism, a synchronous plutonic emplacement phase occurred, associ- ated with brittle-ductile deformation, hydrothermal alteration and contact metamorphism. During this contact metamorphic event, gold was remobilized in post-ore lamprophyre dykes. Veins composed of quartz-muscovite ± bleached selvages and quartz-tourmaline ± carbonate ± pyrite ± K-feldspar ± quartz selvages were also created. This is a minor hydrothermal event, dominated by quartz and tourmaline, as compared to the earlier pre- and syn-mineralization events. 3.5.2 Comparison of new observations with previous knowledge Detailed observations from this study have identified new minerals and paragenetic events. This new information needs to be included for future detailed mineral and/or geochemi- cal studies of the RLGM. Below, a comparison of previous paragenetic sequences and the obser- vations gathered in this study will highlight new information in pre-, syn- and post- mineralization events. 3.5.2.1 Comparison of pre-mineralization events A wide footprint of pre-mineralization alteration assemblages (biotite-Ti-magnetite ± carbonate, blue chlorite ± sulfides, brown chlorite and the regional metamorphic assemblage ± sporadic quartz-muscovite-andalusite assemblage) has been recorded from proximal to ≥ 7 km distally, laterally from ore. Ti-magnetite and rare associated Ti-biotite is a new addition to the 104 initial biotite assemblage in the Red Lake area. This phenomenon could be due to the original basalt being Ti-rich, localized areas of enriched Ti from localized hydrothermal activity, or by the removal of other cations. The fullest lateral extent of the wide-ranging alteration assemblages was not found in this study. These assemblages reflect a belt wide, pre-mineralization, synge- netic hydrothermal alteration event. Figure 3.31 Schematic diagram showing the major geological phases of the RLGM’s development. BA) Balmer assemblage, BC) Bruce Channel assemblage, LVL) Little Vermillion Lake batholith, DL) Douglas lake pluton, Dm) Dome stock, MK) McKenzie stock, ABG) Abino granodiorite, HD) Howey diorite, HLB) Hammell Lake batholith, KB) Killala-Baird batholith, WL) Walsh Lake pluton, CI) Cat Island pluton, H) hydrothermal event, M) metamor- phic event, D) deformation event, P) plutonic event. Deformation details compiled from Sanborn-Barrie et al. (2001) and Dubé et al. (2004). Intrusion emplacement ages from, Corfu and Wallace, (1986), Corfu and Andrews (1987), and McMaster (1987). Yellow stars indicate gold-mineralization events. For mineral abbreviation, refer to list of abbreviations. 105 Figure 3.32 The stages of hydrothermal mineral assemblages identified at the RLGM. 106 Brown chlorite and the transitional facies of non-calcic to calcic amphibole are new ob- servations for this field area. The non-calcic to calcic amphibole could have implications for ex- ploration. Gold-mineralization occurs within the greenschist to amphibolite transition zone (Thompson, 2003; this study, Fig. 3.30). Non-calcic and calcic amphibole can be differentiated in thin section. Microscopic observations of samples could confirm transitional areas for pin- pointing areas of potential economic significance. Albite was identified by McGeehan et al. (1982) and Bouzari, (2007, 2009) as a distal, localized expression. This study identified coarse, plagioclase crystals overprinting calcic- amphibole and epidote at distances of > 5 km distally from mineralization. Although SEM analysis confirmed the presence of feldspar, it could not accurately prove albite. Therefore, pla- gioclase is used as the classification in this dissertation. Blue tourmaline has not been observed previously. Due to limited cross cutting relation- ships, the only confident timing is after peak-metamorphism. The presence of blue tourmaline could suggest two possible formations: either, from syn-mineralization felsic intrusions: Dome stock, McKenzie Stock, Hammell lake batholith, Howey diorite and Abino granodiorite; or con- tinued regional metamorphism. The syn-mineralization intrusions are several kilometers distally from the RLGM. This could explain the limited amount of blue tourmaline noted at the mine site. However, this does not confidently rule out either hypothesis. The significance and implica- tions for blue tourmaline remain elusive. Observations of pre-mineralization, pervasive assemblages are consistent with a wide- spread, primary permeability-controlled, intense hydrothermal alteration event (MacGeehan and Hodgson, 1982; Mathieson, 1982; Penczak, 1996). There are few petrographic observations to suggest that gold-mineralization occurred prior to peak metamorphism (c.f. Kerrich et al. 1981: MacGeehan and Hodgson 1982; Penczak, 1997, Damer 1997). However, new observations of brown chlorite, blue tourmaline, chlorite-muscovite ± carbonate ± quartz continue to highlight the complex, superposing nature of the early hydrothermal alteration event(s). 3.5.2.2 Comparison of main vein and ore-forming stage The vein paragenesis is extremely complex and problematic to define on petrographic details alone. However, multiple generations have been defined on the bases of composition, tex- ture, selvages and cross cutting relationships. These veins are (1) calcite-magnetite, (2) ankerite- quartz with biotite selvages, (3) cryptocrystalline ankerite, (4) medium to coarse ankerite, (5) colloform-crustiform ankerite-calcite veins ± chlorite selvages, (6) ankerite-calcite-quartz veins 107 ± chlorite selvages, (7) quartz-ankerite veins, (8) mineralized quartz veins rarely containing gold, and (9) younger quartz-tourmaline veins. Chlorite selvages to carbonate veins are blue, brown and grey. This is inconsistent with observations by Penczak (1996) and Penczak and Mason (1997) who reported only blue chlorite selvages to carbonate veins. Observations of ore-assemblages confirm that gold-mineralization is composed of pyr- rhotite-pyrite-arsenopyrite-magnetite-stibnite-molybdenite-sphalerite (see Chapter 2). Although previous work in specific ore zones has defined associated alteration assemblages (e.g. Cadieux et al., 2006), little work has been compiled regarding the paragenetic nature of mineralization styles. This study has compiled cross cutting relationships to provide a sequence of mineraliza- tion assemblages. From observations in this study, quartz-molybdenite veins have been added to the ore-stage mineralization assemblages. Molybdenite is a common ore mineral in porphyry systems and pegmatite environments (Kooiman et al., 1986; Lang and Eastoe, 1988). This asso- ciation could indicate that the quartz-molybdenite veins are possibly related to the syn-M2 intru- sions, such as the Dome Stock (Fig. 1.3), indicating a possible magmatic origin for the ore- forming fluids. A full discussion can be found in Chapters 5 and 6. The parallel occurrence of sulfide veins and replacement style mineralization with the S2 foliation plane also confirms a synchronous development with D2 deformation. However, observations of suggested synchro- nous metamorphism, deformation and mineralization support other, more recent publications (Christie, 1986; Thompson, 2003; Dubé et al., 2004). 3.5.2.3 Comparison of post-mineralization events Post-mineralization hydrothermal events have not been widely studied previously. This is because of little economic significance and the minor abundance, compared to earlier stages. Previous post-mineralization observations include lamprophyre dykes, gold remobilization and black line faults (Chapter 2). This study identified late calcite, quartz-muscovite veins ± bleached (K-feldspar-quartz) selvages. Observations confirmed tourmaline-bearing veins ± bleached sel- vages and tourmaline filled faults (black line faults). The late calcite is thought to be remobilized from the older regional metamorphic assemblage. Both paragenetic calcite stages have a dull and brighter red calcite in CL (Fig. 3.9D and 3.25F). Quartz-muscovite veins in lamprophyre dykes exhibit bleached selvages, whereas those in basalts do not. This is a reflection of different bulk rock compositions. Lamprophyre dykes are post-mineralization, hence the quartz-muscovite veins are late. The temporal relationship between quartz-muscovite and quartz-tourmaline veins remains elusive, but it is possible that both may be related to large, post-mineralization intrusions 108 (e.g. Walsh Lake phase of the Cat Island Pluton). These late plutons are known to have remobi- lized gold in the RLGB (Dubé et al., 2004). 3.6 Future discussion topics Several superposed hydrothermal and metamorphic events have been identified at the RLGM (McGeehan et al., 1982; Mathieson and Hodgson, 1984; Parker, 2000; Sanborn-Barrie et al., 2001; Dubé et al., 2004; This study). However, an agreement has not been reached regarding the ore-genesis, the nature and environments of hydrothermal alteration (particularly, pre- and syn-mineralization), or the characteristics and sources of ore-forming fluids. Also, the degree of metamorphism and its influence on the ore-forming event remains elusive. The paragenetic se- quence established in this chapter and the following geochemistry, mineral chemistry and stable isotope data will address these issues (see Chapters 4, 5 and 6). 3.7 Conclusions A detailed petrographic study characterized the mineral assemblages and established a detailed paragenesis and a mappable zonation surrounding the ore zones of the RLGM. Utilizing the established geological evolution of the RLGB (Sanborn-Barrie et al., 2001), the mineralogi- cal patterns, both temporally and spatially, can be linked to aid in understanding how a world- class gold deposit formed. Four distinct phases of development have been identified: 1. An early, intense hydrothermal event (H1) significantly altered the Balmer Basalt causing the precursor mineral assemblages to the earliest recognizable metamorphic assemblages. Abundant micas and clays with associated K2O addition was suggested prior to the for- mation of the biotite-Ti-magnetite ± carbonate assemblage. An assemblage of clays- carbonate-chlorite was proposed for the greenschist-amphibolite facies with the basalt ex- tensively altered to reflect a similar composition to a pelite. Finally, the quartz- muscovite-andalusite assemblage was proposed to be the metamorphic equivalent of in- termediate to advanced argillic alteration (Penczak, 1996). The early H1 hydrothermal system was wide-spread, affecting the RLGM and surrounding area. 2. Synchronous deformation and regional metamorphism (D2 and M2) of the early hydro- thermally-altered basalt created a widespread footprint of (in paragenetic order): - biotite-Ti-magnetite ± carbonate, - berlin blue chlorite ± sulfides and weakly abundant brown chlorite, - greenschist to amphibolite mineral assemblages, 109 - localized areas of quartz-muscovite-andalusite alteration. These early, wide-spread metamorphic assemblages do not represent telescopic zonation around the RLGM, but could have been important for subsequent overprinting minerali- zation by creating a chemical trap. The veins and mineralization event overprinted these earlier assemblages. 3. As metamorphism continued, the main vein and mineralization event occurred. This syn- metamorphic hydrothermal event was localized into D2 corridors and may have reflected a collapsed hydrothermal system (Penczak and Mason, 1997). The main vein stage con- sisted of ankerite-calcite ± magnetite ± chlorite ± biotite veins, followed by quartz- ankerite veins. After the main vein event, gold-mineralization occurred. Mineralization assemblages are composed of various sulfides and magnetite associated with quartz and brown biotite. All mineralization and veins are parallel to the main S2 foliation. The main mineralization stage developed during synchronous deformation and continued M2 re- gional metamorphism. 4. Finally, the Cat Island Pluton was emplaced. Pluton emplacement was associated with brittle deformation and hydrothermal alteration. Hydrothermal fluids formed late calcite, quartz-muscovite ± bleached selvages and quartz-tourmaline ± carbonate ± pyrite veins ± bleached selvages. This event also caused remobilization of gold into lamprophyre dykes, which are known to cut ore zones at the RLGM (Dubé et al., 2004). The distribution of mapped mineral assemblages, in the Balmer and Bruce Channel assemblage basalts, reveals a zonation ≥ 7.5 km surrounding the RLGM gold-mineralization. This zonation is the manifestation of superposed events in the Red Lake area. A widespread, pervasive, meta- morphic footprint of biotite-Ti-magnetite ± carbonate, blue chlorite ± sulfides and amphibole- garnet-magnetite ± epidote/clinozoisite ± chlorite ± chloritoid ± staurolite ± calcite with local- ized occurrences of quartz-muscovite-andalusite is preserved. These assemblages are the meta- morphosed equivalents of precursor alteration minerals. These early metamorphic assemblages were overprinted by a narrower, structurally-controlled vein and mineralization event. Recorded proximal to ore (0-500 m) are abundant carbonate, carbonate-quartz and carbonate-magnetite veins, with occasional chlorite selvages. Quartz-rich ore zones exhibit a zonation of biotite mar- gins, to pyrite, pyrrhotite, magnetite, arsenopyrite ± stibnite and gold over 0-50 m. These mineral zonations can be utilized in exploration efforts throughout the RLGB, as well as at the mine site. 110 Chapter 4: Mineral chemistry and lithogeochemistry of the Red Lake Gold Mines 4.1 Introduction Investigation of the Red Lake Gold Mines (RLGM) and surrounding area involved exten- sive field work (see Chapter 1 and Appendix A.1-A.4) combined with the application of geo- chemical data. This included mineral chemistry and lithogeochemistry applied to a rigorous par- agenesis, which was defined by detailed petrography (Chapter 3). Research focused on the char- acterization of geochemical variations between specific assemblages and minerals, and from proximal to distal expressions. This identified not only geochemical trends potentially important for exploration, but also valuable information about the ore-forming system as a whole. This in- formation has implications for similar Archean lode-gold deposits globally. Geochemical data was primarily obtained from one protolith, the Balmer basalt. Basalt was used as a reference for the comparison of chemical variations to highlight chemical differences. During this study, an emphasis was placed on obtaining mineral chemistry specifically from chlorite, biotite, amphibole, carbonate and garnet. These minerals were chosen because they are common throughout the RLGM and Red Lake greenstone belt (RLGB), occur in multi- ple paragenetic stages (Fig. 3.2), and are easily recognizable. Previous mineral chemistry work at the RLGM has already suggested implications for exploration; chlorite has been reported to vary from Mg-rich distally to Fe-rich proximal to ore zones (Bouzari, 2009). A detailed mineral chemistry analysis will seek a more definitive characterization of the compositional differences. Chemical analysis of the specifically chosen minerals in this study, can also provide physio- chemical constraints for hydrothermal and metamorphic events (c.f. Damer, 1997; Tarnocai, 2000). The hydrothermal and metamorphic influence on gold-mineralization at Red Lake has yet to be agreed upon. The combination of mineral chemistry and whole rock geochemistry data is the best approach to aid exploration, understand the geological influences on ore formation, and characterize the chemical evolution of the host rocks at the RLGM. This chapter provides the methodology and data for the mineral chemistry and lithogeo- chemistry analysis. This also includes petrography, scanning electron microscopy (SEM) and additional carbonate mineral identification (cathodoluminescence (CL) and reactivity with acid). The chemical variations in the basalt host rock and specific minerals are presented and dis- cussed. The influences and distribution on chemical trends are also discussed with regard to ex- 111 ploration and understanding the controls on geochemistry and mineral chemistry in an ancient hydrothermal system. 4.2 Methodology 4.2.1 Petrography Detailed petrography was used to produce the paragenetic sequence (Chapter 3, Fig. 3.2). The paragenesis provided a rigorous context. This was essential to fully interpret mineral chem- istry data. A total of 327 polished thin sections were investigated:  203 core and underground samples along the entirety of the cross sections (Fig. 1.9) to investigate the large km-scale mineral footprint,  10 samples from the mapped outcrop, large carbonate vein (Appendix A.4) to investigate the multiple carbonate vein textures,  114 samples from Bouzari (2007), who originally investigated down drill hole variations. Of the 327 thin sections, various lithology were used:  Basalt = 233  Ultramafic = 48  Felsic = 19  Diorite = 14  Argillite = 11  Lamprophyre dyke = 2 Seventy-five percent of the thin sections had a corresponding whole rock analysis. All the thin sections were analyzed using a Nikon Eclipse E600 POL microscope. Digital photographs were taken either with a mounted Olympus EI/SLR or a Canon EOS rebel T2i camera. Images were processed with dSLR remote pro software. 4.2.2 Cathodoluminescence and acid testing for carbonate mineral identification Selected samples were chosen for additional carbonate mineral identification via CL and reactivity with acid. Both methods are inexpensive, and can easily identify carbonate minerals to test the previously documented carbonate mineral zonation at the RLGM (MacGeehan et al., 1982; Marshall, 1988; Parker, 2000). Cathodoluminescence can also differentiate textural differ- ences not visible in SEM or microscopic analysis (Marshall, 1988; Fig. 3.9C and D). Reactivity with acid used dilute (10%) HCl applied to the whole rock or specific vein. If the carbonate effervesced, calcite was recorded. If the carbonate effervesced only when powered, dolomite/ankerite was recorded. Multiple vein types were tested from 193 samples. Twenty- three samples did not react with HCl. This could be because no carbonate (either pervasive or vein) was present, the carbonate abundance was too low, and/or carbonate was intermixed or re- 112 placed by more abundant quartz. The limitation of acid testing for carbonate mineral identifica- tion is that dolomite and ankerite cannot be differentiated. Sixty-four polished thin sections were analyzed using a Cambridge Image Technology Ltd. 1998 model CLmk4, by cold-cathodoluminescence. The operating conditions were: beam current 15 kv, gun current ~330 µA and power ~40 W. Raw image files were taken using an Olympus EI/SLR, with the images modified to highlight any luminescence variations with dSLR remote pro software. 4.2.3 Scanning electron microscopy SEM was used for mineral identification. Electron dispersive spectra (EDS) were used to establish the bulk chemistry of the mineral. These data, combined with petrographic details (e.g. colour, relief, etc.), were used to determine the mineral analyzed. Supportive paragenetic timing relationships were also identified. The Philips XL-30 with a Princeton Gamma-Tech ELS/IAS SEM at the University of British Columbia was used to analyze polished thin sections. Thin sec- tions were analysed using backscatter imaging with a 15 kV beam, spot size of 6 µm, and a working distance of 10 mm. 4.2.4 Electron microprobe analysis The electron microprobe is a high precision tool used to document the compositional variance of the investigated minerals. Electron microprobe analysis (EMPA) has the potential to accurately define major and trace element abundances in a specific mineral or mineral phase (Raudsepp, 1995). Thus, EMPA was the best method to characterize mineral compositions. All mineral chemistry data was obtained from polished thin sections. Analyses were completed using wavelength dispersive X-ray analysis on a Cameca SX-30 scanning electron microprobe at the University of British Columbia. Four vertical wavelength-dispersion x-ray spectrometers and a fully integrated SAMz energy-dispersion X-ray spectrometer were used. Each mineral was analyzed under the following conditions: accelerating voltage 15.0 kV; beam current, 10 nA (20 nA for amphibole and garnet) peak count time, 20 s (expect F = 60 s and Cl = 40 s for biotite; F = 40 s for amphibole) and spot diameter 10 m (5 m for amphibole and gar- net). Table 4.1 states the standards, X-ray lines and crystals used in EMPA. Data reduction was done using the 'PAP' (Z) method (Pouchou and Pichoir, 1985). EMPA errors are presented in Appendix B.1. 113 The minerals analyzed were chlorite, biotite, amphibole, carbonate and garnet. Samples were selected across both cross sections (Fig. 4.1) with an even distribution to assess proximal and distal compositions. Figure 4.1 also includes which minerals were probed from each sample. Table 4.2 outlines sample numbers and lithology analyzed for each mineral. Basalt was the dominantly investigated lithology. Minerals within other rock types (rhyolite, ultramafic, diorite and chemical sediment) were originally investigated during pilot studies, when the scope of the dissertation was much broader. A thorough investigation of every rock type with regard to geo- chemical, mineral chemical and isotopic geochemistry was beyond the scope of this study. Table 4.1 Standard operating information for EMPA Mineral Standards, X-ray lines and crystals used in EMPA Chlorite Fluor-phologoite, MgK, SiK and KK, TAP; albite, NaK, TAP; kyanite, AlK, TAP; diop- side, CaK, PET; rutile, TiK¸ PET; synthetic magnesio-chromite CrK, LIF; rhodomite, MnK¸LIF; fayalite, FeK, LIF. Biotite Fluor- phologoite, FK, MgKa and SiKa, TAP; fluor-phologoite, KK,PET; albite, NaK, TAP; kyanite, AlK, TAP; scapolite, ClK, PET; diopside, CaK, PET; rutile, TiK¸ PET; synthetic magnesio-chromite CrK, LIF; rhodomite, MnK¸LIF; fayalite, FeK, LIF. Amphibole Fluor-phologoite, FK, TAP; albite, NaK, TAP; diopside, CaK, MgKa and SiKa, PET; kyanite, AlK, TAP; scapolite, ClK, PET; orthoclase, KK, PET; rutile, TiK¸ PET; synthetic magnesio- chromite CrK, LIF; rhodomite, MnK¸LIF; fayalite, FeK, LIF. Carbonate Dolomite, MgK, TAP; calcite CaK, PET; r rhodomite, MnK¸LIF; siderite, FeK¸LIF. Garnet Albite, NaK, TAP; diopside, MgKa, PET; almandine, AlK, SiK, TAP; almandine, FeK, LIF; grossular CaK, PET; rutile, TiK¸ PET; synthetic magnesio-chromite CrK, LIF; rhodomite, MnK¸LIF. The following acronyms are used: thallium acid pthalate (TAP), pentaerythritol (PET) and lithium fluoride (LIF) Table 4.2 Minerals investigated using the electron microprobe with sample numbers and lithology Basalt Ultramafic Diorite Rhyolite Sedimentary unit Lamprophyre dyke Vein Total samples Chlorite 21 2 2 3 1 29 Biotite 12 2 1 1 16 Amphibole 7 7 Carbonate 7 1 1 2 1 3 14 Garnet 16 2 18 For each mineral investigated by EMPA, the chemical variations between mineral types (e.g. non-calcic and calcic amphibole) and mineral occurrences from proximal to distal expres- sions are discussed in detail. These trends, which could be potentially useful for exploration, were defined and discussed for comparison with the field-based short-wave infrared technique. This technique can theoretically identify mineral trends (Thompson et al., 1999; Hauff, 2005). 114 Figure 4.1 Location of all samples selected for electron microprobe analysis showing which minerals were analyzed per sample. A) Campbell, B) Red Lake. 115 The more precise, but slower method of EMPA was compared to short-wave infrared to investi- gate if the rapid field-based tool can identify the sample trends quicker. This comparison and discussion is dealt with in Chapter 7. A summary of previous mineral chemistry investigations from various ore deposit sys- tems, and specifically the RLGM, are also included. This information indicates the possible de- tails that can be obtained, and what is already known from previous mineral chemistry investiga- tions of the RLGM. For each mineral, the number of samples investigated, the method of data recalculation and the selection criteria for establishing good data are provided. 4.2.4.1 Chlorite Chlorite is a common hydrothermal and metamorphic mineral associated with a number of ore systems. In epithermal, and modern geothermal systems, chlorite chemistry has already proven potentially useful for exploration, by exhibiting chemical trends (Ahmad and Walshe, 1990; Yang et al., 2001). Chlorite chemistry can also be used to understand hydrothermal altera- tion. Compositional data can potentially provide geothermometry estimates, indications of fluid- rock interaction and/or clarify different redox environments (Walshe, 1986; Shikazono and Kawahata, 1987; Walker, 1993). Within the Red Lake area, chlorite is abundant. It was formed by both metamorphic and hydrothermal processes and occurs in several paragenetic stages (Fig. 3.2). Chemical informa- tion from paragenetically constrained chlorite can provide information about several processes that have affected the RLGM. Previous research on chlorite at the RLGM has identified several birefringence varieties: blue = Fe-chlorite and green = Fe-Mg-chlorite (Christie, 1986; Penczak, 1996). Ripidolite has been suggested as the main chlorite mineral (Cadieux et al., 2006). Chlorite is also noted to vary spatially toward mineralization; chlorite is Mg-rich distally and Fe-rich proximal to ore zones (Bouzari, 2009). The investigation of chlorite chemistry in this study was to (1) test previous observations (Christie, 1986; Penczak, 1996; Cadieux et al., 2006; Bouzari, 2009); and (2) to provide more information to understand the complex nature of superposed al- teration at Red Lake. Twenty-nine samples for chlorite analysis were selected from both cross sections (Fig. 4.1). Each sample contained approximately 30–50 analyses. Mineral formulae were calculated using O = 14, with H2O determined stoichiometrically and all iron assumed to be Fe2+ (Hey, 116 1954; Walshe, 1986; Likhanov et al., 1995). To select good and representative analyses, the fol- lowing criteria were established (based on Deer et al., 2009): Good analyses: Representative: 1. Total oxide weight % 98.5 < x > 101.5 Fe/Mg closest to Median 2. Mol K <0.05 3. Sum of octahedral site: 5.9 > x < 6.1 4. Sum of tetrahedral site = 4.0 A representative, true analysis closest to the median was selected for each chlorite type identified per sample. For all chlorite EMPA data, see Appendix B.2. 4.2.4.2 Biotite Biotite is a common alteration mineral associated with many deposit types. These include porphyry systems (Cannell et al., 2005) and Archean lode-gold deposits (Neumayr et al., 1993). Biotite compositional variations have been identified and used within porphyry systems to document fluid chemistry (Selby and Nesbitt, 2000). In Archean lode-gold systems, documented biotite compositions display increased abundances of S, K, Al, and Na concentrations proximal to ore (Mueller, 1992). Therefore, biotite chemistry has the potential to aid exploration. Addi- tionally, equilibrated garnet and biotite can be used as a geothermometer. This geothermometer works especially well within metapelites (Henry et al., 2005). Two distinct biotite types were identified in this study; an early pervasive biotite, and an overprinting brown biotite associated with mineralization (Figs. 3.3, 3.24 and 3.25). This sup- ports previous observations (Christie, 1986; Penczak, 1996; Cadieux et al., 2006). In other min- eralized areas within the RLGB, e.g. the Gold Eagle deposit (Fig. 1.3), the same two biotite phases have been identified (Marsden, 2012). Prior research has suggested the brown biotite ranges from biotite to phlogopite in composition (Cadieux et al., 2006). Petrographic information suggests that these two biotite phases reflect two different hydrothermal events. The early meta- morphic biotite-Ti-magnetite ± carbonate assemblage has implications for prior hydrothermal alteration. The later brown biotite-quartz assemblage reflects the hydrothermal ore-forming event. Chemical information from both phases could aid in identifying the conditions and nature of these two hydrothermal events. Differences in biotite composition between phases could also be used in exploration. 117 Sixteen samples were used to analyze the two biotite varieties. Seven were representative of the biotite-Ti-magnetite ± carbonate assemblage, two represented the biotite + abundant car- bonate (a variation of the biotite-Ti-magnetite ± carbonate assemblage), and seven represented the brown biotite. Each sample contained approximately 30 analyses. Mineral formulae were calculated for O = 11, with H2O calculated via stoichiometry and all iron considered to be Fe2+ (Deer et al., 2004). The following criteria were established to reject and to select representative analyses (Deer et al., 2004): Good analyses: Representative: 1. Total oxide weight % 98.5< x >101.5 Mg/Fe closest to Median 2. Mol K >1.70 3. Sum T-site = 4.0 4. Sum of Y-Site = x > 2.7 (octahedral) 5. Sum of X-Site = x > 0.9 (alkali) For each sample a representative analysis was chosen as the closest to the median Mg/(Mg+Fe) value. For all biotite EMPA data, see Appendix B.3. 4.2.4.3 Amphibole Petrographic observations in this study identified one stage of amphibole growth (Chap- ter 3). This occurred during M2 regional metamorphism (Fig. 3.2). Thin section observations clearly indicate that the amphibole type changes from non-calcic fibrous to blocky calcic across the study area (Fig. 3.8A). This occurs particularly in the transitional facies. Previous reports have also documented non-calcic (anthophyllite, cummingtonite) and calcic amphiboles (ferro- tschermakite, hornblende) at the RLGM (Mathieson, 1982; Penczak, 1996; Damer, 1997; Menard and Pattison, 1998; Cadieux et al., 2006). The amphiboles are also suggested to be zoned with tremolite cores to anthophyllite rims (Menard and Pattison, 1998). Because amphi- bole developed during M2 peak-metamorphism, the amphibole chemistry could contain informa- tion regarding the composition of the basalt at the time of metamorphism. Amphibole porphyroblasts were analysed from along both cross sections (Fig. 4.1). Re- calculation of amphibole EMPA data is challenging due to highly variable constituents such as H2O, FeO versus Fe2O3, MnO versus Mn2O3 and Li2O (Hawthrone and Oberti, 2007a). It is es- sential to determine the ferric versus ferrous concentrations, as amphibole classification uses at- oms per unit formula (apfu) Si:Mg/(Mg+Fe2+) ratios (Robinson and Jaffe, 1969, Lal and Moor- 118 house, 1969; Stout, 1972; Leake et al., 1997, 2004; Hawthorne and Oberti, 2007b). In this study, Li2O was not analyzed, H2O was calculated stoichiometrically, and estimates of ferric and fer- rous iron were calculated using the method outlined by Schumacher (1997). No estimate of Mn2+ and Mn3+ was calculated due to the consistently low Mn abundances (regardless of oxidation state) needed to fill the C-site. Data was rejected if it did not meet the following criteria (based on Schumacker, 1997):  No vacancies other than the A-site.  Sum of B site: 4.9 < x ≤ 5.0  Ca only in the B-site  K only in the A-site  Only Si and Al in the T-site  ≤ 23 total oxygen anions (minus F and Cl) when normalized to average of 15eNK and 15eK  15 ≤ Total cations < 16  97.5 ≤ Total oxide ≤ 102.5 For each sample, 3-5 different amphiboles were probed by rim-core-rim profiles. Three represen- tative analyses were chosen to characterize the rim, middle quartile, and core composition of each amphibole type. This profile also identified chemical zoning if present. From each amphi- bole, the median analysis was chosen as the representative. For all amphibole EMPA data, see Appendix B.4. 4.2.4.4 Carbonate Various carbonate minerals form halos contiguous to gold-bearing ore deposits. Hydro- thermal carbonate alteration has been observed to envelope gold veins in Western Australia (Philips and Brown, 1987; Sketchley and Sinclair, 1991; Davis et al., 2001). Compositional variations in carbonate minerals enveloping gold veins have aided exploration by increasing the target size (Sketchley and Sinclair, 1991). Carbonate chemistry can also provide thermometry estimates (Rice, 1977), and possibly distinguish multiple fluid phases (Davis et al., 2001). Multiple carbonate minerals have been identified previously at the RLGM. These include calcite, dolomite, ferroan dolomite and ankerite (Rigg, 1980; MacGeehan and Hodgson, 1982; Andrews and Wallace, 1983; Christie, 1986). The previous identification of a dolomite core as- sociated with mineralization enveloped by distal calcite already has exploration potential (MacGeenhan et al., 1982; Andrews et al., 1986; Parker, 2000). This carbonate mineral zonation was tested in this study through EMPA of selected samples across both cross sections. In total, 14 samples were investigated for carbonate mineral composition. Twelve of these samples were from the RLGM. Two additional samples from the mapped outcrop were 119 also analyzed (Appendix A.4). The mapped outcrop samples contained some veins that were not observed in the RLGM. The mapped outcrop samples also provided a test to confirm that dolo- mite/ankerite is consistent at mineralized occurrences across the RLGB. From the total of 14 samples, pervasive carbonate was analyzed from three samples of the regional metamorphic as- semblage of chlorite-amphibole-epidote-biotite-carbonate ± garnet ± magnetite. Veined carbon- ate was analysed from all 14 samples. Each vein varied in texture and style. This allowed for multiple paragenetic veins (as identified in this study) to be chemically defined. Carbonate veins formed syn- to post-regional metamorphism (Fig. 3.10C). All pervasive and veined carbonate analyses predate mineralization as ore stage sulfides replaced ankerite ± quartz veins (Fig. 3.23B). Late carbonate veins in the lamprophyre dyke postdate mineralization as lamprophyre dykes cut ore zones. For each sample, 30–40 spots were analyzed. The data was calculated based on O = 6 (Deer et al., 1996). Data was rejected if it did not conform to the following criteria: (1) total wt% oxides 99 < x > 101; and (2) C site = 1.98-2.02. The median analysis, with respect to the Ca/Fe ratio, was chosen as the representative datum for each sample. For all carbonate EMPA data, see Appendix B.5. 4.2.4.5 Garnet Garnet chemistry has versatile uses. In skarn deposits, garnet chemistry can be used to identify hydrothermal fluid phases, compositions and oxidation state (Nakano et al., 1989; Jamtveit et al., 1993; Russell et al., 1999; Clechenko and Valley, 2003). In Archean lode-gold systems, garnet has been used to ascertain the metamorphic grade (Groves, 1993). Estimation of peak-metamorphic temperatures is also possible (Neumayr et al., 1993; Neumayr et al., 1994). Garnet chemistry has been utilized previously in thermobarometry calculations at Red Lake to estimate peak-metamorphic conditions of < 3 Kbar and 465–545°C (Tarnocai, 2000). Prior gar- net chemistry research at the RLGM has documented almandine-rich garnets with spessartine- rich cores (Mathieson, 1982; Christie, 1986; Penczak, 1996; Damer, 1997). Garnet, like amphibole, only developed during the M2 metamorphism event (Chapter 3). Therefore, chemical analysis of garnet porphyroblasts could provide information regarding the composition of the basalt at the time of regional metamorphism. This information can be used to infer characteristics of the pre-peak metamorphism hydrothermal event (H1 in Fig. 3.31). In total, 18 garnet bearing samples were selected from both cross sections (Fig. 4.1). Garnet is part of the 120 regional metamorphic assemblage (chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± gar- net ± magnetite). This assemblage also defined the main S2 foliation (c.f. Dubé et al., 2004). Each polished thin section contained 30–60 analyses with 1–4 garnets analyzed per sample. The number of analyses per sample was dependent on the number of garnets present and the porphy- roblast size. EMPA data was normalized to 8 cations, with an estimation of Fe3+ calculated by stoichiometry. Analyses were rejected if they did not conform to the following criteria: (1) Total oxide 99–101; (2) Site X = 2.9–3.1; (3) Site T = 2.9–3.1; and (4) Site Z = 1.9–2.2. For each sam- ple, a representative garnet crystal analysis was chosen with EMPA from the core, middle and rim areas; this distinguished zoning profiles. For all garnet EMPA data, see Appendix B.6. 4.2.5 Lithogeochemistry (whole rock geochemistry) Lithogeochemistry is used in exploration and geological research to identify areas of economic significance through pathfinder or footprint elements (Prendergast, 2007). Pathfinder elements indicate clear trends approaching mineralization, e.g. enrichment proximal to minerali- zation. Whole rock data can also provide constraints on the conditions and nature of hydrother- mal events and fluids. As the RLGM contains superposed hydrothermal events, it is important that these are chemically and physically defined. After such definition, any influence from the pre-mineralization hydrothermal event (H1) on the ore-forming event (H2) can be assessed (Fig. 3.31). Sixty-two (excluding duplicates and standards) whole rock samples were analyzed for major and trace element composition. This sample suite dominantly comprised basalt, with lesser ultramafic, diorite, felsic intrusive, sedimentary units and lamprophyre dykes. This data was combined with a subset of Bouzari’s (2009) database (n = 183). This subset included dominantly basalt samples with lesser ultramafic, sedimentary and felsic units for comparison. In total, 245 samples (of all lithology) were geochemically analyzed. This contained representative samples of all alteration assemblages documented in Chapter 3. Each of these whole rock analyses had a corresponding thin section. Basalt was the chosen lithology to investigate geochemical varia- tions. As a result, the basalt sample suite (n = 142) was the most thoroughly investigated. Other rock types were included, as intense alteration caused challenging identification of the primary protolith (c.f. Mathieson, 1982, Rogers, 1992). Least altered samples of basalt and ultramafic were used to classify more altered samples chemically. Figure 4.2 shows the complete basalt sample suite used, highlighting those data from this study and Bouzari (2009).Whole rock data 121 Figure 4.2 Location of basalt whole rock samples from this study and Bouzari (2009) which are used in the lithogeochemical study of the RLGM. A) Campbell complex, B) Red Lake complex 122 were analyzed for 48 elements (total Fe = FeO) at ALS laboratories (North Vancouver), using four acid (HF-HNO 3 -HCIO 4 -HCl) digestion and ICP-MS and ICP-AES techniques. The labora- tory analytical code was ME-MS61. From these data, weight percent (wt %) oxide concentra- tions were calculated and used. Appendix B.7 contains details regarding the quality control of four acid digestion whole rock data. The Bouzari (2007) samples furthermore contained selected gold assays, also undertaken at ALS laboratories. Approximately one third of the whole rock da- tabase included gold assays. No gold assay analyses were collected during this study. The whole rock geochemistry database was compared with all mineral chemistry data. This includes EMPA, SWIR and magnetic susceptibility data (see Chapter 7). All four acid digestion whole rock geo- chemistry data collected in this study can be found in Appendix B.8. From the 62 whole rock analyses of this study, 25 samples (excluding duplicates) were selected to specifically assess the Fe3+ and Fe2+ variations. These 25 samples underwent lithium borate fusion for major element analysis with X-ray Fluorescence (total iron = Fe2O3). The sam- ples were additionally assessed for ferrous iron (FeO) by H2SO4-HF acid digestion and titrimet- ric finish. These analyses were also completed by ALS laboratories (North Vancouver). The laboratory analytical codes were ME-XRF06 (lithium borate fusion) and Fe-VOL05 (H2SO4-HF acid digestion). The lithium borate fusion FeO and Fe2O3 abundances were only used in the analysis of bulk rock ferric and ferrous ratios. Appendix B.7 contains details regarding the qual- ity control of lithium borate fusion data. All lithium borate fusion data can be found in Appendix B.9. 4.3 Mineral chemistry data 4.3.1 Chlorite Table 4.3 provides the representative chlorite EMPA data with sample details (lithology, metamorphic grade, etc.). Numerous classification schemes of chlorites have been previously proposed (Tschermak, 1890; Orcel, 1926; Orcel et al., 1950; Winchell, 1936; Serdyuchenko, 1953; Hey, 1954; Brindley and Gillery, 1956; Lapham, 1958; Foster, 1962; Bayliss, 1975; Wiewiora and Weiss, 1990; Weiss 1991). However, the simplest and most recent classification, which is based on key cations, was used to classify the chlorite data (Zane and Weiss, 1998). Chlorite derived from all rock types occur in the clinochlorite-chamosite series (Fig. 4.3A-C; Table 4.3; Deer et al., 2009). Chlorite chemistry and petrographic observations indicate distinct 123 Table 4.3 Representative chlorite EMPA Sample D14981-1798 D21708- 2760 D2253-75 D33003- 2004 D39018- 3562 D39018- 4848 D39200- 1496 D39200- 3241 DS172- 123 DS173-499 R87108- 629 Complex CBC CBC CBC CBC CBC CBC CBC CBC CBC CBC CBC Lithology Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Chlorite Colour brown brown blue grey grey grey blue grey grey blue brown blue grey Metamorphic facies T A A A T A T A A A T T A Alteration assemblage Bio-chl Grt-chl ± mag Bio-chl Bio-chl Pervasive chl-carb Chl+carb vein Grt-chl ± mag Bio Grt-chl ± mag Grt-chl ± mag Grt-bio Grt-bio Bio-chl Mineralization pre-min: py-mag pre-min: py-mag syn-min: py syn-min: py syn-min: po pre-min: po-py syn-min: po-py- mag syn-min: po-py- mag syn-min: po-mag syn-min: py-mag pre-min and syn- min: po- py-mag pre-min and syn- min: po- py-mag syn-min: po-py- mag analysis no. 1798-20 2760-21 75-5 75-31 2004-1 3562-8 4848-3 1496-10 3241-12 123-1 499-13 499-24 629-8 K 0.00 0.00 0.01 0.02 0.01 0.02 0.01 0.01 0.00 0.00 0.01 0.00 0.01 Na 0.00 0.00 0.01 0.03 0.02 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 Mg 2.11 2.36 1.96 2.48 2.38 2.64 1.91 2.63 2.82 1.36 2.62 1.84 3.06 Fe2+ 2.36 2.19 2.47 2.01 2.07 2.03 2.72 1.90 1.77 3.41 2.02 2.70 1.63 Mn 0.02 0.02 0.03 0.01 0.02 0.01 0.02 0.02 0.01 0.03 0.02 0.00 0.02 Cr 0.01 0.00 0.01 0.02 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 Ti 0.00 0.01 0.02 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 Al(VI) 1.47 1.41 1.43 1.41 1.44 1.28 1.35 1.40 1.35 1.19 1.31 1.43 1.24 Sum 5.97 5.99 5.93 5.97 5.95 5.99 6.01 5.97 5.97 5.99 6.01 5.99 5.96 Al(IV) 1.43 1.40 1.33 1.34 1.35 1.28 1.38 1.35 1.31 1.20 1.31 1.43 1.20 Si 2.57 2.60 2.67 2.66 2.65 2.72 2.62 2.65 2.69 2.80 2.69 2.57 2.80 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Oxide total (wt%) 98.98 99.13 99.42 98.85 98.77 100.69 99.58 99.00 99.22 98.66 99.46 98.98 99.37 Fe/(Fe+Mg) 0.53 0.48 0.56 0.45 0.47 0.44 0.59 0.42 0.39 0.72 0.43 0.59 0.35 Fe/Fe+Mn+Mg 0.52 0.48 0.55 0.45 0.46 0.43 0.58 0.42 0.38 0.71 0.43 0.59 0.35 Mg/Mg+Fe 0.47 0.52 0.44 0.55 0.53 0.56 0.41 0.58 0.61 0.28 0.57 0.41 0.65 For abbreviations, refer to list of abbreviations 124 Table 4.3 (Continued). Sample R87108-629 CR4611- 581.4 GC04007- 4421 06L337-186 19L547 - 495 34L006- 1235 37L482- 2057 CR4610-947 CR4612- 360 CR466- 145 Complex CBC CBC RLC RLC RLC RLC RLC RLC RLC RLC Lithology Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Chlorite Colour brown blue grey blue grey blue brown blue grey blue late blue brown blue Metamorphic facies A A G G G A A A A A A A A Alteration Assemblage Bio-chl Grt-chl ± mag Br. bio Bio-chl Bio-chl Grt-chl ± mag Grt-chl ± mag Chl-bio- grt with carb-qtz vein Bio Grt-chl ± mag Grt-chl ± mag Grt-chl ± mag Grt-chl ± mag Mineralization syn-min: po-py- mag pre-min and syn- min: po- py-mag pre-min: py-mag pre- min:po- mag pre-min: po-mag syn-min: po-mag syn-min: po-mag syn-min: po syn-min: py-mag pre-min and syn- min: po- py pre-min and syn- min: po- py syn-min: py-po pre-min: py analysis no. 629-30 584-9 4421-10 186-5 186-23 495-16 495-27 1235-29 2057-14 947-1 947-17 360-7 145-14 K 0.00 0.00 0.00 0.00 0.00 0.01 0.05 0.00 0.00 0.00 0.00 0.01 0.00 Na 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.01 0.02 0.02 0.01 0.00 Mg 2.86 2.11 2.72 2.06 2.73 2.23 2.02 1.89 2.86 2.01 1.86 2.27 1.99 Fe2+ 1.81 2.56 1.74 2.42 1.89 2.26 2.52 2.57 1.81 2.63 2.67 2.35 2.57 Mn 0.03 0.01 0.01 0.04 0.03 0.01 0.02 0.03 0.01 0.00 0.02 0.00 0.02 Cr 0.01 0.00 0.04 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 Ti 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.00 Al(VI) 1.23 1.30 1.41 1.43 1.32 1.41 1.38 1.41 1.32 1.34 1.41 1.33 1.38 Sum 5.95 5.99 5.91 5.97 5.98 5.94 5.99 5.94 6.01 6.00 5.99 5.98 5.97 Al(IV) 1.18 1.31 1.28 1.38 1.29 1.30 1.33 1.33 1.35 1.34 1.40 1.31 1.37 Si 2.82 2.69 2.72 2.62 2.71 2.70 2.67 2.67 2.65 2.66 2.60 2.69 2.63 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Oxide total (wt%) 99.03 98.67 99.73 99.60 99.81 99.62 100.33 99.03 99.09 98.83 98.71 98.64 99.24 Fe/(Fe+Mg) 0.39 0.55 0.39 0.54 0.41 0.50 0.56 0.58 0.39 0.57 0.59 0.51 0.56 Fe/Fe+Mn+Mg 0.39 0.55 0.39 0.54 0.41 0.50 0.55 0.57 0.39 0.57 0.59 0.51 0.56 Mg/Mg+Fe 0.61 0.45 0.61 0.46 0.59 0.50 0.44 0.42 0.61 0.43 0.41 0.49 0.44 125 temporal and chemical properties for each chlorite type. The three birefringence colours of the chlorite (Fig. 3.4) demonstrate relative variations in Mg and Fe abundances (c.f. Hey, 1954; Kerr, 1959; Fig. 4.3). Blue chlorite contains XMg [Mg/(Mg+Fe)] values of 0.32–0.53; brown chlorite, 0.43–0.56; grey chlorite, 0.53–0.67; blue chlorite vein, 0.39–0.43; and brown chlorite vein, 0.41–0.43 (Fig. 4.3C). The earliest chlorite was developed during the onset of regional metamorphism and is Fe-richer (blue birefringence). This suggests that iron was abundant at the time of chlorite development during M2 regional metamorphism. Other elements vary in abundances between samples (Fig. 4.4 and Table 4.3). These variations are related to associated minerals or lithology. Samples D39200-1469, 19L547-495 and BK05010-376 contain chlorite with relatively enriched K compared to other samples. Each of these samples contained abundant biotite. The enrichment in K could be due to possible contamination from biotite during spot analyses. Sample GC04003-4421 contains chlorite with relatively enriched Cr, possibly due to an interbedded ultramafic unit. Both the basalt and ul- tramafic units were metamorphosed simultaneously. Samples D33004-2004 and DS173-499 con- tain chlorite with relatively enriched Na. This could be related to the dominance of associated amphibole. Samples DS173-123, 34L006-1235 and 06L337-186 all contain chlorite with rela- tively enriched Mn. Each of these samples contains garnet. As garnet is Mn-rich, it is surprising that the chlorite is also Mn-rich. During metamorphism the chlorite would have been consumed during garnet growth. During development Mn would preferentially be taken up by garnet (Hol- lister, 1966). The probed chlorite from these samples was preserved as garnet inclusions only. Thus, the chlorite was broken down and consumed. As both chlorite and garnet are Mn-rich in these samples, it is possible that this reflects an early hydrothermal enrichment (prior to meta- morphic mineral growth) of Mn to the basalt. The other possibility could have been contamina- tion from garnet during spot analyses. A general trend of decreasing Si with increasing XFe is displayed (Fig. 4.4). With less Si, more Al3+ is required to fill the tetrahedral site of the chlorite crystal. This in turn would leave the A-site more open to 2+ cations such as Fe and Mg. The samples with Si-poor chlorite are found regionally. These rocks have been less altered, particu- larly by quartz-bearing alteration assemblages, e.g. quartz-muscovite-andalusite and brown bio- tite-quartz (see Chapter 3). Chlorite distribution along the cross sections demonstrates a complex arrangement (Fig. 4.5). This is because of the supposed nature of multiple overprinting chlorite phases (Fig. 3.2). Chlorite formation occurred during two main geological processes. The first chlorite stage oc- 126 curred during the M2 regional metamorphic event. This created pervasive and foliation aligned blue, brown and grey birefringent chlorite (Fig. 3.4). The pervasive chlorite varieties are the most abundant. The other, less abundant chlorite, occurs as selvages to ankerite-calcite ± quartz veins (Fig. 3.18E-G). Chlorite selvages also display blue, brown and grey birefringence colours. Both pervasive and selvage chlorite formed distinct chemistry patterns. The pervasive chlorite developed in three paragenetic phases. Foliation aligned blue chlo- rite formed at the onset of M2 regional metamorphism. Blue chlorite was then overprinted by subsequent, foliation aligned, brown chlorite. Finally, both blue and brown chlorite were over- printed by foliation aligned grey chlorite (+ associated minerals) which also formed during M2 regional metamorphism. The progression from blue (Fe-rich) to brown (Fe- Mg-rich) to grey (Mg-rich) chlorite is consistent with prograde metamorphic development of chlorite. Chlorite Fe- abundance will decrease during prograde metamorphism (Spear, 1993). Petrographic observa- tions also support this. Early blue chlorite was overprinted by all metamorphic minerals and pre- served as inclusions in porphyroblastic amphibole, garnet, epidote and clinozoisite (Figs. 3.5H and 3.6D). Spatially, blue chlorite was found to be more abundant distally, with grey and brown chlorite more abundant proximal to ore zones (Fig. 4.5). This appears to contradict the metamor- phic sequence. The metamorphic grade increases distally from mineralization; therefore, grey chlorite would be expected. However, the preservation of chlorite at distances > 5 km distally from mineralization is as inclusions within porphyroblasts of garnet and amphibole only. These chlorite inclusions display blue birefringence, which is why blue chlorite occurs distally. Only rare occurrences of brown and grey chlorite are preserved in the matrix > 5 km laterally from ore. At amphibolite grade metamorphism the grey chlorite is nearly all consumed due to the growth of amphibole and garnet. This explains the low abundance of grey and brown chlorite distally in the matrix. At the mine scale, the metamorphic grade is lower: greenschist to transi- tional to lower amphibolite. The greenschist assemblage is characterized by the presence of grey chlorite-epidote ± clinozoisite-amphibole (non-calcic)-magnetite ± calcite ± biotite ±chloritoid. The lower metamorphic conditions explain the more frequently preserved grey and brown chlo- rite at the mine. Therefore, the pervasive metamorphic chlorite distribution is controlled by metamorphism. Grey chlorite is proximal to mineralization and blue chlorite distally preserved as inclusions only. 127 Figure 4.3 All chlorite EMPA XMg versus Si indicating that the chlorites are part of the chamosite-clinochlore series. A) basalt samples, B) diorite, ultramafic, felsic and lamprophyre units, C) Box plot indicating the range, mean and median of each chlorite birefringence type: blue, brown and grey. 128 Figure 4.4 Variation in chlorite chemistry relative to Fe/(Fe+Mg) apfu. A) Mn variation, B) Cr variation, C) Sitet variation, D) K variation and E) Na variation. Superposed upon the distribution of pervasive metamorphic chlorite are chlorite selvages to ankerite-calcite ± quartz veins. The chlorite selvages added to the complexity of chlorite dis- tribution by overprinting similar chlorite compositions. Ankerite-calcite ± quartz veins with chlorite selvages are abundant at the mine. They were also observed distally, but in lower abun- dances. Ankerite-calcite ± quartz veins are usually associated with D2 deformation. However, there did not appear to be a strong preference for one particular chlorite chemistry/type associ- ated with D2 faults. Although all three chlorite birefringent colours were observed as chlorite selvages, blue chlorite was the most frequently identified. Blue chlorite selvages to carbonate veins proximal to ore zones were originally identified by Penczak (1996). These overprinting blue chlorite selvages explain the blue chlorite occurrences at the mine scale (Fig. 4.5). 129 Figure 4.5 Spatial distribution of the chlorite varieties along the A) Campbell complex and B) Red Lake complex for basalt samples only. 130 Vertical variations in chlorite chemistry are minimal, with most elements constant. The XFe [Fe/(Fe + Mg)] ratio minimally decreases in abundance with depth (Fig. 4.6A). A Cr spike is exhibited at ~ 750 m depth (Fig. 4.6B). This relatively Cr-rich chlorite (from sample GC04007- 4421) was interpreted as influenced by interbedded ultramafic units. A weak increase in Si apfu and a decrease in Mn apfu with depth is observed (Fig. 4.6C-D). These variations could be linked to, (1) pre-metamorphic hydrothermal alteration causing Mn- and Si-rich localized areas; or (2) metamorphism and the development of associated minerals, for example Mn-rich garnet. Despite these observable trends, the vertical chlorite chemistry variations with depth indicate poor potential for vectors toward mineralization. Chlorite EMPA was compared to the four acid digestion whole rock geochemistry for basalt (both types), diorite, sediment and lamprophyre dyke from the RLGM (Fig. 4.7). As ex- pected, there is a linear relationship (y = 1.25x + 0.355), displayed between whole rock and chlo- rite EMPA XFe ratio. This indicates that the bulk rock Fe content is a good potential indicator of specific mineral chemistry. Felsic units have the highest XFe values whereas the diorite and lam- prophyre dykes have the lowest XFe values. The sediment units and basalt demonstrate the wid- est ranges in XFe. The high Fe-chlorite derived from the felsic units was unexpected as felsic rocks usually have lower Fe-Mg abundances compared to mafic rocks. However, these chlorite analyses derived from quartz-ankerite veins with chlorite halos. Consequently, the chlorite sel- vages were influenced by fluid chemistry rather than the bulk rock composition. Other samples of chlorite halos and/or veins explain most outliers, but not all. The other outliers are displayed by pervasive metamorphic chlorite. Before regional metamorphism, early hydrothermal altera- tion affected the rocks. This caused heterogeneity in the basalt composition at the time of meta- morphism. Therefore, metamorphic chlorite with greater Mg or Fe abundances could have de- veloped in unusual basalt compositions. Chlorite chemistry defined in this study is consistent with previous observations. Chlorite found at High Grade ore was previously identified as ripidolite; a clinochlore variety (Cadieux et al., 2006). Chlorite selvages were previously defined as ripidolite and diabantite (Cadieux et al., 2006). Birefringent blue chlorite was also identified as Fe-rich (Christie, 1986; Penczak, 1996). The Mg-chlorite was identified as displaying green birefringence but not grey (Christie, 1986; Penczak, 1996). This research confirmed that the major cation variations in chlorite are between Fe and Mg. The overprinting nature of the chlorite between paragenetic phases also supports Bouzari (2009). Bouzari (2009) identified a broad, pervasive, Mg-rich metamorphic chlorite with 131 overprinting, Fe-rich chlorite proximal to ore. Although the chlorite distribution in the RLGB is more complex, this general trend is identified. Figure 4.6 Vertical distribution of chlorite chemistry with depth for basalt samples only. 4.3.2 Biotite Table 4.4 provides the representative biotite EMPA with corresponding sample details (e.g. lithology, metamorphic grade, alteration, etc.). All biotite analyses were classified by con- sidering the XMg [Mg/(Mg+Fe)] versus AlIV ratios (Deer et al., 2004; Fabbrizio et al., 2006; Fig. 4.8). Both biotites and phlogopites were found to be part of the annite – phlogopite series, re- gardless of lithology (Fig. 4.8A and B). The pervasive black biotite (Fig. 3.3A) has the lowest XMg values 0.35–0.6 (annite rich). The early biotite + abundant carbonate (Fig. 3.3B) has slightly 132 higher XMg values of 0.58–0.67 (biotite to phlogopite). The mineralized vein selvage brown bio- tite (Fig. 3.23) has intermediate XMg values 0.45–0.72 (biotite to phlogopite) (Fig, 4.8B). The early, pervasive biotite(-Ti-magnetite ± carbonate) is more Fe-rich than the brown biotite(- quartz) variety. Figure 4.7 The comparison between chlorite Fe/(Fe+Mg) and whole rock Fe/(Fe+Mg) indicated a overall positive relationship. The whole rock data was obtained by four acid digestion methods. The red dotted line indicated the line of best fit (y = 1.25x +0.355) which was calculated by Windows Excel from all data. Associated alteration influenced biotite chemistry hosted in basalt (Table 4.9 and Fig. 4.9). The biotite chemistry mimics chlorite chemistry (Fig. 4.4 and 4.9). Regional metamorphic samples containing garnet have relatively Mn-rich biotite. Similar to chlorite, the biotite in these samples is preserved as garnet inclusions. This is consistent with metamorphism of a Mn-rich host rock. Samples of syn-mineralization brown biotite-quartz ± sulfides/oxides are relatively enriched in Si and Cr, due to associated quartz and mineralization. The samples which demon- strate significant enrichment in Cr are also significantly enriched in Mg, indicating a possible ultramafic affinity (Fig. 4.9). There is a slight enrichment in Cl for the pervasive biotite phases (biotite-Ti-magnetite ± carbonate assemblage) derived from shallower crustal levels (Fig. 4.9). One sample, 30L1268-574 of the brown biotite-quartz-sulfides assemblage is relatively enriched in F compared to the other samples analyzed. However, the concentration is too low 133 Table 4.4 Representative Biotite EMPA Sample D39018-43 CB1912 V9 CB4043 FV 30L1268- 574 CB302561 D39018- 3562 D33003- 2004 37L482- 2057 D2253-75 34L006- 1235 06L337- 186 Lithology basalt basalt basalt basalt Basalt basalt basalt basalt basalt basalt basalt Complex CBC CBC CBC RLC CBC CBC CBC RLC CBC RLC RLC Biotite type P. Bio Br. Bio Br. Bio Br. Bio Br. Bio P. Bio P. Bio P. Bio P. Bio P. Bio P. Bio Metamorphic Facies A G A T T A T A A A G Alteration Bio-carb Br. bio-qtz Br. bio- qtz Br. bio- qtz Br. bio-qtz Chl-carb vein Chl-carb Bio Bio-chl Chl-bio- grt Chl-bio Mineralization pre-min: mag syn-min: py-po syn-min: po-py- mag syn-min: po-py- mag syn-min: py-po- mag syn-min: po-py syn-min: po syn-min: py-mag syn-min: py syn-min: po pre- min:po- mag EMPA analysis 43-18 1912-29 4043-20 574-7 30256-9 3562-10 2004-10 2057-4 75-15 1235-25 186-15 Si 2.77 2.77 2.79 2.79 2.86 2.72 2.79 2.80 2.74 2.74 2.74 Al (VI) 1.23 1.23 1.21 1.21 1.14 1.28 1.21 1.20 1.26 1.26 1.26 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.35 0.39 0.36 0.43 0.34 0.31 0.47 0.25 0.37 0.35 0.42 Mg 1.59 1.41 1.50 1.13 1.61 1.32 0.90 1.51 1.01 0.98 0.92 Fe 0.76 0.90 0.88 1.22 0.83 1.20 1.32 1.11 1.39 1.45 1.48 Mn 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 Ti 0.12 0.10 0.09 0.11 0.09 0.09 0.10 0.08 0.11 0.11 0.08 sum (Y) 2.83 2.80 2.83 2.90 2.87 2.93 2.80 2.96 2.88 2.90 2.91 K 0.94 0.96 0.92 0.92 0.90 0.93 0.94 0.90 0.94 0.95 0.93 Na 0.01 0.01 0.02 0.02 0.01 0.03 0.02 0.02 0.03 0.01 0.01 Ca 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 Cr 0.01 0.02 0.04 0.00 0.01 0.00 0.00 0.01 0.01 0.01 0.00 sum (X) 0.96 1.01 0.98 0.94 0.92 0.96 0.98 0.94 0.98 0.98 0.94 (OH) 2.00 1.97 1.94 1.80 1.94 1.96 1.95 1.92 1.91 1.90 1.92 F 0.00 0.02 0.05 0.20 0.06 0.04 0.04 0.07 0.07 0.09 0.07 Cl 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.02 0.01 0.01 Sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Oxide wt% Total 100.15 99.51 99.70 100.18 99.71 98.63 99.37 99.71 98.51 98.94 99.51 Fe/(Fe+Mg) 0.32 0.39 0.37 0.52 0.34 0.48 0.59 0.42 0.58 0.60 0.62 Mg(Fe+Mg) 0.68 0.61 0.63 0.48 0.66 0.52 0.41 0.58 0.42 0.40 0.38 For abbreviations, refer to list of abbreviations 134 Figure 4.8 Biotite classification based on Deer et al., (2004) and Fabbrizio et al., (2006). A) All biotite EMPA data. B) Indication of which biotite groups are represented. 135 Figure 4.9 Variations in biotite chemistry relative to F, Cr, Mn, Si and Cr for various alteration assemblages. to be considered F-rich (c.f. Bose et al., 2005; Cesare et al., 2008). The minimal enrichment of both Cl and F could be linked to localized hydrothermal fluids. Calcium and K remain constant between biotite types and associated minerals. Biotite EMPA data versus whole rock data displays a weak positive trend (Fig. 4.10). The data is scattered, but the strongest positive trend is exhibited by the early biotite(-Ti- magnetite ± carbonate) phase. This early biotite phase is metamorphic in origin. It was devel- oped from a precursor assemblage, most likely mica-rich. The biotite was recrystallized during 136 the synchronous M2 and D2 event to form the assemblage observed. Outliers of early biotite(-Ti- magnetite ± carbonate) chemistry are those within diorite and sedimentary units. These rocks have a different bulk rock composition to the basalt. However, the basalt chemistry could poten- tially be used as a proxy for early biotite composition. The syn-mineralization brown biotite- quartz shows the widest range of compositions. These samples show poor correlation between biotite and whole rock XMg values (Fig. 4.10). Brown biotite is considered hydrothermal in ori- gin, as it occurs as selvages to ore veins (Fig. 3.23). Therefore, the bulk rock composition had little control on the brown biotite composition at the time of precipitation. This explains the poor correlation between whole rock and brown biotite XMg. Figure 4.10 Comparison between whole rock XMg and Biotite XMg. Line of best fit statistically generated by Win- dows Excel. The regression was calculated from all data. Vertical trends in biotite chemistry from mine site basalt samples are indicated in figure 4.11. These trends are generally similar between both pervasive early biotite(-Ti-magnetite ± carbonate) and brown biotite. However, there are distinct differences which are the result of the 137 overprinting nature of biotite types. Both trends will be described. Both biotite types display similar trends in increasing XMg, Si with increased depth (Fig. 4.11). Likewise, both biotite types display decreasing K, AlIV, and Cr with increased depth (Fig. 4.11). Brown biotite is more Mg- and Si-rich compared to the early pervasive biotite. As a result, there are subtle differences. At depths, where brown biotite is more abundant, the biotite chemistry is seen to reflect more Mg- and Si-rich concentrations. This is due to the overprinting brown biotite. Similarly, increases in Cr and F at intermediate and deep crustal levels are due to abundant, overprinting brown biotite occurring at these depths. However, the K, Si, and AlIV trends could potentially aid exploration, as they are displayed in both biotite types. Lateral variations in biotite chemistry are subtle (Fig. 4.12). The trends were indentified between one distal sample (1.5 km from the mine) and the others more proximal to mineraliza- tion (0-500 m). It is unsure if these trends would remain if more distal samples were assessed for biotite chemistry. However, from the data collected these trends were observed. The elements Mn, Ti, K and Ca show little variation, and are generally constant from proximal to distal occur- rences from mineralization. However, weak progressive decreases in XMg, Al, F, Cr and Cl are displayed (Fig. 4.12). These differences are influenced significantly by the abundance of the bio- tite type. Brown biotite, which is relatively more Mg-, Cr-, and F-rich compared to early biotite, is concentrated at the mine site. This explains peaks in XMg, Cr and F at the mine, compared to distally. Chlorine, Na, and AlIV all show weak trends that could aid exploration. The Cl abun- dance of both biotite types is elevated at the mine compared to distally. A similar trend, but with a wider spread of data, is displayed by AlIV. Sodium is also widespread, but indicates a weak in- crease with increased distance from mineralization. Although the differences are subtle, chemi- cal differences in biotite have the potential to be compared with the field-based shortwave infra- red technique. Previous research from the RLGM has also placed the biotite compositions ranging be- tween biotite-phlogopite in terms of Fe and Mg compositions (Damer, 1997; Cadieux et al., 2006). The two phases of biotite (pervasive and brown) have also been identified. However, there are differences in the reported biotite composition. Penczak (1996) indicated that the per- vasive biotite was phlogopite with an XMg of 0.59–0.68. This study indicated the opposite (Fig. 4.9). However, it is agreed that the brown biotite is more Mg-rich (c.f. Cadieux et al., 2006). Re- search from elsewhere in the RLGB also agrees that biotite (associated with mineralization at the 138 Figure 4.11 Variation in biotite chemistry with depth in the mine complexes only. Samples > 1 km were removed as these were from the surface only. This removed bias towards the surface expressions. Only basalt data is shown. Chemistry is distinct between older pervasive biotite and younger brown biotite. 139 Figure 4.12 Variation in biotite chemistry with increasing distance from known ore zones of the RLGM. Only basalt data is displayed. Minimal variations are indicated, however, strong variations are seen in the biotites Na, Al and Cr abundances. Line of best fit statistically generated by the software IoGas. The regression was calculated from all data. Gold Eagle property) ranges in composition from biotite to annite (Marsden, 2012). Biotite asso- ciated with mineralization at the Gold Eagle property was reported as more Fe-rich than biotite in non-mineralized shear zones (Marsden, 2012). This is opposite to that reported at the RLGM 140 (Cadieux et al., 2006; this study). The differences in biotite chemistry between Red Lake depos- its emphasize the complexity of gold formation in the greenstone belt. 4.3.3 Amphibole Table 4.5 provides the sample details and the corresponding rim-middle quartile-core amphibole EMPA data. Amphibole classification (Hawthorne and Oberti, 2007b) identified three groups: magnesium-iron-manganese-lithium (group 1), calcic (group 2) and sodium-calcium- magnesium-iron-manganese-lithium (group 5) (Table 4.5). Within these groups, different am- phibole types were recognized (Fig. 4.13). From group 1, ferro-anthophyllite and anthophyllite were defined. Group 2 included ferro-tschermakite, tschermakite, ferro-hornblende, magnesio- hornblende and actinolite. All calcic amphiboles require the prefix ‘alumino’, as Al is >1.0 apfu (Leake et al., 1997; Hawthorne and Oberti, 2007a, 2007b). Finally, group 5 contained a mix of parvo/magno ottoliniite and ferro-ottoliniite. The ottoliniite type depends on the (Ca,Na) and (Mg, Fe2+, Mn, Li) concentrations. The most dominant amphibole identified is (ferro-) tscher- makite. The largest differences in amphibole chemistry are between non-calcic and calcic groups (Fig. 4.14 and Table 4.5). The most distinctive elemental variations are demonstrated by Ca, Si, Fe2+ total, Alvi and MgC-site abundances. Calcium and Alvi were found to be more abundant in cal- cic amphiboles. Likewise, Si, Fe2+ total and MgC-site abundances are greater in non-calcic amphi- boles. More subtle distinctions can be identified between Ti, Natotal and Fe3+. Each of these ele- ments are less abundant in non-calcic amphiboles compared to calcic. Manganese is generally greater in non-calcic compared to calcic amphiboles. Regardless of groups, Cr and K abundance is consistently low. These chemical differences are related to bulk rock composition at the time of amphibole growth (during M2) or metamorphic grade. At lower metamorphic grades non- calcic amphiboles are more common. Amphiboles in the RLGB were formed during M2 regional metamorphism. Amphiboles were derived by the consumption of chlorite, carbonate, quartz, and zoisite (epidote). Possible amphibole formation reactions are as follows (Spear, 1993): (low-Al) chlorite + carbonate + oxide = actinolite ± zoisite + CO2 + H2O Epidote + chlorite + quartz = tschermakite/actinolite + anorthite + H2O Tremolite + chlorite + quartz + epidote = tschermakite + H2O Chlorite + epidote = Al-amphibole 141 The bulk rock composition influences the amphibole composition during isochemical metamor- phism. As expected, in this study bulk rock and amphibole XMg compositions indicate a positive trend (Fig. 4.15). Each of these samples contains the regional metamorphic assemblage (chlorite- amphibole-epidote/clinozoisite-magnetite-calcite ± garnet ± biotite). But, due to heterogeneity in the bulk rock composition at the time of metamorphism, variations in the mineralogy occurred, e.g. some samples contain more abundant amphibole than others, or some samples contain garnet etc. This heterogeneity in the bulk rock composition caused variations in Fe, Mg, K, Cr and Ti (Fig. 4.14). The listed elements all show subtle variations between non-calcic and calcic varie- ties. Calcium, Si, Fe2+ total, Na, Alvi and MgC-site in amphiboles are influenced by metamorphic grade (Fig. 4.16). At low metamorphic grades (transitional facies), non-calcic amphiboles are dominant. At higher metamorphic grades (amphibolite facies), the dominant amphibole is calcic. Non-calcic amphiboles are Ca-, Na- and Al-poor, and relatively enriched in Si, Fe2+ and Mg compared to calcic amphiboles (Fig. 4.14 and 4.16). Metamorphism affected amphibole chemis- try by mineral stabilities at different P-T conditions (Spear, 1993). Associated minerals, e.g. garnet, biotite and carbonate, also affect amphibole composi- tions (Fig. 4.16). Amphibole Mg/(Mg + Fe2+) ratios are greatest in samples containing biotite(- Ti-magnetite ± carbonate assemblage), and least in samples containing garnet. During metamor- phism, amphibole and garnet grew simultaneously. Thus, they were in competition to obtain Mg, and Fe during metamorphic development. Samples which also contain garnet display relatively Mn-poor amphibole. The Mn was preferentially taken up by the garnet during metamorphism (Hollister, 1966). Therefore, less Mn was available to be included in the amphibole. Samples containing little biotite or quartz contain amphibole with greater K and Si abundance respec- tively (Fig. 4.16). More of these cations were available at the time of metamorphic amphibole growth, due to the consumption of biotite and quartz, to be incorporated into the crystal lattice. The compiled mineral distribution along the cross sections determined that the metamor- phic transitional facies occurs within both mine complexes (Fig. 3.30). Metamorphic grade strongly influenced the amphibole composition. As a result, both vertical and lateral trends in amphibole chemistry reflect non-calcic to calcic amphiboles. There are no distinct vertical trends in amphibole chemistry. However, there are some subtle, and weak lateral variations in amphi- bole chemistry. There is not enough data to define strong trends. However the identifiable trends in the EMPA data can potentially be compared to the chemical trends identified by short-wave 142 Table 4.5 Representative Amphibole EMPA data Sample 37L482-2057 37L482-2057 D39018-4848 D39018-4848 Lithology Basalt Basalt Basalt Basalt Metamorphic facies Amphibolite Amphibolite Transition Transition Alteration Bio-Ti-mag ± carb Bio-Ti-mag ± carb grt-chl-amp-bio±mag grt-chl-amp-bio±mag Amphibole group Calcic (group 2) Non-calcic (group 1 or 5) Calcic (group 2) Non-calcic (group 1 or 5) Prefix Alumino Magno Alumino Magno-Parvo Amphibole name Tschermakite Anthophyllite Ferro-tschermakite Ferro-ottoliniite Rim Middle Core Rim Middle Core Rim Middle Core Rim Middle Core EMPA analysis 2057-40 2057-38 2057-37 2057-22 2057-23 2057-27 4848-62 4848-61 4848-60 4848-41 4848-40 4848-39 Total Oxide 98.01 98.63 98.84 100.30 98.95 98.88 98.01 98.01 97.66 98.30 98.48 98.50 Si 6.17 6.36 6.38 7.64 7.76 7.85 5.95 5.90 6.00 7.46 7.04 7.07 Al(iv) 1.83 1.64 1.62 0.36 0.24 0.15 2.05 2.10 2.00 0.54 0.96 0.93 Sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.01 0.91 0.89 0.20 0.21 0.10 1.01 1.04 0.88 0.26 0.46 0.51 Ti 0.03 0.04 0.04 0.00 0.00 0.00 0.05 0.04 0.03 0.01 0.01 0.01 Fe3+ 0.67 0.57 0.58 0.14 0.01 0.05 0.79 0.85 0.94 0.22 0.42 0.34 Cr 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 Mg 1.77 1.91 2.01 3.43 3.57 3.70 1.05 1.06 1.11 2.39 2.06 2.00 Fe2+ 1.45 1.56 1.47 1.22 1.20 1.15 2.04 1.91 1.95 2.11 2.05 2.14 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 4.95 5.00 5.00 5.00 5.00 5.00 4.95 4.91 4.92 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.00 0.01 0.02 1.47 1.58 1.76 0.00 0.00 0.00 1.30 0.86 0.83 Mn 0.03 0.04 0.04 0.09 0.09 0.09 0.03 0.03 0.02 0.09 0.07 0.07 Ca 1.85 1.81 1.80 0.42 0.31 0.14 1.81 1.85 1.84 0.55 0.96 0.99 Na 0.12 0.14 0.13 0.02 0.03 0.01 0.16 0.12 0.13 0.06 0.10 0.11 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.22 0.14 0.14 0.02 0.03 0.01 0.26 0.30 0.30 0.06 0.10 0.11 K 0.07 0.06 0.05 0.01 0.00 0.00 0.12 0.11 0.10 0.03 0.05 0.05 Sum A 0.29 0.20 0.19 0.03 0.03 0.01 0.38 0.41 0.39 0.09 0.16 0.16 Total cations 15.24 15.20 15.19 15.03 15.03 15.01 15.33 15.32 15.31 15.09 15.16 15.16 F 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 OH 2.00 1.99 1.99 2.00 2.00 2.00 1.99 2.00 1.99 1.99 2.00 1.99 Sum W 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 For abbreviations, refer to list of abbreviations 143 Table 4.5 (Continued). Sample CR4610-947 DS172-123.1 GC01018-85.3 Lithology Basalt Basalt Basalt Metamorphic facies Amphibolite Amphibolite Amphibolite Alteration grt-chl-amp-bio±mag grt-chl-amp-bio±mag grt-chl-amp-bio±mag Amphibole group Calcic (group 2) Calcic (group 2) Calcic (group 2) Prefix Alumino Alumino Alumino Amphibole name Ferro-tschermakite Ferro-tschermakite Ferro-tschermakite Rim Middle Core Rim Middle Core Rim Middle Core EMPA analysis 947-14 947-10 947-7 123-11 123-13 123-15 85-26 85-24 85-22 Total Oxide 99.17 98.66 98.11 97.52 98.06 98.76 99.17 99.33 98.12 Si 6.01 6.05 6.04 6.07 6.07 6.11 6.16 6.06 6.09 Al(iv) 1.99 1.95 1.96 1.93 1.93 1.89 1.84 1.94 1.91 Sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.07 1.10 1.04 1.25 1.28 1.19 1.43 1.51 1.18 Ti 0.03 0.03 0.04 0.01 0.00 0.00 0.01 0.01 0.02 Fe3+ 0.78 0.69 0.76 0.50 0.52 0.57 0.33 0.34 0.62 Cr 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.01 Mg 1.16 1.22 1.25 0.75 0.69 0.73 0.95 0.97 1.16 Fe2+ 1.95 1.95 1.91 2.44 2.51 2.50 2.28 2.13 2.01 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 4.96 5.00 5.00 5.00 4.96 4.99 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.05 0.05 0.02 0.00 0.03 0.05 0.00 0.00 0.00 Mn 0.04 0.04 0.04 0.01 0.01 0.02 0.09 0.08 0.09 Ca 1.73 1.74 1.75 1.89 1.86 1.84 1.74 1.78 1.74 Na 0.19 0.17 0.19 0.10 0.10 0.09 0.17 0.14 0.17 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.19 0.18 0.20 0.18 0.10 0.10 0.18 0.22 0.20 K 0.07 0.08 0.07 0.14 0.13 0.11 0.05 0.06 0.06 Sum A 0.26 0.26 0.27 0.33 0.23 0.20 0.23 0.28 0.26 Total cations 15.26 15.26 15.27 15.28 15.23 15.20 15.23 15.24 15.25 F 0.01 0.01 0.00 0.00 0.01 0.00 0.02 0.02 0.02 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 OH 1.99 1.99 2.00 2.00 1.99 2.00 1.98 1.98 1.98 Sum W 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 144 Figure 4.13 Classification of amphibole EMPA data based on Leake et al. (1997) and Hawthorne and Oberti, (2007b). 145 Figure 4.14 Variations in amphibole chemistry in relation to type and name. 146 Figure 4.15 Comparison of whole rock and amphibole EMPA Mg/(Mg+Fe) ratios. Line of best fit statistically gen- erated by Windows Excel. The regression was calculated from all data. infrared (Fig. 4.17). Non-calcic amphiboles are most abundant 0–1.5 km from mineralization. Consequently, the amphibole chemistry at these distances demonstrates higher Si and Fe2+ total abundances than distally. This continues to support a metamorphic control on amphibole chemis- try. Calcic amphiboles are present from the ore zones at depth to ≥ 5 km distally. Minimal varia- tions can be seen between proximal and distally located amphiboles. Small decreases in MnB-site, Fe2+ total and Sitet are seen with corresponding minor increases in Fe3+ and Natotal (Fig. 4.17). The other elements, similar to Ca, remain fairly constant, with variations exhibited by amphibole type rather than a lateral difference. At amphibolite conditions where only calcic amphiboles are present, the amphibole por- phyroblasts are not zoned (Fig. 4.18A). However, in the transitional facies, amphiboles are dis- tinctively zoned. Non-calcic amphibole cores are surrounded by calcic rims (Fig. 4.18B). In the zoned amphiboles Na, Mn, Si, Cr, Cl and F are constant across the grain (only Na is represented in the figure). Calcium, AlIV, and minimally Fe3+ decrease from rim to core, which is associated with an increase in Fe2+ and Mg composition. The zoned amphibole (non-calcic cores with calcic rims) emphasizes the metamorphic control on amphibole type. These observations could aid fu- ture exploration by the identification of transitional areas in the RLGB. Transitional facies areas, 147 Figure 4.16 Variations in amphibole chemistry in relation to the main alteration assemblage affecting the host basalt and metamorphic grade. 148 Figure 4.17 Variation of amphibole chemistry with lateral distance from ore. Line of best fit statistically generated by the software IoGas calculated from all data. 149 Figure 4.18 Zonation of amphibole porphyroblasts. A = calcic amphibole from the amphibolite facies and B = zoned amphibole – non calcic core to calcic rim – as part of the transitional facies. like the one which hosts the RLGM, have the potential to host gold-mineralization (c.f. Thomp- son, 2003). This study confirmed the identification of both Fe-rich non-calcic and calcic amphiboles. Previous research of the RLGM identified hornblende, alumino-ferro tschermakite, actinolite, tremolite, anthophyllite/gedrite and cummingtonite (Mathieson, 1982; Penczak, 1996; Damer, 150 1997; Menard and Pattison, 1998; Cadieux et al., 2006). This study added the identification of ottoliniite. This study also identified the metamorphic control on amphibole type, with lower grade non-calcic changing to higher grade calcic. 4.3.4 Carbonate Table 4.6 summarizes the sample details and the representative carbonate EMPA analy- sis. Using acid staining, CL, SEM and EMPA methods, the identification of two carbonate min- erals, ankerite (e.g. Fe-dolomite) and calcite is possible (see Appendix B.10). Ankerite and cal- cite were differentiated by the following: (1) calcite effervesced with dilute HCl, whereas dolo- mite/ankerite did not; (2) with CL, dolomite was a black to dull crimson-red, calcite was a bright orange-red colour (Fig. 3.25; Marshall, 1988); (3) SEM-EDS spectra differentiated peak posi- tions (Fig. 4.19A and B); and (4) EMPA variations in Fe, Mg and Ca apfu differentiated calcite from dolomite (Fig. 4.19C; Table 4.6). The identification of these two carbonate minerals is con- sistent with prior observations (MacGeehan and Hodgson, 1982; Mathieson, 1982; Andrews and Wallace, 1983; Christie, 1986; Penczak, 1996). Multiple ankerite vein types (Fig. 3.2; Chapter 3) were probed. The carbonate mineral chemistry varies in its Mg and Fe+Mn abundances between paragenetic stages (Figs. 4.19 and 4.20). The oldest recognizable pervasive calcite appears to be the most Ca-rich. In comparison, the late calcite (youngest carbonate phase) is more Fe-rich (Fig. 4.20). The calcite derived from the mapped outcrop (Appendix A.4) is comparably more Mg-rich. This could be due to a local- ized enrichment in Mg at the Cochenour-Willans deposit, as compared to the RLGM. Alterna- tively, the increased Mg could be due to the influence of interbedded ultramafic units causing variations in the Mg-content of the carbonate vein forming fluid through metamorphism. Ankerite veins are observed to become more Fe-rich over time (Fig. 4.20). The earliest carbonate veins (ankerite-biotite, cryptocrystalline-microcrystalline) demonstrate a narrow Fe+Mn range of 0.26–0.30 apfu and Mg of 0.7 ± 0.03 apfu. The second ankerite vein stage contains colloform- crustiform textured, ankerite-calcite-quartz ± chlorite selvages veins. These veins generally con- tain lower Fe-Mn values of < 0.3 apfu and higher Mg abundances of > 0.7 apfu. The colloform- crustiform textured veins exhibit the broadest compositional range: Fe-Mn 0.05–0.43 apfu and Mg 0.56–0.92 apfu. This broad range can be explained due to the fact that samples were derived from both the RLGM and the mapped outcrop (Appendix A.4). Finally, the youngest veins, 151 Table 4.6 Representative carbonate mineral EMPA Sample D39018-3562 D39018- 43 37L768- 98 DS172-123 GC01018- 85.3 CR4611-581.4 CR468-629 ES09_AP_6A Carbonate type P. Carb Carb Vein Carb-bio vein with Coarse carb vein Carb- qtz vein Carb- chl Vein Carb-chl halo vein Carb vein P. Carb Carb vein dark CL Carb vein light CL Cal in vein Late veinlet Lithology Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Carb vein Carb vein EMPA analysis 3562-19 3562-12 43-26 98-15 123-1 123-24 85-19 581-8 581-24 629-6 629-14 6A-7 6A-15 C 2.007 1.990 1.993 1.993 1.984 1.988 2.007 2.013 2.010 2.005 1.983 2.014 1.992 Mg 0.061 0.753 0.766 0.724 0.000 0.000 0.006 0.011 0.025 0.007 0.002 0.076 0.683 Ca 1.860 1.037 1.039 1.031 2.030 2.019 1.955 1.951 1.933 1.960 2.028 1.879 1.057 Mn 0.018 0.017 0.005 0.011 0.002 0.000 0.025 0.011 0.018 0.007 0.002 0.010 0.009 Fe 0.046 0.211 0.204 0.249 0.001 0.004 0.001 0.002 0.004 0.017 0.001 0.007 0.266 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Mg/ (Mg+Fe) 0.57 0.78 0.79 0.74 0.00 0.00 0.83 0.87 0.86 0.28 0.64 0.92 0.72 Fe/ (Mg+Fe) 0.43 0.22 0.21 0.26 1.00 1.00 0.17 0.13 0.14 0.72 0.36 0.08 0.28 Carbonate Mineral Cal Ank Ank Ank Cal Cal Cal Cal Fe-Cal Cal Cal Cal Ank For abbreviations, refer to list of abbreviations 152 ankerite-calcite-quartz and calcite veinlets in lamprophyre dykes (which cut ore) have the high- est Fe-Mn values (>0.3 apfu) and lowest Mg values (0.45–0.65 apfu). Both calcite and ankerite become more Fe-rich over time. This can be explained by progressive rock-buffering with the surrounding Fe-rich minerals within the host basalt. The rock buffered system could have in- creased the Fe-composition of the fluid over time. As carbonate was precipitated from the fluid, the carbonate minerals would become increasingly Fe-rich over time. Figure 4.19 Carbonate mineral identification. A) Calcite using SEM-EDS, B) Dolomite/ankerite using SEM-EDS, C) EMPA carbonate classification of calcite and dolomite/ankerite using triplot, Mg-Ca-Fe+Mn. 153 Figure 4.20 Variation in carbonate chemistry over the paragenetic sequence. Spatially, the ankerite veins do not demonstrate a chemical vector or trend toward mineraliza- tion. Although ankerite veins are abundant at the mine, they occur as a series of complex over- printing events. There is no preferred ankerite vein type more abundant toward mineralization. Even though the paragenetic stages of ankerite veins display different compositions, these chemical differences cannot be used to aid exploration. A broader relationship between ankerite and calcite, however, does display differences which can aid exploration. Carbonate mineral testing using reactivity with acid (Fig. 4. 21), SEM-EDS and EMPA data (Fig. 4.22) identified an ankerite core to mineralization enveloped by distal calcite. These carbonate mineral identification data can be found in Appendix B.10. Electron microprobe data indicated that dolomite/ankerite is present 0–1200 m distally with calcite present 500–5500 m distally. There is an overlap of both carbonate minerals 500-1200 m distally from ore (Fig. 4.23). This broad distribution of ankerite and calcite is consistent with prior observations (MacGeehan et al., 1982; Parker, 2000). This zonation is visible regardless of lithology or paragenetic phase. 154 Figure 4.21 Distribution of carbonate mineral as defined by acid testing. All lithology samples shown. A) Campbell complex, B) Red Lake Complex. 155 Figure 4.22 Distribution of carbonate minerals identified using SEM-EDS and EMPA. A) Campbell complex, B) Red Lake complex. All lithology are shown. 156 Figure 4.23 Variations of major cations of carbonate minerals with increasing distance from ore zones. The zonation in carbonate minerals can be explained by the overprinting nature of veined ankerite upon pervasive calcite. Early calcite is associated with biotite-Ti-magnetite ± carbonate and the regional metamorphic assemblages (Figs. 3.3 and 3.9C-D). Both assemblages are wide- spread and occur ≥ 7 km distally from ore zones. After the formation of the widespread calcite, a series of overprinting ankerite-dominant veins occurred (Fig. 3.2). The carbonate vein emplace- ment was associated with D2 deformation. This deformation phase was most intense at the RLGM, rather than distally. This would explain the localized nature and dominance of ankerite at the RLGM. Late calcite is a very minor phase, only visible with CL (Fig. 3.25). The abun- dance of late calcite is too low to significantly impact the carbonate mineral zonation. This broad halo of carbonate minerals has the greatest potential for use in exploration in the Red Lake area. 4.3.5 Garnet Table 4.7 provides the sample details (lithology, metamorphic grade, alteration, etc) and the corresponding representative garnet EMPA. Regardless of lithology, garnet is almandine (Fe2+) rich (Fig. 4.24). Across crystal variations, the spessartine (Mn) and grossular (Ca) 157 Table 4.7 Representative garnet EMPA data Sample D39018-4848 D39200-3241 D21708-2760 CR4611-581 DS173-499.6 Lithology Basalt Basalt Basalt (type two) Basalt Basalt Metamorphism T A A A T Alteration grt-chl±mag grt-chl±mag grt-chl±mag grt-chl±mag bio-grt EMPA analysis 4848-4 4848- 3 4848- 2 3241-6 3241- 15 3241- 12 2760- 11 2760- 14 2760- 20 581- 23 581- 20 581- 16 499-12 499- 16 499- 21 Fe2 1.931 1.936 1.956 1.871 1.908 2.105 1.692 1.678 1.585 1.976 1.988 1.946 1.696 1.823 1.758 Mn 0.370 0.358 0.375 0.533 0.491 0.344 0.601 0.578 0.474 0.234 0.204 0.172 0.770 0.581 0.453 Mg 0.151 0.150 0.163 0.200 0.199 0.225 0.142 0.162 0.175 0.273 0.292 0.246 0.162 0.168 0.246 Ca 0.501 0.488 0.480 0.325 0.345 0.288 0.514 0.521 0.690 0.439 0.468 0.561 0.336 0.368 0.479 Sum X 2.953 2.932 2.974 2.928 2.944 2.961 2.949 2.939 2.925 2.921 2.952 2.924 2.963 2.940 2.935 Ti 0.012 0.009 0.017 0.007 0.005 0.002 0.007 0.006 0.008 0.007 0.005 0.006 0.013 0.008 0.002 Al 1.961 1.994 1.961 2.024 2.013 2.037 2.013 2.014 1.998 2.022 2.006 2.015 1.998 2.021 2.017 Cr 0.004 0.002 0.005 0.004 0.000 0.001 0.000 0.000 0.000 0.000 0.001 0.001 0.000 0.001 0.001 Fe3 0.106 0.125 0.072 0.100 0.081 0.031 0.086 0.109 0.144 0.127 0.071 0.135 0.047 0.062 0.083 Sum Z 2.083 2.129 2.055 2.135 2.099 2.071 2.105 2.128 2.150 2.156 2.083 2.157 2.059 2.093 2.103 Si 2.958 2.935 2.968 2.933 2.953 2.966 2.945 2.933 2.923 2.921 2.961 2.918 2.971 2.959 2.955 Sum T 2.958 2.935 2.968 2.933 2.953 2.966 2.945 2.933 2.923 2.921 2.961 2.918 2.971 2.959 2.955 Oxide Total 100.28 99.85 99.95 100.13 99.15 99.17 99.84 99.01 99.65 99.88 99.99 100.48 100.04 99.57 99.51 End member almandine 65.391 66.044 65.767 63.889 64.832 71.077 57.377 57.085 54.198 67.643 67.345 66.535 57.231 62.011 59.892 pyrope 5.111 5.121 5.470 6.820 6.773 7.597 4.8153 5.5038 5.9918 9.3322 9.8764 8.4019 5.456 5.720 8.366 grossular 15.984 15.584 15.402 10.530 11.233 9.556 16.664 16.779 21.931 14.094 15.281 17.922 11.004 12.098 15.636 spessartine 12.518 12.194 12.621 18.186 16.680 11.613 20.378 19.677 16.207 7.9995 6.9125 5.8723 25.974 19.746 15.440 uvarovite 0.032 0.012 0.040 0.020 0.002 0.004 0.0031 0 0.0014 0 0.0066 0.012 0.000 0.006 0.011 andradite 0.866 0.977 0.567 0.521 0.454 0.144 0.7081 0.9054 1.5821 0.8844 0.5415 1.2028 0.261 0.371 0.640 For abbreviations, refer to list of abbreviations 158 Table 4.7 (Continued). Sample 34L006-1235 CR4612-360.2 19L547-495.8 CR4610-947 CR466-145 Lithology Basalt Basalt Basalt Basalt Basalt Metamorphism A A A A A Alteration carb vein-chl grt-chl±mag grt-chl±mag grt-chl±mag grt-chl±mag EMPA analysis 1235-12 1235-6 1235-1 360-16 360- 20 360- 27 495- 50 495- 54 495-56 947-10 947- 15 947-18 145-20 145- 16 145-13 Fe2 1.437 1.576 1.750 2.193 2.252 2.319 2.393 2.391 2.398 2.149 2.128 2.142 2.083 2.201 2.222 Mn 0.587 0.663 0.689 0.235 0.177 0.123 0.154 0.148 0.150 0.204 0.209 0.199 0.422 0.295 0.208 Mg 0.123 0.126 0.122 0.276 0.290 0.292 0.169 0.180 0.186 0.231 0.269 0.244 0.186 0.203 0.203 Ca 0.780 0.571 0.415 0.252 0.256 0.217 0.267 0.242 0.236 0.360 0.321 0.337 0.266 0.266 0.316 Sum X 2.927 2.935 2.976 2.956 2.976 2.951 2.982 2.961 2.970 2.944 2.927 2.922 2.956 2.966 2.949 Ti 0.011 0.005 0.002 0.005 0.003 0.001 0.002 0.005 0.004 0.006 0.007 0.005 0.003 0.003 0.001 Al 1.981 1.995 2.015 2.006 2.019 2.027 2.011 2.024 2.023 2.013 2.025 2.020 2.005 2.019 2.002 Cr 0.000 0.000 0.001 0.009 0.000 0.004 0.002 0.002 0.002 0.002 0.004 0.001 0.001 0.003 0.000 Fe3 0.150 0.134 0.030 0.054 0.028 0.035 0.008 0.048 0.026 0.096 0.117 0.114 0.061 0.046 0.097 Sum Z 2.141 2.134 2.048 2.073 2.049 2.068 2.022 2.079 2.055 2.117 2.153 2.140 2.070 2.071 2.100 Si 2.928 2.930 2.976 2.966 2.974 2.973 2.992 2.959 2.972 2.939 2.920 2.933 2.968 2.963 2.950 Sum T 2.928 2.930 2.976 2.966 2.974 2.973 2.992 2.959 2.972 2.939 2.920 2.933 2.968 2.963 2.950 Oxide Total 99.95 99.77 99.58 99.93 99.49 99.35 99.06 99.68 100.03 100.19 99.34 100.05 99.19 99.38 100.08 End member almandine 49.097 53.687 58.796 74.197 75.689 78.575 80.240 80.763 80.730 73.000 72.690 73.316 70.446 74.220 75.364 pyrope 4.213 4.292 4.103 9.333 9.761 9.910 5.662 6.089 6.257 7.851 9.195 8.335 6.277 6.858 6.877 grossular 24.653 18.180 13.706 8.260 8.467 7.201 8.890 7.938 7.834 11.626 10.330 10.887 8.725 8.749 10.205 spessartine 20.043 22.573 23.168 7.934 5.955 4.170 5.160 4.992 5.053 6.923 7.131 6.812 14.269 9.945 7.053 uvarovite 0.000 0.003 0.004 0.037 0.000 0.015 0.008 0.008 0.009 0.011 0.023 0.007 0.004 0.012 0.000 andradite 1.862 1.219 0.206 0.221 0.116 0.124 0.034 0.189 0.101 0.555 0.597 0.614 0.264 0.201 0.493 159 components (Mn >> Ca) are also observed (Fig. 4.24). Consistently, the pyrope (Mg) end mem- ber is low (Fig. 4.24). The chemical zonation is only documented using EMPA. The bell-shaped profiles (Fig. 4.24) between Fe2+ and Mn are consistent with previous garnet chemistry investi- gations (Mathieson, 1982; Christie, 1986; Penczak, 1996; Damer, 1997). This study also identi- fied bell-shaped profiles in argillite units of the Bruce Channel assemblage (Fig. 4.24). The composition of garnet varies systematically with distance from ore (Fig. 4.25). The almandine component is lowest at the mine scale and greatest in abundance at the intermediate and distal scale. The grossular component is generally the least varied. However, proximal to ore zones the Ca-component is the lowest, < 10% within 500 m from ore. From 500 m onward from mineralization, the grossular component is generally > 12.5%. The spessartine component indi- cates a general trend which could be used for exploration purposes. The Mn-component de- creases from ≈ 17.5% proximal to < 7.5% distal to mineralization. The enrichment in Mn at the mine is also displayed in whole rock geochemistry (Bouzari, 2009; this study). Finally, the py- rope component indicates a weak increase with increasing distance from mineralization. From 0– 3 km, the pyrope component is 3–7%; at distances > 3 km from mineralization, the pyrope abun- dance is > 7%. Although these chemical differences are minor, they could potentially be used to aid exploration. The assessment of the vertical garnet chemistry trends was restricted to analyzing mine samples only. This was because the distal and intermediate samples were from the surface or near surface. Their exclusion removed bias for surface samples. Vertical trends in garnet from mine samples are scattered, but potentially useful for exploration (Fig. 4.26). Shallow garnets are the most enriched in Fe2+ (the almandine component), with less Fe2+-rich garnets at depth. The grossular component varies from shallow, to intermediate, to deep. In shallow mine levels (above 900 m), the Ca-component is low, ≈ 8%. At intermediate depths (1–1.5 km), the grossular component is high, > 16%. Finally, at depth (> 1.5 km), the grossular component is again low, < 12%. The spessartine component (Mn) indicates a weak increase from shallow levels of ≈ 7.5% to ≈ 20% at depth. The Fe2+ and Mn2+ indicate an antithetical relationship. When Fe2+ decreases, Mn increases. This trend occurs with increasing depth. Finally, the pyrope component is consis- tently minimal (< 6% Ca-component) from 900–1800 m depth in the mine. At depth (> 1.8 km) in the mine complexes, the pyrope component increases to 7–10%. Garnet chemistry appears to be unaffected by metamorphic grade (Fig. 4.25 and 4.26). With increased depth and distance from ore, the metamorphic grade increases (Fig. 3.30). The 160 Figure 4.24 Examples of rim-core-rim EMPA profiles of garnets in type 1 tholeiitic basalt (A = DS173-499), type 2 calc-alkaline basalt (B = D21708-2760) and argillite (C = GC01018-691). The basalt types are distinguished in sec- tion 4.5.2 below. 161 Figure 4.25 Variation of garnet chemistry with increasing distance from known ore zones of the RLGM versus metamorphic facies. Line of best fit statistically generated by the software IoGas. The regression was calculated from all data. Calculated means are specific to each sample. 162 variations in Fe, Mn, Mg and Ca are more influenced by bulk rock composition at the time of metamorphic garnet development. Garnet chemistry has the potential to infer early alteration events (e.g. H1, Figs. 3.2, 3.31). This early hydrothermal event (H1) is inferred to have enriched the basalt in Fe and Mn prior to regional metamorphism. The addition of both these elements is needed to explain the extreme Fe2+-rich nature, and Mn-rich cores of metamorphic garnets. This early hydrothermal event also possibly created heterogeneity in the Ca abundance, explaining the odd vertical profile. The heterogeneity in basalt composition at the time of regional metamorphism also caused variations in the metamorphic assemblage. For example, garnet can occur in more biotite- rich rocks (assemblage garnet-amphibole-biotite-calcite-epidote) or amphibole-rich rocks (as- semblage amphibole-garnet-epidote-calcite). The associated metamorphic minerals did influence the garnet compositions (Fig. 4.27). Where garnet is a minor aspect of the assemblage (e.g., chlorite-amphibole-epidote rich rocks), the almandine and pyrope components are low (48–58% and 4–7.5% respectively). In contrast, both the grossular and spessartine components are high (14–26% and 17–25% respectively). Garnet associated with abundant biotite(-amphibole) have a moderate Fe2+ (54–70%), with ranging Mg, Ca and Mn (3–11%, 5–25% and 9–28% respec- tively). Garnets belonging to the garnet-chlorite-amphibole ± magnetite assemblage have the widest range in each component: almandine 55–84%, pyrope 3.5–12%, grossular 7.5–22.5% and spessartine 2.5–22.5%. Garnet belonging to the garnet-chlorite-amphibole ± magnetite ± biotite assemblage mimics the garnet-chlorite ± magnetite assemblage chemistry. However, garnets are distinctively low in their pyrope component, only 3–4%. The ranges in Fe and Mn compositions within individual garnets can be partly explained by the bell-shaped curves from rim to core (Fig. 4.24). All element (Fe, Mn, Mg and Ca) varia- tions can also be explained by (1) competition with other synchronously developed metamorphic minerals, e.g. amphibole, epidote and clinozoisite; and (2) heterogeneity in the bulk rock compo- sition at the time of metamorphic growth due to prior hydrothermal alteration. 4.4 Geothermometry The peak P-T conditions for the Red Lake M2 regional metamorphic event have been studied elsewhere as part of more detailed petrologic phase relation studies (Mathieson and Hodgson, 1984; Christie, 1986; Damer, 1997; Tarnocai, 2000; Thompson, 2003). These investi- gations have used a combination of methods ranging from mineral assemblages, computer soft- 163 Figure 4.26 Variation in garnet chemistry at the mine site from shallow to depth. 164 Figure 4.27 Variations of garnet chemistry in relation to the dominant alteration assemblage of the bulk rock. ware and fluid inclusions (Table 4.8). Metabasic rocks, which are the principle lithology investi- gated in this study, are generally unfavorable for P-T work. However, geothermometry calcula- tions can nonetheless put the observations from this study into the metamorphic context. This, in turn, provided additional constraints into the relationship between alteration and regional thermo-tectonic evolution. 165 Table 4.8 Previous peak-metamorphism P-T conditions Publication Pressure estimate Temperature estimate Method Chi et al., 2003 2.7–3.6 kbar 350–550°C Carbonic inclusion isochore with homogenization temperature of -2.4°C Chi et al., 2002, 2003, 2006 252–380°C Fluid inclusions derived from carbonate and quartz syn-mineralization Thompson, 2003 2–4 kbar 500–550°C Greenschist-amphibolite assemblage Tarnocai, 2000 <3 kbar 465–545°C Garnet-biotite Damer, 1997 1.4–2.0 kbar 1.0–2.2 kbar 435–480°C 450–550°C Garnet-biotite:TWEEQU software Garnet-biotite: WEBINVEQ software Christie, 1986 3–4 kbar 440–510°C Arsenopyrite geothermometer Mathieson and Hodgson, 1984 3.8–4.2 kbar 520–540°C Arsenopyrite geothermometer 4.4.1 Carbonate thermometry Paleo-temperatures can be estimated using the distribution of Mg between co-precipitated ankerite (dolomite) and calcite (Rathmell et al., 1999). Carbonate veins in the RLGM frequently contain both, but not co-precipitated. Ankerite veins are cut by later calcite veinlets or fracture fill (Fig. 3.25). Although rare, two samples were found with co-precipitated ankerite and calcite (Fig. 4.28): one sample from the CBC, the other from the mapped outcrop (Appendix A.4). Temperatures from co-existing dolomite/ankerite and calcite were calculated using: Log10 XCteMgCO3 = -1690/T (°K) + 0.795 (Rice, 1977) Sample D39018-3562 calculated an estimated temperature of 459°C, and the mapped outcrop sample 490°C. Both temperatures are slightly higher compared to fluid inclusions reported for pre- to syn-mineralization carbonate veins (171–390°C which have been pressure corrected; Chi et al. 2003). The mapped outcrop displayed slightly hotter temperatures, which could be due to a closer proximity to the syn-D2 (which is synchronous with carbonate vein emplacement) Dome and McKenzie stocks (Fig. 1.3). Regardless of the sample location, carbonate thermometry esti- mates are comparable to peak-metamorphic temperatures, 435-550°C (Table 4.8). This would suggest that the ankerite veins formed during or slightly post-peak regional metamorphism with a hot hydrothermal fluid. This is consistent with syn- to post-peak metamorphic petrographic ob- servations (Fig. 3.2; Chapter 3), and the inference by other workers that the ore fluids were CO2- rich (Chi et al., 2002, 2003, 2006, 2009). 166 Figure 4.28 Synchronous ankerite and calcite from sample ES09_AP_6A used for carbonate thermometry calcula- tions. A) Plane polarized light image showing ankerite-calcite vein with (grey) chlorite selvage. White dashed box is the outline for SEM image B. B) Backscatter image of same sample clearly showing co-precipitated ankerite and calcite. 4.4.2 Garnet-biotite thermometry Garnet-biotite thermometry was calculated from one sample containing rarely observed garnet with associated biotite-amphibole. Estimates were calculated using a downloadable spreadsheet designed by Dr. Waters (University of Oxford) available at: http://www.earth.ox.ac.uk/~davewa/pt/th_tools.html. The spreadsheet calculates and compares the results of previous calibrations of the garnet-biotite Fe-Mg exchange geothermometer. The calculation methods used for comparison are Thompson (1976), Ferry and Spear (1978) and Bhattacharya et al. (1992), who used data from Ganguly and Saxena (1984), and Hackler and Wood (1984). A pressure of 3 ± 1 kbars was assumed due to the average pressure previously de- fined for the Red Lake area (see Table 4.8). This pressure was calculated using GASP (garnet- aluminosilicate-quartz-plagioclase) barometry and the presence of andalusite (Tarnocai, 2000). The garnet-biotite temperature range calculated in this study was 380–460°C (Table. 4.9). The lowest temperature was calculated by Bhattacharya et al. (1992) using the Ganguly and Sax- ena’s (1984) equation. The highest temperature was from Thompson (1976), and the average of the four results was 423 -35/+45°C (Table 4.9). This highest calculated temperature is compara- ble with Christie (1986), Damer (1997) and Chi et al. (2003) (Table 4.8). With only one garnet-biotite thermometry estimate calculated in this study, this tempera- ture cannot be applied extensively to the Red Lake area. However, the estimated garnet-biotite temperature is comparable with peak-metamorphic conditions. The garnet-biotite thermometry estimates support petrographic observations of a regional metamorphic garnet growth. 167 Table 4.9 Summary of temperature estimates derived from multiple calculation methods for garnet-biotite ther- mometry Fe-Mg exchange geothermometer Pressure estimate Temperature estimate Thompson, (1976) 3 kbar 458 ± 6°C Ferry and Spear (1978) 3 kbar 418 ± 4°C Bhattacharya et al., (1992) using data from Ganguly and Saxena (1984) 3 kbar 379 ± 1°C Bhattacharya et al., (1982) using data from Hackler and Wood (1984) 3 kbar 438 ± 6°C Average of all methods 3 kbar 423 -35/+45°C 4.4.3 Chlorite thermometry Chlorite composition can reflect paleotemperature of crystallization (Caritat et al., 1993). Typically, chlorite thermometry is applied to pelites and felsic rocks from geothermal systems with low temperatures (≈ 250°C; Cathelineau and Nieva, 1985; Cathelineau and Izquierdo, 1988; Caritat et al., 1993). Although rare, chlorite thermometry can be applied to basic rocks; Bevins et al. (1991) applied Cathelineau’s (1988) equation. Chlorite thermometry should be used with cau- tion, as chlorite composition is affected by ƒO2, pH, fluid and rock composition (Caritat et al., 1993). Nonetheless, chlorite thermometry calculations can provide broad temperature conditions to test if chlorite is part of the regional metamorphic event at Red Lake. Chlorite thermometry is based on cation substitutions. The most common is tschermaks cation exchange: Mg + Si  Total Al, followed by Fe  Mg. Aluminium and Si substitution are considered to reflect temperature changes due to diagenesis, geothermal activity and/or meta- morphism (McDowell and Elders, 1980; Cathelineau and Nieva, 1985; Cathelineau, 1988; Jahren and Aagaard, 1989; Hillier and Velde, 1991). The Fe and Mg variation is directly propor- tional to the bulk rock composition (Cathelieneau and Nieva, 1985; Bevins et al., 1991). Four chlorite thermometry equations were used in this study to estimate temperatures. The first was the calibration of Cathelineau (1988): T (°C) = -61.92 + 321.98*A1IV This only considered the temperature variations, but has been applied to basic rocks (Bevins et al., 1991). Jowett’s (1991) modified the calibration to account for the variation in bulk rock composition by using the Fe/(Fe+Mg) ratio of the chlorite composition: AlIVCorrected = AlIVMeasured + 0.1[Fe/(Fe + Mg)] T (°C) = 319*AlIVCorrected – 69 168 Kranidiotis and MacLean (1987) modified Cathelineau and Nieva’s (1985) original calibration to take into account the Fe/(Fe+Mg) variations of the chlorite composition. Their calibration is: T (°C) = 106*AlIV + (0.7 * Fe/(Fe+Mg)) + 18 Finally, the most recent calibration applied to metabasic rocks was used (Zang and Fyfe, 1995). This calibration also attempted to correct the bulk rock composition. Zang and Fyfe’s (1995) calibration is below: T (°C) = 106.2* AlIV – 0.88 * (Fe/(Fe+Mg) – 0.34) + 17.5 To calculate estimated temperatures, the above equations were used with the representative me- dian EMPA for each chlorite colour and sample (Table 4.3 and Appendix B.2). For each par- agenetic chlorite stage and type, an estimated temperature range was calculated using the equa- tions above. These variations are summarized in Table 4.10. Table 4.10 Summary of calculated chlorite thermometry estimates Chlorite type (in paragenetic order) Cathelineau, 1988 Jowett, 1991 Zang and Fyfe, 1995 Kranidiotis and MacLean (1987) Berlin blue chlorite minimum 310.2 320.9 109.5 169.7 maximum 403.6 415.6 145.9 225.6 median 374.3 386.6 140.4 204.9 Brown chlorite minimum 318.2 319.9 138.4 171.9 maximum 399.1 404.5 152.6 208.9 median 361.2 365.5 141.9 195.8 Grey chlorite minimum 323.5 323.9 138.3 170.6 maximum 373.8 377.5 156.3 195.9 median 358.6 359.9 148.5 185.6 Late blue (veinlet) minimum 387.2 397.1 131.1 210.4 chlorite maximum 389.5 398.6 143.0 218.5 median 388.4 397.8 137.1 214.4 Chlorite colour is the birefringence The same chlorite composition used in each of the four equations calculated very broad ranges in temperatures (Table 4.10). For example, blue chlorite, the earliest metamorphic chlo- rite, indicated a temperature range of 109–415°C. From petrographic observations (Chapter 3), the chlorite (prograde) sequence is birefringent blue to brown to grey. From these observations, blue chlorite was assumed to be the coolest, and grey chlorite the hottest. This is weakly dis- played by Zang and Fyfe’s (1995) and Kranidiotis and MacLean’s (1987) calibrations. The cali- bration by Cathelineau (1988) and Jowett (1991) indicated that blue is the coolest, but that brown chlorite is the hottest (Table 4.10). None of the equations calculated temperatures that are comparable with those calculated by other thermometry methods. The broad ranges in temperature from chlorite thermometry 169 could be due to several issues: (1) Chlorite thermometry works best in low temperature (< 250°C) settings, and peak-metamorphism at Red Lake was between 450–550°C (Table 4.8); (2) the composition of the host rock at the time of metamorphic chlorite growth affected the ther- mometry outcome; or (3) chlorite was reset during subsequent metamorphism or hydrothermal alteration and/or effected by the pH or ƒO2 of the fluid (Caritat et al., 1993). As distinctive bire- fringence colours are preserved in all chlorite stages, it is unlikely that the chlorite composition was reset by subsequent hydrothermal or metamorphic events. Therefore, the main influences for chlorite thermometry are, 1) peak-metamorphism at Red Lake being was too hot for chlorite thermometry; and 2) bulk rock composition variations. 4.4.4 Geothermometry summary Thermometry calculations were used in this study to apply additional constraints on par- agenetic timing of regional metamorphic events. Both carbonate and garnet-biotite thermometry estimates were comparable with P-T conditions previously reported at Red Lake (Mathieson and Hodgson, 1984; Christie, 1986; Damer, 1997; Tarnocai, 2000; Thompson, 2003). Both ther- mometry methods also correlate to estimates of greenschist-amphibolite transitional facies condi- tions (Spear, 1993). The thermometry calculations constrained the garnet and carbonate veins to have formed syn- to post-peak-regional metamorphism. Chlorite thermometry was less effective. This could be because chlorite thermometry works best at lower temperatures. Nonetheless, chlorite thermometry weakly acknowledged the prograde sequence of blue to brown to grey chlorite. 4.5 Whole rock geochemistry data The majority of geochemical data obtained in this study shares a common protolith of basalt from either the Balmer or Bruce Channel assemblage. Consequently, it is critical to define the basalt sample suite. This needs to be defined in terms of least altered and altered samples. The geochemical data presented below is derived from the Balmer and Bruce Channel basalt units. 4.5.1 Identification of least altered basalt protolith The most complex aspect of the RLGM is the superposed nature of the mineral assem- blages (see Chapter 3). In order to define chemical variations between mineral assemblages, the least altered protolith (basalt) needed to be established. Due to the extensive nature of alteration 170 at the RLGM, samples collected by F. Bouzari (2007–2008) were used to represent the least al- tered rocks. These samples were derived from the RLGB, outside the alteration halo of the RLGM, and so were not overprinted by the main auriferous event. Least altered samples were distinguished chemically using Na/Al molar and K/Al molar ratios. The least altered basalts ranged between 0.15–0.4 Na/Al and 0–0.05 K/Al (Bouzari, 2009). Samples containing veins or sulfides were excluded from the data. The remaining samples were used as the representative, least altered basalts for geochemical comparison. The Bouzari (2009) least altered samples are comparable to other previously reported ‘fresh’ Red Lake basalts (Table 4.11; Pirie, 1981; MacGeehan et al., 1982; Tomlinson et al 1998; Tarnocai, 2000; Cadieux et al., 2006). The reported least altered basalts were metamorphosed to greenschist-amphibolite facies, with preserved pillows, carbonate filled amygdules and mineral- ogy of pyroxene, epidote, plagioclase and albite (Pirie, 1981; MacGeehan et al., 1982; Tarnocai, 2000; Cadieux et al., 2006; Bouzari, 2009). The least altered samples were chemically character- ized by less than 1% loss on ignition, and a ratio of cation Al/(Na+K+Ca) of approximately 1, indicating little alkali bulk leaching (Tomlinson et al 1998; Cadieux et al., 2006; Bouzari, 2009). As none of these rocks were overprinted by the ore-formation hydrothermal fluids (e.g. contain no veins, mineralization, abundant biotite or quartz-muscovite-andalusite alteration), they repre- sent typical least altered metamorphosed basalts from the RLGB. From the previously reported least altered basalts, Bouzari’s (2009) sample suite was the preferred reference suite, as samples underwent the same digestions and analytical procedures as those in this study. The details of the compared least altered sample suite from Bouzari (2009) are provided in Appendix B.11. 4.5.2 Identification of altered basalt protolith Due to intense alteration of all rock types in the RLGM, basalt and ultramafic units are hard to differentiate when logging core (e.g. Rogers, 1992). Accordingly, chemistry was used to distinguish ultramafic from basalt. This isolated the desired basalt protolith for comparison with mineral chemistry data. To chemically separate basalt and ultramafic units, the elements Mg, Cr and Ni were used. These elements are known to have higher abundances in ultramafic rocks than basalt (Arndt and Nisbet, 1982). Ultramafic samples were classified when the Cr2O3 abundance was > 0.1 wt%. It was noted that these samples also corresponded to higher MgO and Ni abun- dances (Fig. 4.29). Some rare basalt samples contained high Mg and Ni abundances. These sam- 171 Table 4.11 Least altered basalt samples from the RLGM Publication Sample name/number of samples Al2O3 wt% CaO wt% FeO wt% Fe2O3 wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total oxide wt% Bouzari (2009) 5565.00 0.00 14.58 12.30 12.22 0.12 7.36 0.33 2.49 0.07 0.85 0.25 0.02 45.88 96.46 Bouzari (2009) CR-04-30 9.84 16.85 10.20 10.84 0.12 7.66 0.19 2.01 0.08 0.89 0.10 0.03 47.61 96.57 Bouzari (2009) DS196 396.00 15.83 10.23 10.74 0.11 8.14 0.20 2.71 0.07 0.80 0.10 0.04 47.61 96.57 Bouzari (2009) MB01-031 16.40 13.56 11.42 10.70 0.24 9.62 0.19 0.88 0.07 0.80 0.25 0.05 48.88 96.66 Bouzari (2009) CR-04-28 16.40 14.68 10.58 10.97 0.35 7.21 0.19 2.57 0.05 0.67 0.17 0.02 49.22 96.68 Bouzari (2009) GC01-015 49.87 16.19 10.52 11.50 0.08 5.59 0.14 1.73 0.08 1.04 0.10 0.02 49.74 96.71 Bouzari (2009) AB01196 65.62 15.30 9.14 11.34 0.11 7.36 0.19 2.02 0.10 1.02 0.17 0.02 49.95 96.73 Bouzari (2009) DS122 175.85 14.75 9.29 10.49 0.05 7.25 0.19 3.57 0.07 0.77 0.10 0.03 50.19 96.74 Bouzari (2009) MC02021 103.35 14.98 5.68 12.42 0.12 7.48 0.17 3.56 0.11 1.14 0.22 0.03 50.87 96.79 Bouzari (2009) MC-01-012 16.40 15.55 9.93 8.67 0.08 8.14 0.18 2.06 0.06 0.65 0.05 0.04 51.41 96.82 Bouzari (2009) IN8728 29.53 14.04 8.98 10.88 0.10 6.35 0.17 2.43 0.08 0.94 0.25 0.02 52.68 96.90 Cadieux et al., (2006) average of 6 samples 15.00 10.60 12.55 0.19 6.88 0.20 2.58 0.19 1.01 0.21 0.04 50.60 100.05 MacGeehan et al. (1982) average of 6 samples 15.36 11.93 12.37 1.48 0.15 7.08 0.29 1.86 0.08 0.89 0.00 49.04 100.52 Pirie (1981) 911 14.80 10.40 13.80 0.14 6.63 0.24 2.29 0.13 1.19 0.02 0.03 49.50 99.17 Pirie (1981) 1027 16.10 11.30 13.00 0.20 6.36 0.23 2.77 0.13 1.16 0.27 0.05 47.30 99.90 Tarnocai (2000) CRL19 16.52 5.33 11.15 0.15 4.81 0.17 0.16 0.13 1.52 0.19 51.51 99.53 Tarnocai (2000) CRL49a 14.91 6.68 7.26 0.50 3.66 0.12 3.35 0.32 0.83 0.41 52.16 99.74 Tomlinson et al., (1998) average of 8 samples 14.53 8.89 12.46 0.38 7.80 0.19 2.90 0.09 1.02 0.03 50.97 100.99 172 Figure 4.29 Chemical identification of ultramafic and basalt samples. 173 ples contained abundant ankerite-calcite ± quartz veins or sulfides. Consequently, Mg and Ni concentrations alone should not be used to classify ultramafic from basaltic units. Basalts were then classified into either tholeiitic (type 1, Balmer assemblage) or calc- alkaline (type 2, Bruce Channel assemblage), following the distinction suggested by Bouzari (2009) (Fig. 4.30A). This distinction is based on high Sc and low Th concentrations (type 1), and high Th and low Sc concentrations (type 2) (Bouzari 2009). The dominant basalt was found to be type 1 tholeiitic. Type 1 basalts also included all the least altered reference samples. Type 2 ba- salt samples were frequently noted to be derived from the intermediate to distal scale (> 3 km from ore zones). This corresponds to the dominance of the Bruce Channel assemblage over the Balmer basalt at these distal occurrences (Figs. 1.6 and 1.9). The classification of basalt type 1 and 2 using Th and Sc concentrations was confirmed using a Pearce and Cann (1973) Ti versus Zr diagram (Fig. 4.30B). The basalt chemistry displayed a range, but island arc type was the dominant type, supporting Hollings et al. (1998) and Sanborn-Barrie et al. (2001). Representative whole rock (four acid digestion method) geochemistry data is presented in Table 4.12. Each of these representative samples contained one diagnostic mineral assemblage, with little to no overprint by other alteration types, veins or sulfides. The representative analyses demonstrate that the earliest recognizable mineral assemblages, at the RLGM (biotite-Ti- magnetite ± carbonate, regional metamorphic facies and quartz-muscovite-andalusite), are rela- tively K2O- and SiO2-rich compared to the least altered samples (Table 4.12). This enrichment could have originated from metamorphism of a mechanical mix of sedimentary rocks (argillite, clastic sediments and chert/BIF packages) and basalt. Basalt and minor sedimentary units com- pose the Balmer assemblage (Table 2.1). A comparison of the earliest mineral assemblages with sedimentary units (from Bouzari, 2009) has indicated that some of the K2O and SiO2 addition could have been caused by metamorphism of interbedded basalt and sediment (Fig. 4.31). Most of the basalt data show distinct K2O and SiO2 compositions compared to the sedimentary pack- ages (Fig. 4.31). Consequently, the bulk of the K2O and SiO2 addition in altered basalts cannot be explained by metamorphism of a mechanical mix of basalt and sedimentary units. The addi- tion of K2O and SiO2 must therefore, be derived from external sources, e.g. hydrothermal fluids. The fluid must have affected the basalt prior to regional metamorphism so that subsequent metamorphism created the metamorphic assemblages of biotite-Ti-magnetite ± carbonate, chlo- rite-amphibole-epidote-calcite-biotite ± garnet ± magnetite and quartz-muscovite-andalusite. 174 Figure 4.30 Chemical divisions of basaltic units of the Balmer assemblage. A) Th versus Sc plot (after Bouzari, 2009). B) The basalt is plotted on a Pearce and Cann (1973) diagram, indicating type 2 basalts are calk-alkaline ba- salts from the Bruce Channel assemblage, whereas type 1 basalts range from MORB to island arc type (IAT) ba- salts, from the Balmer assemblage. 175 Table 4.12 Representative whole rock analysis Sample Dominant Alteration Al2O3 (wt%) CaO (wt%) FeOTotal (wt%) K2O (wt%) MgO (wt%) MnO (wt%) Na2O (wt%) P2O5 (wt%) TiO2 (wt%) SO3 (wt%) Cr2O3 (wt%) SiO2 (wt%) Total (wt%) Ag ppm As ppm Ba ppm D27943-3389.5 bio-Ti-mag ± carb 15.72 4.87 6.61 3.70 5.14 0.07 0.88 0.06 0.58 0.57 0.04 59.10 97.32 0.02 3.40 1060.00 DS172-123 chl-amp- grt-epi/czo- mag-bio-cal 16.13 2.62 18.20 3.08 3.20 0.71 0.24 0.08 0.88 0.07 0.04 51.57 96.83 0.07 38.6 430.00 DS177-1500.8 chl-amp- grt-epi/czo- mag-bio-cal 19.17 6.20 13.82 0.20 4.41 0.68 0.98 0.06 1.29 1.22 0.03 48.55 96.63 0.14 59.5 70.00 D33003-2004 chl-amp- grt-epi/czo- mag-bio-cal 15.79 10.46 13.25 1.10 6.15 0.39 0.61 0.17 1.57 0.27 0.01 46.74 96.52 0.15 30.3 100.00 D39018-635 qtz-mus-and 18.63 0.24 1.02 5.71 0.23 0.01 0.26 0.14 1.29 0.40 0.03 70.10 98.04 0.06 65.4 360.00 D39200-1318 Plag 18.17 3.01 4.63 0.80 1.99 0.07 0.11 0.12 1.23 1.50 0.02 66.14 97.78 0.07 38.9 60.00 CB4043HR Br. bio-qtz ± carb ± sul 14.38 10.87 11.19 1.24 7.06 0.23 0.26 0.08 0.87 3.40 0.04 46.91 96.53 5.94 362 90.00 CB302561 Br. bio-qtz ± carb ± sul 10.98 8.24 9.93 1.02 4.53 0.16 0.32 0.04 0.57 7.29 0.05 53.85 96.98 6.35 10000 100.00 17L1437-556 carb-qtz vein ± chl ± bio selvage 3.19 19.87 7.86 0.19 10.84 0.38 0.09 0.02 0.18 0.17 0.01 54.19 97.00 0.04 39.0 20.00 BK0510-376.12 carb-qtz vein ± chl ± bio selvage 14.00 7.85 5.61 0.84 4.34 0.13 1.20 0.06 0.46 0.12 0.01 62.95 97.58 0.21 1.50 70.00 RL422VG qtz-sul ± carb vein 1.79 5.11 18.97 0.36 2.74 0.07 0.07 0.01 0.06 21.75 0.02 45.49 96.43 106 10000 50.00 16L1067-267.9 qtz-sul ± carb vein 11.50 1.55 6.78 1.75 1.06 0.02 0.24 0.03 0.48 6.57 0.03 67.89 97.90 2.90 10000 240.00 Least altered (average n = 11) least altered 15.12 9.84 10.98 0.13 7.47 0.19 2.37 0.07 0.87 0.16 0.03 49.46 96.69 0.07 12.4 50.91 This data was derived by four acid digestion methods. Total Fe = Fe2+O. Element oxides were calculated from the four acid digestion wt% data. Trace elements indicating pathfinder qualities are indicated. Least altered samples from Bouzari, (2009). For abbreviations, refer to list of abbreviations 176 Table 4.12 (Continued). Sample Be ppm Bi ppm Cd ppm Ce ppm Co ppm Cs ppm Cu ppm Mo ppm Ni ppm Pb ppm Rb ppm Sb ppm Sc ppm Sn ppm Sr ppm Th ppm W ppm Zn ppm Zr ppm D27943- 3389.5 0.43 0.02 0.06 3.28 39.1 4.91 35.1 0.11 94.8 2.1 36.5 2.58 39.7 0.40 89.1 0.20 12.9 53 41.9 DS172-123 1.13 0.02 0.03 12.55 45.0 11.1 52.0 0.21 133 2.2 103.5 4.48 63.8 0.50 182 0.50 1.1 98 51.3 DS177- 1500.8 0.35 0.07 0.22 14.50 90.3 8.73 401 0.27 267 1.3 5.0 3.99 60.4 0.70 85.1 0.3 0.5 315 61.7 D33003- 2004 1.32 0.02 0.17 20.40 49.1 9.66 94.0 0.41 64.3 3.3 38.4 17.45 57.6 1.20 228 0.90 8.0 106 102.5 D39018- 635 0.56 0.09 11.85 28.3 2.88 197 0.23 59.8 0.9 79.4 3.38 37.0 0.90 29.9 0.40 0.4 37 78.7 D39200- 1318 0.27 0.01 0.07 9.59 28.8 5.26 52.2 0.32 57.7 5.9 18.9 18.30 23.6 0.80 52.0 0.60 51.9 45 73.5 CB4043HR 0.55 0.15 0.23 7.50 52.0 3.76 283 0.42 160 5.0 38.9 18.55 38.2 1.10 164 0.40 11.0 81 53.5 CB302561 0.52 0.06 0.14 11.40 59.2 3.73 296 0.54 234 9.1 28.7 60.90 26.8 1.10 84.4 0.40 35.5 48 44.7 17L1437- 556 0.21 0.04 0.24 3.93 12.1 0.68 31.8 0.26 61.6 1.5 4.2 13.90 24.2 0.20 77.5 5.2 108 14.5 BK0510- 376.12 0.81 0.06 0.20 8.53 24.2 1.79 14.6 0.66 52.8 16.2 21.0 3.60 16.0 0.60 105.0 0.40 16.9 135 60.3 RL422VG 0.30 7.37 2.46 4.20 91.6 0.53 1415 0.33 500 51.9 12.2 525.00 6.0 1.40 24.4 3.2 498 8.2 16L1067- 267.9 0.49 0.18 3.23 5.11 45.2 5.92 303 0.18 94 39.8 42.6 589.00 20.3 0.40 62.6 0.30 36.6 661 35.9 Least altered (average n = 11) 0.27 0.03 0.09 9.24 51.3 0.87 139 0.25 118 1.31 2.94 4.55 46.8 0.53 149.9 0.41 2.2 89 31.9 177 Figure 4.31 Comparison of pre-metamorphic altered Balmer basalt samples and sediment packages. The sedimen- tary units are not the source of K2O to the basalt units. Basalt samples within the grey circles can have enrichment in K2O and SiO2 due to mechanical mixture of sediment and basalt. However, the bulk of the basalt data is outside of the grey circles (representing sediment composition), therefore not a viable explanation of K2O and SiO2 in the ba- salt unit. 178 4.5.3 Calculation of mass balances between alteration assemblages Mass balance comparisons between the least altered and altered samples were calculated to identify chemical differences. Chemical differences between least altered and altered samples provided information regarding the nature and composition of the hydrothermal fluid which af- fected the basalt. Mass balance differences were calculated using a modified equation from Gresens (1967), as derived by Warren et al. (2007): (CAAl / CBAl) * CBx - CAx = Δ Massx where: CAAl = least altered immobile element result, CBAl = altered immobile element result, CBx = altered investigated element X, CAx = least altered investigated element X and Δ Mass is change in mass. Al2O3 was chosen as the immobile element for several reasons: (1) Zr is present in low abundances with occasional samples demonstrating large Zr spikes; this is a likely nugget effect, and therefore not consistent across samples; (2) Ti was too low in abundance; (3) Al is a major element in the rock forming minerals chlorite, amphibole, garnet, biotite, etc.; (4) Al has similar concentrations between altered and least altered samples (Fig. 4.32); and (5) Al has the lowest relative percent variation of the immobile elements (Ti, Zr, Al) investigated. Due to the heterogeneity of the least altered protolith samples, error was propagated. This error was calcu- lated using the equation outlined in Taylor (1982). This provided an estimate of error due to both the analytical uncertainty and geological variations between samples. The below equation was used: δΔ Mass = ΔMass x mean * [(δ CAAl/ CAAl mean) + (δ CBAl/ CBAl) + (δ CBx/ CBx )] + δ CAx The notation is the same as that used in the above Gresens (1967) equation, with the addition of δ indicating the laboratory 1σ standard deviation error. All mass balance and propagation error results are in Appendix B.11. Alteration at Red Lake is complex due to several superposed events. To simplify the al- teration events, eight main mineral assemblages were chosen to assess the chemical differences between key stages of the geochemical development of the RLGM. The key hydrothermal stages were the early hydrothermal alteration (implied from regional metamorphic assemblages) and the overprinted mineralization event (ore-stage assemblages). The selected main assemblages were carefully chosen as they were required to represent one of the two main hydrothermal events. Additionally, the main assemblage had to be abundant and easily distinguishable in hand sample as well as thin section. This was to ensure that only the specifically investigated assem- blage was assessed. Assemblages such as blue chlorite ± sulfides, blue tourmaline and chlorite- 179 Figure 4.32 Element ratios of Zr/Al verses Ti/Al to isolate the most immobile element for mass balance calculations. The dashed circle represents chemically similar (Zr/Al and Ti/Al) least altered and altered rock samples from the RLGM. muscovite ± carbonate ± quartz (Fig. 3.2) were only visible in thin section and composed < 2% of the sample. Consequently, low abundant assemblages were not assessed as their chemical in- fluence on the bulk rock composition was minimal. Each representative sample contained the desired alteration assemblage only, with no overprinting alteration, veins or sulfides. The only exception was vein selvages and alteration associated with the mineralization stage. Assessment of vein-hosted alteration was chemically evaluated through vein selvages, with 50–80% of the sample containing wall rock. The representative samples were chosen so as to include the full variation in alteration styles. For example regional metamorphic amphibolite samples can con- tain amphibole-epidote/clinozoisite-biotite-calcite ± magnetite or amphibole-garnet -biotite± magnetite. Both assemblages formed simultaneously during M2 regional metamorphism. These variations in mineralogy are due to localized bulk rock composition differences (caused by early hydrothermal alteration) at the time of regional metamorphism. The eight main alteration assem- blages, their mineralogy and paragenetic timing are provided in Table 4.5. Figure 4.33 demon- strates the paragenesis with the main alteration assemblages highlighted. Selection of these eight main assemblages simplified the complex paragenesis. This al- lowed the documentation of the influential hydrothermal and metamorphic events that affected the RLGM. These events included a pre-metamorphic hydrothermal event (H1), peak- metamorphism creating greenschist-amphibole facies (M2), post-peak metamorphic carbonate- quartz/quartz-carbonate vein event followed by the main mineralization event with associated quartz and brown biotite (synchronous M2-H2-D2 event). These events are outlined in figure 3.31. The pre- and syn-metamorphic events were the most influential for ore-deposition. As a 180 result, these geological stages were characterized. The post-mineralization hydrothermal event did not extensively affect the basalt. Gold formation did occur during post-regional metamorphic events, but as the result of remobilization (related to the contact M3 metamorphic event) rather than hydrothermal fluids (Dubé et al., 2004). Post-mineralization alteration is present as minor calcite and quartz-tourmaline ± carbonate ± pyrite veins and veinlets (Fig. 3.2). These veins were in low abundances often too low for comprehensive geochemical analyses. Consequently, no post-mineralization hydrothermal events were assessed for mass balance differences. Table 4.13 Eight alteration and vein assemblages, their mineralogy and paragenetic timing Paragenetic stage Key assemblage Mineralogy - M2 peak metamorphism - Evidence of H1 Biotite-Ti-magnetite ± carbonate  Biotite- Ti-magnetite ± carbonate Includes biotite + abundant carbonate - M2 peak metamorphism - Evidence of H1 Greenschist-amphibolite or regional metamorphic facies  Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite † - M2 peak metamorphism - Evidence of H1 Bleached zones  Quartz-muscovite-andalusite ± chlorite ± biotite - M2 peak metamorphism Plagioclase  Plagioclase ± quartz - H2, syn- to post-peak metamorphic Carbonate vein + selvage  Ankerite-calcite vein ± quartz ± chlorite ± biotite Includes microcrystalline, colloform- crustiform, medium-coarse veins. Samples contain 50-80% wall rock - H2, syn- to post-peak metamorphic Quartz vein + selvage  Quartz ± carbonate ± sulfides vein Samples contain 50-70% wall rock - H2, syn- to post-peak metamorphic Pervasive quartz ± sulfides  Replacement quartz-sulfides ± carbonate - H2, syn- to post-peak metamorphic Brown biotite  Brown biotite-quartz ± carbonate ± sulfides † In literature, this assemblage is often referred to as garnet-chlorite ± magnetite alteration (Penczak, 1996); howev- er, petrographic observations in this study consistently identified associated amphibole (particularly with garnet), epidote/clinozoisite and biotite (see Chapter 3). H1 = pre-peak metamorphic hydrothermal event, created precursor assemblage to the biotite-Ti-magnetite ± carbonate, greenschist-amphibole and quartz-muscovite-andalusite assem- blages. H2 = vein and ore-forming metasomatic event syn- to post-peak metamorphism. These stages are consistent with the paragenesis Fig. 3.2. Each main assemblage was compared for mass changes in paragenetic order (Table 4.14). The biotite-Ti-magnetite ± carbonate assemblage was compared to Bouzari’s (2009) least altered basalts. Following this, the chlorite-amphibole-epidote/clinozoisite-biotite-calcite-garnet ± mag- netite (regional metamorphic assemblage) and quartz-muscovite-andalusite ± chlorite ± biotite 181 Figure 4.33 The paragenesis with the eight main alteration assemblage highlighted. Group 5, 6 and 7, carbonate veins, quartz veins and quartz-mineralization assemblages respectively, included two paragenetic stages as these are similar in paragenetic timing and share similar characteristics. 182 (bleached assemblage) were compared to the biotite-Ti-magnetite ± carbonate assemblage. Petrographic observations revealed inclusions of biotite, Ti-magnetite and carbonate in garnet, porphyroblasts (Fig. 3.3F). The quartz-muscovite-andalusite assemblage overprinted the biotite- Ti-magnetite ± carbonate assemblage (Fig. 3.12F). Therefore, comparison of the bleached and regional metamorphic assemblages with the biotite-Ti-magnetite ± carbonate was considered representative of the overprinting nature of these assemblages. Subsequent post-peak metamor- phic events included carbonate veins (all types), quartz veins (all types) and sulfides with associ- ated alteration. These were all compared to the chlorite-amphibole-biotite-garnet ± magnetite ± epidote assemblage, as petrographic observations consistently record this assemblage present in all vein and ore zone samples. 4.5.4 Characterization of element variations for the key alteration assemblages Mass balance calculations of both trace and major elements are summarized in Table 4.14 and Fig. 4.34. The elements Be, Cd, Cr, Ce, Co, Ga, Ge, Hf, In, Nb, Pb, Re, Sc, Se, Sn, Ta, Th, Tl, Ti, P, U, V, Y and Zr were relatively constant, regardless of the alteration assemblage assessed due to low abundances. As a result, the above-mentioned elements were not included in figure 4.34. However, the data are available in the Appendix (B.11). The relatively mobile ele- ments Mg, Ca, Na, K, Li, Mn, Rb, Si, Sr, Sb, Cs and Ba and those that are related to mineraliza- tion (Au, Ag, As, Zn, Ni, Cu, Fe, S, W, Mo) were considered the most significant and useful for indentifying trends. These selected elements correlate to the sulfide mineralization and accom- panying alteration products associated with the ore-forming hydrothermal stage (refer to Chapter 3 section 3.3.2). These selected elements have the lowest propagation errors (Appendix B.11). From the petrographic observations (Chapter 3) it was concluded that the earliest recog- nizable metamorphic assemblages were metamorphosed equivalents of previously altered bas- alts. Consequently, with assumed isochemical metamorphism (during M2) the estimated element mass balances would reflect the previous alteration characteristics of the RLGM and RLGB. The earliest assemblage, the biotite-Ti-magnetite ± carbonate, demonstrated gains in K, S, Si, As, Ba, Rb, Sb and minimal gains in Li, Ni and W. These gains were accompanied with loss of Ca, Fe, Mn, Na, Cu and Zn. The chlorite-bearing (regional metamorphic assemblage, Ta- ble 4.6) assemblage indicated gains in Fe, Mn, Na, S, Cu, Sr, Zn and Li with loss of Ca, K, Si, Mg, Ba, Rb and Sb. The quartz-muscovite-andalusite assemblage reflected the dominant miner- alogy with gains in K, Si, As, Cu and Rb, with loss of the major cations, Ca, Fe, Mg, Na, Ba, Li, 183 Sr, W, Sb, and Zn. The plagioclase altered samples indicated gains in S, Si and Sb with loss of Ca, Fe, Mg, Na, As, Ba, Cu, Li, Ni, Sr, W, Zn and Rb. Ankerite-calcite veins with chlorite sel- vages displayed gains in Ca, Fe, Mg, Si, Ni, Sr and Zn with loss of As, Ba, Cu, Li and Rb. Quartz-ankerite veins ± sulfides indicated only gains of Ca, Fe, K, Mg, S, Si, As, Cu, Ni, Sb and Zn. Pervasive quartz ± sulfides demonstrated gains in K, S, Si, As, Au, Sb, Zn and W with loss of Fe, Mg and Na. Finally, the brown biotite-quartz ± carbonate ± sulfides indicated enrichment in Ca, K, Mg, S, Si, As, Au, Cu, Ni and Rb with loss of Fe, Na and Zn. The majority of the element variations were to be expected, as they reflect mineralogy. For example, the quartz-muscovite-andalusite assemblage demonstrated SiO2 and K2O gains with loss of CaO, MgO and FeO. The mass balance differences recognized in his study are large- ly consistent with those identified by Cadieux et al. (2006) (see Chapter 2). There were, howev- er, unexpected gains and losses; these need to be explained. In the following section only the un- expected mass balance differences are discussed. The S, Ni and W gains with loss of Cu and Zn for the biotite-Ti-magnetite ± carbonate reflect minor disseminated pre-mineralization sulfides, or replacement syn-mineralization sul- fides too small for visual identification. It is possible that pyrite or molybdenite was present to explain the S, Ni and W gains, but Cu and Zn loss. The loss of Ca, Mg and Sr was also unex- pected due to the associated carbonate. With comparison to Bouzari’s (2007) least altered bas- alts, the biotite-Ti-magnetite ± carbonate assemblage contains less carbonate minerals. Conse- quently, this explains the loss of Ca, Mg and Sr as the mass balance was calculated relative to the least altered samples (Table 4.14). The regional metamorphic assemblage also demonstrated gains in S, Cu and Zn (Table 4.14). Sphalerite was identified as part of this assemblage, as well as pre-mineralization sulfides of chalcopyrite (Chapter 3). Therefore, these gains are attributed to early sulfides. The loss of Ca, K, Si, Mg, Ba and Rb can be explained with reference to the biotite-Ti-magnetite ± carbonate assemblage (as these two were compared, Table 4.14). The regional metamorphic assemblage contains abundant chlorite, amphibole, garnet, magnetite with minimal biotite and calcite, espe- cially when compared to the biotite-Ti-magnetite ± carbonate assemblage. Therefore, the ele- mental losses are consistent with mineralogical changes. In this study, a K2O loss was identified, which is the opposite reported by Cadieux et al. (2006). The lack of abundant muscovite and bio- tite in this assemblage (see Chapter 3) is consistent with a loss of K2O compared to the biotite- 184 Ti-magnetite ± assemblage. Cadieux et al. (2006) compared every assemblage to the least altered protolith, hence the differences in mass balances calculated between these two studies.. The quartz-muscovite-andalusite assemblage demonstrated significant leaching of all ma- jor cations apart from K and Si. The unexpected gains of As and Cu were attributed to sulfide mineralization. The Cu could possibly be related to pre-mineralization chalcopyrite, associated with blue chlorite (Chapter 3), or both Cu and As could be due to overprinting fine-grained ore- stage sulfides too small for visual identification. Table 4.14 Summary of mass balance differences for mineral assemblages in paragenetic order Key alteration assemblage Compared alteration Compared to previous alteration Mass gain Mass loss Biotite-Ti-magnetite ± carbonate Least altered protolith (Bouzari, 2009) K, S, Si As, Ba, Rb, Sb, Li, Ni, W Ca, Fe, Mg, Na Cu, Sr, Zn Chlorite-amphibole- epidote/clinozoisite-biotite- calcite ± garnet ± magnetite Regional metamorphic assemblage Biotite- Ti-magnetite ± carbonate Fe, Mn, Na, S Cu, Sr, Zn, Li Ca, K, Si, Mg Ba, Rb, Sb Quartz-muscovite-andalusite ± chlorite ± biotite Biotite- Ti-magnetite ± carbonate K, Si As, Cu, Rb Ca, Fe, Mg, ± Na Ba, Li, Sr, W, ± Sb, Zn Plagioclase Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite S, Si Sb Ca, Fe, Mg, Na As, Ba, Cu, Li, Ni, Sr, W, Zn, Rb Ankerite-calcite-quartz veins ± chlorite selvages Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite Ca, Fe, Mg, Si, Ni, Sr, Zn As, Ba, Cu, Li, Rb, Quartz-ankerite veins ± (syn- mineralization) sulfides ± chlorite or biotite selvages Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite Ca, Fe, K, Mg, S, Si As, Cu, Ni, Sb, Zn Quartz ± (syn-mineralization) sulfides Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite K, S, Si Au, As, Sb, Zn, W Fe, Mg, Na Brown biotite-quartz ± car- bonate ± (syn-mineralization) sulfides Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite Ca, K, Mg, S, Si Au, As, Cu, Ni, Rb, Fe, Na Zn Plagioclase altered samples surprisingly demonstrated gains in Sb and loss of Ca and Na. The Sb gain is due to minor replacement ore-stage stibnite. The loss of Ca and Na is uncharacter- istic as the assemblage contains plagioclase. This can be explained by the loss of carbonate and 185 amphibole compared to the greenschist-amphibolite facies (Fig. 3.13). In addition, coarse pla- gioclase only composed < 10% of this assemblage, therefore, the Ca and Na from minor plagio- clase would not have largely affected the overall bulk rock composition. The ankerite-calcite-quartz and quartz-ankerite vein samples demonstrated significant element gains. This was expected as between 20–50% of the sample contained vein material. The element gains are consistent with the mineralogy: carbonate minerals, quartz, sulfides ± chlorite or biotite selvages. The loss of Li and Rb, as well as the lack of gained or lost K2O as demonstrated by the ankerite-calcite veins is due to the lack of significant biotite associated with these veins (see Chapter 3). The loss of As and Cu was unexpected because of the abundance of pyrite and pyrrhotite. However, neither of these minerals contain abundant As or Cu. The alteration assemblages associated with ore (quartz ± sulfides and brown biotite ± sul- fides) demonstrated gains in Au, As, S, Sb, Ca, K, Mg, and Si, but a loss in Fe. The gains are as- sociated with the mineralogy of quartz-brown biotite-carbonate-abundant sulfides and visible gold. The gold gains for the mineralized assemblages in Fig. 4.38 are derived from the selected assays completed by Bouzari, (2007). In this investigation, no samples from ore zones were as- sayed. As a result the gold gains demonstrated by the ankerite-calcite ± quartz veins, quartz ± sulfides and brown biotite ± sulfides assemblages should be significantly higher. These samples were taken from stopes with gold values of 10–100 ppm. The FeO loss demonstrated by the mineralized assemblages was unexpected due to sulfides known to occur in these assemblages. Pyrite, pyrrhotite, and magnetite all contain significant (30–50%) Fe2+ and Fe3+ (Pratt et al., 1994). The abundant sulfides + magnetite which composed ore zones required Fe. The most like- ly explanation is the surrounding wall rock. Ore stage pyrrhotite + magnetite replaced Fe2+-rich garnets in ore zones (Fig. 3.10G). The petrographic observation combined with the geochemistry data could imply that sulfidation reactions were in effect. The S-rich ore-forming fluid stripped abundant Fe from the surrounding wall rock, which is contained in Fe-rich minerals such as gar- net, amphibole, chlorite and early biotite. Narrow halos to the most sulfide rich areas are Mg- biotite. As the Mg-biotite is associated with the sulfide assemblage, this would support the sug- gestion of the fluid containing minimal FeO, with abundant As and S. Geochemical differences between mineral assemblages (Table 4.13) support this suggestion. 186 187 188 Figure. 4.34 The mass balance differences – both trace and major elements –between the main mineral assemblages described at the RLGM, as defined in Table 4.13. Trace elements Be, Cd, Cr, Ce, Co, Ga, Ge, Hf, In, Nb, Pb, Re, Se, Sn, Ta, Th, Tl, Ti, P and U are not depicted, as these elements remained constant for each alteration and vein assemblage investigated. The presented gold values are from the selected assay results from Bouzari (2007). 4.5.5 Ferric and ferrous iron variations The ferric and ferrous iron variations were calculated using the lithium borate fusion FeO and Fe2O3 abundances only. None of the four acid digestion whole rock database was used for this characterization of iron oxidation states. A plot of total FeO (grams) versus the molar ratio of Fe2+/Fetotal illustrates the basalt Fe2+ and Fe3+ variations. The Fe2+/Fetotal molar ratio was calcu- lated for all samples. From the 25 samples assessed for Fe2+ and Fe3+ variations, a subset of 14 representative basalt samples were selected for comparison with EMPA and magnetic suscepti- bility data. Twelve representative samples contained the assemblage chlorite-amphibole-biotite- calcite ± garnet ± magnetite with no veins or mineralization. Two mineralized samples (one sample was analyzed twice) were selected to be representative of the ore-stage event. These con- tained amphibolite facies mineralogy with replacement pyrrhotite-pyrite-magnetite varying in abundance from 5–15% of the sample. These ore-stage samples did not contain veins. The com- plete ferric versus ferrous whole rock data can be found in Appendix B.9. The subset of repre- sentative samples is provided in Table 4.15. As the samples dominantly contained the regional metamorphic assemblages, information relating to the early, pre-peak metamorphic hydrother- mal event (H1) can be assessed (Fig. 3.31). Variations in the ferric:ferrous ratio of mafic volcanics can result from changing the oxi- dation state of Fe in the sample, or by the removal/addition of Fe2+ and/or Fe3+ (Fig. 4.35). Either of these processes could have occurred due to hydrothermal alteration at Red Lake. Compared to both modern and Archean tholeiitic oceanic basalts, the reported Fe2+/Fetotal molar ratio of Red Lake basalts are distinctively higher (Fig. 4.36A). The comparison between Red Lake least al- tered and altered rocks also displays differences in Fe2+/Fetotal molar ratios (Fig. 4.36B). The al- tered rocks are relatively more reduced by 5–15% than the least altered samples (from MacGee- han et al., 1982). The altered rocks from the RLGM display a range in iron abundance and oxida- tion states. All these differences (modern vs. ancient, least altered vs. altered and variations in altered rock) in Fe2+/Fetotal molar ratios require explanation. Samples from Red Lake, both altered and least altered, are significantly more Fe2+-rich compared to modern basalt equivalents (Fig. 4.36A). The difference in Fe2+ and Fe3+ abundances 189 Table 4.15 Representative basalt samples for Fe2+ and Fe3+ Sample ID 19L547- 495.8 D2253 -75 37L482- 2057 DS139- 30.4 D39200 -3241 37L726- 836.6† DS172- 123 (bio) DS172- 123 (chl) DS173- 499.6 DS177- 1500.2 GC01018 -85.3 CR466- 145† CR4610- 947 CR4612- 360.3 Assemblage Amp with min* bio- chl- amp carb- chl-amp carb- chl-amp grt-chl± mag Amp with min* bio-grt- amp Amp- chl-gar ± mag grt-chl± mag grt-chl± mag grt-chl± mag grt-chl± mag grt-chl± mag grt-chl± mag Lithology Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt Basalt SiO2_pct 42.17 56.84 42.21 45.60 53.64 46.56 45.86 43.81 44.97 44.98 47.96 54.00 53.49 50.01 Al2O3_pct 16.62 15.58 20.64 11.89 18.04 18.28 14.48 14.42 17.15 17.69 17.29 16.97 16.93 18.92 Fe2O3_pct 26.25 11.70 13.98 13.22 11.96 17.73 25.86 26.89 20.29 17.46 16.42 14.92 14.22 13.39 FeO_pct 21.00 10.25 11.25 11.00 10.45 14.90 21.80 22.80 17.30 14.45 13.95 12.40 11.65 11.35 CaO_pct 2.62 4.15 5.39 2.52 6.53 3.40 3.77 4.09 6.79 9.77 9.33 5.23 5.44 7.43 MgO_pct 5.54 4.43 9.74 13.46 4.64 6.73 3.63 3.67 4.96 4.73 2.95 4.09 2.60 4.34 Na2O_pct 0.15 0.16 0.52 0.01 0.25 0.14 0.13 0.07 0.38 0.68 0.91 0.20 1.84 1.11 K2O_pct 0.56 0.40 4.38 0.24 0.05 0.03 2.50 0.44 1.42 0.22 0.53 0.07 1.47 1.06 Cr2O3_pct 0.08 0.05 0.06 0.37 0.03 0.03 0.05 0.05 0.03 0.03 0.03 0.03 0.04 0.03 TiO2_pct 0.91 1.10 0.55 0.83 1.29 1.14 0.81 0.80 1.21 1.13 1.12 1.62 1.44 1.53 MnO_pct 0.30 0.18 0.23 0.10 0.28 0.61 0.92 0.93 0.66 0.79 0.74 0.24 0.29 0.32 P2O5_pct 0.10 0.07 0.02 0.02 0.11 0.15 0.07 0.07 0.11 0.07 0.08 0.15 0.09 0.11 SrO_pct <0.01 0.01 0.01 <0.01 0.01 <0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 BaO_pct 0.01 <0.01 0.05 <0.01 <0.01 <0.01 0.04 <0.01 0.03 <0.01 <0.01 <0.01 0.02 0.01 LOI 3.42 3.72 1.94 10.25 2.12 4.17 1.88 3.06 0.64 1.16 0.97 2.37 0.62 0.54 Total 98.74 98.4 99.73 98.51 98.96 98.98 100 98.32 98.66 98.73 98.35 99.9 98.52 98.83 FeO (tot) grams 23.62 10.53 12.58 11.90 10.76 15.95 23.27 24.20 18.26 15.71 14.77 13.43 12.80 12.05 Molar Fe2+/Fetotal 0.889 0.974 0.894 0.925 0.971 0.934 0.937 0.942 0.948 0.920 0.944 0.924 0.910 0.942 Magnetic Sus- ceptibility 60.0 1.26 N/A 1.74 N/A 3.44 2.26 2.26 1.57 3.48 1.35 0.80 4.70 0.97 *Amphibolite facies (amphibole-garnet-biotite-calcite-magnetite) with subsequent pyrite-pyrrhotite ± magnetite mineralization. Mineralization ranges in abundance from < 5 -15% of the sample. † One analysis of a duplicated sample. Both analysis are used in the figures, and are found in the Appendix B.9. This data was derived by lithium borate fusion methods. 190 Figure 4.35 Theoretical trends for oxidation, reduction, addition of hematite, magnetite and ankerite. OIB (ocean island basalt) Fe2+/Fe3+ data from Lai et al., (2004). between modern and ancient basalts could be due to alteration or the environment at the time of formation. The Balmer basalt formed 2.99-2.69 Ga in an oceanic environment (Fig. 4.30; Corfu and Andrews, 1987; Hollings et al., 1999; Sanborn-Barrie, et al., 2001). This was approxi- mately0.4 Ga prior to the great oxidation event at 2.30-2.45 Ga (Guo et al., 2009; Holland, 2009). With a reduced atmosphere and ocean, higher concentrations of Fe2+ would have been dissolved and contained in the seawater (Summer and Grotzing, 1996). In subsea hydrothermal systems, the fluid that affects the rocks is the seawater itself (Alt, 1995). It is possible that the Balmer basalt, which formed in a submarine island arc setting (Hollings et al., 1999; Sanborn- Barrie, et al., 2001) was altered by reduced Archean seawater. Least altered (MacGeehan et al., 1982) and altered samples (this study) from Red lake were taken from two different areas of the RLGB (Fig. 4.37). This study derived the altered samples from the mine and distal areas from along the cross sections. This area corresponds to an old classified domain — the ‘Western Volcanic Complex (WVC)’ (MacGeehan and Hodgson 191 (1980). The least altered samples from MacGeehan et al. (1982) — the only other publication to report Fe2+ and Fe3+ values — were derived from the ‘Eastern Volcanic Belt (EVB)’. Figure 4.37 indicates the locations of both sample suites relative to each other. Both areas comprise mafic- ultramafic units, and both are distinctive in their chemistry (Table. 4.11, 4.12 and 4.15). It is pos- sible that these two mafic packages are different volcanic episodes. The rocks from this study were significantly more altered than the MacGeehan et al. (1982) samples. These packages of rocks could have been affected by different fluids, or the Red Lake samples may have been af- fected by more hydrothermal episodes, enriching basalts there in Fe2+ relative to samples from the EVB. The altered Red Lake samples display a broad variation in FeO versus Fe2+/Fetotal molar ratios (Fig. 4.36). The Fe2+/Fetotal molar ratio is affected by two processes, (1) pre-regional metamorphic hydrothermal alteration; and (2) overprinting mineralization. The early pre- metamorphic hydrothermal alteration caused heterogeneity in the bulk rock composition. Early hydrothermal alteration of the basalt could have caused reduction, or addition of Fe2+. Either would have formed Fe2+ porphyroblastic minerals (garnet and amphibole) during peak- metamorphism. Another influence on bulk rock Fe composition is post-metamorphic sulfides and magnetite related to the mineralization stage. The total Fe abundance between non- mineralized and mineralized samples is fairly similar (11–24 grams and 16–24 grams FeO total respectively). However, the molar Fe2+/Fetotal ratio does vary from non-mineralized, 0.89–0.97, to mineralized 0.89–0.94. The mineralized samples display a slightly lower Fe2+/Fetotal ratio (on av- erage) compared to the non-mineralized samples (Fig. 4.36). This is only a subtle shift, but a change in oxidation state of the iron is recorded between non-mineralized and mineralized sam- ples. The similar total FeO but changed Fe2+/Fetotal ratios would confirm sulfidation reactions oc- curred at Red Lake to form the ore-stage sulfides and magnetite. The Fe would have been locally sourced (e.g. from the wall rock, garnet or amphibole porphyroblasts) and used to precipitate overprinting ore-stage sulfides and magnetite. Both pyrrhotite and magnetite contain Fe2+ and Fe3+ (Pratt et al., 1994). The formation of pyrrhotite and magnetite would have influenced the Fe2+/Fetotal molar ratio as the Fe2+ and Fe3+ abundance has changed. The multiple superposed hydrothermal episodes at Red Lake have significantly altered the Fe oxidation state. The ferric versus ferrous investigation of metamorphosed and mineralized samples indicates that at the time of regional metamorphism the basalt was Fe2+-rich. This enrichment in Fe2+ had to have occurred prior to peak-metamorphism as both garnet and amphibole are significantly Fe-rich. 192 Figure 4.36 Variations in ferric and ferrous iron of basalt. A) Correlation of least altered (MacGeehan et al., 1982) and altered rocks at the RLGM (this study) compared to modern MORB (Thompson and Melson, 1972 and refer- ences therein), T-MORB (Mehl et al., 1991), OIB (Lai et al., 2004), Archean tholeiitic basalt (Peloquin, 1990) and a calculated titration curve for progressive addition of 1 mole of Fe2+. B) Comparison of least altered (MacGeehan et al., 1982) and altered rocks at the RLGM (this study) in relation to a calculated titration curve for progressive addi- tion of 1 mole of Fe2+. Arrows indicate visual differences between samples with those contained at high FeO totals containing sulfides and abundant magnetite. 193 194 Figure 4.37 Locations of samples used for Fe2+/Fetotal ratios from this study and approximate locations of MacGee- han and Hodgson (1980) and MacGeehan et al., (1982). EVB = Eastern Volcanic Belt and WVB = Western Vol- canic Belt defined by MacGeehan and Hodgson (1980). Samples from along the cross sections (A-A’ and B-B’) are more Fe2+ rich, surrounded by samples collected by MacGeehan and Hodgson (1980) and MacGeehan et al (1982) from the EVB, which contain lower Fe2+/Fetotal ratios. 4.6 Chemical vectors, and footprints to mineralization During this investigation patterns of alteration and geochemical features were focused upon, particularly in terms of enrichment or occurrence with physical proximity to gold zones. Therefore, alteration and enriched elemental abundances proximal to known ore zones were identified as pathfinder or footprint features that can potentially aid exploration. A pathfinder or footprint element displays an excellent correlation with gold mineralization. The identified path- finder elements can be used to aid exploration for Archean lode-gold deposits (Prendergast, 2007). Lithogeochemistry is most widely utilized to identify specific pathfinder elements (Pren- dergast, 2007; Bourzai, 209). However, mineral chemistry trends of specific minerals known to be associated with mineralization can be just as useful in expanding the exploration target (Davis et al., 2001). At Red Lake, the superposed nature of the alteration assemblages created a complex spa- tial and temporal arrangement (Fig. 3.2 and 3.28). The simplest interpretation of the overprinting events at the RLGM is an early widespread event, overprinted by a narrower ore-forming event. Both events influenced mineral chemistry and bulk rock geochemistry. Each hydrothermal event also demonstrates chemical differences from proximal to distal expressions that can be useful for exploration. The compiled mineral assemblage zonation surrounding the RLGM (Fig. 3.28) will be referenced to aid in the understanding and interpretation of pathfinder elements and mineral chemistry changes. The chemical trends defined below are derived from basalt samples only: both type 1 and type 2 as chemically defined in section 4.5.2. The key pathfinder elements iden- tified using lithogeochemistry and mineral chemistry for the RLGM will be summarized below. 4.6.1 Lithogeochemistry; pathfinder elements – vectors to ore In this study pathfinder elements were identified as enriched proximal to mineralization. Therefore, patterns of enrichment spatially and temporally associated with the gold-forming event at the RLGM were identified. Pathfinder elements, in the Red Lake area, are the cumula- tive effect of all overprinting events in the RLGM. As a result, these elemental trends were influ- enced by both early hydrothermal alteration and the overprinting ore-formation event. The ele- 195 ments which defined metasomatic alteration (through mass balance calculations) during the early hydrothermal and ore-forming events were used to identify pathfinder elements. The lithogeo- chemistry study as part of this project identified both trace and major pathfinder elements rang- ing from 100’s to 1000’s of meters from mineralization. The clearest pathfinder elements within the Balmer basalt are centered on mineralization at the RLGM. Consequently, they are likely part of the mineralization stage. The hydrothermal fluids infiltrated the surrounding rock pack- ages around the RLGM causing enrichments up to 5 km from mineralization. The narrowest halos (≤ 500 m) enveloping mineralization at the RLGM are exhibited by As, Au, Bi, Mo, Ni, Sb and W (Table. 4.16 and Fig. 4.37). Minor enrichments of Ag and Cu are seen in one or two samples, 0–200 m from mineralization (Fig. 4.37). These elements are typi- cally enriched in brown biotite-quartz altered, mineralized and/or quartz-ankerite + selvage sam- ples (Table 4.12). The enrichment of Ag, As, Au, Bi, Cu, Mo, Ni and Sb are related to the pres- ence of abundant ore-minerals: pyrite, pyrrhotite, arsenopyrite, molybdenite, stibnite, sphalerite, chalcopyrite, magnetite and gold (see Chapter 3, Figs. 3.23 and 3.24). Sulfides of pyrite, pyr- rhotite, chalcopyrite and sphalerite from pyritic gold, carlin and orogenic gold deposits are known to contain trace amounts of the elements listed (Hawley and Nichol, 1961; Axelsson and Rodushkin, 2001; Abraitis et al., 2004). Magnetite from iron-ore deposits and iron-formation hosted orogenic deposits is also known to contain trace amounts of Cd, Cu, Mn, Ni, V and Zn (Kisvarsanyi and Proctor, 1967; Kolb et al., 2004). Tungsten enrichment is thought to be associ- ated with molybdenite, due to the association of minor tungestenite or tungstenoan molybdenite in pegmatite ores (Barkov et al., 2000). Narrow halos of La were also displayed at the mine scale, but in type 2 basalt only (Fig. 4.38). Compared to type 1 basalt, type 2 basalt contains a higher concentrations of La, regardless of location relative to ore, which implies a host rock composition control on the distribution and concentration of La. Broader km-scale features are demonstrated by Ba, Li, Rb and Zn. Barium and Zn show enriched abundances up to 3 km distally (Fig. 4.38). Lithium and Rb demonstrate a wider halo, up to 5 km from mineralization (Fig. 4.38). The km-scale features are typically displayed in bio- tite-Ti-magnetite ± carbonate altered, regionally metamorphosed (chlorite-amphibole-epidote- biotite-calcite ± garnet ± magnetite) and ankerite-calcite veins + selvage samples (Table 4.12). The widespread elements Rb and Li substitute for K ions with biotite, which is present up to 7 km from mineralization (Figs. 3.28 and 4.38). Barium, present in carbonate, can exchange for 196 another 2+ cation (Ca, Mg or Fe). The enrichment of Ba at the mine is likely due to the increased abundance of carbonate veins. Accompanying the trace pathfinder elements, major elements K2O, and SO3 show a pro- gressive increase towards known ore zones (Fig. 4.37). Of those, SO3 forms the narrowest halo, < 500 m distally. K2O (similar to Rb) gradually increase over 5 km. FeO, CaO and MgO are poor indicators, as they are enriched throughout the RLGM and surrounding area. FeO, CaO and MgO are most concentrated, but considerably scattered at the ore zone scale (Fig. 4.38). Outside of this highly altered halo the FeO, CaO and MgO compositions indicate very little variation. The wide ranging FeO, CaO and MgO concentrations proximal to mineralization is because of abundant veins, sulfides and associated alteration. MnO, although varying at the mine scale from 0–1.1 wt% has a wide halo of elevated MnO (0.6–0.9 wt%) which is present at < 3.3 km, with a sharp decrease of <0.6 wt% MnO at distances >3.3 km distally (Fig. 4.38). Table 4.16 Summary of pathfinder elements at the RLGM Pathfinder element Background concentration Estimated width of anomaly Au <0.02 (ppm)* ≤500 m, but most affective < 100m distally Ag <0.3 (ppm) ≤500 m, but most affective < 100m distally As <1000 (ppm) ≤300 m distally Ba < 105(ppm)** ≤5 km distally, but most effective ≈ 1 km distally Bi (weak relationship) <0.5 (ppm) ≤300m from ore, most affective < 100m distally Li <25 (ppm) † Potentially ≤5 km distally Ni <240 (ppm) ‡ <200 m distally Mo <5 (ppm) <500 m distally Rb <50 (ppm) ** ≤2.5 km distally Sb <20 (ppm) < 500 m distally Sn <1.25 (ppm) 500 m distally Tl <1 (ppm) 250 m distally W <20 (ppm) 500 m distally Zn <170(ppm) ** ≤2-3 km distally CaO <15 wt% < 1 km distally K2O <1 wt% Potentially ≤ 5 km distally SO3 <5 wt% 500 m distally * (Bouzari, 2007), **(Tomlinson et al., (1998), † (Pirie,1981), ‡ (Tarnocai, 2000). The elements listed are the most relatively mobile and consistent with ore-stage sulfides and alteration assemblages (see Chapter 3). To summarize, trace elements identified by lithogeochemistry display the sharpest con- trasts between background and enriched values. Pathfinder elements could potentially be used up to 5 km from mineralization (Fig. 4.38). The clearest pathfinder elements however, display a nar- rower envelope of up to 1 km, but most clearly < 500 m from mineralization. These elements are As, Ag, Au, Bi, Cu, Mo, Ni, S, Sb and W. Broader (< 5 km), but less clear, pathfinder elements were identified as Ba, Li, K, Rb and Zn. These pathfinder elements are associated with the over- 197 Figure 4.38 Variation of element abundance derived from four acid digestion methods with increasing distance from mineralization at the RLGM. The elements which were shown to have been added during either the early hydro- thermal or overprinting ore-formation hydrothermal events were included. The key is universal for all following continuations of figure 4.38. Estimated distance from ore is in meters, which is also universal for all the following continuations of figure 4.38. 198 Figure 4.38 (Continued). 199 Figure 4.38 (Continued). 200 printing H2 event; therefore reflect the major auriferous event which was a narrower structurally- controlled event which overprinted the metamorphosed basalts. These findings support previous exploration research at Archean lode-gold deposits by the identifications of Ag, As, Sb, Bi, Mo and W shown to be associated with gold (c.f. Prendergast, 2007; Bouzari, 2009). 4.6.2 Mineral chemistry vectors Mineral chemistry data from carbonate, chlorite, biotite, garnet and amphibole provide chemical trends that vector to ore. This study’s findings are summarized in figure 4.39. The min- eral chemistry trends are mostly exhibited due to the superposed nature of metamorphosed early altered basalts (H1 and M2) overprinted by the narrower ore-forming (H2) event. Early pervasive, metamorphosed basalts demonstrate widespread minerals which are generally very Fe2+-rich (see mineral chemistry section above). These were then overprinted by the narrower H2 event which was dominated by veins, Mg-rich minerals and mineralization. The mineral chemistry variations are discussed below. The most useful mineral chemistry trend is exhibited by carbonate minerals. This investi- gation confirmed the previously identified ankerite core associated with mineralization envel- oped by distal calcite (MacGeehan et al., 1982; Parker 2000; Figs 4.21, 4.22 and 4.23). The pres- ence of ankerite veins can extend the exploration target to > 1 km for Red Lake deposits. The pattern of proximal ankerite and distal calcite can be explained by the overprinting nature of al- teration assemblages. Early, pervasive and widespread calcite (metamorphosed H1 alteration) is overprinted by a narrow, structurally controlled ankerite vein event (during H2) (Fig. 3.2). Chlorite distribution weakly demonstrates Mg-grey chlorite and Fe-Mg-brown chlorite more abundant proximal to ore, with Fe-blue chlorite more abundant distally (Fig. 4.5). Similar to carbonate chemistry, the distribution of chlorite can be explained from overprinting events. The early chlorite is metamorphic in origin and formed in the prograde sequence Fe-blue to Fe- Mg-brown to Mg-grey. Distal Fe-chlorite is preserved as inclusions in later porphyroblastic min- erals and comprises < 5% of the rock. Proximal pervasive chlorite is Mg-rich and abundant in the matrix at the mine which displays greenschist facies mineralogy. Mg-chlorite typifies the greenschist to transitional metamorphic facies. This zonation of metamorphic pervasive chlorite is overprinted by chlorite selvages to ankerite-calcite ± quartz veins formed during H2 (Fig. 3.2). Ankerite-calcite ± quartz veins are abundant at the mine site, localized into D2 structures. These 201 Figure 4.39 Summary of mineral chemistry trends exhibited by chlorite, biotite, amphibole, carbonate and garnet at the Red Lake Gold Mines. chlorite selvages are also Fe-, Fe-Mg- and Mg-rich. However, Fe-rich chlorite selvages are the most abundant. Biotite reflects a similar trend to chlorite. Distal occurrences of biotite are Fe-rich, with proximal occurrences containing Mg-rich compositions. Biotite chemistry, too, is the result of overprinting biotite stages. The early biotite phase, which resulted from metamorphosed altered basalt, is widespread and Fe-rich. Overprinting the early biotite is brown biotite, which is associ- ated with gold mineralization and formed during H2. The brown biotite is Mg-rich and localized to ≤ 100 m from mineralization. Biotite chemistry also demonstrates subtle trends, with increas- ing K and AlIV towards shallower levels. These trends are exhibited by both pervasive and brown biotites. Both garnet and amphibole chemistry vary over larger distances than chlorite and biotite. The porphyroblastic minerals display progressive enrichment in Mn, and Fe2+ towards minerali- zation, from a distance of > 4 km. Sodium, Fe3+, Mg and Ca are noted to decrease in abundance with increasing proximity toward mineralization. Unlike chlorite and biotite, garnet and amphi- bole do not display strong chemical trends with depth. This is possibly due to the metamorphic control, as neither mineral is abundant until the amphibolite facies at depth in the RLGM. The mineral chemistry trends indicated by specific minerals, e.g. biotite, do not necessar- ily reflect bulk rock trends, but rather superposed events. Both Mg-rich chlorite and biotite are 202 abundant proximal to ore. However, whole rock chemistry indicates proximal enrichment in both Mg and Fe due to the presence of Fe-sulfides and Mg-bearing silicates and carbonate. Regardless of the method (either mineral chemistry or whole rock geochemistry), pathfinder elements are identifiable. It is important to know what was analyzed and their paragenetic relationships in or- der to fully interpret the chemical trends observed. The elements: Au, Ag, As, Bi, Cu, Ni, S, Sb, Mo, W, Ba, Li, K, Rb and Zn, and mineral assemblages (e.g. brown biotite) associated with the ore-forming stage provide the clearest pathfinders at the RLGM. 4.7 Summary of the controls on composition and distribution of minerals The chemical analysis of the superposed alteration minerals and assemblages have aided in understanding the geological evolution of the RLGM. Figure 4.40 summarizes the geological events, and the chemical influences on bulk rock and mineral compositions at the time of mineral formation. The most influential events are suggested to have been early hydrothermal alteration (H1), regional metamorphism (M2), and the ore-forming hydrothermal stage (H2). These geologi- cal events affected the bulk rock and fluid chemistry, as well as physical conditions. The early hydrothermal (H1) event affected the basalt bulk rock composition prior to re- gional metamorphism (Mathieson, 1982; This study). Three different early metamorphic assem- blages were identified in the Balmer basalt: biotite-Ti-magnetite ± carbonate, greenschist- amphibolite and quartz-muscovite-andalusite. Each of these assemblages demonstrated slightly different mass balances (Table 4.14) and was concluded to reflect metamorphism of dissimilar precursor assemblages (Chapter 3). From the petrographic observations and geochemical data, there is an indication that the H1 event itself contained superposed alteration. A detail discussion regarding the nature and environment of early H1 alteration will be discussed in Chapter 6. Here, the most significant and generalized gains and losses are discussed for each hydrothermal phase. Bulk rock compositions of early metamorphic samples indicated that during early hydro- thermal alteration the rock was reduced, or Fe2+ was added. This reduction or Fe2+ gain was not universal for all RLGB basalts. Only samples from the RLGM and surrounding area of the WVC (Fig. 4.37) demonstrate this Fe2+ enrichment. This was interpreted as separate volcanic flows, or alternatively, separate fluids affected the RLGM rocks rather than those elsewhere in the RLGB. The Fe2+ enrichment was accompanied by a generalized enrichment in Mn, K, Si and loss of Ca and Na. This event is considered to have been widespread, affecting a large area of the RLGB. This is suggested as early mineral assemblages, which invoke a necessary H1 event, are found > 203 Figure 4.40 Schematic diagram showing the major geological phases of the RLGM’s development with added chemical characteristic of H1 and H2 events. BA) Balmer assemblage, BC) Bruce Channel assemblage, LVL) little Vermillion Lake batholith, DL) Douglas lake pluton, Dm) Dome stock, MK) McKenzie stock, ABG) Abino grano- diorite, HD) Howey diorite, HLB) Hammell Lake Batholith, KB) Killala-Baird batholith, WL) Walsh Lake pluton, CI) Cat Island pluton, H) hydrothermal event, M) metamorphic event, D) deformation event, P) plutonic event. De- formation details compiled from Sanborn-Barrie et al. (2001) and Dubé et al. (2004). Intrusion emplacement ages from, Corfu and Wallace, (1986), Corfu and Andrews (1987), and McMaster (1987). Yellow stars indicate gold- mineralization event. For mineral abbreviation, refer to list of abbreviations. 7 km from ore. The H1 event would have formed the precursor mineral assemblages of the now preserved, metamorphic equivalent assemblages which are observed today. This precursor as- semblage is considered to be composed of clays, chlorite, carbonate, mica (biotite) and argillic 204 alteration. This H1 event caused localized heterogeneity in the bulk rock composition. This is known as metamorphic assemblages vary slightly in their mineralogy due to fluctuations in the bulk rock composition at the time of regional metamorphic growth. The M2 metamorphic event had a significant control on the distribution of metamorphic minerals. At the onset of this metamorphic event the early mineral assemblages were created. These early assemblages include (in paragenetic order), biotite-Ti-magnetite ± carbonate, the re- gional metamorphic assemblage of chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± gar- net ± magnetite and quartz-muscovite-andalusite. The prograde metamorphic sequence is pre- served in the chlorite birefringence colours, where grey (Mg-) chlorite and brown (Fe-Mg-) chlo- rite is dominant in the greenschist facies and then disappears in the amphibolite facies. The distal blue chlorite is in minor abundance (< 5% of the total rock) and preserved only as inclusions in garnet and amphibole porphyroblasts. As inclusions, the blue chlorite would have been protected from further metamorphic break down, thus, preserved. The sequence of metamorphic chlorite is consistent with Spear (1993). The distribution and chemistry of amphibole is controlled, to some degree, by metamorphism. Amphibole chemistry is also affected by the bulk rock composition at the time of growth, and therefore is Fe2+-rich. In the transition facies both non-calcic and calcic amphiboles are preserved. A zonation from non-calcic cores to calcic rims is observed. At hotter, amphibolite conditions, only calcic amphibole is preserved. Garnet, like calcic amphibole, is most frequently observed in amphibolite facies rocks; therefore, distally and at depth in both mine complexes. The Fe2+-Mn-rich garnets necessitated the required pre-M2 hydrothermal en- richment of Mn and Fe2+ to the host rock before metamorphism. The M2 metamorphic event was synchronous with D2 deformation and the ore-forming hydrothermal event (H2). D2 is prevalent in the preservation of the main foliation (S2) fabric by all metamorphic assemblages (see Chapter 3). This deformation event caused brittle-ductile de- formation which is intensely localized at the RLGM. Here, D2 structures were the main fluid conduits for the ore-stage hydrothermal event (H2). The H2 event formed ankerite-calcite ± quartz veins, quartz ± sulfides veins and accompanying selvages of brown biotite and quartz al- teration. Thermometry calculations indicated that the carbonate veins formed post-peak regional metamorphism, but still within a hot environment. Each of these veins and alteration is con- trolled significantly by the fluid composition. However, bulk rock compositional differences be- tween type 1 and type 2 basalts were displayed by the La enrichment in type 2 basalts only. Mass balance calculations of veins + selvages, brown biotite and quartz ± sulfide assemblages indicate 205 that this H2 event caused enrichment of Ca, K, Mg, S, Si, As, Ag, Au, Sb, Ni, Rb, W and Zn with an accompanied loss in Na. It is suggested that sulfidation reactions occurred to form the abun- dant sulfides and magnetite in the ore zones at the RLGM. This is suggested by localized re- placement of Fe2+-rich wall rock (Fig. 3.24) and Fe2+-rich garnet (Fig. 3.11B). Redox differences are implied from the ferric versus ferrous analysis of bulk rock samples (Fig. 4.35). Non- mineralized and mineralized samples display similar total FeO abundances. However, the non- mineralized samples generally indicate higher Fe2+/Fetotal molar ratios than the mineralized sam- ples. This suggests a change in oxidization state of Fe. The influence and significance of this suggested redox difference on ore formation will be discussed in detail in Chapter 6. 4.8 Conclusions and future discussion This chapter demonstrated the application of mineral chemistry and whole rock geo- chemistry to the previously established paragenesis (Chapter 3). The key findings of this chapter are summarized below:  Whole rock geochemistry and mineral chemistry can be used to infer hydrothermal and metamorphic conditions.  Mass balance differences between least altered and key alteration assemblages provided chemical conditions for the early pre-hydrothermal event and ore-forming event. The pre- regional metamorphosed altered rocks demonstrated various mass balance differences. The biotite-Ti-magnetite ± carbonate assemblage displayed K, S, Si, As, Ba, Rb, Sb, Li, Ni and W gains with Ca, Fe, Mg, Na, Cu, Sr and Zn loss. The regional metamorphic as- semblage (chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± garnet ± magnetite) demonstrated gains in Fe2+ (significant), Mn, Na, S, Cu, Sr, Zn and Li with accompanied loss of Ca, K, Si, Mg, Ba, Rb and Sb. Finally, the quartz-muscovite-andalusite assem- blage showed gains in K, Si, As, Cu and Rb with loss of Ca, Fe, Mg, Na, Ba, Li, Sr, W, Sb and Zn. The overprinting ankerite-calcite-quartz and quartz-ankerite veins demon- strated gains in Ca, Fe, K, Mg, Si, Ni and Zn. The ankerite-calcite-quartz veins demon- strated loss of As, Ba, Cu, Li and Rb. The ore forming hydrothermal event (quartz- sulfide-brown biotite assemblages) enriched the basalt host rock in Ca, Si, S, Mg, K, Au, As, Sb, Cu, Ni, Rb, W and Zn with corresponding depletion in Fe, Mg and Na. 206  The identification of Fe2+-rich metamorphic garnet and amphibole, combined with FeO- rich regionally metamorphic basalt, imply that an early reduction of the host rock oc- curred prior to regional metamorphism.  Whole rock geochemistry identified these potential footprint elements: As, Ag, Au, Bi, Cu, Mo, Ni, S, Sb and W, which are most effective < 1 km from mineralization. Broader (< 5 km), but less clear pathfinder elements were identified as Ba, Li, K, Rb and Zn. These elements were added during the overprinting ore-formation event (H2), and are linked with the metasomatic alteration associated with gold-mineralization.  Thermometry calculations confirmed garnet and carbonate veins were formed during peak-metamorphic conditions. The temperatures of approximately 420-490°C are compa- rable with previous P-T conditions for the Red Lake area.  Mineral chemistry trends help to unravel the complex nature of superposed events at the RLGM. Early widespread regional metamorphic minerals are generally Fe-rich. This early metamorphic event was overprinted by the ore-forming event. Minerals related to the ore-forming event are more Mg-rich.  Mineral chemistry also demonstrated vectors to ore. Both chlorite and biotite become in- creasingly Mg-rich proximal to mineralization. Garnet and amphibole become increas- ingly Mn- and Fe2+-rich toward mineralization. The proximal occurrence of ankerite with distal calcite (MacGeehan et al., 1982; Parker, 2000) was also identified in this study.  The mineral and bulk rock chemistry and mineral distribution is most affected by H1 – early pre-metamorphic hydrothermal alteration, M2 – peak regional metamorphism and H2 – the ore forming hydrothermal alteration event. The data presented herein will be synthesized in Chapter 6. Several topics will be discussed and assessed: (1) The nature and environments of hydrothermal alteration required to create the as- semblages characterized in this study; (2) the evolution and ore genesis of the RLGM; and (3) sources, precipitation mechanisms and the influence of metamorphism on ore formation. 207 Chapter 5: Stable isotopes of Carbon, Oxygen and Sulfur from the Red Lake Gold Mines: implications for fluid sources 5.1 Introduction Stable isotopes of carbon, oxygen and sulfur can provide information to decipher the evo- lution and development of ore forming systems. This includes implications for fluid sources, es- timation of fluid-rock interaction, physical and chemical conditions of the fluid and physical conditions of ore formation (Ohmoto 1972; Landis and Rye, 1974; Taylor and O’Neil, 1977; Ohmoto and Rye, 1979; Ohmoto, 1986; Jia and Kerrich, 2000; Jia et al., 2001). Practically, iso- topes of sulfur and oxygen have been used to expand the exploration target of porphyry systems through the identification of fluid characteristics and the mappable extent of fluid-rock interac- tion (Cathles, 1993; Wilson et al., 2007). Within Archean lode-gold deposits, stable isotopes have been used to identify isotopic trends and fluid sources (Goldfarb et al., 2005 and references therein). This study utilized carbon, oxygen and sulfur isotopes to identify: (1) fluid sources for ankerite-calcite ± quartz veins and the mineralization event; (2) assess the affect of metamor- phism on ore-formation; and (3) variations in isotopic composition to construct vectors to miner- alization (e.g. Rye and Ohmoto, 1974; Ohmoto and Rye, 1979; Taylor, 1987; Wilson et al., 2007). This chapter contains the methodology and discussion relating to fluid sources and zona- tion exhibited by the stable isotope data from Red Lake. 5.2 Stable isotopes from Archean lode-gold deposits In Archean lode-gold systems, carbon isotopes from carbonate minerals indicate negative δ13C values of 0 to -10 per mil (PDB) (Kerrich, 1989, 1990; Goldfarb et al., 2005). The negative δ13C has been attributed to a number of possible sources. These suggested fluid sources are: (1) mantle carbon (Fyon et al., 1984; Cameron, 1988); (2) magmatic fluids (Burrow et al., 1986; Burrows and Spooner, 1987); (3) metamorphic devolatilization of biogenic carbon (Kontak et al., 1988); and (4) fluid mixing, fluid-rock interaction or fluid immiscibility (McCuaig and Kerrich, 1998). Oxygen isotopes are documented to range between δ18O 3–16 ‰ (SMOW) in Precambrian lode-gold deposits (Colvine et al., 1988; Kerrich, 1990; Hagemann et al., 1994; McCuaig and Kerrich, 1998). It has been suggested, and then refuted that these δ18O values indi- cate meteoric sources (Hagemann et al., 1994; Hagemann and Luders, 2003). As a result, fluid sources from oxygen isotopes in Archean lode-gold systems remain elusive. 208 Sulfur isotopes from Archean lode-gold deposits typically range between δ34Ssulfide mineral 0 to +9 per mil (CDT) (Kerrich, 1987, 1989; Golding et al., 1990; McCuaig and Kerrich, 1998). It has been suggested that the sulfur-bearing fluid source in these systems has two possible origins. Fluids are either derived from the surrounding wall rock by metamorphic processes (Sangster, 1992; Goldfarb et al., 1997) or from magmatic intrusions (Golding et al., 1990; Goldfarb et al., 2005). Sulfur isotopes have also been used to imply redox conditions. Redox reactions are known to influence gold-precipitation (Evans et al., 2006; Halley, 2007; Neumayer et al., 2008; Evans 2010). Gold is usually transported as a reduced bi-sulfide complex, or less frequently as a chloride complex (Gilbert et al., 1998). One possible way of causing gold to precipitate is to oxi- dize the fluid to create aqueous sulfate. The sulfate ligand does not bond as well with gold which induces precipitation (Phillips and Powell, 2010). It has been reported that gold mineralization has occurred at redox boundaries for lode-gold deposits in Western Australia (Halley, 2007; Neumayer et al., 2008). Consequently, sulfur isotopes can not only suggest fluid sources and physical conditions but also influences on the gold precipitation event. 5.3 Stable isotopes from the Red Lake Gold Mines Previous research from the RLGM either used carbon and oxygen, or sulfur to identify fluid sources. Carbon and oxygen isotopes were derived from carbonate samples across the RLGB (Kerrich, 1990; El Bilali and Hattori, 1998; Tarnocai, 2000). Carbon isotopes have been documented to range between +0.06 to +4.24 ‰ δ13CPDB (Tarnocai, 2000). Oxygen isotopes have been reported to range between +8.9 to +18.1 ‰ δ18OSMOW (Kerrich, 1990). Both carbon and oxygen isotopes have been reported as uncharacteristically high compared to other Archean lode-gold deposits (Kerrich, 1990; Tarnocai, 2000). This isotopic enrichment has previously been explained by: (1) fluid immiscibility between CO2 and CH4; (2) a magmatic influence; or, (3) Rayleigh fractionation during carbonate mineral precipitation or cooling of the fluid (Kerrich, 1990; Tarnocai, 2000). Sulfur isotopes at the RLGM have previously been used to characterize specific ore bod- ies (Lavigne and Crocket, 1982; Lavigne, 1983; Kerckhoff, 2003). From these data fluid sources were determined. The East South ‘C’ (ESC) ore zone (Fig. 1.6) is documented to range from δ34SPY +0.82 to +6.21 ‰ (CDT) (Lavigne and Crocket, 1982). Likewise, the High Grade Zone in the Red Lake Complex exhibited positive sulfur isotopes ranging from δ34SH2S +4 to +7 (CDT) (Kerckhoff, 2003). Graphitic BIF packages associated with the ESC ore zone contain δ34SPY 209 ranging between -6.10 to +4.38‰ (Lavigne and Crocket, 1982). BIF packages located near the High Grade Zone also display negative to weakly positive sulfur isotopes of δ34S -0.5 to 2.1‰ (Kerckoff, 2003). From this data the sulfur source for the gold forming event at Red Lake has been suggested as magmatic (Lavigne and Crocket 1982; Kerckhoff, 2003). The sulfur isotopic fractionation within the deposit was interpreted as resulting from variable temperature, pH, ƒO2 or ƒS2 (Kerckhoff, 2003). The negative δ34S values demonstrated by the sediment hosted sulfides were interpreted to be syn-genetic, formed in anoxic conditions by sulfide reducing bacteria (Lavigne and Crocket 1982; Crocket and Lavigne, 1984). 5.4 Methodology 5.4.1 Carbon and oxygen isotopes δ13CVPDB and δ18OVSMOW isotope ratios were obtained from powered carbonate vein and altered basalts. Powered sample was obtained by drilling the carbonate vein or altered host rocks using a Drexel Multipro 225T2 drill with diamond tipped bits. The carbonate sample was then assessed for its isotopic compositions at the University of British Columbia (UBC). The meas- urements were made on a Los Gatos Research (LGR, model 908-0021) analyzing instrument. An off-axis integrated cavity output spectroscopy (OA-ICOS) technique, outlined by Barker et al. (2011) was used. The carbonate sample was reacted with phosphoric acid to produce CO2 gas. The CO2 gas was then assessed for δ13C and δ18O ratios. The δ13C and δ18O were recorded from absorption spectra of 12C16O16O, 13C16O16O, and 12C16O18O peaks in the near-infrared wave- length region. Prior to analyses the dominant carbonate mineral (ankerite or calcite) was con- firmed by SEM-EDS. Barker et al. (2011) recommended 35 mg of pure calcite. However, as the samples contained a mix of ankerite, calcite and quartz more material was necessary, i.e. 45–50 mg for ankerite-rich samples and 60–70 mg for quartz-ankerite samples. The OA-ICOS technique was limited to the analysis of barren ankerite-calcite ± quartz veins. The reaction between phosphoric acid and sulfide minerals (pyrite, pyrrhotite and arseno- pyrite) created H2S gas. The H2S gas interfered with the produced CO2 gas by displaying an overlap with the key 13C16O16O and 12C16O16O infrared absorption peaks. This caused interfer- ence on both δ13C and δ18O ratios. As a result no mineralized vein samples were analyzed. Oxy- gen isotopes were corrected for fractionation with phosphoric acid prior to interpretation using the formula outlined by Rosenbaum and Sheppard (1986). 210 Previous research defined an analytical uncertainty of better than 0.5‰ δ13C and δ18O (Barker et al., 2011). In addition to the published uncertainty an additional quality control was applied based on four duplicated samples. Each duplicate was run three times. An internal error was defined as approximately δ13C ± 0.13 (1σ) and δ18O ± 0.70 (1σ) (see Appendix C.1). In total, 59 samples were analyzed using the OA-ICOS technique. Samples were derived from both cross sections (Fig. 5.1) and the mapped outcrop (Appendix A.4). The aim was to characterize each paragenetic stage of the carbonate vein sequence (Fig. 3.2). Subsequently, sev- eral paragenetic stages of carbonate were assessed (Fig. 5.2). The initial pervasive carbonate, part of the regional metamorphic assemblage was only sampled from sample CR469-41.6. The limited number of older pervasive carbonate samples was due to low abundance of this carbonate phase and the abundance of disseminated sulfides within samples which interfered with data col- lection. A subset of 10 samples (including standards and duplicates) were analyzed at the GNS Stable Isotope Laboratory in New Zealand for comparative review. Carbonate samples were ana- lysed for δ13C and δ18O on the GVI IsoPrime Carbonate Preparation System at 80oC and run via dual inlet on the IsoPrime mass spectrometer. All results were reported with respect to VPDB. Values were normalized to an internal standard, the GNS marble, with reported values of 2.04‰ for δ13C and -6.40‰ for δ18O. The external precision for these measurements are 0.05‰ for δ13C and 0.15‰ for δ18O. The ankerite samples were corrected using Rosenbaum and Sheppard (1986). To compare with the UBC laboratory, the GNS δ18O data was converted from VPDB relative to VSMOW using, δ18OVSMOW = 1.03091 * δ18OVPDB + 30.91 (Coplen et al., 1983). Ap- pendix C.1 provides the quality control for both laboratories. The data from both laboratories is comparable with δ13C differing by approximately 0.15‰ and δ18O by 0.9‰. It was found that the geological variations between carbon and oxygen isotopes at Red Lake are significantly greater than the analytical differences between laboratories. 5.4.2 Sulfur isotopes δ34SCDT isotopic compositions were obtained from medium to coarse, or massive fine- grained pyrite, pyrrhotite, sphalerite and arsenopyrite. Samples were selected from both mine complexes along the cross sections (Fig. 5.3). Hand samples containing coarse single sulfides (i.e. pyrite, or pyrrhotite) were drilled using a Drexel Multipro 225T2 drill with a diamond drill bit to produce mono-mineralic powders. Samples were then analyzed at the Central Science 211 Figure 5.1 Location of all carbon and oxygen isotopes (derived from carbonate) along both cross sections. A) Campbell, B) Red Lake. 212 Figure 5.2 Examples of carbonate veins. All samples are thin section cut offs of basalt samples allowing SEM-EDS identification of the carbonate mineral prior to isotope analysis. The carbonate veins are in paragenetic sequence. A) Pervasive carbonate (CR469-41.6). B) Cryptocrystalline-microcrystalline ankerite (ES09_AP_27). C) Medium- coarse ankerite-calcite vein (D33003-1106). D) Quartz-ankerite-calcite breccia containing host basalt (D14981- 1798.8). E) Colloform-crustiform (textured) ankerite-calcite vein (D22223-975). F) Ankerite-chlorite vein (D39357- 1308). G) Microcrystalline ankerite-calcite-quartz vein (D27943-2104.2). H) Fine-medium ankerite-calcite-quartz vein (37L768-98). I) Quartz-ankerite vein (37L549-815). J) Quartz-ankerite vein with brown biotite halo (34L235- 944). 213 Laboratory at the University of Tasmania, Australia. The isotope measurements were performed on a VG Sira Series II mass spectrometer using conventional methods (Robinson and Kasakabe, 1975). Previous research established an analytical uncertainty of δ34SCDT ± 0.1‰ (Wilson et al., 2007). This was derived from internal standards of homogeneous galena from Brown Hill (δ34S = + 3.5‰) and Rosebery (δ34S = 1.83‰). Internal standards were run with an SO2 reference gas of δ34S ≈ Cañon Diablo Troilite (CDT). These standards in turn were calibrated against interna- tional sphalerite standards IASA NZI (δ34S = +1.83‰) and NBS 123 (δ34S = +3.4‰). An addi- tional quality control was applied based on duplicates and blank samples (n = 13) (Appendix C.2). From the additional duplicates and blank samples sent for analysis, an internal error was defined as δ34S ± 0.29‰ (σ1). In total, 66 δ34S sulfide analyses were obtained (excluding duplicates). These samples are representative of pre-, syn- and post-mineralization occurrences (Fig. 5.3). Pre-mineralization sulfides are massive textured, cut by ankerite-calcite ± quartz veins and usually occurring as bands typically hosted by chert (BIF), cherty-argillite and argillite. Sulfide rich beds can display ductile deformation (Fig. 5.4A). Basalt hosted pre-mineralization sulfides were identified as massive sulfide occurrences which were overprinted by ankerite-calcite veins. Syn- mineralization sulfides occur in a variety of textures associated with quartz and brown biotite. These textures include: replacement of ankerite-quartz veins or the wall rock, veins and/or dis- seminated massive sulfides (Figs. 3.23B, 3.24 and 5.4B). The mineralization styles investigated for sulfur isotopic variations were styles 1, 2, 3 and 4 (section 2.2.3, Chapter 2). Post- mineralization sulfides are rare but present in quartz-tourmaline-pyrite veins with K-feldspar- rich bleached halos (Fig. 5.4C). This vein type occurs in late lamprophyre dykes, which cut ore zones. Most sulfur isotope samples were derived from the mine scale. Here, sulfides are abun- dant, particularly in ore zones. Distal sulfide occurrences are in lower abundances than at the mine. As a result it was harder to obtain enough sulfide sample for analysis. Consequently, few distal samples were isotopically analyzed. Isotope data derived from pyrite, pyrrhotite and sphalerite was recalculated to provide estimated δ34SH2S for the mineralizing fluid. It was assumed that the sulfide minerals were in equilibrium with the fluid when precipitated. This allowed the direct comparison of each min- eral’s isotopic composition. The temperature of precipitation of the sulfides from the sulfide- bearing fluid was assumed to be approximately 350°C (or 623K) (Mikucki, 1998; Chi et al., 214 Figure 5.3 Location of all sulfur isotope samples indicating the lithology and relative timing of sulfide. A) Campbell, B) Red Lake. 215 Figure 5.4 Examples of pre-, syn- and post-mineralization sulfides. A) R87105-523.6; ductile deformation of pre- mineralization sulfide-rich bands in cherty-argillite. B) RL42-2M hand samples of the RLC 42-2 sub; high grade ore showing syn-mineralization massive sulfides (pyrrhotite-pyrite) replacing basalt. C) CR4612-272.2; a post- mineralization quartz-pyrite-muscovite-tourmaline vein cross cutting a lamprophyre dyke. 216 2003). This temperature was chosen as it is comparable with previous knowledge of the Red Lake system and Archean lode-gold deposits globally (Neall and Phillips, 1987; Mikucki, 1998; Chi et al., 2002, 2003, 2006, 2009). Calculation of the fractionation factors were derived using the formulae: 1000 ln αi – H2S = 0.4/6232 x 106 = 1.03 [pyrite] 1000 ln αi – H2S = 0.1/6232 x 106 = 0.26 [pyrrhotite] 1000 ln αi – H2S = 0.1/6232 x 106 = 0.26 [sphalerite] (Ohmoto and Rye, 1979) 5.5 Results 5.5.1 Carbon and oxygen isotopes Electron microprobe data (Chapter 4) demonstrated that the major element chemical composition of carbonate minerals differs with paragenetic stage (Fig. 4.20). Carbon and oxygen isotope data here confirm that the stable isotopic composition of carbonate minerals also varies (Tables 5.1 and 5.2; Fig 5.5). The earliest, pervasive calcite displays a distinctive isotopic com- position compared to veined samples (Kerrich, 1990; Tarnocai, 2000; this study). Pervasive cal- cite has a δ13Cand δ18O isotopic composition of -10.3 and +11.5‰ respectfully. This early, per- vasive calcite has not been analyzed for its isotopic composition previously (c.f. Kerrich, 1990; Tarnocai, 2000). As only one sample of pervasive calcite was successfully analyzed, it cannot be confirmed as characteristic. Cryptocrystalline-microcrystalline ankerite veins exhibit a range of - 0.05 to +1.58‰ δ13C and +13.57 to +16.99‰ δ18O. Medium-coarse ankerite-calcite veins dem- onstrate a range of -1.44 to +3.34‰ δ13C and +13.20 to +19.29‰ δ18O. Breccia ankerite-calcite- quartz ranges from +0.66 to +1.95‰ δ13C and +17.65 to +18.81‰ δ18O. Colloform-crustiform ankerite-calcite veins range from -1.62 to +2.54‰ δ13C and +14.06 to +20.46‰ δ18O. Ankerite- chlorate veins range from -3.55 to +2.65‰ δ13C and +12.15 to +20.67‰ δ18O. Ankerite-calcite- quartz veins have δ13C values of -4.64 to +4.03‰ and δ18O values of -2.67 to +21.44‰. The quartz-ankerite veins have δ13C values of -1.00 to +1.29‰ and δ18O of +9.95 to +20.90‰. Fi- nally, the syn-mineralization, quartz-ankerite with brown biotite selvage vein demonstrated a δ13C of -1.10‰ and δ18O of +14.27‰. All carbon and oxygen isotope data can be found in the Appendix (C.3). 217 Carbon and oxygen isotopes display a weak zonation centered on mineralization (Figs. 5.6 and 5.7). The variability of the data related to the spatial distribution and density of the sam- ples makes a challenging interpretation. However, a weak trend of enriched carbon isotopes does highlight areas of economic interest with depth. The highest δ13C values of ≥ +1.9 ‰ correlate with the richest ore zones in both complexes (Fig. 5.6). Gold is associated with 13C enriched car- bonate compared to distal occurrences (El Bilali and Hattori, 1998; Tarnocai, 2000; this study). A wider-ranging envelope, of up to 1 km, is demonstrated by δ18O values > + 18 ‰ at shallow mine levels, particularly in the Campbell complex (CBC) (Fig. 5.7). The enrichment in δ18O val- ues is best demonstrated proximal to gold-mineralization (Tarnocai, 2000; this study). At the mine scale, there is a mix of δ18O but a narrower halo of δ18O values > +19.6 ‰ (CBC) and δ18O values > +18.0 ‰ in the Red Lake complex (RLC) can be identified approximately 0–200 m from ore. The distribution of carbon and oxygen isotopic compositions is indicated in the data regardless of the carbonate mineral (ankerite or calcite) or the relative timing of the veins. Each paragenetic vein type is considered part of the ore-forming event synchronous with D2. The heaviest δ18O and δ13C isotopic compositions are proximal to ore zones, approximately 200 m above the highest gold grade areas of the High grade zone and Deep Campbell zone (Fig. 1.6) of RLC and CBC respectively. Table 5.1 Summary of carbon isotopic compositions (δ13CVPDB ‰) Carbonate Type Minimum (δ13C ‰) Maximum (δ13C ‰) No. Analyzes Pervasive calcite -10.3 -10.3 1 Cryptocrystalline- microcrystalline ankerite -0.05 1.58 5 Medium-coarse ankerite- calcite -1.44 3.34 14 Breccia ankerite-calcite- quartz 0.66 1.95 2 Colloform-crustiform ankerite-calcite -1.62 2.54 8 Ankerite-calcite with chlorite selvage -3.55 2.65 6 Ankerite-calcite-quartz -4.64 4.03 20 Quartz-ankerite -1.00 1.29 2 Quartz-ankerite with brown biotite selvage -1.10 -1.10 1 218 Carbon and oxygen isotopes from the RLGB are enriched in both δ13C and δ18O com- pared to other Archean lode-gold deposits (Fig. 5.8; Goldfarb et al., 2005 and references therein). The isotopic compositions of carbonate veins collected in this study are comparable and consistent with previously reported carbon and oxygen isotopes from the CBC and other miner- alized occurrences in the RLGB (Kerrich, 1990; El Bilali and Hattori, 1998; Tarnocai, 2000; Fig. 5.8). The distinctly enriched δ13C and δ18O isotopic compositions at Red Lake compared to other Archean lode-gold deposits globally (Kerrich, 1990; Hagemann et al., 1994) is suggestive of ei- ther a different source region and/or reservoir. Table 5.2 Summary of oxygen isotopic compositions (δ18OVSMOW ‰) Carbonate Type Minimum (δ18O ‰) Maximum (δ18O ‰) No. Analyzes Pervasive calcite 11.5 11.5 1 Cryptocrystalline- microcrystalline ankerite 13.57 16.99 5 Medium-coarse ankerite- calcite 13.20 19.29 14 Breccia ankerite-calcite- quartz 17.65 18.81 2 Colloform-crustiform ankerite-calcite 14.06 20.46 8 Ankerite-calcite with chlorite selvage 12.15 20.67 6 Ankerite-calcite-quartz -2.67 21.44 20 Quartz-ankerite 9.95 20.90 2 Quartz-ankerite with brown biotite selvage 14.27 14.27 1 5.5.2 Sulfur isotopes Three paragenetic stages of sulfide minerals were characterized with sulfur isotope data. These stages included pre-mineralization pyrite-pyrrhotite, ore-stage pyrite-pyrrhotite- arsenopyrite-sphalerite and post-mineralization pyrite. All sulfur isotope data can be found in Appendix C.4. Figure 5.9 and Table 5.3 summarize the variation in sulfur isotopic signatures be- tween each sulfide mineral and paragenetic stage. Values are reported as mineral compositions and as δ34S of H2S in equilibrium with the mineral compositions. H2S equivalent values are not reported for arsenopyrite as no conversion was specified (Ohmoto and Rye, 1979). Due to the few sulfur isotope results from arsenopyrite (n = 2) and the inability to convert the value into δ34SH2S ‰, arsenopyrite is not assessed further. 219 Figure 5.5 Summary plots for carbon and oxygen isotopes for each paragenetic stage of carbonate investigated. A) Bar chart carbon isotopes with accompanying box and whisker plot indicating the range, mean and median of the data. B) Bar chart oxygen isotopes with accompanying box and whisker plot indicating the range, mean and median of the data. The outliers demonstrated by the ankerite-calcite-quartz veins are microcrystalline with 50:50 carbonate minerals and quartz. It is possible that these samples had very low abundances of disseminated sulfides which would have caused interference in the isotopic analysis. 220 Figure 5.6 Distribution of carbon isotopes across the A) Campbell cross section and B) Red Lake cross section. 221 Figure 5.7 Distribution of oxygen isotopes across the A) Campbell complex and B) Red Lake complex. 222 Figure 5.8 Comparison of carbon and oxygen isotopes from mineralized occurrence in the RLGB. Data derived from this study, Kerrich (1990) for the Cochenour-Willans and Hasaga mine and Tarnocai (2000) for Campbell. Archean lode-gold deposits derived from Colvine et al. (1988); Kerrich (1990) and Goldfarb et al. (2005). MORB values from Ohmoto and Rye, (1979). Early sulfides, deposited prior to the main mineralization event display δ34SH2S values of -6.9 to +15.8‰. This wide range in δ34SH2S values could indicate a mix of two possible reser- voirs. The negative δ34SH2S values are most consistent with sulfides formed by biochemical proc- esses. This is consistent with previous observations (Crocket and Lavigne, 1984). The positive δ34SH2S value could be related to granitic intrusions (Marini et al., 2011). Prior to the main min- eralization event, an early plutonism event (P1) has been recorded in the Red Lake area by the emplacement of the Little Vermillion Lake Batholith (Fig. 3.31; Corfu and Andrews, 1987). It is possible that magmatic fluids relating to the P1 event flowed through the sedimentary units of the Bruce Channel precipitating sulfides causing the wide range in δ34SH2S values observed today. The outliers and far outliers displayed in the pre-mineralization pyrite δ34S could indicate the end members of these two sulfur reservoirs; magmatic (positive, possibly oxidized) and biogenic (negative, possibly reduced). The outlier δ34SH2S values are derived from both basalt and chert, each displaying sulfide-rich bands. The sulfides from the outlier samples visually appear no dif- ferent from other pre-mineralization pyrite bands from other samples. 223 Figure 5.9 Summary of sulfur isotopes. A) δ34Ssulfide minerals (per mil CDT) of pyrite, pyrrhotite, arsenopyrite and sphalerite. B) Comparison of pyrite, pyrrhotite and sphalerite sulfur isotopes converted to δ34SH2S (per mil CDT) comparing relative timing to ore. All samples are represented. The outlier and far outliers are derived from basalt samples containing pre-mineralization pyrite. 224 Table 5.3 Summary of sulfur isotopes with regard to mineral and relative timing in relation to ore mineralization. Mineral Pre-/Syn-/Post- mineralization Range Number of samples Pyrite Pre- -6.9 to + 15.8 ‰ δ34SH2S 8 Pyrrhotite Pre- +1.00 to +5.56 ‰ δ34SH2S 4 Pyrite Syn- -4.92 to +6.32 ‰ δ34SH2S 20 Pyrrhotite Syn- +1.62 to +8.22 ‰ δ34SH2S 29 Sphalerite Syn- +3.14 to +4.00 ‰ δ34SH2S 2 Arsenopyrite Syn- +2.7-2.9 ‰ δ34SCDT 2 Pyrite Post- 0 ‰ δ34SH2S 1 Ore-stage sulfides can be present up to 6 km from the mine site in minor quantities. These were identified as ore-stage as they replaced ankerite-calcite-quartz veins or occurred as veinlets themselves which are parallel to the S2 fabric. However, syn-mineralization sulfides are most abundant 0–400 m from ore zones (Fig. 5.10). This localized concentration of sulfides demonstrates a narrow halo (0–350 m) of enriched sulfur isotopes (δ34SH2S ≤ +4.0‰) (Fig. 5.10). There is small variation of 1‰ in 34S with depth in the mine complex with 34S > 4‰ occurring at shallower levels and 34SH2S > 5‰ occurring at depth. The sulfur isotope data collected in this study are consistent with Archean lode-gold de- posits globally (Fig. 5.11). Archean lode-gold deposits from Western Australia and the Canadian Shield generally range from 0 + 9 ‰ δ34S (Goldfarb et al., 2005 and references therein). Miner- alized samples from this study range from -4 to +9 ‰ δ34S (Figs. 5.9 and 5.11 and Table 5.3). The fluid sources invoked for other Archean lode-gold deposits globally could have also affected the RLGM. The fluid sources have been suggested as either magmatic or metamorphic (Goldfarb et al., 2005 and references therein). Data collected is also comparable with prior RLGM investi- gations (Lavigne and Crocket, 1982; Lavigne, 1983; Crocket and Lavigne, 1984; Kerckhoff, 2003; Fig 5.11). Pre-mineralization sulfides from sedimentary packages are consistently largely negative with a wide range (Lavigne, 1983; Kerckhoff, 2003; this study). Syn-mineralization re- placement, vein and disseminated sulfides are more positive in isotopic signatures (Crocket and Lavigne, 1984; Kerckhoff, 2003; this study). No comparison with previous data can be summa- rized with post-mineralization sulfides as this is the first study to collect post-mineralization δ34S isotopic compositions. The post-mineralization pyrite demonstrated a δ34SH2S value of 0‰. This result lies within the ranges exhibited by both pre- and syn-mineralization sulfides, as well as being comparable to the host basalt δ34S composition (Fig. 5.11). As this stage is known to contain remobilized gold, 225 it is possible that the pyrite also was remobilized. Alternatively, the post-mineralization pyrite δ34SH2S value of 0 ‰ could be a magmatic source, related to the emplacement of the Cat Island Pluton during the P3 event (Fig. 3.31). The exact source of post-mineralization pyrite is unknown as a variety of reservoirs are possible. Ore-stage (syn-mineralization) sulfides of pyrite-pyrrhotite-sphalerite contain more posi- tive δ34SH2S values which range from -4.92 to +8.22 ‰ (Fig. 5.9). There is also a broad overlap in δ34SH2S values of both pre- and syn-mineralization sulfides between 1–8 ‰ (Fig. 5.9). This could indicate two possible sources; 1) metamorphism of pre-mineralization sulfides created the ore-forming fluid. The isotopic signature of this metamorphic fluid was affected by temperature and/or redox differences, or partition with coeval sulfides; or 2) a different reservoir compared to pre-mineralization sulfides (Ohmoto and Rye, 1979). A full discussion regarding the fluid sources will follow in section 5.6.2 below. 5.6 Suggested Fluid sources 5.6.1 Origin of carbonate vein-forming fluid Carbon and oxygen from the RLGM are enriched in 13C and 18O compared to the host basalt (Fig. 5.8). This implies that these rocks have undergone hydrothermal alteration. Both iso- topes are also enriched compared to other Archean lode-gold deposits in Canada and Western Australia (Kerrich, 1990; El Bilali and Hattori, 1998; Tarnocai, 2000; This study; Fig. 5.8). The multiple paragenetic stages of ankerite-calcite veins assessed from Red Lake display similar car- bon and oxygen isotopic compositions. This suggests that the carbonate veins formed from a comparable fluid, source region and/or at a similar temperature (c.f. Bierlein et al., 2004). The dominance of carbonate veins and slightly positive δ13C values indicate that the fluid contained oxidized carbon; CO2 (McCraig and Kerrich, 1998). Fluid inclusions from mineralized carbon- ate-quartz veins in the RLGM are consistent with a CO2-rich fluid (Chi et al., 2002, 2003, 2006). The positive values of δ13C and δ18O of carbonate veins from Red Lake could have re- sulted from several mechanisms. These include: (1) cooling of fluid; (2) mixing of source reser- voirs; (3) metamorphic devolatilization, decarbonation and/or dissolution; and (4) phase separa- tion, pH and redox effects (Ohmoto and Rye, 1979; Colvine et al., 1988; Golding et al., 1989; Hoefs, 1997, 2009). The above mentioned mechanisms collectively can cause positive shifts of 2–5‰ (Sheppard and Schwarcz 1970; Ohmoto and Rye, 1979). This is not sufficient to account 226 Figure 5.10 Sulfur isotope halo derived from syn-mineralization sulfides demonstrated along (A) Campbell complex, (B) Red Lake complex. For abbreviations, refer to list of abbreviations. 227 Figure 5.11 Variation of sulfur isotopes at the RLGM and surrounding area compared to prior research in the Red Lake deposits, similar Archean lode-gold deposits in Western Australia and Canada and natural sulfur isotope reser- voirs. Lines represent the range of data, with circles denoting the mean values. Modified from Cameron and Garrles (1980), Strauss (1986), Taylor (1987) with additional data from Lavigne and Crocket (1982), Crocket and Lavigne (1984), Kerckhoff (2003), Jamieson et al. (2006), Ohmoto et al. (2006) and Marini et al. (2011). 228 for the distinctively positive δ13C at Red Lake. Consequently, the origin of 13C and 18O enriched carbonate veins in the RLGB is considered to be due to an enriched source reservoir in the Red Lake area. The δ13C values are too enriched for a variety of source reservoirs commonly inferred for lode-gold deposits. These include: mantle, oxidized juvenile mantle, magmatic, fluid mixing (be- tween oxidized and reduced) or biogenic sources (Ohmoto and Rye, 1979; Golding and Wilson, 1983; Fyon et al., 1984; Kyser, 1986; Taylor, 1986; Burrows et al., 1986; Burrows and Spooner, 1987; Cameron and Hattori, 1987; Cameron 1988; Kontak et al., 1988; Kerrich, 1990; Kontak and Kerrich, 1997; McCuaig and Kerrich, 1998; Jia and Kerrich, 2000). These reservoirs are typically negative in δ13C, with ranges of -25 to -4‰ (Burrows et al., 1986; Kontak and Kerrich, 1997). This emphasizes the requirement of an enriched reservoir in the Red Lake area. There are two possible hypotheses to explain the enrichment in carbon and oxygen iso- topic values at Red lake. First is the hypothesis that prograde metamorphism continued causing devolatilization and decarbonation reactions. The second is the interaction between a fluid (of unknown origin) with a pre-existing isotopic enriched carbonate. If the original carbonate was isotopically enriched, the buffered fluid would reflect this composition. Both hypotheses will be discussed below. However, both infer significant influence from pre-metamorphic carbonate minerals. There are two possible pre-metamorphic carbonate sources in the Red Lake area. The first could be, or similar to, the stromatolite limestone which is part of the Ball assemblage (2940 ± 2 and 2925 ± 3 Ma felsic volcanics (Corfu and Wallace, 1986)). The Ball assemblage is found several km from the RLGM in the western areas of the RLGB (Fig. 1.3). It is possible that strati- graphy from the Ball assemblage occur more proximal to the mine site at depth in the RLGB. The other possible pre-regional metamorphic carbonate source is the early carbonate alteration which is documented in the RLGB (Chapter 3). The earliest identified carbonate is part of the biotite-Ti-magnetite ± carbonate and chlorite-amphibole-garnet ± epidote/clinozoisite ± magnet- ite ± biotite ± calcite assemblages (Fig. 3.2). These assemblages are interpreted to be metamor- phic equivalents of precursor clay, chlorite, mica and carbonate formed during the H1 event (Fig. 3.31). It is possible that these pre-regional metamorphic hydrothermal minerals were due to the interaction between the basalt and seawater when the Balmer assemblage was originally created. 229 The early hydrothermal carbonate minerals, deposited during H1 could have been the pre- metamorphic carbonate source. The regional metamorphic event (M2, Fig. 3.31) at the RLGM formed the greenschist- amphibolite facies mineralogy. This transition is documented at the RLGM (Fig. 3.30). This metamorphic transitional facies has the ability to produce large volumes (2–5 wt %) of H2O- CO2-S (± Au?) low salinity fluid by devolatilization reactions (Yardley, 1989; Spear, 1993; Phil- lips and Powell, 2010). These characteristics are similar to typical Archean lode-gold ore- forming fluids (Mikucki, 1998). Metamorphic fluids at the greenschist-amphibolite transition are formed via the following reaction: chlorite + epidote + carbonate + albite + quartz + pyrite  amphibole + plagioclase + pyrrhotite + fluid (Spear, 1993; Powell and Phillips 2010). The metamorphic devolatilization and decarbonation process would have formed fluids rela- tively enriched in 13C. This process can enrich the fluid’s δ13C by 3-5‰ compared to the source material which is left depleted (Sheppard and Schwarcz, 1970; Faure, 1986; Groves et al., 1988; Kerrich, 1990). The metamorphic devolitization process is common to many metamorphic gold deposits (Phillips and Powell, 1993, 2010). If metamorphic devolitization occurred at Red Lake, the enriched nature of the carbon isotopes would still require a pre-existing isotopically enriched carbonate source. The observation of pervasive (early) carbonate being significantly negative in δ13C compared to the vein carbonate (Fig. 5.8) is however, consistent with a metamorphic de- volitization process. Furthermore, it explains the lack of carbonate present in these early assem- blages. Although metamorphic devolatilization reactions can enrich the δ13C fluid composition, the starting material itself also needed to be enriched. This is required to account for the distinct difference (+5 to +10‰) between Archean lode-gold deposits found elsewhere (Fig. 5.8). The carbonate veins at the RLGM formed post-peak regional metamorphism (Fig. 3.2). This is sug- gested by carbonate veins cutting metamorphic assemblages (Figs. 3.10C and 3.23), and the es- timated temperature of 460–490°C by carbonate thermometry (Chapter 4). As carbonate veins formed post-peak metamorphism, a metamorphic fluid would require ongoing prograde meta- morphism at depth (c.f. Chi et al., 2009). The second hypothesis involved buffering of the fluid with the surrounding wall rock, altering the stable isotopic composition of the fluid and rock. It is possible this fluid was mag- 230 matic. During regional metamorphism, felsic intrusions were emplaced in the center and edges of the RLGB (Fig. 2.1). When these felsic intrusions were emplaced, the Ball assemblage stro- matolite limestone, and the early carbonate altered Balmer assemblage mafics were present. It is possible that these plutons were intruded into the carbonate sequence of the Ball and/or altered Balmer assemblages, e.g. the ~ 2720 Ma Hammell Lake Batholith (Fig. 1.2). As the magmatic fluid migrated, fluid-rock reactions occurred. No prior research has characterized the isotopic composition of the Ball assemblage stromatolite limestone. However, Archean marine limestone of similar age (2.8 Ga) to the Ball and Balmer assemblages displays positive δ13CPDB (-4 to +14‰) and δ18OSMOW (+14 to +20‰) values (Schidlowski et al., 1975; Knoll et al., 1986; Dix et al., 1995). The C and O isotopes from Red Lake are consistent with Archean marine carbonates of West Greenland, and Yilgarn spilites (approximately δl3C = 0‰) (Schidlowski et al., 1975; Schidlowski et al., 1983; Knoll et al., 1986; Valley, 1986; Groves, 1988; Fig. 5.12). Therefore, it is possible that limestones or seafloor altered carbonate altered mafics at depth buffered the fluid causing alteration of isotopic composition. Previous research at the CBC suggested that phase separation resulting from pressure drops caused the positive δ13C at Red Lake (Tarnocai, 2000). Sharp pressure drops which can result in the phase separation of CO2 and CH4 can cause positive shifts in 13CΣC (Cole and Chak- raborty, 2001). Phase separation can occur during fault valve pumping/episodic earthquake driven fluid pulses as described by Sibson et al. (1988) and Cox (2005). A loss of CH4 and corre- sponding 13CΣC increase in the fluid can cause 13C enrichment of precipitated carbonate (Tarno- cai, 2000). However, this is not enough of a positive shift to account for the mine variations nor compared to other Archean lode-gold systems (c.f. Kerrich, 1990). A fluid produced from devolatilization reactions and a magmatic fluid buffered by car- bonate rich rocks would both resemble metamorphic fluid characteristics. The buffering of the fluid with the wall rock would cause equilibrium between the two mediums. Thus, the fluid would have the same isotopic composition as the host rock. Petrographic observations of low abundance and the negative isotopic composition of early pervasive calcite are more consistent with a metamorphic devolatilization model (Fig. 5.8). The outliers can be explained by Rayleigh fractionation resulting from progressive cooling (Valley, 1986; Buick et al., 1998). Cooling oc- curred as the fluids migrated upwards toward shallower crustal levels. A devolatilization model for fluid generation in an Archean lode-gold deposit is not unique to Red Lake. However, the 231 Figure 5.12 A) Comparison of C and O isotope data with common reservoirs: Archean marine carbonates (Schid- lowski et al., 1975; Schidlowski et al., 1979; Knoll et al., 1986; Dix et al., 1995), modern marine carbonate and MORB (Ohmoto and Rye, 1979), granulite facies carbonate (Valley, 1986), Yilgarn and Archean spilite (Groves et al., 1988), Superior and Slave Craton Archean lode-gold deposits (Kerrich, 1987). B) Effect of metamorphic devola- tilization on residual carbonate and produced CO2-fluid on the carbon isotopic signature (Sheppard and Schwarvz, 1970; Faure, 1986) and the effect of Rayleigh fractionation (Valley, 1986). 232 enriched isotopic carbonate reservoir prior to regional metamorphism is a new observation for Archean lode-gold deposits. 5.6.2 Source of the mineralizing (sulfur-bearing) fluid Sulfide minerals formed before and during mineralization vary from known MORB and OIB basalt sulfur signatures (Marini et al., 2011; Fig. 5.11). Therefore, metamorphic breakdown of the original host basalt sulfides at the RLGM could not account for the sulfur isotopic compo- sitions recorded. Consequently, hydrothermal, later metamorphism or magmatic processes are implied to have occurred at Red Lake to establish the isotopic signatures of pre- and syn- mineralization sulfides. The range in sulfur isotope composition of syn-mineralization sulfides from Red Lake is δ34SH2S -4.92 to +8.22‰. This range could represent either metamorphic or magmatic origins. A metamorphic S-rich fluid would have been produced from the breakdown of pre-mineralization sulfides. Pre-mineralization sulfides display δ34SH2S values from -6.9 to +15.8 ‰. The metamor- phic breakdown of pre-existing pyrite by desulfidation reactions would have produced pyrrhotite plus excess sulfur (Tomkins, 2009). The excess sulfur is incorporated into the metamorphic fluid as H2S (Rye and Rye, 1974: Ohmoto and Goldhaber, 1997). The isotopic fractionation during metamorphism is not well constrained (Wagner and Boyce, 2006). However, Rayleigh frac- tionation would have occurred between the parent and daughter isotopes (Ohmoto and Gold- haber, 1997). It is assumed that the produced excess sulfur would have similar, but slightly en- riched δ34S compared to the parent pyrite (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997). Therefore the metamorphic S-rich fluid would potentially have a wide range of δ34S val- ues, which were largely negative to slightly positive: -6 to +5. This range was identified by the majority of the pre-mineralized sulfide isotopic values occurring between -6.9 and + 5.56 ‰ 34SH2S (Table 5.3 and Fig. 5.9). This range is too low (approximately 4-6 ‰) to account for the majority of the syn-mineralization sulfide isotopic signature. Observations of abundant pyr- rhotite in sedimentary packages support the hypothesis that earlier pyrite broke down during re- gional metamorphism (Fig. 5.4A). This implies that metamorphic desulfidation reactions most likely occurred. Processes such as temperature increase, reduction (decrease in the ƒO2) and par- tition between co-precipitated sulfides could have caused enrichment (Ohmoto and Rye, 1979). These processes collectively can cause positive shifts of 0-4‰ δ34S (Ohmoto, 1972; Ohmoto and Rye, 1979). However, the temperature gradient from depth to shallower crustal level is assumed 233 to decrease, e.g. fluids cool as they travel upwards (William-Jones et al., 2009). This would have caused negative shifts. Consequently, the processes of reduction and partitioning would have only caused minimal positive shifts. These would have been too low to account for the majority of syn-mineralized sulfides. Another source is required to account for the bulk of the sulfur iso- topic composition of mineralized samples. The presence of light sulfur isotopes, ≤ 4‰, in ore-stage pyrite from Red Lake could re- flect a demobilized isotopically light sulfur source, for example a granitic intrusion (Walshe et al., 2003, 2006). This has been used to explain light sulfur isotopes at Archean lode-gold depos- its in Western Australia (Neumayer et al., 2008). The P2 plutonic event is synchronous with the main mineralization event (Fig. 3.31). The intrusions emplaced during this phase are, the Dome stock, McKenzie stock, Howey diorite and Hammell Lake batholith. Each of these are located > 4 km away from the RLGM (Fig. 2.2). But, it is possible that these stocks are derived from larger batholiths at depth beneath the RLGM. Felsic dykes which occur in the mine stratigraphy are also suggestive of a batholith at depth beneath the RLGM. Granitic bodies, for example I-type felsic intrusions have δ34S ranges from -5‰ to +7‰ (Ohmoto and Goldhaber, 1997; Marini et al., 2011; Fig. 5.11). An underlying felsic body beneath the RLGM can only be inferred. How- ever, a magmatic source for the mineralizing fluid is most consistent with the most positive sul- fur isotopic data gathered from Red Lake ore zones. There is a broad overlap between the pre- and syn-mineralization sulfides which makes identifying the possible sources challenging. How- ever, metamorphic and magmatic sources are implied by the data, geology and petrographic ob- servations. It is possible that both occurred simultaneously, with a magmatic intrusion emplaced during a regional-contact metamorphic event. 5.6.3 Summary of implied fluid sources The isotopic characteristics for the RLGM are most consistent with a magmatic source emplaced during the M2 regional metamorphic event. Carbon and oxygen isotopes from carbon- ate veins are consistent with regional metamorphic devolatilization, or fluid interaction with pre- existing, isotopically enriched carbonate. Due to the significant enrichment of Red Lake 13C and 18O values compared to other Archean lode-gold deposits, it would suggest that the pre-existing carbonate was isotopically enriched. Similarly aged metamorphic belts globally indicate this pe- riod formed isotopically-enriched marine carbonate deposits (Schidlowski et al., 1975; Knoll et al., 1986; Dix et al., 1995). Sulfur isotopes demonstrated a wide range and overlap between pre- 234 and syn-mineralization sulfides. This caused challenging identification of the sulfur-bearing fluid source. The data, petrographic and geological observations are most consistent with a magmatic source which was emplaced during the M2 regional metamorphic event. It is possible that meta- morphic desulfidation of pre-mineralization sulfides influenced the negative to slightly positive syn-mineralized samples. The more positive syn-mineralization sulfides are more consistent however with a magmatic source, with more enriched δ34S due to crustal contamination during emplacement. 5.7 Explanation of isotope enrichment proximal to gold-mineralization The lateral distribution of sulfur, carbon and oxygen demonstrate an enrichment of all stable isotopes within the core of the system; i.e. the heaviest isotopic compositions are found proximal to the ore zones (Figs. 5.6, 5.7 and 5.10). There is also a vertical zonation demon- strated, with the highest isotopic compositions at depth and lowest nearer surface. The oxygen isotopes can be used to infer that this area, most proximal to ore zones, experienced the greatest fluid flow and fluid-rock interaction (c.f. Cathles, 1993). The area of isotopic enrichment is asso- ciated with the ore zones, and most importantly localized within D2 structures. Ore-forming flu- ids were focused along these conduits resulting in extensive fluid-rock interaction. The enrich- ment in δ18O at the mine, especially proximal to ore zones, support focused fluid flow and con- centrated fluid-rock interactions along the major D2 structures (Fig. 5.7). Extensive fluid-rock interaction is not the only mechanism which can explain isotopic enrichment. Differences in re- dox and temperature conditions are also suggested. Redox differences can potentially cause shifts of 3–4‰ to the sulfur and carbon isotopes (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997; McCuaig and Kerrich, 1998). When the carbonate vein and mineralization event occurred at Red Lake, the host basalt was extremely Fe2+-rich, with a Fe2+/FeOtotal molar ratio of 90–98% (Fig. 4.35). For redox reactions to occur both the fluid and surrounding rock has to be in disequilibrium. The fluid, relative to the sur- rounding wall rock is assumed to be oxidized. This is suggested for two reasons, (1) the wall rock is extremely Fe2+-rich; and (2) syn-mineralization magnetite and pyrrhotite, formed from the ore-forming fluid, are abundant. Both magnetite and pyrrhotite contain more Fe3+ than the surrounding rock (Pratt et al., 1994). Therefore, during fluid-rock interaction the fluid would have oxidized the wall rock converting Fe2+ to Fe3+. This is demonstrated by sulfides and mag- netite replacing garnet (Figs. 3.10G and 3.11B) as well as the Fe2+/FeOtotal molar ratio varying 235 between relatively Fe2+-rich for non-mineralized samples and relatively Fe3+-rich for mineralized samples (Fig. 4.35). Reduction of this relatively (compared to the wall rock) oxidized ore- forming fluid would caused an increase in δ34S and δ13C of approximately 3–4‰ (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997; McCuaig and Kerrich, 1998). A reduction of rela- tively oxidized fluid by the reduced basalt is consistent with observations of replacement style mineralization (Figs. 3.23 and 3.24). The progressive fluid-rock interaction between the ore-forming fluid and surrounding wall rock would have continued as the fluids migrated though the D2 structures. Redox reactions would have continued until equilibrium was achieved. The upward fluid flow would have also cooled the ore-forming fluid as it migrated from depth to shallower crustal levels. Cooling may have lead to a more pronounced Rayleigh fractionation of the isotopes (e.g. Fig. 5.12). A de- crease in temperature can cause +1–2 ‰ shifts in δ34S and δ13C per 100°C, assuming constant ΣS, pH and redox conditions (Ohmoto and Rye, 1979). A temperature gradient from depth to shallower crustal levels in the RLGM can only be suggested. Carbonate thermometry indicated that the ankerite-calcite veins at the RLGM were formed by a hot hydrothermal fluid, which was slightly cooler than the peak-metamorphic conditions (Chapter 4). A temperature difference be- tween depth and shallower crustal levels was estimated to be approximately 50-60°C. This esti- mate was based on a geothermal gradient of 23°C/km (typical estimate for Superior Province Archean continental crust; Burke and Kidd (1978)) over 2.5 km (the depth of the current mine workings). This suggested temperature difference could have caused possibly a +1‰ shift in S and C isotopes which are displayed at the RLGM. 5.8 Conclusions and suggestions for exploration Carbon, oxygen and sulfur isotopes were used to, (1) imply source reservoirs for the car- bonate vein and ore-forming event; (2) identify the influence of any pre-mineralization events on the isotopic signature; (3) assess the influence of regional metamorphism on the vein and miner- alization event; and (4) assess the stable isotopes exploration potential. Each stable isotope was studied from a variety of paragenetic stages in order to assess the issues proposed. Carbon and oxygen isotopes were derived from carbonate altered and vein samples. The earliest recognizable calcite demonstrated a δ13C of -10.3‰ and δ18O value of +11.5‰. The pre- to syn-mineralization carbonate veins display δ13C values of -4 to +4‰ and δ18O values of ≈ +5– 20‰. Both isotopes are enriched compared to other Archean lode-gold deposits (Fig. 5.8). The 236 carbon and oxygen isotopes suggest a metamorphic origin. This could have resulted from devolatilization or interaction of a magmatic fluid with pre-existing carbonate minerals. The pre- existing carbonate (either marine limestone or seafloor carbonate alteration) was already en- riched in 13C and 18O isotopes prior to regional metamorphism. Devolatilization or buffering with this enriched carbonate source material would have emphasized the isotopic enrichment of the fluid compared to other lode-gold deposits. The metamorphic signature of carbon and oxygen isotopes implies that possible prograde metamorphism was ongoing at depth beneath the RLGM, or that an intrusion was emplaced during the M2 peak-regional metamorphic event. Although devolatilization reactions for fluid generation are not unique to Red Lake, the enriched source material is a new observation that has affected mineralization at the RLGM. Sulfur isotope data from pre-mineralization sulfides display negative to weakly positive δ34S values. Pre-mineralization sulfides are typically found in chert, argillite and BIF packages of the Bruce Channel assemblage. The negative to weakly positive δ34S values imply biogenic processes (c.f. Crocket and Lavigne, 1984). In contrast, the syn-mineralization event is more en- riched, with δ34S values of 0 to +9‰. However, there was a broad overlap between the pre- and syn-mineralized samples of 1.0–5.5‰. The negative to slightly positive syn-mineralization sam- ples are consistent with metamorphic desulfidation breakdown of the pre-mineralized samples. The more positive syn-mineralized samples are more consistent with a magmatic source. The overlap and uncertainty in the sulfur isotope data is most consistent with a magmatic source which was emplaced during a contact-regional metamorphic event. The mapped distribution of sulfur isotopic compositions at the RLGM has the potential to aid exploration by increasing the target size. Oxygen isotopes display the widest halo up to 1 km from mineralization. Carbon and sulfur demonstrate narrower halos of up to 350 m from ore zones. The isotopic compositions of carbon, oxygen and sulfur are heaviest proximal to mineral- ization. This corresponds to the location of intense D2 deformation and the ore zones. This im- plies that the highest fluid-rock ratios and the greatest amount of fluid flow occurred in this area. This is consistent with prior observations that the D2 faults were the main ore-forming fluid con- duits (Penczak, 1996). A vertical zonation is also displayed at the mine, with the heaviest isotop- ic values at depth and lightest nearer surface. This difference is 1–3‰. Continued fluid-rock in- teraction, differences in redox between fluid and rock and cooling from depth to surface are in- ferred to have caused these vertical isotopic shifts. 237 Chapter 6: Environments of hydrothermal and metamorphic events: implications for ore genesis at the Red Lake Gold Mines. 6.1 Introduction The RLGM formed as a result of several superposed hydrothermal and metamorphic events (MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Mathieson, 1982; Mathieson and Hodgson., 1984; Christie, 1986; Rogers, 1992; Zhang et al., 1997; Tarnocai et al., 1997; Tarnocai et al., 1998; Twomey and McGibbon, 2001; Dubé et al., 2004; this study). It is not yet fully understood what the environments of hydrothermal alteration were, or how these super- posed events influenced ore genesis and gold-mineralization at the RLGM. Through the mineral chemistry and bulk rock geochemistry investigation of this study (Chapter 4), it has been implied that the earliest recognizable hydrothermal alteration was significant for later gold- mineralization. This early hydrothermal event, prior to gold-deposition, significantly altered the host basalt (Christie, 1986; Penczak, 1996; Damer, 1997; Penczak and Mason, 1997, 1999; this study). Two possible environments have been suggested for this early hydrothermal event. These are a submarine hydrothermal system (Crocket et al., 1980; Kerrich et al., 1981; MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Christie, 1986; Thompson, 2003), or a low-sulfidation epithermal deposit (Penczak, 1996; Damer, 1997; Penczak and Mason, 1997, 1999). There is also no consensus regarding the genetic model or timing of the main mineraliza- tion event at Red Lake. Some authors have suggested that the main gold event at the RLGM was syngenetic (Crocket el a., 1980; Rigg, 1980; Crocket et al., 1981) and formed as part of the sub- marine system (Kerrich et al., 1981; MacGeehan et al., 1982; MacGeehan and Hodgson, 1982). While others have agreed with an early gold event (prior to regional metamorphism), they have differed on the environment. A low-sulfidation epithermal system, which was later metamor- phosed (during peak metamorphism), has been proposed (Penczak, 1996; Damer, 1997; Penczak and Mason, 1997, 1999). Gold mineralization has also been inferred as coeval and directly linked to batholith emplacement (Andrews and Hugon, 1985; Andrews et al., 1986). The most popular genetic model for the RLGM is gold deposition which occurred synchronously with peak metamorphism and the main deformation event (MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Mathieson and Hodgson., 1984; Andrews et al., 1986; Christie, 1986; Rogers, 1992; Tarnocai et al., 1997; Zhang et al., 1997; Tarnocai et al., 1998; Tarnocai, 2000; Twomey and McGibbon, 2001; Dubé et al., 2004; Chi et al., 2009; Liu et al., 2011). It has also 238 been suggested that gold-mineralization occurred syn- to post-peak metamorphism (Wilson et al., 1984). Through detailed petrography and the application of mineral and whole rock chemistry, this study has identified key geological events which have affected the formation of the RLGM. These events are summarized in figure 6.1 and include (1) an early hydrothermal event (H1); (2) a subsequent vein and ore-formation hydrothermal event (H2) which occurred during peak- metamorphism, the main deformation phase and with synchronous plutonism; and (3) A late plu- tonic emplacement event which was associated with contact metamorphism, brittle-ductile de- formation and minor hydrothermal alteration (H3). This chapter will integrate the mineral chemistry, whole rock and isotope geochemistry data presented in Chapters 3–5 to address the following issues: (1) what was the environment, nature and characteristics of the early H1 hydrothermal event?; (2) how did this H1 event influ- ence gold-mineralization during the main H2 event?; (3) suggested sources of gold from within the RLGB; and finally (4) a synthesis of all chemical data collected in this study to improve the genetic model for the formation of the RLGM, with suggested implications for gold deposition. 6.2 The environment and nature of H1: early hydrothermal alteration in the RLGM 6.2.1 Evidence of early hydrothermal alteration from mineral assemblages, mineral chemistry and whole rock geochemistry The early hydrothermal alteration refers to the H1 event (Fig. 6.1). The H1 event is post- dated by the M2 regional metamorphic event and the main gold-mineralization event (H2) (Fig. 6.1). The petrographic, geochemical and mineral chemistry information presented here provide further constraints on the hydrothermal environment, conditions and nature of the fluids respon- sible for the earliest mineral assemblages observed at the RLGM. No gold was observed to be associated with the early alteration at the RLGM in this study (c.f. Penczak, 1996; Damer, 1997; Tarnocai et al., 1997). Early, low abundance sulfides of pyrrhotite-pyrite-chalcopyrite were documented as garnet inclusions (Fig. 3.5D). Additionally, low abundance sphalerite is associ- ated with calcic amphibole, approximately 5 km distally from mineralization (Fig. 3.8H). Neither of these early sulfide occurrences replaced carbonate veins, occurred as veins themselves, or is associated with brown biotite and quartz. These textures and associated minerals are indicative of the main mineralization event, which occurred during H2. Consequently, the early H1 hydro- thermal alteration at Red Lake was barren. 239 Figure 6.1 Schematic diagram showing the major geological phases of the RLGM’s development with added chemi- cal characteristics of H1 and H2 events. Possible hydrothermal environment and fluid sources are also added. BA) Balmer assemblage, BC) Bruce Channel assemblage, LVL) Little Vermillion Lake batholith, DL) Douglas lake plu- ton, Dm) Dome stock, MK) McKenzie stock, ABG) Abino granodiorite, HD) Howey diorite, HLB) Hammell Lake Batholith, KB) Killala-Baird batholith, WL) Walsh Lake pluton, CI) Cat Island pluton, H) hydrothermal event, M) metamorphic event, D) deformation event, P) plutonic event. Deformation details compiled from Sanborn-Barrie et al. (2001) and Dubé et al. (2004). Intrusion emplacement ages from Corfu and Wallace, (1986), Corfu and Andrews (1987), and McMaster (1987). Yellow stars indicate gold-mineralization event. For mineral abbreviations, refer to list of abbreviations. The nature of the early H1 hydrothermal event has been inferred through bulk rock and mineral chemistry data (Chapter 4). The earliest recognizable mineral assemblages in the RLGM are (Fe)biotite-Ti-magnetite ± (Fe)carbonate, chlorite-(Fe2+)amphibole-epidote/clinozoisite- biotite-(Fe)calcite ± (Fe2+Mn) garnet ± magnetite ± staurolite ± chloritoid (regional metamorphic assemblage) and quartz-muscovite-andalusite ± chlorite ± biotite (Chapter 3). These are meta- morphic equivalents of precursor assemblages. The precursor mineral assemblages are thought to have contained clay-chlorite-carbonate-mica-Fe-Mn oxides and intermediate argillic alteration. 240 Whole rock mass balance data (Chapter 4) has demonstrated varying element gains and losses for these metamorphosed alteration assemblages (see Table 4.14). It was found that this early hydrothermal event enriched the basalt significantly in K2O and SiO2 with less enriched S, As, Ba, Rb, Sb, Li, Ni and W, with accompanying removal of MgO, FeO, Na2O, CaO, Cu, Sr and Zn to form the biotite-Ti-magnetite ± carbonate assemblage. The chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite ± staurolite ± chloritoid assemblage in- dicated that the basalt was enriched significantly in FeO and MnO, with less enriched Na2O, S, Cu, Sr, Zn and Li, with accompanied loss of CaO, MgO, K2O, SiO2, Ba, Rb and Sb prior to re- gional metamorphism. This enrichment of FeO was significant, and caused the bulk rock Fe2+/FeOtotal molar ratio to increase by 5–15% (Chapter 4). Consequently, the early hydrothermal event was suggested to be reduced. The quartz-muscovite-andalusite assemblage demonstrated significant gains in SiO2 and lesser K2O, As, Cu and Rb with accompanied removal of MgO, Na2O, FeO, CaO, Ba, Li, Sr, W, Sb and Zn. The overprinting nature of these assemblages (Chap- ter 3) could imply that these are the result of distinct, superposed hydrothermal events, or an evolved system. 6.2.2 Possible early hydrothermal environments Previous authors have suggested that the early, pre-regional metamorphic, hydrothermal event was either a subseafloor system (Crocket et al., 1980; Kerrich et al., 1981; MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Christie, 1986; Thompson, 2003), or a low-sulfidation epithermal deposit (Penczak, 1996; Damer, 1997; Penczak and Mason, 1997, 1999). The earliest mineral assemblages recognized are hosted by basalt units of the RLGM. The basalts were chemically identified to range from MORB to island arc type (IAT) settings (Fig. 4.30B). The earliest mineral assemblages could have been formed synchronously with basalt formation at the seafloor. It is also possible that fluids derived from the early P1 felsic intrusions (such as the Lit- tle Vermilion Lake batholith and Douglas Lake pluton (Fig. 2.1)) could have formed the precur- sor mineral assemblages, similar to those in epithermal settings. The characteristics of both subseafloor and epithermal hydrothermal environments are compared below to the characteris- tics for the H1, which have been inferred through chemical data collected in this study. The addi- tional environment of a detachment fault system was also compared. Hydrothermal alteration associated with detachment faults indicates significant enrichment in K2O and Fe-Mn oxides (Kerrich, 1988); which has been identified as added during H1. Figure 6.2 and Table 6.1 summa- 241 rize the possible hydrothermal environments and characteristics of each system compared to what has been implied at Red Lake. 6.2.2.1 Summary of a subseafloor system Modern submarine hydrothermal systems are typified by spilitic and argillic alteration, Mg-metasomatism, greenschist to sub-greenschist minerals, (Mn-)carbonate, albite, anhydrite, barite, FeMn-oxides/oxyhydroxides and Fe-Pb-Zn sulfides (Nehlig at al., 1994; Alt, 1995; Gillis, 2002; Franklin et al., 2005; Hannington et al., 2005). In modern island-arc settings, advanced argillic alteration can be present (Hannington and Herzig, 1993; Sillitoe et al., 1996; Williams and Davidson, 2004). Alteration is caused by the interaction of circulating seawater, which can affect large areas of the ocean crust (Alt, 1995). Seafloor alteration is not commonly zoned hori- zontally, but vertical zonations of the upper oceanic crust are present (Gillis and Robinson, 1988). This reflects different areas in the seafloor hydrothermal system, and varying intensity of fluid-rock ratios (Gillis and Robinson, 1988). Archean seafloor fluids are considered similar to modern day equivalents (De Ronde et al., 1997). The only variation is that modern seafloor sys- tems are oxidized (Seyfried et al., 1991; Seyfried and Ding, 1995; Alt and Teagle, 2003), whereas Archean seafloor systems were less oxidized, due to the lack of sulfate in seawater at the time (De Ronde et al., 1997). The reduced nature of Archean seafloor fluids enhanced the ability to carry higher concentrations of dissolved Mn and Fe2+ than the more oxidized modern equivalents (Veizer et al., 1989). Archean submarine hydrothermal systems are preserved in the form of metamorphosed and deformed VMS deposits, such as the La Ronde(-Bousquet) mine, Abitibi Subprovince, On- tario (Fig. 6.2A). At the La Ronde deposit, Au-rich mineralization is hosted within tholeiitic ba- saltic flows (Hébécourt Formation) overlain by tholeiitic to calc-alkaline intermediate to felsic rocks (Bousquet Formation) (Mercier-Langevin et al., 2007). Here, metamorphosed equivalents of advanced argillic and propylitic alteration are preserved associated with mineralized lenses (Dubé et al., 2007). These were thought to have resulted from the influence of acidic magmatic fluids, which caused advanced argillic alteration, and near-neutral seawater which caused pro- pylitic alteration (Dubé et al., 2007; Mercier-Langevin et al., 2007). These two metamorphosed alteration assemblages envelope the mineralization (Dubé et al., 2007). The mineralized zones at La Ronde are significantly deformed with no coherency of the original seafloor system pre- served. This supports the idea that the main mineralization event at the RLGM was not a remobi- 242 lized seafloor hydrothermal system (see Chapter 3). However, similarities between Red Lake and La Ronde alteration are identified and will be discussed below. 6.2.2.2 Summary of a low-sulfidation system Epithermal systems are formed in volcanic arcs at convergent or post-collisional tectonic settings. These systems can either be classified as high or low sulfidation. As only low sulfida- tion has been suggested for early alteration at Red Lake, this deposit system will be summarized. Low sulfidation epithermal systems are characterized by alteration by a neutral pH, reduced and sulfur-poor fluid derived from meteoric and magmatic sources (Henley, 1985; White and He- denquist, 1995; Taylor, 2007; Fig. 4.2B). As the fluids migrate outwards, they cool, forming characteristic zonation patterns (Meyer and Hemley, 1967; Rose and Burt, 1979; Reyes, 1990). A typical zonation from proximal to distal is an inner silicified zone, associated with crustiform- colloform banded quartz-chalcedony veins and Au-Ag mineralization, which progresses outward to potassic-sericite, to propylitic, capped by (intermediate) argillic alteration with adularia (Bu- chanan, 1981; Simmons et al., 2005; Taylor, 2007; Fig. 6.2B). At the base of the epithermal sys- tem, where higher temperatures occur, zeolites, Ca-silicates, hydrothermal amphiboles and chlo- rite can form (White and Hedenquist, 1995). The zonation of epithermal deposits can range in width from meters to kilometres (Sander and Einaudi, 1990; Simmons et al., 2005; Taylor, 2007), enveloping vein- or breccia-filled fluid conduits. 6.2.2.3 Summary of a detachment fault system Detachment fault systems are hosted by large scale, normal faults with up to 30–50 km displacement (Roddy et al., 1988). These systems can be associated with metamorphic core complexes (Roddy et al., 1988). Alteration in the lower plate (beneath the detachment fault) is characterized by intense propylitic alteration. The upper plate is characterized by massive K- metasomatism with Mn-Fe-Cu oxides, oxidized minerals and veins of barite-fluorite (Fig. 6.2C). Alteration is widespread in both the upper and lower-plate rocks (Spencer and Welty, 1986; Wilkins et al., 1989). Alteration is not zoned; however, distinct differences between the upper- and lower-plate would create variations (Brooks, 1986). Detachment fault systems formed from the interaction of two different fluids. The first is an oxidizing brine of low- to moderate tem- perature (240-330°C) and neutral to alkaline pH, which accumulates in the extensional basins above the fault (Roddy et al., 1988; Kerrich, 1988; Michalski et al., 2007). This fluid is responsi- ble for the extensive K-metasomatism associated with these systems. The second is a reduced 243 Figure 6.2 Summary sketches of comparable hydrothermal systems responsible for the early, pre-regional metamorphism hydrothermal alteration at Red Lake. A) Ar- chean seafloor system of the La Ronde metamorphosed VMS deposit (modified from Mercier-Langevin et al., 2007a). B) Epithermal (low sulfidation) system modified from White and Hedenquist (1995). C) Schematic of a detachment fault system, modified from Long (2004). D) Summary of early hydrothermal alteration at the RLGM, which has been implied from mineral chemistry and whole rock geochemistry. For abbreviations refer to list of abbreviations. 244 Table 6.1 Summary and comparison of the suggested possible early hydrothermal environments at Red Lake Hydrothermal system La Ronde-Bousquet, Archean VMS deposit Modern Seafloor (fast spreading ridge) Detachment fault Epithermal low sulfidation Red Lake Gold Mines Host lithology  Underlying basaltic to intermediate flows  Rhyolitic domes, dacite- rhyodacite and rhodactie- rholite volcanics  Submarine pillowed mafic to ultramafic volcanic rocks.  Variable pelagic sediments (muds)  Cataclasite and mylonites from felsic volcanic, plu- tonic and sedimentary complexes.  Rare alkali basalt  Calc-alkaline, alkalic, tholeiitic bimodal basalt-rhyolite.  Volcaniclastic and sedimentary rocks most common Submarine pillowed mafic and ultramafic volcanic, lesser occur- ring rhyolite and sediments Tectonic/ Geological setting Back-arc basins Spreading ocean ridge Back-arc basins Metamorphic core complexes  Volcanic arcs in intra-arc, back- arc, convergent plate margins or post-collisional ridge settings  Sub-seafloor epithermal systems can occur Unknown; possibly MORB to IAT setting or continental sys- tem related to synchronous plu- tonism and metamorphism Alteration features  Metamorphosed advanced argillic alteration present as aluminous alteration due to acidic magmatic fluids  Metamorphosed propylitic alteration due to near- neutral seawater fluids  Greenschist-amphibolite metamorphism  Series of complex over- printing events  Replacement of original mineralogy by new miner- als Fault hosted, massive re- placement, stocks and veins.  Regularly zoned, enveloping veins or breccias conduits of, mineralization to potassic- sericite to propylitic capped by intermediate argillic  Open space textures such as banded crustiform and/or collo- form quartz-carbonate veins, chalcedony veins and breccias  Boiling textures, of bladed cal- cite and silica sinters Superposed mineral assemblages with the following sequence of oldest to youngest  Biotite-Ti-magnetite ± carbon- ate  Chlorite-amphibole- epidote /clinozoisite-biotite-calcite ± garnet ± magnetite ± staurolite ± chloritoid ± cordierite ± sphalerite  Quartz-muscovite-andalusite ± chlorite ± biotite Oxidized or reduced Depleted in oxygen, with higher concentrations of Fe2+ and Mn2+) dissolved Oxidized Oxidized and reduced Reduced Reduced: dominance of Fe2+ in metamorphic porphyroblasts Scale Affected 100’s of meters Affected large areas (1- 10km’s) Affected large areas (10 km’s), possibly >70 km2 Usually affected rocks from 0- 100m from ore, can extend sev- eral km laterally Affected rocks over a distance ≥7 km Fluid Source Evolved fluids from near- neutral seawater to acidic magmatic Circulating seawater  Shallow meteoric fluid  Oxidizing basin brines A mix of magmatic and meteoric fluids Unknown Data compiled from: Miyshiro et al., (1971), Coish (1977), Craig et al. (1980), Keith et al. (1983), Henley (1985), Brooks (1986), Spencer and Welt (1986), Kerrich (1988), Roddy et al. (1988), Alt et al. (1992), Kent et al., (1993), Gillis (1995), White and Hedenquist (1995), Sillitoe et al. (1996), Summer and Grotzinger (1996), Plank et al. (2000), Kitajima et al. (2001), Alt and Teagle (2003), Glasby and Notsu (2003), Honnorez (2003), Sillitoe and Hedenquist (2003), Long (2004), Hannington et al. (2005), Van Kranendonk et al. (2004) Franklin et al. (2005), Simmons et al. (2005), Dubé et al. (2007), Mauk and Simpson (2007), Mercier-Langevin et al. (2007a), Mer- cier-Langevin et al. (2007b), Michalski et al. (2007), Taylor (2007), Mercier-Langevin et al. (2008) and Chapters 3 and 4 of this thesis. 245 Table 6.1 (Continued). Hydrothermal system La Ronde-Bousquet, Archean VMS deposit Modern Seafloor (fast spreading ridge) Detachment fault Epithermal low sulfidation Red Lake Gold Mines Alteration assemblages  Quartz-biotite-Mn- garnet-muscovite ± re- placement Mg-chlorite = metamorphosed pro- pylitic alteration  Quartz-muscovite-Mn- garnet-andalusite- kyanite-staurolite –pyrite ± chalcopyrite ± gold = metamorphosed ad- vanced argillic alteration  Argillic  Spilitic  Mg-metasomatism  Characteristic greenschist to subgreenschist facies minerals  (Mn-) carbonate, quartz, smectite, chlorite, epidote, secondary amphibole /clinopyroxene, albite, an- hydrite, barite, zeolite  Propylitic (chlorite- epidote-calcite) alteration in lower plate  Massive K-feldspar re- placement in upper-plate  Sericite-silica alteration associated with barite- fluorite veins  K-feldspar, Mn, Cu and Fe oxides, clays (illite), oxidized hematite, jasper, carbonate and celadonite.  Silicification; replacement chal- cedony  Potassic; quartz-adularia-white mica-calcite-pyrite;  Intermediate argillic; illite- smectite-chlorite-interlayered clays-pyrite-(Fe) calcite- chalcedony  Propylitic; quartz-K-feldspar (adularia)-albite-illite-chlorite- calcite-epidote-pyrite Metamorphosed widespread and pervasive:  Biotite-Ti-magnetite ± carbonate  Chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite ± staurolite ± chloritoid ± cordierite ± sphalerite  Quartz-muscovite-andalusite ± chlo- rite ± biotite Minerals associated with ore Pyrrhotite, pyrite, sphalerite, galena, chal- copyrite FeMn-oxides and oxyhy- droxides, pyrrhotite, pyrite, chalcopyrite, galena, and sphalerite Metal oxides of Fe, Cu and Mn Electrum, Hg-Sb-As sulfides (ar- senopyrite-loellingite), pyrrhotite, and base metal sulfides (Fe- sphalerite), with gold  No gold mineralization  Minor pyrite-pyrrhotite-chalcopyrite associated with Fe-(blue) chlorite which occurs as garnet inclusions Geochemistry  Acidic magmatic fluids responsible for advanced argillic alteration with Na2O and CO2 loss with MnO, MgO and Fe2O3 gains.  Seawater caused loss of NaeO and TiO2 with gains of MnO, MgO, CaO and K3O  Rocks enriched in K, Rb, Cs, and H2O  Local increases in Feto- tal,Mn, Ba, Th, and U  Local losses of Mg and Ni  Enrichment of K, Fe, Mn, Ba, Rb and Zr with deple- tion of Na2O and MgO.  Alkali basalts demonstrate massive addition of Mg, Fe and Mn with K, Si and Na loss  Arsenic, Sb, Hg, and Tl, occur in very low concen- trations  K(-H)-metasomatism  Enrichment of K, Rb, and loss of Na, Sr and Fe  Enrichment of Ca, Mg, Ba, Si, As and Sb in mineralized areas  Biotite-Ti-magnetite ± carbonate indicated gains in K2O, SiO2 and loss of CaO, FeO, MgO and Na2O  Chlorite-amphibole-epidote-biotite- calcite ± garnet ± magnetite indi- cated gains in FeO, MnO, Na2O and loss of CaO, K2O, MgO and Si2O.  Quartz-muscovite-andalusite indi- cated gain in K2O and SiO2 and loss of CaO, FeO, and MgO Fluid conditions  Archean seawater is similar to modern sea- water, but more enriched in Fe and Mn2+ and less oxidizing  Acidic (pH 2-5)  Depleted in Br, SO4, Na, Ca, Mg, and Sr,  Enriched in Fe, Mn, Zn, Cu, CO2, CH4, N2, H2O, HCO3, Si, Li, Mn, Fe, Rb, Cs, Sb, T1, Cl and As  150-440°C  Back arc basin vent fluids are enriched in K+ Mixing of two fluids:  Oxidizing cool fluid  Reduced, 240-330°C, neutral to alkaline pH brines with metal-bearing aqueous solutions Neutral pH, reducing, sulfur-poor Speculated:  Biotite assemblage formed by re- duced (?) fluids enriched in K2O and SiO2  Chlorite assemblage formed by reduced fluids enriched in FeO, MnO, and Na2O  Bleached assemblage formed from acidic fluids enriched in Si and K capable of leaching Fe, Mn, Mg and Ca 246 fluid of metamorphic and/or evolved meteoric origin, at lithostatic conditions. When focused along the detachment faults, these reduced fluids induced Fe-Mn-Mg metasomatism (Kerrich, 1988). The fluids which cause Fe-Mg-Mn metasomatism are related to chlorite breccias and pro- pylitic alteration (Spencer and Welty, 1986; Kerrich 1988; Wilkins et al., 1989). 6.2.3 The comparison of suggested possible hydrothermal environments with Red Lake obser- vations The following discussion will compare the inferred characteristics of the early hydro- thermal alteration (H1) event at Red Lake to the suggested hydrothermal environments outlined in Table 6.1. Each of the hydrothermal environments characterized can be hosted by mafic vol- canics. The La Ronde deposit is hosted primarily within the transitional, mafic to intermediate, effusive and volcaniclastic units at the base (lower member of the Bousquet Formation) and tran- sitional to calc-alkaline, intermediate to felsic, effusive and intrusive rocks on top (upper mem- ber of the Bousquet Formation) (Mercier-Langevin et al., 2007). However basal tholeiitic basal- tic flows of the Hébécourt Formation are present (Mercier-Langevin et al., 2007). Similarly, each hydrothermal environment has the potential to alter rocks several 100’s m distally from the core of the system (Roddy et al., 1988; Sander and Einaudi, 1990; Alt, 1995). As a result, the com- parison of host lithology and scale of the hydrothermal system is not enough to identify the envi- ronment of early hydrothermal alteration at Red Lake. The mineralogy and bulk rock geochemis- try characteristics are more definitive in identifying the potential hydrothermal environment. The early alteration assemblages at Red Lake were formed from regionally metamor- phosed, reduced, Fe2+-rich basalts. Therefore, the early hydrothermal fluids are assumed to have been reduced, and/or enriched the basalt in Fe2+. The early alteration fluids at Red Lake are also inferred to have generally added K2O, FeO, MnO and SiO2 to the host rock, with the removal of CaO, Na2O and MgO (see section 6.2.1 and Fig. 4.33). Modern, fast-spreading ridge seafloor systems have the potential to enrich the surrounding basalt in K, Rb, Cs, Fe, and Mn, with local loss of Mg (Alt and Teagle, 2003). Magnesium addition, however, is more common in these sys- tems (Alt, 1995). Archean seawater would have been be relatively reduced, containing more dis- solved Fe2+ and Mn2+ compared to modern equivalents (Summer and Grotzinger, 1996). At the La Ronde deposit, Mn-rich Fe-Ca spessartine to almandine garnets were recorded (Dubé et al., 2007). These garnets were analyzed from propylitic alteration (quartz-biotite-garnet-muscovite) which was interpreted to have been the metamorphosed equivalent of near-neutral seawater al- 247 teration (Dubé et al., 2007). This is supportive of Archean seafloor systems being capable of en- riching the seafloor rocks in Mn and Fe. Detachment fault systems are reported to have formed from fluids that caused significant K-metasomatism, with addition of Fe, Mn and Mg to alkali basalts (Kerrich, 1988; Roddy et al., 1988). Mineralization in detachment fault systems occurs at the interface between reduced and oxidized fluids — the redox differences caused Fe-Mn oxide precipitation (Spencer and Welty, 1986). Epithermal systems are considered to have formed from reduced fluids (Simmons et al., 2005). These fluids can cause enrichment of K, Rb with addition of Ca, Mg, Ba, Si, As and Sb in mineralized areas, with removal of Na, Sr and Fe (Sander and Einaudi, 1990; Mauk and Simpson, 2007). The redox state of the fluid during early H1 at Red Lake is most consistent with either an Archean seafloor system, or epithermal fluids. The mass balance (elemental gains and losses) from each of the systems is consistent with as- pects of the H1 event implied for Red Lake. The mineral assemblages that are now documented at Red Lake are metamorphic equiva- lents of precursor assemblages. The required precursor minerals are suggested to be clays, bio- tite, chlorite, feldspar, carbonate and metal oxides. These precursor minerals could easily have formed within a seafloor, epithermal or a detachment fault system (Table 6.1; Fig. 6.2). The biotite-Ti-magnetite ± carbonate assemblage required a precursor assemblage rich in K2O. This is demonstrated by the abundance of biotite and the addition of K2O, as identified by mass balance calculations (Chapter 4). Potassium gains could have been present in a modern sea- floor system by the formation of celadonite, or as K-feldspar in an epithermal (as adularia) or detachment fault (orthoclase) system (Alt and Honnorez, 1984; Kerrich, 1988; Sander and Einaudi, 1990; Alt and Teagle, 2003). It is also possible that mica was formed as part of a potassic alteration assemblage in an epithermal system (Saunder and Einaudi, 1990). Distal met- amorphosed alteration at the La Ronde deposit often contains biotite in quartz dominated assem- blages with associated garnet-muscovite-chlorite-epidote-amphibole-pyroxene-clinozoisite ± chloritoid (Dubé et al., 2007). This indicates that Archean seawater fluids were capable of en- riching the basalt in K2O and/or form micas which could have been recrystallized to the now documented biotite. The metamorphic breakdown of seafloor celadonite could have formed biotite via the following reaction: Celadonite  biotite + loss of Fe3+ by reduction + H2O (Wise and Eugster, 1964) 248 The early reduction of the host rock, prior to regional metamorphism, would support the above reaction. Likewise, the breakdown of K-feldspar, in altered basalts in an epithermal or detach- ment fault system could have formed biotite by the following reaction: K-feldspar + magnetite  biotite (modified from Brearley, 1987) The observation of Ti-magnetite within the biotite-Ti-magnetite ± carbonate assemblage, as well as Ti-biotite with abundant Ti-magnetite could indicate that the above reaction occurred. It is also possible that the early biotite assemblage was recrystallized mica, for example, as part of a potassic alteration in an epithermal system. The demonstration of the crenulated S1-S2 foliation fabric (Fig. 3.3) at Red Lake is supportive of recrystallization. Each of the proposed precursor assemblages for the biotite-Ti-magnetite ± carbonate assemblage is consistent with petrographic observations. Therefore, evidence of the precursor minerals for the biotite-Ti-magnetite ± car- bonate assemblage alone cannot clearly distinguish hydrothermal environments. The chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± garnet ± magnetite (± cordi- erite ± chloritoid ± staurolite ± sphalerite) assemblage, characteristic of the greenschist- amphibolite facies at Red Lake, could have been created from a variety of precursor assem- blages. Chlorite would have been an important precursor mineral, as it would have broken down to form more Mg-rich chlorite varieties, and as prograde metamorphism continued, amphibole and garnet porphyroblasts (Spear, 1993). These reactions were indicated in petrographic obser- vations (Chapter 3). The presence of carbonate, micas, Fe-Mn-oxides, and clays were also re- quired to formed the unusual metamorphic minerals (cordierite, chloritoid, staurolite), as well as provide components for garnet, amphibole and epidote (Spear, 1993). The demonstration of the S2 foliation fabric by this assemblage at Red Lake suggests that recrystallization occurred. It is possible that the precursor carbonate and mica could have been recrystallized to have formed the calcite and biotite components of this assemblage. The precursor assemblages for the chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± garnet ± magnetite assemblage could have formed by prograde metamorphic reactions of sub- greenschist mineralogy formed in a seafloor system (Spear, 1993). A spilite potentially could have had the precursor minerals. Similarly, at the La Ronde deposit, associated minerals of amphibole, pyroxene, chlorite, epidote, clinozoisite, anatase and calcite are documented (Dubé et al., 2004). In the underlying mafic units, these minerals could be remnant minerals from the original tholeiitic basalt. However, in the overlying intermediate-felsic units, these minerals could be an indication of hydrothermal alteration. Another possibility is the hydrolysis of K- 249 feldspar and plagioclase, which could have formed in a detachment fault system by the following reaction: K-feldspar + plagioclase + H2O  chlorite (Kerrich, 1988) The propylitic alteration within a detachment fault or epithermal system could have also been the precursor assemblage. This would not have required the breakdown of K-feldspar, but rather prograde metamorphic reactions. However, in both a detachment fault and epithermal system the propylitic alteration is localized. Spilitic alteration of Archean seafloor basalts is far more exten- sive which is more consistent with the wide-spread greenschist-amphibolite assemblage in the RLGB. Garnet can form by the metamorphic breakdown of Mn-bearing chlorite and carbonate formed in a subseafloor system by the following reaction: Mn-chlorite + Mn-carbonate = Spessartine garnet (Spry et al., 2000; Nyame, 2001; Dubé et al., 2007) The reaction was used to explain the abundance of Mn-rich garnets at the La Ronde deposit. The Fe-Mn-rich garnets could also have formed from the breakdown of Fe-Mn oxides deposited in subseafloor, epithermal or detachment fault systems. Iron-Mn oxides are commonly deposited from vent complexes and found as stratabound deposits in seafloor systems (Fitzgerald and Gillis, 2006). Likewise, the Fe-Mn oxides in a detachment fault system formed stratiform depos- its (Long, 2004). Iron-Mn oxides have been identified in epithermal systems as occurring after pyrite, but as abundant coatings of vein walls with open space filling textures (Sander and Ein- audi, 1990). Manganese carbonates and Mn-silicates have also been reported as gangue minerals in recent epithermal systems (Heald et al., 1987; Simmons et al., 2000; Greffié et al., 2002). The concentration of Mn-bearing minerals in these systems is not universal; rather, it is a specific product of weathering of gangue minerals and older quartz-rhodonite-rhodochrosite bands and supergene enrichment (Milési et al., 1999; Greffé et al., 2002). Both grossular and pyrope com- ponents of Red Lake garnets are low compared to the spessartine and almandine components (Table 4.7). This indicates that the Ca- and Mg-bearing minerals at the time of garnet growth in the RLGB were limited, possibly due to simultaneous calcic-amphibole and epidote growth. Unusual metabasite minerals, such as chloritoid, staurolite and andalusite, could have formed via the consumption and breakdown of clays, aluminosilicates, quartz and chlorite via the following reactions: Chloritoid + Andalusite  Staurolite + Quartz (Damer, 1997) Chloritoid + Quartz  Staurolite + Garnet + H2O (Yardley, 1989) 250 Kaolinite  Andalusite + Quartz + H2O (Penczak, 1996) Pyrophyllite  Andalusite + Quartz + H2O (Penczak, 1996) Chlorite + Staurolite  Andalusite + Biotite + H2O (Penczak, 1996) (Mn-)Chlorite + quartz  chloritoid + Fe-oxide + OH- (Kramm, 1973) The precursor clays could have formed from intermediate to advanced argillic alteration in an epithermal (Simmons et al., 2005), or a Archean subseafloor system (Alt and Honnorez, 1984; Nehlig at al., 1994; Gillis, 2002; Dubé et al., 2007). At the La Ronde deposit, particularly proxi- mal to mineralization (0-30 m) abundant quartz-kyanite-andalusite-pyrite is observed. This was interpreted to be the metamorphosed equivalent of advanced argillic alteration similar to a high sulfidation system (Dubé et al., 2007). The sericite-silica alteration in detachment fault systems, could have also potentially been the precursor assemblage for the quartz-muscovite-andalusite assemblage at Red Lake. However, in detachment fault systems there is a lack of abundant clays, which was required to form the unusual minerals within metabasites observed at Red Lake. The muscovite in the Red Lake quartz-muscovite-andalusite assemblage is considered to have formed from recrystallized illite/sericite. This was originally formed with cordierite and/or rutile via the destruction of biotite (Penczak, 1996; Cadieux et al., 2006). The alignment of the quartz- muscovite-andalusite assemblage at the RLGM would support recrystallization as a formation mechanism of this assemblage, with the metamorphic breakdown of clays to form the andalusite porphyroblasts. The precursor minerals for the earliest recognizable metamorphic assemblages in the RLGM are most consistent with formation from recrystallized mica (biotite) or breakdown from K-feldspar, chlorite-carbonate-clay, and possibly Fe-Mn-oxides and argillic alteration (clay-rich rocks). These mineral assemblages are most consistent with either an Archean seafloor (a barren equivalent of the La Ronde VMS system) or epithermal system. Detachment fault systems lack the abundant clay minerals which are required to form the unusual metamorphic minerals identi- fied in Red Lake basalts. The primary permeability control on the distribution of the earliest mineral assemblages within basalt units suggests an in situ hydrothermal exploitation of the rocks at the seafloor (Pirie, 1981; MacGeehan and Hodgson, 1982; Christie, 1986). Observations from this study, such as chlorite altered pillow rims and quartz-muscovite-andalusite altered cores (Fig. 3.12), support the primary permeability control on these early fluids. Detachment fault systems are fault hosted, or alteration is associated with brecciation (Kerrich, 1988). Epithermal systems 251 typically contain open space textured veins and brecciation (Dong et al., 1995; White and He- denquist, 1995; Simmons et al., 2005). There is no documented brecciation during this phase of early alteration at Red Lake. Consequently, this host rock control on early mineral assemblages at Red Lake is most consistent with a seafloor system. 6.2.4 Conclusion of the early hydrothermal environment at Red Lake It is unlikely that the early H1 hydrothermal alteration occurred in a detachment fault sys- tem. Some key characteristic features of this deposit type are not observed at Red Lake. This in- cludes (1) no evidence of large scale faulting, mylonization or brecciation during D1 was identi- fied (Sanborn-Barrie et al., 2001); (2) the early H1 hydrothermal event at Red Lake was wide- spread, and mainly controlled by the primary permeability of the basalt and possibly syn- volcanic faults: early alteration is not localized within D1 structures; (3) there is no observed seg- regation of K-metasomatism in one area and chlorite-breccia in another area of the RLGM or RLGB; (4) there is no mineral evidence to suggest the interaction between two fluids, one re- duced the other oxidized; and (5) within detachment fault systems, no abundant clays are re- corded which is required to form the unusual metabasite minerals at Red Lake. The implied characteristics of the early H1 hydrothermal alteration at Red Lake have con- sistent observations with an Archean seafloor system, similar to the La Ronde metamorphosed VMS system (Table 6.1). At the La Ronde deposit, various alteration assemblages, formed from the interaction of both near-neutral seawater and acidic magmatic fluids are preserved (Dubé et al., 2007). The early metamorphosed alteration assemblages at Red Lake, the biotite-Ti- magnetite ± carbonate, regional metamorphic (chlorite-amphibole-epidote/clinozoisite-biotite- calcite ± garnet ± magnetite) and quartz-muscovite-andalusite assemblages, share common char- acteristics with Archean seafloor systems. These include (1) enrichment of K, Fe and Mn to the host basalt; (2) localized areas of acid fluid alteration which were relatively enriched in Si and Al to form advanced argillic alteration; (3) the ability to form multiple and complex overprinting alteration assemblages (Fig. 3.2; Shikazono et al., 1995; Franklin et al., 2005); (4) the ability to form precursor assemblages of clays, mica, subgreenschist minerals, (Mn-)carbonate and Fe-Mn- oxides, which are considered the precursor minerals for the Red Lake alteration assemblages; (5) Archean seawater was relatively reduced, with abundant dissolved Fe2+ and Mn compared to modern equivalents; (6) seafloor systems affect large areas, with fluid flow controlled by syn- volcanic faults and the primary permeability of the host rock and (7) the most common host 252 lithology is mafic volcanic. However, there are inconsistencies with an early seafloor hydro- thermal event at Red Lake. Common seafloor minerals, such as anhydrite, Mg-chlorite, and Mg- smectite, were not observed. As the Red Lake area was later metamorphosed to greenschist to amphibolite facies it is unlikely these minerals would have been preserved. In addition, the rela- tively reduced nature of the Archean seawater could indicate that oxidized minerals such as an- hydrite were not formed. It could also be possible that original anhydrite was completely broken down by biogenic processes. Biogenic processes were inferred to explain the pre-mineralization sulfur isotopic composition (Chapter 5). The other missing minerals could have also been con- sumed during metamorphic development and prograde reactions to form the greenschist- amphibolite facies mineralogy. However, none of the Mg-rich minerals listed occur as inclusions in porphyroblasts of garnet or amphibole. This implies they were absence from Red Lake rocks during metamorphic growth of garnet and amphibole. Epithermal low sulfidation deposits have characteristics that are consistent with the im- plied early H1 event at Red Lake: (1) K-silicate alteration which could have been recrystallized to have formed the biotite-Ti-magnetite ± carbonate assemblage; (2) although rare, Mn-gangue minerals and Fe-Mn-oxides have been documented; (3) fluids are reduced and acidic, which could have formed the clay-rich precursor assemblage required to form the quartz-muscovite- andalusite assemblage; (4) although not common, epithermal systems can be hosted within mafic volcanics; (5) epithermal fluids can affect large distances; and (6) there is a removal of CaO, MgO and Na2O within intermediate argillic altered areas (John et al., 2003). There are, however, inconsistencies with a low-sulfidation epithermal system as the H1 event. Firstly, there is a lack of open space features, such as colloform-crustiform carbonate veins and brecciation, formed during this early alteration. Both breccias and colloform-crustiform veins are found in the RLGM (Fig. 3.2). However, both are post-peak regional metamorphism. These timing relation- ships are known by carbonate veins cutting garnet porphyroblasts which were formed during the M2 peak-metamorphic event (Figs. 3.10C–F). The carbonate veins are occasionally brecciated; therefore, brecciation must have also postdated carbonate veins in the Red Lake area. The post- peak metamorphic timing of carbonate vein formation at the RLGM is supported by a cooler than peak-metamorphic temperature, which was estimated by carbonate thermometry (Chapter 4). Secondly, there is a lack of significant Fe addition (Table 6.1). Rare basalt hosted epithermal systems have been recorded to be unusually enriched in Fe (John et al., 2003). However, in these systems the Fe is locally derived (by sulfidation reactions) from the Fe-rich mafic host rock, 253 rather than added to the system (John et al., 2003). The early alteration assemblages demon- strated that Fe2+ was added during this H1 event at Red Lake. The other inconsistency with an epithermal environment is the lack of a distinct zonation on a km-scale (Sander and Einaudi, 1990; Simmons et al., 2005). Mineral chemistry from early chlorite, biotite, garnet and amphi- bole from the Red Lake area indicates only minor variations in Fe, Mg, Mn, Ca, Si and Na abun- dances (Chapter 4). None of the demonstrated Red Lake mineral variations would be consistent with a typical epithermal system zonation. To conclude, a hybridized Archean seafloor model, similar to the metamorphosed La Ronde VMS deposit is most consistent with the geology and the bulk of the observations col- lected regarding the H1 event at Red Lake. Seafloor alteration is consistent with the formation of precursor clays, carbonate, chlorite, FeM-oxides and micas. These minerals were the precursor assemblages to the now documented metamorphosed biotite-Ti-magnetite ± carbonate and re- gional metamorphic assemblages (Chapter 3). A magmatic acidic fluid is more consistent with the formation of argillic alteration which was the precursor assemblage for the now present metamorphosed quartz-muscovite-andalusite assemblage. A seafloor system is consistent with the wide nature of early alteration, the primary permeability control on mineral assemblages, the significant reduction of the basalt, the addition of Fe and Mn, and formation of the precursor minerals suggested. The lack of abundant Mg-minerals remains an oddity. In addition, compared to mineralization at the La Ronde deposit, the early H1 alteration at Red Lake was barren. Like- wise, there was not a clear zonation documented in the early metamorphosed alteration assem- blages. The intermittent occurrence of quartz-muscovite-andalusite compared to the continuous biotite-Ti-magnetite ± carbonate and regional metamorphic assemblages could indicate that the magmatic fluids exploited syn-volcanic faults, rather than affected the basalts pervasively. With regard to when this early hydrothermal event occurred, garnet chemistry from the Bruce Channel argillite also demonstrated a bell-shaped profile of Mn-enrichment in garnet cores (Fig. 4.24). This would suggest that the Mn-enrichment occurred after the deposition of both the Balmer and Bruce Channel assemblages. The Bruce Channel assemblage was deposited within a marine setting (Sanborn-Barrie et al., 2001). The lack of pillowed mafics within the Bruce implies this marine setting was not on a mid-ocean ridge, but rather a nearer continental setting. This would suggest that the early hydrothermal Mn enrichment was part of an unusual Archean seafloor event, possibly a bark-arc basin, similar to the La Ronde deposit (Mercier- Langevin et al., 2007). 254 6.3 Nature of H2: the ore-forming hydrothermal system Following the H1 event, the RLGM and RLGB were affected by synchronous deforma- tion (D2), plutonic emplacement (P2), hydrothermal alteration (H2) and peak-regional metamor- phism (M2) (Fig. 6.1). H2 commenced with the formation of ankerite-calcite ± quartz veins ± chlorite/biotite selvages, followed by quartz ± ankerite ± chlorite selvage veins. The veins were overprinted and replaced by gold-mineralization (pyrite-pyrrhotite-magnetite-arsenopyrite ± sphalerite ± molybdenite ± stibnite) and associated brown biotite-quartz (Chapter 3), with narrow halos typical of Archean lode-gold deposits (c.f. Groves et al., 1998). Ore zones are contained in faults and are foliation aligned (i.e. the East South ‘C’ (ESC), hosted in the Red Lake fault), which supports formation during D2 (Penczak, 1996; Dubé et al., 2004). The abundance of veins during this hydrothermal event indicate a stronger structural control on the fluids compared to the early, largely widespread hydrothermal event controlled by primary porosity and permeabil- ity and probable syn-volcanic faults. The primary permeability of the host basalt would have been destroyed during regional metamorphic growth of new minerals during M2. D2 deformation is intense at the mine site with multiple structures hosting carbonate-quartz veins, mineralization and intense associated alteration. The veins and subsequent mineralization could have formed from a single prolonged hydrothermal event which, over time, evolved due to fluid-rock interac- tions (Dubé et al., 2004), or by multiple superposing events (Powell et al., 1991; Yongqing and Pengda, 1998). Whole rock geochemistry (Table 4.14; Fig. 4.33) demonstrated that the ankerite-calcite ± quartz ± chlorite selvages were accompanied by the addition of CaO, FeO, MgO, SiO2, Ni, Sr and Zn with loss of As, Ba, Cu, Li and Rb. Similarly, the quartz ± ankerite ± sulfide veins indi- cated gains in CaO, FeO, MgO, K2O, SO3 and SiO2, as well as many of the identified pathfinder trace elements: As, Cu, Ni, Sb and Zn accompanying sulfides. Associated alteration with miner- alization, both quartz ± sulfides and brown biotite-quartz ± carbonate ± sulfides, indicated the addition of K2O, MgO, SO3, SiO2, As, Sb, W and Zn, with the loss of FeO and Na2O. Economic mineralization associated with K-(alkali) metasomatism is a geochemical feature associated with other Archean lode-gold deposits globally (Goldfarb et al., 2005; Prendergast, 2007). The ferric versus ferrous composition between non-mineralized and mineralized samples indicated that there was not an overall loss in bulk rock Fe, but a slight variation in the iron oxidation state (Fig. 4.35B). This would suggest that sulfidation reactions occurred to form the abundant ore- stage sulfides and magnetite, which constitutes Red Lake ore zones. 255 The abundance of carbonate (both ankerite and calcite) during the H2 event is assumed to have formed from a CO2-bearing fluid. This would support previous research by Chi et al. (2002, 2003), who identified very CO2-rich fluids from fluid inclusion analysis. The formation of car- bonate minerals is influenced by both fluid and host rock composition (Kerrich and Fyfe, 1981; Elmer et al., 2006). Carbonic fluids carry bivalent metal cations derived primarily from the wall rock. When the carbonate veins formed in the RLGM, the host basalts were Fe2+-rich. Interaction with this Fe2+-rich host rock would have produced Fe-carbonate, which is consistently observed throughout the RLGB (Chapter 3). Carbon and oxygen isotopes from ankerite veins indicated a metamorphic source. This could have been produced from (1) metamorphic devolitization of pre-existing carbonate (formed during the H1 event; Chapter 5) or (2) the interaction of a fluid (possibly magmatic) with the pre-existing carbonate, e.g. the fluid was rock buffered causing a metamorphic isotopic sig- nature to the carbonic fluid. The sulfur isotopic compositions of ore-stage sulfides are most con- sistent with a magmatic source (Chapter 5). The syn-mineralization intrusions in the RLGB are considered the source for the magmatic fluids. Fluids, which were presumably generated at depth, focused into D2 structures and migrated toward the surface. These fluids are thought to have been CO2-rich (Chi et al., 2003, 2006, 2009) enriched in CaO, MgO, SO3, As, Au, Sb and SiO2 to form carbonate-quartz veins, sulfide-magnetite mineralization and accompanying Mg- biotite-quartz alteration. The ore-forming fluid would have been chemically capable of dissolv- ing FeO from veined carbonate, or other silicate minerals in the Balmer basalt, to provide the Fe component for sulfide precipitation via sulfidation reactions. The ore-forming fluid also needed to be capable of oxidizing the Fe2+ from the wall rock to form abundant ore-stage pyrrhotite and magnetite; both minerals contain relatively more Fe3+ than the host rock. The chemical character- istics of the ore-forming fluid stages listed above are generally consistent with other Archean lode-gold deposits (Kerrich, 1989; Goldfarb et al., 2005). The interaction and importance of the metamorphic and magmatic fluids inferred from stable isotope data, with regard to the formation of the RLGM, will be discussed in more detail below. 6.4 Nature of H3: minor post-mineralization (syn-D3–D4) hydrothermal alteration Post-mineralization hydrothermal alteration occurred during the late deformation events, D3 to D4, and is localized in these late structures throughout the greenstone belt. The RLGB post- mineralization hydrothermal event formed quartz-muscovite ± carbonate ± pyrite veins, quartz- 256 tourmaline veins and tourmaline filled faults, which cut all lithology, previous alteration assem- blages and mineralization (Dubé et al., 2004; Chapter 3). D3–D4 deformation, hydrothermal al- teration and remobilization of gold was attributed to the late plutonic emplacement of the Killala-Baird Batholith and Walsh Lake plutons (Corfu and Wallace, 1986; Noble, 1989; Dubé et al., 2004). The effect of contact metamorphism by the Cat Island and Walsh Lake plutons can be seen distally, > 5 km from the RLGM, by the coarsening of peak regional-metamorphic am- phibole-epidote-chlorite-carbonate crystals, and sugary textured carbonate veins. The barren hydrothermal activity during this late stage is less than the earlier H1 and H2 events. The formation of quartz-muscovite ± tourmaline ± carbonate ± pyrite veins with pink K- feldspar halos (typically in lamprophyre dykes; Fig. 3.26) were formed by an acidic fluid rich in Si, K and B. The considerable abundance of tourmaline in both veins and faults requires signifi- cant influxes of boron. Boron is inferred to have been from the felsic Walsh Lake pluton (Shearer et al., 1984; Woodford et al., 2001), presumably as high temperature and saline rich flu- ids (Dini et al., 2008). The H3 event postdates the main mineralization event at Red Lake, there- fore these fluids are not involved in ore-formation and so are not discussed as part of the genetic model. 6.5 Genesis of the Red Lake Gold Mines Through detailed petrography, mineral chemistry and bulk rock and stable isotope geo- chemistry (Chapters 3–5), there have been indications as to the importance of pre-mineralization hydrothermal alteration on the ore-forming event. Suggested influences include the precipitation of early carbonate, which was required to form the metamorphic carbonic fluid (which formed the carbonate veins), and the importance of the Fe2+-rich host rock for sulfidation reactions. What will follow is a summary of previous Archean lode-gold deposits’ genetic models, those invoked to explain the RLGM genesis, and improvements to the Red Lake genetic model through the chemical data presented in this thesis. The importance of the early hydrothermal al- teration at Red Lake, suggested gold sources and gold precipitation mechanisms will also be in- cluded. 6.5.1 Previous genetic models of the RLGM and Archean lode-gold deposits Numerous genetic models have been proposed for Archean lode-gold deposits, but a common consensus is yet to be agreed (Goldfarb et al., 2005). Ore genesis at the RLGM is like- wise debated, specifically with regard to the influence and timing of regional metamorphism and 257 mineralization. Mineralization has been suggested as forming pre-, syn- and post-regional meta- morphism at Red Lake (Kerrich et al., 1981; Wilson et al., 1984; Dubé et al., 2004). In this sec- tion, genetic models of Archean lode-gold deposits are summarized, with specific attention to the genetic models suggested for the RLGM. This is followed by a discussion of gold precipitation mechanisms, and finally a proposed genetic model for the RLGM which is consistent with the geochemical, mineralogical and isotope data gathered in this study, as well as previous knowl- edge of these deposits types. Mineralization at Red Lake is hosted in major deformation zones (D2 structures) and is vertically extensive. The current mine workings extend to approximately 2.5 km depth, with con- tinuation toward depth. Mineralization is hosted predominantly by basalt, but also in ultramafic, rhyolite and sedimentary units of the Balmer and Bruce Channel assemblages. The extensive na- ture of mineralization at the RLGM agrees with the crustal continuum model suggested by Groves et al. (1992) and Groves (1993). This model explains the vertically extensive nature and occurrences of lode-gold deposits, hosted by multiple lithology at various crustal depths (origi- nally formed at < 5 km to 20 km depth, (Nesbitt, 1988)), with a variety of mineralization styles and alteration assemblages. The crustal continuum model highlights the necessity of a deep sourced ore-forming fluid derived from basal greenstone belts, deep intrusive granitoid-gneisses, mantle or subducted oceanic lithosphere sources. Mineralization in lode-gold systems is consid- ered to be epigenetic, formed from late-Archean, crustal-scale, deep syn-greenstone hydrother- mal systems, from metamorphic or magmatic fluids (Groves, 1993). The major components are thought to have been derived from either the lower crust, mantle in equilibrium with (older) fel- sic crust, or anatectic granitoids (Groves, 1993). In this model, lode-gold deposits are considered to have formed within accreted terranes with associated granitoids (Groves et al., 1998). Gold mineralization and synchronous deformation at the RLGM was previously sug- gested to be directly related to syn-mineralization intrusions marginal to the RLGB (Hugon and Schwerdtner, 1984; Andrews and Hugon, 1985; Andrews et al., 1986; Corfu and Wallace, 1986; Corfu and Andrews, 1987). This hypothesis suggested a magmatic exsolution model, where the metals and volatiles were released from mantle or crustal melts (Lindgren, 1933; Bateman 1950; Rock and Groves, 1988). Oxidized fluids, or CO2-metasomatic fluids derived from igneous magmas, were suggested to account for the close proximity of intrusions to lode-gold deposits and the presence of relatively oxidized minerals, such as hematite and/or various sulfate minerals (Burrows et al., 1986; Cameron and Hattori, 1987; Burrows and Spooner, 1987; Cameron, 1988, 258 1989). Although lamprophyre dykes (a possible mantle source) are spatially associated with ore at Red Lake, a genetic link was dismissed. These dykes cut ore, therefore, exclude any mantle activity during the mineralization phase (Dubé et al., 2004). There are two previously proposed genetic models from Red Lake which suggest that the main gold formation event occurred prior to peak-metamorphism. The first suggested that the earliest hydrothermal alteration and possible gold event at the RLGM formed in a major dis- charge zone of a submarine system (Crocket et al., 1980; Kerrich et al, 1981; MacGeehan et al., 1982; MacGeehan and Hodgson, 1982). The other proposed pre-regional metamorphic genetic model was a low-sulfidation epithermal deposit (Penczak, 1996; Damer, 1997; Penczak and Ma- son, 1997, 1999). Pre-regional metamorphism mineralization has been refuted by observations in this study, as no significant sulfides or gold occurred prior to regional metamorphism (Chapter 3). There are no gold inclusions within garnet observed. Rather ore-stage sulfides replace garnet, or are present in carbonate veins which also cut garnet. A near surface formation for carbonate veins was also proven unnecessary due to high fluid pressures of CO2-rich fluids, which were shown to be responsible for colloform-crustiform structures and cockade breccias at depths of ≥ 7 km (Liu et al., 2011). The definitive explanation for carbonate veins forming post-peak meta- morphism are repeated observations that multiple carbonate vein types cut garnet porphyroblasts (Chapter 3). Formation of the RLGM due to devolatization reactions is one of the most recent genetic models suggested (Chi et al., 2009). However, the most popular and common consensus is that synchronous metamorphism, deformation and mineralization occurred in the RLGM (MacGee- han and Hodgson, 1982; MacGeehan et al., 1982; Mathieson and Hodgson., 1984; Andrews et al., 1986; Christie, 1986; Rogers, 1992; Tarnocai et al., 1997; Tarnocai et al., 1998; Zhang et al., 1997; Twomey and McGibbon, 2001; Tarnocai, 2000; Dubé et al., 2004; Liu et al., 2011). The RLGM occurs within the greenschist-amphibolite transition (Fig. 3.30). The generation of metamorphic fluids by prograde processes at depth could be a likely source for large volumes (2- 5 wt %) of H2O-CO2-S rich, low salinity fluid capable of transporting gold (Kerrich and Fyfe, 1981; Phillips and Groves, 1983; Phillips et al., 1987; Phillips and Powell, 1993, 2010; Goldfarb et al., 2005). At the greenschist to amphibolite facies, the generation of this metamorphic fluid is most efficient (Fyfe et al., 1978; Powell et al., 1991; Phillips and Powell, 1993, 2010). Fluids would have been channelled into major structures and migrated toward shallower crustal levels, 259 particularly during seismic events, in which gold deposition occurred due to increased fluid-rock interaction (Sibson et al., 1988; Phillips and Powell, 2010). 6.5.2 Gold precipitation mechanisms in Archean lode-gold systems No research has been undertaken at Red Lake to distinguish how gold is transported from the source region. Consequently, previous literature will be used to provide suggestions of gold transportation and precipitation mechanisms. Gold, in hydrothermal systems is transported as either a gold-bisulfide complex (AuHS° or Au(HS)2-) or chloride complex (AuCl2-) (Gilbert et al., 1998). In Archean lode-gold systems, gold is widely accepted as being transported as a bi- sulfide complex, with concentrations ranging from 1–100 ppb at greenschist-amphibolite facies conditions (Gilbert et al., 1998; Phillips and Powell, 1993; Mikcuki, 1998). Gold solubility as a chloride complex is negligible at greenschist-amphibolite conditions, as low pH, high ƒO2 and elevated temperatures are needed (Shenberger and Barnes, 1989; Hayashi and Ohmoto, 1991). In order for gold to be precipitated, variations in either physical (P, T) or chemical (e.g. ΣS, αH2S or ƒO2) conditions are required. These variations can be caused by a variety of methods: (1) cooling (Phillips and Powell, 1993; Gilbert et al., 1998; Loucks and Mavrogenes, 1999); (2) phase separation due to sharp pressure drops (Seward, 1973; Spooner et al., 1985; Sibson et al., 1988; Cox et al., 1995; Benning and Seward, 1996; Palin and Xu, 2000; Cox, 2005); (3) wall rock sulfidation reactions (Phillips and Groves, 1983; Groves and Phillips, 1987; Neall and Phil- lips, 1987; Mikucki and Heinrich, 1993; Mikucki, 1998; Phillips and Powell, 2010); or (4) fluid mixing (Hagemann et al., 1994; Walshe et al., 2003). Differences in redox state could be related to options 3 or 4 (Palin and Xu, 2000; Evans, et al., 2006; Halley, 2007; Neumayer et al., 2008; Evans, 2010). These mechanisms all share a commonality of decreasing the sulfur content of the fluid, or modifying the redox state of sulfur (such as oxidizing the sulfur to SO42-, which does not bond well with gold), which ultimately causes the precipitation of gold from solution. 6.5.3 Improved genetic model for gold deposition at the Red Lake Gold Mines The chemical data collected as part of this study, confirmed that the RLGM formed from several superposed hydrothermal and metamorphic events (MacGeehan and Hodgson, 1982; MacGeehan et al., 1982; Mathieson, 1982; Mathieson and Hodgson., 1984; Christie, 1986; Rogers, 1992; Zhang et al., 1997; Tarnocai et al., 1997; Tarnocai et al., 1998; Twomey and McGibbon, 2001; Dubé et al., 2004). A key observation from this study is the suggested impor- tance of the early hydrothermal alteration for ground preparation, which influenced the subse- 260 quent mineralization event. This early hydrothermal alteration event was barren, therefore dis- missing a low-epithermal and seafloor mineralization model previously proposed for the RLGM (see above). As mentioned in Chapter 3 (section 3.3.2.9) there are multiple observations which indicate that the RLGM was not re-mobilized ore which was deposited during the H1 event. This confirms a barren early H1 event. During this early hydrothermal (H1) event the host basalt was reduced creating a significant FeO-rich composition (Fe2+/Fetotal molar ratio of 90-98%; Fig. 4.36). The formation of the isotopically-enriched carbonate could have also occurred during this early hydrothermal event. However, the isotopically-enriched carbonate source could have also been the marine sediments of the Ball assemblage. The Ball assemblage was deposited prior to regional metamorphism therefore, would have been present to buffer fluids. Subsequent regional metamorphism of these earlier altered basalts formed Fe2+-rich minerals, which were later re- placed by ore-stage mineralization, particularly pyrrhotite and magnetite (Fig. 3.10G). The ore-forming event initiated with the formation of abundant ankerite-calcite ± quartz veins. These veins were replaced by later mineralization. This association of carbonate-quartz veins and gold mineralization is a common feature within Archean lode-gold systems (Kerrich and Fyfe, 1981; Kishida and Kerrich, 1987; Groves et al., 1998; Goldfarb et al., 2005). The car- bon isotopes from the ankerite-calcite ± quartz veins suggested a metamorphic source, whereas the sulfur isotopes were more consistent with a magmatic source. The ore-formation event at the RLGM can therefore, be the result of either, (1) the evolution of a single fluid or (2) two fluids of different suggested origins, one metamorphic the other magmatic. The single fluid model would involve synchronous metamorphism and magmatism. The carbonate thermometry implied that the ankerite-calcite ± quartz veins at the RLGM were formed post-peak regional metamorphism (Chapter 4). This would imply that the fluids were generated at depth, either by prograde regional metamorphic devolatilization reactions, or from another source which was buffered by a pre-existing carbonate. Syn-tectonic intrusions emplaced at depth during regional metamorphism could have been the source of the CO2-sulfur and gold- bearing fluid that formed the RLGM (Cameron, 1989). Syn-tectonic plutons are documented within the RLGB, and therefore, are a possible fluid source. The magmatic fluid would have been buffered by the pre-existing isotopically-enriched carbonate as it migrated through the crust. This rock buffering would have caused the fluid to have a similar isotopic composition to the pre-existing carbonate. The sulfur isotopes, in the magmatic fluid, could have possibly been buffered by the pre-existing syn-sedimentary sulfides. These sediment-hosted sulfides formed 261 prior to gold deposition. Interaction between the isotopically light pre-mineralization sulfides and isotopically heavier ore-forming fluid would have caused a broad overlap in isotope values. This is demonstrated by the sulfur isotope data (Chapter 5). The proposed single ore fluid model would have been derived from a magmatic intrusion emplaced during regional metamorphism. This is consistent with the proposed model of lode-gold deposits forming within accreted ter- ranes during orogenic events (Groves et al., 2003). The suggested two fluids model would have involved distinct overprinting events and/or fluid mixing. The first would have been continued prograde regional metamorphism or mag- matic fluids which were rock buffered with pre-existing carbonates to form the ankerite-calcite ± quartz veins. This event was then overprinted by another hydrothermal event, possibly magmatic in origin, which overprinted the ankerite-calcite ± quartz veins. Although this is possible, syn- tectonic felsic intrusions throughout the RLGM occurred during the M2 regional metamorphic event. This would suggest synchronous metamorphism and magmatism, which is not consistent with two separate events. Fluid mixing has been inferred to form Archean lode-gold deposits in Western Australia (Halley, 2007; Neumayer et al., 2008). A reduced fluid of an unknown origin mixed with an oxidized magmatic fluid, which caused gold deposition at the redox boundary (Halley, 2007; Neumayer et al., 2008). It is possible that fluid mixing between the metamorphic and magmatic fluids at Red Lake occurred. The interaction of these fluids, as they were chan- nelled into D2 structures from depth, would have caused gold-precipitation at the mixing inter- face (assuming the fluids were not in equilibrium and one was carrying gold). Evidence of fluid mixing would be continued mineralization localized in D2 structures toward depth. This is ob- served in Red Lake ore zones, with current exploration identifying mineralization at deeper in- tercepts. However, petrographic observations of ankerite-calcite veins, which are replaced by ore-stage pyrrhotite-arsenopyrite-gold, also suggest that the magmatic ore-forming fluid post- dated the metamorphic fluid. These observations indicate a complex arrangement and possible prolonged hydrothermal event. The simplest explanation, which is most consistent with the Red Lake geology, isotope geochemistry and petrographic observations collected in this study, is the evolution of a single fluid. This proposed model is also the most consistent with Archean lode-gold deposits (Groves et al., 1998). The RLGM was derived from a magmatic source which was emplaced at depth dur- ing a regional-contact metamorphic event. The magmatic CO2-rich fluids would have migrated though the crust interacting with the wall rock and pre-existing isotopically-enriched carbonate 262 rocks. This would have resulted in fluid-buffering which would have enriched the carbon iso- topes. The paragenetic implications as identified in this study would suggest that the RLGM formed during continued metamorphism but post-peak metamorphism; therefore syn- to post- peal M2 regional metamorphism. This is consistent with observations by Wilson et al. (1984), who stated that the mineralization event at Red Lake was syn- to post-peak metamorphism. The exact source of the magmatic ore-forming fluid in the RLGB can only be specu- lated. The syn-mineralization intrusions in the RLGB are the Dome and McKenzie Stocks, Howey granodiorite, Abino granodiorite and Hammell Lake batholith (Fig. 2.1). The Dome Stock is reported to have carbonate alteration, associated with syn-mineralization sulfides hosted in D2 shear zones (Crofu and Wallace, 1986). This would suggest that the Dome Stock formed prior to carbonate veins and the main D2-deformation event documented across the RLGB. Therefore, the Dome Stock could not have contributed to the magmatic ore-forming fluid re- sponsible for gold at the RLGM. However, the association of gold mineralization (The Red Lake Gold Shore, Buffalo, Skookum and McKenzie mines) within intrusions is suggestive of a mag- matic influence (Burrows and Spooner, 1987). It is possible that the Stocks present at the surface of the RLGB are smaller manifestations of a larger batholith at depth. This suggestion would be consistent with the isotopic compositions identified for ore-stage sulfides (Lavigne and Crocket, 1982; Lavigne, 1983; Crocket and Lavinge, 1984; Kerckhoff, 2003; Chapter 5). Mineralization at the buffalo mine can be used to provide more information to increase our understanding of the magmatic influence on the ore-forming system in the Red Lake area. The Buffalo mine is located within the peripheries of the Dome Stock. Mineralization here is reported as auriferous quartz-tourmaline veins, with pink bleached halos of albite- tourmaline-ankerite (Andrews et al., 1986; Pettigrew, 1999; Harris et al., 2006; Chi et al., 2011). The quartz-tourmaline veins at the Buffalo mine are similar in appearance to the quartz- tourmaline veins seen to cut lamprophyre dykes in the RLGM (Fig. 6.3). The formation of these veins is considered to be synchronous with D3 deformation (Pettigrew, 1999) or during the late stages of D2 deformation between 2718-2712 Ma (Chi et al., 2011). Similar auriferous quartz- tourmaline veins cut the 2701 Ma ± 1.5 Ma Wilmar granodiorite (Corfu and Andrews, 1987). Likewise, the similarity with quartz-tourmaline veins in lamprophyre dykes at the RLGM sup- ports a syn-D3 timing, rather than syn-D2 (Dubé et al., 2004; this study). The auriferous veins at the Buffalo mine are interpreted to have derived from deep crustal fluids which are CO2-rich (Gulson et al., 1993; Chi et al., 2011). These fluids could have been either metamorphic or 263 magmatic in origin. From the similarity in fluid characteristics (through fluid inclusions), it has been implied that the same fluids formed gold at both the RLGM and Buffalo mine (Chi et al., 2011). Petrographic and relative timing constraints observed in this study would disagree with that conclusion. The quartz-tourmaline veins at the RLGM clearly postdate the main mineraliza- tion event because of their presence in post-ore lamprophyre dykes. This would suggest that the auriferous quartz-tourmaline veins across the RLGB formed after the main mineralization event at Red Lake, either during late D2 or during D3 deformation. This is consistent with the par- agenetic observations in Chapter 3. The magmatic influence implied from both mine sites (Buf- falo and the RLGM) suggests that several plutonic episodes emplaced at depth were capable of providing the ore-forming fluids during H2 and possibly the H3 events. The gold within the late tourmaline-bearing veins at the Buffalo mine could have contained remobilized gold like that identified at the RLGM (Dubé et al., 2004). Figure 6.3. Examples of tourmaline bearing veins from the Buffalo deposit (photographs A-C) compared to a similar tourmaline-bearing vein in a lamprophyre dyke cutting ore at the RLGM. 264 The source of gold to form the RLGM has not been widely investigated. MacGeehan et al. (1982) demonstrated that the iron-rich tholeiitic volcanic rocks, which host mineralization, are themselves depleted in Au. MacGeehan et al. (1982) suggested that leaching of the basalt provided the gold. However, this would have required significant leaching and abundant fluids to concentrate the 40 Mt at 20g/t of gold at the RLGM (Bouzari et al., 2009). Another option would be a magmatic source. The source of the gold can only be suggested. However, a magmatic source is consistent with the origin of the ore-forming fluids from ore-stage sulfur isotopes. The precipitation of gold at Red Lake could have been influenced by a number of factors. These include: (1) breakdown of pyrite; (2) pressure drops and phase changes; (3) redox differ- ences between fluid and host rock and (4) temperature. Ore zones are Red Lake are dominantly composed of pyrrhotite-pyrite-arsenopyrite- magnetite-gold (Fig. 3.24). Petrographic observations indicate that pyrite is surrounded by pyr- rhotite (Fig. 3.24F and Fig. 6.4). These minerals could have formed by the following reaction which involved the desulfurization of pyrite. 3FeS2 + 7H2O = FeS + Fe3O4 + 7H2S and 3/2O2 Although this reaction can explain the petrographic observations, it does not provide an effective gold precipitation mechanism. This reaction produces H2S which is known to be a ligand for car- rying gold in the fluid phase (Gilbert et al., 1998; Phillips and Powell, 1993; Mikcuki, 1998), Therefore, the desulfidation reaction of pyrite is not considered influential on the gold formation at Red Lake. Phase separation has been used to explain banded quartz-carbonate veins and gold en- dowment at the Yilgarn hosted Archean lode-gold deposits (Cox et al., 1995; Palin and Xu, 2009). During phase separation, resulting from sharp pressure drops, the reduced gaseous phases such as H2S, CH4 and H2 are preferentially partitioned into a vapour phase, which reduces the total sulfur content of the fluid, which causes relative oxidization (Drummond and Ohmoto, 1985; Hodkiewicz et al., 2009). In the case of a sulfur-bearing fluid, this shift can move the fluid from the pyrite stability field to the pyrite-hematite equilibrium curve. Although this mechanism cause a rapid decrease in gold precipitation, pyrite and hematite are formed also (Hodkiewicz et al., 2009). Hematite has not been observed at Red Lake, therefore, although a possible mecha- nism is not considered likely for the RLGM gold formation. During this study it was identified that the Balmer basalt was significantly reduced and enriched in Fe2+ prior to regional metamorphism. It is possible that this early FeO enrichment 265 Figure 6.4 Sample of high grade ore from CBC stope 40_43-FV showing pyrite rimmed by pyrrhotite. Inset A (modified from Mikucki and Ridley, 1993) is a log ƒO2 vs. log aH2S plot indicating pyrite desulfurization reaction: pyrite (red dot) goes to pyrrhotite and magnetite. Inset B (modified from Halley (2007) and Cooke and Simmons (2000)) is a log ƒO2 vs. pH plot indicating that redox differences between fluid and rock can cause gold precipitation. 266 was important for subsequent gold formation mechanisms at Red Lake. The non-mineralized bulk rock samples demonstrate a Fe2+/FeOtotal molar ratio of 90–98% (Fig. 4.36B). The mineral- ized samples demonstrate similar FeO wt%, but the Fe2+/FeOtotal molar ratio is slightly lower, 88–93%. This indicates that 1) sulfidation reactions occurred, with stripping of Fe from the wall rock to deposit sulfides, with no significant change in the bulk rock FeO abundance; and 2) the oxidation state of the Fe changed. Ore-stage pyrrhotite and magnetite contain more Fe3+ than the host basalt. This change in the oxidation state of Fe between non-mineralized (significantly Fe2+- rich) and mineralized (relatively Fe3+-rich) basalt samples indicates that the Fe from the wall rock was oxidized during sulfidation reactions to form ore-stage pyrrhotite and magnetite. As the host rock was reduced, in order to oxidize the iron, the ore-forming fluid must have been rela- tively oxidized compared to the host rock. There are several possibilities for the ore-forming fluid to be oxidized along its transport path: 1) interaction with a relatively oxidized rock; 2) phase separation; 3) breakdown of pre- existing oxidized minerals (e.g. magnetite or carbonate); 4) a naturally oxidized source. In the Red Lake area, the dominant host rocks are Fe2+-rich mafic volcanics, ultramafic units, diorite, argillites and iron formations with less common felsic volcanics (see Chapter 1). These rocks are themselves reduced. Therefore, fluid-rock reactions with these lithology could not have signifi- cantly oxidized the ore-forming fluid. As mentioned above, phase separation can cause signifi- cant relative oxidization of the fluid. However, the lack of supportive petrographic observations of pyrite + hematite indicates this mechanism most likely did not occur in the Red Lake area. The sulfidation of pre-existing Fe-oxides (e.g. magnetite) and pyrrhotite has been suggested as a possible mechanism to raise the oxidation state of the fluids (Phillips et al., 1986; Evans et al., 2006). During the following reaction the oxidation state of sulfur can change: 2FeS + Fe2O3 = Fe2S + 3FeO (Evans et al., 2006) This reaction involves electron transfer between the sulfur. The sulfur derived from the pyr- rhotite (S2-) is oxidized to S- in pyrite (Evans et al., 2006). Although a possible mechanism for relative oxidation of the fluid, the petrographic observations from Red Lake do not support pyr- rhotite  pyrite. The opposite reaction was identified (Fig. 6.4). Finally, a magmatic source could produce relatively oxidized fluids capable of transporting gold (Cameron and Hattori, 1987). It has been proposed that due to the significant transport distances in Lode-gold deposits, the oxidized solutions are unlikely to reflect the primary source (Ridley and Diamond, 2000). However, syn-tectonic plutons were identified throughout the RLGM (Fig. 1.3). Although they 267 are mostly stocks, their presence and multiple felsic dykes in the RLGM indicate there could have been an underlying magmatic source, thus transport distances potentially would have been short. The relatively oxidizing fluid is the most consistent with the geology and petrographic ob- servations from the RLGM collected in this study. Redox differences between the wall rock and ore-forming fluid are supported by several observations. These include: (1) sulfide precipitation in high grade ore replaced Fe2+-wall rock, minerals and carbonate veins (Fig. 3.23); (2) stable isotopes are enriched proximal to ore zones, which is the result of redox differences during fluid-rock interaction (Chapter 5); and (3) ore- stage sulfides and magnetite are zoned, with pyrrhotite surrounding pyrite (Fig. 6.4). Pyrrhotite after pyrite is an indication that the fluid (which was relatively oxidized) was reduced by the in- teraction with the significantly Fe2+-rich host basalt (Fig. 6.4B). The removal of sulfur from the fluid by interaction with Fe-rich rocks is an inferred process for gold mineralization in lode-gold deposits (Philips and Powell, 2010). Stable isotopes of carbon, oxygen and sulfur all demonstrate the heaviest isotopic compositions proximal to ore. Here, the greatest fluid-rock interaction oc- curred. Redox reactions (specifically reduction of the fluid) during fluid-rock interaction can in- crease δ34S and δ13C by approximately 3–4‰ (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997; McCuaig and Kerrich, 1998). These observations all indicate that redox differences be- tween the ore-forming fluid and wall rock was the main driving force behind gold precipitation mechanisms at Red Lake. Temperature differences are inferred to have controlled sulfide distribution with less in- fluence on gold deposition. At depth, correlating to higher temperatures, the ore mineral assem- blage is pyrrhotite-rich. At shallower crustal levels the mineral assemblage is pyrite-rich with more disseminated mineralization which is comparatively lower grade. The distribution of pyr- rhotite and pyrite is consistent with a temperature control (Fig. 6.5); pyrrhotite forms at higher temperatures than pyrite (Mikucki, 1998). Cooling of a fluid is a relatively ineffective process to cause gold precipitation from a bi-sulfide complex (Williams-Jones et al., 2009). Although it is an ineffective process, cooling does influence gold precipitation. However, the redox differences between the fluid and the host rock would have been the main influence on gold precipitation in the RLGM. From this study, the formation of the RLGM has been confirmed as the superposed inter- action of several hydrothermal and metamorphic episodes. This study has demonstrated that early pre-mineralization hydrothermal alteration was important for subsequent gold mineraliza- 268 Figure 6.5 The solubility of gold (represented as dashed lines) as a function of temperature and H2S content, modi- fied from Mikucki, (1998). Calculations assume typical lode-gold fluid conditions, CO2/CH4 = 10, pH = 5.5 and pressure = 2 kbar, assuming γAu(HS)2- = 1. Mag = magnetite, po = pyrrhotite, py = pyrite. The grey star represents an estimated starting temperature and H2S. As fluid migrates from depth to shallower crustal levels, fluid-rock interac- tions occur, as well as the fluid cooling which causes the gold solubility of the fluid to increase (more gold is dis- solved in the fluid). At point A, the fluid has reacted at shallower crustal levels which contain disseminated sulfide style of mineralization. Here, the fluid is more dispersed, causing more rapid cooling. tion at the RLGM. The importance of ground preparation for gold mineralization in the RLGM has not been recognized previously. Redox differences between the ore-forming fluid (relatively oxidized) and significantly reduced host rock is the principal influence for gold-mineralization at Red Lake. The ore-forming fluid is most consistent with a magmatic source, with the magmatic intrusion emplaced at depth during a regional-contact metamorphic event, possibly within an ac- cretionary terrane (Groves et al., 1998). Ore-formation at the RLGM is concluded to be syn- to post-peak regional metamorphism. This conclusion is consistent with previous observations by Wilson et al. (1984) regarding the timing of mineralization and peak-metamorphism in the RLGM. 269 Chapter 7: Application of non-destructive, field-based techniques for explora- tion in the Red Lake area 7.1 Introduction Field-based analytical tools have been applied to active and paleo-hydrothermal systems. These tools have aided in the characterization of alteration assemblages and geophysi- cal/geochemical anomalies (Alva-Valdivia and Urratia-Fuccaganchi, 1995; Li and Oldenburg, 1996; Herrmann et al., 2001; Sun et al., 2001; Yang et al., 2001; Nabighian et al., 2005; Hansen et al., 2005). This, in turn, has assisted scientific understanding and exploration. Two methods in particular, shortwave infrared (SWIR) reflectance spectroscopy and magnetic susceptibility, have been used to identify mineral chemical trends. Both SWIR and magnetic susceptibility are simple field-based tools with rapid data collection and little to no sample preparation (Molyneux and Thompson, 1973; Thompson et al., 1999). Neither method is intended, nor capable of pre- cise mineral identification, but identified chemical trends can be used to vector toward minerali- zation. At the RLGM, SWIR data identified compositional trends in both mica and chlorite which vector toward mineralization (Bouzari, 2009). Muscovite was documented to vary from a K-rich composition distally, to Fe-Mg-rich 3 km, to Fe-rich 500 m laterally from ore (Bouzari, 2009). Likewise, chlorite reflected an Fe-rich composition proximal to mineralization, with Mg- chlorite distally (Bouzari, 2009). Magnetic susceptibility data was collected by Red Lake explo- ration geologists from down drill holes to highlight areas of abundant sulfides. Only weak corre- lations between gold grade and magnetic susceptibility were reported (R. Penczak, and M. Epp pers. comms., 2011). However, there is potential that both tools could expand the exploration target for identifying economic mineralization in the Red Lake area. The main objective of this chapter is to test SWIR and magnetic susceptibility to investi- gate whether it can be used at Red Lake to map trends previously identified using more detailed work (Chapter 4). Detailed work included the time consuming methods of electron microprobe (EMPA) and whole rock geochemistry (Chapter 4). This chapter will also address these issues concerning the SWIR: (1) can the SWIR instrument (the ASD Terraspec©) identify alteration minerals in lode-gold deposits?; (2) what affects SWIR mineral identification?; and (3) can the collected spectra be used to estimate mineral character or composition? The relationship between magnetic susceptibility and alteration-mineralization assemblages will also be investigated. The 270 investigation of magnetic susceptibility of Balmer basalt samples at Red Lake was undertaken with the aspiration to identify bulk Fe, Fe2+ and Fe3+ trends in whole rock samples. Finally, both magnetic susceptibility and SWIR data will test previously documented relationships of trends toward mineralization (Bouzari, 2009). 7.2 Methodology 7.2.1 Shortwave infrared (SWIR) analysis SWIR data compilation used an instrument which collected spectra from the 1300–2500 nm wavelengths of the electromagnetic (EM) spectrum. This region of the EM spectrum is par- ticularly sensitive to stretching and bending vibrations of molecular bonds in a crystal lattice (Thompson et al., 1999; Sun et al., 2001). The SWIR study is based on relative reflectance or absorption features at certain wavelengths. These features are caused by vibrational transitions between the bonds OH, H2O, NH4, CO3, and distinctive cation-OH bonds, e.g. Al-OH (Hunt and Salisbury, 1970; Hunt, 1977; Goetz et al., 1983; Clark et al., 1990) (Table 7.1). Variations in mineral chemistry cause shifts in absorption features due to dominant cation-OH bonds, e.g. Fe- OH vs. Mg-OH (Clark et al., 1990). SWIR reflectance is also affected by crystallinity, grain size and overall albedo (Thompson et al., 1999). Absorption features are dependent on composition, with well defined wavelength positions e.g. Mg-rich < 2250 nm > Fe-rich chlorite, (McLeod et al., 1997; Hauff 2005). Hydrous silicates, carbonate minerals, hydroxides and sulfates are detect- able by SWIR (Sun et al., 2001). However, there are limitations. Minerals generally need to be in abundances of > 5–10% of the rock in order to be detected (Thompson et al., 1999). SWIR can- not identify silica or anhydrous silicates (i.e. garnet), and mixes of similar minerals are not easily differentiated (e.g. co-existing clays and zeolites (Thompson et al., 1999; Yang et al., 2001)). Spectral data were collected using the Analytical Spectral Device (ASD), i.e., Terraspec © spectrometer. This machine uses a halogen light source calibrated to a white tile for an absolute reflectance reference. Spectra were interpreted with the aid of the software, The Spectral Geolo- gist© (TSG) (Merry et al., 1999), as well as manually using reference spectra (Hauff, 2005). For both automated and manual identification of the mineral phases, key characteristic wavelength features were referred to. These key wavelengths and features are outlined in Table 7.1. For a mineral phase to be identified in the spectra, the diagnostic features were required. 271 Table 7.1 Investigated minerals and their distinguishing SWIR absorption features Mineral Absorption λ (nm)† Bond Characteristic λ at minimum position and possible range Investigated depth variations Investigated range in width at FWHM* Distinguishing feature(s) if any Chlorite 1400 2250 2350 OH/trapped H2O Fe-OH Mg-OH 1400 ± 17 2250 ± 17 2340 ± 25 ± 0.3 ± 0.4 ± 0.3 ± 17 ± 17 ± 17  Rarely visible 2200 nm feature  2250 and 2340 nm features are deeper in chlorite com- pared to biotite/amphibole  Lower absorption with these features minus 2200 nm fea- ture indicated chlorite Biotite 1400 2250 2310-2350 2360-2390 OH Fe-OH Mg-OH Fe/Mg 2250 ± 15 2320 ± 10 2375 ± 10 ± 0.3 ± 0.3 ± 0.3 ± 15 ± 10 ± 10  Usually shortened 2250 nm feature compared to chlorite  Yields lower reflectance spectrum than chlorite  Symmetrical 2340 nm feature  2380-2390 nm feature diagnostic of phlogopite  Biotite exhibits a positive slope due to Fe2+. Phlogopite does not.  2340-2350 nm feature diagnostic of biotite Carbonate 1770 1865 1900-1950 2100-2160 2300 2330 2500-2550 OH/H2O trapped Dolomite – calcite H2O trapped CO3 Fe-OH CO3 Mg-Ca substitution CO3 1875 ± 20 1925 ± 10 1950 ± 10 2150 ± 10 2300 ± 20 2330 ± 15 ± 0.3 ± 0.3 ± 0.3 ± 0.3 ± 0.3 ± 0.3 ± 10 ± 30 ± 10 ± 10 ± 10 ± 20  2300-2350 nm absorption feature has a shoulder at 2300 nm  Asymmetric 2340 nm feature  2317 nm = dolomite  2337 nm = calcite  Dolomite < 1870 nm < calcite  Water is seldom present in carbonate  1995 nm absorption feature in calcite  2250 nm feature is not in calcite or dolomite, but can be present in other carbonate minerals Amphibole 800-1200 1400 2330 2400 Fe2+ OH/H2O trapped Mg-OH Fe-OH 1400 ± 15 2330 ± 10 2400 ± 10 ± 0.3 ± 0.3 ± 0.3 ± 10 ± 10 ± 10  Asymmetrical 2300 nm feature  Weak but can be broad absorption at 2400 nm  Fe causes the 2400 nm absorption feature to degrade and the 2300 nm doublet to be rounded  Very minor 2250 nm feature, often this is not present † absorption features derived from Hunt and Salisbury (1970); Hunt and Salisbury (1971); Hunt (1979); Goetz et al. (1983); Gaffey (1987); Clark et al. (1990); Mustard (1992); Clark (1999); Hatchell (1999); Gupta (2003); Rowan et al. (2004); Hauff (2005); Craig et al. (2009); Doublier et al. (2010). * FWHM = full width at half maxi- mum (see Fig. 7.2). Figure 2 graphically indicates what was measured for the depth and width variations. 272 Spectral data was collected from 188 samples using thin section off cuts. The distribution of SWIR analyzed samples along both cross sections is provided in figure 7.1. As each sample had a corresponding thin section, petrography, SEM EDS and EMPA data could be used for comparison. For a comprehensive analysis, 10 separate readings were taken per sample, covering the whole off cut surface. In order to compensate for the darkness of the RLGM host rocks (bas- alt, ultramafic and argillite), the ASD was set up with the below specifics: Dark current = 50 amps Spectrum = 200 White reference = 400 From the 10 analyses per sample, one (to rarely two) representative analysis per sample was se- lected using the following criteria: 1. If the TSG mineral ID was ‘aspectral’, ‘wood’ or ‘dark’ the data were rejected. 2. If the TSG identified two different minerals, the analysis was preferred over an analysis with only one mineral identified. 3. If two different mineral types (e.g. Fe- and Mg-chlorite) were identified, both analyses were kept. 4. The most ‘null’ values per analysis were removed. From the 188 samples analyzed, a complete sample suite of 205 SWIR spectra were selected us- ing the above criteria. Twenty-one samples contained duplicates of multiple chlorite composi- tions, e.g. both Fe- and Mg-chlorite. This data can be found in Appendix D.1. SWIR spectral data corresponding to chlorite, biotite, amphibole and carbonate was spe- cifically gathered. These minerals were the focus of the mineral chemistry investigation (Chapter 4). Each mineral contains several diagnostic peaks used for spectral identification (Table 7.1; Fig. 7.2). For a mineral phase to be present in a sample, each diagnostic wavelength feature was required to be present in the spectra. Table 7.1 outlines the required wavelength features for each mineral, and the range in wavelength variation tested. The range in wavelength features (wave- length position, depth and width) was confined to only the desired mineral investigated, but wide enough to allow for the major element variations to be recorded. These ranges were constrained using Hauff (2005). Numerical data from wavelength features, e.g. position, width and depth, were extracted using TSG. These data were used in the identification of minerals and trends. 273 Figure 7.1 Location of all samples analyzed using the Analytical Spectral Device. A) Campbell, B) Red Lake. 274 Figure 7.2 Reference SWIR spectra for chlorite, carbonate, biotite and hornblende (amphibole). Information from, Hunt (1979), Hauff (2005) and Canet et al. (2010). The shaded boxes indicate the positions of key diagnostic fea- tures. The red arrows on the calcite and dolomite spectra indicate what was collected as the depth variation and width variations of spectral features. 7.2.2 Magnetic susceptibility Magnetic susceptibility is a measure of the magnetization of a sample in response to an applied magnetic field (Maher and Thompson, 1991). It is controlled by the abundance of mag- netic minerals, for example magnetite and pyrrhotite. Magnetism of pyrrhotite is controlled by 275 its crystal structure and iron abundance (Kontny et al., 2000; Williams, 2008). Monoclinic pyrrhotite is magnetic, and hexagonal pyrrhotite is non- to minimally magnetic (Williams, 2008). Pyrrhotite with a low metal abundance demonstrates low magnetic susceptibility values (Kontny et al., 2000). Magnetite is consistently magnetic. Both magnetite and pyrrhotite (approximately 90% of all pyrrhotite) identified at Red Lake are magnetic, and so influence the magnetic suscep- tibly of the sample. In the Red Lake area, magnetite and pyrrhotite occur in several paragenetic stages (Fig. 3.2). Magnetite can be associated with the early assemblages of biotite-Ti-magnetite ± carbonate (Fig. 3.3) and chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± garnet ± magnetite (Fig 3.7F). When present in the chlorite-bearing assemblage, the magnetite can be abundant but invisible in hand sample. This has lead to the previous identification of garnet- chlorite-magnetite alteration (Penczak, 1996). The magnetite in this assemblage is not consistent across the investigated cross sections of this study. Minor pyrrhotite is also observed as inclu- sions within garnet. This early phase of pyrrhotite is very low in abundance, < 0.5% of the host rock. Magnetite and pyrrhotite are also associated with mineralization at the RLGM. Mineralized ore zones contain more pyrrhotite than magnetite. Magnetite associated ore has been reported at Red Lake by previous studies also (Lavigne and Crocket, 1982; Dubé et al., 2001, 2002, 2004). This study identified magnetite-replacement ore associated with pyrrhotite (Fig. 3.22E), as well as high grade ore with arsenopyrite-pyrrhotite-quartz-pyrite-magnetite-gold-brown biotite (Figs. 3.23 and 3.24). Ore-stage pyrrhotite is the most abundant phase in the RLGM. The ore-stage magnetite may not be the more abundant phase in the RLGM. However, the magnetite associated with gold is present within narrow ore zones, and visible in hand sample and thin section. The association of magnetic minerals with mineralization at the RLGM signifies that geophysical analysis using magnetic susceptibilities is a prospective exploration tool. An Exploranium KT-9 Kappameter was used to collect magnetic susceptibility readings. In total 387 samples were analyzed. This sample suite was composed of several rock types (bas- alt being the most abundant), alteration and mineralization styles across both cross sections. Fig- ure 7.3 provides the sample locations. Magnetic susceptibly data was obtained mostly from core samples. Hand samples from ore zones were also assessed. The core samples analyzed ranged in diameter and were often split. A method modified from Mitchinson (2009) was used for data col- lection. From each sample 10 separate readings were taken at regular intervals. These 10 read- ings were then averaged to estimate the magnetic susceptibility of the sample. 276 Figure 7.3 Location of all samples analyzed for magnetic susceptibility values. A) Campbell, B) Red Lake. 277 The core diameters were 2.2, 2.54 (1 inch), 3, 3.6, 4.7 and 5 cm. The Kappameter is set up to collect drill core readings off a fixed, single integer value (e.g. 4 cm diameter) and a non- split core. The only exception was a setting for 1 inch diameter (2.54 cm) core, which was al- ready programmed into the KT-9. Mitchinson (2009) stated that there are variations between the magnetic susceptibility derived from different diameters and whole vs. split core. In order to ob- tain readings of ‘odd’ diameter and split core, two calibrations were required – one for odd core diameters, the other for split core. All corrected magnetic susceptibility values can be found in Appendix D.2. The calibration methods are provided below. 7.2.2.1 Core diameter corrections For the odd core diameters (2.2, 3.6 and 4.7 cm), three separate diameter readings (each an average of 10 separate analyses) were taken: one diameter setting size below and two diame- ter setting sizes above. For example, for core diameter 4.7 cm, an average of 10 readings was taken at each of the settings 4, 5 and 6 cm diameters. This information was plotted with a poly- nomial line of best fit applied. Using this graph, the correct diameter’s reading was obtained (Fig. 7.4A). This value was taken as an estimate of the magnetic susceptibility of the total sam- ple at the ‘odd’ diameter length. 7.2.2.2 Split core corrections Several core samples were split lengthwise for prior geochemical or assay analysis by the mine, leaving only half core to be tested. It was noted that the core diameter also affected the split to whole core ratio. Thus, each diameter size was calibrated separately. For even core diam- eters 2.54, 3 and 5 cm, 10 reference samples were chosen. For odd core diameters 2.2, 3.6 and 4.7 cm, 5 reference samples were chosen. In order to achieve a representative magnetic suscepti- bility for each sample, the process outlined above was used. For each core diameter, 10 magnetic susceptibility readings from the whole reference sample were taken then averaged. The core was then halved with a rock saw and the readings retaken from the same positions. Each analysis for whole then spilt core was compared then averaged. It was noted that the differences between split and whole core was proportional, and related in a weak linear trend (Fig. 7.4B). This rela- tionship breaks down at low magnetic susceptibility values, where there is a broad range in cor- rection factors. Despite this, the mean ratio for each core diameter setting was used, with a cor- rection factor calculated using (1-split:whole core)+1 (Mitchinson, 2009). This correction factor 278 was multiplied by the mean magnetic susceptibility of the split rock to obtain an estimate of the whole rock’s magnetic susceptibility value. Figure 7.4 Examples of magnetic susceptibility calibrations. A) Calibration graph for diameter 4.7 cm. B) Whole: split core conversion factor for core diameter 4.7 cm. Sus = magnetic susceptibility. 7.2.3 A note on analytical techniques Before comparisons between techniques can be made, it is important to remember what they assess. EMPA provides the composition of individual grains. SWIR provides an average of all the hydrous minerals within the sample. Magnetic susceptibility is directly related to the abundance of magnetic minerals, e.g. magnetite and pyrrhotite (Kontny et al., 2000; Williams, 2008). Finally, whole rock geochemical analysis (using the four acid digest method) breaks down nearly all the mineral components of the rock (apart from resistant minerals e.g. zirocn) to provide the abundance of 48 elements. As SWIR and magnetic susceptibility are only semi- quantitative, a direct comparison with whole rock geochemistry or EMPA is not possible. Ra- ther, the more accurate and precise methods (EMPA, whole rock geochemistry) will be used to support or reject the trends displayed by the semi-quantitative methods. 7.3 Identification of minerals and chemical trends using the SWIR Prior to the interpretation and analysis of SWIR data, it is critical to establish whether the investigated mineral is identified in the spectra. This potentially can be difficult, as typically all four investigated minerals (chlorite, biotite, amphibole and carbonate) occur in Red Lake rocks. Several characteristic wavelength features are shared between the investigated minerals (Table 7.1 and Fig. 7.2). Also, chlorite, biotite and carbonate are present in multiple paragenetic stages (Fig. 3.2), but vary in composition and abundance. As SWIR is directly affected by abundance 279 (c.f. Thompson et al., 1999), the most abundant mineral phases are more easily identified. These factors caused complexity in the SWIR data interpretation. Consequently, careful examination of a combination of features was critical for a mineral to be identified. After a mineral was identi- fied in a sample, variations in the wavelength features, and potential chemistry of those samples, could be assessed. SWIR data was addressed in three steps: (1) can the specific minerals be iden- tified; (2) can mineral chemistry be identified; and (3) to assess mappable trends toward mineral- ization. It is important to remember that the SWIR is not designed for precise mineral identifica- tion. Rather, it is important to establish if SWIR can detect minerals, and suggest chemical dif- ferences. For example, can the SWIR correctly identify Fe- and Mg-chlorites? 7.3.1 Chlorite Several paragenetic phases of chlorite occur in the RLGM (Fig. 3.2). Iron-(blue) chlorite formed at the onset of regional metamorphism. This was followed by Fe-Mg-(brown) then Mg- (grey) chlorite, which formed at higher metamorphic grades (Fig. 3.4). These metamorphic chlo- rites are overprinted by chlorite selvages to ankerite-calcite ± quartz and quartz-ankerite veins. Chlorite selvages are dominantly Fe-(blue) chlorite, but Fe-Mg-(brown) chlorite and Mg-(grey) chlorite selvages are also observed (Fig. 3.18E-G). Chlorite compositions correlate with birefrin- gence colour. These relationships were established in Chapter 4. The most abundant chlorite is the early, pervasive, regional metamorphic varieties of blue, grey and brown. Of these, the grey pervasive Mg-chlorite was the most abundant. As the pervasive chlorite varieties are the most abundant, these chlorite phases were more frequently recognized in SWIR spectra. Chlorite was recorded in the sample when both diagnostic peaks (2250 and 2340 nm) were identified in the spectra (see Table 7.1). From the 205 SWIR sample spectra database, chlo- rite, through petrographic observations (in abundances of 1–15%), was known to occur, and therefore was expected, in 200 of these spectra. The SWIR instrument detected chlorite in 179 samples, i.e. in 90% of samples. However, within this subset of 179 samples, chlorite was identi- fied in five samples that, through petrographic observations did not have chlorite. These samples were observed to contain abundant biotite, which shares 2250 and 2320-2350 nm features. Con- sequently, these samples were removed from the SWIR database prior to analysis as they did not reflect chlorite chemistry. The subset of 174 spectral analyses was assessed to establish if the SWIR could identify compositional differences between chlorite phases. 280 Previous research established that variations in the 2250 and 2340 nm wavelength posi- tion can potentially differentiate between Fe- and Mg-rich chlorites (McLeod et al., 1987; Pontual et al., 1997; Scott et al., 1998). For both absorption features, a longer wavelength corre- sponds to higher Fe values relative to Mg (McLeod et al., 1987; Pontual et al., 1997; Scott et al., 1998). Variations in the wavelength’s width and depth can also potentially identify composition- al differences (Whitney et al., 1983; Mustard, 1992; Bouzari, 2009; Doublier et al., 2010). A larger depth and width ratio of the 2250/2350 nm features indicates more Fe-rich chlorite (Bouzari, 2009). These previous relationships were used to investigate the SWIR identification of chlorite chemistry for Red Lake rocks. The previously established compositional differences were classified on the following criteria: Mg-chlorite at wavelengths < 2250 nm, and Fe-chlorite at wavelengths > 2250 nm (Mg-chlorite < 2250 nm < Fe-chlorite) Mg-chlorite at wavelengths < 2340 nm, and Fe-chlorite at wavelengths > 2250 mm (Mg-chlorite < 2340 < Fe-chlorite) These criteria were based on observations by McLeod et al. (1987), and Pontual et al. (1997). Previous research did not establish an intermediate chlorite composition range. As Fe-Mg- (brown) chlorite was identified (Chapters 3 and 4), an intermediate chlorite composition was de- fined as the middle range; 2250 ± 2.5 nm and 2340 ± 2.5 nm respectively (see Fig. 7.5). The sub- set of chlorite identified SWIR spectra was compared to known chlorite birefringence colours and compositions (Fig. 7.5). The comparison of SWIR and chlorite chemistry indicates a poor correlation. All three chlorite compositions (Fe-, Fe-Mg-, and Mg-) occur at a variety of wave- lengths, particularly in the 2250 nm feature. At the 2340 nm feature (Fig. 7.5B) Mg-chlorite is weakly more associated with lower wavelengths, however, the data remains significantly scat- tered. The comparison between chlorite chemistry indicates no clear relationships between wave- length position and birefringence colour (Fig. 7.5A and B). There are also no clear distinguishing relationships between chlorite birefringence colour and SWIR depth and width ratios (Fig. 7.5C and D). SWIR data is scattered for numerous reasons. These include (1) multiple superposed chlorite phases, each with distinct compositions (Chapters 3 and 4); (2) a single sample can con- tain different chlorite paragenetic stages, which can include different compositions (Chapters 3 281 Figure 7.5 Comparison of proposed SWIR chlorite composition classification and known chlorite composition and corresponding birefringence colour. The red markings indicate the proposed chlorite classification in SWIR spectra (McLeod et al., 1987; Pontual et al., 1997). Abbreviations, wlm = wavelength minimum, w = wavelength width ratio, d = wavelength depth ratio. A) Comparison of 2250 nm wavelength feature. Diagonal striped box indicates the range of an intermediate composition (Fe-Mg) chlorite. B) Comparison of 2340 nm wavelength feature. Diagonal striped box indicates the range of an intermediate composition (Fe-Mg) chlorite. C) Comparison of 2250/2340 nm wavelength width ratios. D) Comparison of 2250/2340 nm wavelength depth ratios. and 4); and (3) the samples assessed are composed of several hydrous mineral phases; a more abundant mineral phase (than chlorite) could have had more influence on the SWIR spectra pro- duced. As the SWIR instrument produces average spectra of all hydrous mineral phases in a sample, this can significantly influence the spectral wavelength features. For example, if a sam- ple contained equal amounts of both Fe-chlorite and Mg-chlorite, the SWIR spectra would have been an average, indicating an intermediate composition. Thus, subtle but important information is lost for mineral chemistry identification by the averaging nature of SWIR spectra. Distal sam- ples > 5 km from mineralization contain chlorite in low abundances, commonly as inclusions in garnet porphyroblasts (Fig. 3.6). Even though chlorite is in low abundances, it still composes at least 5 % of the sample, which is theoretically enough for detection with the SWIR instrument (Thompson et al., 1999). Distal samples have abundant amphibole and epidote. Epidote was not 282 identified in any of the spectra, as each lacked diagnostic features at 1850 and 1900 nm (Hauff, 2005). Therefore, epidote is not considered to have influenced the SWIR spectra distally. Am- phibole spectra contain only a minor 2250 nm feature (Hauff, 2005). However, the amphibole doublet at 2300-2330 nm could potentially have influenced the chlorite 2340 nm wavelength fea- ture. As the amphibole doublet feature occurs at a slightly lower wavelength — 2300-2330 nm rather than the 2340 nm feature assessed for chlorite — it was concluded that the amphibole doublet at 2300-2330 had little influence on the chlorite 2340 nm feature. Additionally, as the chlorite abundance is enough to be detected by the SWIR instrument it was concluded that there would have been some influence from chlorite on the spectra produced across the cross section length investigated. Diagnostic chlorite absorption features (2250 and 2340 nm wavelength positions, depth and width ratios) were plotted against estimated distance from mineralization (Fig. 7.6). Sur- rounding mineralization, ± 500 m distally, SWIR data is incredibly scattered, with less signifi- cantly scattered data outside the ore zone area. The scattering of data, especially proximal to ore zones, is due to the intensity of alteration, with all documented mineral assemblages occurring within this area (Chapter 3). The SWIR data outside the area proximal to ore zones (e.g. > 500 m distally) was used to identify trends for exploration purposes through regression analysis (Fig. 7.6). These trends could potentially be used to identify an area 1 km2 surrounding mineralization. The 2250 nm wavelength feature best displays a progressive increase in the wavelength position, with increasing distance toward mineralization up to 1 km distally (Fig. 7.6A). The 2250 nm fea- ture displays the least amount of scatter. The 2340 nm wavelength feature also displays an in- crease toward mineralization, but the scatter of the data is significant (Fig. 7.6B). The 2250/2340 depth ratio feature indicates a subtle decreasing trend toward mineralization, however, the data is considerably scattered (Fig. 7.6C). No identifiable trend is displayed in the 2250/2340 width ra- tios, which exhibit the greatest amount of scatter (Fig. 7.6D). These findings are consistent with the previous SWIR investigation at Red Lake, which identified an increase in the 2250 and 2340 nm feature proximal to mineralization (Bouzari, 2009). This increase in both wavelength features indicates more Fe-rich chlorite proximal to mineralization. Petrographic observations indicated a more complex arrangement of chlorite compositions (Chapter 3). However, this trend is comparable with widespread chlorite ranging 283 Figure 7.6 Comparison of SWIR spectra known to contain the diagnostic wavelength features (2250 and 2340 nm) versus estimated distance from ore. Abbreviations, wlm = wavelength minimum, w = wavelength width ratio at FWHM, d = wavelength depth ratio. Grey shaded boxes indicate the area proximal to ore zones with intense alteration, and extremely scattered SWIR data. In each figure (A–D), the red line indicates the regression calculated for samples > 500 m from mineralization to approxi- mately 5 km distally (data indicated by circles). The samples 500–1500 m from mineralization, indicated by triangles, were not used in the regression calculation as these data are separate spatially and not as wide ranging. All regression lines are accompanied by the R2 as calculated by Windows Excel. A) Comparison of 2250 nm wave- length feature versus distance from mineralization. B) Comparison of 2340 nm wavelength feature. C) Comparison of 2250/2340 nm wavelength width ratios. D) Com- parison of 2250/2340 nm wavelength depth ratios. 284 from Fe- to Mg-compositions, which was overprinted by a narrower halo of dominantly Fe- chlorite selvages proximal to mineralization. 7.3.2 Biotite Two biotite phases have been identified at the RLGM though petrography. The earliest phase was pervasive Fe-biotite associated with Ti-magnetite ± carbonate (Fig. 3.3). This is over- printed by Mg-brown biotite associated with quartz and the mineralization phase (Fig. 3.23). The pervasive biotite varies from 2–35% in abundance, with the greatest abundance proximal to the mine rather than distally. Brown biotite is less common (than pervasive biotite) and varies in abundance from 10–25% of the sample. Brown biotite is also considerably more localized and formed a narrow halo, 0–50 m, surrounding mineralization at the RLGM. The identification of biotite using SWIR is complex for two reasons. First, biotite is a dark mineral, and therefore absorbs light rather than reflecting it. The reflected spectra from dark (biotite-rich samples) were often noisy, or of poor quality. Diagnostic wavelength peaks could have easily been missed in noisy spectra. Second, separation of chlorite and biotite is challenging due to the similar diagnostic features at 2250 and 2350 nm (Table 7.1). Biotite was only identi- fied in a sample if all three diagnostic peaks (2250, 2320 and 2375 nm) were present in the spec- tra. Biotite spectra are distinct from chlorite due to the presence of an absorption feature at ap- proximately 2375 nm (Table 7.1 and Fig. 7.2). From the 205 spectra suite, 176 were known to contain biotite in various abundances (2–35%) by petrography. From the SWIR database, the diagnostic peaks of 2250, 2320 and 2375 nm were present in 93 samples, i.e. 53% of the sam- ples. However, within this subset of 93 samples, biotite was identified in seven samples that did not have biotite identified during petrographic analysis. These samples were observed to contain abundant carbonate minerals (specifically ankerite). Carbonate minerals have diagnostic features at 2300 nm, which could have interfered with the 2375 nm feature. These analyses, which are not representative of biotite, were removed prior to further analysis. Consequently, the biotite SWIR database consisted of 86 samples. Biotite has not been investigated as thoroughly as chlorite in previous SWIR investiga- tions. As some diagnostic wavelengths are shared between biotite and chlorite, the composition of biotite was assessed using similar criteria as for chlorite. SWIR identification of chemical var- iations in biotite compositions were distinguished using the following criteria: Mg-biotite (phlogopite) < 2253 nm < Fe-biotite 285 Mg-biotite (phlogopite) < 2320 nm < Fe-biotite Mg-biotite (phlogopite) < 2375 nm < Fe-biotite This classification is based on Hauff (2005). Using the subset of biotite identifying spectra, the SWIR data was compared to known biotite compositions (Fig. 7.7). Electron microprobe analy- sis (EMPA) defined that pervasive biotite was Fe-rich and brown biotite was relatively Mg-rich (Chapter 4). This was the pretext to which the SWIR data was compared. The biotite phases were identified in thin section by mineral associations and paragenetic timing (Chapter 3 and Fig. 3.2). The pervasive biotite was recognized in samples more frequently. Biotite was frequent- ly overprinted by subsequent minerals, therefore, was defined as early pervasive biotite. The comparison of SWIR data and biotite chemistry is scattered, with poor correlations and no clear distinguishing features documented (Fig. 7.7). The data collected shows that both Fe- and Mg- biotite compositions display multiple wavelength positions (Fig. 7.7). The 2250 and 2320 nm features are skewed to higher wavelengths (suggesting more Fe-rich biotite). This skewed data could be reflecting the Fe-rich nature of the bulk rock composition. The averaging of the SWIR spectra could have been influenced by other Fe-rich minerals such as chlorite and amphibole. It could also be related to the more common occurrence of pervasive Fe-biotite than Mg-biotite. However, not all biotite compositions at higher wavelengths are Fe-rich; some analyses were de- rived from samples with Mg-rich biotite (Fig. 7.7). Overall there is no preferred correlation be- tween Fe- and Mg-biotite and wavelength positions for the 2250, 2320 and 2375 nm features (Fig. 7.7). This is because of (1) the low albedo of biotite, which caused a low identification rate in SWIR spectra; (2) samples contain a mix of minerals, which would have influenced the spec- tral wavelength positions (e.g. the skewing of data toward higher wavelengths); and (3) two biotite phases of different compositions, which occur in samples proximal to ore zones. The comparison of SWIR biotite spectra versus distance from mineralization is scattered across the whole cross section length (Fig. 7.8). Samples from 0–500 m from ore are extremely scattered. This is expected due to the intense alteration and vein phases observed proximal to mineralization (Chapter 3). Samples > 500 m from mineralization (outside the area of intense alteration proximal to ore zones) were used in the assessment of trends for exploration. As Mg- biotite is associated with mineralization and formed narrow halos to ore, < 50 m, only the perva- sive Fe-biotite SWIR data was assessed for trends. Despite the highly scattered SWIR data, trends can be identified in the data > 500 m from mineralization (Fig. 7.9). The 2250 nm feature 286 Figure 7.7 Comparison of biotite chemistry by EMPA and SWIR identification. Only spectra containing all three diagnostic peaks required for biotite identification are included. A) 2250 nm, B) 2320 nm and C) 2375 nm wave- length feature. For each plot the purple markings indicate the SWIR classification based on wavelength position (Hauff, 2005). indicates a decrease in wavelength position with increased distance from mineralization. This mimics the chlorite 2250 nm feature. As both chlorite and biotite share this diagnostic peak both minerals influenced this trend. The abundance of both chlorite and biotite distally ranged from 5–15%, with amphibole as the dominant mineral phase > 3 km from mineralization. As amphi- bole has a minor 2250 nm feature, these trends demonstrated in the 2250 nm feature are related to both biotite and chlorite. Due to similar low abundances and the mixed nature of samples, it cannot be determined which mineral is more influential on the 2250 nm feature. However, the consistent trend would indicate both minerals influenced the spectra in the same way. The 2320 nm feature indicates an increase in wavelength position with increasing distance from minerali- zation (Fig. 7.8B). The 2320 nm feature is specific to biotite, therefore not affected by chlorite (at 2340 nm). The 2375 nm wavelength feature is exceptionally scattered with only a very weak increase in wavelength proximal to mineralization indicated (Fig. 7.8C). The scattering of SWIR 287 Figure 7.8 Variation in diagnostic biotite absorption wavelength peaks at (A) 2250, (B) 2320 and (C) 2375 nm. Ab- breviations: wlm = wavelength minimum, w = wavelength width ratio at FWHM, d = wavelength depth ratio. Grey shaded box indicates the area proximal to ore zones with intense alteration, and SWIR scattered data. In each figure (A–C), the black line indicates the regression calculated for samples > 500 m from mineralization to approximately 5 km distally (circle data). The samples 500–1500 m from mineralization, indicated by triangles, were not used in the regression calculation as this data is separate spatially, not wide ranging and only three samples. All regression lines are accompanied by the R2 as calculated by Windows Excel. data is attributed to the low reflectance from dark rocks and more abundant overprinting miner- als, which had a greater influence on the produced SWIR spectra. 7.3.3 Carbonate Carbonate minerals at Red Lake are Fe-rich varieties of calcite and ankerite (Chapter 4). Multiple paragenetic carbonate phases were identified (Fig. 3.2). This can be simplified into three main stages: (1) an early, but minor in abundance (5–15%) pervasive and widespread cal- cite event; (2) an abundant (10–85%), overprinting ankerite-calcite vein phase, which is concen- trated at the mine; and (3) a very minor, < 1% of the sample late calcite veinlets. Due to such minor abundances of the late calcite this could not be detected with the SWIR instrument. How- ever, the more abundant early calcite and overprinting ankerite-calcite veins can be detected. A well documented pattern of an ankerite/dolomite core to mineralization enveloped by distal cal- cite is recorded (MacGeehan et al., 1982; Parker, 2000; This study). Through detailed EMPA work, the extent of the ankerite/dolomite core is 1.2 km from mineralization (Chapter 4). 288 Carbonate minerals have several diagnostic peaks (Table 7.1). Wavelength features at 1870 and 2300–2330 nm can, theoretically, be used to identify calcite and dolomite (Gaffey, 1985, 1987; Rowan et al., 1986; Craig et al., 2009; Fig. 7.1) Calcite is identified by wavelength features at > 1870 and ≈ 2337 nm (Gaffey, 1985, 1987). Dolomite (ankerite) is identified by fea- tures at < 1870 and ≈ 2317 nm (Gaffey, 1985, 1987). To recognize whether a carbonate mineral was identified in the SWIR spectra, the diagnostic peaks of 1870, 1950, 2150 and 2330 nm were used. The 2250 nm feature is not displayed by calcite and dolomite spectra, therefore was not used for identification (Hauff, 2005). From the complete SWIR spectra sample suite, 200 sam- ples were known to contain carbonate minerals, either as a vein or as pervasive alteration. The SWIR instrument identified the four diagnostic carbonate mineral peaks in 102 samples, i.e. 51% of samples. This subset of samples was used to assess the SWIR instruments ability to assess carbonate chemistry. Many investigations have analyzed SWIR wavelength positions with regard to cation-OH and CO3 bonds (Gaffey, 1985, 1986, 1987; Rowan et al., 1986; Hauff, 2005; Craig et al., 2009). However, little investigation has been done on width and depth variations with carbonate chem- istry. The exception is Gaffey, (1987) who indicated that the Fe2+ cation produces wider features than the Fe3+ cation (siderite vs. magnesite), but did not compare calcite and dolomite. For this reason, SWIR depth and width features have not been compared to EMPA data. The SWIR carbonate composition classification for this study was based on the 1870 and 2300-2330 nm features. The broadness of the 2300–2330 nm feature distinguishes carbonate from biotite and chlorite peaks at 2340 nm. Both of these features are distinctive for carbonate mineral identification in SWIR data. The other diagnostic peaks at 1900 and 2150 nm were not used for classification purposes; however, they were required to be present within the spectra for carbonate mineral identification. Figure 7.9 demonstrates that carbonate mineral identification by the analysis of 1875 and 2330 nm absorption peaks with Red Lake rocks is not easy. The data is widespread and scattered (Fig. 7.9). The accompanying box and whisker plots (Fig. 7.9 A1 and B1) indicate that the mean and median of the calcite (identified using EMPA and EDS) do occur at slightly higher wave- lengths than the ankerite/dolomite. This is consistent with previous knowledge (Gaffey, 1987; Rowan et al., 1986; Craig et al., 2009). However, if the carbonate mineral was not known prior 289 to SWIR analysis of Red Lake rocks, the separation of calcite and dolomite would be difficult, as large overlaps are demonstrated. The scattering of SWIR carbonate mineral identifying spectra is caused by (1) multiple carbonate alteration and vein phases, often occurring in the same sample; (2) different composi- tions of carbonate minerals; and (3) other hydrous mineral phases with similar absorption peaks, such as amphibole, which affected the produced spectra. Most of the samples assessed contained Figure 7.9 Identification of carbonate chemistry though SWIR absorption features. A) Analysis of the 1875 nm fea- ture. The red markings indicate the SWIR classification based on Gaffey, (1985, 1987). B) The accompanying box plot for analysis of the 1875 nm feature. C) Analysis of the 2330 nm wavelength feature. The red markings indicate the SWIR classification based on Gaffey, (1985, 1987). D) The accompanying box plot for analysis of the 2330 nm feature. Wlm = wavelength minimum. 290 multiple paragenetic stages of carbonate veins and alteration. These carbonate phases are com- posed of both ankerite and calcite in various abundances (see Chapter 3). Ankerite is the most abundant carbonate mineral. However, minor calcite, in 5–10% abundance is also present (Chap- ter 3). Ankerite and calcite have distinct spectra (Gaffey, 1985, 1987; Hauff, 2005). In samples where the SWIR instrument detected both ankerite and calcite, the spectra produced would have been an average of these two minerals, therefore losing some distinctive aspects in the spectra and causing wavelength features that were not necessarily diagnostic of a specific mineral. The paragenetic stages of carbonate minerals were demonstrated to progressively increase in Fe- abundance from oldest to youngest occurrences (Figs. 4.19 and 4.20). These compositional var- iations were subtle, with Fe abundance varying from 0.05–0.45 apfu Fe+Mn abundance (Fig. 4.20). The EMPA carbonate data was directly compared to the SWIR spectral wavelengths at 1875 and 2300-2330 nm to investigate if these compositional changes between paragenetic stag- es influenced the spectra (Fig. 7.10). Only a few samples were compared, as not every sample which was probed had a corresponding SWIR analysis or the carbonate was too low in abun- dance for detection. However, there is a positive correlation indicated by samples with abundant carbonate, both pervasive and veined. The Fe-rich carbonate corresponds to higher wavelength features of both 1875 and 2300-2330 nm features. Therefore, with multiple carbonate composi- tions and phases occurring in the sample, scattering of the data can be explained. Carbonate minerals identified by SEM, EMPA and acid reactivity (Chapter 4) confirmed distal calcite surrounding a core of ankerite proximal to mineralization (MacGeehan et al., 1982; Parker, 2000). Re-classification of diagnostic carbonate wavelengths was used to assess whether the same trends could be identified using SWIR spectra. The absorption features were reclassi- fied using the following criteria, based on observations by Gaffey, (1985, 1987): dolomite/ankerite < 1870 nm < calcite, dolomite/ankerite < 2335 nm < calcite The re-classified data was mapped along both cross sections (Figs. 7.11 and 7.12). Both re- classification schemes display a mix of both ankerite/dolomite and calcite across the cross sec- tions. The distinction between distal calcite and proximal ankerite is not clear with either re- classified SWIR absorption feature. Given the scattered nature of the SWIR data, this is not sur- prising. The lack of clarity with the SWIR re-classified data is attributed to the supposed car- bonate occurrences, varying carbonate mineral compositions between paragenetic stages and the 291 Figure 7.10 Direct comparison between EMPA and SWIR carbonate mineral composition. The more Fe-rich car- bonate minerals are associated with higher wavelength features in the 1875 and 2330 nm SWIR features. Sample A) = CR4611-581 which contains pervasive calcite and ankerite vein. B) = DS358-1215, Fe-rich ankerite vein domi- nated sample. The vein in this sample is younger than both carbonate phases in sample CR4611-581. frequent occurrence of both ankerite and calcite and other, more abundant, hydrous minerals within samples. All wavelengths of diagnostic carbonate spectra (Table 7.1) were analyzed for potential trends toward ore zones (Fig. 7.13). The data is extremely scattered across the whole distance investigated. The data < 500 m mineralization was not used in the calculation of trends, as this is where known ore zones with associated intense alteration occur. Rather, the distal data, > 500 m from mineralization was used to calculate trends (regression calculations) to potentially identify areas of intense alteration and economic mineralization. The trends are weak and extremely scat- tered, but identifiable through statistical analysis. The 1875, 1950 and 2150 nm all demonstrate slight decreases in the wavelength position, with increased distance to mineralization. The 2330 nm feature displays the opposite, showing a decrease in wavelength with increasing distance from mineralization. The 2330 nm feature would suggest that ankerite is more common proximal to mineralization, which is consistent with the identified carbonate mineral zonation surrounding the RLGM (Chapter 4). However, the extent of scatter and the different trends between 292 Figure 7.11 Distribution of reclassified carbonate SWIR spectra, dolomite < 1875 nm < calcite, along (A) the Campbell cross section and (B) Red Lake cross section. Wlm = wavelength minimum. 293 Figure 7.12 Distribution of reclassified carbonate SWIR spectra, dolomite < 2330 nm < calcite, along (A) the Campbell cross section and (B) Red Lake cross section. Wlm = wavelength minimum. 294 diagnostic carbonate minerals indicates that the 2330 nm feature (which correlates to the Fe- abundance) is influenced by the bulk rock Fe-composition and other Fe-bearing mineral phases. Regardless of controlling influences, SWIR trends were identified to vector toward mineraliza- tion (Fig. 7.13). Figure 7.13 Variation of diagnostic carbonate SWIR absorption features in relation to increasing distance from min- eralization. A) 1875 nm, B) 1950nm, C) 2150 nm, D) 2330 nm. Abbreviations: wlm = wavelength minimum, w = wavelength width ratio at FWHM, d = wavelength depth ratio. Grey shaded box indicates the area proximal to ore zones with intense alteration, and SWIR scattered data. In each figure (A–C), the red line indicates the regression calculated for samples > 500 m from mineralization to approximately 5 km distally (circle data). The samples 500- 1500 m from mineralization, indicated by triangles, were not used in the regression calculation as this data is sepa- rate spatially, not wide ranging and only nine samples. All regression lines are accompanied by the R2 as calculated by Windows Excel. 7.3.4 Amphibole Two amphibole groups have been identified through petrography and EMPA. Both de- veloped during M2 regional metamorphism. Non-calcic amphiboles occur in the greenschist to transitional facies, and calcic amphiboles in the amphibolite facies (Fig. 3.27). The chemistry of the non-calcic- and calcic-amphibole are influenced significantly by metamorphic grade and the 295 bulk rock composition at the time of metamorphism (Chapter 4). Although the Mg and Fe2+ of amphiboles vary per sample, there is only a weak trend exhibited spatially, e.g. decrease in Fe2+ abundance distally from mineralization at the RLGM (Fig. 4.17). Amphibole has been documented to exhibit multiple diagnostic absorption peaks in SWIR spectra which correlate to the Fe and Mg abundances (Table. 7.1). The most distinctive wavelength feature for identification is a doublet occurring at approximately 2300-2330 to 2400 nm (Hauff, 2005; Fig. 7.2). For the SWIR to identify amphibole within a sample, the diagnostic doublet feature at 2330 to 2400 nm was required to be displayed within the spectra. The 2330 nm feature is diagnostic of carbonate, but without the doublet at 2400 nm, amphibole was not identi- fied in the SWIR spectra. From the 205 SWIR spectral suite, amphibole (through petrography) was identified in 130 samples. The SWIR instrument identified the diagnostic peaks for amphi- bole identification in 92 samples, i.e. 71% of samples. Two of the seven samples which were probed for amphibole mineral chemistry did not display the characteristic doublet feature. There- fore, due to the established criteria for SWIR characterization, amphibole was not identified within theses samples. Consequently, this limited the data set which could be compared with EMPA data. The samples which did not identify amphibole can be explained by thin section ob- servations of low amphibole abundance, with more abundant carbonate, chlorite, and biotite phases. Spectra which did not identify amphiboles present were removed before further analysis. The spectral features at 2330 and 2400 nm were compared to EMPA identified amphi- bole minerals. The limited number of accurately classified amphibole minerals (through EMPA) created challenging interpretation. Calcic amphiboles were identified at a variety of wavelength positions in both the 2330 and 2400 nm features (Fig. 7. 14). As only one sample contained non- calcic amphibole, a trend between wavelength positions could not be identified (Fig. 7.14). Most amphiboles were not probed, therefore they were unable to be classified into a group or a miner- al name identified. Petrographic observations alone could not differentiate accurately enough between amphibole minerals to classify those samples not probed. The unclassified amphibole spectral data are widespread, implying that the distinction of amphibole type by SWIR analysis alone would be challenging. Spectra were also assessed for trends to aid exploration. The amphibole 2330 nm feature is scattered, throughout the investigated lateral distance. Similar to chlorite, biotite and car- bonate, the amphibole spectral data is scattered at both features from 0–500 m from ore (Fig. 296 7.15). The more distal data (> 500 m from mineralization) displays the same degree of scatter (Fig. 7.15). However, statistical analysis of the distal data (500–5500 m from mineralization) did reveal trends, albeit from very scattered data. Both wavelength features (2330 and 2400 nm) demonstrate an increase in wavelength position with increased distance toward mineralization. Figure 7.14 SWIR data that indicated a feature at both 2330 and 2400, implying a doublet diagnostic of amphibole spectra. The scattering of SWIR data is due to (1) the darkness of both the host rock and amphi- boles produced poor quality reflectance data; (2) overlapping Fe and Mg abundances of amphi- bole types (Fig. 4.14; both calcic and non-calcic amphiboles display an Mg/(Mg+Fe2+) ratio of 0.4–0.8 apfu) which caused indistinct wavelength positions; and (3) varying abundance of am- phibole and the influence of other hydrous mineral phases on the produced SWIR spectra. Alt- hough trends were statistically identified, without that analysis a trend exhibited by amphibole SWIR data could not be identified. Therefore, SWIR analysis of amphibole types is limited for aiding exploration. Clear trends are exhibited by the chlorite and biotite spectra, particularly at the 2250 nm feature. 7.3.5 Comparison of SWIR and whole rock geochemistry trends The assessment of SWIR mineral identification indicated that even though the SWIR data is extremely scattered, statistically calculated trends can be identified toward mineralization. The clearest trend is displayed by the 2250 nm wavelength feature, as displayed by chlorite and biotite spectra (Figs. 7.6 and 7.8). The other identified trends were displayed by significantly 297 more scattered data. The 2250 nm feature correlates to the Fe and Mg abundances of chlorite and biotite. The increase in the wavelength positions suggests that both biotite and chlorite become increasingly more Fe-rich toward mineralization. Petrographic observations of the superposed nature of chlorite demonstrated a complex distribution (Fig. 3.29). Pervasive chlorite, ranging Figure 7.15 Distribution of the diagnostic amphibole SWIR absorption peaks, the 2300 and 2400 doublet, with in- creased distance from mineralization. Ore zones are present at 0 m. Abbreviations: wlm = wavelength minimum, w = wavelength width ratio at FWHM, d = wavelength depth ratio. Grey shaded box indicates the area proximal to ore zones with intense alteration, and SWIR scattered data. In each figure (A–C), the red line indicates the regression calculated for samples > 500 m from mineralization to approximately 5 km distally (circle data). The samples 0–500 m from mineralization, indicated by triangles, were not used in the regression calculation as this data is separate spatially, not wide ranging and only eight samples. All regression lines are accompanied by the R2 as calculated by Windows Excel. from Mg to Fe compositions, was overprinted by chlorite selvages also varying in Fe-Mg abun- dances. The simplified chlorite distribution was interpreted, as the metamorphic chlorite is gen- erally more Mg- and Fe-Mg rich proximal to mineralization with distal Fe-chlorite. The meta- morphic chlorite was overprinted by dominantly Fe-chlorite selvages to ankerite-calcite veins which are abundant at the mine site. The biotite distribution is simpler, with widespread Fe- biotite overprinted by a narrow halo of Mg-biotite < 50 m from ore zones. The Fe-biotite is doc- umented at low abundances distally (5–10% abundance), with more abundant occurrences prox- imal to mineralization (5–35%). However, as the SWIR trend was calculated using samples > 500 m distally, the narrow Mg-biotite was not assessed. The complex distribution of chlorite and biotite minerals > 500 m from ore does not fully explain the SWIR trend. Consequently, the 298 2250 nm SWIR trend was compared to whole rock geochemistry data for FeO and MgO abun- dances. If the bulk rock composition was controlled by hydrous minerals, whole rock geochem- istry trends could be used to aid explanation of SWIR trends. Whole rock geochemistry trends of FeO and MgO, like those demonstrated by SWIR, indicate that the widest concentration of abundances were within 500 m of mineralization (Fig. 7.16A and B). This extreme scattering of data is caused by intense alteration and veins proximal to mineralization. In a similar fashion to the SWIR analysis, the whole rock data for samples > 500 m were regressed so that trends could be compared (Fig. 7.16). The scatter of distal samples is less. The whole rock data demonstrates a general decrease in FeO and MgO abundances prox- imal to mineralization. These trends in whole rock data are very subtle, with minimal differences between proximal and distal occurrences. The whole rock trends display the opposite to what was identified by the SWIR 2250 nm feature, which suggests an increase in chlorite and biotite Fe composition (Fig 7.16A-C). The opposite trends exhibited by the SWIR and whole rock data indicates that the bulk rock composition is controlled more by anhydrous phases that are opaque to the SWIR instrument, such as garnet, magnetite and sulfides. As the SWIR instrument is not influenced by the bulk rock composition, the 2250 nm trends therefore reflect the composition of biotite and chlorite. The observations of more abundant Fe-biotite proximal to mineralization compared to > 3 km distally, and the dominance of overprinting Fe-chlorite selvages to ankerite- calcite veins, are concluded to have influenced this trend. The more pronounced SWIR spectral trend in the 2250 nm compared to bulk rock variations could therefore aid exploration. 7.3.6 Influencing factors on SWIR The SWIR instrument operates as a tool for rapid field-based identification of the princi- ple hydrous phases. Using key diagnostic wavelength features (Table 7.1), the investigated hy- drous minerals were successfully identified in most samples (50–90% depending on the mineral) assessed using the SWIR instrument. Chlorite was most commonly recognized in 90% of sam- ples assessed using the SWIR instrument. Carbonate and biotite were only identified in 51-53% of the samples assessed. The influences of the low identification rate will be discussed below. The SWIR instrument also occasionally did not identify known mineral phases or identified phases that were not confirmed by petrographic analysis. For example, sample D39018-4848, which is known to contain amphibole, did not indicate amphibole in the spectra. However, the overall identification rate was successful enough for field-based interpretation and analysis of 299 Figure 7.16 The comparison of whole rock FeO and MgO (derived by four acid digestion methods) with the SWIR 2250 nm feature. A) Whole rock FeO data versus distance from mineralization. B) Whole rock MgO data versus distance from mineralization. C) SWIR 2250 nm feature spectral data versus distance from mineralization. For each figure the red line indicates the calculated regression line for the distal samples (circles) 500–5500 m from minerali- zation. The accompanied R2 number is also included. Both the regression line and R2 were calculated using Win- dows Excel. samples. However, upon comparison with mineral chemistry defined by more precise methods, such as EMPA, the SWIR instrument was not as successful. Through detailed observations of the samples, and what is known regarding mineral compositions, distributions and paragenetic stag- es, the influences and causes of scattered SWIR data can be identified. From Red Lake rocks, the SWIR spectra were interpreted to have been influenced by these factors: (1) the overall darkness of both samples and minerals, which created poor quality spectral data; (2) the minerals investi- gated generally occur in several paragenetic stages, often varied in their Fe and Mg abundances at different stages; (3) varying mineral abundances; and (4) all the samples assessed were com- posed of a mix of minerals, and as the SWIR spectra is an average of all hydrous phases, the oth- 300 er occurring minerals influenced the spectra. These influences will be discussed below with rec- ommended precautions for future SWIR analysis of altered Red Lake rocks. SWIR is a reflectance-based technique. Lighter rocks reflect better, thus produce higher quality spectra for further assessment. The sample suite of RLGM rocks was primarily basalts which are naturally dark rocks. The mineral assemblages themselves are also relatively dark. The quartz-muscovite-andalusite altered and abundant ankerite-calcite vein samples were the excep- tions. The reflected spectra from most of the samples were of a poor quality, often noisy, without clear distinctions (Fig. 7.17). Due to the poor quality of the reflected spectra, the SWIR features were subtle. The dark nature of basalt samples caused 26% of the original data to be rejected. The criteria for selecting representative SWIR spectra required the TSG software to identify a mineral and not an ‘aspectral’ result (section 7.2.1 above). To overcome the issue of poor reflec- tance, these recommendations are suggested. Firstly, ensure that the instrument is set up to ac- count for the darkness of samples (as with this investigation). Multiple analyses of the same sample are necessary to guarantee at least one analysis identifies a mineral trend rather than just noise, as in an aspectral reading. Secondly, as the spectral features are subtle, both manual and automated analysis of spectra is suggested. The extraction of numerical data from wavelength positions is essential to confirm the identification of minerals within poor quality spectra. Analy- sis of spectra with the TSG software aided significantly in deciphering the mineralogy from dark rocks by highlighting whether subtle absorption peaks were present in poor quality data. Petrographic analysis of the minerals investigated indicated a complex spatial and tem- poral relationship. This complexity is reflected in the SWIR data, but with very scattered results. In order to fully interpret the SWIR data, it is essential that a working knowledge of the paragenetic stages, as well as the overall distribution of mineral phases is known. It was proven by the contradicting trends that the SWIR is not influenced by the bulk rock composition. Ra- ther, the SWIR instrument was reflecting hydrous mineral compositions. Without the detailed paragenetic sequence and the knowledge of overprinting mineral phases gathered in this study, a comprehensive interpretation of the SWIR trends could not have been achieved. For future SWIR analysis in the Red Lake area, it is recommended that the mineral framework, both tem- poral and spatial, that has been established in this investigation be used to improve interpretation. The most significant influence on the Red Lake spectra data is the methodology of the SWIR instrument. For each sample assessed, the SWIR instrument produced a spectral result 301 which was the average of all hydrous mineral phases within the sample. The produced SWIR spectra are, in turn, influenced by the samples’ mineralogy, mineral composition and mineral abundance. Abundant or more reflective phases were more easily recognized, therefore, had a stronger influence on the spectra produced. If one mineral composition was greater than another, the more abundant phase would have had more influence on the spectra. For example, abundant Fe-chlorite with minor Mg-chlorite would have produced spectra indicating more Fe-rich com- positions. Additionally, if most minerals were Fe-rich, this could have skewed the data toward higher wavelengths artificially. The averaging nature of the SWIR instrument can explain the successful mineral identification, but the lack of conclusive chemical trends in SWIR data. As each sample contained multiple minerals and mineral compositions, the produced spectra would have indistinct wavelengths, which could not easily be interpreted as either Fe- or Mg-rich min- erals. Through this investigation it was important to localize spectral data correlating to specific mineral phases. This procedure eliminated some of the influence from other mineral phases on the produced spectra, and highlighted trends displayed in specific minerals. The localization of specific minerals was the best approach to removing unwanted effects from other minerals on SWIR spectra. Overall the SWIR instrument was successful for field-based mineral identification. The identification of spectral trends was proven to have been influenced by hydrous minerals rather than bulk rock compositions. However, due to the dark appearance of Red Lake rocks, the com- plex paragenesis and mineral distribution, the multiple compositions of the same mineral and the averaging nature of the SWIR instrument, care is required for interpretation. A working knowledge of the main phases, distribution and relationship to one another is critical for full in- terpretation of the SWIR data. 7.4 Magnetic susceptibility Magnetic susceptibility was investigated as a potential proxy for identifying bulk rock Fe2+ and Fe3+ abundances. Gold mineralization at the RLGM is hosted by Fe2+-rich basalt, sur- rounded by relatively Fe3+-rich rocks distally (MacGeehan and Hodgson, 1980; MacGeehan et al., 1982; Fig. 4.9). Whole rock geochemical analysis indicates that the Fe2+-rich nature of the basalt at the RLGM aided in gold mineralization at the RLGM (Chapter 6). The identification of Fe2+-rich basalt elsewhere in the RLGB could aid in locating future exploration targets. 302 Figure 7.17 The differences in spectral quality between dark basalt rocks and lighter basalt rocks, due to alteration. A) Sample 37L482-1019. B) Sample D39018-635. 7.4.1 Relationship between magnetic susceptibility, mineralization and alteration A generally positive correlation between abundant magnetite and pyrrhotite and high magnetic susceptibilities was identified at the RLGM (Fig. 7.18). Magnetism is related to the presence of magnetic minerals, such as magnetite and pyrrhotite, which contain Fe3+. Rocks that are relatively oxidized (Fe3+ dominated) are magnetic, whereas those that are relatively reduced (Fe2+ dominated) are less so. In reduced rocks, most of the Fe is contained within paramagnetic minerals such as garnet, amphibole, chlorite, etc. Both magnetite and pyrrhotite were formed in several paragenetic stages (Fig. 3.2). Magnetite formed with the earliest metamorphic assem- blage (biotite-Ti-magnetite ± carbonate and chlorite-amphibole-epidote/clinozoisite-biotite- calcite ±garnet ± magnetite). Early magnetite ranged in abundances (1–10%), with irregular oc- currences across the investigated cross section. Magnetite is also associated with ore-stage sul- fide dominated assemblages (Chapter 3). Magnetite associated ore has been reported previously (Dubé et al., 2001, 2002, 2004). The ore-stage magnetite is contained in narrow ore zones. 303 Figure 7.18 Relationship between percentage of magnetite and pyrrhotite in relation to whole rock sample magnetic susceptibilities. Percentage of magnetite and pyrrhotite derived from the samples corresponding thin section obser- vations. A positive relationship is demonstrated between percentage abundance of pyrrhotite and magnetite with high magnetic susceptibility values. Pyrrhotite also occurs in two paragenetic stages. The first is minor (< 1% in abundance) and as- sociated with metamorphic blue chlorite. The most abundant pyrrhotite phase occurred during the mineralization event and is associated with gold, also in narrow ore zones. A comparison of limited gold assays (both ounces per ton and ppb from Bouzari, (2009)) with corresponding magnetic susceptibility values shows only a weak positive trend (Fig. 7.19A and B). Two drill holes that intersected mineralized zones (D39200 and 30L1268) were also in- vestigated to examine if magnetic anomalies corresponded to high gold grades (Fig. 7.19C and D). The down drill hole data indicates no conclusive relationship between magnetic anomalies and gold (Fig. 7.19C and D). The relationship between gold mineralization and magnetic suscep- tibility is therefore controlled by the abundance of magnetite and pyrrhotite; both of which occur with gold (Fig. 3.24). At the deposit scale, a narrow halo, approximately 50–500 m from ore zones, is demonstrated by highly magnetic samples (Fig. 7.20). These magnetic highs are dis- played by ore-stage pyrrhotite and magnetite, which are associated with gold. Despite the narrow magnetic halo, there is potential for magnetic susceptibility to be used at the deposit to belt (through aerial magnetic surveys) scale in order to identify new mineralized areas. 304 Figure 7.19 Relationship of magnetic susceptibility and gold grades in (A) ounces per ton, and (B) ppm. C and D represent down drill hole studies of drill holes in the Campbell and Red Lake complexes, to investigate if magnetic susceptibility can highlight areas of gold mineralization. The assay data for gold grades is derived from Bouzari (2009). 305 Figure 7.20 Distribution of magnetic susceptibility values of basalt samples in relationship to ore zones along the A) Campbell and B) Red Lake cross sections. 306 The main mineral assemblages that contain magnetite and pyrrhotite display higher mag- netic susceptibility values (Fig. 7.21). For example, garnet-chlorite-magnetite (part of the chlo- rite-amphibole-garnet ± epidote ± magnetite ± biotite ± calcite assemblage) display higher mag- netic susceptibility values compared to quartz-muscovite-andalusite altered basalts (Fig. 7.21). Mineralized samples with low magnetic susceptibility values contain abundant disseminated py- rite ± gold, therefore, are less-magnetic. The highly magnetic carbonate-magnetite vein sample forms an outlier. The abundance of magnetite in this carbonate vein caused the high magnetic susceptibility values. The scattering and overlapping of data between mineral assemblages is due to varying abundances of magnetic minerals between alteration assemblages (Fig. 3.2). Over- printing and/or replacement style syn-mineralization pyrrhotite-magnetite can cause artificially higher magnetic susceptibility values. For example, quartz-muscovite-andalusite altered basalt, with less abundant mineralization, displays magnetite susceptibility values from ≈ 0.03–10. Figure 7.21 Variation of magnetic susceptibility values between mineral assemblages. 7.4.2 Comparison of magnetic susceptibility and whole rock chemistry The Fe2+/Fetotal molar ratio of whole rock basalt samples were compared with the corre- sponding magnetic susceptibility values (Fig. 7.22). This was investigated to see if magnetic sus- ceptibility could be used as a field-based proxy for FeO abundance of basalt. In Chapter 6, it was identified that the FeO-rich host basalt played an important role in inducing gold precipitation at the RLGM. Therefore, if magnetic susceptibility could be used in the field to identify FeO rich rocks, these could potentially host gold mineralization in the RLGB. 307 The comparison between bulk rock Fe2+/Fetotal molar ratios and magnetic susceptibility is positive (Fig. 7.22). The bulk rock Fe2+/Fetotal ratio is related to a logarithmic function of magnet- ic susceptibility. High magnetic susceptibility values correlate to the lowest bulk rock Fe2+/Fetotal ratio. The magnetic susceptibility of the bulk rock was identified to be controlled significantly by the abundance of magnetite and pyrrhotite within the sample. Mineralized samples, with the lowest Fe2+/Fetotal ratio, contained the most pyrrhotite and/or magnetite, therefore displaying the Figure 7.22 Comparison of whole rock molar Fe2+/Fetotal ratios and magnetic susceptibility. The highest magnetical- ly susceptible sample correlates to the lowest Fe2+/Total Fe ratio, indicating that the magnetic susceptibility is gov- erned by the presence of magnetite more than pyrrhotite. Mag sus = Magnetic susceptibility, WR = whole rock. highest magnetic susceptibility values (Fig. 7.22). This positive trend suggests that magnetic susceptibility could potentially be used within the field as a proxy for bulk rock Fe2+/Fetotal ratios. However, the identification of mineralized rocks in the field is easy. The relationship demon- strated between bulk rock Fe2+/Fetotal molar ratios and magnetic susceptibility does not add any- thing to detailed field notes. From the data collected, there is no clear distinction between the original FeO of the pre-mineralized samples; all are Fe2+ rich. Visual observations of mineralized rocks within the field would be just as successful for identifying mineralized areas in the RLGB as magnetic susceptibility values. 308 7.5 Conclusions and exploration implications for field-based exploration in the Red Lake area This study of rapid, field-based techniques at Red Lake provided data to support success- ful mineral identification, and trends for exploration by these methods. SWIR was investigated to identify minerals, mineral compositions, and chemical trends to aid exploration. Analysis of diagnostic wavelength features specific to minerals (Table 7.1) successfully identified the major hydrous mineral phases in the Red Lake area. Despite successful mineral identification, the SWIR instrument is limited in its effectiveness to identify different mineral compositions. Min- eral compositions defined by EMPA were compared with SWIR data. Consistently, the SWIR data was scattered, with no distinct trends exhibited to distinguish mineral compositions. The scattering of SWIR data was interpreted to be related to these factors: (1) the darkness of the samples and minerals; (2) varying mineral compositions frequently within the same sample; (3) varying abundances of mineral phases: and (4) the averaging of spectral data from all hydrous minerals by the SWIR instrument. Despite the poor correlation between SWIR and mineral chemistry, a general increase in the 2250 nm feature (of both chlorite and biotite) with increased proximal distance to mineralization can be used for exploration to identify future targets. Magnetic susceptibility was investigated as a possible proxy for whole rock geochemis- try, as well as the identification of trends for exploration. Magnetic susceptibility for Red Lake rocks is controlled by the presence of pyrrhotite and magnetite. Several paragenetic stages of pyrrhotite and magnetite are observed. Early magnetite is associated with biotite-Ti-magnetite ± carbonate and chlorite-amphibole-epidote/clinozoisite-biotite-calcite ± garnet ± magnetite as- semblages. However, early magnetite is sporadic in its abundance and occurrence throughout the RLGB. Early pyrrhotite is also observed to be associated with metamorphic blue chlorite, but in very low abundances. The most abundant pyrrhotite paragenetic phase is associated with gold mineralization. Magnetite is also associated with gold mineralization, but in less abundance than pyrrhotite. The association of magnetic pyrrhotite and magnetite with gold mineralization was used to identify and correlate magnetic susceptibility highs with gold mineralization. Magnetic susceptibility cannot be used as a field-based proxy for mineral and whole rock Fe2+ versus Fe3+ compositions. However, it can be used to identify areas of economic mineralization by the asso- ciation of magnetic highs with abundant pyrrhotite and magnetite with gold mineralization at the deposit scale. 309 Chapter 8: Conclusions 8.1 Introduction The overall aim of this PhD project was to investigate the greater hydrothermal system surrounding the Red Lake Gold Mines, an Archean lode-gold deposit. Information about this greater hydrothermal system was gathered from mineral chemistry, as well as whole rock and isotope geochemistry. Chemical and isotopic data collected in this study were used to reconstruct the geochemical evolution and geological influences on the formation of the RLGM. This provided more information on ore genesis and gold precipitation mechanisms, whose details have not yet been agreed upon in the scientific community. The documentation and characterization of alteration assemblages from proximal to their most distal expression were used to construct vectors to ore, which have exploration implications. This chapter summarizes the main results of this study, with suggestions for future exploration and research in the Red Lake area, as well as Archean lode-gold deposits globally. 8.2 Mineral chemistry The documentation and identification of mineral chemistry variations in the RLGM and surrounding area were fundamental in outlining key geological events and conditions. A detailed paragenesis with the application of mineral chemistry established the following key findings: (1) an early hydrothermal alteration event occurred prior to peak-regional metamorphism; (2) suggested characteristics (physical and chemical) of each hydrothermal event; and (3) trends in mineral chemistry have applications for future exploration. This study focused primarily on documenting the composition of chlorite, biotite, carbonate, amphibole and garnet. These minerals were chosen because they are common throughout the Red Lake area, occur in multiple paragenetic stages (Fig. 3.2), and are easily recognizable. For each mineral, the textural and compositional features found through this investigation are summarized in the following sections. Additionally, the suggested controls on compositional trends for each mineral are also stated. 310 8.2.1 Chlorite Chlorite formed in a variety of paragenetic stages with varying Fe-Mg compositions and a complex superposed spatial arrangement (Chapters 3 and 4). The earliest chlorite phases are widespread, and derived by metamorphism of a pervasively altered the basalt. Each early chlorite phase shows a grain shaped preferred orientation parallel to the D2 foliation (S2). The earliest recognizable chlorite displays a birefringent blue colour and is sometimes associated with early sulfides (pyrrhotite-pyrite-chalcopyrite). This blue chlorite was identified as Fe-rich (XFe (Fe/(Fe/Mg)) = 0.55–0.75). Blue chlorite was overprinted by birefringent brown chlorite, which has an intermediate composition of Fe-Mg (XFe = 0.46–0.54). Both blue and brown chlorite were overprinted by grey birefringent Mg-chlorite (XFe = 0.31–0.46), with associated amphibole-epidote/clinozoisite (Fig. 3.4). The sequence from Fe-rich to Mg-rich metamorphic chlorite is consistent with prograde metamorphism (Spear, 1993). However, the distribution of metamorphic chlorite surrounding the RLGM displays the opposite of that expected. Grey and brown Mg-Fe Mg-chlorite is most abundant proximal to ore zones in lower grade greenschist rocks. Blue Fe-chlorite is more abundant distally in higher grade amphibolite rocks (Fig. 3.29). This was explained by the nature of the chlorite occurrences. At distances of > 5 km from mineralization the chlorite abundance is low, and observed as inclusions within garnet and amphibole porphyroblasts. The decrease in chlorite abundance distally is due to its consumption to form higher grade metamorphic minerals, such as garnet and amphibole. Blue chlorite was consumed to form garnet and amphibole, hence its preservation as inclusions. The mine site occurs at the greenschist to transitional facies, which is a lower metamorphic grade. Typically, chlorite is a characteristic mineral for these metamorphic conditions; hence it is preserved within the matrix with associated amphibole. The metamorphic chlorites were influenced by bulk rock composition as well as metamorphism. The initial chlorite is Fe-rich, therefore suggesting development within an Fe-rich rock. The metamorphic chlorite varieties were overprinted by chlorite selvages to ankerite- calcite and quartz-ankerite veins and late chlorite veinlets. The selvages and veinlets are hydrothermal in origin, as the chlorite does not show a grain shaped preferred orientation, and are localized within D2 structures. These chlorite selvages and veinlets are also birefringent blue, brown and grey. However, they are typically less abundant than the pervasive chlorite varieties. Blue chlorite selvages are the most commonly observed. Veins are most abundant at the RLGM 311 (due to the localization of intense D2 deformation), hence, the overprinting chlorite selvages are most abundant at the RLGM. This overprinting nature of several chlorite compositions and phases creates a complex arrangement, with very complex lateral compositional variations. The chlorite investigation undertaken in this study identified an intermediate composition (not recognized prior, see Chapters 3 and 4), multiple chlorite compositions as vein selvages, and established a rigorous paragenetic sequence of chlorite, which was essential for SWIR analysis. 8.2.2 Biotite Biotite was documented to have formed in two paragenetic stages. The first was a pervasive and widespread biotite-Ti-magnetite ± carbonate assemblage. The second is a brown coloured biotite, documented as narrow halos to ore zones with associated quartz. The pervasive biotite is Fe-rich (XMg [Mg/(Fe+Mg)] = 0.32–0.59) and the brown biotite is relatively Mg-rich (XMg = 0.46–0.73). Compared to the pervasive biotite, the brown biotite is more enriched in Cr and Si. This was interpreted to be related to sulfides and quartz, associated with the brown biotite. The pervasive biotite is metamorphic in origin and displays the main S2 foliation. This biotite assemblage was concluded to have been formed either from recrystallization of pre- existing biotite or K-bearing minerals formed during the pre-regional metamorphic hydrothermal event (H1; see Fig. 6.1). The pervasive biotite composition is largely controlled by this pre- metamorphic hydrothermal alteration of the host basalt. The pervasive biotite is Fe-rich, as the basalt itself was Fe-rich when regional metamorphism occurred. The brown biotite is hydrothermal in origin. This is suggested from its association with veins and ore-stage mineralization. This implies that the composition of the brown biotite was controlled more by the fluid composition than the host rock. These ore-forming fluids were documented to contain SO3, SiO2, CaO, K2O, MgO, As and Sb. The high concentration of MgO within the fluid would have created the Mg-brown biotite. The distribution of biotite along the investigated cross sections (from proximal to mineralization to > 7 km distally) is simpler than the chlorite distribution. The pervasive widespread Fe-biotite was documented to occur > 7 km from mineralization. This was overprinted by a narrow (0–50 m) brown biotite halo surrounding mineralization. Both biotite phases become more K- and Al-rich toward shallower crystal levels. The abundance of Mg in biotite at depth is caused by the dominance of brown biotite within the amphibolite facies. 312 8.2.3 Carbonate Ankerite and calcite were documented in several paragenetic stages during the development of the RLGM. These events can be simplified as an early pervasive calcite (occurred with the biotite-Ti-magnetite ± carbonate and the chlorite-amphibole- epidote/clinozoisite-biotite-calcite ± garnet ± magnetite assemblages), which was overprinted by an abundant ankerite-calcite ± quartz vein event (with biotite and/or chlorite selvages), with a late, minor overprinting calcite veinlet stage. Generally, from oldest to youngest events, the carbonate mineral (both ankerite and calcite) becomes more Fe-rich over time (Fig. 4.20). This was interpreted as progressive fluid-rock interaction with an Fe-rich host rock. The continued fluid-rock interaction caused the Fe-composition of the fluid to increase, therefore forming progressively enriched Fe-carbonate. The documentation of increased Fe-compositions with younger carbonate minerals is a new observation. The temporal and spatial distribution of carbonate minerals demonstrate a widespread calcite event which was overprinted by a narrow ankerite-dominated vein event. This arrangement of carbonate minerals demonstrates an ankeritic core associated with mineralization, which is enveloped by distal calcite. Abundant ankerite veins, which are associated with mineralization in the Red Lake area, were also documented at the Cochenour- Wilmar deposit (Appendix A.4). This carbonate mineral zonation can be identified through CL, EMPA, SEM and reactivity with dilute HCl acid. The EMPA analysis identified the maximum extent of the ankerite core at 1.2 km distally. The documented ankerite to calcite zonation represents the easiest, and potentially most helpful, way to identify new mineralized occurrences in the RLGM. These findings support the previously identified carbonate mineral zonation documentation in the RLGM (MacGeehan et al., 1982; Parker, 2000). 8.2.4 Amphibole Both non-calcic and calcic amphiboles developed during the peak-regional metamorphic event. Amphiboles were classified from three groups: magnesium-iron-manganese-lithium (group 1), calcic (group 2), and sodium-calcium-magnesium-iron-manganese-lithium (group 5) (Table 4.5). Within these groups, different amphibole minerals were recognized (Fig. 4.13). From group 1, ferro-anthophyllite and anthophyllite were defined. Group 2 included ferro- tschermakite, tschermakite, ferro-hornblende, magnesio-hornblende and actinolite. All calcic 313 amphiboles require the prefix ‘alumino’, as Al is > 1.0 apfu (Leake et al., 1997; Hawthorne and Oberti, 2007b). Finally, group 5 contained a mix of parvo/magno ottoliniite and ferro-ottoliniite. The ottoliniite type depends on the (Ca,Na) and (Mn, Fe2+, Mn, Li) concentrations. Most of the amphiboles (regardless of groups) are identified as requiring the ferro- prefix. Chemical differences are greatest between non-calcic and calcic amphiboles. The most distinctive elemental variations are demonstrated by Ca, Si, Fe2+ total, Alvi and MgC-site abundances. Calcium and Alvi were found to be more abundant in calcic amphiboles. Likewise, Si, Fe2+ total Mn and MgC-site abundances are greater in non-calcic amphiboles. Titanium, Natotal and Fe3+ are less abundant in non-calcic amphiboles compared to calcic. Regardless of groups, Cr and K abundance is consistently low. These chemical differences are largely controlled by metamorphic grade, as well as bulk rock composition. Within the transitional facies, both non- calcic and calcic amphiboles are present, whereas in the amphibolite facies only calcic amphiboles occur. Within the transitional facies, the amphiboles are zoned from non-calcic cores to calcic rims. To form such Fe2+-rich amphiboles, it was concluded that the host basalt was enriched in FeO prior to regional metamorphism. The metamorphic link between non-calcic and calcic amphiboles is a new finding, documented first in this study. The identification of ottoliniite is also a new observation to the Red Lake area. 8.2.5 Garnet Garnet in the Red Lake area is metamorphic in origin, developed during the M2 regional metamorphic event. Garnet was identified as almandine (Fe2+) rich, with Mn enriched cores and low abundant Ca and Mg. The chemical zonation of garnet porphyroblasts is only documented using EMPA. The bell-shaped profiles (Fig. 4.24) between Fe2+ and Mn are consistent with previous garnet chemistry investigations (Mathieson, 1982; Christie, 1986; Penczak, 1996; Damer, 1997). The Mn-Fe-compositions of the Red Lake garnets, compared to typical metabasite garnets, implied prior hydrothermal enrichment of Fe and Mn in the basalt prior to metamorphism. Garnet composition varies with increased distance from mineralization (Fig. 4.25). The almandine component is lowest at the mine scale and greatest in abundance at the intermediate and distal scale. The grossular component is generally the least varied. However, proximal to ore 314 zones the Ca-component is the lowest, < 10% within 500 m from ore. From 500 m outward from mineralization, the grossular component is generally > 12.5 %. The spessartine component indicates a general trend which could be used for exploration purposes. The Mn-component decreases from ~ 17.5% proximal to < 7.5% distal to mineralization. The enrichment in Mn at the mine is also displayed in whole rock geochemistry (Bouzari, 2009; Chapter 4). Finally, the pyrope component indicates a weak increase with increasing distance from mineralization. From 0–3 km, the pyrope component is 3–7 %; at distances > 3 km from mineralization, the pyrope abundance is > 7%. Although these chemical differences are minor, they could potentially be used to augment existing exploration practices. 8.2.6 Summary of the influences on mineral composition and distribution The documented influences on mineral composition were identified as bulk rock composition, fluid composition, metamorphism and associated minerals. For the earliest, widespread metamorphic minerals (Stage 1 in Fig. 3.2), prior hydrothermal alteration of the basalt significantly influenced mineral composition, associations, and distribution. This early, pre-metamorphic hydrothermal alteration event was widespread, and resulted in enrichment in Fe, Mn and K, and local heterogeneity (identified in local compositional variations). This early hydrothermal event also created abundant clays, which are the precursor minerals for the unusual (andalusite, chloritoid, staurolite, cordierite) metamorphic minerals within the Red Lake basalt. The Fe2+-rich nature of the basalt also influenced the veined ankerite and calcite compositions. Progressive fluid-rock interaction with the Fe-rich host rock produced Fe enrichment in later fluids, which precipitated more Fe-rich carbonate over time. This early hydrothermal alteration event defined a large-scale variation in mineral chemistry, which has utility in exploration. The identification of FeO rich host basalt could indicate a potentially economic region in the RLGM. Regional metamorphism had a significant influence on the minerals which formed contemporaneously. The effect of regional metamorphism is clearly demonstrated by: (1) the distribution of garnet, which is within the transition-amphibolite facies; (2) amphibole mineral composition and type—non-calcic to calcic with increasing grade; and (3) Fe-chlorite to Mg- chlorite from oldest to youngest. The mineral assemblages which formed post-peak regional metamorphism (Stage 2 in Fig. 3.2), were mainly influenced by fluid composition and fluid-rock interaction (i.e. Fe- 315 abundance in carbonate minerals). The brown biotite formed from the ore-forming fluid, which was deficient in Fe but rich in Mg. Thus, the precipitated biotite was Mg-rich. 8.3 Evolution of the Red Lake Gold Mines Through detailed petrography, and the application of mineral and whole rock chemistry, this study identified several key geological events which have affected the formation of the RLGM. These events are summarized in Figure 8.1 and include the following: (1) an early hydrothermal event (H1); (2) subsequent peak-regional metamorphism (M2); (3) the regional metamorphic assemblages were overprinted by a subsequent vein and ore-formation hydrothermal event (H2), which occurred post-peak-metamorphism, but synchronous with the main deformation phase and plutonism; and (4) a late plutonic emplacement event which is associated with contact metamorphism, brittle-ductile deformation, and minor hydrothermal alteration (H3). These events and their relationship to ore-formation are summarized below, highlighting improvements to the overall genetic model for Red Lake. 8.3.1 Relationship between early, pre-regional hydrothermal alteration and the main ore- formation event A key finding in this study was the identification and characterization of a pre-regional metamorphic hydrothermal event. A fundamental question emerged about how this early hydrothermal alteration related to the overprinting ore-formation event. Through mineral chemistry and whole rock geochemistry, this early, barren, widespread hydrothermal event was inferred to have significantly reduced the basalt, while adding Mn, K and Si, with a loss of Ca and Mg. This early hydrothermal event was also credited with forming the precursor minerals of clay-chlorite-carbonate-mica-Fe-Mn-oxides inferred for the earliest metamorphic assemblage observed (Stage 1 in Fig. 3.2). Through a comparison with similar hydrothermal systems, it was concluded that the early hydrothermal event that affected Red Lake rocks is most consistent with a hybridized magmatic (acid fluids) and Archean seafloor system (near-neutral fluids). The Mn- enrichment in both the Balmer and Bruce Channel assemblage rocks would suggest that the hybridized seafloor system was not related to a MORB system. Rather, the seafloor alteration event was unusual, with commonalities with Archean VMS systems (Dubé et al., 2007). 316 317 Figure 8.1 Schematic diagram showing the major geological phases of the RLGM’s development, with inferred chemical characteristics of each hydrothermal event, proposed fluid sources from stable isotopic data, and suggested hydrothermal environment/tectonic setting. BA) Balmer assemblage, BC) Bruce Channel assemblage, LVL) Little Vermillion Lake batholith, DL) Douglas Lake pluton, Dm) Dome stock, MK) McKenzie stock, ABG) Abino granodiorite, HD) Howey diorite, HLB) Hammell Lake Batholith, KB) Killala-Baird batholith, WL) Walsh Lake pluton, CI) Cat Island pluton, H) hydrothermal event, M) metamorphic event, D) deformation event, P) plutonic event. Deformation details compiled from Sanborn-Barrie et al. (2001) and Dubé et al. (2004). Intrusion emplacement ages from Corfu and Wallace, (1986), Corfu and Andrews (1987), and McMaster (1987). Yellow stars indicate gold-mineralization event. For mineral abbreviations, refer to list of abbreviations. The early hydrothermal event was then overprinted by a regional metamorphic event to create the greenschist-amphibolite facies mineralogy pervasive throughout the RLGB. This, in turn, was overprinted by a post-peak metamorphic vein and mineralization event. Mineralization, consisting of abundant sulfides with minor magnetite, was documented to have replaced ankerite-calcite ± quartz veins and the Fe2+-rich wall rock. Whole rock geochemistry, and specifically the bulk rock Fe2+ versus Fe3+ abundances, indicated no Fe-gain during mineralization. Rather the ore forming fluid oxidized the wall rock Fe2+ to precipitate the relatively Fe3+ ore-stage minerals, pyrrhotite and magnetite. The earlier reduction of the host basalt has been suggested as important for later redox reactions during the gold formation event. 8.3.2 The vein and main mineralization hydrothermal event Abundant ankerite-calcite ± quartz (± chlorite/biotite selvages) formed during post-peak regional metamorphism. This was deduced from carbonate thermometry estimates for the RLGM and the mapped regional outcrop, which were 460–490°C. This is slightly cooler than greenschist-amphibolite conditions (Spear, 1993). The carbon isotopes, derived from the ankerite-calcite veins, indicated a metamorphic fluid. This was either created by devolatilization reactions as prograde metamorphism continued at depth, or from a deep crustal intrusion, with evolved fluids that were rock buffered. Both mechanisms infer the presence of pre-existing carbonate that was deposited during the early hydrothermal (H1) event. This pre-existing carbonate was enriched in 13C and 18O, which explains the unusually isotopically enriched carbonate veins identified at the RLGM (Chapter 5). Following the abundant ankerite-calcite ± veins, quartz veins ± sulfides the main mineralization event occurred, associated with brown Mg-biotite and quartz. Economic mineralization associated with carbonate-quartz veins and K-(alkali) metasomatism is common in Archean lode-gold deposits (Groves et al., 1998; Goldfarb et al., 2005; Prendergast, 2007). 318 Several ore-stage assemblages were documented at various crustal depths within the RLGM (Fig. 3.2). The ore-stage assemblages are composed of varying abundances of pyrite-pyrrhotite- arsenopyrite-magnetite-stibnite-sphalerite-molybdenite-chalcopyrite-gold. The ore zones contain several mineralization styles; veins and replacement ore are most commonly observed (Chapter 3). Ore-stage sulfides and accompanying brown biotite-quartz were documented to replace ankerite-calcite veins, the basalt, and Fe2+-rich minerals such as garnet. The ore-forming fluid was documented to have enriched the basalt in CaO, K2O, MgO, SO3 and SiO2, as well as many of the identified pathfinder trace elements such as Au, Ag, As, Bi, Cu, Mo, Ni, S, Sb and W which accompanied sulfides. Localized loss of FeO was also recorded due to the production of sulfides by sulfidation reactions (Fig. 4.34). The extent of the ore-forming fluid can be chemically identified in the surrounding basalts up to 5 km distally by the following pathfinder elements: As, Ag, Au, Bi, Cu, Mo, Ni, S, Sb, W (which are most effective < 500m from mineralization), Ba, Li, K, Rb and Zn. Sulfur isotopes derived from ore-stage sulfides indicated that the fluid source was magmatic. This was interpreted to have been an intrusion at depth, possibly related to the syn-mineralization intrusions throughout the RLGB. The identification of an evolved ore-forming fluid with complex origins highlights the complex nature of superposed events at the RLGM. 8.3.3 Improvements to the RLGM genetic model A common consensus regarding the ore genesis of the RLGM has yet to be achieved. Several genetic models have been suggested (see Chapters 1 and 6), however, no models currently stress the importance of early hydrothermal alteration, nor the relative timing of regional metamorphic events. This study is one of the few which have deduced that the main ore-formation event at Red Lake was synchronous with, but post-peak regional metamorphism (c.f. Wilson et al., 1984). A detailed paragenesis was crucial to establish this relative timing. Consistently, various carbonate veins were observed to cut regional metamorphic minerals, the clearest of which were carbonate veins cutting garnet porphyroblasts (Chapter 3). This relative timing of peak-metamorphism and carbonate vein formation was confirmed by carbonate thermometry. The ore-forming fluid was suggested to be magmatic-metamorphic in origin. The most consistent model is the evolution of a single fluid, likely derived from a magmatic source. The 319 CO2-rich magmatic fluids were buffered by a pre-existing, isotopically-enriched, carbonate source. This rock buffering would have caused the isotopic signature of the fluid to reflect the isotopically enriched carbonate, which explains the heavier carbon isotopes at the RLGM. The sulfur isotopes from ore-stage sulfides are most consistent with a magmatic source. It is possible that the plutons were emplaced at depth during ongoing regional metamorphism, such as during collisional tectonic settings in accreted terranes (Groves et al., 2003). This would suggest a regional-contact metamorphic event was responsible for the ore-forming fluid at Red Lake. A key observation from this study was the identified importance of redox reactions for gold precipitation. Redox differences occurred between the significantly Fe2+-rich host basalt and the ore-forming fluid. In order to form the abundance of relatively Fe3+-rich minerals (such as pyrrhotite and magnetite) compared to the host rock, the ore-forming fluid had to have been capable of oxidizing the wall rock Fe2+ during sulfidation reactions. The influence of redox differences between vein-forming and ore-forming fluids was also identified by stable isotopes (see below) and petrographic observations, e.g. high grade ore contains zoned sulfides of pyrite surrounded by pyrrhotite, indicating reduction of the fluid during precipitation. This study demonstrated that redox differences between a single fluid and a host rock can produce significant gold-mineralization. Therefore, fluid mixing is not necessarily required to form abundant gold (Neumayer et al., 2008). Temperature differences between crustal depths were concluded to have influenced sulfide distribution, as well as influencing gold deposition. At depth, in hotter temperatures, pyrrhotite is more abundant; at shallower crustal levels pyrite is dominant. The cooling from depth to shallower levels would have also encouraged gold deposition. 8.4 Exploration implications 8.4.1 Mineral chemistry vectors Mineral chemistry vectors were identified though electron microprobe analysis (EMPA), and tested with the rapid, field-based tools of SWIR and magnetic susceptibility. The mineral composition trends found though EMPA, both vertically and horizontally surrounding the RLGM, are summarized in Figure 4.39. However, the clearest mineral trends were identified by the superposed nature of H1 and H2 hydrothermal alteration events. The overprinting mineral trends identified through this study are the following: 320  Pervasive Fe-biotite (related to H1) is overprinted by a narrow (0–50 m) Mg-brown biotite halo to mineralization (syn-H2),  Widespread, early calcite (H1) is overprinted by abundant, localized intense ankerite- calcite veins associated with mineralized occurrences (H2),  A widespread early chlorite weakly displays more common Mg- and Fe-Mg-chlorite proximal to mineralization, with distal Fe-chlorite (H1). This widespread chlorite event was overprinted by chlorite selvages to ankerite-calcite veins (H2), which are abundant at the mine site. Of these chlorite selvages, Fe-chlorite is the most common. Of the above-mentioned trends, the zonation of proximal ankerite to distal calcite is the clearest and easiest to define. The zonation in carbonate minerals can be precisely mapped using EMPA, SEM-EDS, cathodoluminescence and reactivity with dilute HCl acid. The reclassification SWIR diagnostic 1875 nm wavelength feature indicated a decrease in wavelength position with increasing distance to mineralization (Fig. 7.13). This would imply ankerite was more proximal to mineralization. However, the SWIR data should be used with caution and care as the data was scattered and easily influenced by other hydrous mineral compositions. Careful interpretation and reclassification is required for the SWIR data to be used successfully. Garnet and amphibole compositional variation were more subtle that those displayed by chlorite, biotite and carbonate. These minerals only experienced a single phase of development, which resulted in lower variability. Both porphyroblastic minerals displayed progressive enrichment in Mn, and Fe2+ towards mineralization, from a distance of > 4 km. Sodium, Fe3+, Mg and Ca decreased in abundance with increasing proximity toward mineralization. However, caution must be taken with vectors from these minerals, as they developed pre-mineralization. Consequently, care needs to be taken to ensure trends reflect the overprinting, post-peak metamorphic mineralization event. Mineral chemistry trends identified with the SWIR instrument required care during interpretation. It was important to have an established knowledge of the paragenetic sequence and estimation of relative abundance to fully interpret the SWIR data. Because the SWIR instrument averages the composition of all hydrous phases in a sample, the spectra are easily influenced by mineral abundance, composition, and albedo (quality of reflectance). Due to these influences, the SWIR data was always highly scattered. Trends were only identified through 321 statistical analysis of the distal samples at distances of 500–5000 m from mineralization. The SWIR instrument cannot be used to indentify ore zones, however, it can identify trends to within 500 m from ore. From this narrowed target, other geochemical tools could better locate mineralization. The best trend within the SWIR spectral data was defined by the analyzed 2250 nm feature. This wavelength feature correlates to the Fe and Mg abundance of biotite and chlorite. Interpretation of the SWIR data would imply that biotite and chlorite become more Fe- rich in the transition from 5000 to 500 m from mineralization. The Mg-biotite halo to mineralization is too narrow to be detected within this range, as it only extends 0–50 m from ore zones. Consequently, this trend was interpreted to be influenced by the abundant Fe-rich minerals within the rocks samples, such as Fe-amphibole, Fe-carbonate, Fe-biotite and Fe- chlorite, rather than a specific mineral. However, this trend could aid in exploration. Magnetic susceptibility is related to the presence and abundance of magnetite and pyrrhotite, which are both magnetic in the RLGM. Magnetite was documented in several paragenetic stages. It is part of the earliest mineral assemblages, associated with pervasive biotite and the regional metamorphic assemblages (chlorite-amphibole-magnetite ± garnet). However, magnetite was also identified as a minor component of several ore-stage sulfide-bearing assemblages, which compose ore zones (Chapter 3). The ore-stage, sulfide-bearing assemblages are associated with abundant pyrrhotite. The ore-stage pyrrhotite and magnetite are localized at the mine site, dominantly within D2 structures. This localized nature of abundant ore-stage pyrrhotite-magnetite correlates to a narrow halo of magnetic highs enveloping ore zones. Therefore, at the deposit scale, the identification of a narrow magnetic high could be used to identify areas of economic mineralization. Magnetic susceptibility can also be used to identify Fe2+-rich basalts. These are less magnetic, as Fe is contained within paramagnetic minerals such as garnet, amphibole and chlorite. An Fe2+-rich basalt has constitutes a favourable setting for gold mineralization in the Red Lake area. 8.4.2 Isotopic compositional variations The lateral distributions of sulfur, carbon and oxygen isotopes all demonstrate enriched values within the core of the system (Figs. 5.6, 5.7 and 5.10). The isotopic enrichment is associated with D2 structures and mineralization. This isotopic enrichment was used to infer that this area experienced the greatest fluid flow and fluid-rock interaction. The horizontal 322 enrichment of stable isotopes proximal to mineralization was interpreted to have been caused by redox differences. When the carbonate vein-forming and ore-forming fluid occurred, the host basalt was reduced, and Fe2+-rich. Through progressive fluid-rock interaction, the fluid was reduced causing 3–5‰ positive shifts in the isotope values (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997; McCuaig and Kerrich, 1998). Therefore, stable isotopes can be used for future exploration by identifying isotopically enriched areas that have experienced significant fluid- flow. 8.4.3 Pathfinder elements within whole rock geochemistry In this study, patterns of enrichment physically proximal to mineralization were taken as pathfinder elements. Pathfinder elements in the Red Lake area are the cumulative effect of all overprinting events in the RLGM. As a result, these elemental trends were influenced by both early hydrothermal alteration and the overprinting ore-formation event. The lithogeochemistry study identified both trace and major pathfinder elements, ranging from 100’s to 1000’s of meters from mineralization. The pathfinder elements are centered on mineralization at the RLGM. Consequently, they are likely part of the mineralization stage. The hydrothermal fluids infiltrated the surrounding rock packages around the RLGM, causing enrichments up to 5 km distally. The narrowest halos (≤ 500 m) enveloping mineralization at the RLGM exhibit As, Au, Bi, Mo, Ni, Sb and W (Table. 4.16 and Fig. 4.37). Minor enrichments of Ag and Cu are demonstrated in one or two samples, 0–200 m from mineralization (Fig. 4.38). The elements listed are enriched in brown biotite-quartz altered and mineralized samples, and correlate to the dominance of sulfide minerals (Table 4.12). Enrichment of La was only displayed by type 2 basalt (Fig. 4.38). Compared to type 1, type 2 basalt contains higher concentrations of La regardless of location relative to ore. This implies a host rock composition control on the distribution and concentration of La. Broader km-scale features are demonstrated by Ba, Li, Rb and Zn. Barium and Zn show enriched abundances up to 3 km distally (Fig. 4.38). Lithium and Rb demonstrate a wider halo, up to 5 km from mineralization. The km-scale features are typically displayed in biotite-Ti- magnetite ± carbonate altered, regionally metamorphosed (chlorite-amphibole-epidote-biotite- calcite ± garnet ± magnetite), and ankerite-calcite veins + selvage samples (Table 4.12). 323 Accompanying the trace pathfinder elements, major elements K and S show a progressive increase towards known ore zones (Fig. 4.38). Of those, SO3 forms the narrowest halo, < 500 m distally. Potassium (similar to Rb) gradually increases over 5 km toward mineralization. FeO, CaO and MgO are poor indicators, as they are enriched throughout the RLGM and surrounding area. FeO, CaO and MgO are most concentrated, but considerably scattered at the ore scale (Fig. 4.37). Outside of this highly altered halo, the FeO, CaO and MgO compositions indicate very little variation. The wide ranging FeO, CaO and MgO concentrations proximal to mineralization are due to abundant veins, sulfides and associated alteration. MnO, although varying at the mine scale from 0–1.1 wt%, has a wide halo of elevated MnO (0.6–0.9 wt%) which is present at < 3.3 km, with a sharp decrease of < 0.6 wt% MnO at distances > 3.3 km distally. The clearest pathfinder elements (listed above) in the Balmer basalt are most effective < 500 m from ore. Each of the identified pathfinder elements are related to the H2 event, which was a narrow structurally-controlled vein and mineralization event. The km-scale footprint of metamorphosed altered FeO rich host rocks is important for exploration as these were identified as important for gold precipitation (redox reactions) during the overprinting mineralization event. Therefore, two scales of exploration were identified, 1) A km-scale halo of metamorphosed FeO rich host rocks; and 2) a narrower < 500m wide halo of enriched pathfinder elements (As, Au, Bi, Mo, Ni, Sb and W) which correlated to the overprinting H2 event. 8.5 Suggestions for further investigations  This study investigated the RLGM along two cross sections. These cross sections progressed from greenschist conditions proximal to mineralization to amphibole conditions distally from mineralization. There is potential that analysis of the lower grade sequence could produce different alteration assemblages. These could have different exploration implications for lower grade hosted lode-gold deposits.  More distal samples need to be analyzed for carbon, oxygen and sulfur isotopes, to better constrain the suggested isotopic zonation as identified in this study.  A lithogeochemical investigation of each felsic intrusion, specifically the Dome stock, McKenzie Island stock, Howey diorite, Hammell Lake batholith, Killala-Baird Batholith, Walsh Lake and Cat Island plutons, with regard to possible sources of Au is suggested. 324 This information can provide more data into the debate of ore genesis, particularly at the Buffalo mine. Additionally, mass balance calculations could be compiled between different lithology of the Balmer assemblage to investigate if any gold was stripped from these packages.  An integrated structural and chemical analysis for the RLGM and known mineralized occurrences in the RLGB would provide a better understanding of both geological phenomena. Although this study has provided a rigorous geochemical analysis, the structural context is limited. When this project began, a structural investigation of the Red Lake complex was underway at another university. As a result, this study focused on the geochemical aspects of the deposits evolution. To integrate structure and geochemistry, detailed mapping of regional outcrops is suggested. In order to document the larger scale structures and their implications on mineralization, some suggested mapping locations include the area north-east of the Brewis porphyry (the last 3 km of the cross section lines; see Fig. 1.6), Redcon, Abino, McMarmac, and near H.G. Young properties. In Western Australia, gold mineralization is located in 2nd or 3rd order structures, linked to a 1st order large scale fault (Cox and Rumming, 2004). It is possible that a similar scenario occurs at RLGB. 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Zhang, G., Hattori, K., and Cruden, A.R., 1997, Structural evolution of auriferous deformation zones at the Campbell mine, Red Lake greenstone belt, Superior Province of Canada: Precambrian Research, v. 84, p. 83-103. 365 Appendices Appendix A for Chapter 1 A.1 Drill hole logs Appendix A.1 contains a graphic representation of each drill hole re-logged by the author with an accompanying key provided in Fig. A.1. This information was used in the construction of the lithology along both cross sections investigated in this thesis. Figure A.1 Complete key for all lithological units used in the drill core logs. 366 Figure A.2 Graphical log for drill hole 13L833 367 Figure A.3 Graphical log for drill hole 16L1067 368 Figure A.4 Graphical log for drill hole 19L020 369 Figure A.5 Graphical log for drill hole 19L457 370 Figure A.6 Graphical log for drill hole 30L1162 371 Figure A.7 Graphical log for drill hole 30L1268 372 Figure A.8 Graphical log for drill hole 34L814 373 Figure A.8 (Continued) 374 Figure A.8 (Continued) 375 Figure A.9 Graphical log for drill hole 34L235 376 Figure A.9 (Continued) 377 Figure A.10 Graphical log for drill hole 37L26 378 Figure A.11 Graphical log for drill hole BK05009 379 Figure A.12 Graphical log for drill hole BK05010 380 Figure A.13 Graphical log for drill hole BK05011 381 Figure A.14 Graphical log for drill hole CR464 382 Figure A.15 Graphical log for drill hole CR466 383 Figure A.16 Graphical log for drill hole CR467 384 Figure A.17 Graphical log for drill hole CR468 385 Figure A.18 Graphical log for drill hole CR469 386 Figure A.19 Graphical log for drill hole CR4610 387 Figure A.20 Graphical log for drill hole CR4611 388 Figure A.21 Graphical log for drill hole CR4612 389 Figure A.22 Graphical log for drill hole CR4613 390 Figure A.23 Graphical log for drill hole D1981 391 Figure A.23 (Continued) 392 Figure A.24 Graphical log for drill hole D15367 393 Figure A.25 Graphical log for drill hole D16355 394 Figure A.26 Graphical log for drill hole D21708 395 Figure A.26 (Continued) 396 Figure A.26 (Continued) 397 Figure A.27 Graphical log for drill hole D27343 398 Figure A.28 Graphical log for drill hole D27943 399 Figure A.28 (Continued) 400 Figure A.28 (Continued) 401 Figure A.28 (Continued) 402 Figure A.29 Graphical log for drill hole DS11 403 Figure A.30 Graphical log for drill hole DS139 404 Figure A.31 Graphical log for drill hole DS172 405 Figure A.32 Graphical log for drill hole DS173 406 Figure A.33 Graphical log for drill hole DS174 407 Figure A.34 Graphical log for drill hole DS177 408 Figure A.34 (Continued) 409 Figure A.35 Graphical log for drill hole DS80 410 Figure A.36 Graphical log for drill hole DS340 411 Figure A.37 Graphical log for drill hole DS615 412 Figure A.37 (Continued) 413 Figure A.37 (Continued) 414 Figure A.37 (Continued) 415 Figure A.38 Graphical log for drill hole GC01018 416 Figure A.38 (Continued) 417 Figure A.39 Graphical log for drill hole R87105 418 Figure A.40 Graphical log for drill hole R87106 419 Figure A.41 Graphical log for drill hole R87107 420 Figure A.42 Graphical log for drill hole R87108 421 A.2 Sample details of all samples used in this dissertation to obtain data This appendix Table A.1 which contains information on all samples used within this thesis. For each sample, the location (in NAD 27 UTM Zone 15 co-ordinates), scale (mine 0-3 lm, interme- diate 3-5 km and distal > 5km), complex, lithology, main alteration assemblage, the sulfide- oxide assemblage associated with mineralization, metamorphic facies (if applicable) and esti- mated distances from surface and ore zones along the cross sections. The least altered basalt, chert and argillite samples from Bouzari (2009) are also included. 422 Table A.1 Complete sample details Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade 06L337 40 Basalt 7231 9172.3 Red Lake Mine Grey chl-amp-cal-bio po-mag G 06L337 186 Basalt 7085.1 9172.2 Red Lake Mine Blue carb-qtz vein po-mag G 06L337 191 Basalt 7080.5 9170.5 Red Lake Mine N/A qtz-sul po-aspy-py G ? 06L337 448 Komatiitic basalt 6823.36 9165.74 Red Lake Mine Brown bio-Ti-mag ± carb py-po-mag G 06L337 478 Komatiitic basalt 6793.1 9172.3 Red Lake Mine Grey and brown bio-Ti-mag ± carb py-po-mag G 06L337 488 Komatiitic basalt 6823.36 9165.74 Red Lake Mine Grey bio-Ti-mag ± carb py-po-mag G 11L086 266 Komatiitic basalt 7322.4 8297.1 Red Lake Mine Grey carb-mag vein py-po-mag G 11L086 417 Komatiitic basalt 7470.1 8372 Red Lake Mine Grey carb-mag vein mag G 11L086 853 Chert 7883.7 8279.1 Red Lake Mine N/A qtz py G ? 11L086 1038 Komatiitic basalt 8050.4 8249.6 Red Lake Mine Grey carb vein-chl selvage po-mag T 13L833 55 Basalt 6908 8159.7 Red Lake Mine Grey qtz-mus-and py-po-mag G 13L833 138.5 Basalt 6844.6 8212.8 Red Lake Mine N/A carb vein-chl selvage po-py G 13L833 681.4 Basalt 6431.5 8566.4 Red Lake Mine Grey carb vein-chl selvage po-py G 13L833 1144.3 Basalt 6076.4 8863.4 Red Lake Mine N/A qtz py G 13L833 1237.8 Basalt 6002.18 8919.62 Red Lake Mine Blue chl-bio-amp-cal py-mag G 16L1067 267.9 Basalt 6188.8 7633.7 Red Lake Mine N/A qtz-sul aspy-py T? 16L1067 400.8 Basalt 6056.3 7629.4 Red Lake Mine Blue grt-chl-amp ± mag ± bio py-po-mag T 16L1067 1008.3 Komatiitic basalt 5452.7 7679.1 Red Lake Mine N/A bio-talc none T? 16L1067 1208.1 Basalt 5260.2 7731.5 Red Lake Mine Blue bio-Ti-mag ± carb po-py-mag G 17L1437 152 Komatiitic basalt 6289.7 7499.1 Red Lake Mine Grey carb-mag vein, chl sel- vage mag T 17L1437 556 Basalt 5890 7444.7 Red Lake Mine Grey carb-qtz vein py-po G 17L1437 763 Basalt two 5684.2 7422.3 Red Lake Mine N/A qtz-mus-and py-sph G? 17L1437 913 Komatiitic basalt 5534.6 7412.6 Red Lake Mine Grey p. carb py-mag G 19L547 17.1 Basalt 6785.4 7216.9 Red Lake Mine N/A grt-chl-amp ± mag ± bio mag G? 19L547 52.4 Basalt 6811.7 7216.4 Red Lake Mine Brown qtz (syn-min) mag G 19L547 125 Basalt 6865.7 7215.4 Red Lake Mine N/A grt-chl-amp ± mag ± bio none G? 19L547 195.6 Komatiitic basalt 6918.1 7214.2 Red Lake Mine N/A grt-chl-bio-amp ± mag mag G? 19L547 282.4 Rhyolite 6982.6 7213.4 Red Lake Mine N/A qtz-mus-and none G? 19L547 303.4 Rhyolite 6998.3 7212.9 Red Lake Mine N/A qtz-mus-and none G? 19L547 495.3 Basalt 7141.2 7210.2 Red Lake Mine Blue and brown grt-chl-amp ± mag ± bio po-mag A 19L547 548.5 Basalt 7180.3 7209.7 Red Lake Mine N/A grt-chl-amp ± mag ± bio none G? 19L547 592.4 Basalt 7213.1 7208.9 Red Lake Mine N/A grt-chl-amp ± mag ± bio pyrrohitite G? 19L547 866.2 Gabbro 7416.7 7205.1 Red Lake Mine Grey chl-amp-cal-bio po A 24L755 64 Basalt 6158.9 6476.9 Red Lake Mine Grey carb-qtz vein mag G 423 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefringence colour Key/Dominant alteration assemblage Mineralization assemblage Metamorphic Grade 24L755 186 Basalt 6275.3 6476.7 Red Lake Mine Grey carb-qtz vein po-mag G 24L755 769 Basalt 6828.1 6453.5 Red Lake Mine Grey carb vein mag G 24L755 775.5 Basalt 6834.8 6452.7 Red Lake Mine N/A chl-bio-amp po G? 30L1162 24.7 Basalt 5425.1 5605.5 Red Lake Mine Grey br. bio-qtz po-py G 30L1162 695 Basalt 4833.8 5852.9 Red Lake Mine Grey carb-qtz vein po-mag G 30L1162 1419 Basalt 4224.6 6176.9 Red Lake Mine Blue carb-qtz vein py-po G? 30L1268 25.7 Basalt 6003.9 5592.3 Red Lake Mine Blue grt-chl-amp ± mag ± bio po-py-mag T 30L1268 42.7 Basalt 6020.9 5592.3 Red Lake Mine N/A qtz-mus-and py T? 30L1268 66.2 Basalt 6044.4 5591.9 Red Lake Mine N/A chl-amp-cal-bio none G? 30L1268 106.7 Basalt 6084.9 5590.4 Red Lake Mine N/A grt-chl-amp ± mag ± bio mag T? 30L1268 124.9 Basalt 6103 5590.1 Red Lake Mine N/A carb-qtz vein py-po G? 30L1268 175.2 Basalt 6153.3 5588.3 Red Lake Mine N/A grt-chl-amp ± mag ± bio mag T? 30L1268 198.5 Basalt 6176.2 5587.4 Red Lake Mine N/A grt-chl-amp ± mag ± bio po-py T? 30L1268 215.2 Basalt 6193.3 5586.6 Red Lake Mine N/A qtz (syn-min) po G? 30L1268 221 Basalt 6199.2 5586.6 Red Lake Mine N/A bio-Ti-mag ± carb py G? 30L1268 301.5 Basalt 6279.3 5583.5 Red Lake Mine N/A qtz (syn-min) py G? 30L1268 327.9 Basalt 6305.8 5582 Red Lake Mine Blue grt-chl-amp ± mag ± bio po-py-mag T 30L1268 356.1 Basalt 6334 5581 Red Lake Mine N/A chl-amp-cal-bio py G? 30L1268 399.3 Komatiitic basalt 6377.3 5579.7 Red Lake Mine N/A qtz-mus-and none T? 30L1268 403.2 Komatiitic basalt 6381.1 5579.1 Red Lake Mine N/A p. carb none G? 30L1268 448.2 Rhyolite 6426 5577.1 Red Lake Mine N/A bio-Ti-mag ± carb none N/A 30L1268 524.5 Rhyolite 6502.1 5572.3 Red Lake Mine N/A none py N/A 30L1268 533.4 Rhyolite 6511 5571.8 Red Lake Mine N/A none po-py N/A 30L1268 546.3 Argillite 6523.8 5570.9 Red Lake Mine N/A none po N/A 30L1268 574 Basalt 6551.5 5568.5 Red Lake Mine Blue qtz (syn-min) po-py-mag T 34L006 25 Basalt 5832.9 5007.1 Red Lake Mine Brown carb-mag vein po-py-mag T 34L006 706 Argillite 6511.4 5057.2 Red Lake Mine Grey carb-mag vein po-mag A 34L006 1235.1 Basalt 7022.1 5085 Red Lake Mine Blue carb vein with chl selvage po A 34L1352 28 Komatiitic basalt 4843.2 4983 Red Lake Mine Grey and blue carb vein with chl selvage py-po-mag G 34L1352 238 Basalt 4956.1 4805.6 Red Lake Mine N/A bio-chl-amp py G 34L1352 315 Basalt 499.8 4741.5 Red Lake Mine Grey carb vein with bio selvage py-po-mag G 34L1352 814 Basalt 5282 4331.3 Red Lake Mine Brown carb vein with chl selvage py-po-mag A 34L235 23.2 Ultramafic 5348.2 4984.2 Red Lake Mine Brown qtz (syn-min) po-mag A 424 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade 34L235 909.7 Ultramafic 4547 4607.5 Red Lake Mine Grey p. carb po-mag G 34L235 944 Ultramafic 4514.9 4595.6 Red Lake Mine Grey br. bio-qtz + carb vein py-mag A 34L235 1961 Basalt 3530.5 4367.7 Red Lake Mine Brown grt-chl-amp ± mag ± bio po-mag A 34L814 92 Basalt 4254.75 5004.84 Red Lake Mine Brown carb vein with chl sel- vage py-po-mag A 34L814 195.7 Ultramafic 4162 5005.9 Red Lake Mine Brown br. bio-qtz py-po-mag G 34L814 348.2 Basalt 4026.1 5012.3 Red Lake Mine N/A carb-mag vein po-mag G? 34L814 1147.7 Basalt 3332.1 5153.1 Red Lake Mine Blue grt-chl-amp ± mag ± bio po-py A 34L814 2125.4 Gabbro 2540.3 5496.8 Red Lake Mine N/A bio-chl-amp mag-po-py T? 34L814 2333.4 Diorite 2391.9 5586.7 Red Lake Mine Brown bio-chl-amp py G 37L482 14 Basalt 2378.1 4565 Red Lake Mine Blue chl-amp-cal-bio py-po-mag T 37L482 50 Basalt 2394.9 4533.3 Red Lake Mine Blue and Brown bio-chl-amp po-mag T 37L482 72 Basalt 2404.8 4514.4 Red Lake Mine Grey and Brown chl-amp-cal-bio po-py T 37L482 91 Basalt 2419.36 4501.42 Red Lake Mine Grey carb-qtz vein py-po-mag A 37L482 118 Basalt 2432.3 4477.74 Red Lake Mine Blue grt-chl-amp ± mag ± bio po-mag T 37L482 124 Basalt 2429.6 4468.6 Red Lake Mine Blue and Brown p. carb py-po-mag T 37L482 452 Komatiitic basalt 2598.47 4188.53 Red Lake Mine Grey bio-Ti-mag ± carb py-po-mag G 37L482 926 Basalt 2854.06 3790.23 Red Lake Mine Grey bio-Ti-mag ± carb py-po-mag T 37L482 1019 Basalt 2901.2 3709.6 Red Lake Mine Blue carb vein with chl sel- vage po-mag A 37L482 1036 Basalt 3392.51 4007.3 Red Lake Mine Blue and Brown bio-Ti-mag ± carb po-mag T 37L482 1050 Quartz-feldspar porphyry 3405.1 4001.18 Red Lake Mine N/A bio-Ti-mag ± carb po-mag T? 37L482 1077 Basalt 3006.5 3611.4 Red Lake Mine Blue grt-chl-amp ± mag ± bio po-mag A 37L482 1087 Rhyolite 3438.39 3985.06 Red Lake Mine Grey chl-amp-cal-bio mag T 37L482 1116 Ultramafic 3464.51 3972.47 Red Lake Mine N/A chl-amp-mag po-mag T? 37L482 1134 Rhyolite 3480.73 3964.68 Red Lake Mine N/A qtz-mus-and py-po-mag T 37L482 1137 Basalt 2972.86 3616.46 Red Lake Mine Grey and Brown carb-qtz vein po-py-mag G 37L482 1273 Basalt 3054.07 3507.86 Red Lake Mine Blue and Brown chl-amp-cal-bio po-mag T 37L482 1293 Basalt 3049.6 3503.4 Red Lake Mine Grey and Brown grt-chl-amp ± mag ± bio po-mag T 37L482 1322 Basalt 3079 3464.7 Red Lake Mine Grey grt-chl-amp ± mag ± bio po T 425 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade 37L482 1347 Basalt two 3673.41 3874.21 Red Lake Mine N/A qtz-sul mag T? 37L482 1355 Rhyolite 3680.68 3870.88 Red Lake Mine N/A chl-amp-cal-bio py-po-mag N/A 37L482 1404 Quartz-feldspar porphyry 3134.6 3405.11 Red Lake Mine N/A bio-Ti-mag ± carb po-mag A 37L482 1442 Basalt 3153.5 3371.2 Red Lake Mine Grey qtz-mus-and po-mag T 37L482 1605 Ultramafic 3260.81 3249.53 Red Lake Mine Grey qtz-mus-and py-mag T 37L482 1677 Rhyolite 3306.72 3194.45 Red Lake Mine Grey qtz-mus-and py-po-mag A 37L482 1692 Rhyolite 3316.41 3183.08 Red Lake Mine Grey qtz-mus-and po N/A 37L482 2057 Basalt 3556.9 2908.7 Red Lake Mine Grey bio-Ti-mag ± carb py-mag A 37L594 299 Basalt 1435.7 4288.1 Red Lake Mine Grey carb-qtz vein py-po-mag T 37L594 815 Basalt 1520.9 3779.4 Red Lake Mine Grey carb-qtz vein py-po-mag A 37L594 1074.5 Basalt 1571.7 3524.4 Red Lake Mine N/A amp-chl-bio none A 37L594 1218.5 Basalt 1606.1 3385.2 Red Lake Mine N/A amp-chl-bio po-mag A 37L594 1581 Basalt 1708.5 3040.1 Red Lake Mine Grey and Brown carb vein with bio sel- vage mag A 37L594 1609 Basalt 1716.7 3013.5 Red Lake Mine Grey grt-chl-amp ± mag ± bio po-py-mag A 37L667 4 Basalt 2542.33 4582.2 Red Lake Mine Brown chl-amp-cal-bio py-mag T 37L667 25 Basalt 2559.15 4569.77 Red Lake Mine Grey p. carb po-mag A 37L667 131 Basalt 2640.3 4501.1 Red Lake Mine Blue and Brown bio-chl-amp T 37L667 152 Basalt 2660.65 4494 Red Lake Mine Blue chl-amp-cal-bio py-mag T 37L667 157 Basalt 2661 4484.6 Red Lake Mine N/A chl-amp-cal-bio po A? 37L667 194 Basalt 2694.09 4468.69 Red Lake Mine N/A chl-amp-cal-bio py T 37L667 340 Ultramafic 2809.84 4380.06 Red Lake Mine Brown br. bio-qtz py-po-mag A 37L667 490 Peridotite ko-matiite 2928.82 4289.09 Red Lake Mine Grey chl-amp-cal-bio po-py T 37L667 575 Ultramafic 2996.53 4237.98 Red Lake Mine Grey br. bio-qtz po-mag A 37L667 632 Basalt 3038.4 4198.5 Red Lake Mine Grey and Brown bio-chl-amp py-po-mag A 37L667 637 Basalt 3046.06 4200.8 Red Lake Mine Blue chl-amp-cal-bio po-mag A 37L667 651 Basalt 3053.5 4187 Red Lake Mine Blue bio-chl-amp py-po-mag T 37L667 704 Basalt 3096.8 4156.3 Red Lake Mine Blue bio-chl-amp py-po-mag A 37L667 848 Basalt 3221.4 4084.2 Red Lake Mine Blue and Brown p. carb po-mag G 37L667 852 Basalt 3224.7 4082.2 Red Lake Mine Blue bio-chl-amp po-mag A 37L667 974 Basalt 3334.3 4028.7 Red Lake Mine N/A br. bio-qtz po-mag A? 37L667 1036 Basalt 3389.9 4001.3 Red Lake Mine Blue and Brown br. bio-qtz po-mag T 426 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade 37L667 1050 Quartz- feldspar porphyry 3402.3 3995.1 Red Lake Mine N/A bio-Ti-mag ± carb none N/A 37L667 1061 Basalt 2423.37 3544.62 Red Lake Mine N/A qtz-mus-and py-po-mag T 37L667 1067 Basalt 3418.33 3987.54 Red Lake Mine Grey p. carb none T 37L667 1087 Rhyolite 3436 3978.9 Red Lake Mine Grey bio-Ti-mag ± carb po-mag 37L667 1116 Basalt 3462 3966.3 Red Lake Mine Grey chl-amp-cal-bio py-po-mag T 37L667 1134 Rhyolite 3478.3 3958.6 Red Lake Mine Grey bio-Ti-mag ± carb mag 37L667 1347 Argillite 3670.9 3868.1 Red Lake Mine Grey grt-chl-amp ± mag ± bio py-po-mag A ? 37L667 1355 Argillite 3678 3864.7 Red Lake Mine N/A bio-Ti-mag ± carb py-po-mag A ? 37L667 1403 Rhyolite 3724.3 3850.91 Red Lake Mine Grey qtz-mus-and py-po-mag N/A 37L667 1891 Argillite 4322.6 3585.2 Red Lake Mine N/A qtz (syn-min) py A ? 37L667 2054 Basalt 4321.24 3593.26 Red Lake Mine Brown carb-qtz vein + sul po-py A 37L667 2058 Argillite 4168.7 3649.6 Red Lake Mine N/A N/A po A ? 37L726 400.7 Basalt 4687.1 4264.9 Red Lake Mine Grey bio-Ti-mag ± carb po-mag A 37L726 532.1 Basalt 4772.7 4165.1 Red Lake Mine N/A grt-chl-amp ± mag ± bio mag A ? 37L726 836.6 Basalt 4972.9 3937 Red Lake Mine Grey grt-chl-amp ± mag ± bio po-py-mag A 37L768 66 Basalt 2219.5 4514.2 Red Lake Mine Grey carb-mag vein po-py-mag A 37L768 98 Basalt 2224.4 4482.7 Red Lake Mine Grey carb-qtz vein po A 37L768 1061 Basalt 2429.7 3497.3 Red Lake Mine Grey qtz-mus-and py-po-mag T 37L768 1108 Basalt 2429.7 3497.3 Red Lake Mine Grey qtz-sul po-py T 37L768 2005 Rhyolite 2701.2 2643 Red Lake Mine Grey p. carb py-po-mag A AB01196 65.6168 Basalt 446798 5661861 Regional REF Regional REF N/A least altered none N/A BK05009 9 Over burden 13446 9968.94 Campbell Distal N/A N/A N/A N/A BK05010 376.12 Basalt 18121.8 9676.8 Campbell Distal Grey and blue carb vein with chl po-py A BK05010 420.18 Basalt 18142.5 9640 Campbell Distal N/A chl-amp-cal-bio py A BK05011 22 Over burden 17459.6 9955.7 Campbell Distal N/A N/A N/A N/A Bouzari, 2009 5540 Chert 444868 5657966 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 5545 Chert 451172 5657765 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 5546 Chert 449393 5656658 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 5554 Argillite 449438 5656183 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 5555 Argillite 449612 5656336 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 5572 Argillite 445881 5655929 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CR-03-07 Argillite 450748 5656728 Regional REF Regional REF N/A least altered none N/A 427 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefringence colour Key/Dominant al- teration assemblage Mineralization assemblage Metamorphic Grade Bouzari, 2009 CR-04-14 Argillite 449674.51 5656058.17 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CR-04-17 Argillite 449824.51 5656118.16 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW02002 Argillite 442704.48 5657518.6 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW06012 Argillite 442790 5659040 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW06013 Argillite 442750 5657930 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW06015 Argillite 442720 5658860 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW06025 Argillite 443271 5655594 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 CW06026 Argillite 444050 5656413 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC01-017 Argillite 450413.14 5657949.14 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC02-011 Argillite 449175.02 5655025.48 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC02-012 Argillite 449096.71 5655078.48 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC02-013 Argillite 449299.58 5655061.63 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC02-014 Argillite 449234.99 5655041.47 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC04002 Argillite 449437.72 5656934.94 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC98-004 Argillite 449132.04 5654994.91 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC98-005 Argillite 449166.02 5655198.67 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 GC98-006 Argillite 449017.15 5654728.15 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 R8146 Argillite 448256.91 5661358.39 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 SC99004 Argillite 443472.95 5658934 Regional REF Regional REF N/A least altered none N/A Bouzari, 2009 SC99005 Argillite 443531.19 5659047.54 Regional REF Regional REF N/A least altered none N/A CB15-56 Basalt 1791.1 7802.8 Campbell Mine N/A br. bio-qtz po G CB1812M Basalt 2240 7370 Campbell Mine N/A qtz-sul py G CB1912V1 Basalt 3020 7220 Campbell Mine Grey br. bio-qtz py-po G CB22252BA Ultramafic 2390 6780 Campbell Mine N/A carb vein with chl py T CB25-21LZ Basalt 1930.9 6323.9 Campbell Mine N/A br. bio-qtz po-py T CB25-25 Sub Basalt 1930.9 6323.9 Campbell Mine N/A br. bio-qtz po-py T CB25-51 L zone Basalt 1930.9 6323.9 Campbell Mine N/A br. bio-qtz po-py T CB3025161 Basalt 1430 5590 Campbell Mine Grey br. bio-qtz py-po-mag T CB33451AM Basalt 1290.7 5119.8 Campbell Mine N/A qtz-sul aspy T CB33451LP Lamp 1290.7 5119.8 Campbell Mine N/A qtz vein py none CB33451LPQ Lamp 1290.7 5119.8 Campbell Mine N/A qtz vein py none CB33451M Basalt 1290.7 5119.8 Campbell Mine N/A bio-Ti-mag ± carb py-po T CB33451V Basalt 1290.7 5119.8 Campbell Mine N/A qtz-carb vein with bio py-po T 428 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade CB39-2 Basalt 2714.4 4225.3 Campbell Mine N/A br. bio-qtz po A CB4043_0W Basalt 2601.3 4068.3 Campbell Mine N/A br. bio-qtz po A CB4043FV Basalt 2601.3 4068.3 Campbell Mine Grey br. bio-qtz po-py-mag A CB4043HR Basalt 2601.3 4068.3 Campbell Mine N/A chl-amp-cal-bio po A CB4143 po Basalt 2000.8 3923.6 Campbell Mine N/A br. bio-qtz po A CB4143 py Basalt 2000.8 3923.6 Campbell Mine N/A br. bio-qtz py A CB4143-0E Basalt 2000.8 3923.6 Campbell Mine N/A bio-chl-amp none A CB41432W Basalt 2000.8 3923.6 Campbell Mine N/A br. bio-qtz py A CB4143W Basalt 2000.8 3923.6 Campbell Mine N/A bio-chl-amp po A CR-04-28 16.4042 Basalt 451160.51 5655579.17 Regional REF Regional REF N/A least altered none A ? CR-04-30 9.84252 Basalt 451748.49 5655648.17 Regional REF Regional REF N/A least altered none A ? CR4610 7.6 Basalt two 24428.6 9969.8 Red Lake Distal N/A bio-Ti-mag ± carb none A? CR4610 941.1 Basalt 24958 9298.4 Red Lake Distal N/A chl-amp-cal-bio none A? CR4610 947 Basalt 24961.1 9294.5 Red Lake Distal Blue and Late grt-chl-amp ± mag ± bio po-py A CR4611 6 Basalt 19654.4 9974.5 Campbell Distal N/A bio-chl-amp none A? CR4611 185.6 Basalt 19771.4 9850.1 Campbell Distal N/A bio-Ti-mag ± carb none A? CR4611 581.4 Basalt 20035.1 9573.5 Campbell Distal Blue grt-chl-amp ± mag ± bio py-po-mag A CR4612 273.2 Lamprophyre 22637.3 9770.6 Red Lake Distal N/A qtz vein py N/A CR4612 360.3 Basalt 22694.2 9705.9 Red Lake Distal Brown grt-chl-amp ± mag ± bio + cal vein py-po A CR4612 1170 Basalt 23231 9112.6 Red Lake Distal N/A bio-chl-amp none A? CR4613 1.3 Basalt 20832.8 9975 Red Lake Distal Blue grt-chl-amp ± mag ± bio po-py-mag A CR4613 25 Basalt 20853.1 9956.2 Red Lake Distal N/A carb vein with chl none A? CR464 10 Basalt 21719 9967 Red Lake Distal N/A grt-chl-amp ± mag ± bio mag A? CR464 31.2 Basalt 21731.4 9953.7 Red Lake Distal Blue grt-chl-amp ± mag ± bio po-py-mag A CR464 431.5 Basalt 22019.1 9675.1 Red Lake Distal N/A bio-chl-amp none A? CR466 36.6 Basalt 19011.5 9934.9 Red Lake Intermediate N/A chl-amp-cal-bio none A? CR466 145 Basalt 19062.9 9843.9 Red Lake Intermediate Blue grt-chl-amp ± mag ± bio py A CR466 572.1 Cherty argillite 19263.4 9468.1 Red Lake Intermediate N/A qtz (syn-min) py A? CR467 86.3 Argillite 27311.3 9928.3 Red Lake Distal Blue chl-bio-amp + sul py-mag A CR467 117.3 Chert 27330.7 9906.2 Red Lake Distal N/A N/A py N/A CR467 200 Basalt 27504 9709 Red Lake Distal N/A chl-amp-cal-bio none A? CR468 1 Basalt 26621.5 9975.8 Red Lake Distal N/A grt-chl-amp ± mag ± bio mag A? 429 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade CR468 601.1 Basalt 27002.6 9554.5 Red Lake Distal N/A carb-qtz vein with chl none A? CR468 629 Basalt 27021 9536.6 Red Lake Distal Blue grt-chl-amp ± mag ± bio po-py-mag A CR469 13.5 Ultramafic 25619.5 9962.5 Red Lake Distal N/A bio-Ti-mag ± carb none T? CR469 41.6 Basalt 25634.3 9943.7 Red Lake Distal Blue and Brown carb vein with chl po-mag T D14391 191 Basalt 3081.8 7976.5 Campbell Mine Grey br. bio-qtz py-po G D14391 1025 Perdiotitic Ko-matiite 3914.2 7979.4 Campbell Mine Grey p. carb py-po-mag G D14391 1810 Basalt 4695.6 7982.9 Campbell Mine Blue grt-chl-amp ± mag ± bio py-po-mag T D14391 2922 Basalt 5786.5 7797.4 Campbell Mine Grey br. bio-qtz py-mag G D14981 3.2 Basalt 1726.9 7974.1 Campbell Mine Grey qtz (syn-min) py-po T D14981 1045.2 Basalt 769.4 8097 Campbell Mine Blue qtz (syn-min) py T D14981 1727.9 Basalt 188.7 8303 Campbell Mine N/A bio-chl-amp mag T? D14981 1798.8 Basalt 127.2 8240 Campbell Mine Brown bio-chl-amp py-mag T D15367 5.5 Basalt 2234.9 7818 Campbell Mine Grey br. bio-qtz py-mag G D15367 371.1 Ultramafic 1872.3 7799.5 Campbell Mine Grey carb vein with chl sel- vage py-mag G D15367 413.5 Basalt 1830.7 7800.5 Campbell Mine N/A carb vein nono G? D15367 671.7 Lamprophyre 1458.5 7842.7 Campbell Mine N/A qtz-tour vein py N/A D15367 793 Basalt 1458.8 7843 Campbell Mine Blue bio-chl-amp py-mag G D16355 85.3 Ultramafic 2905.1 7671.1 Campbell Mine Grey mag py-po-mag T D16355 431 Perdiotitic Ko-matiite 3247.6 7627.3 Campbell Mine Grey p. carb py-po G D16355 800.5 Basalt 3598.3 7520 Campbell Mine N/A qtz (syn-min) none G? D16355 856.2 Komatiitic basalt 3650.2 7501.7 Campbell Mine N/A bio-Ti-mag ± carb mag G? D16355 925.8 Ultramafic 3715.1 7477.2 Campbell Mine Grey p. carb py-po G D21708 139.3 Basalt 2974.4 6939.6 Campbell Mine Brown carb-qtz vein py-mag G D21708 1118 Basalt 3849.5 6846.4 Campbell Mine N/A grt-chl-amp ± mag ± bio mag T? D21708 1340 Basalt 4044.3 6807.9 Campbell Mine Grey bio-Ti-mag ± carb py-po-mag T D21708 1762.8 Basalt 4422.7 6725.1 Campbell Mine N/A bio-chl-amp none T? D21708 2760 Basalt two 5317.7 6430.8 Campbell Mine Brown grt-chl-amp ± mag ± bio py-mag-cpy A D22203 79 Rhyolite 1742.2 6771.6 Campbell Mine Grey carb-qtz vein py-po-mag T D22203 908 Basalt 914.5 6742.7 Campbell Mine Grey carb-qtz vein py-po-mag G D22203 1544 Basalt 280.45 6720.04 Campbell Mine N/A br. bio-qtz po G D22203 1545 Basalt 279.5 6719.8 Campbell Mine N/A qtz (syn-min) po T D22203 1604 Ultramafic 220.1 6718.5 Campbell Mine Brown p. carb py-po-mag G 430 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D22223 38 Basalt 2580.9 6772.6 Campbell Mine Grey bio-Ti-mag ± carb py-po G D22223 975 Basalt 3516.6 6728.8 Campbell Mine Grey carb-qtz vein py-po G D22223 1399 Basalt 3940.4 6708.6 Campbell Mine N/A qtz py T D22223 1932 Ultramafic 4472.7 6684.1 Campbell Mine Grey p. carb py-po-mag G D2252 162 Basalt 2358.2 6774.1 Campbell Mine Grey p. carb py T D2252 309 Basalt 2501.3 6763.1 Campbell Mine Grey qtz (syn-min) py-mag A D2252 491 Basalt 2678 6725.2 Campbell Mine Grey and Brown p. carb po-py-mag G D2253 75 Basalt 2108 6773.4 Campbell Mine Grey and Blue bio-chl-amp py - cpy - aspy A D2253 252 Basalt 1936.3 6810.8 Campbell Mine Grey and Brown carb-qtz vein py-po-mag G D2253 495 Rhyolite 1705.1 6877.4 Campbell Mine Grey carb vein with bio py-po-mag G D239 95 Ultramafic 2133.4 6620.4 Campbell Mine Grey carb vein with chl py-po-mag G D239 217 Komatiitic basalt 2026 6619.1 Campbell Mine Grey br. bio-qtz py-mag G D2435 182 Komatiitic basalt 2217.09 6463.4 Campbell Mine Grey and Brown br. bio-qtz py-po-mag G D2435 361 Komatiitic basalt 2386.5 6434.6 Campbell Mine Grey qtz (syn-min) py-mag G D2435 454 Basalt 2474.7 6416 Campbell Mine Grey carb-qtz vein po-py-mag G D27343 88 Basalt 977 5942.4 Campbell Mine Grey, Blue and Brown carb-mag vein po-py-mag T D27343 232.8 Basalt 1050.5 5820 Campbell Mine N/A grt-chl-amp ± mag ± bio mag T ? D27343 501.3 Basalt 1203.3 5599.6 Campbell Mine Blue carb-qtz vein po-py-mag G D27343 1181.7 Rhyolite 1703 5143 Campbell Mine Grey carb-qtz vein py-mag A D27943 314 Basalt 604.8 6028.4 Campbell Mine Brown bio-chl-amp mag G D27943 351.2 Basalt 1051 5820.9 Campbell Mine N/A qtz-carb vein po G? D27943 933.8 Basalt -7 6074.1 Campbell Mine Blue carb vein with bio po-py-mag G D27943 1779.5 Basalt -836.3 6223.4 Campbell Mine Blue chl-amp-cal-bio po-py G D27943 2104.2 Basalt -1150.4 6308.3 Campbell Mine Grey and Brown carb vein with chl sel- vage po-py-mag T D27943 2607.6 Basalt -1629.8 6457.9 Campbell Mine Grey chl-amp-cal-bio po-py T D27943 3389.5 Basalt -2359.9 6720.1 Campbell Mine Grey bio-Ti-mag ± carb py G D33003 94 Basalt two 2570.5 5105 Campbell Mine N/A qtz py T D33003 532 Basalt 2136.3 5048.8 Campbell Mine Blue grt-chl-bio-amp ± mag po-mag T D33003 672 Basalt 1997.1 5036.2 Campbell Mine N/A qtz-mus-and po T D33003 782 Basalt 1887.4 5027 Campbell Mine N/A chl-amp-cal-bio none T 431 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D33003 1106 Carb-qtz vein 1564.28 5008.15 Campbell Mine Grey carb vein with bio sel- vage py G D33003 1290 Basalt 1380.6 5003.1 Campbell Mine N/A grt-chl-amp ± mag ± bio po G D33003 2004 Basalt 670.8 5060.3 Campbell Mine Grey p. Carb + chl-amp mag-py-po-cpy T D33003 2625 Rhyolite 61.4 5172.4 Campbell Mine N/A qtz (syn-min) none T D33003 2823 Basalt -129.8 5221.4 Campbell Mine N/A bio-chl-amp none T D33003 2888 Basalt -192.9 5239.1 Campbell Mine N/A bio-chl-amp po T D33003 2923 Lamprophyre -226.5 5247.3 Campbell Mine N/A p. carb none T D33003 3210 Basalt -502.326 5324.28 Campbell Mine Grey carb-qtz vein po-py-mag T D39018 43 Basalt 2606.6 4232.6 Campbell Mine No chlorite carb vein with bio sel- vage mag A D39018 173 Argillite 2734.3 4247.1 Campbell Mine N/A qtz (syn-min) po T D39018 635 Basalt 3195.4 4273.9 Campbell Mine Grey qtz-mus-and po-mag T D39018 1325 Basalt 3884.5 4290.7 Campbell Mine Grey grt-chl-amp ± mag ± bio po A D39018 1820 Basalt 4380.3 4276.5 Campbell Mine Blue carb-qtz vein py-mag A D39018 2555 Basalt 5113.4 4244.4 Campbell Mine Blue bio-Ti-mag ± carb po-py-mag A D39018 3050 Basalt 5605.90 4212.19 Campbell Mine Grey grt-bio-chl-amp ± mag py-mag A D39018 3113 Basalt 5668.8 4206 Campbell Mine Grey chl-amp-cal-bio py-mag A D39018 3562 Basalt 6110.5 4143.8 Campbell Intermediate Grey carb vein with chl po-py A D39018 4819 Basalt 7319.6 3902.5 Campbell Intermediate N/A grt-chl-amp-bio po A? D39018 4844 Basalt 7342.4 3897.4 Campbell Intermediate N/A carb vein po T D39018 4848 Basalt 7347.3 3897.2 Campbell Intermediate Blue grt-chl-amp ± mag ± bio po-py-mag T D39200 52 Komatiitic basalt 2454.71 4.191.42 Campbell Mine N/A carb vein with bio py-po T D39200 109 Ultramafic 2407.3 4159.2 Campbell Mine Grey carb vein with chl py-po A D39200 153 Peridotitic Ko-matiite 2372.42 4134.11 Campbell Mine Grey carb vein with chl po-py A D39200 208 Komatiitic basalt 2325.54 4105.29 Campbell Mine N/A qtz-carb-chl vein none T? D39200 244 Basalt 2296.54 4084.29 Campbell Mine Grey chl-amp-cal-bio py T D39200 249 Komatiitic basalt 2291.29 4082.78 Campbell Mine N/A bio-chl-amp none A D39200 263 Basalt 2279.54 4075.01 Campbell Mine N/A chl-amp-cal-bio none T D39200 268 Lamprophyre 2276.45 4071.25 Campbell Mine Grey bio-Ti-mag ± carb py-mag A D39200 280 Komatiitic basalt 2266.39 4064.74 Campbell Mine N/A br. bio-qtz po-py A D39200 298 Komatiitic basalt 2250.16 4056.12 Campbell Mine N/A carb vein with chl po T 432 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D39200 309 Basalt 2240.94 4050.24 Campbell Mine N/A carb vein with chl sel- vage po T D39200 315 Komatiitic basalt 2235.88 4046.9 Campbell Mine N/A carb vein with bio sel- vage none A D39200 325 Basalt 2227.47 4041.56 Campbell Mine N/A bio-Ti-mag ± carb none T D39200 336 Komatiitic basalt 2218.25 4035.69 Campbell Mine N/A carb vein with bio sel- vage none T D39200 347 Basalt 2208.94 4029.72 Campbell Mine N/A bio-Ti-mag ± carb none T D39200 396 Komatiitic basalt 2168.87 4002.18 Campbell Mine Grey carb vein po-py A D39200 398 Komatiitic basalt 2166.01 4002.43 Campbell Mine N/A carb vein with bio sel- vage none T D39200 415 Basalt 2151.73 3993.3 Campbell Mine N/A chl-bio-amp + carb-qtz vein none T D39200 438 Komatiitic basalt 2132.21 3980.91 Campbell Mine N/A p. carb none T D39200 467 Komatiitic basalt 2108.82 3964.36 Campbell Mine Grey chl-amp-cal-bio po-py A D39200 469 Komatiitic basalt 2105.99 3964.28 Campbell Mine N/A chl-bio-amp none A D39200 483 Komatiitic basalt 2094.06 3957.14 Campbell Mine N/A carb vein with bio sel- vage none A D39200 539 Komatiitic basalt 2046.7 3927.31 Campbell Mine N/A carb vein with chl none T D39200 575 Komatiitic basalt 2016.33 3907.97 Campbell Mine N/A carb vein with bio none T D39200 610 Komatiitic basalt 1986.77 3889.35 Campbell Mine N/A carb-mag vein mag A D39200 651 Komatiitic basalt 1951.97 3867.57 Campbell Mine N/A carb vein with chl none T D39200 695 Komatiitic basalt 1914.64 3844.25 Campbell Mine N/A chl-amp-cal-bio none T D39200 750 Basalt 1867.7 3815.2 Campbell Mine Blue carb-mag vein po-mag A D39200 775 Basalt 1846.58 3802.31 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag T D39200 791 Basalt 1832.93 3793.81 Campbell Mine N/A alb none T D39200 843 Basalt 1789.7 3765.6 Campbell Mine Blue and Brown alb po-py T D39200 878 Basalt 1758.73 3748.89 Campbell Mine N/A carb vein mag T D39200 906 Basalt 1734.59 3734.25 Campbell Mine N/A chl-amp-cal-bio mag T D39200 969 Basalt 1681.9 3700.44 Campbell Mine Blue and Brown grt-chl-amp ± mag ± bio po-py A D39200 1001 Basalt 1654.46 3684.01 Campbell Mine Grey qtz-carb-sul vein po-py T D39200 1002 Basalt 1652.5 3684.4 Campbell Mine Grey chl-amp-cal-bio po-py A D39200 1033 Basalt 1625.95 3668.81 Campbell Mine N/A bio-Ti-mag ± carb po T 433 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D39200 1044 Basalt 1616.46 3663.2 Campbell Mine N/A br. bio-qtz py-po T D39200 1063 Basalt 1600.01 3653.62 Campbell Mine N/A sul py-po T D39200 1064 Basalt 1600.35 3651.81 Campbell Mine Grey qtz-carb-sul vein po-py T D39200 1118 Basalt 1552.83 3625.51 Campbell Mine N/A br. bio-qtz po-py T D39200 1208 Basalt 1474.91 3580.95 Campbell Mine N/A br. bio-qtz po-py T D39200 1210 Basalt 1473.47 3580.32 Campbell Mine N/A br. bio-qtz py T D39200 1211 Basalt 1472.11 3579.42 Campbell Mine N/A carb-mag vein py-mag T D39200 1228 Basalt 1457.29 3572.1 Campbell Mine N/A carb-mag vein with py-mag T D39200 1263 Basalt 1426.92 3554.02 Campbell Mine N/A carb-qtz vein po-aspy T D39200 1267 Basalt 1423.48 3551.94 Campbell Mine N/A qtz (syn-min) none T D39200 1289 Basalt 1404.32 3541.09 Campbell Mine N/A carb vein with chl none T D39200 1318 Basalt 1380.09 3525.83 Campbell Mine Grey alb py T D39200 1358 Basalt 1344.12 3507.65 Campbell Mine N/A chl-amp-cal-bio po-py T D39200 1395 Basalt 1311.95 3489.84 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag T D39200 1406 Basalt 1303.26 3483.17 Campbell Mine Grey qtz (syn-min) py A D39200 1434 Basalt 1277.78 3470.95 Campbell Mine N/A grt-chl-amp ± mag ± bio po A D39200 1455 Basalt 1259.43 3460.92 Campbell Mine N/A grt-chl-amp ± mag ± bio po A D39200 1464 Basalt 1251.39 3456.49 Campbell Mine N/A grt-chl-amp ± mag ± bio po A D39200 1469 Basalt 1246.9 3453.2 Campbell Mine Grey grt-bio-chl-amp ± mag po-py-mag-aspy A D39200 1496 Basalt 1224.39 3440.11 Campbell Mine Blue qtz-mus-and po-py-mag A D39200 1509 Basalt 1211.9 3435.3 Campbell Mine No chlorite grt-chl-amp ± mag ± bio po-py-mag T D39200 1532 Basalt 1191.82 3424.4 Campbell Mine N/A bio-chl-amp none A D39200 1586 Basalt 1144.28 3398.82 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 1600 Basalt 1132.08 3392.12 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 1618 Basalt 1117.12 3382.56 Campbell Mine No chlorite grt-bio-chl-amp ± mag py-mag A D39200 1634 Basalt 1101.98 3376.23 Campbell Mine N/A bio-chl-amp po A D39200 1663 Basalt 1076.58 3362.85 Campbell Mine N/A grt-chl-amp ± mag ± bio py A D39200 1681 Basalt 1061.47 3353.32 Campbell Mine No chlorite qtz-mus-and po-py A D39200 1702 Basalt 1041.78 3344.68 Campbell Mine N/A carb vein with chl po A D39200 1704 Basalt 1040.06 3343.87 Campbell Mine N/A qtz-chl-bio po A D39200 1726 Basalt 1020.72 3334.02 Campbell Mine N/A bio-chl-amp po-py A D39200 1756 Basalt 994.06 3329.19 Campbell Mine N/A chl-amp-cal-bio po A D39200 1804 Basalt 951.21 3298.86 Campbell Mine N/A grt-chl-amp ± mag ± bio mag A D39200 1846 Basalt 913.79 3280.33 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A 434 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D39200 1850 Basalt 910.18 3278.52 Campbell Mine N/A grt-chl-amp ± mag ± bio aspy-mag-po A D39200 1881 Chert 883.421 3263.41 Campbell Mine Grey carb-qtz vein po-py-aspy A D39200 1884 Chert 880.735 3262.09 Campbell Mine Grey qtz (syn-min) py A D39200 1886 Basalt 878.09 3262.52 Campbell Mine N/A grt-bio-chl-amp ± mag po A D39200 1921 Basalt 847.562 3245.92 Campbell Mine Grey qtz-mus-and po A D39200 1958 Basalt 813.19 3231.34 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag-py A D39200 1978 Basalt 795.39 3222.57 Campbell Mine N/A grt-bio-chl-amp ± mag po A D39200 1989 Basalt 785.44 3217.87 Campbell Mine N/A grt-chl-amp ± mag ± bio po-aspy A D39200 2035 Basalt 743.78 3198.62 Campbell Mine N/A chl-amp-cal-bio none A D39200 2077 Basalt 705.81 3180.9 Campbell Mine N/A bio-chl-amp po A D39200 2090 Basalt 695.005 3174.2 Campbell Mine Grey grt-chl-amp ± mag ± bio py A D39200 2106 Basalt 676.6 3169.06 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 2127 Basalt 622.11 3143.39 Campbell Mine N/A chl-bio-amp po A D39200 2133 Basalt 580.99 3125.58 Campbell Mine N/A grt-bio-chl-amp ± mag py A D39200 2169 Basalt 513.11 3096.39 Campbell Mine N/A grt-chl-amp ± mag ± bio mag A D39200 2214 Basalt 441.34 3066.38 Campbell Mine N/A alb po A D39200 2228 Basalt 429.68 3061.4 Campbell Mine Grey br. Bio-qtz po-py-mag A D39200 2251 Basalt 412.6 3054.54 Campbell Mine N/A grt-chl-amp ± mag ± bio po A D39200 2284 Basalt 371.38 3036.83 Campbell Mine N/A grt-bio-chl-amp ± mag po A D39200 2288 Basalt 376.44 3039.81 Campbell Mine N/A qtz (syn-min) po A D39200 2304 Basalt 499.286 3088.76 Campbell Mine Grey chl-amp-cal-bio py A D39200 2366 Diorite 441.34 3066.18 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 2397 Basalt 412.78 3054.34 Campbell Mine N/A grt-chl-amp ± mag ± bio mag A D39200 2402 Basalt 408.97 3051.2 Campbell Mine Grey chl-amp-cal-bio py T D39200 2436 Basalt 376.71 3039.78 Campbell Mine N/A carb vein with chl po A D39200 2452 Basalt 361.89 3033.82 Campbell Mine N/A chl-amp-cal-bio po A D39200 2514 Basalt 304.41 3010.86 Campbell Mine N/A grt-chl-amp ± mag ± bio po-py-magetite A D39200 2556 Basalt 266.278 2994.17 Campbell Mine Grey qtz-sul po-py A D39200 2579 Basalt 244.03 2987.18 Campbell Mine N/A qtz (syn-min) none A D39200 2586 Basalt 237.34 2984.56 Campbell Mine N/A chl-amp-cal-bio po A D39200 2608 Basalt 217.09 2976.88 Campbell Mine N/A bio-Ti-mag ± carb po A D39200 2641 Basalt 186.18 2964.94 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 2652 Basalt 176.869 2959.79 Campbell Mine Grey qtz-mus-and py A D39200 2665 Diorite 163.76 2956.54 Campbell Mine N/A chl-amp-cal-bio none A D39200 2695 Basalt 135.83 2946.14 Campbell Mine N/A chl-amp-cal-bio po A 435 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D39200 2800 Basalt 37.3 2910.7 Campbell Mine Grey grt-bio-chl-amp ± mag po-py-mag A D39200 2801 Basalt 36.41 2910.26 Campbell Mine N/A grt-chl-bio-amp pyrrhitite A D39200 2813 Basalt 25.02 2906.37 Campbell Mine N/A grt-chl-bio-amp pyrrhitite A D39200 2824 Basalt 14.7 2902.7 Campbell Mine Grey grt-bio-chl-amp ± mag po-py-mag A D39200 2827 Basalt 11.91 2901.76 Campbell Mine N/A bio-chl-amp po A D39200 2858 Basalt two -17.28 2891.55 Campbell Mine N/A bio-Ti-mag ± carb po A D39200 2862 Basalt -21.08 2890.47 Campbell Mine N/A bio-Ti-mag ± carb po A D39200 2880 Chert -37.89 2884.41 Campbell Mine N/A bio-Ti-mag ± carb pyrrhite N/A D39200 2884 Basalt -41.6 2882.96 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 2906 Basalt -62.38 2876 Campbell Mine N/A grt-chl-bio-amp po A D39200 2935 Diorite -89.0372 2865.28 Campbell Mine Blue and brown grt-chl-amp ± mag ± bio po-py A D39200 2954 Diorite -107.85 2860.64 Campbell Mine N/A bio-chl-amp none A D39200 2983 Basalt -135.15 2851.33 Campbell Mine N/A chl-amp-cal-bio none A D39200 3029 Basalt -178.71 2837.14 Campbell Mine N/A grt-chl-amp ± mag ± bio mag A D39200 3058 Basalt -206.3 2828 Campbell Mine N/A bio-chl-amp po-py-mag A D39200 3115 Basalt -259.369 2809.2 Campbell Mine N/A chl-amp-cal-bio py-mag A D39200 3171 Basalt -6.52083333 2794.29 Campbell Mine N/A bio-chl-amp none A D39200 3212 Basalt -352.62 2782.63 Campbell Mine N/A grt-chl-amp ± mag ± bio none A D39200 3216 Basalt -355.724 2780.03 Campbell Mine N/A carb vein with chl sel- vage py-po A D39200 3239 Basalt -378.47 2774.86 Campbell Mine N/A grt-chl-amp ± mag ± bio po-mag A D39200 3241 Basalt -380.3 2774.5 Campbell Mine Grey and brown grt-chl-amp ± mag ± bio po-mag - cpy A D39200 3288 Basalt -425.29 2760.94 Campbell Mine N/A bio-chl-amp none A D39200 3291 Basalt -428 2760.1 Campbell Mine Grey grt-chl-amp ± mag ± bio po-py-mag A D39200 3317 Basalt -453.04 2752.9 Campbell Mine N/A bio-chl-amp none A D39204 19 Ultramafic 2478.5 4220.5 Campbell Mine Grey p. carb py-mag A D39204 212 Diorite 2289.94 4188.54 Campbell Mine Grey bio-Ti-mag ± carb py A D39204 307 Komatiitic Basalt 2195.4 4176.9 Campbell Mine Grey carb vein with chl sel- vage po-mag A D39204 481 Basalt 2024.12 4155.83 Campbell Mine Grey bio-Ti-mag ± carb py-po T ? D39204 566 Basalt 1939.85 4147.35 Campbell Mine No chlorite br. bio-qtz py-po T ? D39204 781 Basalt 1725.7 4133.1 Campbell Mine Brown qtz (syn-min) py-po-mag G D39204 810 Basalt 1696.7 4131.7 Campbell Mine No chlorite grt-chl-amp ± mag ± bio po-py-mag T ? D39204 937 Basalt 1570 4126.9 Campbell Mine Blue chl-amp-cal-bio mag A 436 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade D39204 1001 Basalt 1506 4125.3 Campbell Mine Blue and grey grt-chl-amp ± mag ± bio po-mag A D39204 1015 Basalt 1492 4125.3 Campbell Mine Blue grt-chl-amp ± mag ± bio po-mag T D39204 1017 Basalt 1460.1 4125.1 Campbell Mine No chlorite grt-chl-amp ± mag ± bio po-py-mag A D39204 1032 Basalt 1475 4125.6 Campbell Mine Grey carb-qtz vein py-po-mag A D39204 1080 Basalt 1427.4 4124.4 Campbell Mine Blue grt-chl-amp ± mag ± bio po-mag A D39204 1165 Basalt 1342.4 4124.4 Campbell Mine Brown grt-chl-amp ± mag ± bio po-py-mag T D39204 1173 Basalt 1334.2 4124.6 Campbell Mine Blue grt-chl-amp ± mag ± bio po-mag T D39204 1203 Basalt 1304.2 4124.7 Campbell Mine No chlorite qtz (syn-min) po-mag A D39204 1215 Basalt 1292.3 4124.7 Campbell Mine Grey grt-chl-amp ± mag ± bio po-mag T D39204 1226 Basalt 1281.3 4125.3 Campbell Mine Blue grt-chl-amp ± mag ± bio po-mag A D39204 1333 Basalt 1173.8 4127.3 Campbell Mine Grey and brown chl-amp-cal-bio py-po-mag T D39204 1439 Basalt 1068.6 4132.4 Campbell Mine Grey chl-cal-bio-amp po-mag T D39357 37 Ultramafic 2461.4 4208.3 Campbell Mine Grey carb vein with chl py-po A D39357 104 Basalt 2399.2 4185.3 Campbell Mine N/A qtz (syn-min) py T D39357 741 Basalt 1789.1 4010.1 Campbell Mine N/A grt-chl-bio-amp none T D39357 1236 Basalt 1301.2 3928.7 Campbell Mine N/A grt-chl-amp ± mag ± bio po-aspy A D39357 1287 Basalt 1250.5 3923 Campbell Mine Blue grt-chl-amp ± mag ± bio py-po-mag A D39357 1308 Basalt 1229.3 3921 Campbell Mine Grey carb-qtz vein py-mag T D39357 2029 Basalt two 510.113 3892.49 Campbell Mine Grey qtz-sul po-py G D39357 2066 Basalt 473.2 3894.7 Campbell Mine Grey bio-Ti-mag ± carb py-po A D39357 2067 Basalt 472.148 3893.47 Campbell Mine Grey br. bio-qtz po-py A DS11 103.4 Basalt 2458.3 9939.3 Campbell Mine Grey chl-amp-cal-bio py-po T DS122 175.853 Basalt 445173.49 5656929.03 Campbell Distal N/A least altered none DS139 30.4 Basalt 3677.8 9991.9 Campbell Mine Grey bio-chl-amp py-mag G DS139 323.3 Basalt 3862.57 9764.75 Campbell Mine Brown bio-Ti-mag ± carb po-py-mag A DS172 30.5 Over burden 11690 9930 Campbell Intermediate N/A N/A N/A N/A DS172 123.1 Basalt 11736.5 9855.9 Campbell Intermediate Blue grt-chl-amp ± mag ± bio py-mag - cpy A DS172 501 Basalt 11982.8 9573 Campbell Intermediate N/A grt-chl-amp ± mag ± bio mag A? DS173 10.7 Over burden 12480 9960 Campbell Intermediate N/A grt-chl-amp ± mag ± bio mag A? DS173 499.6 Basalt 12840.8 9647.7 Campbell Intermediate Blue and brown grt-bio-chl-amp ± mag po-py-mag T DS173 518 Basalt 12853.5 9634.4 Campbell Intermediate N/A grt-chl-amp ± mag ± bio mag A? DS174 33.2 Over burden 13220 9940 Campbell Distal N/A N/A N/A N/A DS174 606.4 Basalt 13579.23 9497.08 Campbell Distal N/A bio-Ti-mag ± carb py-po A? DS174 708.4 Basalt 13648 9421.6 Campbell Distal Blue grt-chl-amp ± mag ± bio py-po-mag A 437 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade DS177 119.6 Chert 7317.78 9843.24 Campbell Intermediate N/A qtz (syn-min) py A? DS177 460.5 Basalt 7568.6 9615 Campbell Intermediate Grey grt-chl-amp ± mag ± bio po-py A DS177 613 Basalt 7689.20 9523.30 Campbell Intermediate Grey bio-Ti-mag ± carb py-po-mag A DS177 1500.8 Basalt 8420.4 9039.4 Campbell Intermediate Blue grt-chl-amp ± mag ± bio + sul py-po-mag A DS180 50 Over burden 10650 9950 Campbell Intermediate N/A N/A N/A N/A DS180 400.2 Diorite 10780.7 9653.3 Campbell Intermediate Grey chl-amp-cal-bio py-po-mag A DS196 395.9974 Basalt 445857.75 5657096.14 Regional REF Distal N/A least altered none DS340 35.6 Ultramafic 4422.60 9974.29 Campbell Mine Grey carb vein with bio sel- vage py-po-mag G DS340 297.3 Komatiitic Basalt 4565.55 9758.91 Campbell Mine Grey carb vein with bio py-po G DS340 403.4 Komatiitic Basalt 4623.08 9670.89 Campbell Mine N/A carb-qtz vein po-mag-py G? DS340 505.6 Ultramafic 4680.5 9587.7 Campbell Mine N/A carb-qtz vein py G? DS340 694.7 Komatiitic Basalt 4789.06 9436.19 Campbell Mine Grey carb vein with bio py-po-mag T DS343 90 Komatiitic Basalt 4407.1 9930.91 Campbell Mine Grey carb vein with chl py G DS343 264 Komatiitic Basalt 4294.3 9799.2 Campbell Mine N/A qtz vein py G DS343 395 Komatiitic Basalt 4212.31 9698.79 Campbell Mine Grey br. bio-qtz py-po G DS343 455 Komatiitic Basalt 4172.3 9652.6 Campbell Mine N/A carb vein py G DS343 524 Komatiitic Basalt 4130.09 9600.6 Campbell Mine No chlorite br. bio-qtz none G ? DS343 696 Komatiitic basalt 4018.7 9470 Campbell Mine Grey chl-amp-cal-bio py-po G DS352 25 Basalt 2927.97 10021.90 Campbell Mine Brown qtz-mus-and po-mag G DS352 39 Basalt 2938.25 10012.95 Campbell Mine Blue chl-amp-cal-bio py-po G DS352 56 Basalt 2949.64 10000.35 Campbell Mine grey carb-qtz vein + sul py-po G DS352 134 Basalt 3001.92 9942.54 Campbell Mine Brown chl-amp-cal-bio py-po G DS352 243 Basalt 3074.8 9861 Campbell Mine N/A carb vein py G DS352 264 Basalt 3087.9 9845 Campbell Mine Grey qtz (syn-min) py-po-mag G DS352 305 Basalt 3116.54 9815.8 Campbell Mine Grey qtz-sul py-po G DS352 341 Basalt 3139.75 9787.80 Campbell Mine Grey and brown carb vein with chl sel- vage py-po-mag G DS352 390 Basalt 3173.51 9752.8 Campbell Mine Brown qtz (syn-min) py-po G DS352 417 Basalt 3191.61 9732.79 Campbell Mine Grey qtz-mus-and py-po G DS352 512 Komatiitic Basalt 3255.28 9662.38 Campbell Mine Grey qtz (syn-min) po-py-mag G DS352 532 Komatiitic Basalt 3268.69 9647.56 Campbell Mine Grey qtz (syn-min) py-po G 438 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade DS358 109 Diorite 587.488 9867.89 Campbell Mine Brown carb vein with chl selvage py G DS358 132 Lamprophyre 600.4 9848.7 Campbell Mine Brown late cal py-mag T DS358 162 Diorite 618.6 9824.6 Campbell Mine Grey carb vein py-mag G DS358 183 Diorite 632.573 9809.27 Campbell Mine Grey p. carb py-po G DS358 296 Diorite 702.441 9720.55 Campbell Mine Grey p. carb py-po T DS358 321 Basalt 718.043 9701.03 Campbell Mine Grey chl-amp-cal-bio py-po G DS358 462 Basalt 807.924 9592.55 Campbell Mine Blue and brown p. carb py-po G DS358 512 Diorite 829.6 9553.1 Campbell Mine Blue carb vein with chl py-mag G DS358 624 Komatiitic Basalt 914.20 9469.10 Campbell Mine Blue carb-mag vein py-po G DS358 1047 Diorite 1217.2 9175.4 Campbell Mine Brown carb vein with chl py-mag G DS358 1173 Basalt 1319.18 9102.28 Campbell Mine Brown chl-amp-cal-bio py-po G DS358 1213 Diorite 1352.04 9079.53 Campbell Mine Grey carb vein with chl py G DS358 1215 Diorite 1353.4 9076.2 Campbell Mine Blue chl with carb-qtz vein py-po-mag T DS360 124 Basalt 1752.8 9865.07 Campbell Mine Brown p. carb py-po-mag G DS360 329 Basalt 1830.6 9679.6 Campbell Mine N/A carb vein py G DS360 528 Basalt 1914.67 9499.5 Campbell Mine No chlorite carb-mag vein py-po G DS360 751 Komatiitic basalt 2010.1 9298.6 Campbell Mine Brown qtz (syn-min) py-mag G DS615 1214.5 Basalt 10095.7 8846.5 Campbell Intermediate Grey grt-chl-amp ± mag ± bio py-po G DS615 1692.8 Basalt 10295.7 8415.3 Campbell Intermediate N/A grt-bio-chl-amp ± mag mag T? DS615 1905.1 Basalt two 10395.2 8228.7 Campbell Intermediate Blue grt-chl-amp ± mag ± bio po-mag A DS615 3001.1 Basalt 10989 7323.9 Campbell Intermediate Blue and brown grt-chl-amp ± mag ± bio po-mag A DS615 4032.2 Basalt 11638.2 6589.4 Campbell Intermediate Blue grt-chl-amp ± mag ± bio po-mag A ES09_AP_10 Carb-qtz vein 443835.0 5657142.6 Mapped Outcrop Distal No chlorite N/A none N/A ES09_AP_20 Carb-qtz vein 443823.5 5657142.7 Mapped Outcrop Distal No chlorite N/A none N/A ES09_AP_23 Carb-qtz vein 443817.7 5657141.6 Mapped Outcrop Distal No chlorite N/A none N/A ES09_AP_27 Carb-qtz vein 443812.7 5657141.0 Mapped Outcrop Distal No chlorite N/A none N/A ES09_AP_35 Carb-qtz vein 443804.8 5657141.5 Mapped Outcrop Distal No chlorite N/A none N/A 439 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade ES09_AP_37 Carb-qtz vein 443803.2 5657141.6 Mapped Out- crop Distal No chlorite N/A none N/A ES09_AP_49 Carb-qtz vein 443788.6 5657141.7 Mapped Out- crop Distal No chlorite N/A py N/A ES09_AP_6 Basalt 443846.7 5657143.4 Mapped Out- crop Distal Grey qtz-mus-and none G GC01015 49.8 Basalt 450053.2 5657726.44 Regional REF Regional N/A least altered none T? GC01018 67.2 Basalt 14572.2 9951.9 Red Lake Intermediate N/A grt-chl-amp ± mag ± bio po A? GC01018 85.3 Basalt 14585 9940.4 Red Lake Intermediate Blue grt-chl-amp ± mag ± bio + cal vein po-mag A GC01018 691.2 Argillite 15053.1 9555.9 Red Lake Intermediate Blue grt-chl-bio-amp ± mag po-mag A GC01018 1171.8 Cherty argillite 15435.4 9265.7 Red Lake Intermediate N/A none po A? GC01018 1382.2 Argillite 15604.4 9139.9 Red Lake Intermediate Blue and brown grt-chl-amp ± mag ± bio po-py-mag A GC04002 239 Argillite 11187.71 9850.67 Red Lake Intermediate No chlorite grt-chl-amp ± mag ± bio po-py-mag A? GC04002 688 Argillite 11529.9 9560.2 Red Lake Intermediate Grey chl-amp-cal-bio po T GC04002 1522 Rhyolite 12193.29 9057.21 Red Lake Intermediate N/A qtz-mus-and po-mag N/A GC04003 338 Peridotite ko-matiite 8291.4 9711.85 Red Lake Mine Grey and brown carb vein with chl po-mag G GC04003 786.75 Basalt 8615.12 9401.23 Red Lake Mine Grey carb-qtz vein py G GC04003 1716 Megacryst feld-spar 9292.7 8767.5 Red Lake Mine Blue qtz-carb-chl vein py-mag N/A GC04003 1729.5 Quartz-feldspar porphyry 9303.1 8758.4 Red Lake Mine N/A carb-qtz vein none N/A GC04007 134 Rhyolite 3986.7 7986.3 Red Lake Mine Blue and Late chl with carb-qtz vein mag G? GC04007 167 Felsic tuff 2046.6 9838.5 Red Lake Mine N/A qtz (syn-min) py-sph N/A GC04007 911 Gabbro 2557.87 9301.39 Red Lake Mine Blue carb vein with chl py-po-mag G GC04007 2000 Basalt 4786.4 7372.6 Red Lake Mine Blue chl-amp-cal-bio py-mag G GC04007 2859 Gabbro 3990.72 7991.41 Red Lake Mine Grey p. carb py-po-mag G GC04007 3606 Diorite 4563.2 7531 Red Lake Mine N/A bio-chl-amp po G ? GC04007 3890 Ultramafic 3345.5 8552.6 Red Lake Mine Blue chl-bio-amp po-py-mag T GC04007 4421 Basalt 8610.90 9396.30 Red Lake Mine Grey br. bio-qtz py-mag G GC95010 350 Diorite 6014.6 9648.4 Red Lake Mine Blue p. carb py-po-mag G 440 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite birefrin- gence colour Key/Dominant alteration as- semblage Mineralization assemblage Metamorphic Grade GC95010 939 Diorite 6377.9 9185.3 Red Lake Mine Grey chl-amp-cal-bio po-py G GC95010 1173 Basalt 6532 9007.8 Red Lake Mine N/A qtz (syn-min) py G IN8728 29.5 Basalt 446983.37 5662082.47 Regional REF Regional REF N/A least altered none N/A MB01-031 16.4 Basalt 444876.05 5659239.238 Regional REF Regional REF N/A least altered none N/A MC-01-012 16.4 Basalt 446549.203 5659890.871 Regional REF Regional REF N/A least altered none N/A MC02021 103.3 Basalt 446520.131 5660246.774 Regional REF Regional REF N/A least altered none N/A R87105 523.6 Argillite 19070.58 9503.36 Campbell Distal N/A none po-py A? R87105 699.3 Basalt 19181.7 9365.9 Campbell Distal Grey chl-amp-cal-bio po-py-mag A R87105 749.7 Basalt 19213.4 9328.6 Campbell Distal N/A carb vein with chl none A R87107 482.8 Basalt 17235.7 9626.8 Campbell Distal Grey bio-chl-amp po-py-mag A R87108 629.5 Basalt 16378.4 9438.6 Campbell Distal Grey and brown bio-chl-amp + sul po-py-mag A RL16A Basalt 6450.9 7670.6 Red Lake Mine N/A qtz-carb vein aspy G RL33806B Basalt 2751.7 5152.9 Red Lake Mine N/A chl-amp-cal-bio po A RL338261AO Basalt 5911.5 5155.9 Red Lake Mine N/A qtz-sul aspy-py-po T RL348651T Basalt 5602 4972.8 Red Lake Mine N/A bio-Ti-mag ± carb mag T RL34865-3 Basalt 5602 4972.8 Red Lake Mine N/A carb vein mag T RL34875SO Basalt 5568.6 4999.7 Red Lake Mine N/A qtz-sul po-py T RL35-2 Basalt 5759.1 4852.8 Red Lake Mine N/A br. Bio-qtz aspy-py-po T RL352806 Basalt 5702 4850.3 Red Lake Mine N/A br. Bio-qtz aspy-py-po A RL352FW Basalt 5759.1 4852.8 Red Lake Mine N/A qtz-sul aspy A RL357462 Basalt 5615 4849.5 Red Lake Mine N/A br. Bio-qtz po-py A RL358066 Basalt 5461.2 4845.5 Red Lake Mine N/A carb-qtz vein py-po T RL35-826-1 Basalt 5702 4850.3 Red Lake Mine N/A carb-qtz vein po A RL35FW Basalt 5759.1 4852.8 Red Lake Mine N/A qtz-carb vein + sul po-py A RL387462 Basalt 5504 4848.3 Red Lake Mine N/A qtz-carb vein none A RL387462breccia Basalt 5504 4848.3 Red Lake Mine N/A bio-chl-amp none A RL417461 Basalt 2776 4084 Red Lake Mine N/A br. Bio-qtz po-py-aspy A RL417461ASP Basalt 2776 4084 Red Lake Mine N/A br. Bio-qtz aspy A RL42-2 Sub Ultramafic 3430 3850 Red Lake Mine N/A qtz po-py A RL42-2Sub Min Basalt 3430 3850 Red Lake Mine N/A br. Bio-qtz po-aspy-py-stb A 441 Table A.1 (Continued) Sample Depth (ft) Lithology Loc X (NAD 27) Loc Y (NAD 27) Complex Scale Chlorite bire- fringence colour Key/Dominant altera- tion assemblage Mineralization assemblage Metamorphic Grade RL422VG Basalt 3430 3850 Red Lake Mine N/A qtz vein-sul po-py A RL437461B Basalt 3320 3690 Red Lake Mine Grey br. Bio-qtz po-py A RL437461FucM Ultramafic 3320 3690 Red Lake Mine N/A qtz-fucsite po-py A RL447461 Basalt 3160 3540 Red Lake Mine N/A chl-amp-cal-bio po A RL44-746-1SV Basalt 3160 3540 Red Lake Mine N/A carb-qtz vein sph A 442 A.3 Underground map This appendix is the geological map of the underground active stope 44-746-1 which is located at 44 level within the Red Lake complex. Accompanying the map are selected photographs high- lighting vein types, alteration and mineralization in terms of mineralogy and textures. Figure A.43 Geological map of stope 44-746-1 Sill 443 Figure A.44 Accompanying annotated photographs for figure A.43 444 A.4 Regional geological map This appendix is the geological map of the outcrop within the RLGB at the Red Lake Airport. For location in relation to the RLGM please refer to Fig. 1.6. From this outcrop two samples, ES09_AP_06 and ES09_AP_27 were selected to analyze the carbonate chemistry (Chapter 3) to confirm the hypothesis that Fe-carbonate is associated and envelopes mineralized occurrences in the RLGM (Pirie, 1981). Additional samples, ES09_AP_10, ES09_AP_20, ES09_AP_23, ES09_AP_35, ES09_AP_37 and ES09_AP_49 combined with ES09_AP_06 and ES09_AP_27 were chosen for carbon and oxygen isotope analysis. This allowed for additional mineralized ar- eas in the RLGB to be assessed, allowing for the conclusion that mineralized occurrences in the RLGB share common 13C and 18O isotope values. 66 67 78 78 78 82 81 81 81 83 71 70 84 64 85 82 69 79 83 80 76 84 83 81 86 88 8188 84 79 8574 78 87 81 88 79 74 72 88 70 79 81 85 69 76 82 81 79 86 7981 84 79 78 79 81 72 73 87 87 84 82 84 81 79 81 80 84 83 71 78 81 74 88 87 84 81 80 83 82 84 80 83 84 80 83 89 85 87 84 89 83 84 87 83 80 85 84 87 76 82 79 82 87 85 82 65 72 83 71 86 82 84 78 74 66 8089 83 70 73 72 78 79 8376 63 69 72 72 78 73 64 71 58 58 67 56 64 64 70 68 71 62 73 72 82 76 65 89 76 76 63 78 70 78 70 78 64 79 80 87 78 76 71 78 76 78 71 79 79 78 80 78 77 70 79 74 72 71 76 82 86 76 61 70 65 68 76 83 78 86 76 83 88 88 87 78 70 76 85 78 73 73 88 82 83 87 81 64 79 82 84 79 65 71 82 81 81 82 84 54 76 83 78 79 7481 78 83 80 76 79 79 76 76 70 73 83 80 83 69 66 71 55 71 76 76 86 78 74 84 71 76 87 70 71 84 57 63 46 56 55 62 75 77 62 85 74 63 6464 64 75 65 41 41 67 76 76 51 61 62 54 56 70 71 68 66 5835 72 76 66 74 69 66 78 63 73 58 64 53 77 87 71 75 39 45 59 71 5481 70 81 64 78 47 51 56 5738 73 5959 42 67 32 7238 74 42 85 38 61 80 38 70 42 73 81 44 53 79 50 83 77 5379 42 68 39 81 64 64 80 56 80 42 78 87 33 88 47 6463 69 67 69 67 76 48 48 76 64 70 7264 7323 7430 53 83 65 79 70 81 79 56 36 75 67 65 82 78 64 83 5 ft 5 ft Lithology and Veins Basalt Chert/BIF Mafic inclusions Carbonate and Chert 30% Carbonate, 70% basalt 60% Carbonate vein, 20% Chert, 20% basalt Highly rusted carbonate vein Carbonate vein Quartz vein Tourmaline vein Overburden/Glacial deposit Structure Fault Fault inferred N 88 Foliation (metamorphic) 84 Carbonate vein 74 Quartz vein 65 Bedding (sedimentary units) Fold plunge, and axial plane stike/dip A Photograph location STRUCTURAL MAP 66 67 78 78 78 82 81 81 81 83 71 70 84 64 85 82 69 79 83 80 76 84 83 81 86 88 8188 84 79 8574 78 87 81 88 79 74 72 88 70 79 81 85 69 76 82 81 79 86 7981 84 79 78 79 81 72 73 87 87 84 82 84 81 79 81 80 84 83 71 78 81 74 88 87 84 81 80 83 82 84 80 83 84 80 83 89 85 87 84 89 83 84 87 83 80 85 84 87 76 82 79 82 87 85 84 65 72 83 71 86 82 84 78 74 66 8089 83 70 73 72 78 79 8376 63 69 72 72 78 73 64 71 58 58 67 56 64 64 70 68 71 62 73 72 82 76 65 89 76 76 63 78 70 78 70 78 64 79 80 87 78 76 71 78 76 78 71 79 79 78 80 78 77 70 79 74 72 71 76 82 86 76 61 70 65 68 76 83 78 86 76 83 88 88 87 78 70 76 85 78 73 73 88 82 83 87 81 64 79 82 84 79 65 71 82 81 81 82 84 54 76 83 78 79 7481 78 83 80 76 79 79 76 76 70 73 83 80 83 69 66 71 55 71 76 76 86 78 74 84 71 76 87 70 71 84 57 63 46 56 55 62 75 77 62 85 74 63 6464 64 75 65 41 41 67 76 76 51 61 62 54 56 70 71 68 66 5835 72 76 66 74 69 66 78 63 73 58 64 53 77 87 71 75 39 45 59 71 5481 70 81 64 78 47 51 56 5738 73 5959 42 67 32 7238 74 42 85 38 61 80 38 70 42 73 81 44 53 79 50 83 77 5379 42 68 39 81 64 64 80 56 80 42 78 87 33 88 47 6463 69 67 69 67 76 48 48 76 64 70 7264 7323 7430 53 83 65 79 70 81 79 56 36 75 67 65 82 78 64 83 Figure A.45 Regional map of an outcrop near the Cochenour-Willans mine workings. 5 ft 5 ft NAD 27 Zone 15 443788.6 5657141.7 NAD27 Zone 15 443877 5657149 445 446 A.5 Carbonate mineral staining and ultraviolet methods and results This appendix provides details of carbonate staining and ultraviolet fluorescence (UVF) which were both attempted to investigate a cheap and rapid method of assessing carbonate chem- istry to identify ankerite associated with mineralization and envelopes of calcite distally (MacGeehan et al., 1982; Parker 2000: this study). Carbonate staining was tested in the field during summer work. Core samples were first etched with dilute (2%) HCl to obtain a clean surface then stained using alizarin red S and potas- sium ferricyanid individually and together in a variety of concentrations with dilute HCl acid in accordance with Hitzman (1999). A mixed solution of both chemicals was prepared containing 2% HCl + 2 grams alizarin red S + 2 grams potassium ferricyanide, as well as solutions of each compound with dilute HCl (2% HCl + 2 grams alizarin red S and 2% HCl and 2 grams potas- sium ferricyanide). The solutions outlined above were applied to the core sample with a paint brush. Application of the staining solution was repeated for thorough staining. The chemicals were then left for 5 minutes to ensure reactions had taken place before recording any colour changes in the carbonate mineral. The colour difference, if any, was recorded and the sample photographed for comparison. Even though the application of the staining chemicals was generous, occasionally the chemicals did not react with the carbonate, causing only sporadic colour changes. As assumed, the more abundant the carbonate in the sample, the more effective the staining method. The chemicals did cause colour changes in the samples which corresponded to those which Hitzmann (1999) observed for Fe-calcite – pink for Alizarin red S, blue for potassium ferricyanide and purple for the mixed chemicals (Fig. A.45). However, there was no distinction between proximal and distal samples (Fig. A.44). The inability of carbonate staining to identify ankerite proximal and calcite distal to mineralization is thought to be due to the Fe2+-rich nature of the carbonate minerals in the RLGM and surrounding area (Table 3.5). UVF of various carbonate-bearing hand samples was assessed using two short-wave UV lamps (λ = 254 nm). Colour variations exhibited by the carbonate-bearing samples in response to the UV lamps can be linked back to variations in the transition metal composition of the carbon- ate mineral, e.g. an orange-red colour in calcite samples has been linked to high Mn contents (Gies, 1975; White, 1975, Marfunin, 1979). Raw images of the samples assessed for UVF varia- 447 tions were taken using an Olympus EI/SLR with the imagines modified to highlight any fluores- cence variations. Figure A.46. Examples of carbonate staining of samples proximal to distal. A) D33003-1106, B) R87105-699.8, C) 34L235-1168.7, D) CR468-629, E) 19L547-52.4, F) DS177-613, G) 34L814-2333.4 and H) DS614-4032.8. Sam- ples A and B were stained using one solution of 2% HCl + 2 grams alizarin red S + 2 grams potassium ferricyanide. The proximal and distal samples were stained purple indicating ferroan calcite. Samples C and D were stained using two solutions, the first 2% HCl + 2 grams alizarin red S and the second 2% HCl + 2 grams potassium ferricyanide. The proximal and distal samples were stained purple indicating ferroan calcite. Samples E and F were stained using one solution of 2% HCl + 2 grams potassium ferricyanide. The proximal and distal samples were stained sporadi- cally blue indicating ferroan calcite. Samples G and H were stained using one solution of 2% HCl + 2 grams alizarin red S. The proximal and distal samples were stained pink/red indicating ferroan calcite to aragonite. All colour changes and corresponding carbonate mineral chemistry derived from Hitzmann (1999). 448 Despite the known variation from dolomite/ankerite proximally to calcite distally, this in- formation was not differentiated using UVF. Samples from the mine and distal scales all re- flected a dull (low fluorescence) dark purple colour (Fig. A.46). There were variations in the in- tensity of the fluorescence between coarse carbonate and finer carbonate samples. Medium coarse carbonate grains displayed a higher fluorescence, bright pink colour compared to the dull fluorescence of finer grains. This is not considered a reflection of chemistry due to SEM-EDS confirmation, but rather a larger surface for light to reflect causing brighter fluorescence. The inability of UVF to vary in produced fluorescence colours in thought to be due to the dominance of Fe in the carbonate minerals which was identified using the electron microprobe (Table 3.5). Iron is a known quencher (Gies, 1975; Marfunin, 1979). Figure A.47 Example of ultraviolet fluorescence of carbonate on a proximal sample A (D27943-314) and a distal sample B (R87105-699.8). Both samples indicate very weak fluorescence. 449 Appendix B for Chapter 4 B.1 Electron microprobe errors This appendix consists of Table B.1 which outlines the error (+ and - 2σ) for each element and mineral assessed. Table B.1. Calculated error for each element and mineral for the EMPA data Chlorite Biotite Amphibole Carbonate Garnet Norm -2σ +2σ Norm -2σ +2σ Norm -2σ +2σ Norm -2σ +2σ Norm -2σ +2σ Na 0.04 0.02 5.36 0.08 0.03 0.03 0.61 0.05 0.05 0.01 0.01 3.30 Mg 8.60 0.14 0.14 7.14 0.13 0.13 4.72 0.08 0.08 6.28 0.13 1.28 0.89 0.04 0.04 Al 11.36 0.14 0.14 9.46 0.13 0.13 6.89 0.07 0.07 11.15 0.11 0.11 Si 12.10 0.15 0.15 17.27 0.18 0.18 20.02 0.15 0.15 17.04 0.15 0.15 K 0.05 0.02 1.95 7.87 0.20 0.20 0.27 0.03 0.08 Ca 0.30 0.02 1.62 0.05 0.02 1.36 7.07 0.11 0.11 27.64 0.31 0.31 3.40 0.08 0.08 Ti 0.05 0.03 0.31 1.02 0.06 0.06 0.12 0.03 0.30 0.07 0.02 0.29 Cr 0.07 0.04 1.69 0.24 0.06 1.19 0.04 0.03 1.07 0.02 0.02 1.64 Mn 0.15 0.07 0.13 0.07 0.05 0.85 0.31 0.06 0.06 0.35 0.08 0.08 4.28 0.15 0.15 Fe 20.04 0.46 0.46 13.14 0.37 0.37 15.91 0.29 0.29 4.22 0.19 0.36 23.58 0.39 0.39 F 0.24 0.15 1.35 0.12 0.08 2.80 Cl 0.05 0.02 0.88 0.02 0.01 1.04 450 B.2 Chlorite EMPA data This appendix consists of Table B.2 which contains the electron microprobe (EMP) results of all samples probed for chlorite chemistry. Each column identifies the sample, EMP spot number, the weight percent oxides, stoichiometrically calculated OH- wt%, total oxide (plus OH-). The ideal arrangement of the molar calculated elements in the crystal lattice was normalized using oxygen = 14. Sample location, metamorphic grade, main alteration assemblage, mineralization sulfide- oxide assemblage, and distance from ore and surface can be found for all samples in Appendix A.2. 451 Table B.2 Complete electron microprobe data for all samples probed for chlorite chemistry. Sample 06L337-186 19L547-495 EMPA spot 1 2 3 5 7 10 11 13 17 23 26 29 2 3 4 5 6 10 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Grey Grey Grey Brown Brown Brown Brown Brown Blue Na2O wt% 0 0.0335 0.0453 0.0158 0 0.0692 0.0679 0.032 0 0.0093 0.0651 0 0.0538 0 0.0183 0.0284 0.024 0 MgO wt% 13.35 13.081 13.311 13.022 13.226 12.69 11.544 11.82 11.718 17.825 17.814 17.214 14.632 13.678 12.621 13.21 14.458 12.557 Al2O3 wt% 22.247 21.935 22.233 22.537 21.914 22.191 22.847 22.803 22.747 21.494 21.775 21.972 22.05 21.795 22.188 22.022 22.117 21.768 SiO2 wt% 24.515 24.564 24.586 24.691 24.933 24.75 23.69 23.823 24.196 26.387 26 25.487 25.06 24.94 24.964 24.747 25.185 24.686 K2O wt% 0.0406 0.1034 0.0283 0.0148 0.0431 0.1193 0.1117 0.1705 0.2919 0.0087 0.0112 0 0.0363 0.0121 0.0483 0.0748 0.0254 0.0591 CaO wt% 0.0351 0 0.0317 0.0158 0.0113 0.0011 0.0734 0.0079 0.1175 0.0069 0.0126 0.1556 0.0202 0 0.0045 0.0279 0.0302 0.0702 TiO2 wt% 0.0193 0.024 0.0085 0.0578 0 0.027 0.0303 0.0545 0.0521 0.0558 0.0498 0.038 0.017 0.0361 0.0032 0.0302 0.0567 0.0437 Cr2O3 wt% 0.0154 0.0499 0.0269 0.1153 0.0999 0.0537 0.0801 0.0992 0.1528 0 0 0.0039 0.082 0.0311 0.0542 0.1278 0.078 0.0309 MnO wt% 0.678 0.4126 0.5466 0.4781 0.4978 0.5986 0.1338 0.1664 0.0946 0.3447 0.2819 0.2616 0.136 0.0761 0.0727 0.0363 0.0795 0.1681 FeO wt % 27.062 27.148 27.524 27.333 27.224 27.729 28.84 29.016 29.159 22.019 21.684 22.226 25.609 26.892 27.449 27.652 26.085 28.383 OH- wt% 11.27 11.19 11.30 11.32 11.28 11.27 11.10 11.17 11.23 11.66 11.61 11.52 11.37 11.26 11.23 11.27 11.41 11.19 Total Oxide wt% 99.23 98.54 99.64 99.60 99.23 99.50 98.52 99.16 99.76 99.81 99.31 98.88 99.06 98.72 98.65 99.23 99.55 98.96 K 0.01 0.01 0.00 0.00 0.01 0.02 0.02 0.02 0.04 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 Na 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.00 Mg 2.12 2.09 2.11 2.06 2.10 2.01 1.86 1.89 1.87 2.73 2.74 2.67 2.30 2.17 2.01 2.10 2.27 2.01 Fe2+ 2.41 2.43 2.44 2.42 2.42 2.47 2.61 2.61 2.60 1.89 1.87 1.93 2.26 2.40 2.45 2.46 2.29 2.54 Mn 0.06 0.04 0.05 0.04 0.04 0.05 0.01 0.02 0.01 0.03 0.02 0.02 0.01 0.01 0.01 0.00 0.01 0.02 Cr 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.00 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al(VI) 1.40 1.40 1.39 1.43 1.40 1.42 1.47 1.45 1.45 1.32 1.33 1.35 1.39 1.39 1.46 1.39 1.39 1.39 sum 5.99 5.99 6.00 5.97 5.97 5.99 5.99 6.00 5.98 5.98 5.99 5.98 5.99 5.97 5.94 5.98 5.97 5.97 Al(IV) 1.39 1.37 1.39 1.38 1.35 1.37 1.44 1.44 1.42 1.29 1.32 1.35 1.36 1.34 1.33 1.37 1.35 1.36 Si 2.61 2.63 2.61 2.62 2.65 2.63 2.56 2.56 2.58 2.71 2.68 2.65 2.64 2.66 2.67 2.63 2.65 2.64 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 452 Table B.2 (Continued) Sample 19L547-495 (continued) 34L006-1235 EMPA spot 14 16 18 25 26 27 28 29 1 27 29 30 1 2 3 4 5 6 Birefringence colour Brown Brown Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Brown Brown Brown Brown Brown Brown Na2O wt% 0.0143 0.008 0.0161 0.0499 0.0224 0 0.0348 0.0714 0 0.0401 0.0739 0.0701 0.0809 0.0572 0.0295 0.0138 0.0471 0.0373 MgO wt% 12.735 14.302 13.461 13.805 12.669 12.789 12.76 12.117 11.125 11.747 11.804 12.117 15.747 16.207 15.89 16.097 16.281 16.087 Al2O3 wt% 21.398 21.977 22.166 22.535 22.422 21.768 21.984 22.195 23.162 21.315 21.728 20.465 20.888 20.986 21.302 21.065 20.956 21.286 SiO2 wt% 25.093 25.725 24.951 25.34 24.713 25.26 24.602 24.876 23.648 24.709 24.839 25.253 25.753 26.365 26.527 26.171 26.311 26.101 K2O wt% 0.0736 0.0412 0.1499 0.2809 0.1326 0.3532 0.1132 0.354 0.0147 0.1202 0.0123 0.0147 0.1507 0.3162 0.2764 0.0562 0.0587 0.1305 CaO wt% 0.0167 0.0459 0 0.0582 0.029 0.0145 0.0212 0.0145 0.0868 0.0564 0.2111 0.1964 0.0432 0.0592 0.0421 0.042 0.0296 0.0387 TiO2 wt% 0.0287 0.061 0.0496 0.0268 0.0527 0.0999 0.0786 0.1056 0.0768 0.0805 0.1036 0.0771 0.0894 0.1327 0.1203 0.0677 0.081 0.0578 Cr2O3 wt% 0.1121 0.0937 0.1088 0.0078 0.0657 0 0.0578 0.085 0.1293 0.0343 0.0153 0.0191 0 0.0316 0.067 0 0.0237 0 MnO wt% 0.1881 0.0995 0.0728 0.1061 0.1386 0.1715 0.089 0.0725 0.368 0.5186 0.3787 0.4242 0.0721 0.1083 0.1311 0.1802 0.1181 0.0393 FeO wt % 27.744 25.82 27 26.039 28.245 28.528 28.866 28.247 29.758 28.981 28.684 28.944 24.372 24.431 24.41 24.525 23.718 24.148 OH- wt% 11.19 11.44 11.32 11.42 11.31 11.35 11.28 11.25 11.17 11.10 11.18 11.11 11.37 11.57 11.60 11.52 11.49 11.50 Total Oxide wt% 98.59 99.62 99.29 99.67 99.80 100.33 99.88 99.39 99.54 98.71 99.03 98.69 98.57 100.26 100.40 99.74 99.12 99.43 K 0.01 0.01 0.02 0.04 0.02 0.05 0.02 0.05 0.00 0.02 0.00 0.00 0.02 0.04 0.04 0.01 0.01 0.02 Na 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.01 0.02 0.01 0.02 0.01 0.01 0.00 0.01 0.01 Mg 2.03 2.23 2.13 2.16 2.00 2.02 2.02 1.93 1.78 1.89 1.89 1.95 2.48 2.50 2.45 2.50 2.53 2.50 Fe2+ 2.49 2.26 2.39 2.29 2.51 2.52 2.57 2.52 2.67 2.62 2.57 2.61 2.15 2.12 2.11 2.14 2.07 2.11 Mn 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.03 0.05 0.03 0.04 0.01 0.01 0.01 0.02 0.01 0.00 Cr 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 Ti 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 Al(VI) 1.39 1.41 1.41 1.45 1.42 1.38 1.37 1.44 1.47 1.38 1.41 1.33 1.31 1.30 1.34 1.31 1.32 1.34 sum 5.96 5.94 5.97 5.96 5.98 5.99 6.01 5.97 5.97 5.97 5.94 5.95 5.99 5.99 5.96 5.98 5.96 5.97 Al(IV) 1.31 1.30 1.36 1.34 1.38 1.33 1.38 1.35 1.46 1.33 1.33 1.27 1.28 1.27 1.26 1.27 1.25 1.28 Si 2.69 2.70 2.64 2.66 2.62 2.67 2.62 2.65 2.54 2.67 2.67 2.73 2.72 2.73 2.74 2.73 2.75 2.72 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 453 Table B.2 (Continued) Sample 34L814-2333 (continued) 37L482-2057 EMPA spot 12 16 17 18 20 21 23 24 26 28 30 32 33 1 2 3 4 Birefrin- gence colour Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Grey Grey Grey Grey Na2O wt% 0.0334 0.0138 0.0552 0.0355 0.0257 0.0198 0.0434 0 0.0098 0.0079 0.0099 0.0198 0.0059 0.0055 0.0074 0.0037 0.0333 MgO wt% 16.351 15.61 16.297 16.161 15.945 15.98 15.94 15.992 16.173 16.122 16.307 16.063 16.085 18.485 18.419 18.455 18.26 Al2O3 wt% 20.879 20.843 20.998 20.794 21.181 21.048 20.998 21.189 21.263 20.945 21.147 21.275 21.161 21.955 22.108 21.822 21.732 SiO2 wt% 26.086 26.125 25.731 25.648 25.761 25.749 25.811 26.06 25.682 25.93 26.216 25.828 25.693 25.555 25.803 26.4 25.9 K2O wt% 0.1436 0.1304 0.0024 0.0108 0 0.0263 0.0251 0.0371 0 0.1126 0.1509 0.0203 0 0 0.01 0.0536 0 CaO wt% 0 0.0159 0.0705 0.0432 0.0363 0.0386 0.0045 0.025 0.0159 0.0114 0 0.0068 0.0261 0.0138 0.0195 0 0 TiO2 wt% 0.0958 0.0284 0.0842 0.0895 0.0552 0.0513 0.0795 0.0633 0.0748 0.0421 0.1007 0.0329 0.0369 0.0913 0.0444 0.0703 0.0483 Cr2O3 wt% 0 0 0 0.0354 0.0393 0.0314 0 0.0473 0 0 0 0 0 0.0593 0.1504 0.0674 0.0751 MnO wt% 0.1803 0.1277 0.1181 0.1443 0.0949 0.1506 0.1277 0.1017 0.1639 0.1377 0.1574 0.108 0.0786 0.0498 0.0864 0.2161 0.0664 FeO wt % 24.16 24.363 24.223 24.22 24.723 24.739 24.423 24.174 24.044 23.956 24.623 25.027 24.574 21.176 20.774 20.551 21.12 OH- wt% 11.49 11.39 11.44 11.38 11.45 11.44 11.41 11.47 11.43 11.41 11.57 11.51 11.43 11.60 11.64 11.69 11.60 Total Oxide wt% 99.42 98.65 99.02 98.56 99.31 99.27 98.86 99.16 98.86 98.68 100.29 99.89 99.10 99.00 99.06 99.33 98.83 K 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.02 0.00 0.00 0.00 0.00 0.01 0.00 Na 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Mg 2.55 2.45 2.55 2.54 2.49 2.50 2.50 2.49 2.53 2.53 2.52 2.50 2.52 2.85 2.83 2.82 2.82 Fe2+ 2.11 2.14 2.12 2.14 2.17 2.17 2.15 2.11 2.11 2.11 2.13 2.18 2.16 1.83 1.79 1.76 1.83 Mn 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.02 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 Ti 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.00 Al(VI) 1.29 1.34 1.29 1.29 1.31 1.30 1.31 1.33 1.32 1.32 1.30 1.31 1.31 1.32 1.34 1.35 1.33 sum 6.00 5.96 5.99 5.99 5.99 5.99 5.99 5.96 5.98 5.98 6.00 6.00 5.99 6.01 5.99 5.97 5.99 Al(IV) 1.28 1.25 1.30 1.30 1.30 1.30 1.29 1.28 1.31 1.28 1.28 1.31 1.31 1.36 1.34 1.29 1.32 Si 2.72 2.75 2.70 2.70 2.70 2.70 2.71 2.72 2.69 2.72 2.72 2.69 2.69 2.64 2.66 2.71 2.68 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 454 Table B.2 (Continued) Sample 37L482-2057 (continued) EMPA spot 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 22 26 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Na2O wt% 0.0277 0.024 0 0.0297 0 0.0334 0.0185 0.0167 0.0184 0.0259 0 0.0037 0 0 0.0278 0.0222 0.035 0.0074 MgO wt% 19.501 18.19 18.398 17.255 18.42 17.82 18.546 18.212 18.583 18.564 18.563 18.606 18.601 18.512 18.587 18.785 18.928 18.781 Al2O3 wt% 20.708 22.075 21.96 23.192 21.647 23.064 21.551 21.632 21.826 21.922 21.545 21.571 21.399 21.927 21.493 21.722 21.583 21.732 SiO2 wt% 26.948 25.67 25.721 24.817 26.285 25.206 25.894 25.63 26.289 25.693 26.318 26.141 26.336 26.063 26.184 26.38 26.042 25.89 K2O wt% 0.0262 0 0.0137 0.0373 0.0448 0.0162 0.0623 0.0224 0.0424 0.0025 0.0299 0 0.1733 0 0.117 0.1382 0.1184 0.0349 CaO wt% 0.0126 0.0138 0.0184 0 0.0264 0.008 0.0034 0 0 0.0206 0.0723 0.0252 0.023 0.0471 0.0482 0.0057 0.0413 0 TiO2 wt% 0.0666 0.0699 0.0425 0.0093 0.0902 0.0707 0.0491 0.0469 0.0749 0.0064 0.0361 0.0637 0.1111 0.0422 0.0632 0.1285 0.0481 0.0538 Cr2O3 wt% 0.1068 0.087 0.1225 0.0788 0.0671 0.1026 0.1028 0.1894 0.1069 0.1582 0.1307 0.1265 0.0595 0.1385 0.0751 0.186 0.095 0.1464 MnO wt% 0.0997 0.0863 0 0.1061 0.0797 0.2422 0.1694 0.0896 0.1462 0.1129 0.1728 0.0598 0.0665 0.1229 0.1395 0.0997 0.0764 0.1595 FeO wt % 21.265 20.96 21.195 21.561 21.426 21.438 20.977 21.342 20.738 20.962 20.565 21.032 20.535 20.828 21.228 21.142 20.752 20.827 OH- wt% 11.80 11.59 11.62 11.53 11.70 11.66 11.61 11.56 11.70 11.62 11.65 11.66 11.64 11.68 11.67 11.78 11.67 11.65 Total Oxide wt% 100.56 98.77 99.09 98.62 99.79 99.67 98.98 98.74 99.53 99.09 99.09 99.28 98.94 99.36 99.64 100.38 99.39 99.28 K 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.02 0.02 0.02 0.00 Na 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 Mg 2.96 2.81 2.83 2.67 2.82 2.73 2.86 2.82 2.84 2.86 2.85 2.85 2.86 2.83 2.85 2.85 2.90 2.88 Fe2+ 1.81 1.81 1.83 1.87 1.84 1.84 1.81 1.85 1.78 1.81 1.77 1.81 1.77 1.79 1.82 1.80 1.78 1.79 Mn 0.01 0.01 0.00 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Cr 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 Ti 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 Al(VI) 1.22 1.35 1.33 1.42 1.31 1.39 1.30 1.31 1.33 1.32 1.32 1.31 1.31 1.33 1.29 1.29 1.29 1.30 sum 6.01 5.99 6.00 6.00 5.99 6.00 6.01 6.01 5.98 6.01 5.97 5.99 5.98 5.98 6.01 6.00 6.02 6.01 Al(IV) 1.26 1.34 1.35 1.42 1.31 1.41 1.32 1.34 1.31 1.35 1.29 1.31 1.29 1.32 1.31 1.31 1.32 1.34 Si 2.74 2.66 2.65 2.58 2.69 2.59 2.68 2.66 2.69 2.65 2.71 2.69 2.71 2.68 2.69 2.69 2.68 2.66 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 455 Table B.2 (Continued) Sample 37L482-2057 (continued) BK05010-376 CR4610-947 EMPA spot 27 30 5 7 8 9 11 14 18 19 21 24 26 28 1 2 4 5 Birefringence colour Grey Grey Blue Blue Blue Blue Blue Blue Grey Grey Grey Grey Grey Grey Blue Blue Blue Blue Na2O wt% 0.0203 0.0296 0.002 0.0141 0 0.014 0.0121 0.0401 0.0077 0.0271 0.0173 0.0252 0.0387 0.0579 0.0751 0.0107 0.0451 0.03 MgO wt% 18.645 18.973 17.878 17.939 18.689 17.438 17.744 16.815 20.637 20.245 20.947 19.805 20.694 20.14 12.488 12.748 12.447 12.394 Al2O3 wt% 21.13 20.818 20.416 20.113 19.743 20.691 20.005 19.775 20.697 20.533 20.507 21.522 20.643 20.951 21.126 20.93 20.443 21.385 SiO2 wt% 26.388 26.009 26.475 26.939 27.131 27.074 26.523 28.397 27.632 27.561 27.482 26.906 27.216 27.375 24.65 24.581 25.264 24.458 K2O wt% 0.0062 0.0087 0.0024 0.0278 0.0169 0.0798 0 0.0326 0.1694 0.2958 0.0061 0.3829 0.0985 0.3748 0.0193 0.0325 0.0373 0.0241 CaO wt% 0.0264 0.0011 0.0034 0.1324 0.0553 0.0932 0.0449 0.7162 0.0104 0.0673 0.094 0.0359 0.0266 0.0081 0.0444 0 0.0478 0.0114 TiO2 wt% 0.0506 0.0848 0.1759 0.205 0.17 0.0819 0.0743 0.1376 0.0384 0.0652 0.0184 0.0739 0.0148 0.0719 0.0482 0.0852 0.1557 0.1342 Cr2O3 wt% 0.0871 0.1423 0 0.072 0.0761 0.016 0 0.0441 0.0488 0.1422 0.0732 0.0649 0.1176 0.0163 0.0309 0.0077 0 0.031 MnO wt% 0.1362 0.1129 0.2369 0.1805 0.1773 0.1637 0.2504 0.1739 0.1585 0.1112 0.1247 0.1514 0.2086 0.1313 0.0033 0.0657 0.1348 0.1644 FeO wt % 20.771 20.995 22.129 21.858 21.129 21.798 22.273 21.361 18.082 18.322 17.67 18.546 18.388 18.124 29.218 28.936 29.093 28.847 OH- wt% 11.62 11.57 11.54 11.58 11.59 11.60 11.47 11.64 11.83 11.79 11.78 11.78 11.79 11.78 11.13 11.10 11.14 11.12 Total Oxide wt% 98.88 98.75 98.86 99.06 98.78 99.05 98.39 99.14 99.31 99.16 98.72 99.29 99.23 99.03 98.83 98.50 98.81 98.59 K 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.04 0.00 0.05 0.01 0.05 0.00 0.00 0.01 0.00 Na 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.02 0.00 0.01 0.01 Mg 2.87 2.93 2.77 2.77 2.88 2.69 2.77 2.58 3.12 3.07 3.18 3.01 3.14 3.06 2.01 2.05 2.00 1.99 Fe2+ 1.79 1.82 1.92 1.89 1.83 1.88 1.95 1.84 1.53 1.56 1.50 1.58 1.56 1.54 2.63 2.61 2.62 2.60 Mn 0.01 0.01 0.02 0.02 0.02 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.00 0.01 0.01 0.02 Cr 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 Ti 0.00 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 Al(VI) 1.29 1.24 1.25 1.25 1.22 1.32 1.24 1.33 1.27 1.27 1.26 1.32 1.24 1.30 1.34 1.32 1.31 1.36 sum 5.98 6.02 5.98 5.95 5.97 5.93 5.98 5.79 5.97 5.97 5.96 5.98 6.00 5.98 6.00 6.01 5.97 5.99 Al(IV) 1.28 1.30 1.25 1.21 1.19 1.20 1.23 1.07 1.20 1.20 1.20 1.26 1.23 1.21 1.34 1.34 1.28 1.36 Si 2.72 2.70 2.75 2.79 2.81 2.80 2.77 2.93 2.80 2.80 2.80 2.74 2.77 2.79 2.66 2.66 2.72 2.64 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 456 Table B.2 (Continued) Sample CR4610-947 (continued) CR4611-584 EMPA spot 6 7 17 22 25 29 31 32 33 35 1 2 3 4 5 7 8 9 Birefringence colour Blue Blue Blue Late Blue Late Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0 0.035 0.0798 0.0777 0.0392 0.0021 0.0581 0.0129 0.0495 0.0323 0.0349 0.0248 0.0021 0.0083 0.058 0 0.0665 0 MgO wt% 10.816 11.049 11.507 11.6 11.153 13.142 12.448 12.466 12.612 12.483 13.816 13.502 13.501 12.869 12.821 13.492 12.868 13.179 Al2O3 wt% 21.127 21.167 22.063 21.077 20.877 20.745 21.186 21.091 21.392 20.835 20.462 20.213 20.438 21.123 20.566 20.7 20.645 20.596 SiO2 wt% 24.354 24.6 24.018 24.862 24.528 25.024 24.402 24.361 24.483 24.689 25.577 25.467 25.358 24.7 25.146 25.22 24.967 25.044 K2O wt% 0 0.018 0.0265 0.1154 0.066 0.0024 0 0 0 0 0 0.0881 0.0229 0.006 0.1603 0.0012 0.0072 0.006 CaO wt% 0.0499 0.0147 0.083 0.1205 0.0397 0.0501 0.0193 0.0387 0.0137 0.0307 0 0.0135 0.0484 0.0596 0.1294 0 0.0011 0.0236 TiO2 wt% 0.0851 0.1024 0.0997 0.4022 0.1057 0.0924 0.0631 0.0719 0.1282 0.0932 0.1207 0.1353 0.0797 0.0579 0.127 0.1177 0.1229 0.0638 Cr2O3 wt% 0.0689 0 0.0579 0.0696 0.0269 0 0.0193 0.0579 0.0077 0.0347 0 0 0 0 0.0038 0.0614 0.0115 0.0115 MnO wt% 0.085 0.1047 0.174 0.2167 0.1408 0.1974 0.2299 0.1708 0.1642 0.2036 0.1153 0.0724 0.0954 0.1413 0.092 0.0854 0.1742 0.1249 FeO wt % 31.371 31.317 29.513 29.517 30.562 28.806 29.278 29.154 29.518 29.44 27.832 28.156 28.227 28.507 28.46 28.93 28.866 28.465 OH- wt% 11.03 11.10 11.09 11.15 11.02 11.20 11.11 11.08 11.19 11.12 11.27 11.20 11.21 11.14 11.15 11.28 11.15 11.15 Total Oxide wt% 98.99 99.51 98.71 99.20 98.55 99.26 98.81 98.50 99.56 98.97 99.22 98.87 98.98 98.61 98.71 99.89 98.88 98.67 K 0.00 0.00 0.00 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.00 0.00 0.00 Na 0.00 0.01 0.02 0.02 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 Mg 1.75 1.78 1.86 1.86 1.81 2.10 2.00 2.01 2.01 2.01 2.19 2.16 2.15 2.07 2.06 2.14 2.06 2.11 Fe2+ 2.85 2.83 2.67 2.66 2.78 2.58 2.64 2.64 2.64 2.65 2.48 2.52 2.53 2.57 2.56 2.57 2.60 2.56 Mn 0.01 0.01 0.02 0.02 0.01 0.02 0.02 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 Cr 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Ti 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 Al(VI) 1.36 1.35 1.41 1.35 1.35 1.30 1.33 1.33 1.32 1.31 1.29 1.28 1.29 1.34 1.31 1.28 1.30 1.30 sum 5.98 5.99 5.99 5.96 5.98 6.00 6.02 6.01 6.02 6.01 5.99 5.99 5.99 5.99 5.98 6.01 6.00 5.99 Al(IV) 1.35 1.34 1.40 1.32 1.33 1.32 1.37 1.36 1.38 1.34 1.28 1.27 1.29 1.34 1.29 1.32 1.31 1.31 Si 2.65 2.66 2.60 2.68 2.67 2.68 2.63 2.64 2.62 2.66 2.72 2.73 2.71 2.66 2.71 2.68 2.69 2.69 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 457 Table B.2 (Continued) Sample CR4611-584 (continued) CR4612-360 EMPA spot 14 20 21 3 7 11 12 14 20 21 24 25 26 29 30 31 32 33 Birefringence colour Blue Blue Blue Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Na2O wt% 0.0642 0.029 0.0437 0.0966 0.0251 0.0292 0.048 0.025 0.0063 0.0146 0.023 0.0419 0.0317 0.0127 0 0.019 0.0021 0.1311 MgO wt% 13.312 12.649 12.431 14.072 14.325 14.279 14.404 15.047 14.654 14.801 14.577 14.424 13.897 13.904 13.789 13.922 13.818 13.324 Al2O3 wt% 20.535 20.988 20.996 21.438 21.016 21.757 21.926 21.413 21.614 21.601 21.528 21.581 21.875 21.444 21.696 21.62 21.818 21.505 SiO2 wt% 24.731 25.111 24.749 24.688 25.279 25.232 25.198 24.846 24.882 25.243 24.838 24.813 24.775 24.858 24.779 24.921 25.005 24.722 K2O wt% 0.0253 0.3606 0.0494 0.0085 0.0581 0.0327 0.0157 0.0242 0.0339 0.0315 0 0.0121 0.0085 0 0.0036 0.0411 0.0835 0.1449 CaO wt% 0.0833 0.0372 0.0191 0.0297 0.0698 0.0321 0.0298 0.0115 0.0309 0.0103 0.0263 0 0.0274 0.0034 0.0137 0.0411 0.0423 0 TiO2 wt% 0.1091 0.1508 0.1218 0.0548 0.1259 0.1205 0.0804 0.1111 0.103 0.0943 0.0964 0.0522 0.0917 0.0816 0.0443 0.1102 0.1024 0.1237 Cr2O3 wt% 0.0422 0.0461 0 0.1484 0.0509 0.0705 0.0705 0.0353 0.0431 0.051 0.0783 0.0743 0.0234 0 0.0351 0.0507 0 0 MnO wt% 0.1479 0.1316 0.1116 0.0661 0.0463 0.0463 0.0298 0.0795 0.0694 0 0.1322 0.1058 0.0495 0.1221 0.0594 0 0 0.0528 FeO wt % 28.446 28.618 29.049 26.714 26.372 26.141 26.269 25.979 26.369 25.929 26.313 26.462 27.626 27.479 27.194 27.411 26.603 27.528 OH- wt% 11.13 11.21 11.12 11.23 11.27 11.35 11.39 11.31 11.32 11.37 11.30 11.28 11.34 11.27 11.26 11.31 11.28 11.20 Total Oxide wt% 98.62 99.33 98.69 98.54 98.64 99.09 99.46 98.88 99.13 99.14 98.91 98.85 99.74 99.18 98.87 99.45 98.75 98.74 K 0.00 0.05 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 Na 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.03 Mg 2.14 2.02 2.00 2.24 2.27 2.25 2.26 2.38 2.31 2.33 2.31 2.29 2.19 2.21 2.19 2.20 2.19 2.13 Fe2+ 2.56 2.56 2.62 2.39 2.35 2.31 2.31 2.30 2.34 2.29 2.34 2.35 2.44 2.45 2.42 2.43 2.37 2.46 Mn 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 Cr 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.01 Al(VI) 1.27 1.34 1.34 1.34 1.33 1.38 1.38 1.31 1.33 1.35 1.33 1.34 1.35 1.33 1.36 1.34 1.39 1.36 sum 6.02 6.00 5.99 6.01 5.98 5.97 5.98 6.02 6.01 5.99 6.00 6.01 6.01 6.00 5.99 6.00 5.97 6.01 Al(IV) 1.33 1.31 1.33 1.36 1.31 1.33 1.35 1.37 1.36 1.34 1.36 1.36 1.38 1.36 1.36 1.36 1.34 1.35 Si 2.67 2.69 2.67 2.64 2.69 2.67 2.65 2.63 2.64 2.66 2.64 2.64 2.62 2.64 2.64 2.64 2.66 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 458 Table B.2 (Continued) Sample CR466-145 CR467-86.3 EMPA spot 2 3 5 6 7 12 13 14 16 17 20 22 27 30 1 4 12 13 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0521 0.0083 0.0125 0 0.0228 0.1224 0.0209 0.0083 0.0185 0.0145 0.0083 0 0.0124 0.0473 0.052 0.0196 0.0174 0 MgO wt% 11.923 12.111 12.055 11.98 12.39 10.907 11.796 12.446 12.822 12.661 12.351 12.611 13.066 13.472 9.5039 8.9696 9.5779 9.5791 Al2O3 wt% 22.393 22.158 21.729 22.8 21.907 22.753 22.919 21.761 21.36 21.483 21.893 21.731 21.308 20.635 19.11 19.232 19.413 19.066 SiO2 wt% 23.925 23.978 25.679 23.704 24.181 25.994 23.338 24.539 25.071 24.68 24.347 24.602 25.016 25.289 25.446 25.091 25.492 25.153 K2O wt% 0.0132 0.006 0.035 0.006 0.0193 0 0.0145 0.0036 0.035 0.0097 0.0181 0.0121 0.0193 0.0786 0.0634 0.0418 0.043 0.0406 CaO wt% 0.009 0.0135 0.0237 0.2724 0.0642 1.5558 0.0809 0.2421 0.0056 0.0214 0.0135 0.036 0.0428 0.123 0.0826 0.0757 0.0468 0.0412 TiO2 wt% 0.0873 0.0362 0.0149 0.0059 0.1204 0.0094 0.1015 0.0529 0.0759 0.0909 0.0569 0.0564 0.0503 0.0029 0.0894 0.0716 0.0507 0.0673 Cr2O3 wt% 0.1033 0.0536 0.0384 0.0768 0.0461 0.0857 0.0957 0.0269 0.0423 0.1075 0.0499 0.0614 0 0.027 0 0 0 0.0413 MnO wt% 0.1839 0.2266 0.1877 0.2172 0.2172 0.2119 0.1971 0.2271 0.135 0.2403 0.1578 0.1711 0.1844 0.1749 0.6652 0.6891 0.7063 0.6121 FeO wt % 29.301 29.01 28.939 28.566 28.687 26.05 29.351 28.737 28.056 28.709 28.514 28.402 28.81 27.663 32.991 33.996 33.763 33.893 OH- wt% 11.15 11.12 11.33 11.14 11.14 11.34 11.13 11.20 11.21 11.20 11.13 11.18 11.27 11.20 10.91 10.86 11.02 10.91 Total Oxide wt% 99.14 98.72 100.04 98.77 98.80 99.03 99.04 99.24 98.83 99.22 98.54 98.86 99.78 98.71 98.91 99.05 100.12 99.40 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 Na 0.01 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 Mg 1.91 1.95 1.90 1.92 1.99 1.72 1.90 1.99 2.05 2.02 1.98 2.02 2.07 2.15 1.56 1.48 1.55 1.57 Fe2+ 2.63 2.62 2.56 2.57 2.58 2.30 2.65 2.57 2.51 2.57 2.57 2.55 2.56 2.48 3.03 3.14 3.07 3.12 Mn 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.01 0.02 0.02 0.02 0.06 0.06 0.07 0.06 Cr 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 Al(VI) 1.41 1.40 1.43 1.44 1.38 1.59 1.43 1.38 1.38 1.35 1.40 1.39 1.33 1.31 1.27 1.27 1.27 1.23 sum 6.00 6.00 5.92 5.97 5.99 5.66 6.01 5.97 5.97 5.99 5.98 5.98 6.00 5.98 5.96 5.97 5.97 5.99 Al(IV) 1.43 1.41 1.28 1.45 1.40 1.25 1.48 1.37 1.32 1.36 1.38 1.36 1.34 1.29 1.20 1.23 1.22 1.24 Si 2.57 2.59 2.72 2.55 2.60 2.75 2.52 2.63 2.68 2.64 2.62 2.64 2.66 2.71 2.80 2.77 2.78 2.76 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 459 Table B.2 (Continued) Sample CR467-86.3 (continued) D14981-1798 EMPA spot 14 15 19 21 26 5 6 7 8 10 15 16 17 18 20 21 22 23 Birefringence colour Blue Blue Blue Blue Blue Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Na2O wt% 0 0 0.2013 0.2212 0.0218 0 0.0526 0 0.0162 0.0583 0 0.0262 0 0.002 0.008 0.0242 0 0.0382 MgO wt% 9.7346 9.4934 9.1911 8.9983 8.768 13.438 12.77 13.099 12.753 12.95 13.647 13.527 13.765 13.577 13.328 13.532 13.523 13.581 Al2O3 wt% 19.094 19.085 19.082 19.195 19.188 22.964 23.106 23.277 23.416 23.252 23.011 22.894 23.325 22.74 23.207 23.242 23.226 22.951 SiO2 wt% 25.107 25.032 26.198 25.546 25.282 24.524 24.476 24.285 24.284 24.422 24.932 24.661 24.725 24.596 24.194 24.262 24.332 24.558 K2O wt% 0.0431 0.068 0.0359 0.1041 0.068 0 0.0326 0 0.0145 0.1075 0.0061 0.0314 0.0036 0.0169 0 0.0036 0.0121 0.006 CaO wt% 0.029 0.1214 0.2701 0.1004 0.069 0.0123 0.0927 0 0.0547 0.1218 0.0067 0.0089 0.0291 0.038 0 0.0324 0.0067 0.0224 TiO2 wt% 0.0071 0.082 0.2422 0.0297 0.0286 0.0213 0.0617 0.0538 0.057 0.081 0.0323 0.0573 0.0243 0.0485 0.0101 0.1235 0.0455 0.0397 Cr2O3 wt% 0 0.0601 0.0566 0.0829 0.0412 0.167 0.1397 0.159 0.128 0.2881 0.1133 0.1438 0.1714 0.2179 0.1477 0.1127 0.2062 0.1362 MnO wt% 0.5801 0.6443 0.6918 0.7271 0.6274 0.2414 0.2115 0.2246 0.2413 0.2217 0.2887 0.2647 0.2252 0.2052 0.2514 0.1953 0.2681 0.2185 FeO wt % 33.183 33.441 32.987 32.928 33.898 26.892 27.079 26.985 27.117 26.372 25.677 26.808 26.394 26.484 26.534 27.138 26.421 26.456 OH- wt% 10.86 10.87 11.05 10.89 10.85 11.36 11.32 11.33 11.32 11.33 11.38 11.39 11.46 11.34 11.30 11.40 11.35 11.35 Total Oxide wt% 98.64 98.89 100.00 98.82 98.84 99.62 99.34 99.41 99.40 99.20 99.09 99.81 100.12 99.26 98.98 100.06 99.39 99.36 K 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Na 0.00 0.00 0.04 0.05 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 Mg 1.60 1.56 1.49 1.48 1.44 2.11 2.02 2.07 2.01 2.04 2.14 2.12 2.15 2.14 2.11 2.12 2.13 2.14 Fe2+ 3.06 3.09 3.00 3.03 3.13 2.37 2.40 2.39 2.40 2.34 2.26 2.36 2.31 2.34 2.36 2.39 2.33 2.34 Mn 0.05 0.06 0.06 0.07 0.06 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Cr 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.02 0.01 0.01 0.02 0.01 Ti 0.00 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Al(VI) 1.26 1.25 1.29 1.30 1.29 1.45 1.48 1.47 1.50 1.49 1.49 1.44 1.47 1.44 1.47 1.44 1.46 1.45 sum 5.98 5.98 5.90 5.95 5.95 5.97 5.95 5.97 5.95 5.94 5.93 5.97 5.96 5.96 5.97 5.99 5.97 5.97 Al(IV) 1.23 1.24 1.16 1.19 1.21 1.41 1.41 1.43 1.43 1.41 1.37 1.40 1.41 1.40 1.43 1.45 1.43 1.41 Si 2.77 2.76 2.84 2.81 2.79 2.59 2.59 2.57 2.57 2.59 2.63 2.60 2.59 2.60 2.57 2.55 2.57 2.59 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 460 Table B.2 (Continued) Sample D14981-1798 (continued) D21708-2760 EMPA spot 24 25 27 29 30 32 34 1 2 4 7 9 11 12 13 14 15 16 Birefringence colour Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Na2O wt% 0.002 0.0161 0.004 0.0141 0.0708 0.0703 0.0424 0.002 0 0.0218 0.0417 0.0814 0.065 0.016 0.066 0 0.052 0.0636 MgO wt% 13.664 13.626 13.421 12.944 12.661 13.061 12.637 15.562 15.368 15.09 15.365 14.825 15.409 14.997 14.821 14.684 14.53 15.218 Al2O3 wt% 22.926 23.129 22.628 23.104 22.831 22.764 23.475 22.05 21.199 21.741 21.743 22.051 21.955 21.917 21.579 22.243 22.315 21.653 SiO2 wt% 24.7 24.453 24.371 24.612 24.507 24.952 24.235 25.481 25.599 25.331 25.387 24.913 25.739 24.832 24.818 25.015 25.03 25.612 K2O wt% 0.0254 0.0254 0.0193 0.0073 0.0133 0 0.0181 0.0418 0.098 0.0932 0.0323 0.0764 0.0359 0.0107 0 0 0.0119 0.0227 CaO wt% 0.0459 0.0961 0.0313 0.0782 0.0413 0.0369 0.1083 0.0091 0.0136 0.0261 0.0318 0.0215 0 0 0.0136 0.3421 0 0.0272 TiO2 wt% 0.0268 0.1614 0.1458 0.0427 0.0244 0.0537 0.0568 0.0653 0.0861 0.1013 0.0845 0.0391 0.0683 0.0641 0.0577 0.076 0.0419 0.0454 Cr2O3 wt% 0.2145 0.2377 0.2021 0.1399 0.2095 0.035 0.1787 0 0.0039 0.0118 0 0.0352 0 0 0.0391 0.0627 0.0117 0.0235 MnO wt% 0.2054 0.2351 0.2811 0.1819 0.2611 0.2946 0.2579 0.1767 0.2191 0.1473 0.1734 0.1797 0.1475 0.1894 0.271 0.1602 0.2449 0.193 FeO wt % 25.881 26.319 26.635 26.658 26.994 26.334 26.799 25.107 25.155 24.706 25.089 24.98 24.189 25.633 25.655 25.382 25.809 25.178 OH- wt% 11.35 11.39 11.29 11.32 11.26 11.32 11.30 11.52 11.40 11.36 11.43 11.33 11.46 11.35 11.29 11.41 11.40 11.45 Total Oxide wt% 99.04 99.69 99.03 99.10 98.87 98.92 99.11 100.01 99.14 98.63 99.38 98.53 99.07 99.01 98.61 99.37 99.45 99.48 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Na 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.02 0.01 0.00 0.01 0.00 0.01 0.01 Mg 2.15 2.14 2.13 2.04 2.01 2.06 2.00 2.42 2.41 2.37 2.40 2.34 2.40 2.36 2.35 2.30 2.28 2.38 Fe2+ 2.29 2.32 2.37 2.36 2.40 2.33 2.38 2.19 2.21 2.18 2.20 2.21 2.12 2.27 2.28 2.23 2.27 2.21 Mn 0.02 0.02 0.03 0.02 0.02 0.03 0.02 0.02 0.02 0.01 0.02 0.02 0.01 0.02 0.02 0.01 0.02 0.02 Cr 0.02 0.02 0.02 0.01 0.02 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Ti 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.00 Al(VI) 1.47 1.44 1.42 1.49 1.48 1.49 1.51 1.36 1.32 1.38 1.35 1.39 1.40 1.35 1.34 1.39 1.40 1.36 sum 5.95 5.96 5.97 5.93 5.95 5.93 5.94 5.99 5.99 5.97 5.99 5.99 5.96 6.01 6.01 5.94 5.99 5.98 Al(IV) 1.39 1.43 1.41 1.39 1.39 1.36 1.43 1.35 1.31 1.33 1.34 1.36 1.31 1.38 1.36 1.37 1.37 1.32 Si 2.61 2.57 2.59 2.61 2.61 2.64 2.57 2.65 2.69 2.67 2.66 2.64 2.69 2.62 2.64 2.63 2.63 2.68 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 461 Table B.2 (Continued) Sample D21708-2760 (continued) D2253-75 EMPA spot 18 19 20 21 22 23 5 6 15 19 20 25 26 29 30 31 32 33 Birefringence colour Brown Brown Brown Brown Brown Brown Blue Blue Blue Grey Grey Grey Grey Grey Grey Grey Grey Grey Na2O wt% 0.0279 0.0159 0.0139 0 0 0.0099 0.0475 0.0654 0.0298 0.0774 0.0019 0.2518 0.0095 0.1042 0.1491 0.1436 0.4128 0.0834 MgO wt% 15.173 14.493 14.992 15.042 15.524 15.791 12.363 12.517 12.191 16.091 16.23 16.145 16.032 16.279 16.1 15.933 16.139 16.177 Al2O3 wt% 22.257 22.78 22.02 22.644 21.718 21.567 22.042 22.305 21.167 22.481 22.401 22.346 22.67 22.04 22.543 22.375 22.11 22.056 SiO2 wt% 24.855 24.904 24.677 24.761 25.767 25.602 25.149 24.366 25.07 25.532 25.135 25.363 24.895 25.312 25.291 25.455 25.2 25.29 K2O wt% 0 0.0203 0.0096 0.0119 0.0466 0.0323 0.0724 0.1495 0.3325 0.0195 0.0316 0.0365 0.0061 0.0572 0.118 0.1144 0.124 0.0572 CaO wt% 0.0215 0 0.0272 0 0 0.0136 0.0351 0.043 0.0215 0.0069 0.0057 0.0354 0.0708 0.0057 0.0149 0.0355 0.0491 0.0274 TiO2 wt% 0.0105 0.0544 0.044 0.0755 0.0497 0.06 0.2242 0.1402 0.3128 0.0564 0.0444 0.0702 0.0606 0.0674 0.0102 0.0658 0.011 0.0199 Cr2O3 wt% 0.0312 0.0078 0.0196 0.0274 0.0706 0 0.123 0.1382 0.1728 0.2041 0.1253 0.2351 0.1448 0.2468 0.1687 0.204 0.3331 0.2153 MnO wt% 0.1664 0.2124 0.183 0.2257 0.216 0.2454 0.2816 0.3208 0.3502 0.1787 0.2248 0.1025 0.1421 0.1256 0.1158 0.0728 0.1587 0.0595 FeO wt % 25.776 25.364 25.38 24.938 25.005 25.049 27.794 27.924 27.827 22.781 23.376 23.307 23.365 23.32 22.954 22.96 23.265 23.387 OH- wt% 11.43 11.41 11.32 11.41 11.51 11.49 11.29 11.22 11.16 11.52 11.48 11.53 11.46 11.48 11.49 11.49 11.49 11.46 Total Oxide wt% 99.75 99.26 98.69 99.13 99.91 99.86 99.42 99.19 98.63 98.94 99.06 99.42 98.86 99.04 98.96 98.85 99.29 98.83 K 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.02 0.05 0.00 0.00 0.00 0.00 0.01 0.02 0.02 0.02 0.01 Na 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.02 0.00 0.05 0.00 0.02 0.03 0.03 0.08 0.02 Mg 2.37 2.27 2.37 2.36 2.41 2.46 1.96 1.99 1.95 2.50 2.53 2.50 2.50 2.54 2.50 2.48 2.51 2.52 Fe2+ 2.26 2.23 2.25 2.19 2.18 2.19 2.47 2.50 2.50 1.98 2.04 2.03 2.04 2.04 2.00 2.01 2.03 2.05 Mn 0.01 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.03 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Cr 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.02 0.01 0.02 0.03 0.02 Ti 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.01 0.03 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 Al(VI) 1.36 1.44 1.36 1.41 1.35 1.32 1.43 1.41 1.38 1.42 1.38 1.38 1.40 1.36 1.41 1.41 1.35 1.37 sum 6.02 5.97 6.01 5.99 5.98 6.00 5.93 5.99 5.96 5.96 5.99 6.00 5.98 6.00 5.99 5.97 6.04 5.99 Al(IV) 1.39 1.38 1.39 1.40 1.32 1.33 1.33 1.40 1.31 1.34 1.37 1.36 1.39 1.36 1.36 1.34 1.37 1.35 Si 2.61 2.62 2.61 2.60 2.68 2.67 2.67 2.60 2.69 2.66 2.63 2.64 2.61 2.64 2.64 2.66 2.63 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 462 Table B.2 (Continued) Sample D33003-2004 D39018-3562 EMPA spot 1 8 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 18 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Na2O wt% 0.118 0.3347 0.0079 0.0171 0 0.0013 0.0196 0.0091 0 0.0052 0.0079 0.0105 0 0 0.0367 0.0026 0.0391 0.0065 MgO wt% 15.25 11.651 16.391 16.373 16.483 16.106 16.18 17.605 17.228 16.815 16.249 16.597 16.691 16.778 16.135 16.611 16.853 16.684 Al2O3 wt% 22.596 25.014 22.394 22.416 22.77 22.384 22.188 21.236 21.163 21.788 22.786 21.997 22.442 22.008 22.434 22.41 21.79 22.01 SiO2 wt% 25.244 29.459 25.47 25.644 25.413 25.256 25.389 26.532 26.536 25.972 25.036 25.613 25.558 25.724 25.629 25.653 25.449 25.961 K2O wt% 0.0535 0.09 0.0442 0.0343 0.0086 0.0245 0.0675 0.0147 0.1192 0.0074 0 0.0417 0.0675 0.0405 0.2588 0.0503 0.0049 0.011 CaO wt% 0.1336 4.304 0.0069 0.0276 0 0.0276 0.0391 0.0334 0.0138 0.0944 0.1886 0.0507 0.0058 0.0288 0.0553 0.0771 0.0472 0.0311 TiO2 wt% 0.06 0.0552 0.0367 0.0603 0.0201 0.09 0.053 0.103 0.1633 0.0559 0.0549 0.0488 0.1012 0.0412 0.0965 0.066 0.0084 0.0662 Cr2O3 wt% 0.0156 0 0.0394 0.0157 0.059 0.0511 0.0591 0.004 0.0158 0.0473 0.059 0.0867 0.0945 0.0039 0.0709 0.0669 0.0789 0.0473 MnO wt% 0.228 0.0569 0.1134 0.1601 0.1701 0.14 0.1135 0.1839 0.0969 0.0835 0.1434 0.1202 0.1168 0.1067 0.0968 0.1434 0.0969 0.0901 FeO wt % 23.629 18.204 24.348 24.662 24.486 24.663 24.016 23.744 23.67 24.173 24.704 24.062 24.44 24.684 24.447 24.685 23.66 24.28 OH- wt% 11.44 12.07 11.61 11.67 11.68 11.57 11.53 11.74 11.68 11.66 11.63 11.59 11.70 11.67 11.65 11.71 11.53 11.68 Total Oxide wt% 98.77 101.24 100.47 101.08 101.09 100.31 99.65 101.21 100.69 100.70 100.85 100.22 101.21 101.08 100.91 101.48 99.56 100.86 K 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.02 0.00 0.00 0.01 0.01 0.01 0.03 0.01 0.00 0.00 Na 0.02 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 Mg 2.38 1.73 2.52 2.51 2.52 2.49 2.51 2.68 2.64 2.58 2.50 2.56 2.55 2.57 2.48 2.54 2.61 2.55 Fe2+ 2.07 1.51 2.10 2.12 2.10 2.14 2.09 2.03 2.03 2.08 2.13 2.08 2.10 2.12 2.10 2.11 2.06 2.09 Mn 0.02 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.00 Ti 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 Al(VI) 1.44 1.86 1.36 1.35 1.36 1.35 1.36 1.27 1.28 1.31 1.35 1.33 1.33 1.31 1.36 1.33 1.32 1.33 sum 5.95 5.18 6.01 6.00 6.01 6.00 5.99 6.00 5.99 5.99 6.01 6.00 6.02 6.02 6.00 6.01 6.01 5.99 Al(IV) 1.35 1.07 1.37 1.37 1.39 1.38 1.36 1.29 1.28 1.33 1.42 1.35 1.38 1.36 1.36 1.37 1.35 1.33 Si 2.65 2.93 2.63 2.63 2.61 2.62 2.64 2.71 2.72 2.67 2.58 2.65 2.62 2.64 2.64 2.63 2.65 2.67 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 463 Table B.2 (Continued) Sample D39018-3562 (continued) D39018- 4848 EMPA spot 19 20 21 22 23 24 25 26 28 29 30 31 32 33 34 35 37 1 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Blue Na2O wt% 0.0079 0 0.0374 0.0363 0.0181 0.0194 0 0.0477 0.0542 0 0 0 0 0.0272 0.0698 0 0 0.0173 MgO wt% 16.999 16.467 17.701 17.736 17.604 17.699 17.88 18.449 17.672 17.53 17.499 17.904 17.743 17.789 17.776 17.89 17.743 12.5763 Al2O3 wt% 21.542 22.285 20.557 20.632 21.022 21.015 21.209 20.351 20.973 21.149 20.984 20.988 21.226 20.619 20.75 20.832 21.612 20.6669 SiO2 wt% 25.749 25.586 26.431 26.077 26.576 26.785 26.394 26.869 26.694 26.727 26.332 26.662 26.305 26.512 26.486 26.674 26.369 24.6404 K2O wt% 0.0662 0 0.0468 0.0687 0.0996 0.016 0.0246 0.0234 0.032 0 0.0074 0.0148 0.0111 0 0.0738 0.0418 0.0935 0.0083 CaO wt% 0.1715 0.0633 0.3488 1.052 0.1062 0.2562 0.1697 0.2702 0.2598 0.0807 0.075 0.0461 0.0254 0.0738 0.1408 0.3593 0.0901 0 TiO2 wt% 0.125 0.0466 0.103 0.0945 0.1553 0.1299 0.0338 0.0625 0.0732 0.0331 0.0733 0.0895 0.0482 0.0466 0.0391 0.0749 0.0892 0.0338 Cr2O3 wt% 0 0 0 0 0.0555 0.0317 0.0754 0.004 0.0079 0.004 0 0 0.0119 0.0277 0.0476 0.0159 0.0437 0.0886 MnO wt% 0.1068 0.1368 0.1173 0.1407 0.0703 0.1105 0.1005 0.1441 0.1038 0.1873 0.0702 0.0869 0.1238 0.1405 0.1373 0.1207 0.1575 0.2067 FeO wt % 24.331 24.333 22.243 22.806 22.851 23.009 22.705 22.663 22.731 23.39 23.331 23.737 23.227 23.108 22.829 22.222 22.492 30.1192 OH- wt% 11.63 11.63 11.56 11.62 11.67 11.73 11.68 11.71 11.68 11.72 11.62 11.76 11.67 11.62 11.63 11.66 11.71 11.15 Total Oxide wt% 100.73 100.54 99.14 100.26 100.23 100.81 100.27 100.60 100.28 100.82 99.99 101.29 100.39 99.96 99.98 99.89 100.40 99.50 K 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 Na 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 Mg 2.61 2.53 2.74 2.73 2.70 2.70 2.74 2.82 2.70 2.67 2.69 2.72 2.72 2.74 2.73 2.74 2.71 2.02 Fe2+ 2.10 2.10 1.93 1.97 1.96 1.97 1.95 1.94 1.95 2.00 2.01 2.03 2.00 1.99 1.97 1.91 1.93 2.71 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Ti 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 Al(VI) 1.27 1.35 1.26 1.20 1.28 1.27 1.28 1.21 1.28 1.28 1.27 1.24 1.27 1.24 1.25 1.27 1.31 1.27 sum 6.01 6.00 5.96 5.94 5.98 5.96 5.98 5.99 5.96 5.98 5.99 6.01 6.01 6.00 6.00 5.95 5.98 6.03 Al(IV) 1.35 1.36 1.26 1.31 1.27 1.26 1.29 1.25 1.26 1.27 1.28 1.28 1.30 1.26 1.27 1.26 1.30 1.35 Si 2.65 2.64 2.74 2.69 2.73 2.74 2.71 2.75 2.74 2.73 2.72 2.72 2.70 2.74 2.73 2.74 2.70 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 464 Table B.2 (Continued) Sample D39018-4848 (continued) D39200-1469 EMPA spot 2 3 4 5 7 8 9 10 11 12 13 14 15 17 19 20 1 3 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Grey Grey Na2O wt% 0.0086 0.0065 0.0303 0 0 0 0 0 0.0195 0 0 0.0217 0 0.0259 0.0065 0 0.018 0.0379 MgO wt% 12.139 11.931 11.945 12.231 12.148 11.892 12.113 11.993 11.862 11.864 12.128 11.808 11.842 12.43 11.738 11.826 16.486 17.167 Al2O3 wt% 21.2 21.528 21.403 20.809 20.002 21.337 21.181 21.293 21.498 21.431 21.083 20.768 20.985 20.341 21.528 21.236 22.549 22.297 SiO2 wt% 24.263 24.38 24.461 24.623 24.168 24.331 24.576 24.24 24.352 24.605 24.567 24.525 24.464 25.134 24.328 24.321 25.83 25.412 K2O wt% 0.0119 0.0417 0.1119 0.0655 0.0214 0.0976 0 0.0226 0 0.05 0 0.2807 0.0309 0.031 0.1 0.0798 0.3767 0.1471 CaO wt% 0.0113 0 0.0113 0.0351 1.2511 0 0.0136 0.017 0.0023 0.0057 0.0543 0.0215 0.0294 0 0 0.017 0.0057 0.0448 TiO2 wt% 0.0268 0.0871 0.0619 0.1092 0.1449 0.1193 0.0731 0.0691 0.0627 0.0644 0.107 0.1022 0.1113 0.0425 0.0648 0.0903 0.0893 0.0866 Cr2O3 wt% 0.0347 0.0616 0.0693 0 0.0851 0.0809 0.0501 0.1041 0.0154 0.0154 0.0038 0.1039 0 0 0.0925 0.0385 0.1034 0.0678 MnO wt% 0.1707 0.1705 0.1377 0.1771 0.2102 0.2361 0.1411 0.0919 0.1737 0.1934 0.1213 0.1311 0.177 0.1116 0.1607 0.164 0.2229 0.2366 FeO wt % 29.6 30.215 30.447 30.283 29.572 30.068 29.703 30.08 30.408 30.451 30.803 30.602 30.368 29.64 29.971 30.041 22.157 21.541 OH- wt% 11.06 11.16 11.17 11.14 11.00 11.12 11.12 11.09 11.15 11.19 11.19 11.10 11.09 11.12 11.11 11.08 11.59 11.52 Total Oxide wt% 98.53 99.58 99.85 99.47 98.60 99.28 98.97 99.01 99.54 99.86 100.05 99.46 99.10 98.87 99.10 98.89 99.43 98.55 K 0.00 0.01 0.02 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.04 0.00 0.00 0.01 0.01 0.05 0.02 Na 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 Mg 1.96 1.91 1.91 1.96 1.97 1.91 1.95 1.93 1.90 1.90 1.94 1.90 1.91 2.00 1.89 1.91 2.54 2.67 Fe2+ 2.68 2.72 2.73 2.73 2.70 2.71 2.68 2.72 2.74 2.73 2.76 2.77 2.75 2.67 2.71 2.72 1.92 1.88 Mn 0.02 0.02 0.01 0.02 0.02 0.02 0.01 0.01 0.02 0.02 0.01 0.01 0.02 0.01 0.01 0.02 0.02 0.02 Cr 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.01 Ti 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 Al(VI) 1.34 1.35 1.33 1.29 1.21 1.34 1.34 1.33 1.35 1.35 1.30 1.29 1.32 1.30 1.37 1.34 1.42 1.38 sum 6.01 6.01 6.02 6.02 5.92 6.01 5.99 6.01 6.01 6.00 6.02 6.03 6.01 6.00 6.00 6.01 5.97 5.98 Al(IV) 1.37 1.38 1.37 1.35 1.36 1.38 1.35 1.38 1.38 1.36 1.37 1.35 1.35 1.29 1.37 1.37 1.33 1.35 Si 2.63 2.62 2.63 2.65 2.64 2.62 2.65 2.62 2.62 2.64 2.63 2.65 2.65 2.71 2.63 2.63 2.67 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 465 Table B.2 (Continued) Sample D39200-1469 (continued) D39200-3241 EMPA spot 4 5 6 10 11 13 14 16 17 18 19 1 2 3 4 5 6 8 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Na2O wt% 0.0139 0 0.0639 0.012 0.006 0 0 0 0.014 0.046 0.008 0 0 0.0236 0.0197 0.0119 0 0.0099 MgO wt% 17.808 17.068 16.523 16.994 16.837 17.46 17.099 16.971 17.288 17.279 16.709 18.485 18.688 18.648 18.057 18.128 18.529 17.811 Al2O3 wt% 21.933 22.548 22.604 22.49 22.523 22.212 22.503 22.957 22.433 22.161 22.84 21.591 21.438 22.024 22.64 22.623 21.744 22.311 SiO2 wt% 26.005 25.804 26.096 25.58 25.363 25.699 25.49 25.961 25.743 25.985 25.4 26.452 26.34 26.396 26.106 25.977 26.041 25.72 K2O wt% 0.0265 0.1277 0.3474 0.0784 0.0325 0.0277 0.0265 0.1397 0.0169 0 0.0555 0.0072 0 0.0229 0 0.006 0.0254 0.0121 CaO wt% 0.0126 0.0218 0.0149 0.0333 0.0183 0.0138 0 0.0183 0.0092 0.0034 0.0287 0.0322 0.0057 0.0482 0.0276 0.0471 0.0506 0.1587 TiO2 wt% 0.0459 0.0454 0.015 0.1045 0.0355 0.0124 0 0.0605 0.0575 0.0599 0.0535 0.1078 0.0747 0.0408 0.064 0.0763 0.1078 0.055 Cr2O3 wt% 0.1076 0.1234 0.1197 0.0358 0 0.0557 0.0675 0.0716 0.1116 0.0159 0.0199 0.016 0 0.056 0.0481 0.048 0.0881 0.1161 MnO wt% 0.1599 0.2496 0.2233 0.1766 0.256 0.2065 0.2228 0.223 0.2 0.2163 0.2065 0.1102 0.0901 0.0367 0.1269 0.08 0.1068 0.0868 FeO wt % 21.537 21.915 21.603 21.927 22.4 22.189 22.231 22.123 21.705 22.049 21.962 20.483 20.534 20.855 20.385 21.153 20.539 20.714 OH- wt% 11.63 11.63 11.61 11.57 11.54 11.61 11.58 11.72 11.61 11.62 11.55 11.66 11.63 11.75 11.69 11.73 11.63 11.59 Total Oxide wt% 99.27 99.53 99.22 99.00 99.01 99.49 99.22 100.24 99.18 99.44 98.83 98.94 98.80 99.91 99.17 99.88 98.86 98.58 K 0.00 0.02 0.05 0.01 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Na 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Mg 2.74 2.62 2.54 2.63 2.61 2.69 2.64 2.59 2.66 2.66 2.59 2.84 2.87 2.84 2.76 2.76 2.85 2.75 Fe2+ 1.86 1.89 1.87 1.90 1.95 1.92 1.93 1.89 1.88 1.90 1.91 1.76 1.77 1.78 1.75 1.81 1.77 1.79 Mn 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.00 0.01 0.01 0.01 0.01 Cr 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 Ti 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.00 Al(VI) 1.35 1.40 1.45 1.40 1.40 1.36 1.39 1.43 1.39 1.38 1.43 1.34 1.32 1.34 1.41 1.38 1.33 1.38 sum 5.98 5.97 5.95 5.97 5.98 5.99 5.98 5.96 5.97 5.97 5.96 5.96 5.98 5.98 5.95 5.97 5.98 5.95 Al(IV) 1.32 1.34 1.30 1.35 1.36 1.35 1.36 1.34 1.34 1.32 1.36 1.28 1.28 1.31 1.32 1.34 1.31 1.34 Si 2.68 2.66 2.70 2.65 2.64 2.65 2.64 2.66 2.66 2.68 2.64 2.72 2.72 2.69 2.68 2.66 2.69 2.66 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 466 Table B.2 (Continued) Sample D39200-3241 (continued) DS172-123 EMPA spot 11 12 15 16 19 20 1 3 4 5 6 7 8 15 16 22 23 24 Birefringence colour Grey Grey Grey Grey Grey Grey Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0 0.0118 0.0158 0.0138 0.0453 0 0.0089 0 0 0 0.0241 0.0634 0 0.0311 0 0 0.089 0 MgO wt% 18.365 18.436 18.111 18.409 17.773 18.423 8.1234 8.0097 8.1135 8.2644 8.8251 8.8004 8.7095 8.051 8.1127 7.8181 7.7949 7.7135 Al2O3 wt% 22.037 21.928 21.889 22.349 22.123 21.618 18.02 17.982 17.9 17.929 17.961 18.633 18.626 17.956 18.156 18.634 18.371 18.446 SiO2 wt% 26.165 26.228 26.106 25.865 26.675 25.962 24.993 25.502 25.798 25.412 25.877 25.871 25.824 25.615 25.436 25.419 25.034 25.008 K2O wt% 0 0 0.0072 0.0205 0.0073 0.0097 0 0.0333 0.0321 0.0618 0.056 0 0.037 0.0274 0.0262 0 0.0202 0.0392 CaO wt% 0.0356 0.054 0.0425 0.0103 0.0933 0.0471 0.082 0.0743 0.0111 0.0987 0.1045 0.1179 0.0556 0.0632 0.0599 0.0954 0.0377 0.083 TiO2 wt% 0.1055 0.0717 0.0743 0.0092 0.107 0.5635 0.0119 0.0896 0.0499 0.0173 0.0427 0.0979 0.0482 0.1066 0.0459 0.0275 0.0666 0.0689 Cr2O3 wt% 0.0761 0.036 0.06 0.044 0.0321 0.0401 0.0371 0.0223 0.0631 0.0669 0.0636 0.1199 0 0.0372 0.0409 0.0037 0 0 MnO wt% 0.1403 0.1469 0.1235 0.0567 0.1037 0.1838 0.3232 0.4527 0.3136 0.537 0.4544 0.5001 0.5293 0.4692 0.4659 0.4955 0.5269 0.4813 FeO wt % 20.41 20.633 20.648 20.751 20.334 20.488 36.37 36.211 36.717 35.973 34.347 34.203 34.103 35.908 35.883 35.313 36.157 36.841 OH- wt% 11.66 11.68 11.61 11.67 11.68 11.64 10.69 10.76 10.84 10.76 10.80 10.91 10.85 10.77 10.77 10.75 10.72 10.76 Total Oxide wt% 99.00 99.22 98.69 99.20 98.98 98.97 98.66 99.14 99.83 99.12 98.56 99.31 98.78 99.04 98.99 98.56 98.81 99.44 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.01 Na 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.00 0.00 0.02 0.00 Mg 2.82 2.82 2.79 2.82 2.72 2.83 1.36 1.33 1.34 1.37 1.46 1.44 1.43 1.34 1.35 1.30 1.30 1.28 Fe2+ 1.76 1.77 1.78 1.78 1.75 1.77 3.41 3.37 3.40 3.35 3.19 3.15 3.15 3.34 3.34 3.29 3.38 3.44 Mn 0.01 0.01 0.01 0.00 0.01 0.02 0.03 0.04 0.03 0.05 0.04 0.05 0.05 0.04 0.04 0.05 0.05 0.05 Cr 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.01 0.01 0.01 0.00 0.01 0.04 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.01 Al(VI) 1.36 1.35 1.36 1.37 1.41 1.30 1.19 1.20 1.19 1.19 1.22 1.26 1.28 1.21 1.22 1.28 1.23 1.21 sum 5.96 5.97 5.96 5.99 5.91 5.96 5.99 5.96 5.97 5.98 5.94 5.93 5.93 5.96 5.96 5.93 5.99 5.99 Al(IV) 1.31 1.31 1.30 1.34 1.26 1.32 1.20 1.16 1.14 1.17 1.13 1.15 1.15 1.15 1.17 1.17 1.20 1.21 Si 2.69 2.69 2.70 2.66 2.74 2.68 2.80 2.84 2.86 2.83 2.87 2.85 2.85 2.85 2.83 2.83 2.80 2.79 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 467 Table B.2 (Continued) Sample DS172-123 (continued) DS173-499 EMPA spot 27 28 30 2 5 7 8 10 13 14 15 18 19 23 24 26 30 31 Birefringence colour Blue Blue Blue Brown Brown Brown Brown Brown Brown Brown Brown Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0045 0.0178 0.0089 0.0728 0.1578 0.2519 0.0947 0.0986 0.1517 0.0648 0.0688 0.0171 0.0431 0 0 0.0474 0.0108 0.0279 MgO wt% 7.7513 7.7798 8.2537 16.864 16.572 16.834 16.94 17.312 16.905 16.847 16.895 11.077 11.291 11.253 11.425 11.324 11.411 11.695 Al2O3 wt% 18.18 18.547 18.509 21.129 21.253 20.916 21.219 21.259 21.403 21.286 21.308 22.598 22.659 22.506 22.538 23.082 22.331 22.307 SiO2 wt% 25.13 25.068 25.709 25.849 25.866 26.041 26.125 26.095 25.838 25.737 25.364 24.333 23.7 23.586 23.779 23.953 24.029 23.845 K2O wt% 0.0071 0 0.1238 0.0216 0.1574 0.1479 0.0782 0.0385 0.0613 0.0433 0.0697 0.3411 0.0202 0.0392 0.0202 0 0.0404 0.0202 CaO wt% 0.1273 0.0654 0.0499 0.048 0.0034 0.0927 0.0092 0.0126 0.0206 0.0206 0.0172 0.0667 0.0395 0.0203 0.0463 0.0293 0.0102 0 TiO2 wt% 0.1034 0.0329 0.0379 0.0387 0.0962 0.0819 0.0727 0.1068 0.0827 0.0724 0.1372 0.098 0.0742 0.0768 0.0757 0.0186 0.1237 0.1107 Cr2O3 wt% 0.0371 0.0185 0.0149 0 0.1029 0.0753 0 0.1031 0.0514 0.0474 0.0791 0.0039 0.0767 0.0498 0.0653 0.0691 0.0307 0.0423 MnO wt% 0.5395 0.5203 0.4791 0.1192 0.2156 0.1328 0.1527 0.1561 0.2123 0.116 0.0796 0.1048 0.0718 0.0327 0 0.0621 0.0654 0.0425 FeO wt % 36.62 36.441 36.044 23.297 22.962 22.589 22.66 22.639 23.193 23.299 23.075 28.993 29.797 30.132 29.917 30.117 29.585 29.374 OH- wt% 10.74 10.76 10.90 11.48 11.47 11.46 11.51 11.57 11.54 11.49 11.43 11.13 11.10 11.07 11.11 11.22 11.10 11.09 Total Oxide wt% 99.24 99.25 100.13 98.91 98.86 98.63 98.86 99.39 99.46 99.02 98.52 98.76 98.87 98.76 98.98 99.93 98.74 98.55 K 0.00 0.00 0.02 0.00 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.05 0.00 0.01 0.00 0.00 0.01 0.00 Na 0.00 0.00 0.00 0.01 0.03 0.05 0.02 0.02 0.03 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.01 Mg 1.29 1.29 1.35 2.63 2.58 2.63 2.63 2.68 2.62 2.62 2.64 1.78 1.82 1.82 1.84 1.80 1.84 1.89 Fe2+ 3.42 3.40 3.32 2.04 2.01 1.98 1.97 1.96 2.02 2.03 2.03 2.61 2.69 2.73 2.70 2.69 2.67 2.66 Mn 0.05 0.05 0.04 0.01 0.02 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.00 Cr 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.00 Ti 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 Al(VI) 1.20 1.23 1.23 1.30 1.32 1.30 1.33 1.30 1.31 1.31 1.30 1.49 1.45 1.43 1.43 1.47 1.44 1.42 sum 5.97 5.98 5.97 6.00 6.00 6.00 5.98 6.00 6.01 6.00 6.02 5.95 5.99 6.00 5.99 5.98 5.97 5.99 Al(IV) 1.19 1.21 1.17 1.30 1.30 1.28 1.28 1.30 1.31 1.31 1.34 1.38 1.44 1.44 1.43 1.44 1.40 1.42 Si 2.81 2.79 2.83 2.70 2.70 2.72 2.72 2.70 2.69 2.69 2.66 2.62 2.56 2.56 2.57 2.56 2.60 2.58 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 468 Table B.2 (Continued) Sample DS177-1500 EMPA spot 1 2 3 4 5 6 8 9 10 11 12 13 14 15 16 17 18 19 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Brown Brown Brown Brown Na2O wt% 0.0596 0.0212 0.0234 0.0254 0.0426 0.0042 0.0277 0.0595 0.0234 0 0.0042 0.0192 0.0149 0.0468 0.0105 0 0.0189 0.0148 MgO wt% 12.067 12.808 12.158 12.78 12.289 12.344 12.105 12.395 12.265 12.605 12.808 12.045 12.152 12.337 13.525 13.833 13.952 13.616 Al2O3 wt% 22.741 21.977 22.423 22.161 22.458 22.819 22.67 22.225 22.46 22.352 21.759 22.906 22.476 22.448 21.239 20.963 21.121 21.428 SiO2 wt% 24.151 24.723 24.471 24.626 24.789 24.387 24.143 24.92 24.495 24.684 25.004 24.018 23.965 24.213 25.09 25.268 25.369 25.248 K2O wt% 0.0309 0 0 0.0286 0.0262 0.025 0 0 0.019 0.019 0.1023 0 0.0309 0.0512 0.0036 0.0143 0.0143 0.0143 CaO wt% 0.0079 0.0147 0.0385 0 0.0294 0.034 0.0226 0.0272 0.0305 0.0441 0.0294 0.0271 0.035 0 0 0.0023 0.0181 0.0068 TiO2 wt% 0.0927 0.0435 0.0393 0.0501 0.0363 0.0315 0.0256 0.0495 0.0661 0.0694 0.1409 0.0496 0.0509 0.0119 0.0375 0.074 0.0302 0.0772 Cr2O3 wt% 0.0039 0.0464 0.0193 0 0 0 0.0308 0 0 0.0464 0.0387 0.0077 0.0347 0.0039 0.0426 0 0.0466 0.0349 MnO wt% 0.4229 0.3606 0.3641 0.3606 0.3307 0.305 0.3306 0.4232 0.416 0.3344 0.3311 0.3993 0.3173 0.3311 0.3184 0.3552 0.3351 0.2563 FeO wt % 28.226 27.833 27.875 27.846 28.663 28.135 28.583 28.055 28.187 28.615 28.094 28.554 28.723 28.307 27.246 26.814 27.078 27.535 OH- wt% 11.20 11.23 11.18 11.24 11.31 11.26 11.20 11.27 11.23 11.32 11.28 11.21 11.16 11.18 11.23 11.23 11.30 11.32 Total Oxide wt% 99.00 99.06 98.59 99.12 99.97 99.34 99.14 99.43 99.19 100.09 99.59 99.23 98.96 98.94 98.74 98.55 99.29 99.55 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 Na 0.01 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 Mg 1.93 2.04 1.94 2.03 1.94 1.96 1.93 1.97 1.95 1.99 2.03 1.92 1.95 1.97 2.15 2.20 2.21 2.15 Fe2+ 2.53 2.49 2.50 2.49 2.54 2.51 2.56 2.50 2.52 2.54 2.50 2.56 2.58 2.54 2.43 2.40 2.40 2.44 Mn 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.04 0.04 0.03 0.03 0.04 0.03 0.03 0.03 0.03 0.03 0.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 Al(VI) 1.46 1.40 1.46 1.42 1.44 1.46 1.45 1.44 1.44 1.41 1.38 1.46 1.42 1.43 1.35 1.34 1.33 1.35 sum 5.98 5.97 5.95 5.98 5.97 5.96 5.98 5.95 5.96 5.98 5.97 5.98 5.99 5.99 5.98 5.98 5.98 5.98 Al(IV) 1.41 1.36 1.37 1.37 1.37 1.40 1.41 1.35 1.38 1.38 1.34 1.43 1.42 1.40 1.32 1.30 1.31 1.32 Si 2.59 2.64 2.63 2.63 2.63 2.60 2.59 2.65 2.62 2.62 2.66 2.57 2.58 2.60 2.68 2.70 2.69 2.68 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 469 Table B.2 (Continued) Sample DS177-1500 (continued) DS358-1215 EMPA spot 20 21 22 23 24 25 26 28 30 1 2 3 4 5 6 7 8 9 Birefringence colour Brown Brown Brown Brown Brown Brown Brown Brown Brown Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0527 0.0712 0.0843 0.0231 0.067 0.0168 0.0571 0.0251 0.019 0.0387 0.0386 0.0083 0 0.0249 0.0138 0.0097 0.0372 0.0263 MgO wt% 13.396 14.148 13.43 13.65 14.345 13.855 13.454 14.106 14.051 11.714 11.763 11.696 11.538 11.769 11.608 11.563 11.722 11.422 Al2O3 wt% 21.552 21.229 21.453 21.508 21.269 21.203 21.126 21.308 21.382 22.868 22.658 23.017 22.47 22.655 22.719 22.563 22.866 23.082 SiO2 wt% 25.02 25.828 25.297 24.83 25.28 25.424 25.136 25.411 25.474 24.154 24.004 23.968 24.326 24.286 24.137 24.414 24.467 24.137 K2O wt% 0 0 0.0274 0.0322 0.0119 0.0191 0.0143 0 0.0048 0.0097 0.0194 0 0.0267 0.0352 0.0219 0.0413 0.0036 0.0243 CaO wt% 0 0.0193 0.034 0.0147 0 0.0284 0.0113 0.042 0 0.0262 0.0182 0.0262 0.0125 0.0114 0.0114 0.025 0 0.0148 TiO2 wt% 0.1115 0.0456 0.0465 0.0825 0.0644 0.0975 0.0863 0.0893 0.0685 0.0871 0.1497 0.0606 0.1025 0.0733 0.0148 0.1406 0.042 0.0199 Cr2O3 wt% 0 0 0.0311 0.0233 0.0584 0 0.0155 0 0 0.3383 0.2616 0.2883 0.2533 0.1995 0.2268 0.1882 0.2733 0.3071 MnO wt% 0.3381 0.3978 0.3517 0.3255 0.2896 0.3386 0.3251 0.3224 0.3484 0.1549 0.1879 0.1417 0.0593 0.1647 0.2209 0.1186 0.1484 0.1581 FeO wt % 27.393 26.856 27.295 26.961 26.664 27.293 27.55 26.408 27.507 29.827 29.432 29.788 30.214 30.362 29.571 30.032 29.472 30.198 OH- wt% 11.27 11.41 11.30 11.23 11.34 11.33 11.24 11.31 11.40 11.30 11.22 11.27 11.25 11.32 11.22 11.28 11.31 11.30 Total Oxide wt% 99.13 100.01 99.35 98.68 99.38 99.61 99.02 99.03 100.26 100.52 99.75 100.27 100.26 100.90 99.77 100.38 100.34 100.69 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Na 0.01 0.01 0.02 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.01 0.01 Mg 2.13 2.22 2.12 2.17 2.26 2.19 2.14 2.23 2.20 1.85 1.87 1.86 1.83 1.86 1.85 1.83 1.85 1.81 Fe2+ 2.44 2.36 2.42 2.41 2.36 2.42 2.46 2.34 2.42 2.65 2.63 2.65 2.69 2.69 2.64 2.67 2.61 2.68 Mn 0.03 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.01 0.02 0.01 0.01 0.01 0.02 0.01 0.01 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 Ti 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.00 Al(VI) 1.37 1.34 1.37 1.36 1.33 1.33 1.34 1.36 1.33 1.43 1.42 1.44 1.41 1.40 1.44 1.42 1.45 1.45 sum 5.98 5.97 5.97 5.99 6.00 5.98 5.99 5.97 5.99 5.99 5.99 5.99 5.98 6.00 5.98 5.97 5.97 5.98 Al(IV) 1.34 1.29 1.32 1.35 1.33 1.31 1.32 1.31 1.32 1.44 1.43 1.45 1.41 1.43 1.42 1.40 1.41 1.44 Si 2.66 2.71 2.68 2.65 2.67 2.69 2.68 2.69 2.68 2.56 2.57 2.55 2.59 2.57 2.58 2.60 2.59 2.56 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 470 Table B.2 (Continued) Sample DS358-1215 (continued) EMPA spot 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0249 0.0414 0.0511 0.0096 0.0055 0.0152 0.0234 0.0361 0 0 0.0512 0 0.0152 0 0.0526 0.0221 0.0248 0.0041 MgO wt% 11.616 11.496 11.743 11.822 11.922 11.647 11.68 11.805 11.662 11.567 11.664 11.924 11.897 11.699 11.675 11.496 11.799 12.115 Al2O3 wt% 22.969 22.301 22.678 22.751 22.773 22.852 22.646 22.599 23.041 22.979 23.123 22.4 22.64 22.674 22.516 22.486 22.703 22.326 SiO2 wt% 24.341 24.192 24.424 24.339 24.279 23.958 24.139 24.577 24.113 24.366 23.719 24.398 24.271 24.299 24.464 24.074 24.371 24.339 K2O wt% 0.0036 0.0279 0.0291 0.0109 0.0109 0.0607 0.0559 0.0036 0 0 0.0267 0.0049 0 0.0194 0.0716 0.0243 0.0474 0.0365 CaO wt% 0.0239 0.025 0.0432 0 0.0319 0 0.0251 0.0125 0.041 0.0262 0.0296 0.0353 0 0 0.0421 0.0125 0.0376 0.041 TiO2 wt% 0.0511 0.0805 0.0472 0.0594 0.0257 0.0514 0.0468 0.0592 0.0548 0.0534 0.057 0.0555 0.0386 0.0146 0.0676 0.0358 0.0319 0.074 Cr2O3 wt% 0.4769 0.3693 0.2615 0.2194 0.2383 0.315 0.177 0.1841 0.2074 0.1267 0.238 0.1769 0.3305 0.0999 0.2228 0.1768 0.2617 0.2006 MnO wt% 0.145 0.1549 0.178 0.1649 0.1351 0.1944 0.0858 0.1581 0.1054 0.0692 0.1416 0.1352 0.1681 0.1384 0.0923 0.2076 0.2078 0.1453 FeO wt % 29.881 29.357 29.77 29.444 29.96 29.875 29.271 30.668 30.053 30.275 30.163 29.685 29.881 29.785 30.12 29.5 29.443 28.612 OH- wt% 11.34 11.16 11.31 11.28 11.32 11.25 11.19 11.38 11.30 11.33 11.27 11.26 11.30 11.25 11.30 11.15 11.28 11.19 Total Oxide wt% 100.87 99.20 100.53 100.10 100.70 100.22 99.34 101.48 100.58 100.79 100.48 100.07 100.54 99.98 100.62 99.19 100.21 99.09 K 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 Na 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 Mg 1.83 1.84 1.86 1.87 1.88 1.85 1.87 1.85 1.84 1.83 1.85 1.89 1.88 1.86 1.85 1.84 1.87 1.93 Fe2+ 2.64 2.64 2.64 2.62 2.65 2.66 2.62 2.70 2.67 2.68 2.69 2.64 2.65 2.66 2.67 2.65 2.62 2.56 Mn 0.01 0.01 0.02 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.02 0.02 0.01 Cr 0.04 0.03 0.02 0.02 0.02 0.03 0.01 0.02 0.02 0.01 0.02 0.01 0.03 0.01 0.02 0.02 0.02 0.02 Ti 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 Al(VI) 1.44 1.42 1.43 1.44 1.42 1.43 1.45 1.40 1.44 1.45 1.43 1.41 1.41 1.44 1.41 1.44 1.43 1.43 sum 5.97 5.97 5.98 5.97 5.99 6.00 5.98 6.00 5.98 5.97 6.01 5.98 5.99 5.98 5.99 5.98 5.98 5.97 Al(IV) 1.43 1.40 1.41 1.41 1.43 1.45 1.41 1.41 1.44 1.42 1.48 1.40 1.42 1.41 1.40 1.41 1.41 1.39 Si 2.57 2.60 2.59 2.59 2.57 2.55 2.59 2.59 2.56 2.58 2.52 2.60 2.58 2.59 2.60 2.59 2.59 2.61 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 471 Table B.2 (Continued) Sample DS358-1215 (continued) EMPA spot 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0273 0.0028 0 0.0547 0.0302 0.0261 0 0.0055 0 0.0233 0.0138 0.0384 0.0331 0 0.0082 0.0151 0.0259 0 MgO wt% 12.309 12.323 12.319 12.077 12.133 12.574 12.459 12.262 12.268 12.682 11.895 12.044 12.042 12.306 12.432 12.338 12.7 12.246 Al2O3 wt% 22.663 21.911 22.398 22.634 22.653 22.365 22.787 22.26 22.555 22.257 22.631 22.776 23.034 23.106 23.138 22.539 22.466 22.387 SiO2 wt% 24.217 24.436 24.335 25.081 24.404 24.345 24.745 24.873 24.558 24.8 24.196 24.405 24.425 24.489 24.484 24.699 24.416 24.357 K2O wt% 0.0353 0.0243 0 0.1959 0.0657 0.0146 0.0851 0.0657 0.028 0.0341 0.0316 0.0049 0.0012 0.0194 0.0438 0.0134 0.0365 0.0949 CaO wt% 0.0297 0.1127 0.041 0.1461 0.1163 0.164 0.0308 0.0319 0.1357 0.0171 0.0171 0.057 0.0455 0.0194 0.0696 0.0217 0.0422 0.0981 TiO2 wt% 0.0701 0.1561 0.0718 0.1273 0.1043 0.0585 0.1202 0.0933 0.0358 0.0105 0.1067 0.0374 0.1322 0.0481 0.0049 0.1032 0.0747 0.0351 Cr2O3 wt% 0.0734 0.4781 0.0732 0.0619 0.3127 0.1425 0.1697 0.185 0.1313 0.1003 0.1385 0.1659 0.1385 0.1543 0.1816 0.1583 0.1428 0.1119 MnO wt% 0.119 0.1155 0.1683 0.1388 0.0793 0.1287 0.1189 0.132 0.0826 0.1453 0.122 0.0793 0.1088 0.1584 0.0958 0.1024 0.132 0.1486 FeO wt % 28.237 29.167 29.164 28.624 28.839 29.464 29.433 29.297 28.71 28.941 29.441 28.865 29.974 28.828 28.642 28.834 28.622 28.721 OH- wt% 11.21 11.26 11.26 11.38 11.30 11.32 11.44 11.34 11.28 11.34 11.24 11.27 11.40 11.37 11.37 11.33 11.30 11.23 Total Oxide wt% 98.99 99.98 99.83 100.52 100.03 100.61 101.39 100.55 99.79 100.35 99.83 99.75 101.34 100.50 100.47 100.15 99.96 99.43 K 0.00 0.00 0.00 0.03 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 Na 0.01 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 Mg 1.96 1.96 1.96 1.90 1.92 1.99 1.95 1.93 1.94 2.00 1.89 1.91 1.89 1.94 1.95 1.95 2.01 1.95 Fe2+ 2.53 2.60 2.60 2.52 2.56 2.61 2.58 2.59 2.55 2.56 2.63 2.57 2.64 2.54 2.53 2.55 2.54 2.57 Mn 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Cr 0.01 0.04 0.01 0.01 0.03 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 Ti 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.00 Al(VI) 1.45 1.35 1.41 1.45 1.43 1.37 1.41 1.40 1.44 1.40 1.43 1.45 1.42 1.46 1.46 1.43 1.40 1.42 sum 5.97 5.98 5.99 5.94 5.96 6.00 5.98 5.97 5.96 5.99 5.98 5.96 5.99 5.97 5.97 5.96 5.99 5.98 Al(IV) 1.41 1.40 1.41 1.36 1.41 1.42 1.41 1.37 1.39 1.38 1.42 1.40 1.43 1.42 1.42 1.38 1.41 1.40 Si 2.59 2.60 2.59 2.64 2.59 2.58 2.59 2.63 2.61 2.62 2.58 2.60 2.57 2.58 2.58 2.62 2.59 2.60 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 472 Table B.2 (Continued) Sample DS358-1215 (continued) DS358-132 GC01018-691 EMPA spot 46 47 48 49 50 2 3 4 5 6 12 13 19 20 22 25 6 9 Birefringence colour Blue Blue Blue Blue Blue Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Brown Blue Blue Na2O wt% 0.0151 0.0587 0.026 0.011 0.0164 0.0145 0.0228 0 0.0104 0.0248 0 0.0576 0.0021 0.0287 0.0083 0 0.0093 0.0738 MgO wt% 12.137 12.743 12.196 11.987 12.582 14.195 14.495 14.361 13.753 14.527 14.545 14.141 14.608 14.116 14.455 14.235 6.1383 6.1959 Al2O3 wt% 22.285 22.047 22.943 22.805 22.479 22.686 23.182 22.698 23.304 22.598 22.849 23.417 22.714 23.502 22.543 22.882 19.982 20.53 SiO2 wt% 24.809 24.902 24.519 24.444 24.788 25.127 24.674 24.781 24.77 25.067 25.031 25.36 24.691 25.699 24.73 24.728 23.252 23.458 K2O wt% 0.0243 0.0183 0.0803 0.0207 0.0377 0.1696 0.0012 0.0497 0.2049 0 0.1092 0.1554 0.0424 0.3157 0.0024 0.0994 0.3254 0.2452 CaO wt% 0.0388 0.0639 0.0593 0.0673 0.0034 0.0585 0.016 0.0183 0.0298 0.0734 0.0632 0.1183 0.0092 0.1115 0.0034 0.0126 0 0.075 TiO2 wt% 0.0628 0.0254 0.0838 0.0903 0.084 0.0343 0.0426 0.0472 0.0342 0.1271 0.0517 0.033 0.0496 0.0781 0.0183 0.0733 0.0333 0.0522 Cr2O3 wt% 0.0501 0 0.0811 0 0.1701 0 0 0 0.0511 0.0079 0.0079 0.0474 0.0708 0.0593 0.0118 0 0 0.0112 MnO wt% 0.1387 0.205 0.0958 0.0991 0.0231 0.0662 0.0828 0.0894 0.0331 0.0762 0 0.0929 0.0331 0.0465 0.1192 0.1159 0.264 0.4065 FeO wt % 29.042 28.372 28.66 28.898 28.558 25.145 25.826 25.434 25.223 25.272 24.827 24.709 25.181 24.484 25.434 25.594 38.874 37.029 OH- wt% 11.29 11.30 11.32 11.27 11.34 11.38 11.45 11.36 11.36 11.41 11.40 11.51 11.36 11.57 11.33 11.38 10.62 10.64 Total Oxide wt% 99.89 99.73 100.07 99.69 100.08 98.88 99.80 98.83 98.78 99.19 98.89 99.64 98.76 100.01 98.66 99.12 99.50 98.71 K 0.00 0.00 0.01 0.00 0.01 0.02 0.00 0.01 0.03 0.00 0.01 0.02 0.01 0.04 0.00 0.01 0.05 0.04 Na 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.02 Mg 1.92 2.02 1.93 1.90 1.98 2.23 2.26 2.26 2.16 2.28 2.28 2.20 2.30 2.18 2.28 2.24 1.03 1.04 Fe2+ 2.58 2.52 2.54 2.57 2.53 2.22 2.26 2.25 2.23 2.22 2.18 2.15 2.22 2.12 2.25 2.26 3.67 3.49 Mn 0.01 0.02 0.01 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.03 0.04 Cr 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 Ti 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 Al(VI) 1.43 1.40 1.46 1.46 1.42 1.47 1.44 1.44 1.51 1.43 1.46 1.52 1.43 1.54 1.43 1.45 1.28 1.37 sum 5.96 5.97 5.96 5.96 5.97 5.95 5.98 5.97 5.94 5.95 5.95 5.92 5.97 5.90 5.98 5.97 6.07 6.00 Al(IV) 1.36 1.36 1.40 1.40 1.38 1.35 1.42 1.38 1.39 1.37 1.37 1.36 1.39 1.34 1.38 1.39 1.37 1.35 Si 2.64 2.64 2.60 2.60 2.62 2.65 2.58 2.62 2.61 2.63 2.63 2.64 2.61 2.66 2.62 2.61 2.63 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 473 Table B.2 (Continued) Sample GC01018-691 (continued) GC04002-688 GC04003-1716 EMPA spot 10 19 3 5 6 9 10 11 12 13 14 17 1 3 7 9 11 12 Birefringence colour Blue Blue Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Blue Blue Blue Blue Blue Blue Na2O wt% 0.0533 0.0373 0.0418 0.0131 0.0471 0.032 0.0637 0.0416 0.0939 0.0284 0.0188 0.2268 0.0482 0 0 0 0.0131 0 MgO wt% 6.3782 6.1025 16.269 16.564 16.184 16.788 17.032 16.839 16.516 16.584 16.619 16.172 9.1059 9.938 11.065 9.92 11.006 10.331 Al2O3 wt% 19.292 19.397 20.5 22.556 22.032 21.664 21.903 21.556 21.816 22.114 22.273 21.988 23.359 22.919 21.257 22.557 21.183 21.987 SiO2 wt% 24.088 23.522 26.548 25.327 25.908 25.949 26.257 25.848 25.965 25.846 25.621 25.133 24.174 23.872 24.729 23.684 24.633 23.827 K2O wt% 0.3248 0.3361 0.0533 0.0745 0.232 0.0596 0.0584 0.0484 0.1366 0.0496 0.0199 0.2095 0.0534 0.0523 0 0.0392 0.0131 0.0487 CaO wt% 0.056 0.0481 0.0479 0.0149 0.0217 0.032 0.0538 0.0171 0.0114 0.0171 0.0343 0.1222 0.096 0.0203 0 0.009 0.0249 0 TiO2 wt% 0.0346 0.0078 0.0606 0.074 0.0948 0.0099 0.0489 0.1014 0.0364 0.01 0.008 0.0678 0.0093 0.0593 0.0499 0.0371 0.0499 0.0438 Cr2O3 wt% 0 0.052 0 0 0.0549 0 0.0197 0.0626 0.0825 0.0548 0.0392 0 0 0 0.0269 0.0344 0 0.0574 MnO wt% 0.3647 0.248 0.2411 0.235 0.2381 0.2547 0.2417 0.3338 0.2847 0.2676 0.2249 0.2974 0.0948 0.1112 0.1802 0.1733 0.0917 0.1047 FeO wt % 37.445 38.437 23.465 22.407 22.837 22.886 22.4 23.274 22.35 23.602 22.865 23.008 31.663 31.405 30.349 31.39 30.778 31.153 OH- wt% 10.60 10.55 11.45 11.51 11.53 11.54 11.63 11.56 11.51 11.62 11.55 11.42 11.13 11.10 11.07 11.01 11.06 10.99 Total Oxide wt% 98.64 98.74 98.68 98.77 99.18 99.21 99.71 99.68 98.81 100.19 99.27 98.65 99.74 99.48 98.72 98.86 98.85 98.54 K 0.05 0.05 0.01 0.01 0.03 0.01 0.01 0.01 0.02 0.01 0.00 0.03 0.01 0.01 0.00 0.01 0.00 0.01 Na 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.02 0.01 0.00 0.05 0.01 0.00 0.00 0.00 0.00 0.00 Mg 1.08 1.03 2.54 2.57 2.51 2.60 2.62 2.60 2.56 2.55 2.57 2.53 1.46 1.60 1.79 1.61 1.78 1.68 Fe2+ 3.54 3.65 2.06 1.95 1.99 1.99 1.93 2.02 1.95 2.04 1.99 2.02 2.85 2.84 2.75 2.86 2.79 2.84 Mn 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.02 0.02 0.03 0.01 0.01 0.02 0.02 0.01 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Al(VI) 1.30 1.27 1.31 1.41 1.39 1.35 1.37 1.32 1.38 1.36 1.39 1.36 1.57 1.50 1.40 1.47 1.38 1.43 sum 6.01 6.05 5.95 5.97 5.96 5.98 5.96 6.00 5.97 5.99 5.97 6.02 5.91 5.96 5.96 5.97 5.97 5.98 Al(IV) 1.28 1.33 1.22 1.36 1.31 1.30 1.29 1.32 1.30 1.33 1.34 1.36 1.40 1.42 1.32 1.42 1.33 1.40 Si 2.72 2.67 2.78 2.64 2.69 2.70 2.71 2.68 2.70 2.67 2.66 2.64 2.60 2.58 2.68 2.58 2.67 2.60 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 474 Table B.2 (Continued) Sample GC04003-1716 (continued) GC04007-134 EMPA spot 13 14 15 18 1 4 5 6 9 12 13 16 18 20 21 22 24 25 Birefringence colour Blue Blue Blue Blue Blue Blue Blue Late Blue Late Blue Late Blue Blue Blue Blue Blue Blue Blue Blue Blue Na2O wt% 0.0434 0.0285 0.0435 0.0065 0 0 0 0.0195 0 0.0032 0.0016 0 0 0.008 0 0.0032 0.0451 0 MgO wt% 10.439 9.8084 10.335 9.5716 8.0283 7.9744 7.9643 6.8309 7.3497 7.3155 7.2459 7.2076 8.1981 7.7315 7.7897 7.8182 8.1083 7.9574 Al2O3 wt% 22.303 23.01 22.43 22.417 21.396 20.789 21.442 20.57 22.088 21.501 20.942 21.026 21.613 22.133 21.744 21.47 21.489 21.269 SiO2 wt% 24.596 23.581 24.03 24.654 23.8 23.394 23.303 24.082 23.063 23.323 23.544 23.34 23.863 23.338 23.915 23.507 23.471 23.947 K2O wt% 0.0333 0.0831 0.0131 0.2343 0.207 0.1987 0.0268 0.0197 0.0023 0 0.3296 0.2216 0.0047 0.0175 0.1105 0 0.0093 0.0873 CaO wt% 0.0192 0.0316 0.3403 0.0328 0.0186 0.0426 0 0.1922 0.0011 0.0481 0 0.0382 0 0.0022 0.0066 0.0098 0 0.0153 TiO2 wt% 0.0094 0.0192 0.0495 0.0348 0.1262 0.1183 0.0859 0.0533 0 0.0722 0.2351 0.1156 0.0595 0.0551 0.0533 0.0367 0.084 0.0667 Cr2O3 wt% 0 0 0 0.0384 0.7623 0.707 0.8214 0.1197 0 0.0861 0.8418 0.8899 0.0038 0.0113 0.0188 0 0 0.1166 MnO wt% 0.0852 0.0523 0.0655 0.154 0.1228 0.1259 0.21 0.3996 0.3383 0.2353 0.1419 0.1773 0.1844 0.1518 0.1486 0.2066 0.2163 0.1616 FeO wt % 30.296 31.636 30.535 30.384 33.694 34.68 33.983 35.606 35.863 35.596 35.117 35.059 33.938 34.468 35.009 34.741 34.841 34.46 OH- wt% 11.11 11.06 11.07 11.05 10.87 10.77 10.80 10.73 10.83 10.78 10.79 10.75 10.86 10.83 10.92 10.79 10.84 10.85 Total Oxide wt% 98.93 99.31 98.91 98.58 99.03 98.80 98.64 98.63 99.54 98.96 99.19 98.82 98.73 98.74 99.71 98.58 99.10 98.93 K 0.00 0.01 0.00 0.03 0.03 0.03 0.00 0.00 0.00 0.00 0.05 0.03 0.00 0.00 0.02 0.00 0.00 0.01 Na 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 Mg 1.68 1.59 1.67 1.55 1.32 1.32 1.32 1.14 1.21 1.21 1.20 1.20 1.35 1.28 1.28 1.30 1.34 1.31 Fe2+ 2.74 2.87 2.77 2.76 3.11 3.23 3.16 3.33 3.32 3.31 3.26 3.27 3.13 3.19 3.22 3.23 3.22 3.19 Mn 0.01 0.00 0.01 0.01 0.01 0.01 0.02 0.04 0.03 0.02 0.01 0.02 0.02 0.01 0.01 0.02 0.02 0.02 Cr 0.00 0.00 0.00 0.00 0.07 0.06 0.07 0.01 0.00 0.01 0.07 0.08 0.00 0.00 0.00 0.00 0.00 0.01 Ti 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.01 0.02 0.01 0.00 0.00 0.00 0.00 0.01 0.01 Al(VI) 1.49 1.50 1.47 1.54 1.41 1.33 1.39 1.40 1.44 1.42 1.36 1.37 1.45 1.47 1.44 1.43 1.40 1.42 sum 5.93 5.98 5.93 5.90 5.95 6.00 5.97 5.93 6.00 5.98 5.98 5.98 5.95 5.97 5.97 5.98 6.00 5.96 Al(IV) 1.34 1.44 1.40 1.33 1.37 1.39 1.41 1.31 1.45 1.40 1.38 1.40 1.37 1.42 1.37 1.39 1.40 1.35 Si 2.66 2.56 2.60 2.67 2.63 2.61 2.59 2.69 2.55 2.60 2.62 2.60 2.63 2.58 2.63 2.61 2.60 2.65 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 475 Table B.2 (Continued) Sample GC04007-4421 EMPA spot 1 2 3 10 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Na2O wt% 0 0 0.0545 0.0197 0.1065 0.0056 0.007 0.0014 0.0126 0.0098 0.0237 0.0139 0.0209 0 0 0 0.0182 0.0172 MgO wt% 16.778 16.353 16.313 17.902 17.493 18.324 18.243 18.498 18.387 18.623 18.432 19.015 19.014 17.916 18.304 19.294 18.384 16.569 Al2O3 wt% 22.618 22.854 22.778 22.35 22.058 23.052 23.071 23.187 23.129 22.879 23.042 22.072 22.392 22.518 22.626 22.478 22.614 22.895 SiO2 wt% 25.746 25.266 25.28 26.723 26.006 25.884 25.896 25.578 26.023 26.314 25.981 26.517 26.473 25.894 25.972 26.145 26.057 25.464 K2O wt% 0.0393 0.0488 0.019 0.0072 0.0573 0.0562 0.0084 0 0 0 0 0.006 0.0311 0.0203 0.0048 0 0 0.0333 CaO wt% 0.0583 0.0516 0.0594 0.0417 0.0225 0.1488 0.0665 0.0563 0.0282 0.0135 0.0666 0.0226 0.0294 0.0709 0.1128 0.0971 0.0959 0.0056 TiO2 wt% 0.0715 0.0684 0.0277 0.0353 0.06 0.1306 0.0575 0.0679 0.048 0.0482 0.048 0.0337 0.088 0.0062 0.0889 0.0463 0.0665 0.0529 Cr2O3 wt% 0.4769 0.4212 0.4008 0.4369 0.4072 0.49 0.4981 0.4564 0.257 0.2209 0.4107 0.4353 0.4957 0.4362 0.2572 0.3669 0.3495 0.3893 MnO wt% 0.0631 0.0133 0.0796 0.0667 0.0266 0.03 0.0701 0.07 0.0935 0.0835 0.0802 0.1271 0.0502 0.07 0.1603 0.0936 0.1135 0.103 FeO wt % 22.044 22.137 22.117 20.381 21.149 19.985 19.504 20.423 19.519 19.621 19.132 18.617 19.121 20.324 19.552 18.658 19.729 22.25 OH- wt% 11.63 11.52 11.51 11.77 11.61 11.78 11.73 11.78 11.75 11.79 11.73 11.71 11.80 11.65 11.67 11.74 11.71 11.60 Total Oxide wt% 99.52 98.74 98.64 99.73 99.00 99.89 99.15 100.12 99.25 99.61 98.94 98.57 99.51 98.90 98.75 98.92 99.14 99.38 K 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Na 0.00 0.00 0.01 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Mg 2.58 2.54 2.53 2.72 2.69 2.78 2.78 2.81 2.80 2.82 2.81 2.90 2.88 2.75 2.80 2.94 2.81 2.55 Fe2+ 1.90 1.93 1.93 1.74 1.83 1.70 1.67 1.74 1.67 1.67 1.64 1.59 1.63 1.75 1.68 1.59 1.69 1.92 Mn 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 Cr 0.04 0.03 0.03 0.04 0.03 0.04 0.04 0.04 0.02 0.02 0.03 0.04 0.04 0.04 0.02 0.03 0.03 0.03 Ti 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 Al(VI) 1.40 1.43 1.43 1.41 1.37 1.40 1.43 1.38 1.44 1.42 1.43 1.38 1.37 1.40 1.41 1.38 1.40 1.42 sum 5.94 5.94 5.95 5.91 5.96 5.94 5.93 5.98 5.94 5.94 5.93 5.93 5.94 5.94 5.93 5.95 5.94 5.95 Al(IV) 1.34 1.37 1.37 1.28 1.31 1.37 1.35 1.40 1.34 1.32 1.34 1.28 1.31 1.33 1.33 1.33 1.33 1.37 Si 2.66 2.63 2.63 2.72 2.69 2.63 2.65 2.60 2.66 2.68 2.66 2.72 2.69 2.67 2.67 2.67 2.67 2.63 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 476 Table B.2 (Continued) Sample GC04007-4421 (continued) R87108-629 EMPA spot 26 27 28 29 30 32 34 2 3 5 6 7 8 9 11 12 13 18 Birefringence colour Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Grey Brown Na2O wt% 0.0242 0.0243 0.0043 0 0 0.04 0.0456 0.0702 0.0098 0.039 0.0292 0.0547 0.0078 0.0214 0.047 0 0.0466 0 MgO wt% 16.379 16.688 16.537 16.56 16.364 16.657 16.846 20 19.57 20.144 20.438 20.058 20.127 20.223 19.59 20.347 20.378 18.62 Al2O3 wt% 23.236 22.954 22.854 22.4 22.132 22.535 22.15 20.876 20.749 19.832 19.529 20.316 20.295 20.254 20.588 19.677 19.517 19.936 SiO2 wt% 25.848 25.309 25.098 25.198 25.304 26.239 25.817 26.843 26.909 27.511 27.883 27.115 27.521 27.329 26.822 27.591 27.829 27.434 K2O wt% 0.0036 0 0.0036 0.0071 0.0238 0.0238 0.0119 0.0049 0.0485 0 0.0207 0.0061 0.0449 0 0.0158 0 0 0.0618 CaO wt% 0.0371 0.0157 0.0123 0.0797 0.1043 0.073 0.0887 0.0764 0.0254 0.0127 0.0405 0.059 0.0995 0.0243 0.0277 0 0.0289 0.0461 TiO2 wt% 0.0544 0.0327 0.0964 0.037 0.065 0.0547 0.0954 0.0914 0.0847 0.0318 0.1319 0.0505 0.1037 0.0753 0.0704 0.0929 0.0571 0.0784 Cr2O3 wt% 0.4592 0.5653 0.7435 0.7391 0.7588 0.7299 0.6536 0 0.0605 0.0243 0 0.0202 0.0243 0 0 0 0.0364 0 MnO wt% 0.0666 0.1463 0.0897 0.0133 0.0564 0.1697 0.1529 0.2152 0.3086 0.2856 0.3495 0.3093 0.2856 0.3399 0.2483 0.326 0.232 0.3347 FeO wt % 20.94 21.606 21.982 22.107 22.09 21.407 21.174 19.215 19.729 19.028 19.085 19.155 19.085 18.717 19.642 18.871 18.713 20.895 OH- wt% 11.60 11.57 11.54 11.50 11.46 11.67 11.55 11.73 11.71 11.68 11.76 11.70 11.78 11.71 11.66 11.69 11.70 11.64 Total Oxide wt% 98.65 98.91 98.97 98.64 98.36 99.60 98.58 99.12 99.21 98.59 99.27 98.84 99.37 98.70 98.71 98.60 98.54 99.04 K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 Na 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 Mg 2.52 2.58 2.56 2.58 2.55 2.55 2.61 3.05 2.99 3.08 3.11 3.07 3.06 3.09 3.00 3.11 3.11 2.86 Fe2+ 1.81 1.87 1.91 1.93 1.93 1.84 1.84 1.64 1.69 1.63 1.63 1.64 1.63 1.60 1.69 1.62 1.60 1.80 Mn 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.02 0.03 0.02 0.03 0.03 0.02 0.03 0.02 0.03 0.02 0.03 Cr 0.04 0.05 0.06 0.06 0.06 0.06 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.01 Al(VI) 1.50 1.43 1.41 1.38 1.38 1.42 1.39 1.26 1.26 1.22 1.19 1.23 1.24 1.24 1.26 1.21 1.21 1.25 sum 5.89 5.95 5.95 5.95 5.94 5.90 5.92 5.99 5.98 5.98 5.97 5.99 5.96 5.97 5.99 5.97 5.96 5.95 Al(IV) 1.33 1.38 1.39 1.37 1.35 1.30 1.32 1.26 1.24 1.18 1.16 1.22 1.20 1.20 1.24 1.17 1.15 1.17 Si 2.67 2.62 2.61 2.63 2.65 2.70 2.68 2.74 2.76 2.82 2.84 2.78 2.80 2.80 2.76 2.83 2.85 2.83 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 477 Table B.2 (Continued) Sample R87108-629 (continued) EMPA spot 19 20 21 22 24 28 30 Birefringence colour Brown Brown Brown Brown Brown Brown Brown Na2O wt% 0.0558 0.0418 0 0 0.002 0.0258 0.0179 MgO wt% 18.709 18.296 18.59 18.726 18.756 19.128 18.592 Al2O3 wt% 18.92 19.773 20.103 19.532 19.118 19.196 19.837 SiO2 wt% 27.795 27.383 27.459 27.584 28.15 27.707 27.323 K2O wt% 0.046 0.0327 0.0206 0.0545 0.092 0.0557 0.0375 CaO wt% 0.0507 0.0634 0.0473 0.0622 0.1291 0.0357 0.1383 TiO2 wt% 0.047 0.0562 0 0.0539 0.0397 0.0445 0.112 Cr2O3 wt% 0.0401 0 0.016 0.0481 0 0 0.0722 MnO wt% 0.3379 0.3278 0.2944 0.3312 0.2644 0.2978 0.3179 FeO wt % 20.977 21.005 21.116 21.085 21.154 21.063 20.959 OH- wt% 11.57 11.57 11.66 11.63 11.67 11.64 11.62 Total Oxide wt% 98.54 98.55 99.31 99.11 99.38 99.20 99.03 K 0.01 0.00 0.00 0.01 0.01 0.01 0.00 Na 0.01 0.01 0.00 0.00 0.00 0.01 0.00 Mg 2.89 2.83 2.85 2.88 2.87 2.94 2.86 Fe2+ 1.82 1.82 1.82 1.82 1.82 1.81 1.81 Mn 0.03 0.03 0.03 0.03 0.02 0.03 0.03 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Al(VI) 1.19 1.25 1.26 1.22 1.21 1.19 1.23 sum 5.96 5.95 5.95 5.96 5.94 5.98 5.95 Al(IV) 1.12 1.16 1.18 1.16 1.11 1.15 1.18 Si 2.88 2.84 2.82 2.84 2.89 2.85 2.82 Sum 4.00 4.00 4.00 4.00 4.00 4.00 4.00 478 B.3 Biotite EMPA data This appendix consists of Table B.3 which contains the EMP results of all samples probed for biotite chemistry analysis. Each column identifies the sample, EMP spot number, the weight per- cent oxides, stoichiometrically calculated OH- wt%, total oxide (including OH-), and the ideal arrangement of the molar calculated elements in the crystal lattice normalized using oxygen = 11. Sample location, metamorphic grade, main alteration assemblage, mineralization sulfide- oxide assemblage, and distance from ore and surface can be found for all samples in Appendix A.2. 479 Table B.3 Complete electron microprobe data for all samples probed for biotite chemistry. Sample 34L814-195 Biotite Type Biotite + abundant carbonate (part of the biotite-Ti-magnetite ± carbonate assemblage) EMPA spot 4 5 6 7 9 10 11 13 14 16 17 19 20 21 F wt% 0.1543 0.0000 0.1319 0.1468 0.0000 0.0697 0.1778 0.1636 0.2565 0.1014 0.1090 0.0000 0.1087 0.2265 Na2O wt% 0.1225 0.1137 0.0740 0.0998 0.0967 0.1181 0.1364 0.1134 0.1305 0.0583 0.0910 0.1324 0.1557 0.1151 MgO wt% 12.3467 12.5268 12.4821 12.4670 12.5817 12.3818 12.5465 12.5898 12.8370 12.6147 12.4985 12.6198 12.3423 12.4559 Al2O3 wt% 18.5187 18.1620 18.4516 18.1656 17.7538 18.0364 18.4035 18.0807 18.2723 18.8205 18.2865 18.5992 18.5411 18.4500 SiO2 wt% 36.9003 36.9217 36.8399 36.7947 37.1268 37.1892 37.0846 37.2040 37.5877 37.4823 36.7125 37.1525 36.8695 36.7890 Cl wt% 0.0038 0.0116 0.0000 0.0031 0.0170 0.0000 0.0000 0.0116 0.0015 0.0031 0.0000 0.0247 0.0008 0.0216 K2O wt% 9.2623 9.4672 9.4715 9.1866 9.5306 9.2966 9.2839 9.6233 9.2986 9.5921 9.6012 9.6670 9.5861 9.4410 CaO wt% 0.0709 0.0699 0.0117 0.0175 0.0373 0.0186 0.0606 0.0665 0.0909 0.0268 0.0432 0.0466 0.1038 0.0140 TiO2 wt% 1.4399 1.2790 1.3828 1.3368 1.2728 1.1803 1.1414 1.2673 1.1555 1.1652 1.0980 1.0296 1.1086 1.2902 Cr2O3 wt% 0.8252 0.8397 0.9035 0.8605 0.9204 0.9980 0.8238 0.9889 1.1349 1.3729 1.2023 0.9232 1.2840 1.2425 MnO wt% 0.0575 0.0814 0.0068 0.0339 0.0747 0.0000 0.0000 0.0272 0.0476 0.0407 0.0204 0.0237 0.0000 0.0034 FeO wt% 15.7850 15.3637 15.3184 15.6101 15.1982 15.4552 15.3577 14.8079 14.9903 15.2270 15.0436 15.8320 15.6392 14.7303 OH- wt% 3.9380 3.9950 3.9386 3.9131 3.9854 3.9618 3.9166 3.9175 3.9127 4.0188 3.9319 4.0339 3.9657 3.8741 Total Oxide wt% 99.43 98.83 99.01 98.64 98.60 98.71 98.93 98.86 99.72 100.52 98.64 100.08 99.71 98.65 Si 2.76 2.77 2.76 2.77 2.79 2.79 2.78 2.79 2.79 2.76 2.76 2.76 2.75 2.77 Al (VI) 1.24 1.23 1.24 1.23 1.21 1.21 1.22 1.21 1.21 1.24 1.24 1.24 1.25 1.23 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.39 0.37 0.39 0.38 0.36 0.39 0.40 0.39 0.39 0.40 0.39 0.38 0.38 0.40 Mg 1.38 1.40 1.39 1.40 1.41 1.39 1.40 1.41 1.42 1.39 1.40 1.40 1.37 1.40 Fe 0.99 0.96 0.96 0.98 0.96 0.97 0.96 0.93 0.93 0.94 0.95 0.98 0.98 0.93 Mn 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.08 0.07 0.08 0.08 0.07 0.07 0.06 0.07 0.06 0.06 0.06 0.06 0.06 0.07 sum (Y) 2.84 2.82 2.82 2.84 2.80 2.81 2.83 2.80 2.81 2.79 2.80 2.82 2.79 2.80 K 0.88 0.91 0.91 0.88 0.91 0.89 0.89 0.92 0.88 0.90 0.92 0.92 0.91 0.91 Na 0.02 0.02 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.02 0.02 Ca 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 Cr 0.05 0.05 0.05 0.05 0.05 0.06 0.05 0.06 0.07 0.08 0.07 0.05 0.08 0.07 sum (X) 0.96 0.98 0.97 0.95 0.99 0.97 0.96 1.00 0.97 0.99 1.01 0.99 1.02 1.00 (OH) 1.96 2.00 1.97 1.96 2.00 1.98 1.96 1.96 1.94 1.98 1.97 2.00 1.97 1.94 F 0.04 0.00 0.03 0.03 0.00 0.02 0.04 0.04 0.06 0.02 0.03 0.00 0.03 0.05 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 480 Table B.3 (Continued) Sample 34L814-195 (continued) D33003-2004 Biotite Type Biotite + abundant carbonate (part of the biotite-Ti-magnetite ± carbonate assem- blage) Biotite-Ti-magnetite ± carbonate EMPA spot 22 23 24 27 28 29 30 1 3 4 5 10 15 16 F wt% 0.3347 0.0781 0.2027 0.0937 0.1710 0.2115 0.1644 0.0554 0.1603 0.1918 0.0925 0.1751 0.0623 0.2205 Na2O wt% 0.1106 0.0754 0.0640 0.0923 0.1096 0.1023 0.1109 0.1602 0.0948 0.1282 0.1914 0.1334 0.0411 0.1681 MgO wt% 12.1958 12.6178 12.4976 12.3317 12.4391 12.3649 12.5759 7.7553 7.7398 7.8960 7.8634 7.9078 8.0556 11.1883 Al2O3 wt% 18.6209 18.5469 18.5121 18.1317 18.7046 18.1377 18.2399 18.8409 18.3666 18.0787 17.5810 18.6757 17.8309 16.9664 SiO2 wt% 37.2073 37.3135 37.1998 37.1710 37.4352 37.3681 37.5903 35.2860 35.7559 36.0444 35.9614 36.4256 36.9109 37.1149 Cl wt% 0.0000 0.0123 0.0139 0.0046 0.0100 0.0000 0.0046 0.0623 0.0486 0.0691 0.0562 0.0320 0.0487 0.0214 K2O wt% 9.3552 9.3810 9.4270 9.3951 9.2477 9.4520 9.8303 8.9903 9.3833 9.3755 8.8576 9.6745 9.4626 9.1256 CaO wt% 0.0420 0.0292 0.0467 0.0852 0.0524 0.0724 0.0875 0.1422 0.1810 0.2099 0.2624 0.1576 0.2126 0.1339 TiO2 wt% 1.2784 1.3555 1.3390 1.3534 1.4054 1.4796 1.3274 1.5984 1.5368 1.6458 1.6585 1.7817 1.5542 1.5909 Cr2O3 wt% 1.1354 1.2652 1.2195 1.0607 1.1460 1.1678 1.3211 0.0000 0.0000 0.0803 0.0000 0.0000 0.0161 0.0000 MnO wt% 0.0102 0.0748 0.0204 0.0136 0.0441 0.0000 0.0442 0.0000 0.1005 0.0805 0.0503 0.0168 0.0302 0.0473 FeO wt% 14.7494 15.1677 15.0636 14.8709 15.4152 14.6402 14.9769 22.1231 22.1535 21.9823 22.1850 20.6394 21.2392 18.4879 OH- wt% 3.8404 4.0066 3.9242 3.9487 3.9686 3.9054 3.9688 3.8352 3.7936 3.7841 3.8053 3.8278 3.8739 3.8302 Total Oxide wt% 98.88 99.92 99.53 98.55 100.15 98.90 100.24 98.85 99.31 99.57 98.56 99.45 99.34 98.90 Si 2.79 2.76 2.77 2.79 2.77 2.80 2.78 2.73 2.76 2.78 2.79 2.79 2.83 2.82 Al (VI) 1.21 1.24 1.23 1.21 1.23 1.20 1.22 1.27 1.24 1.22 1.21 1.21 1.17 1.18 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.43 0.38 0.40 0.39 0.40 0.40 0.38 0.45 0.43 0.42 0.40 0.47 0.44 0.35 Mg 1.36 1.39 1.39 1.38 1.37 1.38 1.39 0.89 0.89 0.91 0.91 0.90 0.92 1.27 Fe 0.92 0.94 0.94 0.93 0.95 0.92 0.93 1.43 1.43 1.42 1.44 1.32 1.36 1.18 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 Ti 0.07 0.08 0.08 0.08 0.08 0.08 0.07 0.09 0.09 0.10 0.10 0.10 0.09 0.09 sum (Y) 2.80 2.80 2.80 2.78 2.81 2.78 2.77 2.86 2.85 2.84 2.85 2.80 2.81 2.89 K 0.89 0.89 0.90 0.90 0.87 0.90 0.93 0.89 0.92 0.92 0.88 0.94 0.92 0.89 Na 0.02 0.01 0.01 0.01 0.02 0.01 0.02 0.02 0.01 0.02 0.03 0.02 0.01 0.02 Ca 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.02 0.01 Cr 0.07 0.07 0.07 0.06 0.07 0.07 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum (X) 0.98 0.97 0.98 0.98 0.96 0.99 1.03 0.92 0.95 0.96 0.93 0.98 0.95 0.92 (OH) 1.92 1.98 1.95 1.98 1.96 1.95 1.96 1.98 1.95 1.94 1.97 1.95 1.98 1.94 F 0.08 0.02 0.05 0.02 0.04 0.05 0.04 0.01 0.04 0.05 0.02 0.04 0.02 0.05 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.00 0.01 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 481 Table B.3 (Continued) Sample D33003-2004 (continued) DS358-1215 Biotite Type Biotite-Ti-magnetite ± carbonate assemblage Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 18 19 20 22 1 3 4 5 8 9 11 13 14 15 F wt% 0.1390 0.0882 0.1202 0.2889 0.3330 0.3968 0.4543 0.3857 0.4433 0.4159 0.5128 0.2604 0.3759 0.4888 Na2O wt% 0.2153 0.0795 0.1620 0.1651 0.0974 0.0861 0.0771 0.0682 0.1002 0.1318 0.1047 0.0940 0.1077 0.1154 MgO wt% 10.7058 10.4357 10.5719 10.9668 7.2013 7.2509 7.4680 7.5836 7.5285 7.7813 7.2471 6.5179 7.4182 6.9847 Al2O3 wt% 16.9159 17.4280 17.6821 16.9415 18.5445 18.2064 18.8402 18.6268 18.4216 18.2601 18.0963 17.1858 17.7130 18.2364 SiO2 wt% 37.2351 36.6895 36.8606 36.7250 35.0991 35.5145 34.5552 35.0278 34.9310 35.5932 35.4975 35.0193 35.5997 35.4365 Cl wt% 0.0191 0.0160 0.0099 0.0160 0.1661 0.1923 0.1405 0.1075 0.1495 0.1677 0.0946 0.2528 0.2754 0.3091 K2O wt% 9.3774 9.3064 9.4612 8.9936 9.1117 8.9979 8.9968 9.2114 9.2421 9.0661 9.0422 9.2563 9.3306 9.1675 CaO wt% 0.2065 0.1383 0.1534 0.1729 0.0469 0.0160 0.0389 0.0481 0.0332 0.0893 0.0000 0.0570 0.0217 0.0000 TiO2 wt% 1.8344 1.8148 1.8568 1.7514 1.7740 2.1329 1.8477 1.6730 1.7581 1.9179 2.8296 3.6971 2.4848 2.0666 Cr2O3 wt% 0.0000 0.0324 0.0000 0.0000 0.0040 0.0000 0.0000 0.0724 0.0000 0.0725 0.0363 0.0161 0.0000 0.0000 MnO wt% 0.0574 0.0978 0.0878 0.0911 0.0873 0.0973 0.0906 0.1612 0.0772 0.0706 0.1142 0.0436 0.0772 0.0838 FeO wt% 18.7453 19.3157 18.7260 18.9533 22.6724 23.2003 22.7391 22.6162 22.6031 22.4175 22.3923 23.1092 22.7260 23.4060 OH- wt% 3.8814 3.8998 3.9044 3.7819 3.6354 3.6272 3.5769 3.6395 3.5805 3.6321 3.6004 3.6422 3.6123 3.5385 Total Oxide wt% 99.33 99.34 99.60 98.85 98.77 99.72 98.83 99.22 98.87 99.62 99.57 99.15 99.74 99.83 Si 2.82 2.79 2.79 2.81 2.74 2.76 2.71 2.73 2.74 2.76 2.75 2.74 2.76 2.76 Al (VI) 1.18 1.21 1.21 1.19 1.26 1.24 1.29 1.27 1.26 1.24 1.25 1.26 1.24 1.24 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.34 0.35 0.36 0.33 0.45 0.42 0.45 0.44 0.44 0.42 0.41 0.33 0.39 0.43 Mg 1.21 1.18 1.19 1.25 0.84 0.84 0.87 0.88 0.88 0.90 0.84 0.76 0.86 0.81 Fe 1.19 1.23 1.18 1.21 1.48 1.51 1.49 1.47 1.48 1.45 1.45 1.51 1.48 1.52 Mn 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.01 Ti 0.10 0.10 0.11 0.10 0.10 0.12 0.11 0.10 0.10 0.11 0.16 0.22 0.15 0.12 sum (Y) 2.85 2.87 2.85 2.90 2.88 2.90 2.92 2.90 2.90 2.89 2.87 2.82 2.87 2.90 K 0.91 0.90 0.91 0.88 0.91 0.89 0.90 0.92 0.92 0.90 0.89 0.92 0.92 0.91 Na 0.03 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.01 0.02 0.02 Ca 0.02 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum (X) 0.96 0.93 0.95 0.92 0.93 0.90 0.91 0.93 0.94 0.93 0.91 0.94 0.94 0.93 (OH) 1.96 1.98 1.97 1.93 1.90 1.88 1.87 1.89 1.87 1.88 1.86 1.90 1.87 1.84 F 0.03 0.02 0.03 0.07 0.08 0.10 0.11 0.10 0.11 0.10 0.13 0.06 0.09 0.12 Cl 0.00 0.00 0.00 0.00 0.02 0.03 0.02 0.01 0.02 0.02 0.01 0.03 0.04 0.04 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 482 Table B.3 (Continued) Sample DS358-1215 (continued) D2253-75 Biotite Type Biotite-Ti-magnetite ± carbonate assemblage Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 16 17 18 19 20 22 24 25 27 15 16 17 18 19 F wt% 0.5060 0.5412 0.3690 0.3826 0.4741 0.2281 0.5873 0.3514 0.4261 0.2901 0.1866 0.1285 0.2330 0.1817 Na2O wt% 0.0923 0.0920 0.0849 0.0686 0.0936 0.0561 0.0579 0.0860 0.0645 0.1973 0.1383 0.0627 0.1312 0.1023 MgO wt% 7.0159 7.3349 7.3702 7.3683 6.9532 6.7760 7.8102 7.2394 7.2947 8.6391 8.9163 8.7772 8.6293 8.6196 Al2O3 wt% 18.1880 17.7109 17.4267 17.2143 17.4091 16.5585 17.7604 18.2391 17.3560 17.7158 17.7228 17.7800 17.8651 17.9412 SiO2 wt% 34.7945 35.6821 35.0124 35.3820 35.0648 34.7976 35.7112 35.4843 35.0862 35.1224 35.7607 36.0167 35.9040 36.2737 Cl wt% 0.3903 0.3325 0.2113 0.2856 0.3911 0.4104 0.0745 0.1868 0.2527 0.1549 0.0799 0.0875 0.0821 0.0746 K2O wt% 9.2798 8.9921 9.2938 9.2918 9.2574 9.0719 9.0588 9.3205 8.9827 9.3914 9.4780 9.3216 9.3579 9.6155 CaO wt% 0.0605 0.0069 0.0194 0.0160 0.0434 0.0273 0.0378 0.0206 0.0445 0.0885 0.0898 0.0523 0.0443 0.0830 TiO2 wt% 2.2869 2.2306 2.7355 2.7897 2.5103 3.1053 2.2390 2.3094 2.3651 1.8334 1.8213 1.9062 1.9145 1.9272 Cr2O3 wt% 0.0000 0.0000 0.0804 0.0644 0.0362 0.0200 0.0121 0.0000 0.1645 0.1088 0.0000 0.0646 0.0242 0.0849 MnO wt% 0.0972 0.0604 0.0268 0.1007 0.0973 0.1305 0.0504 0.1309 0.1039 0.1476 0.1580 0.0975 0.1746 0.1714 FeO wt% 23.6267 23.3394 23.3227 22.7696 22.9771 24.0258 21.9913 23.1659 23.3781 21.2900 20.9918 20.9413 21.1090 20.6304 OH- wt% 3.4885 3.5084 3.6099 3.5823 3.4741 3.5771 3.5503 3.6646 3.5518 3.6649 3.7750 3.8112 3.7575 3.8058 Total Oxide wt% 99.83 99.83 99.56 99.32 98.78 98.78 98.94 100.20 99.07 98.64 99.12 99.05 99.23 99.51 Si 2.73 2.78 2.73 2.77 2.77 2.75 2.78 2.74 2.76 2.74 2.76 2.77 2.77 2.78 Al (VI) 1.27 1.22 1.27 1.23 1.23 1.25 1.22 1.26 1.24 1.26 1.24 1.23 1.23 1.22 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.40 0.41 0.34 0.35 0.39 0.30 0.41 0.40 0.36 0.37 0.37 0.39 0.39 0.40 Mg 0.82 0.85 0.86 0.86 0.82 0.80 0.91 0.83 0.85 1.01 1.03 1.01 0.99 0.99 Fe 1.55 1.52 1.52 1.49 1.52 1.59 1.43 1.50 1.54 1.39 1.36 1.35 1.36 1.32 Mn 0.01 0.00 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ti 0.13 0.13 0.16 0.16 0.15 0.18 0.13 0.13 0.14 0.11 0.11 0.11 0.11 0.11 sum (Y) 2.91 2.91 2.88 2.87 2.88 2.88 2.89 2.88 2.90 2.88 2.87 2.86 2.87 2.83 K 0.93 0.89 0.93 0.93 0.93 0.92 0.90 0.92 0.90 0.94 0.93 0.92 0.92 0.94 Na 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.03 0.02 0.01 0.02 0.02 Ca 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 sum (X) 0.95 0.91 0.95 0.94 0.95 0.93 0.91 0.93 0.92 0.98 0.96 0.93 0.95 0.97 (OH) 1.82 1.82 1.88 1.87 1.83 1.89 1.85 1.89 1.86 1.91 1.94 1.96 1.93 1.95 F 0.13 0.13 0.09 0.09 0.12 0.06 0.14 0.09 0.11 0.07 0.05 0.03 0.06 0.04 Cl 0.05 0.04 0.03 0.04 0.05 0.06 0.01 0.02 0.03 0.02 0.01 0.01 0.01 0.01 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 483 Table B.3 (Continued) Sample D2253-75 (continued) 06L337-186 Biotite Type Biotite-Ti-magnetite ± carbonate assemblage Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 21 24 25 26 27 28 29 30 4 15 10 20 21 22 F wt% 0.1281 0.1687 0.2037 0.1976 0.2518 0.1634 0.2396 0.2037 0.1368 0.2687 0.0460 0.0968 0.1154 0.1734 Na2O wt% 0.0674 0.0830 0.0443 0.0989 0.0825 0.0943 0.0855 0.0072 0.1477 0.0489 0.1065 0.2621 0.1692 0.1327 MgO wt% 8.7096 8.7048 8.5386 8.7428 8.4231 8.5041 8.3658 8.4607 7.4924 7.9905 7.6436 7.9893 7.8345 8.2079 Al2O3 wt% 17.6416 18.0229 18.3799 17.8851 18.5665 18.3211 18.4212 18.3652 18.7283 18.4165 18.4075 18.0238 18.9040 18.4278 SiO2 wt% 36.0125 35.4024 35.6945 35.5825 35.3989 35.6344 36.2315 35.7923 34.0437 35.3666 35.1312 34.1242 35.2533 35.5206 Cl wt% 0.1054 0.1303 0.1545 0.1363 0.1153 0.1124 0.1666 0.1084 0.1280 0.0945 0.0764 0.2073 0.1222 0.0894 K2O wt% 9.6328 9.5874 9.4267 9.3644 9.4949 9.4631 9.6228 9.7883 9.2052 9.4109 9.5569 8.9474 9.4472 9.2411 CaO wt% 0.0102 0.0739 0.0773 0.1363 0.0558 0.1036 0.0887 0.0421 0.0688 0.0780 0.0068 0.0981 0.0090 0.0000 TiO2 wt% 1.9584 1.7986 1.7578 1.8825 1.7760 1.8238 1.7986 1.6885 1.3343 1.3187 1.5927 1.6557 1.6906 1.6285 Cr2O3 wt% 0.1451 0.0807 0.0888 0.0564 0.1334 0.0364 0.1091 0.1371 0.1792 0.0120 0.0000 0.0000 0.0440 0.0401 MnO wt% 0.1443 0.1511 0.1512 0.1813 0.2152 0.1648 0.1109 0.1075 0.1265 0.0700 0.0667 0.1498 0.1669 0.0869 FeO wt% 21.8458 21.4756 21.3446 21.6667 20.4815 21.1925 21.0106 21.5571 23.2974 22.8395 22.6182 23.3763 22.2740 21.5827 OH- wt% 3.8276 3.7691 3.7626 3.7633 3.7223 3.7882 3.7635 3.7837 3.7170 3.7188 3.8194 3.7154 3.8088 3.7696 Total Oxide wt% 100.23 99.45 99.62 99.69 98.72 99.40 100.01 100.04 98.61 99.63 99.07 98.65 99.84 98.90 Si 2.76 2.73 2.75 2.74 2.74 2.74 2.77 2.75 2.68 2.74 2.73 2.68 2.71 2.75 Al (VI) 1.24 1.27 1.25 1.26 1.26 1.26 1.23 1.25 1.32 1.26 1.27 1.32 1.29 1.25 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.35 0.37 0.41 0.37 0.44 0.41 0.43 0.41 0.41 0.42 0.41 0.35 0.43 0.43 Mg 0.99 1.00 0.98 1.00 0.97 0.98 0.95 0.97 0.88 0.92 0.88 0.94 0.90 0.95 Fe 1.40 1.39 1.37 1.40 1.33 1.36 1.34 1.38 1.53 1.48 1.47 1.54 1.43 1.40 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.01 Ti 0.11 0.10 0.10 0.11 0.10 0.11 0.10 0.10 0.08 0.08 0.09 0.10 0.10 0.09 sum (Y) 2.87 2.88 2.87 2.89 2.85 2.86 2.84 2.86 2.91 2.91 2.86 2.93 2.87 2.87 K 0.94 0.94 0.92 0.92 0.94 0.93 0.94 0.96 0.92 0.93 0.95 0.90 0.93 0.91 Na 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.02 0.01 0.02 0.04 0.03 0.02 Ca 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.00 Cr 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 sum (X) 0.96 0.97 0.94 0.95 0.96 0.95 0.97 0.97 0.96 0.94 0.96 0.95 0.96 0.93 (OH) 1.96 1.94 1.93 1.93 1.92 1.95 1.92 1.94 1.95 1.92 1.98 1.95 1.96 1.95 F 0.03 0.04 0.05 0.05 0.06 0.04 0.06 0.05 0.03 0.07 0.01 0.02 0.03 0.04 Cl 0.01 0.02 0.02 0.02 0.02 0.01 0.02 0.01 0.02 0.01 0.01 0.03 0.02 0.01 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 484 Table B.3 (Continued) Sample 06L337-186 (continued) CB1912V Biotite Type Biotite-Ti-magnetite ± carbonate assem-blage Brown biotite-quartz assemblage EMPA spot 23 25 27 30 1 2 3 5 6 9 10 11 12 13 F wt% 0.1910 0.1211 0.0920 0.0288 0.2806 0.1488 0.0000 0.4203 0.2189 0.2665 0.1335 0.2022 0.1400 0.0312 Na2O wt% 0.0887 0.0883 0.0602 0.0892 0.1155 0.0651 0.0985 0.0766 0.0723 0.1182 0.1291 0.0900 0.0422 0.1112 MgO wt% 7.9908 8.4212 7.8592 7.6643 14.0558 14.1623 13.9302 14.0197 13.8449 13.7532 14.1691 13.2268 12.9485 12.9431 Al2O3 wt% 18.4381 18.5220 18.6864 18.6263 18.2492 18.1618 18.1071 18.1786 18.6644 18.0281 17.9364 18.2563 18.1691 17.6836 SiO2 wt% 35.3180 35.3471 35.1496 34.7759 38.0525 37.6226 37.3889 37.1575 37.0533 37.5999 38.0307 37.4367 36.7674 37.6377 Cl wt% 0.0802 0.0391 0.0938 0.0487 0.0439 0.0270 0.0224 0.0108 0.0386 0.0363 0.0402 0.0416 0.0323 0.0431 K2O wt% 9.7741 9.6143 9.4033 9.6906 9.9068 9.4406 9.7700 9.5298 9.7540 9.8282 9.5573 9.8182 10.0091 9.4966 CaO wt% 0.0124 0.0249 0.0068 0.0350 0.2543 0.2183 0.1964 0.1248 0.0771 0.1414 0.1519 0.3928 0.0280 0.1678 TiO2 wt% 1.6710 1.1448 1.2121 1.5454 1.5145 1.4620 1.5540 1.6005 1.4170 1.4661 1.4768 1.4497 1.5689 1.6008 Cr2O3 wt% 0.0281 0.0000 0.0480 0.0600 0.3150 0.5173 0.3537 0.3780 0.4752 0.5851 0.5936 0.4483 0.4901 0.5068 MnO wt% 0.1469 0.0602 0.0834 0.0867 0.0408 0.0000 0.0647 0.0476 0.0578 0.0000 0.0408 0.0611 0.0000 0.0170 FeO wt% 21.7611 21.4836 22.1466 22.5033 13.7603 13.0693 13.0352 13.4422 13.3010 13.1180 13.1033 14.5751 14.4219 14.4991 OH- wt% 3.7590 3.7964 3.7856 3.8285 3.9372 3.9640 4.0226 3.8076 3.9097 3.8856 3.9864 3.9340 3.9095 3.9876 Total Oxide wt% 99.26 98.66 98.63 98.98 100.53 98.86 98.54 98.79 98.88 98.83 99.35 99.93 98.53 98.73 Si 2.74 2.74 2.74 2.71 2.80 2.79 2.78 2.78 2.76 2.80 2.81 2.78 2.77 2.81 Al (VI) 1.26 1.26 1.26 1.29 1.20 1.21 1.22 1.22 1.24 1.20 1.19 1.22 1.23 1.19 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.42 0.44 0.45 0.41 0.38 0.38 0.37 0.38 0.40 0.39 0.37 0.37 0.38 0.37 Mg 0.92 0.97 0.91 0.89 1.54 1.57 1.55 1.56 1.54 1.53 1.56 1.46 1.45 1.44 Fe 1.41 1.39 1.44 1.46 0.85 0.81 0.81 0.84 0.83 0.82 0.81 0.90 0.91 0.91 Mn 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.10 0.07 0.07 0.09 0.08 0.08 0.09 0.09 0.08 0.08 0.08 0.08 0.09 0.09 sum (Y) 2.86 2.88 2.88 2.86 2.85 2.84 2.82 2.88 2.85 2.82 2.82 2.83 2.83 2.81 K 0.97 0.95 0.93 0.96 0.93 0.89 0.93 0.91 0.93 0.93 0.90 0.93 0.96 0.91 Na 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.01 0.02 Ca 0.00 0.00 0.00 0.00 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.03 0.00 0.01 Cr 0.00 0.00 0.00 0.00 0.02 0.03 0.02 0.02 0.03 0.03 0.03 0.03 0.03 0.03 sum (X) 0.98 0.97 0.95 0.98 0.98 0.95 0.98 0.95 0.97 1.00 0.97 1.00 1.00 0.96 (OH) 1.94 1.97 1.96 1.99 1.93 1.96 2.00 1.90 1.94 1.93 1.96 1.95 1.96 1.99 F 0.05 0.03 0.02 0.01 0.07 0.03 0.00 0.10 0.05 0.06 0.03 0.05 0.03 0.01 Cl 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 485 Table B.3 (Continued) Sample CB1912V (continued) Biotite Type Brown biotite-quartz assemblage EMPA spot 14 15 17 118 19 20 21 22 23 24 26 27 28 29 F wt% 0.3967 0.3878 0.1787 0.2330 0.2876 0.0000 0.1016 0.1243 0.3415 0.4798 0.3888 0.2558 0.1166 0.1015 Na2O wt% 0.0967 0.0745 0.0396 0.0949 0.0753 0.0471 0.1438 0.0808 0.0850 0.0837 0.0722 0.0737 0.0539 0.0943 MgO wt% 13.1617 12.9302 12.7558 12.8569 12.8036 12.2372 12.1240 12.4084 12.5721 12.4773 11.8041 12.3285 12.3533 12.6986 Al2O3 wt% 18.3435 18.4554 17.8087 17.5461 17.6847 17.6691 18.3355 18.2371 17.8554 17.8191 17.4933 18.2702 18.4855 18.4968 SiO2 wt% 37.4070 37.9299 37.6293 37.5507 37.2036 37.0260 37.4138 37.4651 37.5516 37.7360 39.2160 37.0577 36.5162 37.1989 Cl wt% 0.0454 0.0455 0.0308 0.0277 0.0315 0.0345 0.0993 0.0392 0.0469 0.0261 0.0293 0.0330 0.0561 0.0285 K2O wt% 9.9274 9.6593 9.6386 9.8378 9.7264 9.6725 9.6687 9.9418 9.9637 9.7073 9.5596 9.9350 9.8229 10.0867 CaO wt% 0.0899 0.1049 0.1328 0.1327 0.1186 0.0511 0.1736 0.0384 0.0407 0.0815 0.1363 0.0500 0.0570 0.1737 TiO2 wt% 1.4321 1.4990 1.4368 1.5482 1.5896 1.5598 1.9247 1.9062 1.9395 1.9689 1.7123 1.8619 1.8903 1.8100 Cr2O3 wt% 0.5287 0.4022 0.7152 0.6733 1.0404 0.6077 0.4902 0.5099 0.4307 0.3303 0.4144 0.4848 0.5977 0.4150 MnO wt% 0.0068 0.0611 0.0678 0.0746 0.0847 0.0676 0.0611 0.0305 0.0780 0.0780 0.0238 0.0000 0.0339 0.0339 FeO wt% 14.0278 14.5209 14.8843 14.9925 15.1430 15.9473 14.4216 15.2709 15.0764 15.1369 14.8290 15.2243 15.0718 14.4392 OH- wt% 3.8137 3.8491 3.9222 3.8929 3.8636 3.9771 3.9376 3.9698 3.8443 3.7790 3.8455 3.8752 3.9225 3.9752 Total Oxide wt% 99.28 99.92 99.24 99.46 99.65 98.90 98.90 100.02 99.83 99.70 99.52 99.45 98.98 99.55 Si 2.79 2.81 2.81 2.81 2.78 2.79 2.80 2.78 2.80 2.82 2.91 2.77 2.74 2.77 Al (VI) 1.21 1.19 1.19 1.19 1.22 1.21 1.20 1.22 1.20 1.18 1.09 1.23 1.26 1.23 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.41 0.42 0.38 0.35 0.34 0.35 0.41 0.38 0.37 0.39 0.44 0.39 0.38 0.39 Mg 1.47 1.43 1.42 1.43 1.43 1.37 1.35 1.37 1.40 1.39 1.31 1.38 1.38 1.41 Fe 0.88 0.90 0.93 0.94 0.95 1.00 0.90 0.95 0.94 0.95 0.92 0.95 0.95 0.90 Mn 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ti 0.08 0.08 0.08 0.09 0.09 0.09 0.11 0.11 0.11 0.11 0.10 0.10 0.11 0.10 sum (Y) 2.83 2.84 2.81 2.82 2.81 2.82 2.78 2.81 2.83 2.84 2.77 2.82 2.82 2.80 K 0.95 0.91 0.92 0.94 0.93 0.93 0.92 0.94 0.95 0.93 0.91 0.95 0.94 0.96 Na 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ca 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.01 Cr 0.03 0.02 0.04 0.04 0.06 0.04 0.03 0.03 0.03 0.02 0.02 0.03 0.04 0.02 sum (X) 1.00 0.96 0.98 1.00 1.01 0.98 0.99 0.99 0.99 0.96 0.95 0.99 0.99 1.01 (OH) 1.90 1.90 1.95 1.94 1.93 2.00 1.96 1.97 1.91 1.88 1.90 1.94 1.97 1.97 F 0.09 0.09 0.04 0.06 0.07 0.00 0.02 0.03 0.08 0.11 0.09 0.06 0.03 0.02 Cl 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 486 Table B.3 (Continued) Sample CB1912V (continued) 34L006-1235 D39018-43 Biotite Type Brown biotite- quartz Biotite-Ti-magnetite ± carbonate assemblage Biotite + abundant carbonate (part of the biotite-Ti-magnetite ± carbonate EMPA spot 30 6 7 8 111 15 23 25 28 30 6 7 9 10 F wt% 0.1486 0.3096 0.3507 0.3175 0.2396 0.3117 0.3796 0.3625 0.2365 0.4027 0.1262 0.0000 0.0000 0.1096 Na2O wt% 0.1481 0.1327 0.0814 0.0985 0.0480 0.0681 0.2084 0.0934 0.1091 0.2323 0.0647 0.0497 0.1256 0.0388 MgO wt% 12.2066 8.0549 8.3603 8.7133 8.9255 8.4912 8.1836 8.4052 8.3644 8.0588 13.9709 14.2412 14.4081 14.3277 Al2O3 wt% 18.1607 16.4767 16.1779 16.2106 16.5908 16.6478 17.5797 17.4608 17.6317 18.7455 19.5873 19.2213 19.5123 18.8550 SiO2 wt% 37.5787 35.3407 35.1162 35.3639 34.5881 35.6090 35.3118 35.0677 35.0232 36.3988 38.4697 37.6398 38.4519 37.9339 Cl wt% 0.0254 0.0695 0.0546 0.0471 0.0569 0.0411 0.0690 0.0718 0.0390 0.0654 0.0000 0.0085 0.0078 0.0155 K2O wt% 9.9300 8.9151 9.1789 8.9763 8.8008 9.1497 9.2552 9.5293 9.4569 8.6189 9.7886 10.1469 9.6950 10.0539 CaO wt% 0.0757 0.1755 0.2117 0.1160 0.3265 0.0721 0.2553 0.1049 0.1605 1.2648 0.0400 0.0470 0.0247 0.0047 TiO2 wt% 2.0850 2.4311 2.5507 2.6686 1.8936 2.6062 1.6048 1.8478 1.6739 1.2653 1.2254 1.2857 1.3278 1.2913 Cr2O3 wt% 0.3772 0.1075 0.0080 0.2157 0.1434 0.1877 0.0400 0.1239 0.0841 0.0040 0.1186 0.0000 0.1650 0.0000 MnO wt% 0.0849 0.2596 0.1998 0.1866 0.1565 0.2066 0.1869 0.1500 0.1502 0.2110 0.1266 0.1504 0.0547 0.0990 FeO wt% 14.4409 23.6693 23.1438 22.7942 23.5096 22.9865 22.1274 22.2368 22.0096 20.4624 12.3724 12.7547 12.8528 13.1072 OH- wt% 3.9434 3.6807 3.6420 3.6881 3.6936 3.7205 3.6388 3.6485 3.7141 3.7048 4.0555 4.0805 4.1463 4.0277 Total Oxide wt% 99.21 99.62 99.08 99.40 98.97 100.10 98.84 99.10 98.65 99.43 99.95 99.63 100.77 99.86 Si 2.80 2.76 2.75 2.75 2.71 2.75 2.76 2.74 2.74 2.79 2.80 2.76 2.78 2.79 Al (VI) 1.20 1.24 1.25 1.25 1.29 1.25 1.24 1.26 1.26 1.21 1.20 1.24 1.22 1.21 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.40 0.27 0.25 0.24 0.25 0.27 0.38 0.35 0.36 0.48 0.48 0.43 0.44 0.42 Mg 1.36 0.94 0.98 1.01 1.04 0.98 0.95 0.98 0.97 0.92 1.52 1.56 1.55 1.57 Fe 0.90 1.54 1.52 1.48 1.54 1.49 1.45 1.45 1.44 1.31 0.75 0.78 0.78 0.80 Mn 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 Ti 0.12 0.14 0.15 0.16 0.11 0.15 0.09 0.11 0.10 0.07 0.07 0.07 0.07 0.07 sum (Y) 2.78 2.91 2.91 2.91 2.96 2.90 2.89 2.90 2.88 2.80 2.83 2.85 2.85 2.87 K 0.94 0.89 0.92 0.89 0.88 0.90 0.92 0.95 0.94 0.84 0.91 0.95 0.89 0.94 Na 0.02 0.02 0.01 0.01 0.01 0.01 0.03 0.01 0.02 0.03 0.01 0.01 0.02 0.01 Ca 0.01 0.01 0.02 0.01 0.03 0.01 0.02 0.01 0.01 0.10 0.00 0.00 0.00 0.00 Cr 0.02 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.01 0.00 sum (X) 0.99 0.93 0.95 0.93 0.92 0.93 0.98 0.98 0.98 0.98 0.93 0.96 0.92 0.95 (OH) 1.96 1.91 1.91 1.92 1.93 1.92 1.90 1.90 1.94 1.89 1.97 2.00 2.00 1.97 F 0.04 0.08 0.09 0.08 0.06 0.08 0.09 0.09 0.06 0.10 0.03 0.00 0.00 0.03 Cl 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 487 Table B.3 (Continued) Sample D39018-43 (continued) Biotite Type Biotite + abundant carbonate (part of the biotite-Ti-magnetite ± carbonate assemblage) EMPA spot 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 F wt% 0.0865 0.0000 0.1731 0.0000 0.0000 0.0716 0.0396 0.0000 0.0000 0.1270 0.0159 0.0555 0.0398 0.1667 0.0000 Na2O wt% 0.0359 0.1106 0.0772 0.0842 0.0828 0.0524 0.0759 0.0773 0.0718 0.0844 0.0802 0.0788 0.0359 0.0580 0.0729 MgO wt% 14.5708 14.2683 14.3976 14.3511 14.5314 13.9741 15.0746 14.6101 15.0597 14.6481 14.7445 14.7388 14.6203 14.5084 14.2328 Al2O3 wt% 18.8320 19.2308 19.2940 19.3705 19.0394 19.0289 18.7586 18.4427 17.6415 18.2613 18.8695 18.1820 18.2344 18.1783 18.9384 SiO2 wt% 38.0158 38.0872 38.1241 38.3809 38.3139 38.1915 37.9590 37.8805 38.8279 38.2928 37.6497 37.9192 38.3369 38.2020 38.0899 Cl wt% 0.0202 0.0000 0.0116 0.0000 0.0000 0.0000 0.0023 0.0000 0.0000 0.0031 0.0015 0.0101 0.0000 0.0000 0.0008 K2O wt% 10.0976 9.7812 10.1078 9.9978 9.8347 9.7603 10.0888 10.1075 9.7796 9.8189 10.0215 9.9095 9.7283 9.9093 9.7977 CaO wt% 0.0129 0.0528 0.0329 0.0000 0.0153 0.0375 0.0141 0.0340 0.0082 0.0375 0.0434 0.0000 0.0059 0.0035 0.0258 TiO2 wt% 1.2217 1.2397 1.3544 1.1788 1.2052 2.0902 1.8295 2.1500 2.2085 2.1582 2.0542 2.0721 2.1684 2.2117 2.1121 Cr2O3 wt% 0.0381 0.0423 0.0593 0.0000 0.0000 0.0169 0.0212 0.1100 0.0931 0.0212 0.0677 0.0381 0.1016 0.0423 0.0932 MnO wt% 0.1367 0.0718 0.0342 0.0683 0.1128 0.3076 0.3146 0.2323 0.4066 0.3146 0.3725 0.3688 0.3724 0.2767 0.3179 FeO wt% 12.7404 12.9433 12.5596 13.0002 12.8407 12.0894 12.4367 12.3971 12.2703 12.4185 12.5539 12.4049 12.2282 12.2030 11.9276 OH- wt% 4.0434 4.1062 4.0236 4.1311 4.1149 4.0708 4.1089 4.1058 4.1335 4.0497 4.1110 4.0625 4.0918 4.0123 4.1090 Total Oxide wt% 99.85 99.93 100.25 100.56 100.09 99.69 100.72 100.15 100.50 100.24 100.59 99.84 99.96 99.77 99.72 Si 2.79 2.78 2.78 2.79 2.79 2.79 2.76 2.77 2.82 2.79 2.74 2.78 2.80 2.80 2.78 Al (VI) 1.21 1.22 1.22 1.21 1.21 1.21 1.24 1.23 1.18 1.21 1.26 1.22 1.20 1.20 1.22 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.41 0.44 0.44 0.44 0.43 0.43 0.36 0.35 0.32 0.36 0.36 0.35 0.36 0.37 0.41 Mg 1.59 1.55 1.57 1.55 1.58 1.52 1.63 1.59 1.63 1.59 1.60 1.61 1.59 1.59 1.55 Fe 0.78 0.79 0.77 0.79 0.78 0.74 0.76 0.76 0.74 0.76 0.76 0.76 0.75 0.75 0.73 Mn 0.01 0.00 0.00 0.00 0.01 0.02 0.02 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Ti 0.07 0.07 0.07 0.06 0.07 0.11 0.10 0.12 0.12 0.12 0.11 0.11 0.12 0.12 0.12 sum (Y) 2.86 2.85 2.85 2.85 2.86 2.82 2.87 2.83 2.84 2.85 2.86 2.86 2.84 2.84 2.82 K 0.94 0.91 0.94 0.93 0.91 0.91 0.93 0.94 0.90 0.91 0.93 0.93 0.91 0.93 0.91 Na 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 sum (X) 0.95 0.93 0.96 0.94 0.93 0.92 0.95 0.96 0.92 0.93 0.95 0.94 0.92 0.94 0.93 (OH) 1.98 2.00 1.96 2.00 2.00 1.98 1.99 2.00 2.00 1.97 2.00 1.99 1.99 1.96 2.00 F 0.02 0.00 0.04 0.00 0.00 0.02 0.01 0.00 0.00 0.03 0.00 0.01 0.01 0.04 0.00 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 488 Table B.3 (Continued) Sample D39018-43 (continued) RL437461B Biotite Type Biotite + abundant carbonate (part of the biotite-Ti-magnetite ± carbonate assem- blage) Brown biotite-quartz assemblage EMPA spot 26 27 28 30 1 3 4 6 7 8 10 11 12 13 14 F wt% 0.0636 0.0797 0.1830 0.0000 0.1821 0.2925 0.0000 0.2856 0.1666 0.2062 0.0952 0.0159 0.1191 0.2691 0.0000 Na2O wt% 0.0594 0.0605 0.0759 0.0810 0.1117 0.1119 0.1073 0.1035 0.1308 0.0649 0.0746 0.1792 0.1371 0.1266 0.1294 MgO wt% 14.5747 14.8018 14.5071 14.9884 15.2396 15.1376 15.0154 14.8013 15.1314 15.0916 15.0389 15.2611 15.2638 15.5462 15.4583 Al2O3 wt% 18.6163 18.3234 18.4239 18.4237 17.4527 17.9996 18.0852 18.0435 17.3266 16.7503 18.1799 17.5778 17.6020 17.1980 17.6661 SiO2 wt% 37.5348 38.1843 38.4255 38.2362 38.6607 38.1024 37.9890 38.2434 38.3894 39.3492 37.7648 38.1636 38.0493 38.8165 37.8674 Cl wt% 0.0000 0.0163 0.0000 0.0085 0.0371 0.0000 0.0147 0.0000 0.0000 0.0100 0.0201 0.0518 0.0495 0.0472 0.0580 K2O wt% 9.7398 9.6572 9.9703 9.7973 9.4635 9.6429 9.8481 9.8540 9.3886 9.7137 9.7052 9.6306 9.5981 9.6609 9.6986 CaO wt% 0.0410 0.0164 0.1336 0.0317 0.0912 0.0526 0.0714 0.0339 0.1146 0.0631 0.0152 0.0504 0.0515 0.0480 0.0621 TiO2 wt% 2.1028 2.1439 2.1478 1.8223 1.6125 1.5741 1.6861 1.8247 1.7372 1.8018 1.7135 1.5328 1.5353 1.5589 1.5320 Cr2O3 wt% 0.0720 0.1187 0.1313 0.0381 0.9629 1.0890 0.9936 1.0096 0.9086 0.9460 1.1101 1.0036 0.8505 0.9044 0.8542 MnO wt% 0.3419 0.3897 0.3314 0.2598 0.0511 0.0613 0.0784 0.0477 0.0750 0.0000 0.0477 0.0375 0.0682 0.1091 0.0273 FeO wt% 12.2321 11.8231 12.1649 11.9767 12.2695 12.3745 11.9132 12.1970 11.9973 12.3741 12.3695 11.3834 11.6049 12.0697 12.1532 OH- wt% 4.0499 4.0605 4.0339 4.1072 4.0116 3.9637 4.0992 3.9696 4.0022 4.0150 4.0514 4.0543 3.9959 3.9677 4.0696 Total Oxide wt% 99.43 99.68 100.53 99.77 100.15 100.40 99.90 100.41 99.37 100.39 100.19 98.94 98.93 100.32 99.58 Si 2.76 2.79 2.80 2.79 2.82 2.78 2.78 2.79 2.82 2.87 2.76 2.81 2.81 2.83 2.78 Al (VI) 1.24 1.21 1.20 1.21 1.18 1.22 1.22 1.21 1.18 1.13 1.24 1.19 1.19 1.17 1.22 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.37 0.37 0.38 0.37 0.32 0.34 0.33 0.35 0.32 0.31 0.33 0.33 0.34 0.31 0.31 Mg 1.60 1.61 1.57 1.63 1.66 1.65 1.64 1.61 1.66 1.64 1.64 1.67 1.68 1.69 1.69 Fe 0.75 0.72 0.74 0.73 0.75 0.76 0.73 0.75 0.74 0.75 0.76 0.70 0.72 0.74 0.75 Mn 0.02 0.02 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 Ti 0.12 0.12 0.12 0.10 0.09 0.09 0.09 0.10 0.10 0.10 0.09 0.08 0.09 0.09 0.08 sum (Y) 2.86 2.85 2.83 2.85 2.82 2.83 2.80 2.81 2.82 2.80 2.82 2.79 2.82 2.83 2.83 K 0.91 0.90 0.93 0.91 0.88 0.90 0.92 0.92 0.88 0.90 0.91 0.90 0.90 0.90 0.91 Na 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.01 0.02 0.01 0.01 0.03 0.02 0.02 0.02 Ca 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Cr 0.00 0.01 0.01 0.00 0.06 0.06 0.06 0.06 0.05 0.05 0.06 0.06 0.05 0.05 0.05 sum (X) 0.93 0.92 0.95 0.93 0.96 0.98 1.00 0.99 0.96 0.97 0.98 0.99 0.98 0.97 0.98 (OH) 1.99 1.98 1.96 2.00 1.95 1.93 2.00 1.93 1.96 1.95 1.98 1.99 1.97 1.93 1.99 F 0.01 0.02 0.04 0.00 0.04 0.07 0.00 0.07 0.04 0.05 0.02 0.00 0.03 0.06 0.00 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 489 Table B.3 (Continued) Sample RL437461B (continued) CB4043FV Biotite Type Brown biotite-quartz assemblage Brown biotite- quartz EMPA spot 15 16 17 19 20 21 22 24 25 26 27 28 29 30 1 F wt% 0.1499 0.3869 0.3314 0.1910 0.1681 0.1271 0.0000 0.2464 0.3016 0.0717 0.0000 0.2863 0.0240 0.1756 0.0861 Na2O wt% 0.1315 0.1441 0.1084 0.1812 0.2287 0.0496 0.0935 0.0954 0.0965 0.1073 0.0878 0.1201 0.0662 0.0673 0.0777 MgO wt% 16.0397 15.7959 15.8085 15.6124 15.2794 15.1682 15.2037 14.6805 15.0204 14.6703 14.8441 14.9808 14.8502 15.1512 14.2924 Al2O3 wt% 17.7095 17.7770 17.5444 17.4079 17.1524 18.2582 17.8860 17.5481 17.6458 17.6425 17.5930 18.0822 17.9486 17.2031 17.5913 SiO2 wt% 37.5969 38.2378 37.4919 37.9795 37.9525 38.5287 38.2072 38.4762 38.2731 38.9358 39.3190 38.2989 38.2536 38.4371 38.1122 Cl wt% 0.0673 0.0564 0.0348 0.0726 0.0394 0.0124 0.0031 0.0186 0.0224 0.0000 0.0047 0.0000 0.0000 0.0093 0.0325 K2O wt% 9.1852 9.8020 9.3736 9.6489 9.7697 9.8090 9.4450 9.4531 9.7436 9.3735 9.2257 9.7985 9.8981 9.6273 9.3636 CaO wt% 0.0070 0.0199 0.0538 0.0421 0.0363 0.0902 0.0959 0.0328 0.0644 0.0949 0.0937 0.0784 0.0702 0.0445 0.0912 TiO2 wt% 1.4696 1.5842 1.5735 1.5406 1.6676 1.5684 1.5698 1.7118 1.6124 1.6879 1.5349 1.6165 1.7188 1.7629 1.6638 Cr2O3 wt% 0.7482 0.7443 0.7609 1.3749 1.3941 1.0322 1.0904 1.1120 1.0153 0.8764 0.9322 1.3028 1.1804 0.9112 0.2530 MnO wt% 0.0682 0.0784 0.0853 0.0307 0.0205 0.0239 0.0307 0.0921 0.0785 0.0546 0.0103 0.0239 0.0819 0.0786 0.0546 FeO wt% 11.8450 11.9063 11.8056 11.6075 11.0855 12.1619 11.9918 12.0797 11.9859 11.7937 11.6065 12.0581 12.0105 11.4495 13.2432 OH- wt% 3.9779 3.9043 3.8781 3.9714 3.9620 4.0773 4.1048 3.9585 3.9326 4.0679 4.1164 3.9794 4.1014 3.9816 3.9996 Total Oxide wt% 99.00 100.44 98.85 99.66 98.76 100.91 99.72 99.51 99.79 99.38 99.37 100.63 100.20 98.90 98.86 Si 2.77 2.79 2.78 2.79 2.81 2.79 2.79 2.83 2.81 2.85 2.86 2.79 2.79 2.83 2.82 Al (VI) 1.23 1.21 1.22 1.21 1.19 1.21 1.21 1.17 1.19 1.15 1.14 1.21 1.21 1.17 1.18 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.31 0.33 0.31 0.30 0.30 0.35 0.33 0.35 0.34 0.37 0.37 0.34 0.33 0.33 0.36 Mg 1.76 1.72 1.75 1.71 1.69 1.64 1.66 1.61 1.64 1.60 1.61 1.63 1.61 1.67 1.58 Fe 0.73 0.73 0.73 0.71 0.69 0.74 0.73 0.74 0.74 0.72 0.71 0.73 0.73 0.71 0.82 Mn 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Ti 0.08 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.08 0.09 0.09 0.10 0.09 sum (Y) 2.89 2.87 2.88 2.81 2.77 2.81 2.81 2.80 2.81 2.78 2.78 2.80 2.78 2.80 2.85 K 0.86 0.91 0.89 0.90 0.92 0.91 0.88 0.89 0.91 0.87 0.86 0.91 0.92 0.91 0.88 Na 0.02 0.02 0.02 0.03 0.03 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.01 0.01 Ca 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.01 Cr 0.04 0.04 0.04 0.08 0.08 0.06 0.06 0.06 0.06 0.05 0.05 0.08 0.07 0.05 0.01 sum (X) 0.93 0.98 0.95 1.01 1.04 0.98 0.96 0.97 0.99 0.95 0.93 1.01 1.00 0.97 0.92 (OH) 1.96 1.90 1.92 1.95 1.96 1.97 2.00 1.94 1.93 1.98 2.00 1.93 1.99 1.96 1.98 F 0.03 0.09 0.08 0.04 0.04 0.03 0.00 0.06 0.07 0.02 0.00 0.07 0.01 0.04 0.02 Cl 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 490 Table B.3 (Continued) Sample CB4043FV (continued) Biotite Type Brown biotite-quartz assemblage EMPA spot 2 3 4 7 8 12 13 14 15 16 17 18 19 20 27 F wt% 0.0000 0.0938 0.2185 0.1704 0.0000 0.2259 0.0935 0.2661 0.0850 0.0775 0.0780 0.0000 0.1561 0.2029 0.0384 Na2O wt% 0.0432 0.0461 0.0475 0.0704 0.0618 0.0648 0.1110 0.0987 0.0753 0.1994 0.1130 0.0382 0.1156 0.1364 0.0602 MgO wt% 14.4441 14.1315 14.4489 14.1802 13.6768 13.7956 14.0127 13.7614 13.8781 13.8931 13.6185 13.7129 13.5850 13.5474 13.0575 Al2O3 wt% 17.6821 17.1516 17.4590 16.8597 17.5471 18.0317 17.5501 17.8779 17.4004 17.1302 17.4412 17.3938 17.7945 17.8861 17.1861 SiO2 wt% 38.1845 38.9620 38.0653 38.0779 38.2218 37.8659 37.4861 37.8306 37.7835 37.7592 38.0524 37.6174 37.5256 37.6635 37.1289 Cl wt% 0.0278 0.0402 0.0317 0.0471 0.0317 0.0185 0.0734 0.0224 0.0525 0.0641 0.0456 0.0147 0.0533 0.0695 0.0278 K2O wt% 9.3718 9.3580 9.7183 9.4083 9.6357 9.6171 9.3725 9.3359 9.0972 9.2666 9.4856 9.6788 9.6971 9.7256 9.3066 CaO wt% 0.0514 0.0152 0.0363 0.0514 0.0082 0.0269 0.0817 0.0490 0.0676 0.0047 0.0245 0.0491 0.0456 0.0538 0.2018 TiO2 wt% 1.7217 1.8080 1.8093 1.8309 1.7289 1.6800 1.6579 1.9374 1.7467 1.6250 1.8092 1.8080 1.7296 1.6949 1.7180 Cr2O3 wt% 0.3199 0.2948 0.2654 0.1722 0.1765 0.5678 0.5464 0.9509 0.5983 0.5666 0.6303 0.6804 0.7486 0.6146 0.0878 MnO wt% 0.0341 0.0171 0.0750 0.0000 0.0034 0.0784 0.1124 0.0477 0.0985 0.0306 0.1056 0.0477 0.0307 0.0000 0.0204 FeO wt% 13.8391 13.9589 13.9189 14.7203 14.5666 14.5296 14.3299 14.3731 15.7381 15.0659 14.7872 14.9662 14.5138 14.2668 16.4877 OH- wt% 4.0756 4.0316 3.9548 3.9463 4.0542 3.9617 3.9730 3.9444 4.0177 3.9861 4.0179 4.0511 3.9593 3.9302 3.9741 Total Oxide wt% 99.80 99.91 100.05 99.54 99.71 100.46 99.40 100.50 100.64 99.67 100.21 100.06 99.95 99.79 99.30 Si 2.80 2.86 2.81 2.83 2.82 2.79 2.78 2.78 2.78 2.80 2.81 2.78 2.78 2.79 2.78 Al (VI) 1.20 1.14 1.19 1.17 1.18 1.21 1.22 1.22 1.22 1.20 1.19 1.22 1.22 1.21 1.22 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.33 0.34 0.32 0.30 0.35 0.35 0.32 0.33 0.29 0.30 0.32 0.30 0.33 0.36 0.30 Mg 1.58 1.55 1.59 1.57 1.50 1.51 1.55 1.51 1.52 1.54 1.50 1.51 1.50 1.50 1.46 Fe 0.85 0.86 0.86 0.91 0.90 0.89 0.89 0.88 0.97 0.94 0.91 0.93 0.90 0.88 1.03 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 Ti 0.10 0.10 0.10 0.10 0.10 0.09 0.09 0.11 0.10 0.09 0.10 0.10 0.10 0.09 0.10 sum (Y) 2.86 2.85 2.88 2.89 2.85 2.86 2.86 2.84 2.89 2.87 2.84 2.84 2.83 2.83 2.89 K 0.88 0.88 0.91 0.89 0.91 0.90 0.89 0.88 0.85 0.88 0.89 0.91 0.92 0.92 0.89 Na 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.03 0.02 0.01 0.02 0.02 0.01 Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.02 Cr 0.02 0.02 0.02 0.01 0.01 0.03 0.03 0.06 0.03 0.03 0.04 0.04 0.04 0.04 0.01 sum (X) 0.91 0.90 0.94 0.92 0.93 0.95 0.94 0.95 0.91 0.94 0.95 0.96 0.98 0.98 0.92 (OH) 2.00 1.97 1.95 1.95 2.00 1.95 1.97 1.94 1.97 1.97 1.98 2.00 1.96 1.94 1.99 F 0.00 0.02 0.05 0.04 0.00 0.05 0.02 0.06 0.02 0.02 0.02 0.00 0.04 0.05 0.01 Cl 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 491 Table B.3 (Continued) Sample CB4043FV (continued) 30L1268-574 Biotite Type Brown biotite- quartz Brow Brown biotite-quartz assemblage n biotite-quartz assemblage EMPA spot 28 3 4 5 6 7 8 9 10 11 12 13 14 15 16 F wt% 0.0538 0.9549 0.7868 1.0821 0.6807 0.8184 0.7368 0.7451 0.8566 1.0165 0.6569 0.8189 0.6965 0.9939 0.8759 Na2O wt% 0.0831 0.1609 0.1343 0.1305 0.1726 0.1135 0.1071 0.0857 0.1157 0.0515 0.1154 0.1260 0.0989 0.0679 0.1003 MgO wt% 12.6894 10.1511 9.5508 9.7409 9.9584 9.9618 10.1782 9.7253 10.3785 10.3569 10.1364 10.3518 9.8463 9.7965 9.6692 Al2O3 wt% 17.5932 18.5887 19.2759 18.7102 18.7804 18.3019 18.3922 18.3404 18.4389 18.3010 18.9326 18.8465 18.8213 19.1311 18.0985 SiO2 wt% 36.9223 36.7150 37.4273 36.8151 36.2259 36.7748 36.5232 36.6932 36.8104 36.9082 37.0571 36.3969 36.2059 36.5950 36.3862 Cl wt% 0.0054 0.0461 0.0377 0.0377 0.0407 0.0430 0.0177 0.0215 0.0461 0.0215 0.0154 0.0584 0.0169 0.0384 0.0368 K2O wt% 9.3514 9.4733 9.6463 9.3854 9.1875 9.5292 9.6101 9.5598 9.4729 9.6200 9.4983 9.4964 9.4839 9.5362 9.4362 CaO wt% 0.0583 0.0383 0.0500 0.0895 0.0719 0.0035 0.0035 0.0000 0.0000 0.0058 0.0000 0.0151 0.0093 0.0302 0.0301 TiO2 wt% 1.7968 1.7249 1.7277 1.7492 1.7278 1.9751 1.6831 2.2102 1.5417 1.4812 1.6375 1.6976 1.8418 1.7838 2.5113 Cr2O3 wt% 0.1505 0.0373 0.0291 0.0000 0.0248 0.0331 0.0000 0.0538 0.0041 0.0000 0.0000 0.0456 0.0455 0.0538 0.0539 MnO wt% 0.0612 0.2402 0.1288 0.2167 0.2264 0.1826 0.1591 0.2028 0.2674 0.1928 0.1829 0.1760 0.1521 0.2062 0.1826 FeO wt% 16.3447 18.3566 18.2223 18.4472 19.5130 19.2503 18.7011 19.3909 18.5356 19.0371 18.3219 18.6693 19.5461 19.5798 18.8337 OH- wt% 3.9658 3.4690 3.6027 3.4007 3.6091 3.5501 3.5739 3.5954 3.5209 3.4509 3.6575 3.5428 3.6097 3.4846 3.4912 Total Oxide wt% 99.08 99.96 100.62 99.81 100.22 100.54 99.69 100.62 99.99 100.44 100.21 100.24 100.37 101.30 99.71 Si 2.77 2.80 2.82 2.81 2.76 2.79 2.79 2.78 2.80 2.81 2.80 2.77 2.75 2.77 2.79 Al (VI) 1.23 1.20 1.18 1.19 1.24 1.21 1.21 1.22 1.20 1.19 1.20 1.23 1.25 1.23 1.21 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.33 0.47 0.52 0.50 0.44 0.43 0.44 0.42 0.46 0.45 0.48 0.45 0.44 0.47 0.42 Mg 1.42 1.15 1.07 1.11 1.13 1.13 1.16 1.10 1.18 1.18 1.14 1.17 1.12 1.10 1.10 Fe 1.03 1.17 1.15 1.18 1.24 1.22 1.19 1.23 1.18 1.21 1.16 1.19 1.24 1.24 1.21 Mn 0.00 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 Ti 0.10 0.10 0.10 0.10 0.10 0.11 0.10 0.13 0.09 0.08 0.09 0.10 0.11 0.10 0.14 sum (Y) 2.88 2.91 2.85 2.90 2.92 2.90 2.90 2.89 2.92 2.94 2.88 2.92 2.91 2.93 2.89 K 0.90 0.92 0.93 0.92 0.89 0.92 0.94 0.92 0.92 0.93 0.91 0.92 0.92 0.92 0.92 Na 0.01 0.02 0.02 0.02 0.03 0.02 0.02 0.01 0.02 0.01 0.02 0.02 0.01 0.01 0.01 Ca 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Cr 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum (X) 0.92 0.95 0.95 0.94 0.92 0.94 0.95 0.94 0.94 0.94 0.93 0.94 0.94 0.94 0.94 (OH) 1.99 1.76 1.81 1.73 1.83 1.80 1.82 1.82 1.79 1.75 1.84 1.80 1.83 1.76 1.78 F 0.01 0.23 0.19 0.26 0.16 0.20 0.18 0.18 0.21 0.24 0.16 0.20 0.17 0.24 0.21 Cl 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 492 Table B.3 (Continued) Sample 30L1268-574 (continued) CB302561 Biotite Type Brown biotite-quartz assemblage Brown biotite-quartz assemblage EMPA spot 17 18 19 20 24 25 26 27 30 2 3 4 5 6 7 F wt% 0.8849 0.8812 0.7734 0.8572 0.7247 0.5984 0.5799 0.7889 0.6589 0.3027 0.1013 0.2573 0.3574 0.0705 0.2810 Na2O wt% 0.0887 0.0953 0.0485 0.0778 0.1695 0.1058 0.1153 0.1592 0.1339 0.0850 0.1185 0.1160 0.1227 0.0803 0.0416 MgO wt% 9.5678 9.8596 9.8942 9.8041 9.6776 9.6176 9.1350 9.0921 9.3306 14.8771 14.6199 14.2904 14.4200 14.8427 14.8867 Al2O3 wt% 18.6031 18.6354 18.9924 19.0752 18.5220 18.4637 19.4349 19.3998 19.4587 16.5085 17.0625 17.1166 17.1953 16.7501 17.0318 SiO2 wt% 36.3897 36.5536 36.4467 37.0412 36.1266 35.6447 35.5674 35.7302 35.9873 38.4032 38.7423 38.4717 37.5845 39.5842 39.6059 Cl wt% 0.0238 0.0177 0.0277 0.0284 0.0475 0.0268 0.0330 0.0391 0.0484 0.0201 0.0108 0.0216 0.0331 0.0278 0.0178 K2O wt% 9.4974 9.6823 9.5309 9.4373 9.3057 9.3027 9.1712 9.6021 9.0665 9.2922 9.7204 9.5205 9.6192 9.5155 9.5568 CaO wt% 0.0035 0.0023 0.0023 0.0395 0.0544 0.0000 0.0615 0.0244 0.0325 0.0653 0.0140 0.1014 0.1096 0.0000 0.0444 TiO2 wt% 2.1122 1.8352 1.5537 1.8222 2.1770 2.2641 1.9958 1.8986 1.4389 1.4877 1.5984 1.7522 1.6824 1.5343 1.5158 Cr2O3 wt% 0.0372 0.0249 0.0787 0.0207 0.1856 0.1940 0.1242 0.1035 0.0869 0.3232 0.3650 0.5034 0.2686 0.3155 0.2733 MnO wt% 0.1622 0.1185 0.2064 0.0880 0.1485 0.0675 0.1692 0.1386 0.1386 0.0068 0.0442 0.0577 0.0509 0.0714 0.0884 FeO wt% 19.4165 18.4625 18.9194 18.7991 20.3256 20.3852 19.1969 19.0666 19.0296 13.7350 14.0481 13.9923 13.7430 13.2394 13.4252 OH- wt% 3.5064 3.5012 3.5657 3.5588 3.5970 3.6366 3.6292 3.5241 3.5853 3.8818 4.0440 3.9436 3.8352 4.0681 3.9820 Total Oxide wt% 100.29 99.67 100.04 100.65 101.06 100.31 99.21 99.57 99.00 98.99 100.49 100.14 99.02 100.10 100.75 Si 2.77 2.79 2.77 2.80 2.74 2.72 2.73 2.74 2.76 2.86 2.84 2.83 2.81 2.89 2.88 Al (VI) 1.23 1.21 1.23 1.20 1.26 1.28 1.27 1.26 1.24 1.14 1.16 1.17 1.19 1.11 1.12 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.45 0.47 0.48 0.49 0.40 0.38 0.48 0.50 0.52 0.30 0.31 0.32 0.32 0.33 0.34 Mg 1.09 1.12 1.12 1.10 1.09 1.09 1.04 1.04 1.07 1.65 1.60 1.57 1.61 1.61 1.62 Fe 1.24 1.18 1.20 1.19 1.29 1.30 1.23 1.22 1.22 0.85 0.86 0.86 0.86 0.81 0.82 Mn 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 Ti 0.12 0.11 0.09 0.10 0.12 0.13 0.12 0.11 0.08 0.08 0.09 0.10 0.09 0.08 0.08 sum (Y) 2.90 2.89 2.91 2.89 2.91 2.91 2.88 2.88 2.90 2.89 2.86 2.85 2.88 2.84 2.86 K 0.92 0.94 0.93 0.91 0.90 0.91 0.90 0.94 0.89 0.88 0.91 0.89 0.92 0.89 0.89 Na 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.02 0.02 0.01 0.01 Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 Cr 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.03 0.02 0.02 0.02 sum (X) 0.94 0.96 0.94 0.92 0.94 0.93 0.93 0.97 0.91 0.92 0.95 0.95 0.96 0.92 0.91 (OH) 1.78 1.78 1.81 1.79 1.82 1.85 1.86 1.80 1.83 1.93 1.98 1.94 1.91 1.98 1.93 F 0.21 0.21 0.19 0.20 0.17 0.14 0.14 0.19 0.16 0.07 0.02 0.06 0.08 0.02 0.06 Cl 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 493 Table B.3 (Continued) Sample CB302561 (continued) 34L235-944 Biotite Type Brown biotite-quartz assemblage Brown biotite-quartz assemblage EMPA spot 8 9 10 11 12 13 16 17 18 19 27 28 29 1 2 F wt% 0.1175 0.2648 0.3500 0.0624 0.1795 0.0000 0.2710 0.2338 0.2394 0.3414 0.4139 0.2894 0.2430 0.0623 0.0543 Na2O wt% 0.0971 0.0625 0.0997 0.0697 0.0584 0.0918 0.0810 0.0528 0.0854 0.0824 0.0664 0.1133 0.0607 0.1366 0.1882 MgO wt% 14.6756 14.6865 14.8416 14.3151 14.8430 14.5524 14.8491 15.0209 14.8218 14.9454 15.1926 15.1517 15.2027 11.6003 11.1128 Al2O3 wt% 16.6787 17.0615 16.7866 17.4975 16.8048 18.1850 16.7204 16.3088 16.5047 16.3101 17.0448 16.7578 16.6645 18.0310 18.4480 SiO2 wt% 39.3645 38.8235 39.6324 38.3068 39.0695 37.1728 38.4343 39.1802 38.2494 38.7955 38.7686 38.7181 39.2417 38.1334 36.9046 Cl wt% 0.0116 0.0000 0.0085 0.0231 0.0000 0.0247 0.0193 0.0000 0.0224 0.0000 0.0131 0.0209 0.0232 0.0361 0.0169 K2O wt% 9.2258 9.5938 9.4750 9.6503 9.3117 9.5289 9.3388 9.3670 9.3205 9.2595 9.4718 9.4639 9.3801 9.4527 9.5425 CaO wt% 0.0128 0.0058 0.0000 0.0000 0.0408 0.0280 0.1329 0.0874 0.1561 0.1783 0.0759 0.0584 0.0234 0.0685 0.1427 TiO2 wt% 1.5140 1.5394 1.3184 1.4818 1.6421 1.5328 1.6596 1.6601 1.4847 1.6070 1.7090 1.6501 1.5471 2.1910 2.0831 Cr2O3 wt% 0.4121 0.2437 0.3234 0.5454 0.3277 0.3230 0.0671 0.2057 0.1466 0.2265 0.1179 0.1937 0.2107 0.6383 0.5042 MnO wt% 0.1088 0.0306 0.0340 0.0781 0.0646 0.0000 0.0713 0.1121 0.0441 0.1087 0.1429 0.0885 0.1396 0.0135 0.0000 FeO wt% 13.1950 13.5588 13.4001 13.8949 13.5927 13.9070 14.1709 13.5072 14.4104 13.9906 12.9579 12.8163 12.6807 15.5227 15.6689 OH- wt% 4.0240 3.9478 3.9272 4.0410 4.0038 4.0464 3.9220 3.9632 3.9167 3.8945 3.8756 3.9157 3.9558 4.0114 3.9535 Total Oxide wt% 99.44 99.82 100.20 99.97 99.94 99.39 99.74 99.70 99.40 99.74 99.85 99.24 99.37 99.90 98.62 Si 2.89 2.86 2.90 2.82 2.86 2.75 2.84 2.88 2.84 2.87 2.85 2.86 2.89 2.82 2.78 Al (VI) 1.11 1.14 1.10 1.18 1.14 1.25 1.16 1.12 1.16 1.13 1.15 1.14 1.11 1.18 1.22 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.33 0.34 0.35 0.33 0.32 0.34 0.30 0.30 0.29 0.29 0.33 0.32 0.33 0.40 0.41 Mg 1.61 1.61 1.62 1.57 1.62 1.60 1.64 1.65 1.64 1.65 1.67 1.67 1.67 1.28 1.25 Fe 0.81 0.83 0.82 0.85 0.83 0.86 0.88 0.83 0.90 0.86 0.80 0.79 0.78 0.96 0.99 Mn 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.00 Ti 0.08 0.09 0.07 0.08 0.09 0.09 0.09 0.09 0.08 0.09 0.09 0.09 0.09 0.12 0.12 sum (Y) 2.84 2.87 2.87 2.85 2.87 2.89 2.91 2.88 2.91 2.90 2.90 2.88 2.87 2.76 2.77 K 0.86 0.90 0.88 0.91 0.87 0.90 0.88 0.88 0.88 0.87 0.89 0.89 0.88 0.89 0.92 Na 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.03 Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.01 Cr 0.02 0.01 0.02 0.03 0.02 0.02 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.04 0.03 sum (X) 0.90 0.92 0.92 0.95 0.90 0.93 0.91 0.91 0.92 0.91 0.91 0.92 0.90 0.96 0.99 (OH) 1.97 1.94 1.92 1.98 1.96 2.00 1.93 1.95 1.94 1.92 1.90 1.93 1.94 1.98 1.98 F 0.03 0.06 0.08 0.01 0.04 0.00 0.06 0.05 0.06 0.08 0.10 0.07 0.06 0.01 0.01 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 494 Table B.3 (Continued) Sample 34L235-944 (continued) D39018-3562 Biotite Type Brown biotite-quartz assemblage Biotite-Ti-magnetite ± carbon-ate assemblage EMPA spot 4 6 8 10 12 14 17 24 26 27 28 29 1 2 4 F wt% 0.0388 0.3246 0.1090 0.1471 0.0777 0.0233 0.0620 0.1319 0.0000 0.2017 0.0000 0.2098 0.1192 0.3134 0.2003 Na2O wt% 0.1473 0.0891 0.0801 0.1319 0.1044 0.1303 0.1397 0.1030 0.1252 0.0786 0.1163 0.1216 0.1813 0.1491 0.1698 MgO wt% 11.2198 11.2455 11.4041 11.1467 11.2422 11.5082 11.4280 10.9933 11.0685 11.4123 11.2303 11.2213 11.0404 10.9185 11.5097 Al2O3 wt% 18.3461 18.0764 18.1700 18.1594 18.2905 17.9141 19.0132 18.4176 18.1834 18.0369 18.0630 18.5894 18.3765 18.4234 17.3383 SiO2 wt% 36.8688 36.4354 36.9275 36.9207 36.9320 38.0020 36.2976 36.7822 37.0000 36.9762 37.1090 36.5516 35.0096 35.1656 35.8105 Cl wt% 0.0261 0.0391 0.0054 0.0590 0.0314 0.0261 0.0138 0.0123 0.0192 0.0161 0.0314 0.0299 0.0015 0.0183 0.0137 K2O wt% 9.3556 9.5201 9.4861 9.6447 9.3900 9.4277 9.3896 9.4219 9.2497 9.3319 9.3693 9.6297 9.5980 9.6753 9.4890 CaO wt% 0.1101 0.0348 0.0000 0.0290 0.0139 0.0000 0.0534 0.0267 0.0209 0.0267 0.0023 0.0186 0.0323 0.0185 0.0000 TiO2 wt% 2.0533 2.1211 2.0440 1.9887 2.0755 2.1281 1.6710 2.0799 2.1622 2.0261 2.1201 2.1114 1.6423 1.6317 1.5929 Cr2O3 wt% 0.7742 0.9396 1.1538 0.9026 1.0367 0.9364 0.9787 0.8741 0.9441 0.9703 1.1144 0.9254 0.0284 0.0528 0.0000 MnO wt% 0.0101 0.0574 0.0237 0.0270 0.0169 0.0439 0.0237 0.0270 0.0000 0.0203 0.0000 0.0406 0.0438 0.0000 0.0809 FeO wt% 15.9318 16.1274 15.6498 16.1397 15.7880 16.1780 15.6172 15.8268 16.4351 15.6993 16.2408 15.7310 18.8811 18.8812 19.0077 OH- wt% 3.9649 3.7907 3.9396 3.8995 3.9479 4.0379 3.9486 3.9099 3.9962 3.8777 4.0002 3.8747 3.8528 3.7530 3.8179 Total Oxide wt% 98.85 98.80 98.99 99.20 98.95 100.36 98.64 98.61 99.20 98.67 99.40 99.05 98.81 99.00 99.03 Si 2.77 2.76 2.77 2.78 2.77 2.81 2.73 2.77 2.77 2.79 2.78 2.75 2.68 2.70 2.74 Al (VI) 1.23 1.24 1.23 1.22 1.23 1.19 1.27 1.23 1.23 1.21 1.22 1.25 1.32 1.30 1.26 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.40 0.38 0.38 0.39 0.39 0.37 0.42 0.41 0.38 0.39 0.37 0.40 0.35 0.37 0.31 Mg 1.26 1.27 1.28 1.25 1.26 1.27 1.28 1.24 1.24 1.28 1.25 1.26 1.26 1.25 1.31 Fe 1.00 1.02 0.98 1.02 0.99 1.00 0.98 1.00 1.03 0.99 1.02 0.99 1.21 1.21 1.22 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Ti 0.12 0.12 0.12 0.11 0.12 0.12 0.09 0.12 0.12 0.11 0.12 0.12 0.09 0.09 0.09 sum (Y) 2.77 2.80 2.76 2.77 2.76 2.76 2.78 2.76 2.77 2.78 2.76 2.77 2.92 2.92 2.93 K 0.90 0.92 0.91 0.93 0.90 0.89 0.90 0.91 0.88 0.90 0.89 0.93 0.94 0.95 0.93 Na 0.02 0.01 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.02 0.03 0.02 0.03 Ca 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Cr 0.05 0.06 0.07 0.05 0.06 0.05 0.06 0.05 0.06 0.06 0.07 0.06 0.00 0.00 0.00 sum (X) 0.97 0.99 0.99 1.00 0.98 0.96 0.99 0.98 0.96 0.97 0.98 1.00 0.97 0.97 0.95 (OH) 1.99 1.92 1.97 1.96 1.98 1.99 1.98 1.97 2.00 1.95 2.00 1.95 1.97 1.92 1.95 F 0.01 0.08 0.03 0.04 0.02 0.01 0.01 0.03 0.00 0.05 0.00 0.05 0.03 0.08 0.05 Cl 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 495 Table B.3 (Continued) Sample D39018-3562 (continued) Biotite Type Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 F wt% 0.0563 0.0378 0.1007 0.1885 0.2697 0.1630 0.0501 0.0752 0.0692 0.0943 0.0947 0.0443 0.1762 0.0313 0.1393 Na2O wt% 0.1261 0.1216 0.1747 0.1994 0.2048 0.1939 0.1730 0.1657 0.1468 0.1992 0.1552 0.2190 0.1767 0.1979 0.1468 MgO wt% 11.6350 11.6111 11.4469 11.0890 11.8070 11.5366 11.5972 11.4428 11.9410 11.8375 12.0248 11.8902 11.9926 11.9449 11.6300 Al2O3 wt% 17.2428 17.0929 17.3147 18.3078 17.0750 17.6244 17.4268 18.6114 17.5779 17.8369 17.2522 17.2038 17.0881 17.1069 17.1812 SiO2 wt% 35.9861 36.1632 36.1982 35.0300 36.2099 35.4509 36.3197 35.1526 36.5471 36.4905 37.2920 36.9104 37.1681 36.4684 37.0599 Cl wt% 0.0252 0.0382 0.0137 0.0038 0.0107 0.0069 0.0015 0.0130 0.0000 0.0054 0.0229 0.0138 0.0214 0.0000 0.0199 K2O wt% 9.4478 9.5737 9.4052 9.5169 9.6727 9.4963 9.3837 9.5787 9.5757 9.3066 9.2423 9.4739 9.4381 9.2158 9.6460 CaO wt% 0.0461 0.0242 0.0000 0.0577 0.0138 0.0184 0.0023 0.0392 0.0923 0.0577 0.0889 0.0868 0.0520 0.0945 0.0740 TiO2 wt% 1.5311 1.6118 1.8549 1.6857 1.5901 1.5924 1.0284 1.2795 1.3838 1.2691 1.3856 1.3169 1.3638 1.3377 1.4948 Cr2O3 wt% 0.0000 0.0000 0.0122 0.0000 0.0000 0.0000 0.0325 0.0811 0.0325 0.0650 0.1302 0.0000 0.0366 0.0000 0.0611 MnO wt% 0.0877 0.0439 0.0978 0.0607 0.1147 0.0573 0.0135 0.0843 0.0506 0.0608 0.0405 0.0541 0.0946 0.0742 0.1149 FeO wt% 19.4679 18.7538 18.7595 18.6664 18.9650 18.7305 18.7058 19.0354 18.6160 18.3116 18.0350 17.6653 18.5626 19.0753 18.1221 OH- wt% 3.9068 3.9017 3.8914 3.8123 3.8082 3.8287 3.9023 3.8986 3.9451 3.9212 3.9380 3.9285 3.8925 3.9411 3.8960 Total Oxide wt% 99.56 98.97 99.27 98.62 99.74 98.70 98.64 99.46 99.98 99.46 99.70 98.81 100.06 99.49 99.59 Si 2.74 2.76 2.75 2.69 2.76 2.72 2.77 2.68 2.75 2.76 2.80 2.80 2.80 2.76 2.80 Al (VI) 1.26 1.24 1.25 1.31 1.24 1.28 1.23 1.32 1.25 1.24 1.20 1.20 1.20 1.24 1.20 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.29 0.30 0.30 0.35 0.29 0.31 0.34 0.35 0.32 0.35 0.33 0.34 0.32 0.29 0.33 Mg 1.32 1.32 1.30 1.27 1.34 1.32 1.32 1.30 1.34 1.33 1.35 1.34 1.35 1.35 1.31 Fe 1.24 1.20 1.19 1.20 1.21 1.20 1.19 1.21 1.17 1.16 1.13 1.12 1.17 1.21 1.15 Mn 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 Ti 0.09 0.09 0.11 0.10 0.09 0.09 0.06 0.07 0.08 0.07 0.08 0.08 0.08 0.08 0.08 sum (Y) 2.94 2.91 2.91 2.92 2.93 2.93 2.92 2.94 2.91 2.91 2.89 2.88 2.91 2.93 2.88 K 0.92 0.93 0.91 0.93 0.94 0.93 0.91 0.93 0.92 0.90 0.89 0.92 0.91 0.89 0.93 Na 0.02 0.02 0.03 0.03 0.03 0.03 0.03 0.02 0.02 0.03 0.02 0.03 0.03 0.03 0.02 Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 sum (X) 0.94 0.95 0.94 0.97 0.97 0.96 0.94 0.96 0.95 0.94 0.92 0.96 0.94 0.93 0.96 (OH) 1.98 1.99 1.97 1.95 1.93 1.96 1.99 1.98 1.98 1.98 1.97 1.99 1.96 1.99 1.96 F 0.01 0.01 0.02 0.05 0.06 0.04 0.01 0.02 0.02 0.02 0.02 0.01 0.04 0.01 0.03 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 496 Table B.3 (Continued) Sample D39018-3562 (continued) 37L482-2057 Biotite Type Biotite-Ti-magnetite ± carbonate assemblage Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 20 21 23 24 25 26 27 28 29 30 4 7 12 15 17 F wt% 0.3057 0.1509 0.0189 0.0000 0.1879 0.0689 0.1880 0.0815 0.1194 0.1261 0.2948 0.2620 0.2839 0.1520 0.1689 Na2O wt% 0.2151 0.1374 0.1938 0.1424 0.1493 0.1128 0.1543 0.1284 0.1897 0.1441 0.1327 0.1659 0.0867 0.1465 0.1090 MgO wt% 11.7441 11.7623 11.4767 11.8185 11.9696 11.7267 11.8871 11.6733 11.9482 11.4362 13.4670 12.8333 13.2666 13.2441 13.5069 Al2O3 wt% 17.7497 17.4188 18.2797 17.6870 16.7758 17.4579 17.3513 17.4779 17.7288 16.8931 16.2672 16.2130 16.1319 16.8948 16.0956 SiO2 wt% 35.7025 36.1315 35.3969 35.8948 36.6693 36.1832 35.8719 35.8337 35.8018 36.2572 37.1440 38.3060 37.5169 37.5106 37.2933 Cl wt% 0.0130 0.0008 0.0015 0.0229 0.0160 0.0168 0.0153 0.0000 0.0175 0.0175 0.0409 0.0000 0.0205 0.0289 0.0220 K2O wt% 9.1806 9.7923 9.5117 9.5151 9.6023 9.5032 9.5751 9.5825 9.4959 9.4999 9.3935 9.1713 9.1379 9.2303 9.3888 CaO wt% 0.0277 0.1004 0.1258 0.0127 0.0138 0.0000 0.0000 0.0000 0.0127 0.0761 0.0497 0.1657 0.0255 0.0417 0.0000 TiO2 wt% 1.2907 1.6864 1.4704 1.4938 1.6022 1.6449 1.6355 1.6416 1.6886 1.8777 1.4155 1.4144 1.2812 1.3565 1.4556 Cr2O3 wt% 0.0568 0.0244 0.0772 0.0567 0.0122 0.0365 0.0690 0.0689 0.0446 0.0609 0.1353 0.2099 0.1971 0.1934 0.1231 MnO wt% 0.0877 0.0776 0.0473 0.0741 0.0202 0.0809 0.0067 0.0607 0.0776 0.1080 0.0509 0.0612 0.0509 0.0850 0.0441 FeO wt% 19.0156 19.1105 18.7041 19.2323 19.3305 19.3039 19.0927 19.1858 18.6827 18.8647 17.6234 16.3650 17.0065 16.4527 17.4446 OH- wt% 3.7734 3.8929 3.9310 3.9557 3.8706 3.9287 3.8484 3.9061 3.8937 3.8678 3.8257 3.8633 3.8187 3.9149 3.8924 Total Oxide wt% 99.16 100.29 99.24 99.91 100.22 100.06 99.70 99.64 99.70 99.23 99.84 99.03 98.82 99.25 99.54 Si 2.73 2.73 2.69 2.72 2.77 2.74 2.73 2.72 2.71 2.76 2.80 2.88 2.84 2.82 2.81 Al (VI) 1.27 1.27 1.31 1.28 1.23 1.26 1.27 1.28 1.29 1.24 1.20 1.12 1.16 1.18 1.19 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.33 0.29 0.33 0.29 0.27 0.29 0.28 0.29 0.30 0.28 0.25 0.32 0.28 0.31 0.24 Mg 1.34 1.33 1.30 1.33 1.35 1.32 1.35 1.32 1.35 1.30 1.51 1.44 1.50 1.48 1.52 Fe 1.22 1.21 1.19 1.22 1.22 1.22 1.21 1.22 1.18 1.20 1.11 1.03 1.08 1.03 1.10 Mn 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 Ti 0.07 0.10 0.08 0.09 0.09 0.09 0.09 0.09 0.10 0.11 0.08 0.08 0.07 0.08 0.08 sum (Y) 2.96 2.92 2.91 2.93 2.93 2.93 2.94 2.93 2.93 2.90 2.96 2.87 2.93 2.91 2.94 K 0.90 0.94 0.92 0.92 0.93 0.92 0.93 0.93 0.92 0.92 0.90 0.88 0.88 0.88 0.90 Na 0.03 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.01 0.02 0.02 Ca 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 sum (X) 0.93 0.97 0.97 0.94 0.95 0.94 0.96 0.95 0.95 0.96 0.94 0.93 0.91 0.92 0.93 (OH) 1.92 1.96 2.00 2.00 1.95 1.98 1.95 1.98 1.97 1.97 1.92 1.94 1.93 1.96 1.96 F 0.07 0.04 0.00 0.00 0.04 0.02 0.05 0.02 0.03 0.03 0.07 0.06 0.07 0.04 0.04 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 497 Table B.3 (Continued) Sample 37L482-205 (continued) GC04002-688 Biotite Type Biotite-Ti-magnetite ± carbonate assemblage Biotite-Ti-magnetite ± carbonate assemblage EMPA spot 19 20 25 26 30 1 2 3 4 5 6 7 8 12 14 F wt% 0.1747 0.1865 0.1324 0.1626 0.1756 0.5730 0.4245 0.4661 0.4952 0.4783 0.3901 0.4955 0.6883 0.5428 0.5348 Na2O wt% 0.1025 0.1136 0.0790 0.0816 0.1127 0.2894 0.1609 0.2468 0.1679 0.1581 0.2006 0.2646 0.1793 0.1673 0.1788 MgO wt% 13.0088 13.2590 13.2121 13.2086 13.5450 11.4479 12.0686 11.7977 11.9780 11.9058 11.8716 12.1719 11.9858 12.0552 11.3183 Al2O3 wt% 16.1723 16.0211 15.9971 16.1693 16.4123 17.5804 17.2979 17.3387 17.0355 17.1820 17.7330 17.4207 17.5244 17.4770 16.3466 SiO2 wt% 37.0667 36.9505 36.7236 36.8304 37.2668 37.2813 36.1990 36.3494 36.2217 36.6148 36.0727 36.1473 35.7609 36.3914 36.8273 Cl wt% 0.0288 0.0189 0.0114 0.0038 0.0167 0.0326 0.0197 0.0144 0.0212 0.0098 0.0189 0.0106 0.0341 0.0000 0.0174 K2O wt% 9.2746 9.4484 9.4409 9.1595 9.3740 8.6438 9.3798 9.2649 9.1261 9.3486 9.0418 8.8189 9.0348 9.2975 9.0683 CaO wt% 0.0197 0.0243 0.0393 0.0254 0.0000 0.7092 0.0000 0.0788 0.0354 0.0046 0.0433 0.0810 0.0057 0.0537 0.1332 TiO2 wt% 1.5462 1.5028 1.5284 1.4636 1.4765 1.5828 1.5185 1.5259 1.5385 1.5160 1.5445 1.4508 1.6314 1.4836 1.5339 Cr2O3 wt% 0.1147 0.0942 0.0573 0.0656 0.0781 0.2169 0.2567 0.2772 0.3056 0.2650 0.4277 0.4605 0.4153 0.2203 0.0972 MnO wt% 0.0644 0.0543 0.0000 0.0780 0.0951 0.1725 0.1485 0.1249 0.1350 0.1925 0.1822 0.1992 0.2227 0.1318 0.0673 FeO wt% 17.7736 17.8690 17.7800 17.5918 16.9464 16.5958 18.1975 18.0816 18.0350 18.0615 17.8765 17.9340 18.1967 17.8389 20.0070 OH- wt% 3.8685 3.8646 3.8752 3.8656 3.8949 3.6721 3.7284 3.7078 3.6715 3.7114 3.7490 3.6958 3.5777 3.6804 3.6637 Total Oxide wt% 99.22 99.41 98.88 98.71 99.39 98.80 99.40 99.27 98.77 99.45 99.15 99.15 99.26 99.34 99.79 Si 2.81 2.80 2.79 2.80 2.81 2.83 2.76 2.77 2.78 2.79 2.75 2.76 2.74 2.77 2.82 Al (VI) 1.19 1.20 1.21 1.20 1.19 1.17 1.24 1.23 1.22 1.21 1.25 1.24 1.26 1.23 1.18 sum (T) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Al (IV) 0.25 0.23 0.23 0.25 0.26 0.40 0.31 0.33 0.32 0.33 0.34 0.32 0.32 0.34 0.29 Mg 1.47 1.50 1.50 1.50 1.52 1.29 1.37 1.34 1.37 1.35 1.35 1.38 1.37 1.37 1.29 Fe 1.13 1.13 1.13 1.12 1.07 1.05 1.16 1.15 1.16 1.15 1.14 1.14 1.17 1.14 1.28 Mn 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 Ti 0.09 0.09 0.09 0.08 0.08 0.09 0.09 0.09 0.09 0.09 0.09 0.08 0.09 0.08 0.09 sum (Y) 2.94 2.95 2.95 2.95 2.94 2.85 2.94 2.92 2.94 2.93 2.92 2.94 2.97 2.94 2.95 K 0.90 0.91 0.92 0.89 0.90 0.84 0.91 0.90 0.89 0.91 0.88 0.86 0.88 0.90 0.88 Na 0.02 0.02 0.01 0.01 0.02 0.04 0.02 0.04 0.02 0.02 0.03 0.04 0.03 0.02 0.03 Ca 0.00 0.00 0.00 0.00 0.00 0.06 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 Cr 0.01 0.01 0.00 0.00 0.00 0.01 0.02 0.02 0.02 0.02 0.03 0.03 0.03 0.01 0.01 sum (X) 0.92 0.94 0.93 0.91 0.92 0.95 0.95 0.96 0.94 0.95 0.94 0.93 0.94 0.95 0.93 (OH) 1.95 1.95 1.97 1.96 1.96 1.86 1.90 1.89 1.88 1.88 1.90 1.88 1.83 1.87 1.87 F 0.04 0.04 0.03 0.04 0.04 0.14 0.10 0.11 0.12 0.12 0.09 0.12 0.17 0.13 0.13 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 sum 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 498 B.4 Amphibole EMPA data This appendix consists of Table B.4 which contains the EMP results of all samples probed for amphibole chemistry analysis. Each column identifies the sample, EMP spot number, the weight percent oxides, stoichiometrically calculated OH- wt%, total oxide (plus OH-), and the ideal ar- rangement of the molar calculated elements in the crystal lattice normalized using the average of 15eNK and 15eK (best representation for Fe3+ and Fe2+ estimated) cations and anions = 23 as outlined by Schumacker (2007). Sample location, metamorphic grade, main alteration assem- blage, mineralization sulfide-oxide assemblage, and distance from ore and surface can be found for all samples in Appendix A.2. 499 Table B.4 Complete electron microprobe data for all samples probed for amphibole chemistry. Sample CR4610-947 EMPA spot 1 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 F wt% 0.2186 0.2482 0.0000 0.0872 0.1671 0.0000 0.0348 0.1913 0.0000 0.1164 0.1097 0.1730 0.2827 0.2249 0.0463 0.1275 Na2O wt% 1.2272 1.1719 1.2237 1.0224 1.3063 1.3235 1.1826 1.1978 1.1332 1.1445 1.2505 1.2822 1.4195 1.2446 1.2289 1.3295 MgO wt% 4.9188 5.3869 5.4466 5.6696 5.3899 5.4987 5.8994 5.3772 5.5270 5.7505 4.9708 5.1579 5.1733 5.5734 5.5991 5.3767 Al2O3 wt% 16.7391 16.8389 16.8559 16.5509 17.0185 16.6613 16.7368 17.0030 16.5180 16.3226 16.9095 17.1117 17.4814 16.8840 16.7770 17.1150 SiO2 wt% 39.8832 39.2818 39.6873 40.0081 38.9427 39.6287 39.5483 39.8107 39.0437 40.1935 39.8146 39.6833 39.8324 39.1518 39.0527 39.4716 Cl wt% 0.0412 0.0283 0.0458 0.0550 0.0359 0.0428 0.0451 0.0397 0.0367 0.0497 0.0359 0.0786 0.0290 0.0237 0.0695 0.0359 K2O wt% 0.4388 0.3671 0.3905 0.3512 0.3462 0.3573 0.3594 0.4228 0.4113 0.3902 0.3637 0.3583 0.3782 0.3319 0.3802 0.3930 CaO wt% 10.4226 10.5880 10.4581 10.9072 10.5026 10.6887 10.3672 10.6967 10.6920 10.6698 10.4936 10.6560 10.4453 10.2735 10.7847 10.7045 TiO2 wt% 0.3589 0.3421 0.3010 0.3369 0.3154 0.3771 0.3029 0.2881 0.3079 0.4945 0.2975 0.2963 0.2946 0.2565 0.3589 0.3142 Cr2O3 wt% 0.0509 0.0122 0.0714 0.0511 0.0265 0.0348 0.0163 0.0552 0.0409 0.0246 0.0204 0.0571 0.0694 0.0122 0.0429 0.0082 MnO wt% 0.2590 0.2526 0.2744 0.2076 0.3393 0.2998 0.3165 0.2763 0.2545 0.2580 0.3278 0.2877 0.2879 0.2879 0.2795 0.2863 FeO wt% 22.1508 21.3799 21.4203 21.1102 21.6995 21.0856 21.0484 21.1995 21.0202 20.9070 21.9040 21.9280 21.5525 21.2209 21.4414 21.2257 OH- wt% 2.1027 2.1012 2.1144 2.1093 2.1051 2.1144 2.1123 2.1042 2.1145 2.1081 2.1088 2.1038 2.0995 2.1026 2.1107 2.1076 Total oxides 98.81 98.00 98.29 98.47 98.20 98.11 97.97 98.66 97.10 98.43 98.61 99.17 99.35 97.59 98.17 98.50 Si 6.08 6.01 6.05 6.08 5.95 6.04 6.03 6.05 6.02 6.11 6.07 6.01 6.02 6.01 5.95 6.00 Al(iv) 1.92 1.99 1.95 1.92 2.05 1.96 1.97 1.95 1.98 1.89 1.93 1.99 1.98 1.99 2.05 2.00 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.09 1.05 1.07 1.04 1.01 1.04 1.03 1.10 1.02 1.04 1.10 1.07 1.13 1.06 0.97 1.07 Ti 0.04 0.04 0.03 0.04 0.04 0.04 0.03 0.03 0.04 0.06 0.03 0.03 0.03 0.03 0.04 0.04 Fe3+ 0.65 0.78 0.73 0.73 0.90 0.76 0.79 0.69 0.81 0.65 0.68 0.78 0.69 0.80 0.91 0.77 Cr 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.00 Mg 1.12 1.23 1.24 1.28 1.23 1.25 1.34 1.22 1.27 1.30 1.13 1.16 1.17 1.27 1.27 1.22 Fe2+ 2.10 1.90 1.92 1.90 1.83 1.91 1.80 1.95 1.87 1.95 2.05 1.95 1.97 1.83 1.80 1.90 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.08 0.06 0.08 0.05 0.05 0.02 0.09 0.05 0.03 0.06 0.06 0.05 0.07 0.09 0.02 0.03 Mn 0.03 0.03 0.04 0.03 0.04 0.04 0.04 0.04 0.03 0.03 0.04 0.04 0.04 0.04 0.04 0.04 Ca 1.70 1.74 1.71 1.77 1.72 1.75 1.69 1.74 1.77 1.74 1.71 1.73 1.69 1.69 1.76 1.74 Na 0.18 0.17 0.18 0.15 0.19 0.19 0.17 0.17 0.17 0.17 0.18 0.19 0.21 0.18 0.18 0.19 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.18 0.18 0.18 0.15 0.20 0.20 0.18 0.18 0.17 0.17 0.19 0.19 0.21 0.19 0.18 0.20 K 0.09 0.07 0.08 0.07 0.07 0.07 0.07 0.08 0.08 0.08 0.07 0.07 0.07 0.06 0.07 0.08 Sum A 0.27 0.25 0.26 0.22 0.26 0.27 0.25 0.26 0.25 0.25 0.26 0.26 0.28 0.25 0.26 0.27 500 Table B.4 (Continued) Sample CR4610-947 (continued) GC01018-85.3 EMPA spot 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 1 F wt% 0.0349 0.1391 0.0000 0.0289 0.1039 0.1968 0.1271 0.2204 0.0000 0.0403 0.2193 0.2419 0.3064 0.1273 0.0869 0.3403 Na2O wt% 1.2776 1.1858 0.9362 0.8983 0.9794 1.0660 1.0972 1.0244 1.0635 1.0904 1.1468 1.1248 1.1863 1.1098 1.1130 1.0251 MgO wt% 5.5184 5.3735 4.8055 4.2253 4.5339 5.1479 5.1434 5.0003 4.8066 5.4377 5.4745 5.4056 5.3104 5.3605 4.9179 5.5381 Al2O3 wt% 16.7324 17.1425 16.0750 16.2226 16.6353 16.4471 16.5081 16.6250 16.5413 16.4273 16.4526 16.2592 16.3730 16.7696 16.8299 15.7263 SiO2 wt% 39.9531 39.6637 40.2039 40.1596 39.6628 39.6866 39.5389 39.9186 39.9271 39.5066 39.7877 39.6835 39.6069 39.2935 39.1400 40.9634 Cl wt% 0.0352 0.0298 0.0206 0.0404 0.0419 0.0389 0.0397 0.0465 0.0252 0.0496 0.0382 0.0420 0.0588 0.0389 0.0443 0.0000 K2O wt% 0.3613 0.3651 0.3306 0.3574 0.3749 0.3745 0.3668 0.4037 0.4126 0.3545 0.3500 0.3783 0.4307 0.3913 0.4153 0.2570 CaO wt% 10.3565 10.6555 10.7080 10.9320 10.9750 11.0299 10.9439 11.0607 10.6995 10.3494 10.6718 10.6218 10.7857 10.8246 10.6669 10.9958 TiO2 wt% 0.3051 0.2590 0.3245 0.7034 0.2996 0.3140 0.3839 0.3759 0.3386 0.3444 0.3185 0.3735 0.3576 0.3456 0.3326 0.2396 Cr2O3 wt% 0.0143 0.0143 0.0102 0.0325 0.0590 0.0592 0.0326 0.0388 0.0346 0.0509 0.0469 0.0367 0.0082 0.0449 0.1061 0.0984 MnO wt% 0.3635 0.3014 0.2389 0.2471 0.2840 0.3261 0.2408 0.3446 0.2775 0.3408 0.1908 0.2792 0.2962 0.3011 0.2661 0.6491 FeO wt% 20.8768 21.2121 22.5081 22.8876 22.4092 21.8716 22.0296 21.7262 22.2228 22.4454 21.6788 22.0870 21.4620 21.7309 21.5598 20.1292 OH- wt% 2.1130 2.1072 2.1153 2.1134 2.1089 2.1037 2.1074 2.1024 2.1152 2.1118 2.1025 2.1011 2.0972 2.1073 2.1097 2.0975 Total oxides 97.94 98.45 98.28 98.85 98.47 98.66 98.56 98.89 98.46 98.55 98.48 98.63 98.28 98.45 97.59 98.06 Si 6.10 6.03 6.16 6.14 6.07 6.05 6.03 6.07 6.10 6.02 6.06 6.05 6.06 5.99 6.03 6.26 Al(iv) 1.90 1.97 1.84 1.86 1.93 1.95 1.97 1.93 1.90 1.98 1.94 1.95 1.94 2.01 1.97 1.74 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.11 1.10 1.06 1.07 1.07 1.00 0.99 1.06 1.08 0.97 1.02 0.97 1.02 1.00 1.08 1.09 Ti 0.04 0.03 0.04 0.08 0.03 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.03 Fe3+ 0.64 0.73 0.64 0.55 0.70 0.80 0.81 0.70 0.65 0.86 0.77 0.81 0.75 0.85 0.71 0.53 Cr 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 Mg 1.26 1.22 1.10 0.96 1.03 1.17 1.17 1.13 1.09 1.23 1.24 1.23 1.21 1.22 1.13 1.26 Fe2+ 1.96 1.92 2.16 2.33 2.15 1.99 1.98 2.06 2.13 1.90 1.93 1.94 1.98 1.89 2.02 2.04 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 4.97 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.07 0.05 0.07 0.04 0.02 0.00 0.02 0.00 0.06 0.11 0.07 0.06 0.02 0.03 0.04 0.00 Mn 0.05 0.04 0.03 0.03 0.04 0.04 0.03 0.04 0.04 0.04 0.02 0.04 0.04 0.04 0.03 0.08 Ca 1.69 1.74 1.76 1.79 1.80 1.80 1.79 1.80 1.75 1.69 1.74 1.74 1.77 1.77 1.76 1.80 Na 0.19 0.17 0.14 0.13 0.14 0.16 0.16 0.15 0.16 0.16 0.17 0.16 0.17 0.16 0.16 0.12 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.19 0.18 0.14 0.13 0.15 0.16 0.16 0.15 0.16 0.16 0.17 0.17 0.18 0.17 0.17 0.19 K 0.07 0.07 0.06 0.07 0.07 0.07 0.07 0.08 0.08 0.07 0.07 0.07 0.08 0.08 0.08 0.05 Sum A 0.26 0.25 0.20 0.20 0.22 0.23 0.24 0.23 0.24 0.23 0.24 0.24 0.26 0.24 0.25 0.24 501 Table B.4 (Continued) Sample GC01018-85.3 (continued) EMPA spot 2 3 4 5 6 7 8 10 11 12 13 14 15 16 18 19 F wt% 0.3750 0.2572 0.2451 0.2284 0.3674 0.3043 0.3341 0.2797 0.1681 0.2336 0.2218 0.4321 0.2214 0.4361 0.4437 0.2091 Na2O wt% 0.9690 0.9128 0.9536 1.0065 1.2273 1.0439 0.9363 0.9781 1.1215 0.9777 1.0862 1.1560 1.1171 0.9890 1.3856 1.2125 MgO wt% 4.6239 5.7074 5.5891 4.6788 4.7756 4.8638 4.7873 4.2408 4.0842 3.9554 4.1861 5.3536 4.7051 5.2896 5.0628 4.4209 Al2O3 wt% 17.5768 15.6663 15.2846 17.0568 17.0556 16.8253 16.6486 17.5059 17.3410 17.8501 18.0497 16.3873 17.1737 15.8866 16.9890 18.6112 SiO2 wt% 40.5207 41.4994 41.3671 40.1081 39.7801 40.1514 40.5658 39.5300 39.1645 39.9349 39.7924 41.1625 40.2977 40.9110 40.2675 38.2899 Cl wt% 0.0107 0.0038 0.0046 0.0145 0.0000 0.0000 0.0000 0.0092 0.0000 0.0122 0.0000 0.0054 0.0099 0.0046 0.0237 0.0084 K2O wt% 0.3473 0.2374 0.2701 0.2782 0.2849 0.2893 0.2710 0.3431 0.3175 0.3484 0.2746 0.2191 0.2910 0.2273 0.2215 0.3268 CaO wt% 11.0394 10.6797 10.6766 11.0705 10.7117 11.0935 11.3020 10.9967 10.4334 10.8169 10.8390 10.8252 10.3341 10.2733 10.2894 10.7833 TiO2 wt% 0.2406 0.2124 0.1936 0.2111 0.1558 0.1617 0.1677 0.1516 0.1484 0.1443 0.0785 0.0738 0.1940 0.2228 0.2460 0.1412 Cr2O3 wt% 0.0328 0.0696 0.0348 0.0450 0.0266 0.0614 0.0000 0.0612 0.0793 0.0286 0.0000 0.0000 0.0552 0.3023 0.3296 0.0306 MnO wt% 0.7090 0.7573 0.7019 0.6384 0.8109 0.7923 0.6387 0.7178 0.9271 0.7101 0.8136 0.7059 0.6882 0.6328 0.7392 0.6294 FeO wt% 20.5136 20.8249 20.9214 20.5787 20.6376 20.6967 20.4593 21.2122 21.8603 21.0390 20.9585 20.3534 20.8263 20.9874 20.3368 21.0811 OH- wt% 2.0955 2.1020 2.1026 2.1032 2.0959 2.0993 2.0979 2.1005 2.1067 2.1033 2.1040 2.0923 2.1040 2.0922 2.0912 2.1039 Total oxides 99.05 98.93 98.35 98.02 97.93 98.38 98.21 98.13 97.75 98.15 98.40 98.77 98.02 98.26 98.43 97.85 Si 6.15 6.28 6.31 6.14 6.11 6.13 6.20 6.07 6.04 6.13 6.08 6.25 6.18 6.26 6.15 5.87 Al(iv) 1.85 1.72 1.69 1.86 1.89 1.87 1.80 1.93 1.96 1.87 1.92 1.75 1.82 1.74 1.85 2.13 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.29 1.08 1.06 1.22 1.19 1.16 1.20 1.24 1.20 1.36 1.32 1.18 1.28 1.13 1.20 1.23 Ti 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.03 0.03 0.02 Fe3+ 0.43 0.53 0.53 0.53 0.61 0.61 0.50 0.58 0.65 0.40 0.52 0.51 0.44 0.47 0.51 0.79 Cr 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.04 0.04 0.00 Mg 1.05 1.29 1.27 1.07 1.09 1.11 1.09 0.97 0.94 0.91 0.95 1.21 1.07 1.21 1.15 1.01 Fe2+ 2.17 2.07 2.12 2.11 2.04 2.03 2.11 2.14 2.18 2.30 2.15 2.07 2.18 2.13 2.07 1.91 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 4.97 5.00 5.00 4.95 4.95 4.93 4.93 4.95 4.99 4.98 4.96 4.98 5.00 5.00 5.00 4.97 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.00 0.04 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.09 0.02 0.00 Mn 0.09 0.10 0.09 0.08 0.11 0.10 0.08 0.09 0.12 0.09 0.11 0.09 0.09 0.08 0.10 0.08 Ca 1.79 1.73 1.74 1.82 1.76 1.81 1.85 1.81 1.73 1.78 1.77 1.76 1.70 1.69 1.68 1.77 Na 0.11 0.13 0.14 0.10 0.13 0.08 0.07 0.10 0.15 0.13 0.12 0.15 0.16 0.15 0.20 0.15 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.17 0.14 0.14 0.20 0.23 0.23 0.21 0.19 0.18 0.16 0.20 0.19 0.17 0.15 0.21 0.21 K 0.07 0.05 0.05 0.05 0.06 0.06 0.05 0.07 0.06 0.07 0.05 0.04 0.06 0.04 0.04 0.06 Sum A 0.24 0.18 0.19 0.25 0.29 0.28 0.26 0.26 0.24 0.23 0.25 0.23 0.22 0.19 0.25 0.28 502 Table B.4 (Continued) Sample GC01018-85.3 (continued) D33003-2004 EMPA spot 20 21 22 24 25 26 28 30 33 34 4 5 7 9 10 11 F wt% 0.3147 0.3612 0.2976 0.3415 0.3167 0.3157 0.2051 0.3452 0.3441 0.3103 0.0000 0.0000 0.0416 0.0227 0.1990 0.0644 Na2O wt% 1.1918 1.2748 1.2373 1.2242 0.8877 1.1869 1.1471 1.0956 1.0662 0.8436 0.3492 0.1576 0.6944 0.3734 0.6293 0.5544 MgO wt% 4.3744 4.4056 5.0776 4.3108 4.9493 4.1943 4.6070 4.9788 5.1428 5.7082 11.5782 13.5908 7.9986 11.5308 9.3322 10.3295 Al2O3 wt% 18.5750 18.3703 17.1556 19.3941 16.8698 18.3335 17.5952 17.3108 16.8364 15.3182 7.1809 3.2552 13.3698 6.9388 11.0766 9.3505 SiO2 wt% 39.0606 39.5991 39.8021 40.2383 41.8380 40.6399 40.8771 39.7329 39.8681 41.9107 48.4013 50.3945 43.2692 48.3164 44.9925 46.7742 Cl wt% 0.0000 0.0099 0.0138 0.0077 0.0138 0.0000 0.0160 0.0237 0.0221 0.0268 0.0247 0.0202 0.0154 0.0039 0.0000 0.0239 K2O wt% 0.2968 0.3283 0.3231 0.2974 0.3023 0.2787 0.2597 0.3081 0.2625 0.2348 0.1220 0.0121 0.2758 0.0847 0.1820 0.1235 CaO wt% 10.5746 10.7381 10.6040 11.0314 10.4222 10.6927 10.6547 10.8618 10.4221 9.9718 5.4507 1.8248 11.3185 6.6729 9.5627 9.2488 TiO2 wt% 0.1307 0.1082 0.1813 0.1215 0.2146 0.0940 0.1746 0.1208 0.2272 0.2108 0.1234 0.0630 0.3103 0.1413 0.2776 0.2360 Cr2O3 wt% 0.0000 0.0041 0.0962 0.0329 0.1148 0.0532 0.0552 0.1839 0.2225 0.5916 0.0000 0.0000 0.0186 0.0183 0.0617 0.0144 MnO wt% 0.6735 0.6718 0.7140 0.6349 0.6610 0.6874 0.6754 0.6554 0.6333 0.7786 0.6877 0.9533 0.2408 0.6312 0.3565 0.4811 FeO wt% 20.3784 20.5528 20.5202 19.5996 20.3543 20.5890 20.2914 20.2298 20.4522 20.6888 24.0134 26.2677 18.8431 22.3128 19.5759 19.6640 OH- wt% 2.0989 2.0961 2.0993 2.0976 2.0992 2.0993 2.1049 2.0964 2.0966 2.0988 2.1160 2.1165 2.1135 2.1154 2.1056 2.1125 Total oxides 97.67 98.52 98.12 99.33 99.04 99.16 98.66 97.94 97.60 98.69 100.05 98.66 98.51 99.16 98.35 98.98 Si 6.00 6.04 6.09 6.06 6.34 6.16 6.21 6.08 6.13 6.38 7.18 7.60 6.49 7.21 6.77 6.97 Al(iv) 2.00 1.96 1.91 1.94 1.66 1.84 1.79 1.92 1.87 1.62 0.82 0.40 1.51 0.79 1.23 1.03 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.36 1.34 1.18 1.51 1.36 1.43 1.36 1.21 1.18 1.13 0.44 0.18 0.86 0.43 0.73 0.61 Ti 0.02 0.01 0.02 0.01 0.02 0.01 0.02 0.01 0.03 0.02 0.01 0.01 0.04 0.02 0.03 0.03 Fe3+ 0.55 0.53 0.62 0.34 0.18 0.33 0.33 0.59 0.55 0.33 0.32 0.20 0.52 0.31 0.40 0.34 Cr 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.02 0.03 0.07 0.00 0.00 0.00 0.00 0.01 0.00 Mg 1.00 1.00 1.16 0.97 1.12 0.95 1.04 1.14 1.18 1.30 2.56 3.06 1.79 2.57 2.09 2.29 Fe2+ 2.07 2.09 2.01 2.13 2.31 2.28 2.24 2.00 2.03 2.16 1.66 1.56 1.79 1.68 1.74 1.73 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 4.97 4.99 4.96 5.00 5.00 5.00 4.97 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.00 0.00 0.00 0.00 0.09 0.00 0.01 0.00 0.04 0.15 1.00 1.56 0.05 0.80 0.32 0.38 Mn 0.09 0.09 0.09 0.08 0.08 0.09 0.09 0.09 0.08 0.10 0.09 0.12 0.03 0.08 0.05 0.06 Ca 1.74 1.75 1.74 1.78 1.69 1.74 1.73 1.78 1.72 1.63 0.87 0.29 1.82 1.07 1.54 1.48 Na 0.17 0.16 0.17 0.14 0.13 0.17 0.17 0.13 0.16 0.12 0.05 0.02 0.10 0.05 0.09 0.08 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.18 0.22 0.20 0.22 0.13 0.18 0.17 0.19 0.16 0.13 0.05 0.02 0.10 0.05 0.09 0.08 K 0.06 0.06 0.06 0.06 0.06 0.05 0.05 0.06 0.05 0.05 0.02 0.00 0.05 0.02 0.03 0.02 Sum A 0.24 0.28 0.26 0.28 0.19 0.23 0.22 0.25 0.21 0.17 0.07 0.03 0.15 0.07 0.13 0.10 503 Table B.4 (Continued) Sample D33003-2004 (continued) EMPA spot 15 16 18 19 20 21 22 23 24 25 26 27 28 30 33 34 F wt% 0.0702 0.0456 0.0000 0.0000 0.0959 0.1816 0.0587 0.0000 0.0802 0.0000 0.1869 0.1340 0.0295 0.0000 0.0412 0.0705 Na2O wt% 0.4473 0.4261 0.2896 0.2990 0.3904 0.6989 0.5628 0.4818 0.4769 0.3344 0.3855 0.5034 0.4810 0.5460 0.8441 0.8462 MgO wt% 9.9604 10.0757 11.9595 11.3076 9.8694 8.2421 8.7192 10.2484 9.7733 11.9023 10.4404 9.1930 9.6785 8.9288 7.1354 6.9107 Al2O3 wt% 9.3814 9.2336 6.6583 6.3635 8.5999 12.1315 11.1857 10.1423 9.9808 5.7981 7.9445 11.1095 10.3339 10.9578 14.2447 14.6173 SiO2 wt% 45.6076 45.6116 47.5216 48.3711 46.7280 44.1687 44.6465 44.9312 45.1336 48.7750 47.0600 44.6734 46.0219 43.7286 42.5457 42.0156 Cl wt% 0.0038 0.0077 0.0131 0.0155 0.0077 0.0015 0.0085 0.0231 0.0085 0.0046 0.0193 0.0262 0.0092 0.0300 0.0307 0.0338 K2O wt% 0.2036 0.1247 0.0656 0.0397 0.0605 0.2012 0.2260 0.2043 0.1551 0.0939 0.0696 0.1203 0.1228 0.1626 0.2966 0.3383 CaO wt% 9.5940 7.3081 5.1985 4.2284 6.5506 10.5131 10.2488 9.4971 8.1707 5.1103 6.8675 9.5947 10.2048 10.6008 11.1240 10.9650 TiO2 wt% 0.1438 0.2178 0.0997 0.1547 0.2018 0.2621 0.2125 0.1356 0.1758 0.1210 0.1704 0.2426 0.2442 0.2788 0.0000 0.0038 Cr2O3 wt% 0.0000 0.0549 0.0445 0.0000 0.0040 0.0082 0.0000 0.0329 0.0082 0.0000 0.0304 0.0123 0.0000 0.0103 0.0412 0.0226 MnO wt% 0.3649 0.4637 0.6416 0.8109 0.6714 0.4134 0.3330 0.3702 0.4106 0.6986 0.6070 0.3898 0.2696 0.4292 0.2893 0.2538 FeO wt% 19.7048 21.8873 22.9654 24.8900 23.2642 20.2874 19.8636 19.5963 21.7173 23.3692 22.6879 20.3297 19.0418 19.0496 19.5835 19.7164 OH- wt% 2.1125 2.1138 2.1163 2.1167 2.1114 2.1062 2.1130 2.1154 2.1116 2.1170 2.1059 2.1081 2.1148 2.1152 2.1130 2.1113 Total oxides 97.59 97.57 97.57 98.60 98.56 99.22 98.18 97.78 98.20 98.32 98.58 98.44 98.55 96.84 98.29 97.91 Si 6.90 6.93 7.21 7.32 7.07 6.61 6.74 6.76 6.82 7.36 7.10 6.72 6.88 6.67 6.42 6.38 Al(iv) 1.10 1.07 0.79 0.68 0.93 1.39 1.26 1.24 1.18 0.64 0.90 1.28 1.12 1.33 1.58 1.62 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.58 0.59 0.40 0.45 0.60 0.75 0.73 0.56 0.59 0.39 0.52 0.69 0.70 0.64 0.96 0.99 Ti 0.02 0.02 0.01 0.02 0.02 0.03 0.02 0.02 0.02 0.01 0.02 0.03 0.03 0.03 0.00 0.00 Fe3+ 0.45 0.40 0.35 0.19 0.27 0.54 0.44 0.60 0.52 0.20 0.32 0.52 0.34 0.59 0.55 0.56 Cr 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Mg 2.25 2.28 2.70 2.55 2.23 1.84 1.96 2.30 2.20 2.68 2.35 2.06 2.16 2.03 1.61 1.56 Fe2+ 1.71 1.70 1.53 1.79 1.88 1.84 1.84 1.52 1.67 1.72 1.79 1.71 1.77 1.70 1.88 1.88 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.33 0.69 1.03 1.17 0.80 0.16 0.22 0.35 0.56 1.04 0.76 0.33 0.26 0.13 0.04 0.06 Mn 0.05 0.06 0.08 0.10 0.09 0.05 0.04 0.05 0.05 0.09 0.08 0.05 0.03 0.06 0.04 0.03 Ca 1.56 1.19 0.84 0.69 1.06 1.69 1.66 1.53 1.32 0.83 1.11 1.55 1.63 1.73 1.80 1.78 Na 0.07 0.06 0.04 0.04 0.06 0.10 0.08 0.07 0.07 0.05 0.06 0.07 0.07 0.08 0.12 0.12 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.07 0.06 0.04 0.04 0.06 0.10 0.08 0.07 0.07 0.05 0.06 0.07 0.07 0.08 0.12 0.13 K 0.04 0.02 0.01 0.01 0.01 0.04 0.04 0.04 0.03 0.02 0.01 0.02 0.02 0.03 0.06 0.07 Sum A 0.11 0.09 0.06 0.05 0.07 0.14 0.13 0.11 0.10 0.07 0.07 0.10 0.09 0.11 0.18 0.19 504 Table B.4 (Continued) Sample D33003-2004 37L482-2057 EMPA spot 35 36 37 38 39 40 1 2 3 4 5 6 7 8 9 10 F wt% 0.0000 0.0827 0.0766 0.0000 0.0000 0.0000 0.1437 0.1078 0.0652 0.0059 0.0000 0.1436 0.0238 0.0358 0.0597 0.0600 Na2O wt% 0.8199 0.8552 0.8364 0.8004 0.7801 0.8196 1.1155 1.1472 0.7613 0.7559 0.8639 1.1245 0.9853 1.1412 1.1883 1.0807 MgO wt% 6.6326 6.8709 6.7347 7.4053 7.4457 6.4609 7.9756 7.8859 10.3893 10.4391 9.1334 7.6619 8.3164 7.3533 7.9429 8.0703 Al2O3 wt% 15.6879 15.4110 15.7935 14.6150 13.6839 15.8255 16.4796 16.8002 13.7955 12.0504 14.2162 16.2312 16.2709 17.0552 16.5013 16.5642 SiO2 wt% 41.1348 41.9673 41.4262 41.8467 42.2797 41.3397 40.7646 41.1670 42.6583 44.4268 43.2557 41.5517 41.0042 40.5389 41.1238 40.8775 Cl wt% 0.0429 0.0077 0.0146 0.0130 0.0315 0.0184 0.0315 0.0346 0.0278 0.0000 0.0069 0.0062 0.0315 0.0184 0.0200 0.0031 K2O wt% 0.3507 0.3330 0.3824 0.3657 0.3145 0.3857 0.3539 0.3702 0.2604 0.1866 0.2870 0.3577 0.3397 0.3742 0.3230 0.3164 CaO wt% 11.2103 11.3046 11.2419 11.4136 11.1894 11.2888 11.3726 11.4497 9.9685 9.7278 10.4659 11.5123 11.0690 11.2523 11.1345 11.3753 TiO2 wt% 0.0000 0.0001 0.0240 0.0000 0.0259 0.0420 0.2622 0.2920 0.2487 0.2612 0.2893 0.2578 0.2935 0.4600 0.2844 0.2836 Cr2O3 wt% 0.0021 0.0000 0.0000 0.0041 0.0371 0.0185 0.2220 0.1453 0.1533 0.1820 0.1056 0.1183 0.0331 0.1554 0.1658 0.1080 MnO wt% 0.2657 0.3164 0.2792 0.2288 0.2540 0.2437 0.3190 0.2499 0.2634 0.3678 0.2480 0.2702 0.2716 0.2160 0.3004 0.3276 FeO wt% 19.4782 19.1674 19.4432 19.3797 19.3711 19.8307 17.1304 17.1277 17.4921 18.0540 18.0585 17.4403 17.6951 17.7958 17.4565 16.9884 OH- wt% 2.1147 2.1114 2.1114 2.1154 2.1151 2.1155 2.1069 2.1090 2.1112 2.1158 2.1159 2.1079 2.1134 2.1134 2.1119 2.1123 Total oxides 97.74 98.43 98.36 98.19 97.53 98.39 98.28 98.89 98.20 98.57 99.05 98.78 98.45 98.51 98.61 98.17 Si 6.24 6.32 6.25 6.31 6.42 6.24 6.10 6.12 6.34 6.59 6.41 6.19 6.11 6.06 6.13 6.10 Al(iv) 1.76 1.68 1.75 1.69 1.58 1.76 1.90 1.88 1.66 1.41 1.59 1.81 1.89 1.94 1.87 1.90 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.05 1.06 1.06 0.90 0.88 1.06 1.00 1.06 0.75 0.70 0.89 1.05 0.97 1.07 1.02 1.02 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.05 0.03 0.03 Fe3+ 0.64 0.56 0.61 0.72 0.63 0.61 0.75 0.67 0.79 0.59 0.57 0.62 0.78 0.67 0.70 0.73 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.02 0.02 0.02 0.01 0.01 0.00 0.02 0.02 0.01 Mg 1.50 1.54 1.51 1.66 1.69 1.45 1.78 1.75 2.30 2.31 2.02 1.70 1.85 1.64 1.76 1.80 Fe2+ 1.81 1.84 1.81 1.72 1.80 1.87 1.40 1.46 1.11 1.35 1.48 1.56 1.36 1.55 1.46 1.39 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 4.98 4.98 5.00 5.00 5.00 4.97 5.00 5.00 5.00 4.98 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.02 0.01 0.03 0.01 0.03 0.02 0.00 0.00 0.27 0.30 0.19 0.00 0.06 0.01 0.02 0.00 Mn 0.03 0.04 0.04 0.03 0.03 0.03 0.04 0.03 0.03 0.05 0.03 0.03 0.03 0.03 0.04 0.04 Ca 1.82 1.82 1.82 1.84 1.82 1.83 1.82 1.82 1.59 1.55 1.66 1.84 1.77 1.80 1.78 1.82 Na 0.12 0.12 0.12 0.12 0.11 0.12 0.14 0.15 0.11 0.11 0.12 0.13 0.14 0.16 0.17 0.14 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.12 0.13 0.12 0.12 0.12 0.12 0.19 0.18 0.11 0.11 0.13 0.20 0.14 0.17 0.17 0.17 K 0.07 0.06 0.07 0.07 0.06 0.07 0.07 0.07 0.05 0.04 0.05 0.07 0.06 0.07 0.06 0.06 Sum A 0.19 0.19 0.20 0.19 0.18 0.20 0.25 0.25 0.16 0.14 0.18 0.27 0.21 0.24 0.23 0.23 505 Table B.4 (Continued) Sample 37L482-2057 (continued) EMPA spot 11 13 14 15 16 17 18 19 21 22 23 24 25 27 28 29 F wt% 0.0776 0.0000 0.1863 0.0597 0.2586 0.0420 0.1496 0.1254 0.0280 0.0000 0.0111 0.0000 0.0441 0.0000 0.0000 0.0991 Na2O wt% 0.9630 0.7583 1.1125 0.9631 1.0923 0.8689 1.0639 1.1268 0.2485 0.1553 0.1805 0.0884 0.1349 0.0578 0.1325 0.1604 MgO wt% 8.7605 10.1695 8.3012 9.3409 8.7536 10.1543 9.2217 8.0140 14.5963 15.7696 16.2142 16.4577 15.8159 16.7708 16.4637 16.7791 Al2O3 wt% 15.0158 13.1529 16.1181 13.5360 14.8655 12.3841 13.7056 16.0939 4.3711 3.2255 2.5940 1.6884 2.2991 1.4207 1.9336 2.1358 SiO2 wt% 42.3154 43.0711 41.4292 43.6660 42.5574 44.5180 42.9608 41.9902 51.1960 52.3136 52.5331 52.7699 52.3113 52.9818 52.5514 52.7899 Cl wt% 0.0231 0.0324 0.0000 0.0224 0.0177 0.0093 0.0362 0.0046 0.0000 0.0023 0.0031 0.0000 0.0000 0.0070 0.0086 0.0000 K2O wt% 0.2630 0.3798 0.3096 0.2642 0.3144 0.2444 0.2504 0.3292 0.0654 0.0558 0.0243 0.0413 0.0370 0.0024 0.0201 0.0267 CaO wt% 10.9518 10.1637 11.4610 10.3472 11.5173 10.7428 11.1118 11.3048 3.7171 2.6871 1.9334 1.4788 1.9008 0.8565 1.2761 1.6910 TiO2 wt% 0.2386 0.2804 0.3068 0.2443 0.3521 0.2460 0.2745 0.2471 0.0563 0.0183 0.0368 0.0235 0.0363 0.0078 0.0387 0.0350 Cr2O3 wt% 0.0643 0.0518 0.1290 0.0540 0.0749 0.0812 0.1225 0.1598 0.0791 0.0606 0.0566 0.0020 0.0000 0.0502 0.0564 0.0020 MnO wt% 0.2770 0.2432 0.2571 0.3297 0.2774 0.2979 0.3092 0.2145 0.7190 0.7214 0.7152 0.7570 0.7544 0.7538 0.7660 0.7753 FeO wt% 17.4577 17.3762 16.5735 17.0615 16.4557 16.7001 17.0079 17.5725 22.5173 23.1769 22.5259 23.8441 23.1563 23.8568 23.2127 23.0502 OH- wt% 2.1110 2.1150 2.1057 2.1125 2.1014 2.1137 2.1067 2.1090 2.1157 2.1172 2.1169 2.1173 2.1151 2.1173 2.1173 2.1118 Total oxides 98.52 97.79 98.29 98.00 98.64 98.40 98.32 99.29 99.71 100.30 98.95 99.27 98.61 98.88 98.58 99.66 Si 6.30 6.44 6.18 6.53 6.33 6.61 6.41 6.22 7.54 7.64 7.76 7.79 7.78 7.85 7.80 7.74 Al(iv) 1.70 1.56 1.82 1.47 1.67 1.39 1.59 1.78 0.46 0.36 0.24 0.21 0.22 0.15 0.20 0.26 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.93 0.76 1.01 0.91 0.94 0.77 0.82 1.03 0.30 0.20 0.21 0.09 0.19 0.10 0.14 0.11 Ti 0.03 0.03 0.03 0.03 0.04 0.03 0.03 0.03 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.66 0.66 0.66 0.44 0.58 0.51 0.65 0.61 0.13 0.14 0.01 0.11 0.01 0.05 0.03 0.13 Cr 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.00 Mg 1.94 2.27 1.85 2.08 1.94 2.25 2.05 1.77 3.20 3.43 3.57 3.62 3.51 3.70 3.64 3.67 Fe2+ 1.43 1.28 1.41 1.53 1.47 1.44 1.44 1.54 1.35 1.22 1.20 1.18 1.29 1.15 1.17 1.08 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 4.98 5.00 4.97 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.08 0.23 0.00 0.16 0.00 0.13 0.03 0.02 1.29 1.47 1.58 1.66 1.58 1.76 1.68 1.62 Mn 0.03 0.03 0.03 0.04 0.03 0.04 0.04 0.03 0.09 0.09 0.09 0.09 0.10 0.09 0.10 0.10 Ca 1.75 1.63 1.83 1.66 1.84 1.71 1.78 1.79 0.59 0.42 0.31 0.23 0.30 0.14 0.20 0.27 Na 0.14 0.11 0.14 0.14 0.13 0.12 0.15 0.16 0.04 0.02 0.03 0.01 0.02 0.01 0.02 0.02 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.14 0.11 0.19 0.14 0.19 0.13 0.16 0.16 0.04 0.02 0.03 0.01 0.02 0.01 0.02 0.02 K 0.05 0.07 0.06 0.05 0.06 0.05 0.05 0.06 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 Sum A 0.19 0.18 0.24 0.19 0.25 0.17 0.20 0.23 0.05 0.03 0.03 0.02 0.03 0.01 0.02 0.03 506 Table B.4 (Continued) Sample 37L482-2057 (continued) D39018-4848 EMPA spot 30 31 32 33 34 35 36 37 38 39 40 19 21 22 23 24 F wt% 0.0113 0.0660 0.0328 0.0000 0.1138 0.0659 0.0179 0.0965 0.1618 0.0422 0.0000 0.0321 0.0054 0.0000 0.0894 0.0875 Na2O wt% 0.2884 0.0596 0.0218 0.1968 1.1437 1.1548 1.0892 0.9349 0.9898 1.0154 1.1618 0.4468 0.6381 0.6634 0.1635 0.7031 MgO wt% 14.4366 17.0851 17.0673 15.7514 7.8938 7.9031 8.1057 9.0853 8.6177 9.2998 7.9491 10.5597 9.1932 9.1183 11.5376 8.8583 Al2O3 wt% 5.4110 1.3970 0.9219 2.8445 16.3033 16.0959 15.9521 14.3423 14.4948 13.8073 16.0954 3.9991 7.2062 7.2214 2.0723 7.4329 SiO2 wt% 50.1108 53.4538 53.4831 51.3219 41.5651 41.5912 41.8810 43.0677 42.7188 43.6654 41.1703 49.1535 46.1828 46.3973 50.2253 46.1001 Cl wt% 0.0086 0.0094 0.0000 0.0039 0.0315 0.0162 0.0077 0.0077 0.0000 0.0254 0.0077 0.0023 0.0176 0.0323 0.0131 0.0000 K2O wt% 0.0920 0.0146 0.0000 0.0358 0.3100 0.3383 0.3118 0.2624 0.3064 0.2463 0.3678 0.0984 0.6772 0.2283 0.0654 0.1769 CaO wt% 4.3911 1.1934 0.8545 2.6806 11.2682 11.1663 10.9369 11.3468 11.3295 11.3788 11.5426 2.9729 4.9823 5.5172 1.6680 5.4483 TiO2 wt% 0.0885 0.0364 0.0514 0.0468 0.2667 0.2720 0.3380 0.3613 0.3942 0.3030 0.2818 0.0468 0.1172 0.0402 0.0090 0.1030 Cr2O3 wt% 0.0773 0.0665 0.0241 0.0686 0.1619 0.1641 0.1533 0.2040 0.0706 0.1395 0.1433 0.0000 0.0000 0.0000 0.0137 0.0000 MnO wt% 0.6361 0.8033 0.8178 0.7178 0.2888 0.3058 0.2598 0.3383 0.2787 0.2487 0.2584 0.7263 0.5253 0.5278 0.7440 0.4764 FeO wt% 21.3549 23.0461 23.6211 23.0137 17.1121 17.0740 17.6918 16.6836 17.1615 16.6105 16.9178 28.2395 27.1295 26.5155 29.8328 26.3845 OH- wt% 2.1162 2.1136 2.1157 2.1168 2.1089 2.1120 2.1149 2.1106 2.1072 2.1131 2.1156 2.1154 2.1159 2.1156 2.1119 2.1119 Total oxides 99.02 99.34 99.01 98.80 98.57 98.26 98.86 98.84 98.63 98.90 98.01 98.39 98.79 98.38 98.55 97.88 Si 7.40 7.87 7.91 7.61 6.20 6.22 6.22 6.38 6.36 6.46 6.17 7.56 7.10 7.12 7.73 7.12 Al(iv) 0.60 0.13 0.09 0.39 1.80 1.78 1.78 1.62 1.64 1.54 1.83 0.44 0.90 0.88 0.27 0.88 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.35 0.11 0.07 0.11 1.06 1.06 1.02 0.89 0.91 0.87 1.01 0.29 0.41 0.43 0.11 0.47 Ti 0.01 0.00 0.01 0.01 0.03 0.03 0.04 0.04 0.04 0.03 0.03 0.01 0.01 0.00 0.00 0.01 Fe3+ 0.20 0.01 0.01 0.26 0.60 0.57 0.60 0.58 0.57 0.54 0.67 0.12 0.33 0.39 0.14 0.35 Cr 0.01 0.01 0.00 0.01 0.02 0.02 0.02 0.02 0.01 0.02 0.02 0.00 0.00 0.00 0.00 0.00 Mg 3.18 3.75 3.76 3.48 1.75 1.76 1.80 2.01 1.91 2.05 1.77 2.42 2.11 2.09 2.65 2.04 Fe2+ 1.25 1.12 1.15 1.14 1.54 1.56 1.53 1.47 1.56 1.49 1.45 2.17 2.14 2.09 2.10 2.13 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 4.95 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 1.18 1.70 1.76 1.46 0.00 0.01 0.07 0.02 0.01 0.02 0.00 1.35 1.02 0.93 1.60 0.93 Mn 0.08 0.10 0.10 0.09 0.04 0.04 0.03 0.04 0.04 0.03 0.03 0.09 0.07 0.07 0.10 0.06 Ca 0.70 0.19 0.14 0.43 1.80 1.79 1.74 1.80 1.81 1.80 1.85 0.49 0.82 0.91 0.28 0.90 Na 0.04 0.01 0.00 0.03 0.16 0.17 0.16 0.13 0.14 0.14 0.12 0.07 0.09 0.10 0.02 0.10 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.04 0.01 0.00 0.03 0.17 0.17 0.16 0.14 0.14 0.15 0.22 0.07 0.10 0.10 0.02 0.11 K 0.02 0.00 0.00 0.01 0.06 0.06 0.06 0.05 0.06 0.05 0.07 0.02 0.13 0.04 0.01 0.03 Sum A 0.06 0.01 0.00 0.04 0.23 0.23 0.22 0.19 0.20 0.19 0.29 0.09 0.23 0.14 0.04 0.14 507 Table B.4 (Continued) Sample D39018-4848 (continued) EMPA spot 25 26 28 29 30 32 33 34 37 38 39 40 41 42 44 47 F wt% 0.0000 0.0168 0.1059 0.1333 0.0000 0.0000 0.0000 0.0279 0.0842 0.0841 0.0992 0.0000 0.0858 0.0000 0.0000 0.0464 Na2O wt% 0.9265 1.0379 1.0154 0.7809 1.2632 1.1918 0.3908 0.8981 0.1655 0.9430 0.7127 0.6914 0.3969 1.3130 1.5205 1.6365 MgO wt% 8.2827 7.7105 8.0159 8.5839 8.0437 7.3178 10.5094 7.9956 11.8527 7.8058 8.7305 9.0115 10.4045 4.4822 4.6103 4.8363 Al2O3 wt% 9.0490 9.8365 9.3770 8.4945 11.0064 11.7086 4.1674 9.4238 1.8345 9.8870 7.9472 7.8329 4.4008 17.5347 18.3749 18.5769 SiO2 wt% 44.8669 44.0788 44.6997 45.6633 43.4147 42.8749 48.7865 44.4712 50.8694 43.9427 46.0858 45.9732 48.4005 37.6334 38.4083 38.4540 Cl wt% 0.0230 0.0605 0.0084 0.0207 0.0215 0.0000 0.0116 0.0023 0.0046 0.0061 0.0161 0.0230 0.0200 0.0122 0.0130 0.0183 K2O wt% 0.2566 0.2934 0.2772 0.2612 0.2315 0.2441 0.1445 0.2595 0.0462 0.3055 0.2605 0.2718 0.1528 1.5497 0.4351 0.5432 CaO wt% 7.0337 7.5506 7.4841 6.4298 8.3506 9.0183 3.4238 7.3176 1.8127 8.1107 6.0537 5.8713 3.3504 9.8580 10.9090 10.8738 TiO2 wt% 0.0877 0.1189 0.1492 0.1044 0.1918 0.2602 0.0661 0.1217 0.0242 0.1424 0.1201 0.1025 0.1109 0.5202 0.3052 0.3160 Cr2O3 wt% 0.0000 0.0000 0.0422 0.0060 0.0101 0.0385 0.0000 0.0060 0.0000 0.0000 0.0000 0.0000 0.0198 0.0774 0.0246 0.0000 MnO wt% 0.4325 0.4030 0.4227 0.4910 0.3841 0.4072 0.6195 0.3763 0.6816 0.4230 0.5102 0.5430 0.6817 0.1737 0.2413 0.2161 FeO wt% 25.3588 24.5568 25.1614 24.8425 23.0463 23.4835 27.6173 24.6830 29.9741 24.6413 25.8531 26.0449 28.1598 22.0079 20.5389 20.9561 OH- wt% 2.1155 2.1136 2.1101 2.1088 2.1152 2.1157 2.1169 2.1147 2.1124 2.1111 2.1108 2.1158 2.1117 2.1159 2.1154 2.1125 Total oxides 98.43 97.78 98.87 97.92 98.08 98.66 97.85 97.70 99.46 98.40 98.50 98.48 98.30 97.28 97.50 98.59 Si 6.87 6.80 6.83 7.03 6.63 6.52 7.54 6.86 7.75 6.73 7.07 7.04 7.46 5.89 5.90 5.84 Al(iv) 1.13 1.20 1.17 0.97 1.37 1.48 0.46 1.14 0.25 1.27 0.93 0.96 0.54 2.11 2.10 2.16 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.50 0.59 0.51 0.58 0.61 0.62 0.30 0.57 0.08 0.52 0.51 0.46 0.26 1.13 1.22 1.17 Ti 0.01 0.01 0.02 0.01 0.02 0.03 0.01 0.01 0.00 0.02 0.01 0.01 0.01 0.06 0.04 0.04 Fe3+ 0.55 0.52 0.57 0.31 0.67 0.74 0.12 0.49 0.16 0.65 0.34 0.42 0.22 0.53 0.72 0.80 Cr 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Mg 1.89 1.77 1.82 1.97 1.83 1.66 2.42 1.84 2.69 1.78 2.00 2.06 2.39 1.05 1.06 1.10 Fe2+ 2.04 2.10 2.07 2.13 1.87 1.94 2.15 2.09 2.07 2.03 2.14 2.05 2.11 2.22 1.92 1.86 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 4.95 4.96 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.65 0.55 0.57 0.76 0.40 0.30 1.29 0.61 1.59 0.47 0.83 0.86 1.30 0.13 0.00 0.00 Mn 0.06 0.05 0.05 0.06 0.05 0.05 0.08 0.05 0.09 0.05 0.07 0.07 0.09 0.02 0.03 0.03 Ca 1.15 1.25 1.22 1.06 1.37 1.47 0.57 1.21 0.30 1.33 0.99 0.96 0.55 1.65 1.79 1.77 Na 0.14 0.15 0.15 0.12 0.18 0.17 0.06 0.13 0.02 0.14 0.11 0.10 0.06 0.20 0.17 0.20 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.14 0.16 0.15 0.12 0.19 0.18 0.06 0.14 0.02 0.14 0.11 0.10 0.06 0.20 0.28 0.28 K 0.05 0.06 0.05 0.05 0.05 0.05 0.03 0.05 0.01 0.06 0.05 0.05 0.03 0.31 0.09 0.11 Sum A 0.19 0.21 0.21 0.17 0.23 0.23 0.09 0.19 0.03 0.20 0.16 0.16 0.09 0.51 0.36 0.39 508 Table B.4 (Continued) Sample D39018-4848 (continued) BK05010-376 EMPA spot 54 56 57 58 59 60 61 62 1 2 3 4 7 8 9 11 F wt% 0.1792 0.0929 0.1221 0.1625 0.1386 0.1266 0.0000 0.0983 0.0000 0.0601 0.1205 0.0000 0.1393 0.0000 0.0000 0.0606 Na2O wt% 1.4834 1.4651 1.4060 1.4882 1.4638 1.4331 1.4272 1.3936 1.0880 1.1251 1.0812 0.9748 0.8461 0.9516 0.9171 0.9973 MgO wt% 5.1932 4.5953 4.8449 5.0569 4.7398 4.8206 4.6150 4.5658 8.8639 8.6651 9.3602 10.2833 10.3022 10.0408 10.2432 9.9146 Al2O3 wt% 16.2250 17.2818 17.3970 16.6513 17.3822 15.8391 17.3598 16.8246 15.1358 14.8031 13.4030 11.7447 11.1522 11.6247 11.3382 12.3965 SiO2 wt% 39.0780 39.0048 38.7042 38.9282 38.5599 38.8365 38.4340 38.6448 41.5409 42.1220 43.3541 44.3507 44.7491 44.6322 44.6798 43.9314 Cl wt% 0.0000 0.0000 0.0336 0.0153 0.0053 0.0122 0.0008 0.0000 0.0507 0.0454 0.0293 0.0347 0.0069 0.0277 0.0439 0.0370 K2O wt% 0.6981 0.5123 0.6249 0.5996 0.5814 0.4871 0.5544 0.6147 0.4198 0.4393 0.2990 0.2661 0.3068 0.3458 0.3153 0.3277 CaO wt% 11.1455 11.1971 11.0012 11.0055 11.1821 11.1361 11.2688 10.9774 11.6480 11.4740 11.3999 11.4338 11.3514 11.4059 11.2711 11.4493 TiO2 wt% 0.6282 0.2588 0.3490 0.4831 0.2068 0.3008 0.3890 0.4736 0.2158 0.0765 0.0865 0.3244 0.5463 0.5107 0.5624 0.2830 Cr2O3 wt% 0.0571 0.0000 0.0225 0.0593 0.0163 0.0122 0.0898 0.1182 0.0499 0.0291 0.0541 0.1209 0.0688 0.1397 0.1210 0.1792 MnO wt% 0.2524 0.2210 0.1826 0.1708 0.1606 0.1888 0.2158 0.2190 0.3429 0.3634 0.3992 0.3926 0.3673 0.4215 0.4757 0.4602 FeO wt% 22.1645 21.1768 20.8697 21.1227 21.6842 22.3572 21.5383 21.9706 16.7165 16.4452 16.1840 16.0417 15.9870 15.8343 15.8052 16.0040 OH- wt% 2.1055 2.1106 2.1081 2.1063 2.1076 2.1079 2.1154 2.1102 2.1140 2.1113 2.1086 2.1150 2.1085 2.1157 2.1151 2.1117 Total oxides 99.21 97.92 97.67 97.85 98.23 97.66 98.01 98.01 98.19 97.76 97.88 98.08 97.93 98.05 97.89 98.15 Si 5.95 5.99 5.96 5.99 5.91 6.00 5.90 5.95 6.19 6.32 6.48 6.60 6.69 6.66 6.67 6.55 Al(iv) 2.05 2.01 2.04 2.01 2.09 2.00 2.10 2.05 1.81 1.68 1.52 1.40 1.31 1.34 1.33 1.45 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.86 1.11 1.11 1.01 1.04 0.88 1.04 1.01 0.85 0.94 0.84 0.66 0.65 0.70 0.67 0.72 Ti 0.07 0.03 0.04 0.06 0.02 0.03 0.04 0.05 0.02 0.01 0.01 0.04 0.06 0.06 0.06 0.03 Fe3+ 0.90 0.73 0.72 0.76 0.88 0.94 0.85 0.79 0.81 0.64 0.59 0.60 0.47 0.44 0.45 0.58 Cr 0.01 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.02 0.01 0.02 Mg 1.18 1.05 1.11 1.16 1.08 1.11 1.06 1.05 1.97 1.94 2.09 2.28 2.30 2.23 2.28 2.20 Fe2+ 1.92 1.99 1.97 1.95 1.90 1.95 1.91 2.04 1.27 1.42 1.43 1.40 1.51 1.54 1.52 1.41 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 4.93 4.91 4.96 4.95 4.93 4.92 4.91 4.95 4.94 4.95 4.97 4.99 5.00 4.99 5.00 4.97 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 Mn 0.03 0.03 0.02 0.02 0.02 0.02 0.03 0.03 0.04 0.05 0.05 0.05 0.05 0.05 0.06 0.06 Ca 1.82 1.84 1.81 1.81 1.84 1.84 1.85 1.81 1.86 1.84 1.83 1.82 1.82 1.82 1.80 1.83 Na 0.15 0.13 0.16 0.16 0.14 0.13 0.12 0.16 0.10 0.11 0.12 0.13 0.12 0.12 0.13 0.11 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.29 0.31 0.26 0.28 0.29 0.30 0.30 0.26 0.22 0.22 0.19 0.15 0.12 0.15 0.13 0.17 K 0.14 0.10 0.12 0.12 0.11 0.10 0.11 0.12 0.08 0.08 0.06 0.05 0.06 0.07 0.06 0.06 Sum A 0.42 0.41 0.38 0.40 0.40 0.39 0.41 0.38 0.30 0.30 0.25 0.20 0.18 0.22 0.19 0.24 509 Table B.4 (Continued) Sample BK05010-376 (continued) EMPA spot 12 13 14 15 16 17 18 19 20 21 23 24 25 26 27 28 F wt% 0.0847 0.0060 0.0000 0.1799 0.0060 0.0838 0.0781 0.0000 0.0000 0.0663 0.0000 0.0000 0.0000 0.1808 0.0421 0.0989 Na2O wt% 1.0459 1.0220 0.9106 0.9631 0.9324 0.9855 0.8458 0.8590 0.5220 0.6815 0.2317 0.2569 0.4719 0.1878 0.2708 0.2378 MgO wt% 9.7405 9.8474 10.3359 9.2330 8.4676 8.4167 10.3768 9.9545 11.9578 10.4748 15.2844 15.3175 13.3614 15.6189 14.8620 15.7284 Al2O3 wt% 12.7493 12.9055 11.4101 13.1256 14.0060 14.4399 11.3525 12.1141 9.2204 11.0778 3.8345 3.7201 6.8301 3.4576 3.9748 3.3098 SiO2 wt% 43.8408 43.4544 44.8333 42.3870 42.3427 41.9772 44.4101 44.2915 45.7472 44.8932 51.6509 51.7745 48.9213 52.8919 51.4704 52.7065 Cl wt% 0.0385 0.0216 0.0185 0.0108 0.0223 0.0184 0.0139 0.0385 0.0386 0.0193 0.0054 0.0086 0.0000 0.0148 0.0054 0.0000 K2O wt% 0.3585 0.3435 0.2733 0.3770 0.3699 0.4617 0.2605 0.3530 0.1958 0.2441 0.0217 0.0514 0.1825 0.0320 0.0381 0.0563 CaO wt% 11.3653 11.3018 11.5959 11.8477 11.6526 11.6487 11.3809 11.0939 9.8466 11.2342 11.6076 10.8300 11.7303 11.8971 9.0943 10.8653 TiO2 wt% 0.1361 0.1316 0.0375 0.1071 0.2028 0.2013 0.1900 0.1741 0.1797 0.1584 0.0830 0.1084 0.2435 0.0755 0.1284 0.0935 Cr2O3 wt% 0.1313 0.1230 0.2563 0.0914 0.1681 0.0974 0.0229 0.1102 0.0954 0.1103 0.0000 0.0274 0.0505 0.0275 0.0000 0.0316 MnO wt% 0.4096 0.4146 0.4112 0.3664 0.3089 0.2902 0.4243 0.3347 0.5152 0.3435 0.4229 0.4451 0.2893 0.2989 0.5901 0.4757 FeO wt% 15.7851 15.8344 16.1083 17.0165 17.1812 17.4873 16.8206 16.7105 17.1907 16.5201 13.0725 12.9714 13.8453 12.4271 15.9955 13.2384 OH- wt% 2.1105 2.1151 2.1155 2.1053 2.1150 2.1106 2.1111 2.1151 2.1148 2.1119 2.1167 2.1170 2.1168 2.1068 2.1146 2.1118 Total oxides 97.80 97.52 98.31 97.81 97.78 98.22 98.29 98.15 97.62 97.94 98.33 97.63 98.04 99.22 98.59 98.95 Si 6.56 6.50 6.66 6.36 6.37 6.29 6.61 6.60 6.83 6.70 7.52 7.60 7.20 7.64 7.55 7.64 Al(iv) 1.44 1.50 1.34 1.64 1.63 1.71 1.39 1.40 1.17 1.30 0.48 0.40 0.80 0.36 0.45 0.36 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.80 0.78 0.65 0.68 0.85 0.84 0.60 0.73 0.45 0.64 0.18 0.24 0.38 0.22 0.23 0.20 Ti 0.02 0.01 0.00 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.03 0.01 0.01 0.01 Fe3+ 0.53 0.60 0.60 0.84 0.65 0.72 0.70 0.54 0.64 0.56 0.27 0.12 0.33 0.11 0.18 0.12 Cr 0.02 0.01 0.03 0.01 0.02 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 Mg 2.17 2.20 2.29 2.07 1.90 1.88 2.30 2.21 2.66 2.33 3.32 3.35 2.93 3.36 3.25 3.40 Fe2+ 1.45 1.38 1.40 1.29 1.51 1.48 1.38 1.48 1.22 1.43 1.22 1.27 1.33 1.29 1.32 1.26 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 4.98 4.99 4.97 4.91 4.95 4.95 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.06 0.29 0.06 0.10 0.20 0.05 0.10 0.46 0.22 Mn 0.05 0.05 0.05 0.05 0.04 0.04 0.05 0.04 0.07 0.04 0.05 0.06 0.04 0.04 0.07 0.06 Ca 1.82 1.81 1.84 1.91 1.88 1.87 1.81 1.77 1.57 1.80 1.81 1.70 1.85 1.84 1.43 1.69 Na 0.13 0.14 0.10 0.05 0.08 0.09 0.12 0.12 0.08 0.10 0.03 0.04 0.07 0.03 0.04 0.03 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.18 0.16 0.16 0.23 0.19 0.19 0.12 0.13 0.08 0.10 0.03 0.04 0.07 0.03 0.04 0.03 K 0.07 0.07 0.05 0.07 0.07 0.09 0.05 0.07 0.04 0.05 0.00 0.01 0.03 0.01 0.01 0.01 Sum A 0.24 0.23 0.21 0.30 0.26 0.28 0.17 0.19 0.11 0.15 0.04 0.05 0.10 0.03 0.05 0.04 510 Table B.4 (Continued) Sample BK05010-376 (continued) DS172-123 EMPA spot 29 30 31 32 33 34 36 37 38 1 2 3 5 6 7 8 F wt% 0.1686 0.0249 0.0000 0.0496 0.0684 0.0000 0.0000 0.0617 0.0435 0.0404 0.1144 0.0345 0.0000 0.0796 0.0172 0.0000 Na2O wt% 0.1956 0.1969 0.1980 0.2026 0.3312 0.3136 0.2721 0.3610 0.3085 0.7087 0.6890 0.6867 0.7540 0.7215 0.6664 0.6025 MgO wt% 15.9233 15.7547 15.5002 15.4658 15.2657 15.0902 15.0617 14.4490 14.8364 2.8835 2.8557 2.8096 2.7877 3.0675 3.0366 3.0878 Al2O3 wt% 3.3005 3.7263 3.6804 3.5529 3.9391 4.3054 3.9457 4.6234 5.0692 17.9896 17.7939 17.7605 18.0666 17.6097 17.5755 17.3685 SiO2 wt% 52.7412 51.9112 52.0214 52.1353 51.7703 51.1284 51.5696 50.4034 50.5293 38.7833 38.8216 39.2712 38.7676 38.6317 39.0188 39.1803 Cl wt% 0.0124 0.0194 0.0054 0.0000 0.0023 0.0148 0.0272 0.0023 0.0078 0.0053 0.0609 0.0153 0.0099 0.0244 0.0091 0.0076 K2O wt% 0.0532 0.0472 0.0943 0.0696 0.0930 0.0338 0.0671 0.0766 0.0779 0.6270 0.6386 0.4561 0.6215 0.6556 0.6794 0.6880 CaO wt% 12.0373 11.5811 11.7391 11.0648 11.6467 9.9551 9.6754 11.6538 11.5032 11.1167 11.0425 10.8770 10.8847 10.7600 11.2270 11.2316 TiO2 wt% 0.0792 0.0927 0.1215 0.0914 0.1031 0.1464 0.1250 0.1713 0.1673 0.1200 0.0444 0.0141 0.0569 0.0479 0.0297 0.0504 Cr2O3 wt% 0.0169 0.0063 0.0000 0.0063 0.0000 0.0188 0.0000 0.0000 0.0190 0.1199 0.0142 0.0630 0.0811 0.0162 0.0223 0.0447 MnO wt% 0.3195 0.3705 0.4164 0.4368 0.4555 0.6135 0.5911 0.3407 0.3804 0.1536 0.0717 0.2120 0.1034 0.0517 0.0818 0.0868 FeO wt% 12.2313 12.5187 13.0429 12.8357 12.8477 15.0366 15.0633 13.8097 12.7386 23.1328 23.8374 23.1998 23.9253 24.4158 23.8225 23.3737 OH- wt% 2.1074 2.1150 2.1168 2.1146 2.1131 2.1164 2.1163 2.1132 2.1143 2.1140 2.1081 2.1142 2.1159 2.1108 2.1149 2.1161 Total oxides 99.19 98.36 98.94 98.03 98.64 98.77 98.51 98.07 97.80 97.79 98.09 97.51 98.17 98.19 98.30 97.84 Si 7.60 7.54 7.53 7.62 7.53 7.45 7.55 7.40 7.40 6.03 6.03 6.11 6.01 5.99 6.04 6.09 Al(iv) 0.40 0.46 0.47 0.38 0.47 0.55 0.45 0.60 0.60 1.97 1.97 1.89 1.99 2.01 1.96 1.91 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 0.17 0.18 0.16 0.23 0.20 0.19 0.23 0.20 0.28 1.32 1.29 1.37 1.31 1.21 1.24 1.27 Ti 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.02 0.01 0.01 0.00 0.01 0.01 0.00 0.01 Fe3+ 0.20 0.25 0.26 0.11 0.23 0.31 0.18 0.35 0.26 0.48 0.54 0.41 0.54 0.65 0.58 0.49 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 Mg 3.42 3.41 3.35 3.37 3.31 3.28 3.29 3.16 3.24 0.67 0.66 0.65 0.64 0.71 0.70 0.72 Fe2+ 1.20 1.15 1.22 1.27 1.25 1.20 1.29 1.27 1.20 2.50 2.50 2.56 2.49 2.42 2.47 2.51 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.07 0.12 0.10 0.18 0.08 0.33 0.37 0.07 0.10 0.02 0.05 0.05 0.07 0.10 0.03 0.03 Mn 0.04 0.05 0.05 0.05 0.06 0.08 0.07 0.04 0.05 0.02 0.01 0.03 0.01 0.01 0.01 0.01 Ca 1.86 1.80 1.82 1.73 1.81 1.56 1.52 1.83 1.81 1.85 1.84 1.81 1.81 1.79 1.86 1.87 Na 0.03 0.03 0.03 0.03 0.05 0.04 0.04 0.05 0.04 0.11 0.10 0.10 0.11 0.11 0.10 0.09 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.03 0.03 0.03 0.03 0.05 0.04 0.04 0.05 0.04 0.11 0.10 0.10 0.11 0.11 0.10 0.09 K 0.01 0.01 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.12 0.13 0.09 0.12 0.13 0.13 0.14 Sum A 0.04 0.04 0.05 0.04 0.06 0.05 0.05 0.07 0.06 0.23 0.23 0.19 0.24 0.24 0.23 0.23 511 Table B.4 (Continued) Sample DS172-123 (continued) EMPA spot 9 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 F wt% 0.0000 0.0174 0.1436 0.1377 0.0400 0.0858 0.0057 0.0401 0.0287 0.1951 0.0000 0.0115 0.0860 0.0000 0.1662 0.0851 Na2O wt% 0.6206 0.9284 0.6922 0.6456 0.6316 0.6324 0.6692 0.7266 0.6743 0.6498 0.6541 0.6815 0.6939 0.7051 0.6623 0.5813 MgO wt% 3.2896 3.2309 3.2755 3.0040 2.7574 3.1680 2.8831 2.7383 3.0929 3.2090 3.1295 2.8995 2.7414 2.7894 2.8367 3.3549 Al2O3 wt% 17.2279 17.3350 17.3109 17.5356 17.9652 16.9728 17.8850 18.0969 17.6810 17.4986 17.4154 18.0056 18.2950 17.9593 18.0015 18.0619 SiO2 wt% 39.1626 38.9846 39.0435 39.1064 38.6848 39.6740 39.2065 38.6999 38.8577 39.0729 39.3427 38.8667 38.7277 39.2176 39.0977 38.1557 Cl wt% 0.0167 0.0168 0.0206 0.0091 0.0145 0.0122 0.0000 0.0015 0.0046 0.0107 0.0000 0.0274 0.0023 0.0168 0.0160 0.0076 K2O wt% 0.7077 0.7221 0.7362 0.6440 0.5479 0.5419 0.5690 0.6456 0.6526 0.7186 0.7677 0.6766 0.6042 0.5374 0.6277 2.1049 CaO wt% 11.1003 11.3164 11.3209 11.1770 10.9384 11.1191 10.9956 11.1862 11.2745 11.2295 11.4735 11.2631 11.2116 10.8584 10.9941 9.1375 TiO2 wt% 0.0775 0.1071 0.0844 0.0317 0.0410 0.0362 0.0111 0.0528 0.0358 0.1137 0.0438 0.0361 0.0480 0.0572 0.0464 0.1381 Cr2O3 wt% 0.0670 0.0631 0.0406 0.0102 0.0223 0.0344 0.0203 0.0446 0.0345 0.0548 0.1037 0.0366 0.0183 0.0650 0.0528 0.0728 MnO wt% 0.0984 0.1103 0.0885 0.1102 0.1267 0.1484 0.0584 0.0751 0.0968 0.0634 0.1236 0.0451 0.1168 0.1336 0.1135 0.1415 FeO wt% 23.5900 22.5756 23.5573 23.5421 23.9210 24.2196 23.8049 23.7593 23.8652 23.5618 23.2668 23.5245 23.7373 23.2073 23.6166 24.4215 OH- wt% 2.1157 2.1149 2.1076 2.1084 2.1136 2.1111 2.1160 2.1139 2.1143 2.1051 2.1163 2.1148 2.1114 2.1161 2.1068 2.1121 Total oxides 98.07 97.52 98.42 98.06 97.80 98.76 98.22 98.18 98.41 98.48 98.44 98.19 98.39 97.66 98.34 98.37 Si 6.07 6.07 6.04 6.07 6.02 6.11 6.06 6.00 6.00 6.04 6.08 6.02 5.99 6.10 6.05 5.99 Al(iv) 1.93 1.93 1.96 1.93 1.98 1.89 1.94 2.00 2.00 1.96 1.92 1.98 2.01 1.90 1.95 2.01 sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Al(vi) 1.22 1.25 1.19 1.28 1.31 1.19 1.32 1.30 1.22 1.23 1.25 1.30 1.32 1.39 1.34 1.34 Ti 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.02 Fe3+ 0.55 0.50 0.60 0.52 0.55 0.57 0.49 0.55 0.64 0.55 0.50 0.53 0.56 0.38 0.47 0.21 Cr 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 Mg 0.76 0.75 0.76 0.69 0.64 0.73 0.66 0.63 0.71 0.74 0.72 0.67 0.63 0.65 0.65 0.79 Fe2+ 2.46 2.44 2.44 2.51 2.49 2.50 2.51 2.50 2.42 2.46 2.50 2.49 2.48 2.57 2.53 2.65 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sum C 5.00 4.96 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 4.99 5.00 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe2+ 0.05 0.00 0.01 0.03 0.07 0.05 0.07 0.02 0.02 0.03 0.00 0.02 0.03 0.07 0.06 0.36 Mn 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.02 0.01 0.02 Ca 1.84 1.89 1.88 1.86 1.82 1.84 1.82 1.86 1.87 1.86 1.90 1.87 1.86 1.81 1.82 1.54 Na 0.09 0.10 0.10 0.10 0.09 0.09 0.10 0.11 0.10 0.10 0.09 0.10 0.10 0.11 0.10 0.09 Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Na 0.09 0.18 0.10 0.10 0.10 0.10 0.10 0.11 0.10 0.10 0.11 0.10 0.10 0.11 0.10 0.09 K 0.14 0.14 0.15 0.13 0.11 0.11 0.11 0.13 0.13 0.14 0.15 0.13 0.12 0.11 0.12 0.42 Sum A 0.23 0.33 0.25 0.23 0.20 0.20 0.21 0.24 0.23 0.24 0.26 0.24 0.22 0.21 0.22 0.51 512 Table B.4 (Continued) Sample DS172-123 DS172- 123 DS172- 123 DS172- 123 EMPA spot 26 27 28 29 F wt% 0.0000 0.0000 0.0574 0.0000 Na2O wt% 0.6690 0.6511 0.6748 0.6664 MgO wt% 2.9077 2.8731 2.8099 3.1076 Al2O3 wt% 17.9362 17.9979 18.2829 17.7054 SiO2 wt% 39.0690 38.9746 38.3728 39.0477 Cl wt% 0.0251 0.0000 0.0076 0.0168 K2O wt% 0.6389 0.5680 0.6308 0.6506 CaO wt% 11.1356 11.0094 11.0720 11.1850 TiO2 wt% 0.0664 0.0213 0.0378 0.0730 Cr2O3 wt% 0.0731 0.0731 0.0670 0.0264 MnO wt% 0.0902 0.1152 0.1335 0.0901 FeO wt% 23.4236 23.3185 23.5895 23.6334 OH- wt% 2.1156 2.1164 2.1127 2.1157 Total oxides 98.15 97.72 97.85 98.32 Si 6.05 6.05 5.96 6.03 Al(iv) 1.95 1.95 2.04 1.97 sum T 8.00 8.00 8.00 8.00 Al(vi) 1.32 1.35 1.31 1.26 Ti 0.01 0.00 0.00 0.01 Fe3+ 0.48 0.47 0.58 0.56 Cr 0.01 0.01 0.01 0.00 Mg 0.67 0.67 0.65 0.72 Fe2+ 2.51 2.51 2.44 2.46 Mn 0.00 0.00 0.00 0.00 Sum C 5.00 5.00 5.00 5.00 Mg 0.00 0.00 0.00 0.00 Fe2+ 0.04 0.06 0.04 0.04 Mn 0.01 0.02 0.02 0.01 Ca 1.85 1.83 1.84 1.85 Na 0.10 0.10 0.10 0.10 Sum B 2.00 2.00 2.00 2.00 Na 0.10 0.10 0.10 0.10 K 0.13 0.11 0.13 0.13 Sum A 0.23 0.21 0.23 0.23 513 B.5 Carbonate EMPA data This appendix consists of Table B.5 which contains the EMP results of all samples probed for carbonate chemistry analysis. Each column identifies the sample, EMP spot number, the weight percent oxides, total oxide, and the molar normalized element abundance per formula unit which was normalized to oxygen = 6. Sample location, metamorphic grade, main alteration assemblage, mineralization sulfide-oxide assemblage, and distance from ore and surface can be found for all samples in Appendix A.2. 514 Table B.5 Complete electron microprobe data for all samples probed for carbonate chemistry. Sample GC04003-1716 Carbonate type Ankerite-calcite-quartz vein EMPA Spot 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 CO2 wt% 43.515 43.034 43.898 43.979 44.267 43.632 45.113 45.271 44.8 44.222 45.059 45.432 45.038 44.768 43.515 44.007 43.876 44.235 MgO wt% 0.0289 0.0417 0.0642 0.0011 0.0267 0.0674 0.436 0.6225 0.092 0.0353 0.6987 0.6945 0.4094 0.2906 0.2087 0.3168 0.0375 0.7499 CaO wt% 56.129 56.811 55.892 55.774 55.642 56.122 52.079 50.98 54.683 55.423 51.282 50.723 51.943 53.798 55.91 54.904 55.389 52.102 MnO wt% 0.1822 0.0877 0.0807 0.1858 0.0211 0.1193 0.6987 0.9141 0.2174 0.2489 0.6839 0.8242 0.8275 0.4061 0.2139 0.3782 0.3922 0.4783 FeO wt% 0.1441 0.0262 0.0656 0.0601 0.0438 0.059 1.6733 2.2123 0.2076 0.071 2.2769 2.3259 1.7825 0.7377 0.1519 0.394 0.3056 2.4346 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 1.97 2.00 2.00 2.01 1.99 2.03 2.04 2.02 2.01 2.03 2.04 2.03 2.02 1.99 2.00 2.00 2.01 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.03 0.00 0.00 0.03 0.03 0.02 0.01 0.01 0.02 0.00 0.04 Ca 2.01 2.05 2.00 1.99 1.98 2.01 1.84 1.80 1.94 1.97 1.82 1.79 1.84 1.91 2.00 1.96 1.98 1.86 Mn 0.01 0.00 0.00 0.01 0.00 0.00 0.02 0.03 0.01 0.01 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 Fe 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.06 0.01 0.00 0.06 0.06 0.05 0.02 0.00 0.01 0.01 0.07 515 Table B.5 (Continued) Sample GC04003-1716 (continued) GC04003-338 Carbonate type Ankerite-calcite-quartz vein Coarse colloform-crustiform vein EMPA Spot 20 21 22 23 24 25 26 27 28 29 30 31 32 33 1 2 3 4 CO2 wt% 44.458 43.318 44.523 43.184 44.149 44.007 43.8 43.408 43.209 43.771 43.431 43.285 43.939 43.278 45.968 46.74 45.876 47.279 MgO wt% 0.5375 0.061 0.4787 0.1595 0.0171 0.0374 0.0396 0 0.0214 0.0482 0.0471 0.0599 0 0.0471 18.008 17.745 17.993 19.68 CaO wt% 52.715 56.382 53.146 56.278 55.788 55.605 55.885 56.504 56.526 55.793 56.362 56.409 55.803 56.375 30.282 30.241 30.22 30.414 MnO wt% 0.3881 0.1684 0.2659 0.284 0.0456 0.3365 0.2243 0.0632 0.1578 0.2841 0.0842 0.2243 0.2211 0.1438 0.5535 0.5124 0.5225 0.4696 FeO wt% 1.9023 0.071 1.5863 0.095 0 0.0142 0.0513 0.0251 0.0863 0.1038 0.0765 0.0218 0.0361 0.1562 5.1889 4.7621 5.3889 2.1572 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.02 1.98 2.02 1.98 2.00 2.00 2.00 1.98 1.98 2.00 1.99 1.98 2.00 1.98 1.99 2.01 1.98 2.00 Mg 0.03 0.00 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.85 0.83 0.85 0.91 Ca 1.88 2.03 1.89 2.02 1.99 1.98 2.00 2.03 2.03 2.00 2.02 2.03 1.99 2.03 1.03 1.02 1.03 1.01 Mn 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.01 Fe 0.05 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.13 0.14 0.06 516 Table B.5 (Continued) Sample GC04003-338 (continued) Carbonate type Coarse colloform-crustiform vein EMPA Spot 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 CO2 wt% 46.551 46.707 45.919 45.785 45.921 46.289 46.419 46.427 46.53 46.383 46.556 46.52 46.286 46.25 46.953 46.425 46.515 46.978 MgO wt% 17.793 18.086 17.562 17.638 17.789 17.818 18.11 18.691 19.173 18.993 17.606 18.109 18.145 18.299 18.364 18.011 17.977 18.141 CaO wt% 30.175 29.931 30.262 29.985 29.875 30.092 29.868 30.191 30.08 30.267 30.092 29.925 30.199 30.307 30.371 30.264 30.614 30.008 MnO wt% 0.4007 0.5199 0.4943 0.574 0.4803 0.4705 0.4881 0.6846 0.6322 0.5801 0.4562 0.5192 0.5122 0.4845 0.5349 0.5785 0.5929 0.6636 FeO wt% 5.0799 4.7563 5.7642 6.0182 5.9347 5.3304 5.1156 4.0073 3.5849 3.7775 5.2904 4.9265 4.8572 4.6591 3.7768 4.7216 4.3019 4.2099 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 2.00 1.99 1.98 1.99 2.00 2.00 1.99 1.99 1.99 2.00 2.00 1.99 1.99 2.01 2.00 2.00 2.01 Mg 0.84 0.85 0.83 0.83 0.84 0.84 0.85 0.88 0.90 0.89 0.83 0.85 0.85 0.86 0.86 0.85 0.84 0.85 Ca 1.02 1.01 1.03 1.02 1.01 1.02 1.01 1.02 1.01 1.02 1.02 1.01 1.02 1.02 1.02 1.02 1.03 1.01 Mn 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.02 Fe 0.13 0.12 0.15 0.16 0.16 0.14 0.13 0.11 0.09 0.10 0.14 0.13 0.13 0.12 0.10 0.12 0.11 0.11 517 Table B.5 (Continued) Sample GC04003-338 (continued) D39018-3562 Carbonate type Coarse colloform-crustiform vein Ankerite-calcite vein EMPA Spot 24 25 26 27 28 29 30 1 2 3 4 5 6 7 8 9 10 CO2 wt% 46.138 46.021 45.745 45.884 46.12 46.304 46.454 44.247 43.869 44.031 44.154 44.033 44.388 43.884 44.785 43.94 45.977 MgO wt% 17.757 17.9 17.952 17.951 17.737 18.176 17.919 0.9715 1.1956 1.3659 1.2278 1.2954 1.2246 1.3015 1.2964 1.1383 16.174 CaO wt% 29.929 30.094 30.556 30.62 30.161 29.927 29.965 52.23 51.973 51.542 51.684 52.003 51.922 52.173 51.122 52.32 30.382 MnO wt% 0.5223 0.519 0.432 0.4183 0.5086 0.5439 0.4881 0.6511 0.6679 0.7098 0.6366 0.5634 0.5772 0.6333 0.539 0.5809 0.4488 FeO wt% 5.654 5.4664 5.3153 5.1264 5.4742 5.0496 5.174 1.8996 2.2949 2.3516 2.2977 2.1054 1.8875 2.0081 2.257 2.0213 7.0186 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 1.99 1.98 1.98 1.99 1.99 2.00 2.01 2.00 2.00 2.01 2.00 2.01 2.00 2.02 2.00 2.00 Mg 0.84 0.84 0.85 0.85 0.84 0.85 0.84 0.05 0.06 0.07 0.06 0.06 0.06 0.06 0.06 0.06 0.77 Ca 1.01 1.02 1.04 1.04 1.02 1.01 1.01 1.86 1.86 1.84 1.84 1.86 1.85 1.86 1.81 1.87 1.04 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 Fe 0.15 0.14 0.14 0.14 0.14 0.13 0.14 0.05 0.06 0.07 0.06 0.06 0.05 0.06 0.06 0.06 0.19 518 Table B.5 (Continued) Sample D39018-3562 (continued) Carbonate type Ankerite-calcite vein EMPA Spot 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 CO2 wt% 44.719 45.5 44.241 44.051 44.543 44.891 44.529 44.365 44.234 44.56 45.315 44.003 43.563 44.452 44.31 41.984 43.803 44.901 MgO wt% 16.102 15.767 1.169 1.0787 0.9462 1.1223 1.1952 1.2148 1.2376 0.9651 1.3553 1.0359 0.9156 1.2849 1.1364 1.1743 1.1003 1.4157 CaO wt% 30.69 30.218 52.377 52.661 52.475 51.677 52.22 52.013 52.234 52.253 50.836 52.675 53.234 51.741 52.207 54.365 52.806 51.266 MnO wt% 0.4523 0.63 0.4549 0.5569 0.5888 0.6026 0.5432 0.6198 0.6473 0.6061 0.5466 0.6968 0.6791 0.6401 0.4868 0.6781 0.6337 0.5815 FeO wt% 8.0378 7.8848 1.7581 1.6525 1.4471 1.707 1.5127 1.7879 1.6466 1.616 1.9466 1.5899 1.6079 1.8819 1.8601 1.7993 1.6574 1.8358 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.97 1.99 2.01 2.00 2.02 2.03 2.01 2.01 2.01 2.02 2.04 2.00 1.99 2.01 2.01 1.95 2.00 2.02 Mg 0.77 0.75 0.06 0.05 0.05 0.06 0.06 0.06 0.06 0.05 0.07 0.05 0.05 0.06 0.06 0.06 0.05 0.07 Ca 1.06 1.04 1.87 1.88 1.86 1.83 1.85 1.85 1.86 1.86 1.79 1.88 1.91 1.84 1.86 1.98 1.89 1.81 Mn 0.01 0.02 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.02 0.02 Fe 0.22 0.21 0.05 0.05 0.04 0.05 0.04 0.05 0.05 0.04 0.05 0.04 0.05 0.05 0.05 0.05 0.05 0.05 519 Table B.5 (Continued) Sample D39018-3562 (continued) D39018-43 Carbonate type Ankerite-calcite vein Ankerite with biotite selvage EMPA Spot 29 30 1 2 3 4 5 6 7 8 9 10 11 12 13 CO2 wt% 44.654 44.54 46.387 47.012 45.919 45.808 45.123 45.644 47.104 46.987 45.364 45.372 46.064 45.404 45.889 MgO wt% 1.3469 0.9874 17.813 18.104 16.232 16.117 14.858 15.689 18.001 18.268 16.12 16.066 16.171 15.717 15.442 CaO wt% 51.617 52.335 30.188 30.258 30.417 30.367 29.93 30.741 30.723 30.726 30.629 30.068 30.346 30.538 30.007 MnO wt% 0.5534 0.5291 0.1432 0.126 0.2644 0.1565 1.1559 0.1564 0.1612 0.0421 0.3649 0.5569 0.348 0.3864 0.5117 FeO wt% 1.8289 1.6086 5.4685 4.4992 7.1674 7.552 8.9328 7.7698 4.0107 3.9775 7.5227 7.9372 7.0711 7.9547 8.1495 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.02 2.02 2.00 2.01 2.00 1.99 1.99 1.99 2.01 2.01 1.98 1.99 2.00 1.99 2.00 Mg 0.07 0.05 0.84 0.84 0.77 0.77 0.72 0.75 0.84 0.85 0.77 0.77 0.77 0.75 0.74 Ca 1.83 1.86 1.02 1.01 1.04 1.04 1.04 1.05 1.03 1.03 1.05 1.03 1.03 1.05 1.03 Mn 0.02 0.01 0.00 0.00 0.01 0.00 0.03 0.00 0.00 0.00 0.01 0.02 0.01 0.01 0.01 Fe 0.05 0.04 0.14 0.12 0.19 0.20 0.24 0.21 0.10 0.10 0.20 0.21 0.19 0.21 0.22 520 Table B.5 (Continued) Sample D39018-43 (continued) Carbonate type Ankerite with biotite selvage EMPA Spot 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 CO2 wt% 45.082 45.755 45.72 44.776 45.363 45.691 45.306 45.404 44.815 45.339 45.779 46.128 45.721 45.817 45.355 45.362 45.368 45.538 MgO wt% 15.408 16.623 16.102 15.154 15.272 16.039 14.836 16.502 14.694 15.147 15.857 15.949 16.085 15.375 15.718 14.73 14.958 15.643 CaO wt% 30.256 30.438 30.82 29.899 29.988 30.547 31.503 30.876 31.308 30.44 29.794 30.074 30.378 29.989 30.303 29.701 29.999 30.066 MnO wt% 0.9976 0.2367 0.2331 0.6488 0.5004 0.1356 0.2541 0.2433 0.855 0.1843 0.8808 0.2052 0.1947 0.8073 0.1948 0.1735 0.5662 1.3016 FeO wt% 8.2564 6.9472 7.1262 9.5223 8.8773 7.5869 8.1007 6.9754 8.3281 8.8902 7.6886 7.6439 7.6221 8.0107 8.4296 10.033 9.1097 7.4513 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.98 1.99 1.99 1.98 1.99 1.99 1.99 1.98 1.98 1.99 2.00 2.00 1.99 2.00 1.99 2.00 1.99 1.99 Mg 0.74 0.79 0.77 0.73 0.73 0.76 0.71 0.79 0.71 0.73 0.76 0.76 0.77 0.73 0.75 0.71 0.72 0.75 Ca 1.04 1.04 1.05 1.04 1.03 1.05 1.09 1.06 1.08 1.05 1.02 1.03 1.04 1.03 1.04 1.03 1.03 1.03 Mn 0.03 0.01 0.01 0.02 0.01 0.00 0.01 0.01 0.02 0.01 0.02 0.01 0.01 0.02 0.01 0.00 0.02 0.04 Fe 0.22 0.19 0.19 0.26 0.24 0.20 0.22 0.19 0.23 0.24 0.21 0.20 0.20 0.21 0.23 0.27 0.25 0.20 521 Table B.5 (Continued) Sample D39018-43 (continued) 37L768-98 Carbonate type Ankerite with biotite selvage Coarse colloform-crustiform vein EMPA Spot 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 CO2 wt% 44.517 44.033 43.996 44.485 44.494 44.353 43.892 44.68 43.963 44.105 44.295 45.346 46.119 45.999 45.74 45.361 45.718 44.839 MgO wt% 14.546 12.49 12.216 13.05 12.655 12.384 11.423 12.159 12.087 12.104 12.516 15.618 15.989 16.225 16.647 15.094 16.445 14.437 CaO wt% 30.186 29.716 29.565 29.871 29.405 29.498 29.117 29.008 29.312 29.367 29.291 30.169 30.092 30.046 30.595 29.902 30.056 29.823 MnO wt% 0.4955 0.4584 0.5096 0.5665 0.5036 0.6239 0.5874 0.5478 0.5437 0.5611 0.4097 0.3444 0.3509 0.3896 0.2403 0.3925 0.2119 0.5094 FeO wt% 10.255 13.303 13.713 12.028 12.943 13.141 14.981 13.606 14.095 13.863 13.489 8.5231 7.4496 7.3409 6.7779 9.2503 7.5694 10.392 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.98 1.98 1.98 1.99 1.99 1.99 1.99 2.00 1.98 1.99 1.99 1.99 2.00 2.00 1.99 1.99 1.99 1.99 Mg 0.70 0.61 0.60 0.64 0.62 0.61 0.56 0.59 0.59 0.59 0.61 0.75 0.76 0.77 0.79 0.72 0.78 0.70 Ca 1.05 1.05 1.04 1.05 1.03 1.04 1.03 1.02 1.04 1.04 1.03 1.04 1.03 1.02 1.04 1.03 1.03 1.04 Mn 0.01 0.01 0.01 0.02 0.01 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Fe 0.28 0.37 0.38 0.33 0.35 0.36 0.42 0.37 0.39 0.38 0.37 0.23 0.20 0.20 0.18 0.25 0.20 0.28 522 Table B.5 (Continued) Sample 37L768-98 (continued) Carbonate type Coarse colloform-crustiform vein EMPA Spot 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 32 35 CO2 wt% 45.832 45.491 46.457 45.95 44.658 44.691 45.422 47 45.829 45.095 47.293 46.655 46.252 46.002 45.885 47.341 46.227 45.658 MgO wt% 15.439 15.893 17.377 15.576 13.945 14.188 15.825 16.083 16.39 13.884 18.521 16.03 16.341 15.585 15.911 15.543 16.165 15.392 CaO wt% 30.158 29.994 30.253 30.135 29.777 30.269 30.104 29.514 29.641 30.023 29.741 29.526 29.95 30.384 30.336 29.494 30.045 29.85 MnO wt% 0.3547 0.2923 0.2023 0.3378 0.391 0.315 0.355 0.296 0.3719 0.2807 0.1296 0.2749 0.2784 0.4032 0.5563 0.3969 0.5324 0.4695 FeO wt% 8.2165 8.3298 5.7111 8.0011 11.23 10.537 8.2939 7.1073 7.7677 10.718 4.3163 7.5136 7.1778 7.625 7.3114 7.2249 7.0306 8.6313 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 1.99 2.00 2.00 1.98 1.98 1.99 2.02 2.00 1.99 2.01 2.02 2.00 2.00 2.00 2.04 2.01 2.00 Mg 0.74 0.76 0.82 0.74 0.68 0.69 0.76 0.76 0.78 0.67 0.86 0.76 0.77 0.74 0.76 0.73 0.77 0.74 Ca 1.03 1.03 1.02 1.03 1.04 1.05 1.03 1.00 1.01 1.04 0.99 1.00 1.02 1.04 1.04 1.00 1.02 1.02 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.02 0.01 0.01 0.01 Fe 0.22 0.22 0.15 0.21 0.31 0.29 0.22 0.19 0.21 0.29 0.11 0.20 0.19 0.20 0.20 0.19 0.19 0.23 523 Table B.5 (Continued) Sample 37L768-98 (continued) 37L768-2005 Carbonate type Coarse colloform-crustiform vein Coarse colloform-crustiform vein EMPA Spot 36 37 38 39 40 41 42 43 1 2 3 4 5 6 7 8 9 CO2 wt% 45.792 46.044 45.766 47.045 46.119 47.043 45.84 45.931 47.136 47.645 47.214 47.249 46.651 47.329 47.152 47.245 46.097 MgO wt% 16.403 16.208 17.057 18.092 17.221 18.249 16.692 15.345 18.931 19.419 19.144 19.351 18.355 19.342 19.256 16.568 17.297 CaO wt% 30.227 29.927 30.104 30.252 29.783 30.218 30.12 29.843 30.278 30.892 30.475 30.791 30.349 30.714 30.74 29.077 30.26 MnO wt% 0.4522 0.32 0.289 0.2134 0.3589 0.2171 0.3794 0.4663 0.1263 0.0211 0.0983 0.0984 0.2765 0.0738 0.1475 0.3102 0.3557 FeO wt% 7.1254 7.5018 6.7839 4.397 6.5185 4.2729 6.9685 8.4151 3.5291 2.0241 3.0693 2.5111 4.3692 2.5409 2.7045 6.7994 5.9899 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 2.00 1.99 2.01 2.00 2.01 1.99 2.00 2.01 2.01 2.01 2.01 2.00 2.01 2.00 2.03 1.99 Mg 0.78 0.77 0.81 0.84 0.81 0.85 0.79 0.73 0.88 0.90 0.89 0.90 0.86 0.90 0.89 0.78 0.82 Ca 1.03 1.02 1.03 1.01 1.01 1.01 1.03 1.02 1.01 1.02 1.02 1.03 1.02 1.02 1.03 0.98 1.03 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.01 Fe 0.19 0.20 0.18 0.12 0.17 0.11 0.19 0.22 0.09 0.05 0.08 0.07 0.11 0.07 0.07 0.18 0.16 524 Table B.5 (Continued) Sample 37L768-2005 Carbonate type Coarse colloform-crustiform vein EMPA Spot 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 CO2 wt% 46.53 46.873 46.12 45.167 46.693 46.814 46.433 47.106 46.16 46.575 46.621 46.695 47.067 46.716 47.276 46.541 46.896 46.575 MgO wt% 19.442 18.265 18.22 16.193 17.889 18.052 18.019 17.949 15.756 18.446 19.272 19.211 18.802 18.92 18.335 18.189 18.544 17.978 CaO wt% 30.411 30.409 30.779 30.457 30.09 30.356 30.778 30.354 29.801 30.346 30.683 30.646 30.532 30.652 30.385 30.331 30.248 30.217 MnO wt% 0.1506 0.1854 0.2203 0.5775 0.3981 0.2765 0.1819 0.1786 0.5039 0.238 0.1649 0.1158 0.1017 0.1648 0.1613 0.2309 0.2277 0.1993 FeO wt% 3.4662 4.2671 4.6612 7.6046 4.93 4.5024 4.5885 4.4115 7.7785 4.3955 3.2588 3.3314 3.4972 3.5472 3.8433 4.7075 4.0851 5.0318 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 2.00 1.99 1.98 2.00 2.00 2.00 2.01 2.01 2.00 1.99 1.99 2.01 2.00 2.01 2.00 2.00 2.00 Mg 0.91 0.85 0.86 0.77 0.84 0.84 0.85 0.84 0.75 0.86 0.90 0.90 0.87 0.88 0.85 0.85 0.87 0.84 Ca 1.02 1.02 1.04 1.05 1.01 1.02 1.04 1.02 1.02 1.02 1.03 1.03 1.02 1.03 1.02 1.02 1.01 1.02 Mn 0.00 0.00 0.01 0.02 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 Fe 0.09 0.11 0.12 0.20 0.13 0.12 0.12 0.12 0.21 0.12 0.09 0.09 0.09 0.09 0.10 0.12 0.11 0.13 525 Table B.5 (Continued) Sample 37L768-2005 (continued) DS358-132 Carbonate type Coarse colloform-crustiform vein Carbonate vein in Lamprophyre EMPA Spot 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 1 2 CO2 wt% 46.492 46.865 46.237 46.844 46.308 45.657 45.963 46.992 47.585 47.247 46.024 46.127 45.859 46.111 45.833 46.304 43.303 42.975 MgO wt% 17.807 18.045 17.652 18.671 18.347 16.815 17.119 18.709 19.378 19.72 17.621 16.752 16.578 16.818 16.94 16.706 11.45 11.416 CaO wt% 30.192 30.062 30.271 30.569 30.612 30.277 30.289 30.438 30.358 30.466 30.377 29.997 29.833 30.346 30.72 30.116 29.85 30.595 MnO wt% 0.2062 0.2659 0.4364 0.1402 0.1714 0.6161 0.596 0.2244 0.1265 0.0668 0.516 0.3796 0.4765 0.5123 0.5821 0.4948 0.6925 0.5694 FeO wt% 5.3029 4.7629 5.4037 3.7768 4.5613 6.6354 6.0331 3.636 2.5523 2.4994 5.4627 6.7445 7.2545 6.2128 5.925 6.3785 14.705 14.445 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 2.01 1.99 2.00 1.99 1.99 1.99 2.00 2.01 2.00 1.99 2.00 1.99 2.00 1.99 2.00 1.97 1.96 Mg 0.84 0.84 0.83 0.87 0.86 0.80 0.81 0.87 0.90 0.91 0.83 0.79 0.79 0.80 0.80 0.79 0.57 0.57 Ca 1.02 1.01 1.02 1.02 1.03 1.03 1.03 1.02 1.01 1.01 1.03 1.02 1.02 1.03 1.05 1.02 1.07 1.09 Mn 0.01 0.01 0.01 0.00 0.00 0.02 0.02 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.02 Fe 0.14 0.12 0.14 0.10 0.12 0.18 0.16 0.10 0.07 0.06 0.14 0.18 0.19 0.16 0.16 0.17 0.41 0.40 526 Table B.5 (Continued) Sample DS358-132 (continued) Carbonate type Carbonate vein in Lamprophyre EMPA Spot 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 CO2 wt% 43.618 43.475 43.778 43.721 43.216 43.052 43.758 42.614 43.137 43.847 43.571 43.846 43.57 43.264 43.191 43.768 43.641 43.797 MgO wt% 11.742 13.005 12.415 11.748 12.511 11.511 12.002 10.994 11.213 11.585 12.218 12.78 11.55 12.372 12.578 13.17 12.747 12.928 CaO wt% 29.936 29.947 30.277 29.8 30.049 30.264 30.12 29.809 29.467 29.714 30.579 29.933 30.213 29.969 30.248 30.026 29.761 30.259 MnO wt% 0.6248 0.5159 0.6055 0.6454 0.6871 0.6618 0.8008 0.6122 0.5991 0.7175 0.8358 0.9464 0.8927 0.8827 0.818 0.9126 0.9697 0.9505 FeO wt% 14.08 13.058 12.925 14.085 13.537 14.512 13.319 15.97 15.585 14.136 12.796 12.495 13.773 13.512 13.165 12.124 12.882 12.066 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.97 1.96 1.97 1.98 1.96 1.96 1.98 1.95 1.97 1.98 1.97 1.97 1.97 1.96 1.96 1.97 1.97 1.97 Mg 0.58 0.64 0.61 0.58 0.62 0.57 0.59 0.55 0.56 0.57 0.60 0.63 0.57 0.61 0.62 0.65 0.63 0.63 Ca 1.06 1.06 1.07 1.06 1.07 1.08 1.07 1.07 1.05 1.05 1.08 1.06 1.07 1.07 1.08 1.06 1.05 1.07 Mn 0.02 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.02 0.02 0.03 0.03 0.03 Fe 0.39 0.36 0.36 0.39 0.38 0.40 0.37 0.45 0.44 0.39 0.35 0.34 0.38 0.38 0.37 0.33 0.36 0.33 527 Table B.5 (Continued) Sample DS358-132 (continued) DS358-1215 Carbonate type Carbonate vein in Lamprophyre Ankerite-calcite with chlorite selvage EMPA Spot 21 22 23 24 25 26 27 28 29 30 31 32 1 3 4 7 8 10 CO2 wt% 42.895 43.958 43.508 44.003 43.629 43.738 43.3 43.716 43.511 43.419 43.057 44.017 44.449 45.101 44.644 44.403 45.092 44.335 MgO wt% 11.934 11.382 12.532 12.363 11.2 13.004 11.811 9.0023 10.281 11.18 11.668 11.727 12.644 12.351 14.135 13.341 14.687 12.755 CaO wt% 30.402 32.646 29.755 30.39 29.713 30.514 29.73 35.181 29.345 29.721 29.672 30.106 29.573 29.399 29.827 29.476 29.845 29.759 MnO wt% 0.7515 1.2731 0.7594 1.0639 0.7372 1.013 0.7649 0.5448 0.7832 0.7882 0.795 0.8456 0.7093 0.8338 0.5148 0.5583 0.3393 0.6337 FeO wt% 14.018 10.741 13.446 12.18 14.722 11.731 14.394 11.556 16.08 14.893 14.808 13.304 12.625 12.315 10.88 12.222 10.037 12.518 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.95 1.98 1.97 1.98 1.98 1.97 1.97 1.98 1.98 1.97 1.96 1.98 1.99 2.01 1.98 1.98 1.99 1.98 Mg 0.59 0.56 0.62 0.61 0.55 0.64 0.59 0.45 0.51 0.55 0.58 0.58 0.62 0.60 0.69 0.65 0.71 0.62 Ca 1.09 1.15 1.06 1.07 1.06 1.08 1.06 1.25 1.05 1.06 1.06 1.06 1.04 1.03 1.04 1.03 1.03 1.05 Mn 0.02 0.04 0.02 0.03 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.01 0.02 Fe 0.39 0.30 0.37 0.34 0.41 0.32 0.40 0.32 0.45 0.41 0.41 0.37 0.35 0.34 0.30 0.33 0.27 0.34 528 Table B.5 (Continued) Sample DS358-1215 DS172-123 Carbonate type Ankerite-calcite with chlorite selvage Ankerite-calcite-quartz vein Ankerite-calcite with chlorite selvage EMPA Spot 19 20 22 24 1 4 5 6 7 8 12 13 14 15 16 18 CO2 wt% 44.256 44.073 43.954 44.68 43.356 43.299 43.698 43.729 43.303 43.547 43.41 43.397 43.519 43.702 43.581 43.318 MgO wt% 11.368 10.698 12.095 12.874 0 0.0308 0.0185 0 0.2155 0.04 0.0108 0 0.0154 0 0 0 CaO wt% 28.935 29.345 29.843 29.957 56.539 56.568 56.152 56.172 56.334 56.192 56.523 56.337 56.136 56.008 56.36 56.606 MnO wt% 1.211 1.1277 0.825 0.4517 0.0794 0.0596 0.0762 0.0629 0.0861 0.0795 0.0563 0.1193 0.1721 0.1192 0.0298 0.0298 FeO wt% 14.231 14.756 13.283 12.038 0.0252 0.042 0.0546 0.0367 0.0609 0.1418 0 0.147 0.1584 0.171 0.0294 0.0462 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 1.99 1.98 1.99 1.98 1.98 1.99 1.99 1.98 1.99 1.98 1.99 1.99 1.99 1.99 1.98 Mg 0.56 0.53 0.59 0.63 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ca 1.02 1.04 1.06 1.05 2.03 2.03 2.01 2.01 2.02 2.01 2.03 2.02 2.01 2.00 2.02 2.03 Mn 0.03 0.03 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe 0.39 0.41 0.37 0.33 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 529 Table B.5 (Continued) Sample DS172-12 GC01018-85 Carbonate type Ankerite-calcite with chlorite selvage Ankerite-calcite with chlorite selvage EMPA Spot 22 23 24 25 1 2 3 4 5 6 7 8 10 11 12 13 CO2 wt% 43.498 43.352 43.526 43.701 44.06 43.823 43.709 44.137 44.011 43.859 44.215 44.322 44.29 44.362 43.914 44.374 MgO wt% 0 0 0 0 0 0 0.0447 0.313 0.0556 0.074 0 0.1975 0.4012 0.2204 0.3039 0.3039 CaO wt% 56.339 56.55 56.33 56.238 54.671 55.312 55.231 54.347 54.55 54.955 54.866 54.126 54.109 54.491 54.762 54.363 MnO wt% 0.1127 0.0298 0.0133 0.0199 1.0518 0.8109 0.9255 1.1369 1.2599 1.1006 0.9193 1.2722 1.0654 0.8202 0.9364 0.8574 FeO wt% 0.0504 0.0683 0.1302 0.041 0.217 0.0546 0.0901 0.066 0.1237 0.0115 0 0.0817 0.1343 0.1069 0.0839 0.1018 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 1.98 1.99 1.99 2.01 2.00 2.00 2.01 2.00 2.00 2.01 2.01 2.01 2.01 2.00 2.01 Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.01 0.02 0.01 0.02 0.02 Ca 2.02 2.03 2.02 2.01 1.95 1.98 1.98 1.94 1.95 1.97 1.96 1.93 1.93 1.94 1.96 1.93 Mn 0.00 0.00 0.00 0.00 0.03 0.02 0.03 0.03 0.04 0.03 0.03 0.04 0.03 0.02 0.03 0.02 Fe 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 530 Table B.5 (Continued) Sample GC01018-85 (continued) CR4611-581 Carbonate type Ankerite-calcite with chlorite selvage Ankerite-calcite vein EMPA Spot 15 16 17 18 19 21 11 23 24 25 2 3 4 6 7 8 10 13 CO2 wt% 43.831 44.625 44.498 43.714 44.153 44.053 44.137 44.147 44.043 44.025 44.529 44.154 44.199 44.069 43.768 44.448 44.651 44.51 MgO wt% 0.0108 0.1729 0.1203 0 0.1171 0.2455 0.3573 0.0693 0.2311 0.3006 0.0154 0.034 0.3131 0.2529 0.0371 0.2131 0.1698 0.1528 CaO wt% 55.124 54.031 54.614 55.651 54.818 54.339 54.622 55.053 54.837 54.553 54.757 55.172 54.983 55.186 55.438 54.884 54.401 54.727 MnO wt% 0.8272 1.1087 0.7551 0.5954 0.8697 1.2104 0.8466 0.6748 0.8069 1.0015 0.567 0.6398 0.4278 0.4012 0.6296 0.3984 0.6332 0.5206 FeO wt% 0.2066 0.063 0.0136 0.0398 0.0419 0.152 0.0377 0.0566 0.0828 0.1194 0.1324 0 0.0778 0.0904 0.1281 0.0568 0.145 0.0904 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 2.02 2.02 1.99 2.01 2.00 2.01 2.01 2.00 2.00 2.02 2.01 2.01 2.00 2.00 2.01 2.02 2.02 Mg 0.00 0.01 0.01 0.00 0.01 0.01 0.02 0.00 0.01 0.01 0.00 0.00 0.02 0.01 0.00 0.01 0.01 0.01 Ca 1.97 1.92 1.94 1.99 1.96 1.94 1.95 1.96 1.96 1.95 1.95 1.97 1.96 1.97 1.98 1.95 1.93 1.94 Mn 0.02 0.03 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.03 0.02 0.02 0.01 0.01 0.02 0.01 0.02 0.01 Fe 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 531 Table B.5 (Continued) Sample CR4611-581 (continued) CR468-629 Carbonate type Pervasive Dark CL ankerite-calcite vein EMPA Spot 14 15 16 18 19 22 23 24 25 1 2 4 5 6 7 8 9 CO2 wt% 43.754 43.797 43.989 44.13 44.628 44.506 44.447 44.352 44.485 44.075 44.38 43.808 43.776 44.098 43.953 43.974 44.146 MgO wt% 0.0587 0.0757 0.4043 0.1313 0.0943 0.051 0.3569 0.4973 0.3679 0.1468 0.1777 0.1714 0.1206 0.1315 0.1668 0.1483 0.1407 CaO wt% 55.524 55.342 54.79 55.214 54.493 54.812 54.394 54.36 54.153 54.867 54.519 55.212 55.359 54.922 55.102 55.013 54.847 MnO wt% 0.6137 0.6958 0.6594 0.5045 0.7235 0.5145 0.647 0.6437 0.7629 0.2717 0.2552 0.2982 0.2454 0.2421 0.1922 0.2286 0.2985 FeO wt% 0.0494 0.0893 0.1576 0.021 0.061 0.1168 0.1546 0.1473 0.2314 0.6397 0.6682 0.5105 0.4995 0.6068 0.5862 0.6365 0.5679 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 2.00 2.00 2.01 2.02 2.02 2.01 2.01 2.01 2.00 2.01 2.00 2.00 2.01 2.00 2.00 2.01 Mg 0.00 0.00 0.02 0.01 0.00 0.00 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ca 1.99 1.98 1.96 1.97 1.93 1.95 1.93 1.93 1.92 1.96 1.94 1.98 1.98 1.96 1.97 1.97 1.96 Mn 0.02 0.02 0.02 0.01 0.02 0.01 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Fe 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.02 0.01 0.01 0.02 0.02 0.02 0.02 CL = cathodoluminescence 532 Table B.5 (Continued) Sample CR468-629 (continued) ES09_AP_6A Carbonate type Dark CL ankerite-calcite vein Light CL ankerite- calcite vein Dark CL ankerite-calcite vein Light CL pervasive Dark CL pervasive Coarse colloform-crustiform vein EMPA Spot 10 11 12 14 15 16 17 18 19 21 22 23 25 1 2 3 CO2 wt% 43.487 43.544 43.724 43.358 44.662 44.348 43.427 43.778 43.768 44.468 44.233 43.915 44.305 46.116 46.018 46.039 MgO wt% 0.1546 0.1577 0.1778 0.0463 0.1639 0.1484 0.0571 0.1591 0.0756 0.1841 0.0324 0.1377 0.0867 16.448 16.562 17.002 CaO wt% 55.464 55.388 55.297 56.487 54.37 54.566 56.339 55.646 55.792 54.396 55.326 55.001 54.566 30.1 30.241 30.516 MnO wt% 0.252 0.2851 0.252 0.0631 0.2157 0.3479 0.0498 0.0332 0.1791 0.3184 0.3055 0.2885 0.2752 0.3245 0.3905 0.3611 FeO wt% 0.6421 0.6253 0.5499 0.0463 0.5882 0.5894 0.1273 0.384 0.186 0.6331 0.1031 0.6581 0.7675 7.0119 6.7886 6.0824 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 1.99 1.99 1.98 2.02 2.01 1.99 2.00 2.00 2.02 2.01 2.00 2.01 2.00 2.00 1.99 Mg 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.78 0.78 0.80 Ca 1.99 1.99 1.98 2.03 1.93 1.94 2.02 1.99 2.00 1.93 1.97 1.97 1.94 1.02 1.03 1.04 Mn 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Fe 0.02 0.02 0.02 0.00 0.02 0.02 0.00 0.01 0.01 0.02 0.00 0.02 0.02 0.19 0.18 0.16 533 Table B.5 (Continued) Sample ES09_AP_6A (continued) Carbonate type Coarse colloform-crustiform vein Calcite Late cal- cite veinlet EMPA Spot 4 5 23 24 25 26 27 28 29 30 31 32 33 7 8 9 11 CO2 wt% 46.458 45.371 46.006 45.48 46.132 46.093 46.178 45.811 46.015 45.817 45.975 45.998 46.538 44.718 44.464 44.889 45.657 MgO wt% 16.855 15.496 17.029 15.992 16.453 16.331 17.111 16.806 16.304 16.751 17.166 17.462 17.051 1.5371 1.5812 3.7929 14.397 CaO wt% 30.092 30.044 30.497 30.089 29.936 30.057 30.538 30.817 30.615 30.73 30.226 30.154 30.195 53.157 53.424 49.475 29.994 MnO wt% 0.3221 0.4031 0.3385 0.3905 0.3346 0.3509 0.3519 0.4008 0.3315 0.3941 0.3252 0.3484 0.4012 0.3446 0.2618 0.4232 0.3371 FeO wt% 6.2737 8.6854 6.1301 8.0486 7.1442 7.1683 5.8213 6.1643 6.7347 6.3075 6.3079 6.0373 5.8144 0.2438 0.269 1.4195 9.6147 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.01 1.99 1.99 1.99 2.00 2.00 2.00 1.99 2.00 1.99 1.99 1.99 2.01 2.01 2.01 2.01 2.00 Mg 0.79 0.74 0.81 0.76 0.78 0.77 0.81 0.80 0.77 0.79 0.81 0.83 0.80 0.08 0.08 0.19 0.69 Ca 1.02 1.03 1.04 1.03 1.02 1.02 1.04 1.05 1.04 1.05 1.03 1.02 1.02 1.88 1.89 1.74 1.03 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Fe 0.17 0.23 0.16 0.22 0.19 0.19 0.15 0.16 0.18 0.17 0.17 0.16 0.15 0.01 0.01 0.04 0.26 534 Table B.5 (Continued) Sample ES09_AP_6A (continued) ES09_AP_27 Carbonate type Late calcite veinlet Dark CL veinlet EMPA Spot 12 14 15 16 17 18 20 22 35 38 40 1 2 3 4 5 6 7 CO2 wt% 45.166 45.343 45.14 44.97 46.159 45.131 44.842 45.076 44.197 44.916 45.32 46.924 47.15 46.99 46.952 46.83 47.284 47.292 MgO wt% 13.301 14.557 14.167 14.376 15.783 13.79 13.77 15.163 12.656 14.315 14.743 18.332 18.609 18.186 18.101 19.008 18.742 19.166 CaO wt% 31.374 30.335 30.521 30.175 30.053 30.34 29.74 30.253 29.743 29.627 29.615 30.66 30.891 30.571 31.054 30.87 30.768 30.516 MnO wt% 0.3565 0.3797 0.3369 0.4278 0.3768 0.4084 0.4567 0.4617 0.6664 0.5616 0.5298 0.0595 0.0595 0.0991 0.1123 0.1389 0.086 0.0463 FeO wt% 9.803 9.3861 9.8349 10.051 7.6276 10.331 11.191 9.0457 12.738 10.581 9.7919 4.0245 3.2913 4.155 3.7812 3.153 3.1197 2.9796 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 2.00 1.99 1.99 1.99 2.01 2.00 1.99 1.98 1.98 1.99 1.99 2.00 2.01 2.01 2.01 2.00 2.01 2.01 Mg 0.64 0.70 0.68 0.69 0.75 0.67 0.67 0.73 0.62 0.69 0.71 0.86 0.87 0.85 0.84 0.89 0.87 0.89 Ca 1.09 1.05 1.06 1.05 1.03 1.05 1.04 1.05 1.05 1.03 1.02 1.03 1.03 1.03 1.04 1.03 1.03 1.02 Mn 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe 0.27 0.25 0.27 0.27 0.20 0.28 0.30 0.24 0.35 0.29 0.26 0.11 0.09 0.11 0.10 0.08 0.08 0.08 535 Table B.5 (Continued) Sample ES09_AP_27 (continued) Carbonate type Dark CL veinlet Light CL veinlet Coarse colloform-crustiform vein EMPA Spot 8 9 10 12 13 14 16 17 20 50 23 24 25 26 27 28 29 CO2 wt% 46.577 46.92 46.908 44.716 44.435 44.645 44.93 44.794 44.731 44.605 47.469 47.252 46.644 46.756 46.43 46.365 46.164 MgO wt% 18.695 18.852 18.401 14.734 13.704 13.98 13.663 13.831 14.057 13.798 19.318 19.13 18.706 17.79 18.004 17.382 17.74 CaO wt% 30.807 30.551 30.704 29.902 29.925 29.595 29.802 29.79 29.978 29.951 30.439 30.541 30.622 30.701 30.524 30.867 30.632 MnO wt% 0.1387 0.0595 0.1024 0.4215 0.4824 0.4761 0.4986 0.4958 0.3982 0.4631 0.0861 0.0993 0.0826 0.112 0.1615 0.1647 0.1976 FeO wt% 3.7836 3.6178 3.885 10.227 11.454 11.305 11.106 11.089 10.836 11.183 2.6881 2.9772 3.9453 4.641 4.88 5.2217 5.2669 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.99 2.00 2.00 1.98 1.98 1.98 1.99 1.99 1.98 1.98 2.01 2.01 2.00 2.00 2.00 2.00 1.99 Mg 0.87 0.88 0.86 0.71 0.67 0.68 0.66 0.67 0.68 0.67 0.89 0.89 0.87 0.83 0.85 0.82 0.84 Ca 1.04 1.02 1.03 1.04 1.05 1.03 1.04 1.04 1.04 1.05 1.01 1.02 1.03 1.03 1.03 1.04 1.04 Mn 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Fe 0.10 0.09 0.10 0.28 0.31 0.31 0.30 0.30 0.29 0.30 0.07 0.08 0.10 0.12 0.13 0.14 0.14 536 Table B.5 (Continued) Sample ES09_AP_27 (continued) Carbonate type Microcrystalline-cryptocrystalline EMPA Spot 31 33 35 39 40 41 42 43 45 46 47 48 49 CO2 wt% 45.055 45.264 45.245 44.922 44.883 45.024 44.825 45.273 45.032 45.157 44.862 44.848 45.03 MgO wt% 15.319 14.305 14.971 15.087 14.831 14.72 14.834 14.732 14.992 14.918 14.157 14.649 14.937 CaO wt% 29.872 29.64 29.744 30.234 29.927 30.09 29.7 29.843 29.724 30.079 30.231 29.865 29.971 MnO wt% 0.4059 0.4738 0.4384 0.4156 0.5492 0.4906 0.4607 0.5757 0.4059 0.4713 0.3851 0.3202 0.314 FeO wt% 9.349 10.318 9.6022 9.3412 9.811 9.6756 10.181 9.5764 9.8468 9.375 10.365 10.318 9.7474 Total ox- ide wt% 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 C 1.98 2.00 1.99 1.98 1.98 1.99 1.98 1.99 1.99 1.99 1.99 1.98 1.99 Mg 0.74 0.69 0.72 0.73 0.72 0.71 0.72 0.71 0.72 0.72 0.68 0.71 0.72 Ca 1.03 1.03 1.03 1.05 1.04 1.04 1.03 1.03 1.03 1.04 1.05 1.04 1.04 Mn 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 Fe 0.25 0.28 0.26 0.25 0.27 0.26 0.28 0.26 0.27 0.25 0.28 0.28 0.26 537 B.6 Garnet EMPA data This appendix consists of Table B.6 which contains the EMP results of all samples probed for garnet chemistry analysis. Each column identifies the sample, EMP spot number, the weight per- cent oxides, the ideal arrangement of the molar calculated elements in the crystal lattice which were normalized to cations = 8 and for Fe3+ estimates. The last 5 columns provide percentage abundances of garnet end remembers: Almandine = Fe2+3Al2(SiO4)3, Pyrope = Mg2+3Al2(SiO4)3, Grossular = Ca2+3Al2(SiO4)3, Spessartine = Mn2+3Al2(SiO4)3, Uvarovite Ca2+3Cr2(SiO4)3, An- dradite = Ca2+3Fe3+2(SiO4)3.Sample location, metamorphic grade, main alteration assemblage, mineralization sulfide-oxide assemblage, and distance from ore and surface can be found for all samples in Appendix A.2. 538 Table B.6 Complete electron microprobe data for all samples probed for garnet chemistry. Sample D33003-532 EMPA spot 1 2 3 4 6 7 8 9 10 11 12 13 14 15 16 Na2O wt% 0.0177 0.0676 0.0831 0.0632 0.0742 0.0277 0.0277 0.0414 0.0124 0.0485 0.0537 0.0302 0.0052 0.0178 0.0217 MgO wt% 1.1903 1.2860 1.2664 1.3052 1.2690 1.2111 1.7256 1.4415 1.3239 1.3696 1.2167 1.2041 1.2343 1.1943 1.2863 Al2O3 wt% 21.0601 20.5356 20.7437 20.8033 20.9401 20.7739 20.9639 20.8638 20.8273 20.8793 21.0328 20.8292 20.8738 20.8609 20.9479 SiO2 wt% 36.3636 36.6020 35.8544 36.5811 36.6436 36.2823 36.5919 36.1780 36.4731 36.1383 36.0884 36.0962 36.6209 36.1996 36.2087 CaO wt% 2.1563 2.4283 2.9210 2.7247 3.6615 4.4877 3.4431 3.1486 3.9499 3.2577 3.4441 2.7190 2.7589 2.1310 2.8488 TiO wt% 0.0566 0.1333 0.1173 0.1761 0.2185 0.2124 0.0769 0.0957 0.1034 0.1227 0.0837 0.1455 0.1253 0.0770 0.0670 Cr2O3 wt% 0.0019 0.0252 0.0563 0.0234 0.0823 0.0276 0.0157 0.0527 0.0684 0.1036 0.0625 0.0777 0.0738 0.0657 0.0311 MnO wt% 8.0246 8.9999 9.1935 10.0923 10.7329 10.8283 10.5386 10.4420 8.9175 10.1999 9.6951 10.0888 8.7091 8.1660 9.6511 FeO wt% 30.8460 29.4584 29.1186 28.1424 26.7634 25.4113 26.0574 27.4359 28.1139 27.2010 27.4805 28.9024 29.8236 31.2107 28.3826 Total oxide wt% 99.72 99.54 99.35 99.91 100.39 99.26 99.44 99.70 99.79 99.32 99.16 100.09 100.22 99.92 99.45 Fe2+ 2.08 1.97 1.85 1.86 1.73 1.67 1.73 1.76 1.84 1.78 1.81 1.85 1.99 2.05 1.88 Mn 0.56 0.62 0.64 0.70 0.74 0.75 0.73 0.72 0.61 0.71 0.67 0.70 0.60 0.56 0.67 Mg 0.14 0.16 0.15 0.16 0.15 0.15 0.21 0.17 0.16 0.17 0.15 0.15 0.15 0.15 0.16 Ca 0.19 0.21 0.26 0.24 0.32 0.39 0.30 0.27 0.34 0.29 0.30 0.24 0.24 0.19 0.25 Sum X 2.96 2.97 2.90 2.96 2.94 2.96 2.97 2.93 2.96 2.94 2.93 2.93 2.98 2.95 2.95 Ti 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 Al 2.03 1.98 2.00 2.00 2.00 2.00 2.01 2.00 2.00 2.01 2.03 2.00 2.00 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 Fe3+ 0.03 0.04 0.14 0.05 0.08 0.07 0.04 0.11 0.07 0.08 0.07 0.12 0.04 0.08 0.06 Sum Z 2.06 2.03 2.15 2.06 2.09 2.08 2.05 2.12 2.07 2.10 2.11 2.13 2.05 2.09 2.09 Si 2.97 2.99 2.94 2.98 2.96 2.96 2.98 2.95 2.96 2.95 2.95 2.94 2.98 2.96 2.96 Sum T 2.97 2.99 2.94 2.98 2.96 2.96 2.98 2.95 2.96 2.95 2.95 2.94 2.98 2.96 2.96 % Al 70.02 66.53 63.86 63.06 58.97 56.44 58.36 60.08 62.26 60.55 61.71 63.18 66.79 69.62 63.61 % Pyr 4.89 5.28 5.33 5.36 5.21 4.98 7.05 5.97 5.41 5.68 5.06 4.99 5.02 4.93 5.31 % Gr 6.26 7.00 8.22 7.80 10.32 12.78 9.89 8.86 11.19 9.28 9.91 7.61 7.88 6.06 8.18 % Sp 18.73 21.01 21.98 23.54 25.02 25.31 24.47 24.58 20.72 24.05 22.92 23.74 20.12 19.14 22.63 % Uv 0.00 0.01 0.01 0.01 0.03 0.01 0.00 0.02 0.02 0.03 0.02 0.02 0.02 0.01 0.01 % An 0.10 0.14 0.58 0.20 0.40 0.42 0.20 0.48 0.37 0.38 0.35 0.44 0.15 0.23 0.25 Al = almandine, Pyr = pyrope, Gr = grossular, Sp = spessartine, Uv = uvarovite, and An = andradite. 539 Table B.6 (Continued) Sample D33003-532 (continued) EMPA spot 17 18 20 21 22 23 25 26 28 29 30 31 32 33 34 Na2O wt% 0.0217 0.0602 0.0314 0.0094 0.0178 0.0136 0.0094 0.0447 0.0000 0.0000 0.0114 0.0000 0.0000 0.0052 0.0114 MgO wt% 1.3074 1.2927 1.1792 1.1657 1.2641 1.3097 1.2701 1.3174 1.2334 1.2553 1.3076 1.2078 1.2237 1.3099 1.2761 Al2O3 wt% 20.7609 20.9190 21.0208 21.0629 21.0321 20.9201 20.9954 21.0236 20.7429 20.8468 20.9887 21.0064 21.1104 20.8501 21.0102 SiO2 wt% 36.3106 36.4322 36.2354 36.1079 36.2919 36.0431 36.2419 36.3904 36.5538 36.3726 36.4260 36.7191 36.7316 36.3000 36.8853 CaO wt% 2.8276 2.2719 2.0743 2.2247 2.1686 2.2429 2.7688 2.6388 3.1226 2.4259 2.4024 1.9124 2.5824 2.5118 2.4653 TiO wt% 0.2589 0.1527 0.0616 0.0426 0.0294 0.0598 0.1249 0.0815 0.1334 0.1079 0.0230 0.0000 0.1630 0.1147 0.0685 Cr2O3 wt% 0.0760 0.0408 0.0482 0.1158 0.0406 0.0715 0.0214 0.0855 0.0624 0.0388 0.0291 0.0386 0.0466 0.0816 0.0930 MnO wt% 10.7645 10.5113 8.0972 8.1444 8.4139 8.9178 9.7458 10.2238 9.6874 9.7933 8.3891 8.3379 9.4229 9.3195 8.8647 FeO wt% 27.4650 28.2180 31.2658 31.2730 31.0080 30.5481 29.0989 28.7366 28.0950 28.9658 30.1841 31.1579 29.5558 29.0769 30.1782 Total oxide wt% 99.79 99.90 100.01 100.15 100.27 100.13 100.28 100.54 99.63 99.81 99.76 100.38 100.84 99.57 100.85 Fe2+ 1.81 1.87 2.06 2.04 2.02 1.96 1.88 1.84 1.90 1.93 2.02 2.10 1.96 1.95 2.00 Mn 0.74 0.73 0.56 0.56 0.58 0.61 0.67 0.70 0.67 0.68 0.58 0.57 0.64 0.65 0.61 Mg 0.16 0.16 0.14 0.14 0.15 0.16 0.15 0.16 0.15 0.15 0.16 0.15 0.15 0.16 0.15 Ca 0.25 0.20 0.18 0.19 0.19 0.20 0.24 0.23 0.27 0.21 0.21 0.17 0.22 0.22 0.21 Sum X 2.96 2.95 2.94 2.94 2.94 2.93 2.94 2.93 2.99 2.97 2.97 2.98 2.97 2.97 2.98 Ti 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.00 Al 2.00 2.01 2.02 2.02 2.01 2.01 2.01 2.01 2.00 2.01 2.02 2.01 2.01 2.01 2.00 Cr 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.01 Fe3+ 0.06 0.06 0.07 0.09 0.09 0.12 0.10 0.11 0.02 0.05 0.04 0.02 0.04 0.04 0.04 Sum Z 2.07 2.08 2.10 2.12 2.10 2.13 2.11 2.12 2.03 2.06 2.06 2.03 2.06 2.06 2.04 Si 2.96 2.97 2.95 2.94 2.95 2.93 2.94 2.95 2.98 2.97 2.97 2.98 2.97 2.97 2.98 Sum T 2.96 2.97 2.95 2.94 2.95 2.93 2.94 2.95 2.98 2.97 2.97 2.98 2.97 2.97 2.98 % Al 61.19 63.32 69.96 69.45 68.69 66.92 63.83 62.82 63.44 64.96 68.03 70.28 65.85 65.49 67.30 % Pyr 5.37 5.33 4.87 4.82 5.21 5.42 5.22 5.43 5.02 5.14 5.36 4.90 4.95 5.37 5.16 % Gr 8.03 6.52 5.93 6.30 6.14 6.28 7.78 7.39 8.99 6.95 6.93 5.52 7.34 7.22 7.01 % Sp 25.10 24.62 19.01 19.12 19.68 20.98 22.77 23.94 22.40 22.77 19.54 19.23 21.68 21.73 20.37 % Uv 0.02 0.01 0.01 0.02 0.01 0.01 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.02 0.02 % An 0.24 0.18 0.22 0.28 0.26 0.37 0.38 0.39 0.10 0.16 0.14 0.06 0.14 0.15 0.12 540 Table B.6 (Continued) Sample D33003-532 (continued) D39018-4848 EMPA spot 36 38 39 40 41 42 44 45 46 2 3 4 5 7 8 Na2O wt% 0.0548 0.0082 0.0566 0.0483 0.0744 0.0342 0.0083 0.1192 0.0155 0.0237 0.0258 0.0350 0.0124 0.0339 0.0082 MgO wt% 1.6041 1.3876 1.4929 1.5384 1.6585 1.4961 1.5318 1.4358 1.6374 1.3469 1.2429 1.2544 1.4284 1.4604 1.6069 Al2O3 wt% 21.0298 20.9995 20.5646 21.0292 21.1857 20.9949 20.5809 20.6805 21.1590 20.5368 20.8779 20.6147 20.8618 20.8977 21.0677 SiO2 wt% 36.4947 36.9342 37.5950 36.6687 36.1682 36.9410 36.5343 36.4053 36.6772 36.6384 36.2261 36.6415 36.4199 36.3938 37.3566 CaO wt% 2.9603 5.0953 3.2713 3.2635 3.1292 2.7321 3.5112 3.7111 2.9856 5.5304 5.6202 5.7987 4.8120 5.5059 4.6708 TiO wt% 0.0000 0.1070 0.1970 0.1720 0.0944 0.0270 0.2012 0.2109 0.0473 0.3872 0.2016 0.2804 0.0889 0.1715 0.1374 Cr2O3 wt% 0.0000 0.0297 0.0176 0.0589 0.0468 0.0019 0.0176 0.0334 0.0000 0.0805 0.0235 0.0608 0.0098 0.0157 0.0430 MnO wt% 8.5609 11.3042 9.4149 12.1704 8.9779 8.3150 10.0111 12.0093 9.0454 5.4699 5.2093 5.4073 5.2038 5.0072 4.3478 FeO wt% 29.0214 24.2914 27.7555 25.3508 28.5922 29.6051 27.4595 25.2283 28.3911 29.9341 30.4202 30.1834 31.0352 30.4163 31.5306 Total oxide wt% 99.73 100.16 100.37 100.30 99.93 100.15 99.86 99.83 99.96 99.95 99.85 100.28 99.87 99.90 100.77 Fe2+ 1.90 1.60 1.88 1.65 1.81 1.99 1.79 1.59 1.89 1.96 1.94 1.93 2.00 1.94 2.11 Mn 0.59 0.77 0.64 0.83 0.62 0.57 0.69 0.83 0.62 0.38 0.36 0.37 0.36 0.34 0.30 Mg 0.19 0.17 0.18 0.19 0.20 0.18 0.19 0.17 0.20 0.16 0.15 0.15 0.17 0.18 0.19 Ca 0.26 0.44 0.28 0.28 0.27 0.24 0.31 0.32 0.26 0.48 0.49 0.50 0.42 0.48 0.40 Sum X 2.94 2.98 2.98 2.95 2.90 2.98 2.97 2.91 2.97 2.97 2.93 2.95 2.95 2.93 3.00 Ti 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.02 0.01 0.01 0.00 0.01 0.01 Al 2.01 2.00 1.96 2.00 2.02 2.01 1.97 1.98 2.02 1.96 1.99 1.96 1.99 1.99 1.99 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.04 0.00 0.07 0.13 0.02 0.07 0.13 0.04 0.07 0.12 0.11 0.10 0.12 0.01 Sum Z 2.09 2.04 1.97 2.08 2.16 2.02 2.05 2.12 2.06 2.05 2.13 2.08 2.10 2.12 2.01 Si 2.96 2.98 3.04 2.96 2.93 2.99 2.97 2.96 2.97 2.97 2.94 2.96 2.95 2.94 3.00 Sum T 2.96 2.98 3.04 2.96 2.93 2.99 2.97 2.96 2.97 2.97 2.94 2.96 2.95 2.94 3.00 % Al 64.58 53.71 62.88 55.87 62.47 66.81 60.31 54.53 63.67 65.77 66.04 65.39 67.87 66.06 70.35 % Pyr 6.61 5.60 6.03 6.29 6.91 6.07 6.24 5.97 6.67 5.47 5.12 5.11 5.85 6.00 6.41 % Gr 8.46 14.45 9.45 9.23 8.79 7.89 9.87 10.37 8.58 15.40 15.58 15.98 13.45 15.28 13.29 % Sp 20.04 25.92 21.60 28.26 21.25 19.16 23.17 28.39 20.93 12.62 12.19 12.52 12.11 11.69 9.85 % Uv 0.00 0.01 0.01 0.02 0.01 0.00 0.01 0.01 0.00 0.04 0.01 0.03 0.00 0.01 0.02 % An 0.31 0.28 0.00 0.30 0.55 0.06 0.36 0.66 0.15 0.57 0.98 0.87 0.68 0.91 0.04 541 Table B.6 (Continued) Sample D39018-4848 EMPA spot 9 10 11 13 14 15 17 18 19 20 21 22 23 25 26 Na2O wt% 0.0082 0.0508 0.0473 0.0352 0.0051 0.0041 0.0031 0.0062 0.0134 0.0041 0.0227 0.0000 0.0427 0.0407 0.0231 MgO wt% 1.7267 1.3585 1.5963 1.5140 1.5727 1.6527 0.9267 0.9335 1.0451 1.0645 1.1583 1.1917 1.1196 1.0541 1.0249 Al2O3 wt% 21.1393 20.8293 20.8783 20.9280 21.1660 21.2248 20.8899 20.7984 20.7025 20.8504 20.8160 21.3440 20.6782 20.7859 20.9850 SiO2 wt% 36.6208 36.9867 36.5253 36.5069 37.0767 36.6825 36.5723 36.4151 36.4659 36.7837 36.4306 36.8338 35.9921 36.2975 36.0894 CaO wt% 5.8763 4.3446 5.0706 3.9389 5.5254 7.0395 5.3662 5.7295 6.8097 5.6347 5.4486 3.8049 4.0586 3.7295 2.7968 TiO wt% 0.1474 0.1523 0.2762 0.1537 0.0911 0.1272 0.1085 0.0644 0.1311 0.1147 0.0701 0.0331 0.2899 0.1541 0.0523 Cr2O3 wt% 0.0765 0.0350 0.0372 0.0195 0.0724 0.0375 0.0390 0.0761 0.0510 0.0117 0.0117 0.0445 0.0000 0.0058 0.0558 MnO wt% 3.5793 4.6767 5.6107 5.4029 3.5932 3.0778 4.3132 4.0005 3.1427 2.9950 3.0039 3.9080 5.0713 5.3495 5.0564 FeO wt% 31.1740 32.4380 30.1007 31.2368 31.6262 30.4627 32.2511 32.0154 31.6461 32.6239 32.5159 33.8376 32.2113 32.7115 34.2386 Total oxide wt% 100.35 100.87 100.14 99.74 100.73 100.31 100.47 100.04 100.01 100.08 99.48 101.00 99.46 100.13 100.32 Fe2+ 1.99 2.10 1.92 2.06 2.07 1.93 2.09 2.07 2.02 2.16 2.13 2.23 2.09 2.12 2.21 Mn 0.24 0.32 0.38 0.37 0.24 0.21 0.30 0.27 0.22 0.21 0.21 0.27 0.35 0.37 0.35 Mg 0.21 0.16 0.19 0.18 0.19 0.20 0.11 0.11 0.13 0.13 0.14 0.14 0.14 0.13 0.12 Ca 0.51 0.37 0.44 0.34 0.47 0.60 0.46 0.50 0.59 0.49 0.47 0.33 0.36 0.32 0.24 Sum X 2.94 2.96 2.94 2.95 2.97 2.94 2.96 2.95 2.95 2.98 2.96 2.96 2.93 2.94 2.93 Ti 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.00 Al 2.00 1.97 1.99 2.00 2.00 2.00 1.99 1.99 1.97 1.99 2.00 2.02 1.99 1.99 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.08 0.11 0.06 0.05 0.11 0.09 0.10 0.12 0.05 0.08 0.05 0.11 0.11 0.12 Sum Z 2.12 2.06 2.11 2.08 2.06 2.12 2.09 2.10 2.10 2.04 2.08 2.08 2.12 2.11 2.14 Si 2.94 2.97 2.95 2.96 2.97 2.94 2.95 2.95 2.95 2.98 2.96 2.96 2.94 2.95 2.93 Sum T 2.94 2.97 2.95 2.96 2.97 2.94 2.95 2.95 2.95 2.98 2.96 2.96 2.94 2.95 2.93 % Al 67.53 71.06 65.48 69.62 69.52 65.66 70.55 70.01 68.41 72.41 72.18 75.13 71.27 72.06 75.52 % Pyr 7.02 5.51 6.54 6.20 6.32 6.71 3.77 3.82 4.27 4.31 4.75 4.82 4.65 4.35 4.25 % Gr 16.23 12.11 14.06 11.19 15.48 19.40 14.96 15.96 18.76 15.95 15.43 10.78 11.41 10.46 7.84 % Sp 8.27 10.77 13.06 12.58 8.20 7.10 9.98 9.31 7.30 6.89 7.00 8.98 11.97 12.54 11.90 % Uv 0.04 0.01 0.02 0.01 0.04 0.02 0.02 0.04 0.03 0.01 0.01 0.02 0.00 0.00 0.01 % An 0.86 0.49 0.77 0.36 0.41 1.06 0.69 0.83 1.17 0.40 0.61 0.26 0.63 0.56 0.46 542 Table B.6 (Continued) Sample D39018-4848 (continued) EMPA spot 27 28 29 30 32 34 35 36 37 38 39 40 41 42 44 Na2O wt% 0.0145 0.0269 0.0010 0.0289 0.0031 0.0693 0.0156 0.0643 0.0240 0.0073 0.0475 0.0062 0.0945 0.0309 0.0308 MgO wt% 0.8983 0.9926 1.1098 1.1817 2.2124 1.5961 1.1383 1.5334 1.5731 1.5103 1.9142 1.5051 1.8528 1.7864 2.1277 Al2O3 wt% 20.8370 20.8697 20.9370 20.8317 21.4530 21.0115 20.9944 20.9575 20.9073 21.3521 21.1354 21.1761 21.0336 20.8495 21.4476 SiO2 wt% 36.4904 36.7785 36.1990 36.7053 37.0163 36.4960 36.2440 36.3951 36.0861 36.0931 36.5839 36.4275 36.3815 36.6175 36.7894 CaO wt% 5.1459 5.8108 5.6793 5.4669 4.8402 3.9697 3.6458 2.8517 2.7990 3.1171 4.1176 3.5894 3.0868 4.8537 4.9429 TiO wt% 0.0647 0.0624 0.1367 0.1130 0.0379 0.1348 0.0908 0.1273 0.1299 0.2172 0.0585 0.0214 0.0455 0.1156 0.0281 Cr2O3 wt% 0.0682 0.0508 0.0702 0.0313 0.0352 0.0273 0.0000 0.0369 0.0676 0.0000 0.0000 0.0407 0.0116 0.0215 0.0274 MnO wt% 4.2739 3.6898 2.9905 3.1409 3.0849 5.9933 7.2230 8.1004 5.1882 4.4274 2.8315 4.3666 3.9160 3.2870 3.1181 FeO wt% 32.1392 32.1893 32.8053 32.2281 31.8667 31.1805 30.4787 30.0542 32.7864 33.3345 33.4239 33.2169 33.5311 32.1896 32.1897 Total oxide wt% 99.93 100.47 99.93 99.73 100.55 100.48 99.83 100.12 99.56 100.06 100.11 100.35 99.95 99.75 100.70 Fe2+ 2.11 2.08 2.11 2.13 2.07 1.97 1.99 1.94 2.14 2.18 2.15 2.15 2.14 2.09 2.04 Mn 0.29 0.25 0.21 0.22 0.21 0.41 0.50 0.56 0.36 0.30 0.19 0.30 0.27 0.23 0.21 Mg 0.11 0.12 0.13 0.14 0.26 0.19 0.14 0.19 0.19 0.18 0.23 0.18 0.22 0.22 0.25 Ca 0.45 0.50 0.49 0.48 0.41 0.34 0.32 0.25 0.24 0.27 0.36 0.31 0.27 0.42 0.42 Sum X 2.96 2.95 2.94 2.97 2.96 2.91 2.95 2.93 2.94 2.93 2.93 2.94 2.90 2.95 2.92 Ti 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 Al 1.99 1.98 2.00 1.99 2.02 2.00 2.01 2.00 2.01 2.04 2.01 2.02 2.01 1.99 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.09 0.12 0.05 0.06 0.13 0.08 0.10 0.09 0.09 0.10 0.09 0.13 0.09 0.11 Sum Z 2.08 2.08 2.13 2.05 2.08 2.13 2.10 2.11 2.11 2.14 2.11 2.11 2.14 2.08 2.13 Si 2.96 2.96 2.93 2.98 2.96 2.94 2.95 2.95 2.94 2.93 2.95 2.94 2.95 2.96 2.94 Sum T 2.96 2.96 2.93 2.98 2.96 2.94 2.95 2.95 2.94 2.93 2.95 2.94 2.95 2.96 2.94 % Al 71.26 70.45 71.68 71.91 70.02 67.62 67.62 66.19 72.96 74.17 73.41 73.11 73.82 70.83 69.67 % Pyr 3.67 4.04 4.56 4.81 8.91 6.58 4.69 6.33 6.51 6.23 7.85 6.16 7.70 7.30 8.66 % Gr 14.54 16.21 15.77 15.55 13.59 11.00 10.35 8.03 7.92 8.82 11.53 10.08 8.66 13.61 13.68 % Sp 9.93 8.53 6.98 7.27 7.06 14.04 16.90 19.01 12.20 10.37 6.60 10.16 9.25 7.63 7.21 % Uv 0.03 0.03 0.04 0.02 0.01 0.01 0.00 0.01 0.02 0.00 0.00 0.01 0.00 0.01 0.01 % An 0.54 0.72 0.92 0.40 0.39 0.72 0.42 0.41 0.37 0.37 0.59 0.47 0.55 0.59 0.76 543 Table B.6 (Continued) Sample D39018-4848 (continued) D39200-3241 EMPA spot 45 46 47 48 1 2 3 4 5 6 8 10 11 12 13 Na2O wt% 0.0485 0.0010 0.0322 0.0708 0.0258 0.0000 0.0031 0.0567 0.0000 0.0247 0.0114 0.0277 0.0103 0.0144 0.0062 MgO wt% 1.7488 1.8681 1.8691 1.8208 1.7627 1.7483 1.5270 1.5237 1.6074 1.6575 1.6231 1.7252 1.8925 1.8522 1.8621 Al2O3 wt% 21.4247 21.1816 20.9745 21.2041 21.2063 21.2084 20.9345 21.1194 21.1331 21.2474 21.2684 21.1870 21.0746 21.2135 21.0215 SiO2 wt% 36.4519 36.3191 36.2238 36.5893 36.1060 36.3614 36.0386 36.3239 36.1446 36.2923 36.0996 36.7053 36.2386 36.4041 36.0305 CaO wt% 4.5582 2.7612 2.7878 5.1202 3.1346 3.7296 3.8090 3.6288 3.5915 3.7556 3.1487 4.1405 3.3078 3.2952 3.4419 TiO wt% 0.0671 0.0734 0.1039 0.0548 0.0463 0.0783 0.0885 0.0528 0.1299 0.1563 0.0819 0.0786 0.0860 0.0505 0.0716 Cr2O3 wt% 0.0000 0.0850 0.0000 0.0000 0.0486 0.0351 0.0566 0.0313 0.0568 0.0587 0.0195 0.0920 0.0486 0.0117 0.0973 MnO wt% 3.0210 4.6453 5.6461 2.6953 5.1300 6.0206 7.2045 8.8693 8.6299 7.7794 8.4055 5.9134 5.0404 4.9835 5.3530 FeO wt% 33.1453 33.3651 32.1952 32.1047 31.6359 30.5478 29.4491 28.2974 28.1436 29.1609 28.9300 29.8405 31.6645 31.3413 31.1380 Total oxide wt% 100.47 100.30 99.83 99.66 99.10 99.73 99.11 99.90 99.44 100.13 99.59 99.71 99.36 99.17 99.02 Fe2+ 2.10 2.16 2.07 2.08 2.09 2.00 1.93 1.81 1.85 1.87 1.88 1.99 2.08 2.10 2.04 Mn 0.21 0.32 0.39 0.18 0.35 0.41 0.50 0.61 0.60 0.53 0.58 0.41 0.35 0.34 0.37 Mg 0.21 0.23 0.23 0.22 0.21 0.21 0.19 0.18 0.20 0.20 0.20 0.21 0.23 0.22 0.23 Ca 0.39 0.24 0.24 0.44 0.27 0.32 0.33 0.32 0.31 0.33 0.27 0.36 0.29 0.29 0.30 Sum X 2.91 2.94 2.93 2.92 2.94 2.95 2.95 2.92 2.95 2.93 2.93 2.96 2.95 2.96 2.94 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 Al 2.03 2.02 2.01 2.02 2.04 2.03 2.02 2.02 2.03 2.02 2.04 2.02 2.02 2.04 2.02 Cr 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 Fe3+ 0.13 0.10 0.11 0.09 0.07 0.07 0.08 0.11 0.07 0.10 0.08 0.03 0.07 0.03 0.08 Sum Z 2.16 2.13 2.12 2.11 2.11 2.10 2.11 2.13 2.11 2.13 2.13 2.06 2.10 2.07 2.11 Si 2.93 2.94 2.94 2.95 2.95 2.95 2.95 2.94 2.94 2.93 2.94 2.97 2.95 2.97 2.94 Sum T 2.93 2.94 2.94 2.95 2.95 2.95 2.95 2.94 2.94 2.93 2.94 2.97 2.95 2.97 2.94 % Al 72.24 73.38 70.75 71.05 71.29 67.86 65.46 62.05 62.57 63.89 64.21 67.16 70.64 71.08 69.48 % Pyr 7.20 7.66 7.72 7.50 7.30 7.16 6.31 6.31 6.62 6.82 6.71 7.03 7.79 7.60 7.70 % Gr 12.69 7.73 7.82 14.48 9.02 10.59 10.83 10.23 10.22 10.53 8.96 11.89 9.41 9.56 9.79 % Sp 7.07 10.82 13.25 6.31 12.08 14.01 16.92 20.85 20.18 18.19 19.73 13.69 11.79 11.61 12.58 % Uv 0.00 0.02 0.00 0.00 0.01 0.01 0.02 0.01 0.02 0.02 0.01 0.03 0.01 0.00 0.03 % An 0.79 0.38 0.44 0.65 0.29 0.36 0.45 0.54 0.36 0.52 0.37 0.18 0.34 0.14 0.40 544 Table B.6 (Continued) Sample D39200-3241 (continued) EMPA spot 14 15 16 17 18 19 22 23 24 25 26 27 29 30 31 Na2O wt% 0.0359 0.0288 0.0010 0.0093 0.0000 0.0000 0.0124 0.0000 0.0000 0.0000 0.0000 0.0258 0.0000 0.0083 0.0103 MgO wt% 1.5725 1.6397 1.5885 1.8268 1.6146 1.6627 1.6659 1.6347 2.0393 1.9945 1.6124 1.4704 1.5722 1.7981 1.6134 Al2O3 wt% 20.8169 20.9379 21.0214 21.0750 21.1491 21.2524 21.1780 21.2139 21.1652 21.1234 20.9768 20.9657 21.0811 21.3822 21.4064 SiO2 wt% 36.6636 36.2015 36.5603 36.2775 36.2457 36.2644 36.3418 36.3630 36.5209 35.9698 36.4821 35.7870 36.4605 36.5304 36.3914 CaO wt% 4.3602 3.9462 4.1505 3.5076 3.5237 3.8646 3.1987 4.3523 3.1283 3.6321 4.2021 4.3046 4.8690 3.3107 3.3658 TiO wt% 0.1401 0.1058 0.1628 0.0593 0.0972 0.0649 0.0551 0.0963 0.0832 0.0670 0.1469 0.0921 0.1577 0.0572 0.0590 Cr2O3 wt% 0.0294 0.0059 0.0470 0.0000 0.0448 0.0410 0.0546 0.0626 0.0175 0.1031 0.0352 0.0332 0.0333 0.0214 0.0000 MnO wt% 6.8082 7.1074 7.0837 4.8765 6.7816 6.2220 7.0164 6.0197 5.1495 4.7579 6.5047 6.3827 5.9956 5.1567 5.6395 FeO wt% 28.6174 29.1722 29.1354 31.9752 30.2238 30.0721 29.7454 30.1105 31.7962 31.6156 29.8644 30.1083 29.5621 31.5688 31.1943 Total oxide wt% 99.04 99.15 99.75 99.61 99.68 99.44 99.27 99.85 99.90 99.26 99.82 99.17 99.73 99.83 99.68 Fe2+ 1.94 1.91 1.93 2.08 1.98 1.98 1.99 1.96 2.09 2.04 1.96 1.92 1.94 2.10 2.08 Mn 0.47 0.49 0.49 0.34 0.47 0.43 0.48 0.41 0.35 0.33 0.45 0.44 0.41 0.35 0.39 Mg 0.19 0.20 0.19 0.22 0.20 0.20 0.20 0.20 0.25 0.24 0.19 0.18 0.19 0.22 0.20 Ca 0.38 0.34 0.36 0.31 0.31 0.34 0.28 0.38 0.27 0.32 0.36 0.38 0.42 0.29 0.29 Sum X 2.98 2.94 2.97 2.94 2.95 2.95 2.96 2.95 2.96 2.93 2.96 2.91 2.96 2.96 2.95 Ti 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 Al 2.00 2.01 2.01 2.02 2.03 2.04 2.03 2.02 2.02 2.03 2.00 2.02 2.01 2.04 2.05 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.02 0.08 0.04 0.09 0.07 0.06 0.04 0.08 0.06 0.11 0.07 0.14 0.07 0.04 0.04 Sum Z 2.02 2.10 2.06 2.11 2.11 2.10 2.08 2.11 2.09 2.14 2.08 2.16 2.09 2.08 2.09 Si 2.99 2.95 2.97 2.95 2.94 2.95 2.96 2.94 2.96 2.93 2.96 2.92 2.95 2.96 2.95 Sum T 2.99 2.95 2.97 2.95 2.94 2.95 2.96 2.94 2.96 2.93 2.96 2.92 2.95 2.96 2.95 % Al 65.01 64.83 65.03 70.73 67.14 67.25 67.35 66.50 70.59 69.74 66.04 65.78 65.42 70.98 70.33 % Pyr 6.42 6.77 6.46 7.51 6.63 6.83 6.84 6.69 8.31 8.26 6.57 6.14 6.41 7.34 6.61 % Gr 12.64 11.23 11.82 9.92 10.00 11.05 9.25 12.28 8.87 10.21 11.86 12.06 13.76 9.51 9.71 % Sp 15.79 16.68 16.37 11.39 15.82 14.52 16.37 14.00 11.93 11.19 15.07 15.15 13.90 11.96 13.14 % Uv 0.01 0.00 0.02 0.00 0.01 0.01 0.02 0.02 0.00 0.03 0.01 0.01 0.01 0.01 0.00 % An 0.10 0.45 0.26 0.44 0.36 0.33 0.16 0.47 0.28 0.55 0.40 0.83 0.45 0.18 0.20 545 Table B.6 (Continued) Sample D39200-3241 (continued) EMPA spot 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 Na2O wt% 0.0082 0.0000 0.0154 0.0010 0.0123 0.0000 0.0401 0.0246 0.0051 0.0052 0.0370 0.0299 0.0082 0.0000 0.0165 MgO wt% 1.8759 1.9234 1.7156 1.6546 1.6113 1.5833 1.7139 1.7219 1.9398 1.9156 1.9088 1.8257 1.6876 1.8208 1.8443 Al2O3 wt% 21.1853 20.8060 21.1081 21.1506 21.1644 21.2231 21.1498 21.2026 21.5454 21.0751 21.3286 21.1233 21.1073 21.1084 20.9972 SiO2 wt% 36.2780 36.5474 36.6516 36.1808 36.6051 36.2161 36.7610 36.2710 36.5375 36.3723 36.5596 36.1673 36.5538 36.3129 36.6614 CaO wt% 3.5954 3.4399 4.3185 4.4724 4.1456 4.2515 4.3025 4.6733 3.4898 3.4719 3.3315 3.4117 4.0887 3.8057 3.5078 TiO wt% 0.0413 0.0745 0.1625 0.2064 0.0729 0.0771 0.0616 0.0878 0.0836 0.0664 0.0489 0.0608 0.0837 0.0607 0.0684 Cr2O3 wt% 0.0370 0.0915 0.0196 0.0372 0.0529 0.0078 0.0235 0.0020 0.0253 0.0603 0.0000 0.1188 0.0294 0.0117 0.0097 MnO wt% 4.8481 5.0184 5.7053 6.0284 6.4790 6.2069 5.8403 5.6626 5.0934 4.8241 4.9542 5.2491 6.0062 5.3605 5.0391 FeO wt% 31.4888 31.2219 29.7673 29.9474 29.5574 29.8829 30.0919 29.9976 31.4212 31.7079 30.9563 31.2955 29.5081 30.6404 31.1156 Total oxide wt% 99.36 99.12 99.46 99.68 99.70 99.45 99.98 99.64 100.14 99.50 99.12 99.28 99.07 99.12 99.26 Fe2+ 2.07 2.10 2.00 1.94 1.96 1.96 1.97 1.93 2.06 2.09 2.10 2.05 2.00 2.04 2.10 Mn 0.33 0.35 0.39 0.41 0.44 0.43 0.40 0.39 0.35 0.33 0.34 0.36 0.41 0.37 0.35 Mg 0.23 0.23 0.21 0.20 0.19 0.19 0.21 0.21 0.23 0.23 0.23 0.22 0.21 0.22 0.22 Ca 0.31 0.30 0.38 0.39 0.36 0.37 0.37 0.41 0.30 0.30 0.29 0.30 0.36 0.33 0.31 Sum X 2.95 2.98 2.97 2.94 2.96 2.95 2.95 2.93 2.95 2.96 2.96 2.93 2.98 2.96 2.98 Ti 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.03 2.00 2.02 2.02 2.02 2.03 2.01 2.02 2.05 2.02 2.05 2.03 2.03 2.03 2.01 Cr 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 Fe3+ 0.07 0.03 0.02 0.09 0.04 0.07 0.06 0.10 0.05 0.07 0.01 0.08 0.01 0.05 0.02 Sum Z 2.10 2.04 2.05 2.12 2.07 2.11 2.07 2.13 2.11 2.09 2.06 2.12 2.04 2.08 2.03 Si 2.95 2.98 2.97 2.93 2.97 2.94 2.97 2.94 2.95 2.95 2.98 2.95 2.98 2.96 2.98 Sum T 2.95 2.98 2.97 2.93 2.97 2.94 2.97 2.94 2.95 2.95 2.98 2.95 2.98 2.96 2.98 % Al 70.33 70.47 67.21 65.92 66.28 66.43 66.87 65.80 70.06 70.69 70.82 69.96 67.21 68.82 70.56 % Pyr 7.71 7.84 6.98 6.80 6.57 6.51 6.99 7.10 7.91 7.85 7.82 7.55 6.88 7.47 7.51 % Gr 10.26 9.90 12.44 12.57 11.88 12.10 12.23 13.14 9.94 9.87 9.75 9.72 11.90 10.93 10.17 % Sp 11.33 11.62 13.19 14.07 15.01 14.50 13.53 13.26 11.80 11.23 11.54 12.34 13.92 12.49 11.66 % Uv 0.01 0.03 0.01 0.01 0.02 0.00 0.01 0.00 0.01 0.02 0.00 0.04 0.01 0.00 0.00 % An 0.34 0.13 0.13 0.57 0.23 0.44 0.35 0.67 0.26 0.32 0.05 0.38 0.05 0.27 0.08 546 Table B.6 (Continued) Sample D39200-3241 (continued) D39200-1469 EMPA spot 47 56 57 3 4 5 6 7 10 13 14 16 17 18 19 Na2O wt% 0.0021 0.0000 0.0000 0.0122 0.0051 0.0267 0.0000 0.0000 0.0215 0.0360 0.0165 0.0000 0.0000 0.0134 0.0000 MgO wt% 1.6748 1.6332 1.6985 2.6760 2.6928 2.4920 2.3211 2.4476 2.5721 2.4089 2.3980 2.3772 2.5705 2.5957 2.5731 Al2O3 wt% 21.1028 21.1824 21.3503 21.2782 21.3874 21.4455 20.8511 21.2698 21.3614 21.4141 21.2300 21.2652 21.1397 21.2213 21.2251 SiO2 wt% 36.2221 36.6676 36.3125 36.3411 36.2675 36.5206 36.1568 36.5389 36.2048 36.4373 35.9239 36.0246 36.0326 36.1833 36.3722 CaO wt% 4.3363 4.7698 3.9499 2.4559 2.3640 2.0197 1.7467 2.3456 2.1477 2.2214 2.4385 2.4272 2.0296 1.8516 2.1623 TiO wt% 0.0700 0.1076 0.0555 0.0497 0.0434 0.0109 0.0216 0.0239 0.0000 0.0118 0.0171 0.0291 0.0308 0.0275 0.0852 Cr2O3 wt% 0.0860 0.0629 0.1057 0.0216 0.0549 0.0039 0.0000 0.0000 0.0528 0.0565 0.0000 0.0234 0.0410 0.0918 0.0411 MnO wt% 5.9837 5.8314 6.4042 10.6496 10.1240 8.0131 8.3113 8.9744 9.1233 8.2268 8.5430 8.4770 9.8365 10.4190 10.3268 FeO wt% 30.2449 29.2696 29.6742 25.5870 26.1220 28.9111 30.0481 27.7046 27.6427 28.9164 28.5442 28.7161 27.8577 27.2054 27.1711 Total oxide wt% 99.72 99.52 99.55 99.07 99.06 99.44 99.46 99.30 99.13 99.73 99.11 99.34 99.54 99.61 99.96 Fe2+ 1.95 1.96 1.96 1.68 1.72 1.92 1.94 1.85 1.81 1.88 1.82 1.85 1.76 1.74 1.74 Mn 0.41 0.40 0.44 0.73 0.70 0.55 0.57 0.62 0.63 0.56 0.59 0.58 0.68 0.72 0.71 Mg 0.20 0.20 0.21 0.32 0.33 0.30 0.28 0.30 0.31 0.29 0.29 0.29 0.31 0.31 0.31 Ca 0.38 0.41 0.34 0.21 0.21 0.18 0.15 0.20 0.19 0.19 0.21 0.21 0.18 0.16 0.19 Sum X 2.94 2.98 2.95 2.95 2.94 2.95 2.95 2.97 2.93 2.93 2.92 2.93 2.92 2.93 2.94 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.02 2.02 2.04 2.04 2.05 2.05 2.00 2.03 2.05 2.04 2.04 2.04 2.02 2.03 2.02 Cr 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 Fe3+ 0.10 0.02 0.05 0.06 0.06 0.04 0.11 0.03 0.07 0.07 0.12 0.11 0.13 0.11 0.10 Sum Z 2.13 2.05 2.10 2.10 2.11 2.09 2.11 2.07 2.12 2.12 2.16 2.14 2.15 2.14 2.12 Si 2.94 2.97 2.95 2.95 2.95 2.96 2.94 2.97 2.94 2.95 2.92 2.93 2.92 2.93 2.94 Sum T 2.94 2.97 2.95 2.95 2.95 2.96 2.94 2.97 2.94 2.95 2.92 2.93 2.92 2.93 2.94 % Al 66.31 66.01 66.46 56.91 58.30 65.18 65.80 62.35 61.58 64.29 62.54 63.03 60.23 59.36 59.09 % Pyr 6.89 6.63 6.97 10.99 11.07 10.21 9.57 9.98 10.63 9.91 9.98 9.83 10.63 10.71 10.53 % Gr 12.15 13.73 11.30 7.03 6.78 5.84 4.91 6.77 6.15 6.33 6.89 6.85 5.66 5.20 6.05 % Sp 13.98 13.45 14.93 24.85 23.65 18.66 19.46 20.80 21.42 19.23 20.19 19.92 23.11 24.43 24.02 % Uv 0.03 0.03 0.04 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.02 0.01 % An 0.61 0.13 0.30 0.21 0.19 0.11 0.27 0.10 0.22 0.22 0.40 0.36 0.36 0.27 0.29 547 Table B.6 (Continued) Sample D39200-1469 (continued) D39018-3050 EMPA spot 20 21 22 23 24 40 41 42 43 49 1 2 3 4 5 Na2O wt% 0.0082 0.0000 0.0000 0.0000 0.0072 0.0226 0.0062 0.0083 0.0369 0.0235 0.0092 0.0580 0.0430 0.0355 0.0072 MgO wt% 2.5328 2.5509 2.5658 2.5755 2.2429 2.5616 2.3474 2.1712 2.3224 2.3944 1.1388 1.1159 1.2587 1.0272 1.2702 Al2O3 wt% 21.0883 21.2710 21.4194 21.3735 21.4665 21.2926 21.4468 21.1782 21.3414 21.1094 21.4954 21.0482 21.0007 20.8686 21.2747 SiO2 wt% 35.7495 36.2285 36.1472 36.3066 35.7815 36.1295 36.5181 36.1385 36.4558 36.2888 36.3956 36.8125 36.4330 36.8060 36.2253 CaO wt% 1.9517 2.1935 2.2925 2.3859 2.1486 2.4702 2.1807 2.3446 3.1532 3.0415 7.3611 7.0617 5.9159 7.5317 4.3097 TiO wt% 0.0796 0.0331 0.0564 0.0244 0.0103 0.0147 0.0066 0.0000 0.0562 0.0668 0.0364 0.1283 0.2530 0.1981 0.1602 Cr2O3 wt% 0.0429 0.0548 0.0997 0.0489 0.0778 0.0000 0.0000 0.0117 0.0411 0.0453 0.0000 0.0000 0.0217 0.0040 0.0569 MnO wt% 10.2667 10.8259 10.1183 9.5279 8.1869 8.8184 7.7682 7.8124 8.2891 10.4908 4.4972 5.7720 5.8499 6.7505 8.2795 FeO wt% 27.3396 26.4091 27.4061 26.9588 29.3360 28.2256 28.9574 29.5334 28.3039 25.5844 29.2483 28.0741 28.7101 26.4894 28.3676 Total oxide wt% 99.06 99.57 100.11 99.20 99.26 99.54 99.23 99.20 100.00 99.04 100.18 100.07 99.49 99.71 99.95 Fe2+ 1.73 1.69 1.72 1.77 1.89 1.79 1.96 1.93 1.81 1.66 1.84 1.80 1.88 1.73 1.84 Mn 0.71 0.74 0.69 0.66 0.56 0.60 0.53 0.54 0.57 0.72 0.31 0.39 0.40 0.46 0.57 Mg 0.31 0.31 0.31 0.31 0.27 0.31 0.28 0.26 0.28 0.29 0.14 0.13 0.15 0.12 0.15 Ca 0.17 0.19 0.20 0.21 0.19 0.21 0.19 0.20 0.27 0.26 0.63 0.61 0.51 0.65 0.37 Sum X 2.91 2.94 2.92 2.95 2.91 2.92 2.97 2.94 2.92 2.94 2.92 2.94 2.95 2.96 2.94 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 Al 2.03 2.03 2.03 2.04 2.06 2.03 2.05 2.03 2.03 2.02 2.03 2.00 2.01 1.99 2.03 Cr 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.14 0.09 0.13 0.06 0.11 0.12 0.01 0.08 0.10 0.07 0.12 0.08 0.07 0.06 0.08 Sum Z 2.17 2.13 2.17 2.10 2.18 2.16 2.07 2.11 2.13 2.10 2.16 2.09 2.09 2.06 2.12 Si 2.91 2.93 2.91 2.95 2.91 2.93 2.97 2.94 2.94 2.95 2.92 2.96 2.96 2.97 2.94 Sum T 2.91 2.93 2.91 2.95 2.91 2.93 2.97 2.94 2.94 2.95 2.92 2.96 2.96 2.97 2.94 % Al 59.26 57.73 58.95 60.17 64.81 61.30 65.97 65.74 61.78 56.58 63.17 61.37 63.74 58.27 62.71 % Pyr 10.56 10.49 10.57 10.57 9.35 10.61 9.59 8.97 9.55 9.86 4.67 4.55 5.17 4.17 5.22 % Gr 5.46 6.18 6.36 6.84 6.09 6.93 6.37 6.70 8.85 8.66 20.47 19.81 16.77 21.23 12.19 % Sp 24.33 25.30 23.69 22.22 19.40 20.74 18.03 18.33 19.36 24.55 10.48 13.38 13.64 15.58 19.34 % Uv 0.01 0.01 0.02 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.02 % An 0.37 0.29 0.40 0.19 0.33 0.42 0.04 0.26 0.44 0.32 1.21 0.84 0.58 0.66 0.48 548 Table B.6 (Continued) Sample D39018-3050 (continued) EMPA spot 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Na2O wt% 0.0660 0.0514 0.0258 0.0319 0.0235 0.0453 0.0441 0.0327 0.0274 0.0175 0.0193 0.0000 0.0000 0.0000 0.0133 MgO wt% 1.1992 0.7809 1.0215 1.0134 1.2330 1.2231 1.1372 1.2083 0.9236 1.0248 1.0803 0.8692 0.8825 1.0105 0.8960 Al2O3 wt% 20.8324 20.8985 20.2713 20.8538 20.8988 21.2983 20.9414 21.4578 20.8708 21.0428 20.7660 21.4146 20.9970 21.3077 20.9117 SiO2 wt% 36.4604 35.9890 35.3579 36.2632 36.6658 36.0579 36.7534 36.5651 36.4391 36.2450 36.8019 36.4987 37.0308 36.4077 36.4833 CaO wt% 3.7187 5.2642 4.9782 4.5462 5.7372 5.3003 5.9093 6.7045 7.2947 4.7451 7.6012 7.2396 8.4280 5.5105 5.9298 TiO wt% 0.2747 0.3289 1.7905 0.2235 0.2267 0.4016 0.1601 0.0767 0.2359 0.1658 0.1970 0.1679 0.1782 0.1118 0.2600 Cr2O3 wt% 0.0000 0.0000 0.0000 0.0039 0.0217 0.0000 0.0079 0.0138 0.0299 0.0216 0.0000 0.0516 0.0000 0.0000 0.0000 MnO wt% 10.7043 11.5936 9.4361 8.7989 7.0784 5.9928 5.3183 4.8749 7.9616 8.9485 6.8399 5.4945 6.1097 6.5562 6.5072 FeO wt% 26.5556 24.8264 26.7294 27.4903 27.6678 29.9278 29.5758 29.1863 25.4263 27.8522 26.6122 27.8407 26.0211 29.0126 28.4724 Total oxide wt% 99.81 99.73 99.61 99.23 99.55 100.25 99.85 100.12 99.21 100.06 99.92 99.58 99.65 99.92 99.47 Fe2+ 1.74 1.57 1.75 1.83 1.84 1.89 1.95 1.87 1.66 1.79 1.71 1.85 1.74 1.90 1.90 Mn 0.74 0.80 0.66 0.61 0.49 0.41 0.36 0.33 0.55 0.61 0.47 0.38 0.42 0.45 0.45 Mg 0.15 0.09 0.12 0.12 0.15 0.15 0.14 0.14 0.11 0.12 0.13 0.10 0.11 0.12 0.11 Ca 0.32 0.46 0.44 0.40 0.50 0.46 0.51 0.58 0.64 0.41 0.66 0.63 0.73 0.48 0.52 Sum X 2.95 2.92 2.97 2.96 2.97 2.91 2.96 2.93 2.96 2.94 2.97 2.96 3.00 2.95 2.97 Ti 0.01 0.01 0.08 0.01 0.01 0.02 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.01 Al 2.00 2.00 1.96 2.01 2.00 2.03 2.00 2.03 2.00 2.01 1.97 2.04 2.00 2.03 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.12 0.08 0.05 0.04 0.13 0.06 0.09 0.06 0.10 0.08 0.03 0.01 0.06 0.04 Sum Z 2.08 2.14 2.12 2.07 2.05 2.17 2.06 2.13 2.08 2.12 2.06 2.09 2.02 2.10 2.05 Si 2.97 2.93 2.90 2.96 2.97 2.91 2.97 2.94 2.96 2.94 2.97 2.95 2.99 2.95 2.97 Sum T 2.97 2.93 2.90 2.96 2.97 2.91 2.97 2.94 2.96 2.94 2.97 2.95 2.99 2.95 2.97 % Al 59.04 53.65 58.95 61.78 61.86 65.07 65.75 63.99 56.23 60.83 57.75 62.54 58.20 64.45 63.88 % Pyr 4.94 3.25 4.21 4.17 5.02 5.06 4.63 4.95 3.78 4.22 4.38 3.54 3.54 4.13 3.65 % Gr 10.58 14.71 13.61 13.06 16.37 14.71 16.78 18.86 20.67 13.30 21.17 20.76 24.08 15.68 16.97 % Sp 25.03 27.38 22.10 20.59 16.36 14.10 12.31 11.34 18.52 20.92 15.74 12.72 13.94 15.23 15.08 % Uv 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.02 0.01 0.00 0.03 0.00 0.00 0.00 % An 0.35 0.91 0.59 0.33 0.31 0.94 0.46 0.82 0.67 0.67 0.87 0.33 0.15 0.47 0.32 549 Table B.6 (Continued) Sample D39018-3050 (continued) EMPA spot 21 22 23 24 25 26 27 28 29 30 31 33 34 35 36 Na2O wt% 0.0000 0.0000 0.0195 0.0153 0.0000 0.0061 0.0000 0.0000 0.0010 0.0186 0.0330 0.0092 0.0000 0.0010 0.0000 MgO wt% 0.8879 1.0594 0.9984 1.0511 1.0428 0.9819 1.0363 0.8950 1.0478 0.9926 0.9546 0.9167 0.9997 0.9470 0.9280 Al2O3 wt% 21.0692 21.0199 21.0659 21.1284 21.2189 21.1432 21.4505 21.3176 21.1944 21.1421 21.0848 21.3075 21.0334 21.4896 21.1270 SiO2 wt% 36.2713 36.8029 36.2696 36.6813 36.2606 36.5305 36.7547 36.7649 36.4253 36.5545 36.2415 36.2873 36.5091 36.4435 36.6298 CaO wt% 7.1189 4.9780 5.2370 6.1309 5.7071 6.0643 8.1990 7.9165 5.7989 4.4383 4.6143 7.1472 7.3291 6.9227 6.0868 TiO wt% 0.1604 0.2188 0.2279 0.2168 0.1939 0.1558 0.0935 0.1295 0.1798 0.1380 0.1662 0.0432 0.0551 0.0993 0.0855 Cr2O3 wt% 0.0000 0.0039 0.0000 0.0000 0.0000 0.0810 0.0000 0.0139 0.0000 0.0236 0.0256 0.0614 0.0416 0.0277 0.0118 MnO wt% 6.7916 7.5464 8.4653 7.4720 7.1310 6.4175 4.6397 5.7321 6.8289 9.1669 8.7005 4.7442 4.5808 5.5353 6.6591 FeO wt% 27.1069 28.5224 27.1817 27.2196 28.2081 28.2812 27.7016 27.0161 28.1890 27.8305 27.8756 29.0016 28.9594 28.8645 28.3752 Total oxide wt% 99.41 100.15 99.47 99.92 99.76 99.66 99.88 99.79 99.67 100.31 99.70 99.52 99.51 100.33 99.90 Fe2+ 1.76 1.91 1.79 1.80 1.84 1.88 1.81 1.79 1.86 1.82 1.82 1.88 1.89 1.85 1.87 Mn 0.47 0.52 0.58 0.51 0.49 0.44 0.32 0.39 0.47 0.63 0.60 0.33 0.31 0.38 0.46 Mg 0.11 0.13 0.12 0.13 0.13 0.12 0.12 0.11 0.13 0.12 0.12 0.11 0.12 0.11 0.11 Ca 0.62 0.43 0.46 0.53 0.50 0.53 0.71 0.68 0.50 0.38 0.40 0.62 0.64 0.60 0.53 Sum X 2.95 2.99 2.95 2.97 2.95 2.97 2.96 2.97 2.96 2.95 2.94 2.94 2.96 2.93 2.97 Ti 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 Al 2.02 2.00 2.02 2.01 2.03 2.02 2.03 2.03 2.03 2.02 2.02 2.03 2.01 2.04 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.08 0.02 0.06 0.04 0.08 0.04 0.05 0.03 0.05 0.06 0.07 0.08 0.07 0.09 0.05 Sum Z 2.10 2.03 2.09 2.06 2.11 2.07 2.09 2.07 2.08 2.08 2.11 2.12 2.09 2.14 2.07 Si 2.94 2.98 2.95 2.97 2.94 2.96 2.95 2.96 2.95 2.96 2.95 2.94 2.96 2.93 2.96 Sum T 2.94 2.98 2.95 2.97 2.94 2.96 2.95 2.96 2.95 2.96 2.95 2.94 2.96 2.93 2.96 % Al 59.56 63.96 60.67 60.60 62.30 63.38 61.26 60.17 62.87 61.67 61.99 64.03 63.81 62.96 63.07 % Pyr 3.64 4.28 4.10 4.27 4.27 4.00 4.20 3.62 4.28 4.05 3.94 3.77 4.08 3.87 3.77 % Gr 20.09 14.24 14.96 17.45 16.14 17.33 23.25 22.57 16.54 12.59 13.14 20.23 20.69 19.38 17.33 % Sp 15.82 17.31 19.76 17.24 16.61 14.86 10.68 13.18 15.84 21.26 20.39 11.08 10.62 12.85 15.38 % Uv 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.01 0.00 0.01 0.01 0.04 0.03 0.02 0.01 % An 0.82 0.14 0.44 0.36 0.60 0.33 0.57 0.39 0.41 0.38 0.48 0.84 0.75 0.89 0.42 550 Table B.6 (Continued) Sample D39018-3050 (continued) EMPA spot 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 Na2O wt% 0.0082 0.0000 0.0000 0.0184 0.0165 0.0000 0.0031 0.0185 0.0000 0.0143 0.0122 0.0318 0.0102 0.0163 0.0052 MgO wt% 0.9324 0.9452 0.9052 0.8803 0.8310 0.8001 0.9054 0.9471 0.9645 0.9169 0.9925 0.8200 0.9349 0.9923 0.9206 Al2O3 wt% 20.9550 20.8851 21.2155 20.8341 21.0807 20.8218 21.1347 21.0385 21.0688 20.8470 21.1430 21.1051 21.1808 21.1235 21.0890 SiO2 wt% 36.0148 36.5241 36.3294 36.7029 35.9937 36.3546 36.4783 36.6321 36.4248 36.7612 36.3473 36.3210 36.3778 36.6118 36.3375 CaO wt% 6.0116 5.3391 4.5833 6.4727 5.4130 5.1732 5.7875 6.0222 6.1251 7.4367 7.7950 6.2968 7.7028 7.6538 5.7363 TiO wt% 0.1937 0.1873 0.1747 0.2056 0.2542 0.1793 0.1950 0.2187 0.1064 0.1944 0.0931 0.1072 0.1552 0.1284 0.2025 Cr2O3 wt% 0.0000 0.0000 0.0196 0.0139 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0218 0.0079 0.0457 0.0119 0.0394 MnO wt% 5.9232 6.4336 7.5976 6.9887 7.6513 7.7465 6.7142 6.0350 6.1349 5.6329 4.1148 6.5708 5.2695 3.9843 6.5043 FeO wt% 29.3355 29.0228 29.1321 27.7549 28.9274 28.6834 29.0921 29.3568 29.2439 27.9796 29.0071 28.2962 28.3658 29.2535 29.4569 Total oxide wt% 99.37 99.34 99.96 99.87 100.17 99.76 100.31 100.27 100.07 99.78 99.53 99.56 100.04 99.78 100.29 Fe2+ 1.89 1.96 1.93 1.83 1.82 1.88 1.88 1.91 1.88 1.83 1.86 1.84 1.80 1.90 1.89 Mn 0.41 0.44 0.52 0.48 0.53 0.53 0.46 0.41 0.42 0.39 0.28 0.45 0.36 0.27 0.45 Mg 0.11 0.11 0.11 0.11 0.10 0.10 0.11 0.11 0.12 0.11 0.12 0.10 0.11 0.12 0.11 Ca 0.52 0.47 0.40 0.56 0.47 0.45 0.50 0.52 0.53 0.64 0.68 0.55 0.66 0.66 0.50 Sum X 2.94 2.99 2.96 2.97 2.92 2.97 2.95 2.96 2.95 2.97 2.94 2.94 2.93 2.95 2.94 Ti 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.01 Al 2.01 2.01 2.03 1.99 2.01 2.00 2.01 2.00 2.01 1.99 2.02 2.02 2.01 2.01 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.02 0.05 0.05 0.14 0.07 0.08 0.07 0.09 0.06 0.10 0.08 0.12 0.08 0.10 Sum Z 2.13 2.03 2.09 2.05 2.16 2.07 2.10 2.08 2.11 2.05 2.12 2.11 2.14 2.09 2.12 Si 2.93 2.98 2.95 2.97 2.92 2.96 2.95 2.96 2.94 2.97 2.94 2.95 2.93 2.95 2.94 Sum T 2.93 2.98 2.95 2.97 2.92 2.96 2.95 2.96 2.94 2.97 2.94 2.95 2.93 2.95 2.94 % Al 64.38 65.66 65.15 61.41 62.48 63.52 63.80 64.59 63.83 61.65 63.34 62.61 61.24 64.32 64.23 % Pyr 3.85 3.85 3.70 3.58 3.44 3.27 3.69 3.85 3.94 3.72 4.07 3.38 3.83 4.04 3.77 % Gr 16.89 15.41 13.09 18.30 15.00 14.65 16.24 16.92 17.14 20.96 21.84 17.87 21.35 21.54 15.99 % Sp 13.91 14.88 17.67 16.13 17.98 18.00 15.55 13.95 14.24 12.97 9.59 15.38 12.26 9.22 15.13 % Uv 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.03 0.01 0.02 % An 0.90 0.14 0.33 0.50 1.01 0.50 0.65 0.60 0.81 0.62 1.09 0.72 1.22 0.81 0.80 551 Table B.6 (Continued) Sample D39018-3050 (continued) D21708-2760 EMPA spot 52 53 54 55 56 57 58 59 1 2 5 6 8 9 10 Na2O wt% 0.0420 0.0041 0.0376 0.0573 0.0102 0.0267 0.0051 0.0092 0.0091 0.0000 0.0000 0.0000 0.0225 0.0000 0.0146 MgO wt% 0.7953 0.9459 0.8255 0.8986 0.8708 0.8631 0.9223 0.9340 1.6716 1.7368 1.0971 1.6149 1.1970 2.1278 1.4802 Al2O3 wt% 21.1213 21.2941 20.9140 21.1776 20.8244 21.2071 21.2044 21.2565 21.2607 21.1135 21.1039 21.2533 20.8013 20.5530 21.0368 SiO2 wt% 36.9526 36.3612 36.8594 36.5822 36.7703 36.2056 36.8526 36.3396 36.5232 35.8873 36.5768 36.1768 35.9747 36.7279 36.5616 CaO wt% 6.2821 7.2766 7.5881 6.7978 6.7174 6.0999 7.4665 7.7614 4.8580 5.7016 6.1862 5.5414 7.3392 5.5800 6.7848 TiO wt% 0.0501 0.0459 0.1418 0.1433 0.1869 0.2198 0.1405 0.0711 0.0410 0.0336 0.1315 0.0760 0.1203 0.0592 0.1287 Cr2O3 wt% 0.0000 0.0000 0.0080 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0156 0.0234 0.0117 0.0000 0.0000 0.0000 MnO wt% 5.8187 4.6721 5.1523 6.0759 6.4277 6.4385 4.8509 4.5151 8.1415 7.2982 7.1519 7.7811 6.9120 7.3952 7.5034 FeO wt% 28.6821 29.2986 27.7118 28.2759 28.0437 28.4603 28.7475 28.9542 27.6357 27.6251 27.7701 27.1228 26.8271 27.8570 26.4475 Total oxide wt% 99.74 99.90 99.24 100.01 99.85 99.52 100.19 99.84 100.14 99.41 100.04 99.58 99.19 100.30 99.96 Fe2+ 1.93 1.87 1.87 1.82 1.85 1.86 1.88 1.84 1.76 1.70 1.80 1.72 1.66 1.71 1.67 Mn 0.40 0.32 0.35 0.42 0.44 0.44 0.33 0.31 0.56 0.50 0.49 0.53 0.48 0.50 0.51 Mg 0.10 0.11 0.10 0.11 0.11 0.10 0.11 0.11 0.20 0.21 0.13 0.19 0.14 0.25 0.18 Ca 0.55 0.63 0.66 0.59 0.58 0.53 0.64 0.67 0.42 0.49 0.54 0.48 0.64 0.48 0.59 Sum X 2.97 2.93 2.98 2.93 2.98 2.94 2.97 2.93 2.94 2.91 2.96 2.93 2.92 2.95 2.94 Ti 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 Al 2.02 2.02 2.00 2.01 1.99 2.03 2.01 2.02 2.02 2.02 2.01 2.03 1.99 1.94 2.00 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.01 0.11 0.01 0.09 0.05 0.07 0.05 0.11 0.10 0.17 0.07 0.11 0.16 0.16 0.11 Sum Z 2.03 2.13 2.02 2.11 2.04 2.11 2.07 2.14 2.12 2.19 2.09 2.14 2.16 2.10 2.11 Si 2.99 2.93 2.99 2.95 2.98 2.94 2.96 2.93 2.94 2.91 2.95 2.93 2.92 2.95 2.94 Sum T 2.99 2.93 2.99 2.95 2.98 2.94 2.96 2.93 2.94 2.91 2.95 2.93 2.92 2.95 2.94 % Al 65.03 63.80 62.62 62.10 62.13 63.29 63.46 62.75 60.01 58.56 60.92 58.76 56.83 58.07 56.68 % Pyr 3.23 3.88 3.35 3.69 3.53 3.56 3.73 3.83 6.83 7.21 4.46 6.65 4.97 8.63 6.04 % Gr 18.23 20.36 21.91 19.15 19.02 17.36 21.09 21.63 13.59 15.69 17.40 15.50 20.18 15.03 18.78 % Sp 13.42 10.88 11.89 14.17 14.79 15.08 11.14 10.53 18.90 17.22 16.53 18.20 16.30 17.04 17.39 % Uv 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 % An 0.07 1.06 0.16 0.84 0.45 0.63 0.53 1.23 0.66 1.31 0.63 0.87 1.67 1.21 1.06 552 Table B.6 (Continued) Sample D21708-2760 (continued) EMPA spot 11 13 14 18 19 20 21 22 23 24 25 26 27 28 29 Na2O wt% 0.0045 0.0000 0.0000 0.0238 0.0168 0.0134 0.0000 0.0214 0.0000 0.0057 0.0489 0.0000 0.0057 0.0080 0.0125 MgO wt% 1.1777 0.9987 1.3318 1.5301 1.4976 1.4600 1.7798 1.6199 1.5257 1.2105 1.0722 1.1228 1.1350 1.1549 1.1866 Al2O3 wt% 21.1110 20.9596 20.9740 21.1828 21.8214 21.0498 21.5079 21.3217 21.3708 21.1529 21.1528 21.1946 21.1061 21.2436 21.0139 SiO2 wt% 36.4054 36.2649 35.9996 35.8984 36.5637 36.3023 36.1355 36.6590 36.6816 36.1548 36.3397 36.4107 36.1674 35.8525 36.1128 CaO wt% 5.9315 6.2832 5.9708 4.9115 6.5730 8.0023 4.0125 5.7494 6.3297 5.8047 5.9120 6.3034 6.0254 5.5953 6.2929 TiO wt% 0.1513 0.1971 0.1365 0.0841 0.0268 0.1873 0.0667 0.1001 0.1079 0.0602 0.0933 0.0995 0.0946 0.0635 0.0989 Cr2O3 wt% 0.0059 0.0000 0.0000 0.0097 0.0000 0.0020 0.0000 0.0097 0.0000 0.0000 0.0000 0.0000 0.0194 0.0523 0.0000 MnO wt% 8.7718 9.2998 8.3803 7.7371 7.0606 6.9507 6.0293 5.5443 5.2630 5.7853 5.7694 5.7319 5.7530 5.7714 5.3975 FeO wt% 26.2796 25.9703 26.2184 28.0453 26.4737 25.6815 30.2851 28.3882 29.0040 29.8043 29.7316 29.3819 29.3426 29.4526 29.6096 Total oxide wt% 99.84 99.97 99.01 99.42 100.03 99.65 99.82 99.41 100.28 99.98 100.12 100.24 99.65 99.19 99.72 Fe2+ 1.69 1.64 1.68 1.76 1.70 1.59 1.95 1.89 1.86 1.88 1.88 1.87 1.88 1.89 1.86 Mn 0.60 0.64 0.58 0.53 0.48 0.47 0.41 0.38 0.36 0.40 0.39 0.39 0.40 0.40 0.37 Mg 0.14 0.12 0.16 0.19 0.18 0.18 0.21 0.20 0.18 0.15 0.13 0.13 0.14 0.14 0.14 Ca 0.51 0.54 0.52 0.43 0.56 0.69 0.35 0.50 0.54 0.50 0.51 0.54 0.52 0.49 0.55 Sum X 2.95 2.94 2.94 2.91 2.93 2.92 2.93 2.96 2.95 2.92 2.91 2.94 2.93 2.92 2.92 Ti 0.01 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.01 2.00 2.01 2.03 2.06 2.00 2.05 2.03 2.02 2.02 2.01 2.01 2.02 2.04 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.09 0.12 0.11 0.14 0.07 0.14 0.10 0.03 0.08 0.14 0.13 0.11 0.11 0.11 0.14 Sum Z 2.11 2.12 2.13 2.17 2.14 2.15 2.15 2.07 2.11 2.15 2.14 2.13 2.13 2.16 2.15 Si 2.94 2.93 2.93 2.92 2.93 2.92 2.92 2.97 2.94 2.92 2.93 2.93 2.93 2.92 2.92 Sum T 2.94 2.93 2.93 2.92 2.93 2.92 2.92 2.97 2.94 2.92 2.93 2.93 2.93 2.92 2.92 % Al 57.38 55.74 57.08 60.63 58.18 54.20 66.66 63.73 63.22 64.25 64.49 63.57 64.02 64.83 63.75 % Pyr 4.82 4.09 5.50 6.37 6.12 5.99 7.34 6.60 6.19 4.99 4.43 4.59 4.68 4.80 4.90 % Gr 16.66 17.42 16.78 13.71 18.63 21.93 11.33 16.52 17.69 16.09 16.47 17.51 16.86 15.80 17.41 % Sp 20.38 21.66 19.68 18.30 16.39 16.21 14.12 12.83 12.13 13.55 13.53 13.31 13.47 13.64 12.67 % Uv 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.03 0.00 % An 0.71 1.02 0.91 0.96 0.66 1.58 0.54 0.28 0.72 1.09 1.04 0.97 0.93 0.88 1.23 553 Table B.6 (Continued) Sample D21708-2760 (continued) CR4611-584 EMPA spot 30 31 32 33 35 40 41 49 50 51 52 53 1 2 3 Na2O wt% 0.0057 0.0000 0.0000 0.0045 0.0000 0.0763 0.0000 0.0180 0.0426 0.0224 0.0135 0.0545 0.0000 0.0000 0.0162 MgO wt% 1.1964 1.1606 1.2632 1.3435 1.5529 1.2712 1.3155 1.3265 1.2917 1.2805 1.4046 1.8199 1.9765 2.3001 2.3831 Al2O3 wt% 21.2531 21.1719 21.0201 21.4017 21.1800 21.7238 20.9760 21.1960 21.0231 20.9017 21.2055 21.0176 21.5261 21.5058 21.5836 SiO2 wt% 36.4991 36.6640 35.9713 36.6897 36.7167 36.3825 36.1408 36.0047 36.4619 36.4587 36.0542 36.7979 36.5376 36.9475 36.4409 CaO wt% 6.0166 5.7868 6.1573 5.7988 6.3089 6.2974 7.0169 7.5315 7.4423 7.8724 6.6153 3.8703 3.8690 4.5504 4.4168 TiO wt% 0.0908 0.0854 0.0865 0.0398 0.1200 0.0960 0.1321 0.0944 0.1178 0.1309 0.0376 0.0469 0.0399 0.0983 0.0278 Cr2O3 wt% 0.0058 0.0000 0.0427 0.0097 0.0234 0.0000 0.0137 0.0000 0.0000 0.0039 0.0274 0.0000 0.0000 0.0000 0.0058 MnO wt% 5.6260 5.6299 5.3359 5.7750 5.6843 5.9445 6.3732 6.1196 6.0748 6.1085 6.4589 5.7025 4.1048 3.5377 3.2250 FeO wt% 29.5563 29.4680 29.3270 29.7525 28.6560 27.4199 27.5055 27.1464 26.9108 26.4794 27.3584 30.2928 31.4364 32.0217 32.0376 Total oxide wt% 100.25 99.97 99.20 100.82 100.24 99.21 99.47 99.44 99.37 99.26 99.18 99.60 99.49 100.96 100.14 Fe2+ 1.89 1.94 1.87 1.89 1.84 1.81 1.73 1.67 1.72 1.69 1.73 2.01 2.10 2.05 2.03 Mn 0.38 0.39 0.37 0.39 0.39 0.41 0.44 0.42 0.42 0.42 0.44 0.39 0.28 0.24 0.22 Mg 0.14 0.14 0.15 0.16 0.19 0.15 0.16 0.16 0.16 0.15 0.17 0.22 0.24 0.27 0.28 Ca 0.52 0.50 0.54 0.50 0.54 0.55 0.61 0.65 0.64 0.68 0.57 0.34 0.34 0.39 0.38 Sum X 2.94 2.97 2.93 2.94 2.95 2.91 2.93 2.91 2.93 2.95 2.92 2.96 2.96 2.95 2.92 Ti 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 Al 2.02 2.02 2.02 2.02 2.00 2.07 2.00 2.02 2.00 1.99 2.03 2.01 2.05 2.02 2.04 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.10 0.05 0.12 0.10 0.09 0.05 0.14 0.16 0.10 0.10 0.12 0.04 0.02 0.09 0.12 Sum Z 2.12 2.07 2.14 2.13 2.10 2.13 2.14 2.18 2.11 2.10 2.15 2.05 2.08 2.11 2.16 Si 2.94 2.96 2.93 2.94 2.95 2.95 2.93 2.91 2.95 2.95 2.92 2.98 2.96 2.94 2.92 Sum T 2.94 2.96 2.93 2.94 2.95 2.95 2.93 2.91 2.95 2.95 2.92 2.98 2.96 2.94 2.92 % Al 64.41 65.41 63.91 64.27 62.24 62.00 58.92 57.64 58.53 57.37 59.29 67.98 71.09 69.46 69.70 % Pyr 4.88 4.71 5.23 5.46 6.29 5.27 5.42 5.50 5.31 5.24 5.82 7.43 8.06 9.27 9.77 % Gr 16.81 16.44 17.21 16.09 17.56 18.27 19.39 20.76 20.86 21.98 18.52 11.12 11.20 12.61 12.30 % Sp 13.05 12.99 12.55 13.33 13.09 13.99 14.91 14.42 14.18 14.21 15.20 13.23 9.51 8.10 7.51 % Uv 0.00 0.00 0.02 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 % An 0.80 0.42 1.05 0.83 0.75 0.44 1.31 1.65 1.07 1.13 1.14 0.23 0.13 0.54 0.70 554 Table B.6 (Continued) Sample CR4611-584 (continued) EMPA spot 4 5 6 7 9 10 11 12 13 15 16 17 18 19 20 Na2O wt% 0.0065 0.0076 0.0086 0.0000 0.0108 0.0011 0.0000 0.0011 0.0172 0.0185 0.0000 0.0086 0.0000 0.0171 0.0301 MgO wt% 2.3206 2.5073 2.3859 2.6382 2.4735 2.2627 2.5021 2.4199 2.4206 2.2342 2.0648 2.3229 2.4348 2.4416 2.4408 Al2O3 wt% 21.5306 21.2047 21.4531 21.6678 21.3479 21.4674 21.5809 21.4285 21.3805 21.4009 21.4179 21.5267 21.6880 21.4881 21.2433 SiO2 wt% 37.0726 36.0648 36.8192 36.5540 36.6621 36.9789 36.6961 36.9966 36.2676 36.1636 36.5603 36.5350 37.2047 36.7409 36.9553 CaO wt% 4.7249 4.0059 4.7280 4.0979 4.7004 6.5645 4.6343 4.9083 5.5678 4.1113 6.5621 5.6675 5.1526 5.7794 5.4558 TiO wt% 0.0863 0.0555 0.1241 0.0202 0.0766 0.0747 0.0620 0.0820 0.1320 0.1020 0.1411 0.1230 0.1232 0.1500 0.1148 Cr2O3 wt% 0.0000 0.0000 0.0193 0.0250 0.0270 0.0039 0.0019 0.0000 0.0000 0.0115 0.0213 0.0348 0.0000 0.0000 0.0136 MnO wt% 3.1959 3.0619 3.0408 3.0578 2.8652 2.6881 2.7625 2.8421 2.5670 3.3012 2.5400 2.5905 2.7187 2.9200 3.0067 FeO wt% 32.0377 32.4428 32.1311 32.6335 31.8320 30.4845 31.7281 31.6980 31.3823 32.4255 31.1734 31.2438 31.1942 30.3434 30.7291 Total oxide wt% 100.98 99.35 100.71 100.69 100.00 100.53 99.97 100.38 99.74 99.77 100.48 100.05 100.52 99.88 99.99 Fe2+ 2.06 2.06 2.05 2.05 2.05 1.94 2.06 2.06 1.97 2.06 1.95 1.99 2.06 1.96 1.99 Mn 0.22 0.21 0.21 0.21 0.19 0.18 0.19 0.19 0.17 0.23 0.17 0.18 0.18 0.20 0.20 Mg 0.28 0.30 0.28 0.31 0.30 0.27 0.30 0.29 0.29 0.27 0.25 0.28 0.29 0.29 0.29 Ca 0.40 0.35 0.40 0.35 0.40 0.56 0.40 0.42 0.48 0.36 0.56 0.49 0.44 0.50 0.47 Sum X 2.95 2.92 2.94 2.92 2.94 2.95 2.95 2.96 2.91 2.91 2.92 2.93 2.97 2.94 2.95 Ti 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.00 Al 2.02 2.02 2.02 2.04 2.02 2.01 2.04 2.02 2.02 2.04 2.01 2.03 2.04 2.03 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.14 0.10 0.13 0.09 0.09 0.07 0.06 0.14 0.12 0.14 0.10 0.02 0.08 0.07 Sum Z 2.10 2.16 2.12 2.17 2.12 2.11 2.11 2.08 2.17 2.16 2.16 2.14 2.06 2.11 2.08 Si 2.95 2.92 2.94 2.91 2.94 2.94 2.94 2.96 2.91 2.92 2.92 2.93 2.97 2.94 2.96 Sum T 2.95 2.92 2.94 2.91 2.94 2.94 2.94 2.96 2.91 2.92 2.92 2.93 2.97 2.94 2.96 % Al 69.72 70.53 69.60 70.15 69.57 65.73 69.96 69.56 67.58 70.84 66.54 67.91 69.27 66.49 67.34 % Pyr 9.33 10.37 9.66 10.76 10.06 9.11 10.16 9.74 9.96 9.22 8.40 9.47 9.74 9.91 9.88 % Gr 13.14 11.13 13.07 11.27 13.12 18.14 13.07 13.77 15.35 11.47 17.92 15.74 14.62 16.20 15.28 % Sp 7.30 7.19 6.99 7.08 6.62 6.15 6.37 6.50 6.00 7.74 5.87 6.00 6.18 6.74 6.91 % Uv 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.00 0.00 0.01 % An 0.49 0.76 0.64 0.72 0.59 0.83 0.43 0.41 1.07 0.70 1.20 0.81 0.15 0.61 0.54 555 Table B.6 (Continued) Sample CR4611-584 (continued) DS172-123 EMPA spot 21 22 23 24 25 26 27 29 30 1 2 3 4 5 6 Na2O wt% 0.0183 0.0205 0.0140 0.0000 0.0022 0.0140 0.0118 0.0032 0.0194 0.0000 0.0000 0.0000 0.0275 0.0386 0.0000 MgO wt% 2.3714 2.4511 2.2735 2.4322 2.3729 2.4315 2.3745 2.0653 1.9567 0.7890 0.9194 0.9532 0.8967 0.9473 0.9357 Al2O3 wt% 21.3446 21.3695 21.3347 21.3571 21.3051 21.5034 21.4609 21.3522 21.6406 21.5798 20.8702 20.9694 21.0797 20.9403 21.2904 SiO2 wt% 36.3565 36.9723 36.3153 36.9750 36.5886 36.9048 36.5843 36.5023 36.7152 36.1880 36.4939 36.1017 36.5158 35.9244 36.5516 CaO wt% 4.7932 4.3824 5.0932 4.6948 4.8739 4.8574 5.3471 5.1898 5.2859 5.6639 4.2586 4.5928 4.5985 3.6491 5.1036 TiO wt% 0.1365 0.0954 0.1560 0.1335 0.1135 0.0937 0.0853 0.0844 0.0872 0.0105 0.2768 0.1705 0.1412 0.3141 0.0848 Cr2O3 wt% 0.0077 0.0058 0.0000 0.0328 0.0039 0.0058 0.0000 0.0000 0.0077 0.0672 0.0496 0.0134 0.0000 0.0362 0.0307 MnO wt% 3.4768 3.7765 3.4300 3.3245 3.4382 3.1456 2.9989 2.7188 3.0332 1.8179 3.2070 3.7238 3.8153 3.9740 2.9621 FeO wt% 31.1757 31.7234 31.2621 31.5746 31.7476 31.9129 30.9621 31.7263 31.4664 34.0561 34.4015 33.5337 33.8889 34.0669 33.6385 Total oxide wt% 99.68 100.80 99.88 100.52 100.45 100.87 99.82 99.64 100.21 100.17 100.48 100.06 100.96 99.89 100.60 Fe2+ 1.99 2.02 1.98 2.04 2.00 2.02 1.99 2.06 2.04 2.22 2.27 2.17 2.17 2.22 2.20 Mn 0.24 0.26 0.23 0.22 0.23 0.21 0.20 0.19 0.21 0.12 0.22 0.26 0.26 0.27 0.20 Mg 0.28 0.29 0.27 0.29 0.28 0.29 0.28 0.25 0.23 0.10 0.11 0.12 0.11 0.12 0.11 Ca 0.41 0.37 0.44 0.40 0.42 0.41 0.46 0.45 0.45 0.49 0.37 0.40 0.40 0.32 0.44 Sum X 2.93 2.94 2.92 2.96 2.93 2.93 2.94 2.95 2.94 2.93 2.97 2.94 2.93 2.93 2.95 Ti 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.00 Al 2.03 2.01 2.02 2.01 2.01 2.02 2.03 2.03 2.04 2.06 1.99 2.01 2.00 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.09 0.13 0.07 0.13 0.10 0.09 0.08 0.07 0.09 0.06 0.11 0.11 0.11 0.07 Sum Z 2.14 2.11 2.16 2.09 2.14 2.13 2.13 2.11 2.11 2.15 2.07 2.13 2.12 2.14 2.10 Si 2.93 2.95 2.92 2.95 2.93 2.94 2.94 2.94 2.94 2.93 2.96 2.93 2.94 2.93 2.95 Sum T 2.93 2.95 2.92 2.95 2.93 2.94 2.94 2.94 2.94 2.93 2.96 2.93 2.94 2.93 2.95 % Al 68.02 68.71 67.64 69.03 68.14 68.83 67.70 70.05 69.58 75.73 76.39 73.76 73.94 75.78 74.39 % Pyr 9.73 9.90 9.33 9.79 9.66 9.83 9.68 8.43 7.96 3.25 3.74 3.93 3.67 3.94 3.81 % Gr 13.37 12.13 14.09 13.09 13.37 13.39 14.97 14.65 14.94 16.05 11.98 12.84 12.76 10.27 14.38 % Sp 8.11 8.67 8.00 7.60 7.95 7.23 6.95 6.30 7.01 4.25 7.41 8.71 8.87 9.38 6.86 % Uv 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.03 0.02 0.01 0.00 0.01 0.01 % An 0.73 0.57 0.88 0.43 0.84 0.69 0.67 0.55 0.48 0.68 0.38 0.70 0.72 0.54 0.52 556 Table B.6 (Continued) Sample DS172-123 (continued) EMPA spot 7 8 9 10 12 13 14 17 20 21 22 23 25 26 27 28 Na2O wt% 0.0044 0.0142 0.0429 0.0121 0.0384 0.0251 0.0197 0.0308 0.0000 0.0000 0.0220 0.0177 0.0210 0.0022 0.0055 0.0153 MgO wt% 0.9506 1.0220 0.9005 0.9414 0.8314 0.6884 0.7076 0.8016 0.8994 0.9758 0.9849 0.9457 0.9182 0.9652 0.9415 0.8846 Al2O3 wt% 21.2018 21.3487 20.8988 20.9583 20.7784 21.0265 21.1066 21.1889 21.2189 21.3154 21.1562 21.0363 21.1257 21.1258 21.1639 20.9187 SiO2 wt% 35.9754 36.6469 35.6906 36.2630 36.2842 36.0176 36.2876 36.0263 36.2708 36.0896 36.3239 35.7569 36.1313 36.2272 36.1091 36.4578 CaO wt% 4.9740 5.1890 4.4682 4.2875 4.1291 5.1308 4.4435 4.4253 4.8874 5.6299 5.3462 4.2602 3.9455 5.2446 5.4283 5.0471 TiO wt% 0.1020 0.0397 0.1971 0.2348 0.2211 0.2119 0.1926 0.1935 0.0747 0.0783 0.0699 0.2575 0.1910 0.1899 0.1032 0.1025 Cr2O3 wt% 0.0287 0.0441 0.0573 0.0497 0.0537 0.0289 0.1502 0.0191 0.0976 0.1132 0.0517 0.0495 0.0247 0.0613 0.0134 0.0096 MnO wt% 2.4132 1.8897 3.3388 3.9474 6.5106 7.0840 8.3908 4.4112 2.7595 1.6415 1.1863 2.1736 3.0123 2.3906 2.9955 3.5158 FeO wt% 34.2063 34.2791 33.6835 33.6306 31.1937 29.8314 29.3885 33.0404 34.0549 34.4125 35.2741 35.6458 35.1787 34.4015 33.3604 32.7167 Total oxide wt% 99.86 100.47 99.28 100.32 100.04 100.04 100.69 100.14 100.26 100.26 100.42 100.14 100.55 100.61 100.12 99.67 Fe2+ 2.21 2.25 2.18 2.19 2.04 1.91 1.89 2.13 2.22 2.20 2.26 2.27 2.27 2.20 2.14 2.18 Mn 0.17 0.13 0.23 0.27 0.45 0.49 0.57 0.30 0.19 0.11 0.08 0.15 0.21 0.16 0.21 0.24 Mg 0.12 0.12 0.11 0.11 0.10 0.08 0.09 0.10 0.11 0.12 0.12 0.11 0.11 0.12 0.11 0.11 Ca 0.43 0.45 0.39 0.37 0.36 0.45 0.39 0.39 0.42 0.49 0.46 0.37 0.34 0.45 0.47 0.44 Sum X 2.93 2.95 2.91 2.95 2.95 2.92 2.93 2.92 2.94 2.92 2.93 2.91 2.93 2.93 2.93 2.97 Ti 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 Al 2.03 2.03 2.02 2.00 1.99 2.01 2.01 2.03 2.03 2.03 2.01 2.02 2.02 2.01 2.02 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.06 0.13 0.09 0.09 0.12 0.10 0.11 0.09 0.12 0.12 0.15 0.12 0.12 0.12 0.05 Sum Z 2.15 2.09 2.16 2.11 2.09 2.15 2.13 2.15 2.12 2.16 2.14 2.18 2.14 2.15 2.15 2.06 Si 2.92 2.95 2.92 2.94 2.95 2.93 2.93 2.93 2.94 2.92 2.93 2.91 2.93 2.92 2.92 2.97 Sum T 2.92 2.95 2.92 2.94 2.95 2.93 2.93 2.93 2.94 2.92 2.93 2.91 2.93 2.92 2.92 2.97 % Al 75.59 76.26 74.80 74.28 69.10 65.20 64.38 73.10 75.45 75.43 77.37 78.16 77.44 74.99 73.00 73.36 % Pyr 3.94 4.16 3.78 3.86 3.43 2.85 2.91 3.32 3.69 4.03 4.05 3.94 3.79 3.96 3.88 3.62 % Gr 13.98 14.72 12.58 12.01 11.64 14.34 12.40 12.45 13.76 15.66 14.89 11.80 11.01 14.49 15.13 14.43 % Sp 5.68 4.37 7.96 9.21 15.24 16.67 19.59 10.39 6.44 3.85 2.77 5.14 7.07 5.58 7.02 8.18 % Uv 0.01 0.02 0.02 0.02 0.02 0.01 0.06 0.01 0.04 0.06 0.02 0.02 0.01 0.03 0.01 0.00 % An 0.78 0.45 0.81 0.56 0.52 0.86 0.61 0.67 0.60 0.95 0.88 0.87 0.64 0.89 0.92 0.38 557 Table B.6 (Continued) Sample DS172-123 (continued) DS173-499 EMPA spot 29 30 2 3 4 6 7 8 9 10 11 12 13 14 15 16 Na2O wt% 0.0186 0.0011 0.0509 0.0826 0.0485 0.0501 0.0535 0.0480 0.0543 0.0683 0.0125 0.0444 0.0411 0.0809 0.0479 0.0569 MgO wt% 0.8876 0.9801 1.8234 1.5942 1.4344 1.4644 1.5002 1.5097 1.4832 1.5916 1.3717 1.3378 1.2113 1.3007 1.2394 1.3885 Al2O3 wt% 21.2788 21.5189 21.1170 21.0666 21.1552 21.0301 20.8522 20.9535 20.9853 21.1172 21.0285 20.9167 21.0762 20.7826 21.0239 21.1125 SiO2 wt% 36.0462 36.4676 36.6341 36.4813 36.8619 36.6171 36.4673 35.8003 36.4663 36.7658 36.5211 36.6455 36.3030 36.7621 36.1616 36.4199 CaO wt% 5.2023 4.7305 4.9191 5.5414 6.0664 4.2196 4.1765 3.6336 5.3640 3.8527 5.2794 3.8684 4.0295 4.1126 4.1073 4.2303 TiO wt% 0.0552 0.0000 0.0954 0.1360 0.0612 0.1842 0.2961 0.1098 0.1733 0.2444 0.1731 0.3069 0.2528 0.3625 0.2489 0.1874 Cr2O3 wt% 0.0211 0.0363 0.0194 0.0000 0.0000 0.0058 0.0019 0.0328 0.0273 0.0485 0.0449 0.0000 0.0000 0.0563 0.0000 0.0155 MnO wt% 2.3248 1.4582 6.4717 6.4642 6.7691 9.1815 9.2662 9.3150 9.0550 9.5979 9.8801 11.2090 11.4681 10.4010 9.7695 8.4367 FeO wt% 33.7878 35.5050 28.4720 28.3838 27.3236 27.1933 27.2254 27.7945 26.1123 27.3427 25.7774 25.7140 25.7917 26.4319 26.8866 27.7482 Total oxide wt% 99.62 100.70 99.60 99.75 99.72 99.95 99.84 99.20 99.72 100.63 100.09 100.04 100.17 100.29 99.49 99.60 Fe2+ 2.20 2.31 1.85 1.80 1.79 1.78 1.76 1.76 1.67 1.76 1.65 1.70 1.65 1.73 1.75 1.82 Mn 0.16 0.10 0.44 0.44 0.46 0.63 0.64 0.64 0.62 0.65 0.68 0.77 0.79 0.71 0.67 0.58 Mg 0.11 0.12 0.22 0.19 0.17 0.18 0.18 0.18 0.18 0.19 0.17 0.16 0.15 0.16 0.15 0.17 Ca 0.45 0.41 0.43 0.48 0.52 0.37 0.36 0.32 0.46 0.33 0.46 0.34 0.35 0.36 0.36 0.37 Sum X 2.93 2.94 2.94 2.91 2.95 2.95 2.95 2.91 2.93 2.94 2.95 2.96 2.93 2.95 2.93 2.94 Ti 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 Al 2.04 2.04 2.01 2.00 2.01 2.01 1.99 2.02 2.00 2.00 2.00 2.00 2.01 1.98 2.02 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.09 0.08 0.07 0.12 0.05 0.06 0.08 0.14 0.10 0.08 0.09 0.05 0.10 0.06 0.08 0.06 Sum Z 2.14 2.13 2.09 2.13 2.06 2.08 2.09 2.16 2.11 2.10 2.10 2.06 2.12 2.06 2.11 2.09 Si 2.93 2.94 2.96 2.95 2.97 2.96 2.96 2.92 2.95 2.96 2.95 2.97 2.94 2.97 2.95 2.96 Sum T 2.93 2.94 2.96 2.95 2.97 2.96 2.96 2.92 2.95 2.96 2.95 2.97 2.94 2.97 2.95 2.96 % Al 75.35 78.70 62.98 61.78 60.75 60.24 59.91 60.56 56.88 59.92 56.02 57.23 56.25 58.46 59.68 62.01 % Pyr 3.68 4.01 7.47 6.59 5.84 5.99 6.16 6.33 6.10 6.50 5.60 5.46 4.99 5.31 5.13 5.72 % Gr 14.79 13.36 13.95 15.51 17.31 11.98 11.76 10.21 15.04 10.80 14.76 11.00 11.31 11.60 11.69 12.10 % Sp 5.47 3.39 15.06 15.18 15.66 21.35 21.61 22.17 21.16 22.27 22.90 25.97 26.83 24.15 22.97 19.75 % Uv 0.01 0.02 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.02 0.00 0.00 0.02 0.00 0.01 % An 0.68 0.52 0.50 0.91 0.42 0.39 0.48 0.70 0.74 0.43 0.65 0.26 0.55 0.37 0.47 0.37 558 Table B.6 (Continued) Sample DS173-499 (continued) EMPA spot 17 18 19 20 21 22 23 24 26 27 28 29 30 32 33 34 Na2O wt% 0.1070 0.0600 0.0410 0.0564 0.0461 0.0486 0.0450 0.0326 0.0295 0.0113 0.0205 0.0079 0.0248 0.0513 0.0249 0.0125 MgO wt% 1.3888 1.3229 1.5216 1.6317 2.0433 1.4404 1.2166 1.3191 1.2127 1.1608 1.0799 1.3554 1.0894 1.1145 1.1187 1.1408 Al2O3 wt% 20.9467 21.0519 21.0327 21.3243 21.2255 21.1778 21.1999 21.3156 20.8787 20.9234 20.9931 20.8554 20.7403 20.8394 20.6700 20.8216 SiO2 wt% 36.4175 36.6632 36.6154 37.0045 36.6542 37.0333 36.5176 36.9831 37.0613 36.4362 36.6339 36.3601 36.6581 36.6333 36.7933 36.7383 CaO wt% 4.8452 5.8014 5.1929 5.8154 5.5399 5.7482 7.6070 6.9090 5.5643 5.9536 5.7763 6.1942 7.1368 4.8216 5.8318 5.6200 TiO wt% 0.2432 0.1190 0.1269 0.1180 0.0452 0.0642 0.1116 0.0977 0.1671 0.1680 0.1631 0.1591 0.1647 0.0859 0.1386 0.1657 Cr2O3 wt% 0.0291 0.0000 0.0233 0.0293 0.0215 0.0311 0.0255 0.0724 0.0000 0.0487 0.0000 0.0390 0.0274 0.0000 0.0097 0.0370 MnO wt% 6.9710 5.8400 5.8558 6.4474 6.6372 5.2963 5.5460 5.8639 6.0480 6.1075 6.3660 6.1024 5.9392 7.4771 7.1925 7.3039 FeO wt% 28.7990 28.8281 29.8059 27.9321 27.3008 28.9113 27.3747 27.7240 28.7963 28.5416 28.8614 28.4043 27.5702 28.7022 27.4409 28.3274 Total oxide wt% 99.75 99.69 100.22 100.36 99.51 99.75 99.64 100.32 99.76 99.35 99.89 99.48 99.35 99.73 99.22 100.17 Fe2+ 1.84 1.88 1.91 1.81 1.76 1.94 1.75 1.80 1.95 1.88 1.90 1.83 1.81 1.89 1.85 1.85 Mn 0.48 0.40 0.40 0.44 0.45 0.36 0.38 0.40 0.41 0.42 0.44 0.42 0.41 0.51 0.50 0.50 Mg 0.17 0.16 0.18 0.19 0.25 0.17 0.15 0.16 0.15 0.14 0.13 0.16 0.13 0.13 0.14 0.14 Ca 0.42 0.50 0.45 0.50 0.48 0.50 0.66 0.59 0.48 0.52 0.50 0.54 0.62 0.42 0.51 0.49 Sum X 2.91 2.94 2.94 2.94 2.94 2.97 2.93 2.95 2.99 2.96 2.96 2.95 2.97 2.95 2.99 2.97 Ti 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 Al 2.00 2.01 2.00 2.01 2.02 2.01 2.01 2.01 1.99 2.00 2.00 1.99 1.98 1.99 1.98 1.98 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.07 0.10 0.06 0.08 0.01 0.10 0.05 0.00 0.06 0.06 0.10 0.06 0.06 0.02 0.07 Sum Z 2.12 2.08 2.11 2.08 2.10 2.03 2.12 2.08 2.00 2.07 2.07 2.10 2.05 2.06 2.01 2.06 Si 2.95 2.97 2.95 2.97 2.95 2.99 2.94 2.96 3.00 2.96 2.97 2.95 2.97 2.98 3.00 2.97 Sum T 2.95 2.97 2.95 2.97 2.95 2.99 2.94 2.96 3.00 2.96 2.97 2.95 2.97 2.98 3.00 2.97 % Al 63.35 63.89 64.90 61.56 59.89 65.23 59.63 61.09 65.13 63.57 63.96 62.02 60.93 63.83 61.85 62.16 % Pyr 5.76 5.42 6.22 6.62 8.37 5.84 4.99 5.34 4.89 4.75 4.40 5.55 4.44 4.57 4.54 4.63 % Gr 13.63 16.47 14.47 16.42 15.64 16.58 21.32 19.48 16.07 16.93 16.37 17.32 20.18 13.74 16.80 15.76 % Sp 16.44 13.60 13.61 14.86 15.44 12.20 12.94 13.48 13.85 14.19 14.73 14.20 13.74 17.41 16.59 16.83 % Uv 0.01 0.00 0.01 0.02 0.01 0.02 0.02 0.04 0.00 0.03 0.00 0.02 0.02 0.00 0.01 0.02 % An 0.73 0.57 0.74 0.49 0.64 0.12 1.06 0.52 0.00 0.47 0.48 0.83 0.62 0.44 0.16 0.54 559 Table B.6 (Continued) Sample DS173-499 (continued) DS177-1500 EMPA spot 36 37 38 40 42 43 45 46 47 1 2 4 5 6 7 9 Na2O wt% 0.0637 0.0808 0.0397 0.0215 0.0443 0.0693 0.0521 0.0023 0.0215 0.0572 0.0501 0.0034 0.0273 0.0068 0.0000 0.0000 MgO wt% 1.2553 1.1020 1.1450 1.1523 1.1447 1.3836 1.3756 1.3438 1.5326 1.1641 1.0933 1.0477 1.3261 1.1568 1.0600 1.0901 Al2O3 wt% 20.9385 21.0356 20.9637 20.9924 20.8860 21.1396 21.0295 21.0027 21.1731 21.0654 21.5668 20.8385 21.1984 20.7779 20.7833 20.9984 SiO2 wt% 36.2843 36.2001 36.4668 36.7556 36.4141 36.0575 36.4085 36.9173 36.3511 36.5316 37.0139 36.8786 36.6656 36.8033 36.4974 36.4814 CaO wt% 5.5405 5.1797 5.7296 6.8513 6.1988 5.2194 5.9201 6.9912 6.0238 6.9052 7.3878 7.6479 4.7798 4.9832 5.7285 5.6205 TiO wt% 0.1208 0.1234 0.1470 0.1514 0.5029 0.1823 0.1480 0.2212 0.0905 0.1735 0.0947 0.2486 0.0497 0.2794 0.2130 0.1016 Cr2O3 wt% 0.0369 0.0000 0.0097 0.0313 0.0000 0.0116 0.0564 0.0254 0.0350 0.0333 0.0157 0.0176 0.0328 0.0503 0.0310 0.0813 MnO wt% 7.3070 7.6134 7.1772 6.2581 5.9730 5.9984 5.8545 5.5069 5.1697 7.8107 8.2664 7.2734 6.7084 7.1142 6.8831 6.5815 FeO wt% 28.3051 28.0006 27.7628 28.0636 28.6973 28.9795 28.7427 28.0390 29.1812 25.8079 24.4718 25.9992 29.5573 28.7761 28.6138 28.7498 Total oxide wt% 99.85 99.34 99.44 100.28 99.86 99.04 99.59 100.05 99.58 99.55 99.96 99.95 100.35 99.95 99.81 99.70 Fe2+ 1.78 1.80 1.82 1.80 1.86 1.88 1.85 1.84 1.87 1.66 1.62 1.70 1.91 1.93 1.87 1.89 Mn 0.50 0.52 0.49 0.43 0.41 0.41 0.40 0.38 0.35 0.54 0.56 0.50 0.46 0.49 0.47 0.45 Mg 0.15 0.13 0.14 0.14 0.14 0.17 0.17 0.16 0.18 0.14 0.13 0.13 0.16 0.14 0.13 0.13 Ca 0.48 0.45 0.50 0.59 0.54 0.46 0.51 0.60 0.52 0.60 0.64 0.66 0.41 0.43 0.50 0.49 Sum X 2.91 2.91 2.95 2.95 2.95 2.91 2.93 2.98 2.93 2.94 2.95 2.98 2.94 2.99 2.97 2.96 Ti 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 Al 2.00 2.02 2.01 1.99 1.99 2.03 2.01 1.99 2.02 2.01 2.04 1.98 2.01 1.99 1.99 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Fe3+ 0.14 0.10 0.07 0.09 0.08 0.10 0.10 0.05 0.10 0.08 0.02 0.05 0.08 0.02 0.07 0.06 Sum Z 2.14 2.13 2.08 2.09 2.09 2.14 2.11 2.05 2.12 2.10 2.07 2.05 2.10 2.02 2.07 2.08 Si 2.94 2.95 2.96 2.96 2.95 2.94 2.95 2.97 2.94 2.95 2.97 2.97 2.96 2.98 2.96 2.96 Sum T 2.94 2.95 2.96 2.96 2.95 2.94 2.95 2.97 2.94 2.95 2.97 2.97 2.96 2.98 2.96 2.96 % Al 61.10 61.89 61.66 60.89 63.19 64.38 63.10 61.76 63.84 56.60 55.00 56.97 65.02 64.54 63.00 63.81 % Pyr 5.20 4.59 4.70 4.68 4.68 5.77 5.67 5.41 6.30 4.78 4.43 4.22 5.41 4.67 4.32 4.45 % Gr 15.39 14.72 16.30 19.05 17.35 14.85 16.64 19.66 16.90 19.48 21.27 21.44 13.47 14.21 16.10 15.94 % Sp 17.20 18.01 16.74 14.44 13.89 14.21 13.70 12.60 12.07 18.23 19.04 16.65 15.55 16.32 15.92 15.26 % Uv 0.02 0.00 0.01 0.02 0.00 0.01 0.03 0.02 0.02 0.02 0.01 0.01 0.01 0.02 0.02 0.04 % An 1.05 0.75 0.55 0.86 0.69 0.73 0.81 0.46 0.84 0.82 0.20 0.58 0.52 0.14 0.57 0.47 560 Table B.6 (Continued) Sample DS177-1500 (continued) EMPA spot 10 11 14 15 16 17 18 19 20 21 22 23 24 26 27 28 Na2O wt% 0.0181 0.0158 0.0226 0.0270 0.0124 0.0000 0.0247 0.0056 0.0147 0.0147 0.0056 0.0000 0.0000 0.0000 0.0000 0.0147 MgO wt% 1.2481 1.1639 1.2574 1.3712 1.2583 1.2301 1.1592 1.1680 1.1913 1.2127 1.1505 1.1904 1.2236 1.1749 1.1923 1.3294 Al2O3 wt% 20.9112 21.0619 21.1872 21.4085 21.1312 20.9731 21.1693 21.1511 21.0285 21.1185 21.1607 21.2202 21.0276 20.9449 21.0815 20.9550 SiO2 wt% 36.7641 36.6235 36.7108 36.6217 36.6363 36.5655 36.7998 36.5724 37.1077 36.4373 36.9034 36.9218 36.8984 36.9381 37.1659 36.8630 CaO wt% 5.4205 6.3266 5.3242 5.8692 5.8201 6.7186 6.7012 5.7492 6.0319 5.9423 6.2842 6.7989 6.7127 6.3355 5.5951 5.5302 TiO wt% 0.1697 0.1531 0.1019 0.1886 0.1106 0.1878 0.1327 0.0926 0.1154 0.1765 0.2013 0.1906 0.1064 0.1399 0.0703 0.2243 Cr2O3 wt% 0.1259 0.0136 0.0988 0.0273 0.0155 0.0623 0.0117 0.0156 0.0253 0.0292 0.0175 0.0000 0.0839 0.0700 0.0330 0.1513 MnO wt% 7.2219 6.7560 7.6859 8.1670 7.1582 6.2234 8.3233 9.1556 8.7935 8.7453 8.9731 8.6589 7.0211 6.4894 6.9880 7.4114 FeO wt% 28.5652 28.1396 27.9511 26.5105 27.6691 27.6760 25.6696 25.9215 26.5301 26.3951 26.2481 25.4305 26.6796 27.7793 27.6038 27.9214 Total oxide wt% 100.44 100.25 100.34 100.19 99.81 99.64 99.99 99.83 100.84 100.07 100.94 100.41 99.75 99.87 99.73 100.40 Fe2+ 1.85 1.80 1.82 1.71 1.81 1.81 1.67 1.69 1.71 1.68 1.67 1.66 1.78 1.86 1.87 1.83 Mn 0.49 0.46 0.52 0.56 0.49 0.43 0.57 0.63 0.60 0.60 0.61 0.59 0.48 0.44 0.48 0.51 Mg 0.15 0.14 0.15 0.16 0.15 0.15 0.14 0.14 0.14 0.15 0.14 0.14 0.15 0.14 0.14 0.16 Ca 0.47 0.55 0.46 0.51 0.50 0.58 0.58 0.50 0.52 0.51 0.54 0.58 0.58 0.55 0.49 0.48 Sum X 2.96 2.95 2.95 2.94 2.96 2.97 2.96 2.96 2.97 2.94 2.96 2.97 2.98 2.99 2.98 2.97 Ti 0.01 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.01 0.01 0.00 0.01 0.00 0.01 Al 1.99 2.00 2.01 2.03 2.01 2.00 2.01 2.02 1.99 2.01 2.00 2.01 2.00 1.99 2.01 1.99 Cr 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 Fe3+ 0.07 0.09 0.07 0.07 0.06 0.06 0.06 0.06 0.06 0.10 0.08 0.05 0.03 0.02 0.00 0.05 Sum Z 2.08 2.10 2.09 2.11 2.08 2.08 2.07 2.08 2.05 2.12 2.09 2.07 2.04 2.03 2.02 2.06 Si 2.96 2.95 2.96 2.95 2.96 2.96 2.96 2.96 2.97 2.94 2.95 2.96 2.98 2.98 3.01 2.97 Sum T 2.96 2.95 2.96 2.95 2.96 2.96 2.96 2.96 2.97 2.94 2.95 2.96 2.98 2.98 3.01 2.97 % Al 62.49 61.12 61.54 58.29 61.30 60.99 56.55 57.21 57.70 57.25 56.60 55.72 59.51 62.08 62.77 61.56 % Pyr 5.06 4.74 5.12 5.59 5.12 5.00 4.71 4.76 4.79 4.96 4.64 4.79 4.94 4.73 4.83 5.37 % Gr 15.12 17.63 14.99 16.56 16.52 18.92 18.96 16.31 16.84 16.58 17.41 19.11 19.12 18.06 16.26 15.51 % Sp 16.64 15.63 17.77 18.92 16.55 14.38 19.20 21.19 20.08 20.32 20.55 19.81 16.09 14.85 16.09 17.01 % Uv 0.06 0.01 0.05 0.01 0.01 0.04 0.01 0.01 0.01 0.02 0.01 0.00 0.05 0.04 0.02 0.08 % An 0.57 0.82 0.50 0.56 0.46 0.60 0.53 0.49 0.54 0.81 0.71 0.49 0.25 0.19 0.00 0.40 561 Table B.6 (Continued) Sample DS177-1500 (continued) 34L006-1235 EMPA spot 29 30 31 33 34 37 38 39 40 41 42 1 2 4 5 6 Na2O wt% 0.0102 0.0157 0.0068 0.0000 0.0236 0.0000 0.0000 0.0225 0.0000 0.0000 0.0045 0.0051 0.0000 0.0379 0.0092 0.0000 MgO wt% 1.2256 2.1011 1.2663 1.2610 1.2671 1.1568 1.1396 1.1809 1.1611 1.1739 1.1470 1.0066 1.0239 1.0325 1.0179 1.0439 Al2O3 wt% 20.7680 20.0537 20.8460 21.1932 21.3559 20.8909 21.1104 20.9232 21.0845 21.1804 20.9738 21.0103 21.1264 21.3452 21.1556 20.9110 SiO2 wt% 36.5477 37.5621 36.5676 37.0139 36.9400 36.9014 37.1886 36.9588 36.7282 36.8653 36.9828 36.5722 36.3292 36.3434 36.5845 36.1942 CaO wt% 6.3564 5.5195 5.1324 7.4963 5.7944 7.0223 6.6759 5.8480 6.8909 5.8543 5.4037 4.7560 7.3111 5.3436 5.4259 6.5811 TiO wt% 0.1921 0.0731 0.2649 0.2060 0.0428 0.1410 0.1336 0.0766 0.1536 0.1505 0.0963 0.0562 0.2106 0.0976 0.0985 0.1146 Cr2O3 wt% 0.0913 0.0292 0.0968 0.0000 0.0039 0.0000 0.0156 0.0526 0.0723 0.0000 0.0039 0.0099 0.0180 0.0238 0.0059 0.0060 MnO wt% 6.9138 8.5922 7.5272 8.7787 7.7790 8.7328 9.0380 9.0477 8.7423 8.9210 9.0466 10.0035 9.1310 10.5449 10.3287 9.6621 FeO wt% 27.7036 26.4973 27.7652 24.9981 27.1175 24.7007 25.0966 25.9688 25.2607 25.4473 26.0008 26.1577 24.5131 25.5333 25.0625 25.2517 Total oxide wt% 99.81 100.44 99.47 100.95 100.32 99.55 100.40 100.08 100.09 99.59 99.66 99.58 99.66 100.30 99.69 99.76 Fe2+ 1.79 1.70 1.86 1.58 1.78 1.64 1.67 1.71 1.63 1.72 1.76 1.75 1.56 1.61 1.66 1.58 Mn 0.47 0.58 0.52 0.59 0.53 0.60 0.61 0.62 0.60 0.61 0.62 0.69 0.63 0.72 0.71 0.66 Mg 0.15 0.25 0.15 0.15 0.15 0.14 0.14 0.14 0.14 0.14 0.14 0.12 0.12 0.12 0.12 0.13 Ca 0.55 0.47 0.45 0.64 0.50 0.61 0.57 0.51 0.59 0.51 0.47 0.41 0.63 0.46 0.47 0.57 Sum X 2.96 3.01 2.98 2.96 2.96 2.99 2.99 2.97 2.96 2.99 2.99 2.98 2.95 2.92 2.97 2.94 Ti 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 Al 1.98 1.90 2.00 1.99 2.02 1.99 2.00 1.99 2.00 2.02 2.00 2.01 2.01 2.03 2.02 2.00 Cr 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.09 0.08 0.03 0.09 0.04 0.03 0.02 0.04 0.07 0.00 0.00 0.03 0.09 0.11 0.04 0.13 Sum Z 2.08 1.98 2.04 2.09 2.07 2.02 2.02 2.04 2.08 2.03 2.01 2.05 2.12 2.15 2.06 2.13 Si 2.96 3.01 2.97 2.95 2.97 2.98 2.99 2.98 2.96 2.99 3.00 2.98 2.94 2.93 2.97 2.93 Sum T 2.96 3.01 2.97 2.95 2.97 2.98 2.99 2.98 2.96 2.99 3.00 2.98 2.94 2.93 2.97 2.93 % Al 60.39 56.48 62.47 53.27 60.12 54.99 55.70 57.45 55.13 57.74 58.92 58.80 53.09 55.23 56.05 53.69 % Pyr 4.99 8.35 5.15 5.06 5.13 4.66 4.56 4.77 4.70 4.75 4.63 4.10 4.19 4.25 4.15 4.29 % Gr 17.71 15.10 14.68 20.61 16.49 20.02 18.95 16.58 19.30 16.96 15.65 13.71 20.44 14.97 15.57 18.18 % Sp 16.00 19.40 17.39 20.03 17.89 20.00 20.55 20.79 20.12 20.50 20.76 23.17 21.22 24.69 23.91 22.57 % Uv 0.05 0.01 0.05 0.00 0.00 0.00 0.01 0.03 0.04 0.00 0.00 0.00 0.01 0.01 0.00 0.00 % An 0.77 0.62 0.19 0.93 0.35 0.26 0.18 0.36 0.65 0.00 0.00 0.21 0.95 0.82 0.28 1.22 562 Table B.6 (Continued) Sample 34L006-1235 (continued) EMPA spot 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Na2O wt% 0.0338 0.0546 0.0456 0.0362 0.0252 0.0232 0.0141 0.0081 0.0000 0.0111 0.0000 0.0367 0.0061 0.0081 0.0223 MgO wt% 1.0545 0.9619 1.1290 0.9949 1.0108 1.0297 0.9790 1.0305 1.0927 1.1137 1.0067 1.2389 0.9656 1.0171 1.8666 Al2O3 wt% 21.1220 21.0540 20.7864 20.8453 20.6928 20.9178 20.6817 20.8317 20.7027 20.9112 20.7718 21.0338 20.9423 20.9429 20.0065 SiO2 wt% 36.8958 36.5677 36.6361 36.3140 37.1356 36.4356 36.9580 36.5027 37.2715 36.5700 37.0088 36.3844 36.9669 36.3572 37.4493 CaO wt% 4.7675 8.1948 7.4666 9.2867 9.2606 9.0611 9.0651 9.1475 8.4955 8.3774 8.6414 6.4139 8.4975 8.2886 5.8404 TiO wt% 0.0341 0.2113 0.1673 0.2525 0.2120 0.2455 0.2095 0.2380 0.2323 0.1981 0.2022 0.1107 0.2199 0.1860 0.1357 Cr2O3 wt% 0.0237 0.0140 0.0060 0.0020 0.0000 0.0000 0.0181 0.0000 0.0000 0.0361 0.0361 0.0675 0.0241 0.0000 0.0239 MnO wt% 10.3030 8.8416 8.7296 8.3224 8.5460 8.6211 8.6047 8.4940 8.4413 8.4690 7.9391 8.5492 8.4357 8.6641 8.8003 FeO wt% 25.8657 23.8704 24.5418 23.3509 23.5344 23.6154 23.0632 23.6907 23.9540 24.1913 23.9246 25.9458 24.2125 24.0148 25.2179 Total oxide wt% 100.10 99.77 99.51 99.40 100.42 99.95 99.59 99.94 100.19 99.88 99.53 99.78 100.27 99.48 99.36 Fe2+ 1.72 1.50 1.57 1.43 1.47 1.44 1.49 1.45 1.57 1.51 1.58 1.64 1.55 1.51 1.69 Mn 0.71 0.60 0.60 0.57 0.58 0.59 0.59 0.58 0.57 0.58 0.54 0.59 0.57 0.59 0.60 Mg 0.13 0.12 0.14 0.12 0.12 0.12 0.12 0.12 0.13 0.13 0.12 0.15 0.12 0.12 0.23 Ca 0.41 0.71 0.65 0.80 0.79 0.78 0.78 0.79 0.73 0.72 0.75 0.56 0.73 0.72 0.51 Sum X 2.97 2.93 2.95 2.93 2.97 2.93 2.98 2.94 3.00 2.95 3.00 2.93 2.97 2.94 3.03 Ti 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 Al 2.01 2.00 1.98 1.98 1.95 1.98 1.97 1.97 1.96 1.98 1.98 2.00 1.98 2.00 1.91 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.03 0.10 0.09 0.14 0.10 0.15 0.06 0.14 0.04 0.11 0.03 0.12 0.07 0.11 0.02 Sum Z 2.04 2.11 2.08 2.14 2.06 2.14 2.04 2.12 2.01 2.11 2.02 2.13 2.06 2.12 1.93 Si 2.98 2.95 2.96 2.93 2.97 2.93 2.98 2.93 2.99 2.94 2.99 2.94 2.97 2.94 3.03 Sum T 2.98 2.95 2.96 2.93 2.97 2.93 2.98 2.93 2.99 2.94 2.99 2.94 2.97 2.94 3.03 % Al 58.04 51.32 53.16 49.00 49.69 49.10 50.09 49.34 52.19 51.36 52.90 55.95 52.26 51.29 55.89 % Pyr 4.28 3.94 4.62 4.09 4.06 4.21 3.95 4.20 4.36 4.53 4.04 5.10 3.89 4.16 7.44 % Gr 13.71 22.83 20.89 25.48 25.33 24.65 25.34 24.88 23.72 23.05 24.43 17.86 23.59 22.99 16.54 % Sp 23.77 20.59 20.28 19.45 19.51 20.04 19.70 19.67 19.12 19.59 18.12 19.99 19.29 20.16 19.93 % Uv 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.03 0.03 0.04 0.02 0.00 0.01 % An 0.18 1.20 0.97 1.84 1.29 1.86 0.79 1.78 0.50 1.34 0.37 1.03 0.85 1.31 0.13 563 Table B.6 (Continued) Sample 34L006-1235 (continued) CR4612-360 EMPA spot 22 23 24 25 26 27 28 29 1 2 3 4 5 6 7 Na2O wt% 0.0707 0.0143 0.0394 0.0404 0.0475 0.0756 0.0537 0.0422 0.0460 0.0332 0.0263 0.0011 0.0481 0.0410 0.0251 MgO wt% 1.0648 1.0907 1.0201 1.1040 0.9965 1.0684 1.2238 1.0838 2.4196 2.9748 2.8033 2.6745 2.4879 2.3272 2.2301 Al2O3 wt% 21.3729 20.9081 20.8849 20.7535 20.6786 20.6037 20.9648 20.8867 21.1748 21.4036 21.2720 21.4321 21.3009 21.0957 21.2187 SiO2 wt% 36.2105 36.6314 36.3951 37.0105 36.3167 36.8103 36.3703 36.7702 36.7764 36.5172 36.6393 36.7010 36.6790 36.9632 36.8274 CaO wt% 5.1817 6.1613 8.7129 8.0589 8.7453 8.4808 7.1306 8.6389 2.4180 2.3913 2.4763 2.9560 2.8438 3.1487 3.1757 TiO wt% 0.0988 0.1479 0.1964 0.1766 0.2375 0.2536 0.1813 0.2321 0.0412 0.0371 0.0815 0.0499 0.0504 0.0505 0.0568 Cr2O3 wt% 0.0178 0.0000 0.0000 0.0260 0.0381 0.0161 0.0000 0.0382 0.0209 0.0076 0.0458 0.0038 0.0325 0.0345 0.0000 MnO wt% 9.8382 9.4738 8.5207 8.2804 8.4954 8.7556 8.8271 8.3213 1.8910 1.4292 1.7510 2.1347 2.6052 3.2006 3.6027 FeO wt% 26.0113 24.8040 23.7864 24.3955 23.7393 23.3266 24.2817 23.1631 35.6239 35.0701 34.4742 34.4682 34.2712 32.5841 32.6189 Total oxide wt% 99.87 99.23 99.56 99.85 99.29 99.39 99.03 99.18 100.41 99.86 99.57 100.42 100.32 99.45 99.76 Fe2+ 1.65 1.66 1.47 1.58 1.47 1.49 1.56 1.51 2.31 2.27 2.28 2.23 2.21 2.20 2.18 Mn 0.67 0.65 0.58 0.56 0.58 0.60 0.61 0.57 0.13 0.10 0.12 0.14 0.18 0.22 0.25 Mg 0.13 0.13 0.12 0.13 0.12 0.13 0.15 0.13 0.29 0.36 0.34 0.32 0.30 0.28 0.27 Ca 0.45 0.54 0.75 0.70 0.76 0.73 0.62 0.75 0.21 0.21 0.21 0.25 0.24 0.27 0.28 Sum X 2.90 2.98 2.93 2.97 2.93 2.95 2.94 2.96 2.94 2.93 2.95 2.94 2.93 2.98 2.97 Ti 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.04 2.00 1.99 1.97 1.97 1.96 2.01 1.99 2.01 2.03 2.03 2.03 2.02 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.11 0.03 0.14 0.07 0.14 0.09 0.09 0.05 0.09 0.10 0.05 0.09 0.10 0.00 0.03 Sum Z 2.16 2.04 2.13 2.05 2.13 2.06 2.10 2.06 2.10 2.13 2.08 2.11 2.12 2.02 2.05 Si 2.93 2.98 2.94 2.98 2.94 2.97 2.95 2.97 2.96 2.94 2.96 2.94 2.95 2.99 2.98 Sum T 2.93 2.98 2.94 2.98 2.94 2.97 2.95 2.97 2.96 2.94 2.96 2.94 2.95 2.99 2.98 % Al 56.84 55.63 50.17 53.10 50.09 50.43 53.14 51.11 78.65 77.42 77.24 75.59 75.40 74.00 73.36 % Pyr 4.43 4.44 4.19 4.46 4.11 4.36 5.05 4.41 9.87 12.20 11.44 10.86 10.18 9.44 9.06 % Gr 14.65 17.70 23.98 22.55 24.04 23.68 20.16 24.46 6.79 6.72 7.07 8.27 7.97 9.14 9.13 % Sp 23.24 21.91 19.90 19.02 19.90 20.31 20.68 19.23 4.38 3.33 4.06 4.92 6.06 7.38 8.31 % Uv 0.01 0.00 0.00 0.02 0.03 0.01 0.00 0.03 0.00 0.00 0.01 0.00 0.01 0.01 0.00 % An 0.80 0.26 1.65 0.76 1.71 1.07 0.89 0.64 0.29 0.32 0.17 0.35 0.38 0.02 0.13 564 Table B.6 (Continued) Sample CR4612-360 (continued) EMPA spot 8 9 10 11 12 13 14 15 16 17 18 20 21 22 23 Na2O wt% 0.0320 0.0218 0.0389 0.0240 0.0366 0.0459 0.0194 0.0057 0.0309 0.0011 0.0365 0.0034 0.0239 0.0023 0.0719 MgO wt% 2.1783 2.2443 2.1377 2.2254 2.2041 2.2386 2.2575 2.1742 2.2904 2.3072 2.3109 2.4043 2.5010 2.6156 2.8516 Al2O3 wt% 21.0909 21.2066 21.1432 21.3875 21.1453 21.3026 21.0243 21.4317 21.0605 21.2501 21.1272 21.1353 21.1619 21.2324 21.3969 SiO2 wt% 36.9095 36.7426 36.7802 36.5579 36.7365 36.2139 37.0482 36.6974 36.7101 36.6180 36.9072 36.7013 36.6457 37.3146 36.7588 CaO wt% 3.2530 2.7326 2.8718 2.9406 3.1232 2.7972 3.1479 2.8593 2.9149 3.3309 3.1352 2.9461 2.8367 2.7792 2.5918 TiO wt% 0.0419 0.0857 0.0760 0.0193 0.1015 0.1063 0.0396 0.0549 0.1044 0.0418 0.1685 0.0731 0.0728 0.0729 0.0769 Cr2O3 wt% 0.0000 0.0478 0.0249 0.0000 0.0211 0.0649 0.0077 0.0000 0.1397 0.0000 0.0038 0.0000 0.0268 0.0344 0.0725 MnO wt% 3.8689 4.1001 4.1966 3.8399 3.8341 4.0290 3.7836 3.5306 3.4273 2.9781 2.6751 2.5816 2.4394 1.9852 1.7731 FeO wt% 32.6475 33.2312 33.0244 32.7515 33.1840 33.5261 32.7156 33.4532 33.2548 33.4525 33.2703 33.6408 33.3435 34.3327 34.6539 Total oxide wt% 100.02 100.41 100.29 99.75 100.39 100.32 100.04 100.21 99.93 99.98 99.63 99.49 99.05 100.37 100.25 Fe2+ 2.16 2.17 2.16 2.16 2.15 2.12 2.18 2.21 2.19 2.19 2.24 2.25 2.25 2.30 2.23 Mn 0.26 0.28 0.29 0.26 0.26 0.27 0.26 0.24 0.23 0.20 0.18 0.18 0.17 0.13 0.12 Mg 0.26 0.27 0.26 0.27 0.26 0.27 0.27 0.26 0.28 0.28 0.28 0.29 0.30 0.31 0.34 Ca 0.28 0.24 0.25 0.25 0.27 0.24 0.27 0.25 0.25 0.29 0.27 0.26 0.25 0.24 0.22 Sum X 2.96 2.95 2.95 2.95 2.94 2.90 2.98 2.96 2.96 2.95 2.98 2.98 2.97 2.99 2.92 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 Al 2.01 2.01 2.01 2.04 2.01 2.02 2.00 2.04 2.01 2.02 2.01 2.02 2.03 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.05 0.07 0.07 0.06 0.08 0.14 0.03 0.05 0.05 0.07 0.01 0.03 0.01 0.00 0.09 Sum Z 2.05 2.09 2.08 2.09 2.10 2.17 2.03 2.08 2.07 2.09 2.03 2.05 2.05 2.01 2.12 Si 2.98 2.96 2.96 2.96 2.96 2.92 2.99 2.96 2.97 2.95 2.99 2.97 2.98 2.99 2.95 Sum T 2.98 2.96 2.96 2.96 2.96 2.92 2.99 2.96 2.97 2.95 2.99 2.97 2.98 2.99 2.95 % Al 72.76 73.42 73.17 73.32 72.99 72.93 73.10 74.67 74.20 73.98 75.34 75.69 75.83 77.04 76.55 % Pyr 8.84 9.13 8.71 9.11 8.98 9.27 9.11 8.83 9.33 9.39 9.37 9.76 10.20 10.46 11.68 % Gr 9.27 7.69 8.11 8.42 8.75 7.74 8.99 8.15 8.26 9.41 9.06 8.47 8.24 7.97 7.28 % Sp 8.92 9.47 9.71 8.93 8.88 9.48 8.67 8.15 7.93 6.89 6.16 5.95 5.65 4.51 4.13 % Uv 0.00 0.01 0.01 0.00 0.01 0.02 0.00 0.00 0.04 0.00 0.00 0.00 0.01 0.01 0.02 % An 0.21 0.27 0.27 0.23 0.37 0.55 0.13 0.19 0.22 0.33 0.04 0.12 0.06 0.00 0.33 565 Table B.6 (Continued) Sample CR4612-360 (continued) EMPA spot 24 25 26 27 29 30 31 32 33 34 35 36 38 40 41 Na2O wt% 0.0320 0.0364 0.0239 0.0493 0.0000 0.0398 0.0331 0.0389 0.0182 0.0000 0.0000 0.0148 0.0068 0.0183 0.0309 MgO wt% 2.8071 2.8381 3.0186 2.4171 1.6251 1.9493 1.6289 1.6472 1.5575 1.5468 1.5119 1.5205 1.5926 1.8367 2.2796 Al2O3 wt% 21.1447 21.3574 21.3697 21.1923 21.0235 21.1053 21.2192 20.9499 20.9672 20.9303 21.1107 21.1781 21.1052 20.9785 21.3294 SiO2 wt% 36.9063 36.9925 37.4885 36.6319 36.3365 36.7457 36.3846 36.7168 36.7532 36.5830 36.2435 36.4599 36.5739 36.5453 36.5483 CaO wt% 2.6390 2.7265 2.5930 2.4926 3.2465 3.5181 3.1863 3.1101 3.7624 3.4444 3.5439 4.1058 3.4884 3.0944 3.1220 TiO wt% 0.0549 0.0499 0.0314 0.0291 0.0916 0.0936 0.0714 0.1256 0.0556 0.0889 0.0448 0.0925 0.0948 0.0642 0.0510 Cr2O3 wt% 0.0687 0.0096 0.0096 0.0668 0.0672 0.0539 0.0000 0.0385 0.0482 0.0616 0.0000 0.0116 0.0347 0.0441 0.0000 MnO wt% 1.6782 1.4584 1.4362 1.7903 6.5467 5.5219 6.7881 6.9552 6.8149 7.0919 6.8810 6.9156 6.8342 5.6571 3.4614 FeO wt% 34.6398 34.1449 34.4537 34.6788 30.4770 30.4986 30.0259 29.9951 29.3994 29.7259 29.8321 29.5848 29.7939 31.3669 32.9291 Total oxide wt% 99.97 99.61 100.42 99.35 99.41 99.53 99.34 99.58 99.38 99.47 99.17 99.88 99.52 99.61 99.75 Fe2+ 2.28 2.29 2.30 2.32 2.03 2.04 2.01 2.02 2.00 2.01 1.99 1.94 2.01 2.08 2.16 Mn 0.11 0.10 0.10 0.12 0.45 0.38 0.47 0.48 0.47 0.49 0.48 0.47 0.47 0.39 0.24 Mg 0.34 0.34 0.36 0.29 0.20 0.24 0.20 0.20 0.19 0.19 0.18 0.18 0.19 0.22 0.27 Ca 0.23 0.24 0.22 0.22 0.28 0.31 0.28 0.27 0.33 0.30 0.31 0.36 0.30 0.27 0.27 Sum X 2.96 2.97 2.98 2.95 2.97 2.97 2.95 2.97 2.99 2.98 2.96 2.95 2.98 2.96 2.94 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.01 2.03 2.01 2.03 2.02 2.02 2.04 2.01 2.01 2.01 2.03 2.02 2.02 2.01 2.03 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.05 0.01 0.00 0.03 0.04 0.02 0.04 0.02 0.00 0.02 0.05 0.07 0.02 0.05 0.07 Sum Z 2.07 2.04 2.02 2.07 2.07 2.05 2.08 2.03 2.02 2.04 2.08 2.09 2.05 2.06 2.10 Si 2.97 2.98 3.00 2.97 2.96 2.98 2.96 2.99 2.99 2.98 2.96 2.95 2.97 2.97 2.95 Sum T 2.97 2.98 3.00 2.97 2.96 2.98 2.96 2.99 2.99 2.98 2.96 2.95 2.97 2.97 2.95 % Al 77.05 77.21 77.23 78.57 68.54 68.95 68.01 68.05 66.94 67.23 67.25 65.62 67.47 70.27 73.42 % Pyr 11.39 11.49 12.06 9.91 6.66 7.95 6.70 6.72 6.33 6.30 6.21 6.22 6.49 7.51 9.34 % Gr 7.47 7.88 7.44 7.20 9.32 10.15 9.23 9.00 10.95 9.94 10.23 11.66 10.09 8.85 8.89 % Sp 3.87 3.36 3.26 4.17 15.24 12.79 15.87 16.11 15.74 16.40 16.07 16.08 15.82 13.14 8.06 % Uv 0.02 0.00 0.00 0.02 0.02 0.02 0.00 0.01 0.02 0.02 0.00 0.00 0.01 0.01 0.00 % An 0.20 0.04 0.00 0.12 0.21 0.12 0.17 0.07 0.02 0.09 0.23 0.39 0.09 0.22 0.29 566 Table B.6 (Continued) Sample CR4612-360 (continued) 19L547-495 EMPA spot 42 43 44 46 1 4 6 7 10 14 20 21 24 26 36 Na2O wt% 0.0126 0.0639 0.0228 0.0126 0.0035 0.0035 0.0312 0.0484 0.0115 0.0347 0.0207 0.0346 0.0231 0.0172 0.0242 MgO wt% 2.3984 2.6653 2.8444 2.5555 1.3841 1.3859 1.3680 1.5010 1.5271 1.8994 1.7100 1.7625 1.5639 1.4846 1.2310 Al2O3 wt% 21.1573 21.2101 21.2641 21.3535 21.0284 20.9630 20.8361 21.0727 20.9722 20.1529 20.8309 20.3845 20.9332 21.0297 20.8912 SiO2 wt% 37.0898 36.6479 37.0354 37.0289 36.1286 36.4295 36.4430 36.2488 36.5571 36.7496 36.7725 36.7444 36.2566 36.3479 36.2174 CaO wt% 3.1857 2.8790 2.9372 2.8520 2.7812 3.2351 3.0437 3.0183 3.0194 2.6937 3.5676 2.8020 2.9479 3.7190 3.2110 TiO wt% 0.0354 0.1051 0.0513 0.0458 0.0338 0.0590 0.0259 0.0383 0.0088 0.1012 0.0535 0.0419 0.0850 0.0732 0.2783 Cr2O3 wt% 0.0402 0.0000 0.0230 0.0268 0.0723 0.0210 0.0458 0.0763 0.0534 0.0267 0.1341 0.0534 0.0951 0.0115 0.0479 MnO wt% 2.7883 1.9846 1.7602 1.6796 3.6751 4.2723 3.9367 3.6531 3.7420 3.5221 3.8359 3.8352 2.0941 1.9839 6.2484 FeO wt% 33.6015 33.8198 34.1599 34.3923 34.1824 33.2582 33.8697 33.6568 33.6306 34.2269 33.1702 33.5130 35.4668 34.5825 31.4528 Total oxide wt% 100.31 99.38 100.10 99.95 99.29 99.63 99.60 99.31 99.52 99.41 100.10 99.17 99.47 99.25 99.60 Fe2+ 2.22 2.23 2.25 2.31 2.29 2.22 2.25 2.24 2.27 2.28 2.19 2.26 2.36 2.32 2.10 Mn 0.19 0.14 0.12 0.11 0.25 0.29 0.27 0.25 0.26 0.24 0.26 0.27 0.14 0.14 0.43 Mg 0.29 0.32 0.34 0.31 0.17 0.17 0.17 0.18 0.19 0.23 0.21 0.21 0.19 0.18 0.15 Ca 0.27 0.25 0.25 0.25 0.24 0.28 0.27 0.26 0.26 0.24 0.31 0.25 0.26 0.33 0.28 Sum X 2.98 2.94 2.97 2.98 2.96 2.97 2.96 2.94 2.97 2.99 2.97 2.99 2.95 2.96 2.96 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 Al 2.00 2.02 2.01 2.03 2.03 2.01 2.00 2.03 2.01 1.94 1.99 1.97 2.01 2.02 2.01 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 Fe3+ 0.03 0.06 0.04 0.01 0.05 0.04 0.06 0.06 0.03 0.06 0.05 0.03 0.06 0.04 0.05 Sum Z 2.04 2.08 2.06 2.04 2.09 2.06 2.06 2.09 2.04 2.00 2.05 2.00 2.09 2.07 2.08 Si 2.98 2.97 2.97 2.98 2.96 2.97 2.97 2.96 2.98 3.00 2.98 3.01 2.96 2.97 2.96 Sum T 2.98 2.97 2.97 2.98 2.96 2.97 2.97 2.96 2.98 3.00 2.98 3.01 2.96 2.97 2.96 % Al 74.75 75.95 75.96 77.59 77.42 74.89 76.20 76.20 76.21 76.23 73.77 75.72 79.92 78.29 70.83 % Pyr 9.65 10.94 11.48 10.30 5.71 5.67 5.62 6.22 6.24 7.74 6.95 7.19 6.45 6.10 5.07 % Gr 9.05 8.24 8.33 8.23 8.02 9.30 8.73 8.70 8.74 7.63 10.09 8.07 8.43 10.74 9.19 % Sp 6.38 4.63 4.04 3.85 8.62 9.93 9.19 8.60 8.68 8.15 8.86 8.88 4.90 4.63 14.61 % Uv 0.01 0.00 0.01 0.01 0.02 0.01 0.01 0.02 0.01 0.01 0.04 0.01 0.03 0.00 0.01 % An 0.15 0.23 0.17 0.02 0.20 0.20 0.24 0.25 0.11 0.23 0.28 0.11 0.26 0.22 0.24 567 Table B.6 (Continued) Sample 19L547-495 (continued) CR4610-947 EMPA spot 38 39 40 41 41 46 48 50 51 52 56 1 4 5 6 Na2O wt% 0.0242 0.0000 0.0162 0.0323 0.0243 0.0000 0.0080 0.0243 0.0116 0.0058 0.0139 0.0411 0.0229 0.0296 0.0000 MgO wt% 1.3179 1.4815 1.5213 1.4614 1.3453 1.5997 1.2656 1.3818 1.3426 1.4836 1.5355 1.7264 2.0903 2.1454 2.1474 Al2O3 wt% 20.6631 20.6662 21.2771 21.2312 21.0435 21.0170 20.4405 20.8226 20.7669 21.0616 21.1408 21.3938 21.1726 21.2289 21.3612 SiO2 wt% 36.4352 36.7170 36.2821 36.3583 36.3848 36.2153 37.5072 36.5037 36.4339 36.2901 36.6096 36.1935 36.2238 36.0498 36.4096 CaO wt% 3.5551 2.4810 2.6502 2.9639 2.9078 3.6761 3.3570 3.0350 2.9547 2.7650 2.7179 4.2705 4.1094 4.3602 4.8487 TiO wt% 0.2563 0.1031 0.0602 0.0613 0.0663 0.1305 0.1766 0.0341 0.2125 0.1197 0.0982 0.0667 0.1071 0.0973 0.1026 Cr2O3 wt% 0.0267 0.0417 0.0095 0.0000 0.0152 0.0268 0.0000 0.0267 0.0343 0.0323 0.0361 0.0231 0.0480 0.0000 0.0212 MnO wt% 2.4990 1.9312 2.1127 1.7167 1.8208 3.5704 5.6045 2.2163 4.2752 2.1405 2.1822 3.6437 2.8459 2.9150 2.9287 FeO wt% 34.3645 36.0889 35.9338 35.5476 35.7883 33.0586 30.7908 35.0185 33.8191 35.7838 35.6956 32.5226 33.2726 32.8279 32.2449 Total oxide wt% 99.14 99.51 99.86 99.37 99.40 99.29 99.15 99.06 99.85 99.68 100.03 99.88 99.89 99.65 100.06 Fe2+ 2.34 2.47 2.38 2.40 2.42 2.20 2.11 2.39 2.26 2.39 2.40 2.08 2.12 2.07 2.06 Mn 0.17 0.13 0.15 0.12 0.13 0.25 0.39 0.15 0.30 0.15 0.15 0.25 0.19 0.20 0.20 Mg 0.16 0.18 0.18 0.18 0.16 0.19 0.15 0.17 0.16 0.18 0.19 0.21 0.25 0.26 0.26 Ca 0.31 0.22 0.23 0.26 0.25 0.32 0.29 0.27 0.26 0.24 0.24 0.37 0.36 0.38 0.42 Sum X 2.99 3.00 2.95 2.95 2.97 2.96 2.95 2.98 2.97 2.96 2.97 2.91 2.92 2.90 2.93 Ti 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 Al 2.00 1.99 2.04 2.04 2.03 2.02 1.97 2.01 2.00 2.02 2.02 2.04 2.01 2.02 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.02 0.00 0.06 0.03 0.03 0.06 0.00 0.01 0.05 0.05 0.03 0.12 0.13 0.15 0.11 Sum Z 2.02 2.00 2.10 2.07 2.06 2.09 1.98 2.02 2.05 2.08 2.06 2.16 2.15 2.18 2.14 Si 2.99 3.00 2.95 2.97 2.97 2.95 3.07 2.99 2.97 2.96 2.97 2.93 2.93 2.91 2.93 Sum T 2.99 3.00 2.95 2.97 2.97 2.95 3.07 2.99 2.97 2.96 2.97 2.93 2.93 2.91 2.93 % Al 78.34 82.27 80.96 81.19 81.63 74.24 71.57 80.24 75.91 80.76 80.73 71.56 72.53 71.22 70.17 % Pyr 5.39 6.02 6.26 6.02 5.53 6.57 5.24 5.66 5.49 6.09 6.26 7.15 8.62 8.90 8.78 % Gr 10.30 7.22 7.61 8.65 8.46 10.51 9.96 8.89 8.43 7.94 7.83 12.00 11.40 12.08 13.47 % Sp 5.81 4.46 4.94 4.02 4.25 8.33 13.19 5.16 9.93 4.99 5.05 8.58 6.67 6.87 6.80 % Uv 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.00 0.01 % An 0.08 0.00 0.22 0.12 0.11 0.30 0.00 0.03 0.20 0.19 0.10 0.69 0.73 0.90 0.74 568 Table B.6 (Continued) Sample CR4610-947 (continued) EMPA spot 7 8 9 10 11 12 13 14 15 16 17 18 21 22 Na2O wt% 0.0159 0.0296 0.0194 0.0011 0.0228 0.0227 0.0000 0.0217 0.0000 0.0421 0.0216 0.0354 0.0000 0.0389 MgO wt% 2.0543 1.9952 1.9279 1.9233 2.1366 2.0555 2.1415 2.0993 2.2229 2.1839 2.2204 2.0249 1.9594 2.0968 Al2O3 wt% 21.2436 21.1096 21.1059 21.1832 21.1707 21.1902 21.2721 21.1971 21.1551 21.2344 21.6134 21.2405 21.3617 21.0973 SiO2 wt% 36.3567 36.3154 36.3246 36.4539 36.0552 36.3809 36.1571 36.0021 35.9574 36.2949 36.1955 36.3534 36.0738 36.2994 CaO wt% 4.9202 4.2188 4.1636 4.1680 4.1682 4.9883 4.4144 3.9975 3.6946 4.5986 4.0668 3.8994 4.3397 4.0525 TiO wt% 0.1596 0.0660 0.0810 0.1390 0.1350 0.1299 0.1270 0.1282 0.1533 0.1218 0.0507 0.1249 0.0509 0.0944 Cr2O3 wt% 0.0251 0.0827 0.0576 0.0307 0.0480 0.0212 0.0231 0.0633 0.0691 0.0694 0.0000 0.0192 0.0077 0.0364 MnO wt% 2.7852 2.9023 2.9662 2.9850 3.0410 2.9084 2.9470 3.0057 3.0343 2.9335 2.9942 2.9125 2.6092 2.4070 FeO wt% 32.1228 32.7742 33.3565 33.3059 33.0154 32.4645 32.4615 33.1875 33.0493 32.6820 32.4515 33.4366 32.6564 33.9191 Total oxide wt% 99.68 99.49 100.00 100.19 99.79 100.16 99.54 99.70 99.34 100.16 99.61 100.05 99.06 100.04 Fe2+ 2.07 2.13 2.13 2.15 2.08 2.05 2.09 2.10 2.13 2.05 2.09 2.14 2.14 2.15 Mn 0.19 0.20 0.20 0.20 0.21 0.20 0.20 0.21 0.21 0.20 0.20 0.20 0.18 0.16 Mg 0.25 0.24 0.23 0.23 0.26 0.25 0.26 0.25 0.27 0.26 0.27 0.24 0.24 0.25 Ca 0.43 0.37 0.36 0.36 0.36 0.43 0.38 0.35 0.32 0.40 0.35 0.34 0.38 0.35 Sum X 2.93 2.93 2.93 2.94 2.91 2.92 2.93 2.91 2.93 2.90 2.91 2.92 2.94 2.91 Ti 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.00 Al 2.02 2.02 2.01 2.01 2.02 2.01 2.03 2.02 2.02 2.01 2.06 2.02 2.05 2.01 Cr 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.10 0.10 0.12 0.10 0.15 0.14 0.11 0.14 0.12 0.15 0.10 0.11 0.08 0.14 Sum Z 2.13 2.12 2.14 2.12 2.17 2.15 2.14 2.17 2.15 2.17 2.16 2.14 2.13 2.15 Si 2.94 2.94 2.93 2.94 2.91 2.92 2.93 2.91 2.92 2.92 2.92 2.93 2.93 2.93 Sum T 2.94 2.94 2.93 2.94 2.91 2.92 2.93 2.91 2.92 2.92 2.92 2.93 2.93 2.93 % Al 70.58 72.49 72.84 73.00 71.59 70.06 71.24 72.30 72.69 70.46 71.73 73.32 72.91 73.68 % Pyr 8.42 8.22 7.93 7.85 8.85 8.44 8.81 8.71 9.19 9.01 9.17 8.34 8.09 8.65 % Gr 13.78 11.88 11.57 11.63 11.51 13.73 12.35 11.08 10.33 12.63 11.50 10.89 12.38 11.20 % Sp 6.49 6.79 6.93 6.92 7.16 6.78 6.89 7.08 7.13 6.88 7.03 6.81 6.12 5.64 % Uv 0.01 0.03 0.02 0.01 0.02 0.01 0.01 0.02 0.02 0.03 0.00 0.01 0.00 0.01 % An 0.66 0.56 0.69 0.56 0.85 0.94 0.66 0.78 0.60 0.95 0.56 0.61 0.49 0.79 569 Table B.6 (Continued) Sample CR4610-947 (continued) EMPA spot 23 24 25 26 27 28 29 30 31 33 35 36 37 38 39 Na2O wt% 0.0102 0.0182 0.0000 0.0148 0.0148 0.0308 0.0228 0.0057 0.0274 0.0411 0.0000 0.0125 0.0080 0.0263 0.0000 MgO wt% 2.3514 2.3394 2.2619 2.2758 2.3102 2.3105 2.1987 2.1422 2.3415 2.1460 2.1444 2.1297 2.1834 2.0303 2.0304 Al2O3 wt% 21.5013 21.4801 21.3757 21.2222 21.3567 21.3183 21.3286 21.3754 21.4646 21.1176 21.1136 21.3344 21.2680 21.1803 20.7609 SiO2 wt% 36.2247 36.2630 36.2439 36.4998 36.4950 36.6593 36.2620 36.3525 36.2689 36.3529 36.1730 36.4682 36.0922 36.4227 36.1935 CaO wt% 3.6307 3.6898 3.9285 3.8785 3.7329 3.7242 3.6966 3.6061 3.5009 3.8677 4.2956 3.9312 3.6425 3.3203 3.4918 TiO wt% 0.1155 0.0682 0.0692 0.1124 0.0969 0.0885 0.0673 0.1104 0.0864 0.1273 0.1393 0.1126 0.1009 0.1924 0.2226 Cr2O3 wt% 0.0000 0.0882 0.0442 0.0844 0.0576 0.0192 0.0326 0.0000 0.0767 0.0557 0.0577 0.0365 0.0709 0.0230 0.0364 MnO wt% 2.0521 2.1528 2.2154 2.1293 2.1581 2.2003 2.0101 2.2013 2.2010 2.3718 2.2407 2.3504 2.5476 3.0614 3.4984 FeO wt% 33.4045 33.9086 33.4364 33.9595 33.6101 33.9195 34.1100 33.5569 33.7763 33.4925 33.4476 33.4471 33.4641 33.2658 33.0933 Total oxide wt% 99.29 100.01 99.58 100.18 99.83 100.27 99.73 99.35 99.74 99.57 99.61 99.82 99.38 99.52 99.33 Fe2+ 2.20 2.17 2.17 2.18 2.19 2.19 2.20 2.23 2.18 2.17 2.15 2.19 2.17 2.21 2.17 Mn 0.14 0.15 0.15 0.15 0.15 0.15 0.14 0.15 0.15 0.16 0.15 0.16 0.18 0.21 0.24 Mg 0.28 0.28 0.27 0.27 0.28 0.28 0.26 0.26 0.28 0.26 0.26 0.26 0.26 0.25 0.25 Ca 0.32 0.32 0.34 0.33 0.32 0.32 0.32 0.31 0.30 0.34 0.37 0.34 0.32 0.29 0.30 Sum X 2.94 2.91 2.93 2.93 2.94 2.93 2.92 2.95 2.92 2.93 2.93 2.94 2.93 2.95 2.96 Ti 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.01 Al 2.05 2.04 2.04 2.01 2.03 2.02 2.03 2.04 2.04 2.02 2.01 2.03 2.03 2.03 1.99 Cr 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.11 0.09 0.10 0.07 0.09 0.11 0.05 0.10 0.10 0.12 0.07 0.10 0.05 0.09 Sum Z 2.13 2.16 2.14 2.13 2.11 2.12 2.14 2.10 2.15 2.12 2.14 2.11 2.14 2.09 2.09 Si 2.94 2.92 2.93 2.94 2.94 2.95 2.93 2.95 2.93 2.94 2.93 2.94 2.93 2.96 2.95 Sum T 2.94 2.92 2.93 2.94 2.94 2.95 2.93 2.95 2.93 2.94 2.93 2.94 2.93 2.96 2.95 % Al 74.79 74.40 73.93 74.36 74.57 74.54 75.28 75.48 74.82 74.15 73.25 74.28 74.20 74.77 73.20 % Pyr 9.68 9.64 9.29 9.30 9.45 9.43 9.06 8.78 9.65 8.84 8.82 8.71 9.02 8.32 8.34 % Gr 10.37 10.30 11.07 10.79 10.54 10.43 10.39 10.35 9.87 10.89 11.96 11.12 10.27 9.50 9.80 % Sp 4.80 5.04 5.17 4.94 5.01 5.10 4.71 5.13 5.16 5.55 5.24 5.46 5.98 7.13 8.16 % Uv 0.00 0.03 0.02 0.03 0.02 0.01 0.01 0.00 0.02 0.02 0.02 0.01 0.02 0.01 0.01 % An 0.34 0.58 0.50 0.55 0.38 0.47 0.54 0.25 0.47 0.52 0.68 0.39 0.49 0.24 0.44 570 Table B.6 (Continued) Sample CR4610-947 (continued) EMPA spot 40 41 44 45 46 47 48 50 52 53 54 55 56 56 Na2O wt% 0.0469 0.0000 0.0435 0.0320 0.0000 0.0217 0.0228 0.0352 0.0194 0.0284 0.0102 0.0227 0.0193 0.0330 MgO wt% 1.9272 1.7078 2.0568 1.9360 2.0344 2.1847 1.9857 2.1871 2.3403 2.1123 2.3410 2.2320 2.3535 2.2462 Al2O3 wt% 21.1012 20.8413 21.0642 21.0495 21.1472 20.9240 20.9868 21.1280 21.4273 21.3195 21.3112 21.2331 21.1938 21.1373 SiO2 wt% 36.3515 35.9199 36.0650 36.2084 37.0073 36.5802 36.3558 36.7866 36.7041 36.6294 36.5618 36.5648 36.6898 36.2864 CaO wt% 3.3423 3.8744 3.5811 4.0621 4.2574 4.0722 4.5556 4.6052 3.5324 4.2556 4.1840 4.1940 4.3110 4.2912 TiO wt% 0.1306 0.1473 0.1904 0.1322 0.1270 0.1388 0.1086 0.1246 0.0434 0.0796 0.0956 0.0660 0.0847 0.0539 Cr2O3 wt% 0.0000 0.0307 0.0000 0.0365 0.0000 0.0384 0.0789 0.0617 0.0268 0.0173 0.0404 0.1019 0.0135 0.0385 MnO wt% 3.8644 3.7536 2.9678 2.7696 2.6157 2.4271 2.4557 2.0518 2.2357 2.4552 2.6119 2.2009 1.9621 2.1301 FeO wt% 33.0274 32.8616 33.3232 33.2164 33.3985 33.4682 32.9997 33.1405 33.7540 32.8694 33.1545 33.1257 33.2218 33.1679 Total oxide wt% 99.79 99.14 99.29 99.44 100.59 99.86 99.55 100.12 100.08 99.77 100.31 99.74 99.85 99.38 Fe2+ 2.14 2.13 2.16 2.15 2.19 2.17 2.14 2.15 2.21 2.16 2.12 2.16 2.16 2.14 Mn 0.27 0.26 0.20 0.19 0.18 0.17 0.17 0.14 0.15 0.17 0.18 0.15 0.13 0.15 Mg 0.23 0.21 0.25 0.23 0.24 0.26 0.24 0.26 0.28 0.25 0.28 0.27 0.28 0.27 Ca 0.29 0.34 0.31 0.35 0.37 0.35 0.40 0.40 0.30 0.37 0.36 0.36 0.37 0.37 Sum X 2.93 2.94 2.92 2.93 2.97 2.95 2.94 2.95 2.95 2.95 2.93 2.94 2.95 2.92 Ti 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.02 2.01 2.02 2.01 2.00 1.99 2.00 2.00 2.03 2.03 2.02 2.02 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 Fe3+ 0.10 0.11 0.11 0.10 0.05 0.09 0.10 0.08 0.06 0.06 0.11 0.07 0.08 0.11 Sum Z 2.12 2.13 2.14 2.13 2.06 2.09 2.11 2.09 2.10 2.09 2.13 2.10 2.09 2.13 Si 2.95 2.93 2.93 2.94 2.97 2.95 2.94 2.96 2.95 2.96 2.93 2.95 2.95 2.94 Sum T 2.95 2.93 2.93 2.94 2.97 2.95 2.94 2.96 2.95 2.96 2.93 2.95 2.95 2.94 % Al 73.09 72.57 73.78 73.45 73.54 73.51 72.66 72.90 74.96 73.19 72.14 73.44 73.27 73.01 % Pyr 7.95 7.07 8.54 8.00 8.18 8.92 8.16 8.90 9.53 8.63 9.55 9.12 9.58 9.27 % Gr 9.43 10.88 10.09 11.43 11.95 11.37 12.75 12.89 10.01 12.09 11.60 11.83 12.12 12.04 % Sp 9.05 8.83 7.00 6.50 5.98 5.63 5.73 4.74 5.17 5.70 6.05 5.11 4.54 4.99 % Uv 0.00 0.01 0.00 0.01 0.00 0.01 0.03 0.03 0.01 0.01 0.01 0.04 0.01 0.01 % An 0.45 0.60 0.56 0.58 0.32 0.52 0.64 0.52 0.31 0.37 0.63 0.43 0.46 0.66 571 Table B.6 (Continued) Sample CR467-86 EMPA spot 1 3 4 5 6 8 11 12 13 14 15 16 17 18 19 20 Na2O wt% 0.0073 0.0263 0.0011 0.0242 0.0201 0.0032 0.0188 0.0000 0.0319 0.0000 0.0340 0.0279 0.0085 0.0158 0.0052 0.0157 MgO wt% 1.0873 1.0214 0.9412 1.0103 0.9518 0.9664 1.0659 0.9174 0.9977 0.9957 0.9003 1.1796 1.0741 0.9844 1.0907 1.1060 Al2O3 wt% 21.0896 21.0449 20.8946 20.9438 21.0559 20.9543 20.6189 20.8457 20.7823 20.7261 20.2790 20.2232 20.8472 21.1517 21.2679 20.9693 SiO2 wt% 36.7955 36.6679 37.0102 36.5536 36.6076 36.5809 37.6093 36.7440 36.7810 36.5000 37.2411 36.2242 36.5357 36.8254 36.6666 37.0362 CaO wt% 9.7562 8.3134 8.0636 8.0532 7.9937 8.1374 9.6249 7.6772 6.6548 6.3047 6.2897 6.1263 6.3551 8.2019 10.0248 9.9005 TiO wt% 0.0403 0.0365 0.0842 0.0876 0.0852 0.0897 0.0989 0.0497 0.1331 0.2057 0.2739 0.1842 0.1866 0.0803 0.0400 0.0401 Cr2O3 wt% 0.0335 0.0216 0.0862 0.0392 0.0960 0.0608 0.0946 0.0548 0.0506 0.0485 0.0214 0.0252 0.0330 0.0510 0.0217 0.0611 MnO wt% 5.2214 7.4737 7.6668 7.5990 7.8309 7.4534 4.9328 7.6616 7.7635 8.3534 8.9882 7.8253 7.9428 7.1756 4.3291 5.0725 FeO wt% 25.2650 24.7592 24.8271 24.9227 25.1154 24.8142 25.2427 25.3875 26.4877 26.9483 25.6903 27.5701 26.7947 25.0381 25.7932 25.1786 Total oxide wt% 99.30 99.36 99.58 99.23 99.76 99.06 99.31 99.34 99.68 100.08 99.72 99.39 99.78 99.52 99.24 99.38 Fe2+ 1.63 1.60 1.66 1.61 1.61 1.63 1.70 1.68 1.74 1.72 1.74 1.73 1.74 1.65 1.66 1.64 Mn 0.36 0.51 0.52 0.52 0.53 0.51 0.34 0.53 0.53 0.57 0.62 0.54 0.54 0.49 0.30 0.35 Mg 0.13 0.12 0.11 0.12 0.11 0.12 0.13 0.11 0.12 0.12 0.11 0.14 0.13 0.12 0.13 0.13 Ca 0.84 0.72 0.70 0.70 0.69 0.71 0.83 0.67 0.58 0.55 0.55 0.53 0.55 0.71 0.86 0.85 Sum X 2.96 2.95 2.99 2.95 2.95 2.97 3.00 2.98 2.97 2.96 3.02 2.94 2.96 2.97 2.95 2.97 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 Al 2.00 2.00 1.99 2.00 2.00 2.00 1.96 1.99 1.98 1.98 1.94 1.94 1.99 2.01 2.02 1.99 Cr 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.08 0.02 0.08 0.09 0.05 0.00 0.04 0.05 0.10 0.00 0.15 0.08 0.04 0.08 0.05 Sum Z 2.07 2.08 2.02 2.08 2.10 2.06 1.97 2.04 2.05 2.09 1.95 2.10 2.08 2.06 2.10 2.05 Si 2.96 2.96 2.99 2.96 2.95 2.97 3.03 2.98 2.98 2.95 3.02 2.95 2.96 2.97 2.95 2.98 Sum T 2.96 2.96 2.99 2.96 2.95 2.97 3.03 2.98 2.98 2.95 3.02 2.95 2.96 2.97 2.95 2.98 % Al 55.14 54.13 55.37 54.55 54.52 55.01 56.76 56.26 58.56 58.17 57.79 58.66 58.62 55.59 56.26 55.22 % Pyr 4.41 4.17 3.79 4.13 3.88 3.94 4.27 3.72 4.06 4.05 3.61 4.86 4.38 3.99 4.44 4.46 % Gr 27.43 23.46 22.98 22.72 22.36 23.15 27.58 21.82 18.84 17.46 18.00 16.77 17.82 23.35 28.19 27.89 % Sp 12.03 17.33 17.53 17.65 18.15 17.24 11.23 17.65 17.93 19.33 20.48 18.33 18.39 16.53 10.00 11.62 % Uv 0.03 0.02 0.06 0.03 0.07 0.05 0.08 0.04 0.03 0.03 0.01 0.01 0.02 0.04 0.02 0.05 % An 0.94 0.88 0.23 0.88 0.98 0.58 0.00 0.48 0.52 0.89 0.00 1.30 0.70 0.46 1.06 0.73 572 Table B.6 (Continued) Sample CR467-86 (continued) CR466-145 EMPA spot 21 22 23 24 25 26 27 28 30 1 2 3 4 5 7 8 Na2O wt% 0.0084 0.0000 0.0126 0.0084 0.0000 0.0178 0.0000 0.0105 0.0261 0.0000 0.0000 0.0065 0.0129 0.0033 0.0000 0.0151 MgO wt% 1.1126 1.0534 1.0375 0.9727 1.0101 1.1666 1.0614 1.0299 1.1111 1.7052 1.7240 1.6565 1.5629 1.6928 1.5690 1.5766 Al2O3 wt% 21.1605 21.0634 21.0790 20.9770 20.9114 20.9402 21.0962 21.0845 21.0510 21.3613 20.9272 21.0771 20.7289 21.1071 20.9469 21.0298 SiO2 wt% 36.8927 36.8699 36.6402 37.0499 36.5299 36.5269 36.6109 37.0402 37.0222 36.3523 36.6463 36.6102 37.9156 36.1955 36.3497 36.5516 CaO wt% 9.7565 9.8016 9.7382 9.5765 9.7376 9.3143 9.6962 9.5765 10.0342 3.5529 3.6541 3.5044 3.6321 3.4656 3.5466 3.2160 TiO wt% 0.0309 0.0513 0.0532 0.0375 0.0447 0.0484 0.0719 0.0261 0.0316 0.0266 0.1122 0.0487 0.0611 0.0683 0.0912 0.0494 Cr2O3 wt% 0.0472 0.0768 0.0413 0.0295 0.0000 0.0315 0.0256 0.0315 0.0316 0.0095 0.0000 0.0133 0.0057 0.0000 0.0000 0.0343 MnO wt% 5.0598 5.3055 5.3360 5.5820 5.7212 6.2525 5.4839 5.8211 4.8417 3.3774 3.6360 3.6935 4.3862 3.6984 5.2075 4.9978 FeO wt% 25.6253 25.4457 25.6756 25.4994 25.2262 25.0942 25.3820 25.4738 25.3857 33.2867 33.3713 33.4069 32.0682 33.6628 31.3846 32.0130 Total oxide wt% 99.69 99.67 99.61 99.73 99.18 99.39 99.43 100.09 99.54 99.67 100.07 100.02 100.37 99.89 99.10 99.48 Fe2+ 1.64 1.63 1.62 1.65 1.60 1.57 1.61 1.62 1.64 2.20 2.20 2.21 2.16 2.18 2.11 2.16 Mn 0.34 0.36 0.36 0.38 0.39 0.43 0.37 0.39 0.33 0.23 0.25 0.25 0.30 0.25 0.36 0.34 Mg 0.13 0.13 0.12 0.12 0.12 0.14 0.13 0.12 0.13 0.21 0.21 0.20 0.19 0.20 0.19 0.19 Ca 0.84 0.84 0.84 0.82 0.84 0.80 0.84 0.82 0.86 0.31 0.32 0.30 0.31 0.30 0.31 0.28 Sum X 2.96 2.96 2.94 2.97 2.95 2.94 2.95 2.96 2.96 2.95 2.97 2.96 2.97 2.94 2.97 2.97 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.00 1.99 2.00 1.99 1.99 1.99 2.00 1.99 1.99 2.04 2.00 2.01 1.97 2.02 2.02 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.08 0.08 0.11 0.06 0.11 0.12 0.10 0.08 0.07 0.06 0.06 0.06 0.00 0.11 0.03 0.03 Sum Z 2.08 2.08 2.11 2.05 2.10 2.12 2.10 2.07 2.06 2.10 2.06 2.07 1.97 2.13 2.05 2.05 Si 2.96 2.96 2.94 2.98 2.95 2.94 2.95 2.96 2.97 2.95 2.97 2.96 3.06 2.94 2.97 2.98 Sum T 2.96 2.96 2.94 2.98 2.95 2.94 2.95 2.96 2.97 2.95 2.97 2.96 3.06 2.94 2.97 2.98 % Al 55.51 55.10 54.91 55.60 54.08 53.32 54.66 54.79 55.25 74.68 73.94 74.45 72.97 74.13 71.02 72.52 % Pyr 4.50 4.26 4.23 3.92 4.12 4.77 4.32 4.15 4.49 6.99 7.00 6.75 6.34 6.97 6.43 6.44 % Gr 27.24 27.32 26.95 26.86 27.06 25.71 26.99 26.59 28.13 10.18 10.32 9.97 10.57 9.73 10.25 9.31 % Sp 11.63 12.18 12.35 12.77 13.26 14.53 12.67 13.33 11.12 7.87 8.39 8.55 10.11 8.65 12.12 11.60 % Uv 0.04 0.07 0.04 0.03 0.00 0.03 0.02 0.03 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.01 % An 1.06 1.04 1.49 0.81 1.46 1.62 1.29 1.11 0.96 0.28 0.32 0.28 0.00 0.51 0.17 0.12 573 Table B.6 (Continued) Sample CR466-145 (continued) EMPA spot 10 11 12 13 14 15 16 17 18 20 21 22 23 24 25 26 Na2O wt% 0.0011 0.0000 0.0065 0.0065 0.0033 0.0292 0.0000 0.0065 0.0022 0.0325 0.0076 0.0337 0.0239 0.0054 0.0011 0.0054 MgO wt% 1.6749 1.7826 1.6674 1.6804 1.8076 1.7294 1.6729 1.5387 1.5142 1.5217 1.5637 1.7646 1.6823 1.7356 1.7213 1.7443 Al2O3 wt% 21.1001 21.4071 21.2270 20.9847 21.0677 21.1342 20.9985 20.9686 21.0360 20.8014 21.0544 21.1116 20.8348 20.9740 21.0720 21.1988 SiO2 wt% 36.6147 36.2625 36.5208 36.4476 36.3776 36.4381 36.3226 36.0002 36.2304 36.2888 36.4292 36.2545 36.2914 36.2903 36.3228 36.7611 CaO wt% 3.1728 3.6571 3.5367 3.6393 3.2390 3.2085 3.0466 3.0587 3.0742 3.0385 2.8991 2.8941 3.3276 3.0896 3.0275 3.2331 TiO wt% 0.1026 0.0848 0.0750 0.0283 0.0401 0.0864 0.0779 0.0693 0.0599 0.0747 0.0440 0.0496 0.0386 0.0385 0.0301 0.0526 Cr2O3 wt% 0.0742 0.0000 0.0095 0.0000 0.0608 0.0419 0.0418 0.0000 0.0648 0.0153 0.0057 0.0000 0.0437 0.0360 0.0000 0.0323 MnO wt% 4.9989 3.7516 3.2954 3.0333 3.4041 3.8193 4.2699 5.2854 6.2248 6.0883 5.5398 4.4445 3.9786 3.2455 3.3602 3.4607 FeO wt% 32.7172 32.8003 33.7420 34.2544 34.3736 33.1942 32.9530 32.1192 31.8191 31.3304 32.1080 33.5910 33.3433 34.6275 33.8418 33.8859 Total oxide wt% 100.46 99.75 100.08 100.07 100.37 99.68 99.38 99.05 100.03 99.19 99.65 100.14 99.56 100.04 99.38 100.37 Fe2+ 2.14 2.15 2.22 2.22 2.21 2.20 2.20 2.13 2.06 2.08 2.14 2.15 2.18 2.24 2.26 2.24 Mn 0.34 0.26 0.23 0.21 0.23 0.26 0.29 0.37 0.43 0.42 0.38 0.30 0.27 0.22 0.23 0.24 Mg 0.20 0.22 0.20 0.20 0.22 0.21 0.20 0.19 0.18 0.19 0.19 0.21 0.20 0.21 0.21 0.21 Ca 0.27 0.32 0.31 0.32 0.28 0.28 0.27 0.27 0.27 0.27 0.25 0.25 0.29 0.27 0.26 0.28 Sum X 2.96 2.94 2.95 2.95 2.94 2.95 2.97 2.95 2.94 2.96 2.96 2.92 2.94 2.94 2.96 2.97 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.01 2.04 2.02 2.00 2.00 2.02 2.02 2.02 2.01 2.01 2.02 2.01 2.00 2.00 2.02 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.07 0.06 0.10 0.11 0.06 0.05 0.07 0.10 0.06 0.05 0.12 0.09 0.11 0.05 0.05 Sum Z 2.08 2.12 2.09 2.10 2.12 2.09 2.07 2.10 2.12 2.07 2.07 2.14 2.10 2.12 2.08 2.07 Si 2.96 2.94 2.95 2.95 2.94 2.96 2.96 2.95 2.94 2.97 2.97 2.94 2.95 2.94 2.96 2.97 Sum T 2.96 2.94 2.95 2.95 2.94 2.96 2.96 2.95 2.94 2.97 2.97 2.94 2.95 2.94 2.96 2.97 % Al 72.37 73.14 75.18 75.36 75.13 74.53 74.22 72.09 70.14 70.45 72.18 73.68 73.89 76.17 76.18 75.53 % Pyr 6.81 7.32 6.81 6.88 7.41 7.10 6.86 6.37 6.23 6.28 6.40 7.29 6.93 7.13 7.06 7.07 % Gr 8.93 10.41 10.05 10.21 9.00 9.18 8.75 8.77 8.64 8.73 8.33 8.10 9.39 8.64 8.70 9.19 % Sp 11.55 8.75 7.64 7.05 7.93 8.91 9.95 12.44 14.54 14.27 12.89 10.43 9.32 7.58 7.83 7.97 % Uv 0.02 0.00 0.00 0.00 0.02 0.01 0.01 0.00 0.02 0.00 0.00 0.00 0.01 0.01 0.00 0.01 % An 0.30 0.36 0.31 0.49 0.51 0.26 0.20 0.32 0.41 0.26 0.19 0.49 0.44 0.46 0.22 0.21 574 Table B.6 (Continued) Sample CR466-145 (continued) GC01018-691 EMPA spot 27 28 29 30 31 1 2 3 4 5 6 7 8 10 11 Na2O wt% 0.0000 0.0119 0.0000 0.0314 0.0206 0.0161 0.0372 0.0245 0.0000 0.0058 0.0000 0.0963 0.0000 0.0047 0.0058 MgO wt% 1.7527 1.7087 1.6714 1.6381 1.7197 0.6946 0.8570 0.8002 0.7318 0.7377 0.6889 0.7426 0.7156 0.7029 0.7084 Al2O3 wt% 21.1425 21.1618 21.1364 21.3060 21.1557 21.3219 21.0534 21.0729 20.9891 20.9006 20.6325 21.0035 20.6285 20.8436 20.8363 SiO2 wt% 36.3601 36.5053 36.3449 36.5525 36.3706 36.0709 35.7629 35.8357 36.1254 36.1464 35.7548 36.2915 36.0405 35.7055 36.2813 CaO wt% 3.1722 3.2232 3.1381 2.9340 3.1505 4.1387 3.3636 3.0162 3.7733 4.3690 3.4412 4.2083 4.1825 4.3022 3.9170 TiO wt% 0.0752 0.0313 0.0409 0.0360 0.0539 0.0060 0.0134 0.0498 0.0127 0.0165 0.0445 0.0000 0.0106 0.0217 0.0048 Cr2O3 wt% 0.0399 0.0000 0.0152 0.0665 0.0000 0.0134 0.0000 0.0000 0.0000 0.0381 0.0000 0.0000 0.0000 0.0038 0.0114 MnO wt% 3.5074 3.5128 3.4856 3.2795 3.2676 5.6574 2.8712 1.7215 1.3037 1.3845 1.5807 1.5594 1.7004 1.6173 1.4521 FeO wt% 33.8802 33.8956 33.6230 33.9271 34.1215 31.9324 35.1393 36.9890 37.2691 36.2799 36.9473 36.0857 36.2496 36.4310 35.9839 Total oxide wt% 99.93 100.05 99.46 99.77 99.86 99.85 99.10 99.51 100.21 99.88 99.09 99.99 99.53 99.63 99.20 Fe2+ 2.22 2.22 2.24 2.28 2.24 2.09 2.32 2.45 2.43 2.38 2.45 2.34 2.38 2.34 2.44 Mn 0.24 0.24 0.24 0.23 0.22 0.39 0.20 0.12 0.09 0.10 0.11 0.11 0.12 0.11 0.10 Mg 0.21 0.21 0.20 0.20 0.21 0.08 0.10 0.10 0.09 0.09 0.08 0.09 0.09 0.09 0.09 Ca 0.28 0.28 0.27 0.26 0.27 0.36 0.30 0.26 0.33 0.38 0.30 0.37 0.37 0.38 0.34 Sum X 2.95 2.95 2.96 2.95 2.94 2.93 2.92 2.93 2.94 2.94 2.95 2.91 2.95 2.92 2.98 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.02 2.02 2.03 2.04 2.02 2.05 2.04 2.04 2.01 2.01 2.00 2.01 1.99 2.01 2.02 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.07 0.07 0.05 0.03 0.08 0.08 0.09 0.09 0.10 0.10 0.10 0.11 0.10 0.15 0.03 Sum Z 2.10 2.09 2.08 2.07 2.10 2.13 2.13 2.13 2.12 2.11 2.10 2.13 2.09 2.16 2.04 Si 2.95 2.96 2.96 2.97 2.95 2.94 2.94 2.94 2.94 2.95 2.95 2.95 2.95 2.92 2.98 Sum T 2.95 2.96 2.96 2.97 2.95 2.94 2.94 2.94 2.94 2.95 2.95 2.95 2.95 2.92 2.98 % Al 75.32 75.38 75.79 77.02 76.00 71.48 79.43 83.53 82.74 80.75 83.08 80.59 80.61 80.31 82.12 % Pyr 7.18 6.99 6.85 6.71 7.07 2.88 3.59 3.34 3.02 3.04 2.87 3.10 2.96 2.94 2.91 % Gr 8.98 9.15 9.03 8.50 8.95 11.85 9.69 8.66 10.64 12.35 9.82 11.95 11.82 12.02 11.42 % Sp 8.16 8.16 8.12 7.63 7.63 13.32 6.84 4.08 3.06 3.25 3.74 3.70 4.00 3.84 3.39 % Uv 0.01 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.00 % An 0.33 0.32 0.20 0.12 0.35 0.46 0.45 0.38 0.55 0.59 0.47 0.67 0.61 0.88 0.15 575 Table B.6 (Continued) Sample GC01018-691 (continued) EMPA spot 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Na2O wt% 0.0081 0.0140 0.0058 0.0625 0.0138 0.0035 0.0288 0.0230 0.0256 0.0152 0.0257 0.0000 0.0082 0.0035 0.0012 MgO wt% 0.7540 0.7616 0.8190 0.8003 0.7180 0.6789 0.7079 0.8129 0.7644 0.8449 0.7725 0.7706 0.7074 0.6975 0.7310 Al2O3 wt% 20.7756 20.6642 20.8578 21.1207 20.9401 21.3786 21.2010 21.0245 20.6548 21.0064 20.9559 20.8391 20.6716 21.0427 21.0931 SiO2 wt% 36.1132 36.2031 36.3221 36.0928 36.6286 36.2262 36.4172 36.0421 36.5230 36.3289 36.2211 35.9083 36.3049 36.2074 36.0371 CaO wt% 4.3939 3.6576 3.3580 3.6677 4.8011 4.2431 4.7333 4.5004 3.4745 3.0708 3.3501 3.7367 3.8994 2.8531 3.1117 TiO wt% 0.0183 0.0169 0.0337 0.0000 0.0034 0.0001 0.0027 0.0104 0.0000 0.0639 0.0392 0.0173 0.0425 0.0000 0.0214 Cr2O3 wt% 0.0000 0.0000 0.0000 0.0000 0.0366 0.0000 0.0135 0.0000 0.0000 0.0246 0.0000 0.0000 0.0190 0.0000 0.0285 MnO wt% 1.3508 1.2857 1.2909 3.3492 5.0026 6.1649 5.1233 3.6097 1.3417 1.1981 1.7371 1.8547 1.7733 2.1575 2.3217 FeO wt% 36.1828 36.7967 36.9743 34.2250 32.0827 31.6085 32.2213 32.9820 37.2196 38.0746 36.9797 36.6823 36.5215 37.0478 36.3638 Total oxide wt% 99.60 99.40 99.66 99.32 100.23 100.30 100.45 99.01 100.00 100.63 100.08 99.81 99.95 100.01 99.71 Fe2+ 2.38 2.46 2.49 2.27 2.12 2.06 2.09 2.20 2.48 2.49 2.44 2.39 2.41 2.47 2.43 Mn 0.09 0.09 0.09 0.23 0.34 0.42 0.35 0.25 0.09 0.08 0.12 0.13 0.12 0.15 0.16 Mg 0.09 0.09 0.10 0.10 0.09 0.08 0.09 0.10 0.09 0.10 0.09 0.09 0.09 0.08 0.09 Ca 0.38 0.32 0.29 0.32 0.42 0.37 0.41 0.40 0.30 0.27 0.29 0.33 0.34 0.25 0.27 Sum X 2.95 2.96 2.97 2.93 2.96 2.94 2.93 2.95 2.97 2.94 2.94 2.94 2.96 2.96 2.95 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.00 2.00 2.01 2.04 2.00 2.04 2.02 2.03 1.99 2.01 2.01 2.01 1.99 2.03 2.03 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.09 0.06 0.04 0.07 0.06 0.08 0.09 0.06 0.06 0.09 0.09 0.12 0.08 0.06 0.06 Sum Z 2.10 2.06 2.06 2.11 2.06 2.13 2.12 2.09 2.05 2.11 2.10 2.13 2.07 2.08 2.10 Si 2.95 2.97 2.97 2.96 2.97 2.94 2.95 2.96 2.98 2.95 2.95 2.93 2.96 2.96 2.95 Sum T 2.95 2.97 2.97 2.96 2.97 2.94 2.95 2.96 2.98 2.95 2.95 2.93 2.96 2.96 2.95 % Al 80.66 83.00 83.72 77.72 71.40 70.23 71.13 74.69 83.51 84.66 82.79 81.28 81.44 83.63 82.27 % Pyr 3.12 3.14 3.36 3.34 2.93 2.80 2.91 3.37 3.13 3.47 3.19 3.20 2.91 2.87 3.02 % Gr 12.45 10.50 9.69 10.63 13.65 12.07 13.36 13.02 9.93 8.66 9.53 10.51 11.05 8.21 8.96 % Sp 3.17 3.01 3.01 7.94 11.59 14.42 11.97 8.51 3.12 2.80 4.08 4.37 4.14 5.05 5.46 % Uv 0.00 0.00 0.00 0.00 0.02 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.01 % An 0.59 0.34 0.21 0.36 0.40 0.48 0.62 0.40 0.31 0.40 0.40 0.63 0.45 0.24 0.27 576 Table B.6 (Continued) Sample GC01018-691 (continued) EMPA spot 28 29 30 31 32 33 34 35 36 37 38 39 41 42 43 Na2O wt% 0.0116 0.0256 0.0151 0.0116 0.0035 0.0000 0.0035 0.0409 0.0257 0.0000 0.0046 0.0402 0.0116 0.0184 0.0092 MgO wt% 0.6855 0.6744 0.6697 0.6583 0.6894 0.7034 0.7506 0.7673 0.9142 0.7896 0.6510 0.9271 0.8135 0.7031 0.7260 Al2O3 wt% 20.9553 20.7132 20.8525 20.6135 20.7118 20.8059 20.6261 20.8016 20.8704 21.1234 20.8759 21.3669 21.0738 20.8993 21.0994 SiO2 wt% 35.8799 36.0056 35.4196 36.1049 35.5915 36.0072 35.7403 35.8624 35.8763 36.1211 36.1673 36.3086 36.0995 36.2290 36.2317 CaO wt% 3.9567 3.6804 4.0355 4.6315 3.5706 3.7826 3.2798 3.0941 3.3648 4.0082 4.1711 4.7403 4.5977 5.4171 4.4842 TiO wt% 0.0462 0.0372 0.0074 0.0328 0.0290 0.0519 0.0310 0.0559 0.0379 0.0264 0.0169 0.0241 0.0370 0.0039 0.0000 Cr2O3 wt% 0.0000 0.0000 0.0190 0.0000 0.0000 0.0000 0.0436 0.0000 0.0246 0.0000 0.0000 0.0000 0.0249 0.0404 0.0000 MnO wt% 2.1906 2.2783 2.4149 2.2374 2.2819 2.3476 1.6811 1.3651 1.1094 3.7550 6.3079 4.1047 2.1960 2.7090 2.2808 FeO wt% 35.7160 36.1625 35.7116 34.9607 36.3366 35.9794 36.9819 37.4333 37.3227 33.8782 31.2498 32.4015 34.9188 33.6408 34.6988 Total oxide wt% 99.44 99.58 99.15 99.25 99.21 99.68 99.14 99.42 99.55 99.70 99.44 99.91 99.77 99.66 99.53 Fe2+ 2.35 2.38 2.30 2.31 2.37 2.37 2.45 2.47 2.44 2.24 2.08 2.12 2.29 2.20 2.32 Mn 0.15 0.16 0.17 0.16 0.16 0.16 0.12 0.09 0.08 0.26 0.44 0.28 0.15 0.19 0.16 Mg 0.08 0.08 0.08 0.08 0.08 0.09 0.09 0.09 0.11 0.10 0.08 0.11 0.10 0.09 0.09 Ca 0.35 0.32 0.36 0.41 0.31 0.33 0.29 0.27 0.30 0.35 0.37 0.41 0.40 0.47 0.39 Sum X 2.94 2.94 2.91 2.96 2.93 2.95 2.94 2.93 2.93 2.95 2.96 2.93 2.94 2.94 2.95 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.02 2.00 2.02 1.99 2.01 2.01 2.00 2.01 2.01 2.03 2.01 2.04 2.02 2.01 2.03 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.09 0.10 0.16 0.08 0.13 0.09 0.10 0.10 0.11 0.07 0.06 0.08 0.09 0.09 0.05 Sum Z 2.12 2.10 2.18 2.08 2.14 2.10 2.11 2.12 2.13 2.10 2.08 2.12 2.12 2.10 2.08 Si 2.94 2.95 2.91 2.96 2.93 2.95 2.94 2.95 2.94 2.95 2.96 2.95 2.94 2.95 2.96 Sum T 2.94 2.95 2.91 2.96 2.93 2.95 2.94 2.95 2.94 2.95 2.96 2.95 2.94 2.95 2.96 % Al 80.14 80.83 79.15 78.26 80.93 80.33 83.05 84.25 83.47 76.06 70.17 72.46 77.81 74.68 78.39 % Pyr 2.85 2.80 2.83 2.72 2.89 2.91 3.13 3.21 3.81 3.26 2.68 3.83 3.36 2.90 2.99 % Gr 11.29 10.45 11.35 13.20 10.09 10.73 9.33 8.83 9.54 11.49 11.98 13.56 13.04 15.33 12.94 % Sp 5.18 5.38 5.79 5.26 5.43 5.52 3.98 3.24 2.63 8.80 14.78 9.63 5.16 6.35 5.34 % Uv 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.02 0.00 % An 0.53 0.53 0.88 0.55 0.66 0.50 0.48 0.46 0.53 0.39 0.37 0.51 0.60 0.72 0.34 577 Table B.6 (Continued) Sample GC01018-691 (continued) EMPA spot 44 45 46 47 48 49 50 51 52 53 55 56 57 58 Na2O wt% 0.0172 0.0103 0.0104 0.0333 0.0081 0.0195 0.0311 0.0035 0.0174 0.0196 0.0000 0.0220 0.0415 0.0081 MgO wt% 0.5094 0.5121 0.5290 0.5250 0.5894 0.4383 0.5375 0.6105 0.7123 0.6938 0.8958 0.8319 0.9128 0.7902 Al2O3 wt% 20.7770 20.8851 21.0229 21.0641 20.9190 20.9813 21.1842 21.0739 20.9422 21.1315 21.0337 20.8747 21.1824 20.9871 SiO2 wt% 36.0745 35.9809 35.7489 36.2940 36.0074 36.5357 36.0526 36.3119 35.9173 36.3542 36.6160 35.9109 36.3223 36.0074 CaO wt% 6.3268 6.0074 4.7014 5.1475 4.3715 5.3990 4.8144 4.9551 4.2998 4.7101 4.2041 4.4226 4.9284 4.4960 TiO wt% 0.0357 0.0193 0.0142 0.0613 0.0538 0.0304 0.0441 0.0211 0.0000 0.0629 0.0142 0.0367 0.0107 0.0084 Cr2O3 wt% 0.0039 0.0154 0.0077 0.0077 0.0000 0.0000 0.0135 0.0000 0.0000 0.0479 0.0096 0.0000 0.0000 0.0058 MnO wt% 3.8469 4.8419 5.5570 5.6959 4.7330 6.4224 4.8471 3.5428 2.4673 3.1155 1.6788 1.6997 1.5366 4.4069 FeO wt% 31.8658 31.5916 31.5375 30.9068 32.5924 30.0601 32.2066 33.0746 34.9251 34.0113 35.5700 35.3816 35.1160 32.3367 Total oxide wt% 99.46 99.86 99.13 99.74 99.27 99.89 99.73 99.59 99.28 100.15 100.02 99.18 100.05 99.05 Fe2+ 2.06 2.00 2.07 2.04 2.17 2.00 2.11 2.21 2.30 2.24 2.39 2.33 2.28 2.15 Mn 0.27 0.33 0.39 0.39 0.33 0.44 0.33 0.24 0.17 0.21 0.12 0.12 0.11 0.31 Mg 0.06 0.06 0.06 0.06 0.07 0.05 0.07 0.07 0.09 0.08 0.11 0.10 0.11 0.10 Ca 0.55 0.52 0.41 0.45 0.38 0.47 0.42 0.43 0.38 0.41 0.37 0.39 0.43 0.40 Sum X 2.94 2.92 2.93 2.94 2.95 2.96 2.93 2.96 2.94 2.95 2.98 2.94 2.93 2.95 Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Al 2.00 2.00 2.03 2.02 2.02 2.01 2.04 2.03 2.02 2.02 2.01 2.02 2.02 2.03 Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ 0.12 0.15 0.10 0.07 0.07 0.05 0.09 0.05 0.09 0.07 0.03 0.10 0.10 0.07 Sum Z 2.12 2.15 2.13 2.09 2.09 2.06 2.13 2.07 2.12 2.10 2.05 2.12 2.12 2.10 Si 2.94 2.93 2.93 2.96 2.95 2.97 2.94 2.96 2.94 2.95 2.98 2.94 2.94 2.95 Sum T 2.94 2.93 2.93 2.96 2.95 2.97 2.94 2.96 2.94 2.95 2.98 2.94 2.94 2.95 % Al 70.00 68.55 70.49 69.22 73.41 67.40 71.96 74.60 78.34 75.96 80.17 79.28 77.99 72.95 % Pyr 2.11 2.12 2.21 2.17 2.44 1.79 2.23 2.51 2.96 2.85 3.65 3.46 3.77 3.28 % Gr 17.76 16.68 13.45 14.74 12.57 15.50 13.74 14.29 12.29 13.40 12.10 12.61 13.95 12.97 % Sp 9.05 11.41 13.19 13.35 11.14 14.93 11.44 8.27 5.83 7.27 3.88 4.02 3.61 10.38 % Uv 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.00 0.00 0.00 0.00 % An 1.05 1.21 0.66 0.50 0.43 0.36 0.61 0.33 0.57 0.48 0.19 0.62 0.68 0.42 578 B.7 Quality control for four acid digestion and lithium borate fusion geochemistry methods This appendix provides the quality control data for the four acid digestion whole rock geochemi- cal database (Table B.7) and lithium borate fusion whole rock geochemical database (Table B.8). Duplicates and the standard BAS-1 were run simultaneously with the geochemistry samples. Also provided are the ALS laboratory detection range and standard deviation percentage error (1σ %). 579 Table B.7 Four acid digestion methodology whole rock geochemistry quality control Sample Lab ID Ag_ppm Al_pct As_ppm Ba_ppm Be_ppm Bi_ppm Ca_pct Cd_ppm Ce_ppm Co_ppm Cr_ppm Cs_ppm Fe_pct Ga_ppm BAS-1 ES10_0021 0.12 8.63 2.9 180 0.68 0.01 5.98 0.11 20.8 44.1 165 0.1 7.6 20.8 BAS-1 ES10_0042 0.09 8.26 3.7 170 0.8 0.01 5.59 0.1 19.25 44.5 156 0.1 7.11 19.55 BAS-1 ES10_0063 0.09 8.17 41.3 160 0.6 <0.01 5.76 0.12 21.2 42.9 150 0.11 6.93 20.8 Ave. 0.10 8.35 15.97 170.00 0.69 0.01 5.78 0.11 20.42 43.83 157.00 0.10 7.21 20.38 1 σ 0.02 0.24 21.94 10.00 0.10 0.00 0.20 0.01 1.03 0.83 7.55 0.01 0.35 0.72 1 σ (%) 17.32 2.92 137.43 5.88 14.52 0.00 3.38 9.09 5.04 1.90 4.81 5.59 4.81 3.54 30L1268-25.7 ES10_0009 0.15 6.73 8 60 0.32 0.03 1.05 0.09 13.2 44.5 189 0.6 16.15 15.65 30L1268-25.7 ES10_0010 0.24 6.56 4.8 60 0.3 0.02 0.85 0.08 13.65 41.5 180 0.53 15.9 15.6 Ave. 0.20 6.65 6.40 60.00 0.31 0.03 0.95 0.09 13.43 43.00 184.50 0.57 16.03 15.63 1 σ 0.06 0.12 2.26 0.00 0.01 0.01 0.14 0.01 0.32 2.12 6.36 0.05 0.18 0.04 1 σ (%) 32.64 1.81 35.36 0.00 4.56 28.28 14.89 8.32 2.37 4.93 3.45 8.76 1.10 0.23 D14931-1810 ES10_0030 0.08 9.24 54.1 20 0.22 <0.01 2.7 0.06 7.36 71 193 0.51 10.65 19.75 D14931-1810 ES10_0031 0.09 9.24 53.3 10 0.19 <0.01 2.64 0.08 7.47 77.9 213 0.41 11 19.55 Ave. 0.09 9.24 53.70 15.00 0.21 <0.01 2.67 0.07 7.42 74.45 203.00 0.46 10.83 19.65 1 σ 0.01 0.00 0.57 7.07 0.02 0.00 0.04 0.01 0.08 4.88 14.14 0.07 0.25 0.14 1 σ (%) 8.32 0.00 1.05 47.14 10.35 0.00 1.59 20.20 1.05 6.55 6.97 15.37 2.29 0.72 CB22252 ES10_0052 0.08 10.05 147 70 0.62 0.01 4.36 0.07 9.97 58.7 2320 1.85 8.05 29.3 CB22252 ES10_0053 0.11 10.4 30.2 20 0.62 0.01 4.6 0.1 10.85 54 1970 1.8 8.87 27.5 Ave. 0.10 10.23 88.60 45.00 0.62 0.01 4.48 0.09 10.41 56.35 2145.00 1.83 8.46 28.40 1 σ 0.02 0.25 82.59 35.36 0.00 0.00 0.17 0.02 0.62 3.32 247.49 0.04 0.58 1.27 1 σ (%) 22.33 2.42 93.22 78.57 0.00 0.00 3.79 24.96 5.98 5.90 11.54 1.94 6.85 4.48 ALS Range 0.01-100 0.01- 50 % 0.2- 10,000 10- 10,000 0.05- 1,000 0.01- 10,000 0.01- 50% 0.02- 1,000 0.01- 500 0.1- 10,000 1- 10,000 0.05- 500 0.01- 50% 0.05- 10,000 ALS 1 σ 10% 10% 10% 15% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 580 Table B.7 (Continued) Sample Ge_ppm Hf_ppm In_ppm K_pct La_ppm Li_ppm Mg_pct Mn_ppm Mo_ppm Na_pct Nb_ppm Ni_ppm P_ppm Pb_ppm Rb_ppm Re_ppm BAS-1 0.2 2.2 0.061 0.46 9.8 6.4 4.46 1120 2.06 2.53 7.5 167 1040 2.6 4.4 <0.002 BAS-1 0.11 2.1 0.054 0.43 8.4 7 4.31 1080 1.97 2.43 7.3 166.5 1000 1.9 3.1 <0.002 BAS-1 0.11 2.5 0.066 0.44 8.7 5.7 4.24 1090 2.06 2.49 8 155 1000 1.5 3.4 <0.002 Ave. 0.14 2.27 0.06 0.44 8.97 6.37 4.34 1096.67 2.03 2.48 7.60 162.83 1013.33 2.00 3.63 <0.002 1 σ 0.05 0.21 0.01 0.02 0.74 0.65 0.11 20.82 0.05 0.05 0.36 6.79 23.09 0.56 0.68 0.00 1 σ (%) 37.12 9.18 9.99 3.45 8.22 10.22 2.59 1.90 2.56 2.03 4.74 4.17 2.28 27.84 18.73 0.00 30L1268- 25.7 0.25 1.4 0.065 0.14 6.2 31.9 2.39 4170 0.3 0.06 2.3 112 210 1.1 5.8 0.003 30L1268- 25.7 0.22 1.4 0.063 0.15 6.4 33.5 2.41 3800 0.27 0.08 2.3 107 240 1.3 6.9 0.002 Ave. 0.24 1.40 0.06 0.15 6.30 32.70 2.40 3985.00 0.29 0.07 2.30 109.50 225.00 1.20 6.35 0.00 1 σ 0.02 0.00 0.00 0.01 0.14 1.13 0.01 261.63 0.02 0.01 0.00 3.54 21.21 0.14 0.78 0.00 1 σ (%) 9.03 0.00 2.21 4.88 2.24 3.46 0.59 6.57 7.44 20.20 0.00 3.23 9.43 11.79 12.25 28.28 D14931- 1810 0.12 2 0.048 0.06 2.9 63.1 3.04 3110 0.61 0.07 4.2 220 420 1.5 1.7 0.003 D14931- 1810 0.14 2.1 0.057 0.03 3 65.8 3.09 3870 0.73 0.07 4.2 238 430 1.4 0.8 0.003 Ave. 0.13 2.05 0.05 0.05 2.95 64.45 3.07 3490.00 0.67 0.07 4.20 229.00 425.00 1.45 1.25 0.00 1 σ 0.01 0.07 0.01 0.02 0.07 1.91 0.04 537.40 0.08 0.00 0.00 12.73 7.07 0.07 0.64 0.00 1 σ (%) 10.88 3.45 12.12 47.14 2.40 2.96 1.15 15.40 12.66 0.00 0.00 5.56 1.66 4.88 50.91 0.00 CB22252 0.14 1.1 0.077 0.13 3.5 88.3 3.45 1300 0.22 0.35 3.3 494 470 4.6 2.8 0.002 CB22252 0.16 1.2 0.095 0.06 3.8 87.7 3.85 1570 0.17 0.29 3.2 374 390 4 2.2 <0.002 Ave. 0.15 1.15 0.09 0.10 3.65 88.00 3.65 1435.00 0.20 0.32 3.25 434.00 430.00 4.30 2.50 0.00 1 σ 0.01 0.07 0.01 0.05 0.21 0.42 0.28 190.92 0.04 0.04 0.07 84.85 56.57 0.42 0.42 0.00 1 σ (%) 9.43 6.15 14.80 52.10 5.81 0.48 7.75 13.30 18.13 13.26 2.18 19.55 13.16 9.87 16.97 0.00 ALS Range 0.05- 500 0.1-500 0.005- 500 0.01- 10% 0.5- 10,000 0.2- 10,000 0.01- 50% 5- 100,000 0.05-10, 000 0.01- 10% 0.1-500 0.2- 10,000 10- 10,000 0.5- 10,000 0.1- 10,000 0.005- 50 ALS 1 σ 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% 581 Table B.7 (Continued) Sample S_pct Sb_ppm Sc_ppm Se_ppm Sn_ppm Sr_ppm Ta_ppm Te_ppm Th_ppm Ti_pct Tl_ppm U_ppm V_ppm W_ppm Y_ppm Zn_ppm Zr_ppm BAS-1 0.02 0.25 17.6 2 1 532 0.44 <0.05 0.8 0.797 0.06 0.3 153 0.2 15.6 101 90.3 BAS-1 0.04 0.27 19.4 3 1 499 0.4 <0.05 0.7 0.766 0.04 0.3 147 0.2 13.6 93 76.8 BAS-1 0.04 0.35 16.1 1 1.1 502 0.46 <0.05 0.9 0.756 0.06 0.3 149 0.2 16.5 97 84.4 Ave. 0.03 0.29 17.70 2.00 1.03 511.00 0.43 <0.05 0.80 0.77 0.05 0.30 149.67 0.20 15.23 97.00 83.83 1 σ 0.01 0.05 1.65 1.00 0.06 18.25 0.03 0.00 0.10 0.02 0.01 0.00 3.06 0.00 1.48 4.00 6.77 1 σ (%) 34.64 18.25 9.33 50.00 5.59 3.57 7.05 0.00 12.50 2.77 21.65 0.00 2.04 0.00 9.74 4.12 8.07 30L1268- 25.7 0.66 19.25 65.5 3 0.3 52.5 0.16 0.11 0.3 0.463 0.14 0.1 333 17.4 38.7 114 53.1 30L1268- 25.7 0.55 19.15 62.7 3 0.3 50.5 0.16 0.11 0.4 0.455 0.13 0.1 324 16.3 35.6 117 55.3 Ave. 0.61 19.20 64.10 3.00 0.30 51.50 0.16 0.11 0.35 0.46 0.14 0.10 328.50 16.85 37.15 115.50 54.20 1 σ 0.08 0.07 1.98 0.00 0.00 1.41 0.00 0.00 0.07 0.01 0.01 0.00 6.36 0.78 2.19 2.12 1.56 1 σ (%) 12.86 0.37 3.09 0.00 0.00 2.75 0.00 0.00 20.20 1.23 5.24 0.00 1.94 4.62 5.90 1.84 2.87 D14931- 1810 0.28 28.9 42.4 3 0.3 34 0.25 <0.05 0.6 0.698 0.08 0.2 313 50.1 11.4 84 71.6 D14931- 1810 0.3 28.6 44.1 3 0.4 31.3 0.25 <0.05 0.6 0.702 0.06 0.2 312 49.2 13.9 85 71.4 Ave. 0.29 28.75 43.25 3.00 0.35 32.65 0.25 <0.05 0.60 0.70 0.07 0.20 312.50 49.65 12.65 84.50 71.50 1 σ 0.01 0.21 1.20 0.00 0.07 1.91 0.00 0.00 0.00 0.00 0.01 0.00 0.71 0.64 1.77 0.71 0.14 1 σ (%) 4.88 0.74 2.78 0.00 20.20 5.85 0.00 0.00 0.00 0.40 20.20 0.00 0.23 1.28 13.97 0.84 0.20 CB22252 0.25 23.5 50.7 2 0.7 70.5 0.19 0.12 0.2 0.757 0.13 0.1 451 47.2 5.2 75 38.3 CB22252 0.28 22.2 61.3 2 0.6 67.1 0.18 0.11 0.3 0.715 0.12 0.1 440 30.8 5.7 67 37.9 Ave. 0.27 22.85 56.00 2.00 0.65 68.80 0.19 0.12 0.25 0.74 0.13 0.10 445.50 39.00 5.45 71.00 38.10 1 σ 0.02 0.92 7.50 0.00 0.07 2.40 0.01 0.01 0.07 0.03 0.01 0.00 7.78 11.60 0.35 5.66 0.28 1 σ (%) 8.00 4.02 13.38 0.00 10.88 3.49 3.82 6.15 28.28 4.04 5.66 0.00 1.75 29.73 6.49 7.97 0.74 ALS Range 0.01- 10% 0.05- 10,000 0.1- 10,000 1- 11,000 0.1-500 0.2- 10,000 0.05- 100 0.05- 500 0.2- 10,000 0.005- 10% 0.02- 10,000 0.1- 10,000 1- 10,000 0.1-500 0.1- 500 2- 10,000 0.5-500 ALS 1 σ 10% 15% 10% 10% 10% 10% 10% 10% 10% 10% 15% 10% 10% 15% 10% 10% 15% 582 Table B.8 Quality control for lithium borate fusion whole rock geochemistry Sample ID SiO2 wt% Al2O3 wt% Fe2O3 wt% CaO wt% MgO wt% Na2O wt% K2O wt% Cr2O3 wt% TiO2 wt% MnO wt% P2O5 wt% SrO wt% BaO wt% LOI wt% Total wt% FeO wt%* R87108-629.5 ES10_0078 44.1 13.41 17.26 11.05 7.21 0.68 0.51 0.02 0.81 0.4 0.039 0.01 0.01 2.72 98.24 11.95 R87108-629.5 ES10_0079 40.43 13.81 18.49 11.92 6.83 0.93 0.79 0.02 1.06 0.43 0.058 0.01 0.01 3.39 98.19 14.15 Ave. 42.27 13.61 17.88 11.49 7.02 0.81 0.65 0.02 0.94 0.42 0.05 0.01 0.01 3.06 98.22 13.05 1 σ 2.60 0.28 0.87 0.62 0.27 0.18 0.20 0.00 0.18 0.02 0.01 0.00 0.00 0.47 0.04 1.56 1 σ % 6.14 2.08 4.87 5.36 3.83 21.96 30.46 0.00 18.91 5.11 27.70 0.00 0.00 15.51 0.04 11.92 37L726-836.6 ES10_0085 43.62 18.34 18.82 2.94 7.71 0.17 0.04 0.04 1.09 0.2 0.145 <0.01 <0.01 5.43 98.56 15.4 37L726-836.6 ES10_0086 46.56 18.28 17.73 3.4 6.73 0.14 0.03 0.03 1.14 0.61 0.153 <0.01 <0.01 4.17 98.98 14.9 Ave. 45.09 18.31 18.28 3.17 7.22 0.16 0.04 0.04 1.12 0.41 0.15 <0.01 <0.01 4.80 98.77 15.15 1 σ 2.08 0.04 0.77 0.33 0.69 0.02 0.01 0.01 0.04 0.29 0.01 0.00 0.00 0.89 0.30 0.35 1 σ % 4.61 0.23 4.22 10.26 9.60 13.69 20.20 20.20 3.17 71.58 3.80 0.00 0.00 18.56 0.30 2.33 CR466-145 ES10_0092 53.9 16.11 12.57 7.1 4.22 0.21 0.09 0.03 1.48 0.25 0.13 0.01 <0.01 2.75 98.86 10.6 CR466-145 ES10_0093 54 16.97 14.92 5.23 4.09 0.2 0.07 0.03 1.62 0.24 0.145 0.01 <0.01 2.37 99.9 12.4 Ave. 53.95 16.54 13.75 6.17 4.16 0.21 0.08 0.03 1.55 0.25 0.14 0.01 <0.01 2.56 99.38 11.50 1 σ 0.07 0.61 1.66 1.32 0.09 0.01 0.01 0.00 0.10 0.01 0.01 0.00 0.00 0.27 0.74 1.27 1 σ % 0.13 3.68 12.09 21.45 2.21 3.45 17.68 0.00 6.39 2.89 7.71 0.00 0.00 10.50 0.74 11.07 DS358-132 ES10_0098 50.38 16.38 9.37 7.23 3.7 1.81 1.13 0.01 1.23 0.12 0.182 0.03 0.04 7.72 99.34 6.48 DS358-132 ES10_0099 50.76 16.43 9.42 7.5 3.73 1.97 1.01 0.01 1.16 0.13 0.192 0.03 0.03 7.73 100.1 6.42 Ave. 50.57 16.41 9.40 7.37 3.72 1.89 1.07 0.01 1.20 0.13 0.19 0.03 0.04 7.73 99.72 6.45 1 σ 0.27 0.04 0.04 0.19 0.02 0.11 0.08 0.00 0.05 0.01 0.01 0.00 0.01 0.01 0.54 0.04 1 σ % 0.53 0.22 0.38 2.59 0.57 5.99 7.93 0.00 4.14 5.66 3.78 0.00 20.20 0.09 0.54 0.66 ALS Range 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 0.001- 100 0.01- 100 0.01- 100 0.01- 100 0.01- 100 ALS 1 σ % 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 2.50% 583 B.8 Four acid digestion whole rock geochemistry data This appendix consists of Table B.9 which contains the all the whole rock data (including refer- ence and duplicate samples) collected as part of this study. The whole rock geochemistry ana- lyzed pulp samples from the RLGM and the surrounding area along the investigated cross sec- tions. The recalculated wt% oxides are also included. The individual columns identify the ele- mental concentrations in ppm (for trace elements) and pct (for major elements). Corresponding information regarding lithology, location in X-Y co-ordinates for a NAD 27 Zone 25 UTM sys- tem, main alteration assemblage, scale (mine = 0-3 km, intermediate = 0-5 km and distal = > 5km), metamorphic grade and mineralization sulfide-oxide assemblage information can all be found in Appendix A.2 rather than repetitive information. 584 Table B.9 Complete four acid digestion whole rock geochemistry data for the RLGM and surrounding are along the cross sections. Hole ID Depth (ft) Ag_pp m Al_p ct Ba_pp m Be_pp m Bi_pp m Ca_p ct Cd_pp m Ce_pp m Co_pp m Cr_pp m Cs_pp m Cu_pp m Fe_p ct Ga_pp m Ge_pp m 06L337 186 0.51 5.29 170 0.81 0.04 5.74 0.18 7.43 50.00 212 4.65 68.2 7.75 38.40 0.09 13L833 681.4 0.06 7.53 60 0.29 0.02 5.73 0.13 8.98 30.10 236 11.30 75.6 5.88 17.05 0.07 16L1067 267.9 2.90 6.09 240 0.49 0.18 1.11 3.23 5.11 45.20 173 5.92 303 5.27 13.70 0.05 16L1067 400.8 0.13 6.27 340 0.79 0.01 2.62 0.07 9.03 31.30 169 5.15 169 7.63 15.55 0.10 19L547 495.8 0.28 8.58 50 0.39 0.04 2.21 0.14 12.60 48.60 221 2.38 237 18.40 21.10 0.31 30L1268 25.7 0.15 6.73 60 0.32 0.03 1.05 0.09 13.20 44.50 189 0.60 112 16.15 15.65 0.25 30L1268 25.7D 0.24 6.56 60 0.30 0.02 0.85 0.08 13.65 41.50 180 0.53 85.1 15.90 15.60 0.22 34L006 1235.1 0.06 9.59 190 1.06 0.02 6.22 0.46 11.35 44.90 234 7.51 8.8 8.74 23.10 0.18 34L235 944 B 0.16 2.92 170 0.17 0.01 11.50 0.10 3.97 43.90 796 2.28 53.4 4.68 7.73 <0.05 34L235 944 C 0.34 4.12 140 0.27 0.04 9.70 0.10 5.92 52.40 1480 3.01 194 7.47 10.90 0.07 34L814 195.7 0.11 6.22 320 0.67 0.03 9.10 0.11 7.04 57.90 1090 6.86 62.0 5.18 14.50 0.08 34L814 2333.4 0.09 7.49 230 0.29 0.01 2.71 0.07 9.56 40.60 53 2.58 200 9.14 20.30 0.12 37L482 2057 0.08 9.62 500 0.55 0.02 4.82 0.08 1.77 108.00 430 7.30 29.1 7.42 18.75 0.23 37L726 836.6 0.08 10.60 40 0.22 0.02 3.91 0.06 11.00 54.80 254 0.81 136 9.62 24.40 0.22 BK0510 376.12 0.21 7.41 70 0.81 0.06 5.61 0.20 8.53 24.20 86 1.79 14.6 4.36 18.70 0.17 CB1812M 0.52 7.60 110 1.33 0.18 1.77 0.06 7.11 57.10 253 5.10 107 7.47 15.40 0.13 CB22252BA 0.08 10.05 70 0.62 0.01 4.36 0.07 9.97 58.70 2320 1.85 157 8.05 29.30 0.14 CB22252BA- D 0.11 10.40 20 0.62 0.01 4.60 0.10 10.85 54.00 1970 1.80 230 8.87 27.50 0.16 CB25510LZ 1.43 5.71 180 0.75 0.2 9.4 0.26 5.57 147 264 4.36 155 10.05 13.55 0.17 CB302561-D 0.54 7.24 50 0.33 0.02 5.55 0.12 7.74 78.2 359 3.34 86.7 7.49 16.25 0.08 CB302561 6.35 5.81 100 0.52 0.06 5.89 0.14 11.40 59.20 332 3.73 296 7.72 15.95 0.12 CB4043HR 5.48 7.10 50 0.58 0.10 7.64 0.24 8.13 51.50 310 1.50 226 7.84 15.60 0.07 CB4043HR-D 5.94 7.61 90 0.55 0.15 7.77 0.23 7.50 52.00 295 3.76 283 8.70 16.90 0.09 CR4610 947 0.14 8.78 180 0.52 0.06 4.11 0.08 6.57 58.90 181 2.45 236 8.95 23.20 0.20 CR4611 581.4 2.74 7.76 150 0.89 0.05 5.07 0.64 24.90 60.70 45 3.09 459 14.65 22.70 0.29 CR4612 360.3 0.13 9.80 100 0.68 0.15 5.25 0.19 11.90 71.10 169 3.79 112 10.05 24.90 0.22 CR4613 1.3 0.13 7.77 30 0.45 0.04 6.96 0.17 10.70 56.40 133 0.66 117 15.50 18.05 0.25 CR464 31.2 0.08 8.59 210 0.60 0.01 3.06 0.06 13.10 32.90 161 2.50 112 7.48 25.30 0.19 CR466 145 0.11 8.51 10 0.50 0.01 3.82 0.11 13.35 38.50 152 0.15 161 10.05 22.40 0.20 CR467 86.3 0.33 5.45 200 0.88 0.48 6.34 0.27 26.40 39.60 235 1.94 232 11.75 12.75 0.22 CR468 629 0.12 6.01 40 0.15 0.02 13.05 0.19 11.10 70.10 39 0.23 307 13.95 15.90 0.18 CR469 41.6 0.12 1.90 10 0.07 0.08 0.36 0.02 1.20 96.00 1660 0.09 22.1 6.50 3.83 0.10 D14391 1810 0.08 9.24 20 0.22 <0.01 2.70 0.06 7.36 71.00 193 0.51 115 10.65 19.75 0.12 D14391 1810 D 0.09 9.24 10 0.19 <0.01 2.64 0.08 7.47 77.90 213 0.41 169 11.00 19.55 0.14 D14981 1798.8 0.16 10.10 110 0.41 0.02 4.00 0.18 8.70 69.60 483 1.46 209 9.89 29.50 0.21 D15367 793 0.11 6.37 100 0.39 0.02 4.30 0.16 15.25 40.80 96 2.34 73.8 14.35 15.60 0.26 D21708 2760 0.15 7.73 140 0.67 0.05 2.25 0.06 62.20 17.10 47 5.58 25.7 11.80 19.00 0.25 D2253 75 0.26 8.51 30 0.35 0.08 4.30 0.21 9.90 37.90 328 6.41 188 8.34 18.75 0.18 D = duplicate, C = chlorite and b = biotite altered 585 Table B.9 (Continued) Hole ID Depth (ft) Hf_ppm In_pp m K_pc t La_pp m Li_pp m Mg_p ct Mn_pp m Mo_pp m Na_p ct Nb_pp m Ni_pp m P_pp m Pb_pp m Rb_pp m 06L337 186 0.80 0.05 1.03 3.60 28.50 2.83 2430 14.90 0.28 2.30 255 100 2.90 34.8 13L833 681.4 1.50 0.04 0.85 4.00 13.90 2.31 1340 0.28 0.21 2.70 106 220 2.60 20.3 16L1067 267.9 0.90 0.08 1.45 2.70 50.50 0.64 175 0.18 0.18 1.30 94 130 39.8 42.6 16L1067 400.8 1.30 0.06 0.67 4.00 60.30 2.00 2040 0.25 0.08 2.40 80 310 2.60 27.5 19L547 495.8 1.60 0.05 0.37 5.80 39.30 3.40 2910 0.31 0.11 3.60 177 380 2.30 10.5 30L1268 25.7 1.40 0.07 0.14 6.20 31.90 2.39 4170 0.30 0.06 2.30 112 210 1.10 5.8 30L1268 25.7D 1.40 0.06 0.15 6.40 33.50 2.41 3800 0.27 0.08 2.30 107 240 1.30 6.9 34L006 1235.1 2.10 0.08 1.41 4.30 42.70 1.92 3250 0.41 0.86 3.60 120 490 8.90 35.8 34L235 944 B 0.50 0.04 0.81 1.70 133.00 5.47 1660 0.12 0.16 0.80 157 130 3.90 34.7 34L235 944 C 0.70 0.05 0.64 2.50 134.00 5.85 1460 0.16 0.26 1.60 288 170 3.20 32.8 34L814 195.7 1.10 0.05 1.80 3.00 229.00 3.38 1100 0.15 0.44 1.80 209 200 5.50 67.8 34L814 2333.4 1.40 0.08 0.67 4.10 47.40 3.25 749 0.22 1.84 3.40 44 410 0.70 26.4 37L482 2057 0.50 0.03 3.19 0.60 120.50 4.22 1320 0.26 0.67 1.20 855 100 7.60 49.7 37L726 836.6 2.40 0.15 0.12 3.80 93.40 3.70 2050 0.15 0.24 3.50 167 670 2.20 4.1 BK0510 376.12 1.80 0.04 0.70 3.50 21.70 2.62 988 0.66 0.89 1.60 53 270 16.2 21.0 CB1812M 0.90 0.05 1.16 2.80 111.00 1.18 704 0.90 0.38 2.10 108 210 7.30 39.5 CB22252BA 1.10 0.08 0.13 3.50 88.30 3.45 1300 0.22 0.35 3.30 494 470 4.60 2.8 CB22252BA-D 1.20 0.10 0.06 3.80 87.70 3.85 1570 0.17 0.29 3.20 374 390 4.00 2.2 CB25510LZ 0.8 0.054 1.39 2.2 111.5 5.29 2120 0.11 0.48 0.8 283 30 7.9 46.8 CB302561-D 1.2 0.056 0.54 3.1 30.1 3.6 1720 0.24 0.23 2.6 324 340 5.4 20.3 CB302561 1.40 0.06 0.85 4.20 40.60 2.73 1260 0.54 0.24 1.70 234 180 9.10 28.7 CB4043HR 1.60 0.06 0.44 3.30 62.10 3.88 1720 0.25 0.19 2.70 163 310 4.60 15.9 CB4043HR-D 1.50 0.07 1.03 3.00 86.50 4.26 1800 0.42 0.19 2.60 160 330 5.00 38.9 CR4610 947 2.50 0.09 1.29 2.20 27.20 1.48 1600 0.50 1.59 4.70 111 420 2.40 31.2 CR4611 581.4 2.80 0.13 1.69 10.10 26.60 3.02 4360 0.82 0.52 8.70 55 750 20.4 45.7 CR4612 360.3 1.60 0.11 0.90 4.20 46.20 2.62 3020 0.30 0.89 4.90 183 560 3.20 12.8 CR4613 1.3 1.40 0.08 0.25 4.50 24.80 3.03 6560 0.33 0.54 2.80 177 390 2.00 3.2 CR464 31.2 2.00 0.08 1.60 4.60 25.00 1.14 2040 0.30 2.37 6.00 43 780 1.20 45.1 CR466 145 1.90 0.11 0.08 4.90 15.90 2.47 1610 0.33 0.17 4.80 52 650 1.40 0.7 CR467 86.3 1.50 0.09 2.14 13.90 6.60 1.33 3010 1.28 0.66 2.80 128 410 7.40 108.5 CR468 629 1.00 0.06 0.18 4.20 8.20 3.10 4680 0.36 0.28 2.30 155 290 0.70 4.0 CR469 41.6 0.10 0.02 0.01 0.50 1.30 20.80 841 0.25 0.01 0.30 1615 40 0.90 0.3 D14391 1810 2.00 0.05 0.06 2.90 63.10 3.04 3110 0.61 0.07 4.20 220 420 1.50 1.7 D14391 1810 D 2.10 0.06 0.03 3.00 65.80 3.09 3870 0.73 0.07 4.20 238 430 1.40 0.8 D14981 1798.8 2.50 0.09 0.33 3.00 128.50 3.22 2030 0.20 0.76 3.30 287 430 3.70 3.4 D15367 793 2.00 0.08 0.45 6.40 82.50 4.33 3190 0.58 0.04 3.50 94 470 1.40 18.6 D21708 2760 2.90 0.03 0.91 34.60 54.80 1.44 3670 0.95 1.33 6.60 53 400 10.1 47.9 D2253 75 2.00 0.08 0.28 3.80 12.10 3.14 2020 0.19 0.15 3.30 146 360 2.60 14.6 586 Table B.9 (Continued) Hole ID Depth (ft) Re_ppm S_pct Sb_pp m Sc_pp m Se_pp m Sn_pp m Sr_pp m Ta_pp m Te_pp m Th_pp m Ti_pc t Tl_pp m U_pp m V_pp m 06L337 186 0.00 0.57 23.50 24.4 2 0.50 102.0 0.16 0.28 0.60 0.35 1.84 0.20 275 13L833 681.4 <0.002 1.25 7.31 43.9 2 0.60 49.7 0.19 <0.05 0.50 0.46 0.53 0.20 303 16L1067 267.9 <0.002 2.63 589.00 20.3 2 0.40 62.6 0.08 <0.05 0.30 0.29 1.08 0.10 221 16L1067 400.8 <0.002 0.17 32.60 34.7 2 0.50 70.4 0.16 <0.05 0.40 0.48 0.91 0.10 251 19L547 495.8 0.00 0.73 57.10 46.8 3 0.80 31.9 0.24 <0.05 0.60 0.53 0.33 0.20 315 30L1268 25.7 0.00 0.66 19.25 65.5 3 0.30 52.5 0.16 0.11 0.30 0.46 0.14 0.10 333 30L1268 25.7D 0.00 0.55 19.15 62.7 3 0.30 50.5 0.16 0.11 0.40 0.46 0.13 0.10 324 34L006 1235.1 0.00 <0.01 7.00 43.7 2 1.70 119.5 0.22 <0.05 0.40 0.76 0.51 0.30 340 34L235 944 B <0.002 0.05 7.42 45.5 1 0.20 94.6 0.06 <0.05 <0.2 0.25 0.43 0.10 189 34L235 944 C 0.00 0.15 9.46 66.5 2 0.30 95.7 0.10 0.05 0.20 0.37 0.34 0.10 276 34L814 195.7 <0.002 0.49 6.77 53.5 2 0.60 181.5 0.12 1.12 0.30 0.38 0.97 0.10 301 34L814 2333.4 0.00 0.03 0.78 45.9 2 0.70 93.8 0.22 <0.05 0.50 0.71 0.06 0.10 390 37L482 2057 0.00 0.06 6.59 19.9 1 0.30 213 0.08 0.05 <0.2 0.26 1.20 <0.1 154 37L726 836.6 0.01 0.26 16.0 67.5 3 0.80 108 0.22 <0.05 0.40 0.76 0.17 0.20 490 BK0510 376.12 0.00 0.05 3.60 16.0 2 0.60 105 0.11 <0.05 0.40 0.28 0.29 0.30 133 CB1812M 0.00 5.94 42.0 33.9 4 0.50 108 0.11 1.71 0.30 0.46 2.18 0.10 281 CB22252BA 0.00 0.25 23.5 50.7 2 0.70 70.5 0.19 0.12 0.20 0.76 0.13 0.10 451 CB22252BA-D <0.002 0.28 22.2 61.3 2 0.60 67.1 0.18 0.11 0.30 0.72 0.12 0.10 440 CB25510LZ <0.002 4.24 7.85 58.6 5 0.4 141 <0.05 0.8 <0.2 0.238 0.61 <0.1 255 CB302561-D 0.002 0.3 42.9 30.0 2 0.7 48.8 0.16 0.09 0.4 0.523 0.26 0.1 248 CB302561 0.00 2.92 60.9 26.8 8 1.10 84.4 0.11 8.36 0.40 0.34 0.39 0.10 332 CB4043HR 0.00 1.02 22.7 35.3 2 1.10 144 0.18 0.74 0.40 0.53 0.19 0.10 307 CB4043HR-D <0.002 1.36 18.6 38.2 2 1.10 164 0.17 0.78 0.40 0.52 0.43 0.10 317 CR4610 947 0.00 0.29 0.67 48.3 3 1.00 198 0.29 0.10 0.40 0.85 0.35 0.20 473 CR4611 581.4 0.00 0.82 1.83 20.6 3 1.20 115.5 0.56 0.07 1.00 1.08 0.65 0.30 293 CR4612 360.3 0.00 0.08 0.67 32.6 3 1.00 164 0.31 <0.05 0.40 0.91 0.33 0.10 342 CR4613 1.3 0.00 0.36 1.49 20.7 2 0.70 64.9 0.17 <0.05 0.30 0.53 0.13 0.20 238 CR464 31.2 0.00 0.03 0.62 39.9 3 0.50 133 0.40 <0.05 0.60 1.06 0.31 0.10 431 CR466 145 0.00 0.08 1.87 47.5 3 1.10 32.6 0.32 <0.05 0.40 0.89 0.02 0.10 386 CR467 86.3 0.00 2.13 0.70 13.3 3 0.80 193 0.19 0.87 2.40 0.25 0.63 0.90 98 CR468 629 0.00 0.38 0.63 49.6 4 0.50 66.1 0.14 0.06 0.30 0.52 0.02 0.10 316 CR469 41.6 <0.002 0.29 1.37 19.6 2 0.20 2.1 <0.05 0.06 <0.2 0.08 0.02 <0.1 84 D14391 1810 0.00 0.28 28.9 42.4 3 0.30 34.0 0.25 <0.05 0.60 0.70 0.08 0.20 313 D14391 1810 D 0.00 0.30 28.6 44.1 3 0.40 31.3 0.25 <0.05 0.60 0.70 0.06 0.20 312 D14981 1798.8 0.00 0.20 11.75 42.7 2 1.10 104 0.26 <0.05 0.40 0.90 0.17 0.20 402 D15367 793 0.00 0.25 16.4 40.0 2 0.70 77.8 0.21 0.06 0.50 0.71 0.15 0.20 324 D21708 2760 <0.002 0.77 1.13 10.4 2 0.90 134 0.54 <0.05 9.20 0.30 0.24 2.60 68 D2253 75 0.00 0.31 32.60 42.6 2 0.60 66.3 0.21 0.06 0.60 0.66 0.20 0.20 315 587 Table B.9 (Continued) Hole ID Depth (ft) W_pp m Y_p pm Zn_p pm Zr_pp m Al2O3 wt% CaO wt% FeO wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total 06L337 186 79.4 6.2 78 26.4 9.99 8.03 9.97 1.24 4.69 0.31 0.38 0.02 0.59 1.42 0.03 60.75 97.43 13L833 681.4 4.2 6.3 58 54.7 14.22 8.02 7.56 1.02 3.83 0.17 0.28 0.05 0.77 3.12 0.03 58.18 97.26 16L1067 267.9 36.6 12.7 661 35.9 11.50 1.55 6.78 1.75 1.06 0.02 0.24 0.03 0.48 6.57 0.03 67.89 97.90 16L1067 400.8 7.6 9.6 47 48.2 11.84 3.67 9.81 0.81 3.32 0.26 0.11 0.07 0.79 0.42 0.02 66.69 97.82 19L547 495.8 52.8 25.1 52 65.1 16.21 3.09 23.66 0.45 5.64 0.38 0.15 0.09 0.89 1.82 0.03 43.93 96.33 30L1268 25.7 17.4 38.7 114 53.1 12.71 1.47 20.77 0.17 3.96 0.54 0.08 0.05 0.77 1.65 0.03 54.85 97.05 30L1268 25.7D 16.3 35.6 117 55.3 12.39 1.19 20.45 0.18 4.00 0.49 0.11 0.05 0.76 1.37 0.03 56.11 97.13 34L006 1235.1 8.2 15.7 267 77.3 18.12 8.70 11.24 1.70 3.18 0.42 1.16 0.11 1.27 0.02 0.03 50.82 96.78 34L235 944 B 1.2 5.3 31 19.0 5.52 16.09 6.02 0.98 9.07 0.21 0.22 0.03 0.41 0.12 0.12 58.50 97.29 34L235 944 C 1.1 13.6 64 26.0 7.78 13.57 9.61 0.77 9.70 0.19 0.35 0.04 0.62 0.37 0.22 53.76 96.97 34L814 195.7 11.3 9.0 44 44.5 11.75 12.73 6.66 2.17 5.60 0.14 0.59 0.05 0.63 1.22 0.16 55.37 97.08 34L814 2333.4 0.2 12.7 98 53.7 14.15 3.79 11.75 0.81 5.39 0.10 2.48 0.09 1.18 0.07 0.01 57.39 97.21 37L482 2057 7.7 4.8 85 17.7 18.17 6.74 9.54 3.84 7.00 0.17 0.90 0.02 0.43 0.15 0.06 49.67 96.71 37L726 836.6 21.6 9.2 70 87.2 20.02 5.47 12.37 0.14 6.13 0.27 0.32 0.15 1.26 0.65 0.04 49.89 96.72 BK0510 376.12 16.9 13.1 135 60.3 14.00 7.85 5.61 0.84 4.34 0.13 1.20 0.06 0.46 0.12 0.01 62.95 97.58 CB1812M 79.2 3.8 36 30.6 14.36 2.48 9.61 1.40 1.96 0.09 0.51 0.05 0.76 14.83 0.04 50.70 96.77 CB22252BA 47.2 5.2 75 38.3 18.98 6.10 10.35 0.16 5.72 0.17 0.47 0.11 1.26 0.62 0.34 52.61 96.90 CB22252BA-D 30.8 5.7 67 37.9 19.65 6.44 11.41 0.07 6.38 0.20 0.39 0.09 1.19 0.70 0.29 49.92 96.72 CB25510LZ 10.0 6.5 60 24.5 10.79 13.15 12.92 1.67 8.77 0.27 0.65 0.01 0.40 10.59 0.04 62.21 97.53 CB302561-D 75.0 10.9 95 42.3 13.68 7.76 9.63 0.65 5.97 0.22 0.31 0.08 0.87 0.75 0.05 80.17 98.70 CB302561 35.5 6.9 48 44.7 10.98 8.24 9.93 1.02 4.53 0.16 0.32 0.04 0.57 7.29 0.05 53.85 96.98 CB4043HR 11.3 19.5 75 55.7 13.41 10.69 10.08 0.53 6.43 0.22 0.26 0.07 0.89 2.55 0.05 51.66 96.84 CB4043HR-D 11.0 19.6 81 53.5 14.38 10.87 11.19 1.24 7.06 0.23 0.26 0.08 0.87 3.40 0.04 46.91 96.53 CR4610 947 0.8 17.4 102 81.9 16.59 5.75 11.51 1.55 2.45 0.21 2.14 0.10 1.42 0.72 0.03 54.56 97.03 CR4611 581.4 10.1 28.2 416 111.5 14.66 7.09 18.84 2.04 5.01 0.56 0.70 0.17 1.79 2.05 0.01 43.38 96.30 CR4612 360.3 0.4 26.2 119 70.8 18.51 7.34 12.92 1.08 4.34 0.39 1.20 0.13 1.51 0.20 0.02 49.00 96.66 CR4613 1.3 0.5 24.0 121 54.6 14.68 9.74 19.93 0.30 5.02 0.85 0.73 0.09 0.88 0.90 0.02 43.14 96.28 CR464 31.2 0.2 25.9 92 77.9 16.23 4.28 9.62 1.93 1.89 0.26 3.19 0.18 1.77 0.07 0.02 57.79 97.24 CR466 145 0.5 31.9 108 68.8 16.08 5.34 12.92 0.10 4.10 0.21 0.23 0.15 1.48 0.20 0.02 56.32 97.14 CR467 86.3 0.9 15.5 184 64.6 10.30 8.87 15.11 2.58 2.21 0.39 0.89 0.09 0.41 5.32 0.03 50.57 96.77 CR468 629 0.7 30.1 150 27.6 11.35 18.26 17.94 0.22 5.14 0.61 0.38 0.07 0.86 0.95 0.01 40.32 96.10 CR469 41.6 1.0 1.4 56 1.4 3.59 0.50 8.36 0.01 34.49 0.11 0.01 0.01 0.14 0.72 0.24 48.44 96.63 D14391 1810 50.1 11.4 84 71.6 17.45 3.78 13.70 0.07 5.04 0.40 0.09 0.10 1.16 0.70 0.03 54.50 97.02 D14391 1810 D 49.2 13.9 85 71.4 17.45 3.69 14.15 0.04 5.12 0.50 0.09 0.10 1.17 0.75 0.03 53.89 96.98 D14981 1798.8 4.8 9.1 158 86.1 19.08 5.60 12.72 0.40 5.34 0.26 1.02 0.10 1.51 0.50 0.07 50.15 96.74 D15367 793 10.5 10.9 126 75.0 12.03 6.02 18.45 0.54 7.18 0.41 0.05 0.11 1.18 0.62 0.01 50.12 96.74 D21708 2760 0.6 18.5 162 115.0 14.60 3.15 15.17 1.10 2.39 0.47 1.79 0.09 0.50 1.92 0.01 55.92 97.12 D2253 75 20.6 8.6 105 71.0 16.08 6.02 10.73 0.34 5.21 0.26 0.20 0.08 1.10 0.77 0.05 56.32 97.14 588 Table B.9 (Continued) Hole ID Depth (ft) Ag_pp m Al_p ct Ba_pp m Be_pp m Bi_pp m Ca_p ct Cd_pp m Ce_pp m Co_pp m Cr_pp m Cs_pp m Cu_pp m Fe_p ct Ga_pp m Ge_pp m D27943 2104.2 0.07 9.12 410 0.94 0.01 6.06 0.07 8.15 37.20 331 4.74 109 7.25 17.75 0.05 D27943 3389.5 0.02 8.32 1060 0.43 0.02 3.48 0.06 3.28 39.10 279 4.91 35.1 5.14 18.05 0.05 D33003 532 2.84 7.90 170 0.88 0.01 2.78 0.20 6.88 52.70 215 10.15 74.5 5.37 18.20 0.05 D33003 2004 0.15 8.36 100 1.32 0.02 7.48 0.17 20.40 49.10 39 9.66 94.0 10.30 20.90 0.15 D39018 43 0.02 8.73 360 0.19 <0.01 5.74 0.04 4.74 17.70 203 1.74 11.3 2.60 19.05 <0.05 D39018 43 0.03 9.06 360 0.18 7.92 0.04 5.65 30.60 195 2.40 21.7 3.63 16.50 0.11 D39018 3562 0.09 9.68 170 0.45 0.01 8.86 0.10 7.79 62.70 164 10.25 35.3 8.89 20.30 0.13 D39018 4848 0.16 7.11 70 0.46 0.05 5.07 0.65 9.58 55.80 160 2.81 145 17.50 16.65 0.26 D39200 1469 2.79 5.27 140 1.10 0.05 0.54 0.88 8.87 116.00 139 7.28 102 12.80 15.05 0.18 D39200 3241 0.12 9.69 30 0.72 0.01 5.10 0.15 11.55 66.90 156 0.13 104 8.04 22.60 0.09 DS139 30.4 0.32 6.20 20 0.30 0.02 2.69 0.07 5.04 146.00 2330 1.57 80.1 9.28 14.85 0.12 DS172 123.1 B 0.07 8.54 430 1.13 0.02 1.87 0.03 12.55 45.00 249 11.05 52.0 14.15 21.50 0.20 DS172 123.1 C 0.14 8.16 70 1.11 0.06 3.45 0.04 13.75 55.40 276 4.28 90.0 16.65 21.40 0.25 DS173 499.6 0.13 9.59 210 0.62 0.02 5.94 0.13 13.75 81.50 153 1.29 440 13.55 22.10 0.24 DS174 708.4 0.1 9.38 70 0.61 0.01 8.5 0.67 13.05 62.8 138 1.21 126 13.7 21.8 0.21 DS177 1500.8 0.14 10.15 70 0.35 0.07 4.43 0.22 14.50 90.30 239 8.73 401 10.75 25.10 0.18 DS180 400.2 0.15 8.54 320 1.03 0.02 5.33 0.07 40.90 33.60 32 8.74 40.2 6.48 21.60 0.12 DS358 132 0.20 8.66 610 1.90 0.09 4.91 1.40 97.00 29.50 116 38.70 45.8 5.17 21.40 0.19 DS358 1215 0.10 2.95 20 0.10 0.01 9.48 0.16 7.62 40.80 163 2.38 109 9.25 5.75 0.18 DS615 1905.1 0.09 6.16 150 0.97 0.15 3.41 0.07 18.55 14.70 20 18.50 24.7 19.30 16.55 0.26 GC01018 85.3 0.09 8.91 10 0.31 0.02 6.66 0.35 17.65 63.20 188 0.68 203 11.05 23.30 0.17 GC01018 691.7 0.22 7.49 350 3.94 0.31 1.13 0.17 6.01 14.10 37 16.30 14.0 23.90 20.40 0.62 GC04003 1716 0.06 8.03 60 0.21 0.01 9.58 0.04 4.23 39.90 93 11.50 73.6 1.88 15.40 0.06 GC04007 3890 0.12 2.67 30 0.38 0.04 5.89 0.14 4.87 60.40 796 0.91 74.4 18.15 6.81 0.23 GC04007 134ES 0.06 5.00 100 0.51 0.01 0.29 0.06 9.57 112.00 4600 10.30 111 14.50 13.00 0.19 R87105 699.8 0.42 7.30 50 0.42 0.10 4.63 0.09 11.90 54.60 164 0.59 151 8.51 15.90 0.13 R87107 482.3 0.17 8.18 220 0.76 0.10 6.28 0.08 8.64 37.50 153 2.19 79.1 7.53 22.50 0.14 R87108 629.5 0.16 6.89 50 0.64 0.10 9.12 0.19 8.92 31.00 118 0.61 92.8 9.87 16.25 0.13 RL338261AO 6.97 3.86 100 0.71 0.20 1.21 1.13 5.40 25.90 161 2.70 24.1 3.71 14.55 0.05 RL34875SO 2.44 6.54 40 0.42 0.03 4.05 0.20 6.83 45.80 144 2.04 86.9 9.48 13.45 0.18 RL35FW 3.53 1.16 30 0.26 0.07 10.20 0.95 2.95 159.00 71 0.44 89.7 12.70 3.80 0.32 RL422VG 106.00 0.95 50 0.30 7.37 3.65 2.46 4.20 91.60 151 0.53 1415 14.75 3.82 0.72 BAS-1 0.09 8.26 170 0.80 0.01 5.59 0.10 19.25 44.50 156 0.10 55.3 7.11 19.55 0.11 BAS-1 0.09 8.17 160 0.60 <0.01 5.76 0.12 21.20 42.90 150 0.11 64.8 6.93 20.80 0.11 BAS-1 0.12 8.63 180 0.68 0.01 5.98 0.11 20.80 44.10 165 0.10 63.1 7.60 20.80 0.20 589 Table B.9 (Continued) Hole ID Depth (ft) Hf_ppm In_pp m K_pc t La_pp m Li_pp m Mg_p ct Mn_pp m Mo_pp m Na_p ct Nb_pp m Ni_pp m P_pp m Pb_pp m Rb_pp m D27943 2104.2 1.20 0.06 2.29 3.10 78.60 2.99 1680 0.13 0.49 2.40 101 300 1.60 64.4 D27943 3389.5 1.30 0.05 3.07 1.20 42.80 3.10 510 0.11 0.65 1.20 95 250 2.10 36.5 D33003 532 1.20 0.06 2.37 2.70 26.10 1.52 1490 0.36 0.38 2.20 105 270 10.1 68.2 D33003 2004 2.90 0.12 0.91 8.20 156.50 3.71 3030 0.41 0.45 5.80 64 760 3.30 38.4 D39018 43 2.00 0.02 2.02 1.70 42.90 2.35 1330 0.12 0.27 0.90 65 180 1.00 25.6 D39018 43 2.30 0.02 2.55 2.10 45.70 3.31 1830 0.29 0.24 1.10 103 170 1.10 42.4 D39018 3562 1.30 0.07 1.72 2.80 68.00 4.43 1660 0.15 0.68 3.00 129 340 2.10 38.4 D39018 4848 1.60 0.09 0.62 3.50 20.00 2.56 5740 0.67 1.42 3.40 137 330 2.90 11.4 D39200 1469 0.40 0.08 1.89 3.50 33.00 0.98 1780 0.36 0.41 1.70 141 190 28.9 65.1 D39200 3241 1.20 0.08 0.03 4.20 26.30 2.79 2180 0.27 0.21 4.00 141 500 3.50 0.5 DS139 30.4 1.00 0.06 0.21 1.70 51.80 8.75 943 1.84 0.01 1.70 1035 70 0.90 9.7 DS172 123.1 B 1.70 0.07 2.56 6.20 90.60 1.93 5500 0.21 0.18 2.00 133 360 2.20 103.5 DS172 123.1 C 1.40 0.07 0.41 7.00 69.30 2.21 6670 0.24 0.05 1.80 152 320 1.50 15.6 DS173 499.6 2.00 0.11 0.82 5.40 16.80 3.35 4860 0.32 0.34 3.90 144 550 0.80 14.1 DS174 708.4 2.3 0.089 0.54 5.3 31.7 2.99 6110 0.23 1.49 4.2 113 420 0.6 12.3 DS177 1500.8 1.80 0.09 0.17 4.80 60.60 2.66 5220 0.27 0.73 3.80 267 270 1.30 5.0 DS180 400.2 3.90 0.07 0.84 16.40 69.30 2.26 1060 0.47 1.47 6.50 54 970 3.70 21.3 DS358 132 4.40 0.06 0.93 43.00 91.60 3.42 869 0.13 2.88 10.50 138 1920 23.3 46.2 DS358 1215 0.50 0.02 0.12 3.10 24.00 4.69 3690 0.13 0.03 0.80 155 100 0.60 5.2 DS615 1905.1 1.50 0.02 2.11 9.70 45.80 1.48 5210 1.18 0.20 2.60 23 180 4.20 60.2 GC01018 85.3 1.50 0.09 0.22 6.90 78.10 1.79 5210 0.33 0.86 3.60 119 300 0.70 1.0 GC01018 691.7 2.10 0.36 2.21 3.00 89.30 1.41 15600 0.31 0.17 5.20 25 20 5.00 58.3 GC04003 1716 0.70 0.04 0.26 1.80 49.60 0.34 817 0.09 1.33 1.70 109 190 0.90 8.0 GC04007 3890 0.50 0.20 0.07 1.90 21.60 5.40 10850 0.10 0.03 1.00 416 120 0.90 4.0 GC04007 134ES 1.00 0.06 0.81 3.70 91.10 2.12 3950 0.20 0.03 2.10 1300 280 0.70 45.1 R87105 699.8 1.30 0.05 0.24 4.60 80.30 5.31 2260 0.21 2.79 3.10 100 310 8.80 4.1 R87107 482.3 2.20 0.09 0.93 3.20 61.80 3.45 1820 0.42 0.54 4.40 103 550 5.10 12.6 R87108 629.5 1.60 0.07 0.28 3.70 38.40 4.17 3470 0.89 0.54 3.10 86 200 3.90 10.3 RL338261AO 0.90 0.08 1.22 2.20 24.90 0.58 136 0.13 0.12 0.70 78 30 8.10 40.4 RL34875SO 0.80 0.06 0.28 2.60 37.20 1.57 1710 2.74 0.14 1.80 108 70 5.10 3.1 RL35FW 0.30 0.03 0.10 1.30 14.40 5.46 4020 0.44 0.05 0.70 561 50 6.40 4.0 RL422VG 0.20 0.22 0.30 2.60 17.00 1.65 557 0.33 0.05 0.30 500 30 51.9 12.2 BAS-1 2.10 0.05 0.43 8.40 7.00 4.31 1080 1.97 2.43 7.30 167 1000 1.90 3.1 BAS-1 2.50 0.07 0.44 8.70 5.70 4.24 1090 2.06 2.49 8.00 155 1000 1.50 3.4 BAS-1 2.20 0.06 0.46 9.80 6.40 4.46 1120 2.06 2.53 7.50 167 1040 2.60 4.4 590 Table B.9 (Continued) Hole ID Depth (ft) Re_ppm S_pct Sb_pp m Sc_pp m Se_pp m Sn_pp m Sr_pp m Ta_pp m Te_pp m Th_pp m Ti_pc t Tl_pp m U_pp m V_pp m D27943 2104.2 0.00 0.03 3.18 61.0 3 0.50 236 0.15 <0.05 0.40 0.53 0.32 0.10 338 D27943 3389.5 <0.002 0.23 2.58 39.7 2 0.40 89.1 0.08 <0.05 0.20 0.35 0.31 0.10 291 D33003 532 0.00 0.26 130 43.9 2 0.60 92.1 0.13 <0.05 0.30 0.49 6.66 0.10 271 D33003 2004 0.00 0.11 17.45 57.6 4 1.20 228 0.34 0.05 0.90 0.94 0.61 0.20 395 D39018 43 0.01 <0.01 2.04 36.5 2 <0.2 24.6 0.06 <0.05 0.30 0.42 0.14 0.20 385 D39018 43 0.01 1.88 37.6 2 0.20 25.3 0.08 0.40 0.47 0.16 0.20 428 D39018 3562 0.00 0.02 3.39 48.1 3 0.60 142 0.17 <0.05 0.30 0.65 0.21 0.10 316 D39018 4848 0.00 1.82 2.86 36.7 4 0.90 73.8 0.20 0.16 0.40 0.61 0.08 0.20 278 D39200 1469 0.00 4.45 129 42.3 3 0.40 99.4 0.09 0.09 0.30 0.36 6.94 0.10 254 D39200 3241 0.00 0.21 12.1 62.6 4 0.70 83.9 0.23 <0.05 0.30 0.77 0.06 0.10 399 DS139 30.4 0.00 0.44 37.5 49.4 2 0.30 55.3 0.09 0.23 0.20 0.41 0.13 <0.1 253 DS172 123.1 B <0.002 0.03 4.48 63.8 3 0.50 182 0.13 <0.05 0.50 0.53 0.43 0.10 344 DS172 123.1 C <0.002 0.10 9.32 60.8 3 0.60 332 0.11 0.06 0.40 0.47 0.09 0.10 329 DS173 499.6 0.00 0.45 3.54 58.0 4 1.00 49.6 0.21 0.05 0.40 0.74 0.12 0.10 376 DS174 708.4 0.003 0.09 2.4 66.7 3 0.9 127 0.25 <0.05 0.4 0.83 0.1 0.1 413 DS177 1500.8 0.00 0.49 3.90 60.4 5 0.70 85.1 0.23 0.08 0.30 0.78 0.30 0.10 360 DS180 400.2 <0.002 0.07 15.6 24.8 4 1.20 307 0.38 <0.05 2.40 0.71 0.20 0.60 163 DS358 132 <0.002 0.21 6.19 18.7 3 1.20 924 0.60 <0.05 10.4 0.59 0.39 2.50 129 DS358 1215 0.32 4.88 25.3 2 0.20 34.3 0.05 0.11 0.14 0.05 123 DS615 1905.1 <0.002 0.11 3.29 3.8 1 0.50 86.9 0.18 0.07 1.80 0.10 0.25 0.70 31 GC01018 85.3 0.00 0.28 1.44 63.9 3 0.50 99.5 0.22 0.08 0.40 0.67 0.02 0.20 350 GC01018 691.7 <0.002 0.55 5.16 7.8 2 2.90 61.8 1.33 0.20 7.10 0.05 1.85 1.70 16 GC04003 1716 <0.002 0.12 2.69 16.9 2 0.30 134 0.10 0.07 0.20 0.33 0.28 0.10 133 GC04007 3890 <0.002 0.88 39.5 38.1 2 0.20 22.2 0.05 0.17 <0.2 0.15 0.04 0.10 160 GC04007 134ES <0.002 0.05 2.66 43.7 1 0.40 10.7 0.13 0.07 0.40 0.40 0.30 0.60 229 R87105 699.8 <0.002 0.03 2.04 30.5 2 0.50 380 0.18 0.10 0.60 0.42 0.04 0.20 238 R87107 482.3 0.00 0.03 3.04 38.1 2 0.90 174 0.26 0.08 0.50 0.82 0.30 0.20 416 R87108 629.5 0.00 1.13 2.53 41.8 2 0.70 195 0.17 0.11 0.50 0.53 0.07 0.20 242 RL338261AO <0.002 2.19 240.0 18.4 9 3.60 49.1 0.05 5.59 0.30 0.16 0.64 0.10 730 RL34875SO 0.00 7.94 67.30 50.2 4 0.50 85.0 0.12 1.75 0.30 0.47 0.40 0.10 269 RL35FW <0.002 2.55 45.90 23.2 18 0.40 99.3 <0.05 0.90 <0.2 0.09 0.09 <0.1 141 RL422VG <0.002 8.71 525.0 6.0 101 1.40 24.4 <0.05 101.50 <0.2 0.04 0.14 <0.1 166 BAS-1 <0.002 0.04 0.27 19.4 3 1.00 499 0.40 <0.05 0.70 0.77 0.04 0.30 147 BAS-1 <0.002 0.04 0.35 16.1 1 1.10 502 0.46 <0.05 0.90 0.76 0.06 0.30 149 BAS-1 <0.002 0.02 0.25 17.6 2 1.00 532 0.44 <0.05 0.80 0.80 0.06 0.30 153 591 Table B.9 (Continued) Hole ID Depth (ft) W_pp m Y_pp m Zn_p pm Zr_pp m Al2O3 wt% CaO wt% FeO wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total D27943 2104.2 2.3 18.2 74 40.9 17.23 8.48 9.32 2.76 4.96 0.22 0.66 0.07 0.89 0.07 0.05 52.16 96.87 D27943 3389.5 12.9 5.2 53 41.9 15.72 4.87 6.61 3.70 5.14 0.07 0.88 0.06 0.58 0.57 0.04 59.10 97.32 D33003 532 105.5 5.4 55 35.9 14.92 3.89 6.91 2.86 2.52 0.19 0.51 0.06 0.82 0.65 0.03 64.31 97.66 D33003 2004 8.0 34.5 106 102.5 15.79 10.46 13.25 1.10 6.15 0.39 0.61 0.17 1.57 0.27 0.01 46.74 96.52 D39018 43 6.9 8.4 16 67.2 16.49 8.03 3.34 2.43 3.90 0.17 0.36 0.04 0.71 0.01 0.03 61.99 97.51 D39018 43 7.0 11.5 24 63.3 17.11 11.08 4.67 3.07 5.49 0.24 0.32 0.04 0.79 0.00 0.03 54.16 97.00 D39018 3562 6.3 13.9 139 41.1 18.29 12.40 11.43 2.07 7.34 0.21 0.92 0.08 1.09 0.05 0.02 42.32 96.23 D39018 4848 0.5 26.3 269 51.9 13.43 7.09 22.51 0.75 4.24 0.74 1.91 0.08 1.02 4.54 0.02 39.71 96.06 D39200 1469 102.5 16.3 74 12.1 9.96 0.76 16.46 2.28 1.62 0.23 0.55 0.04 0.60 11.11 0.02 53.31 96.95 D39200 3241 21.8 20.2 94 42.2 18.30 7.13 10.34 0.04 4.63 0.28 0.28 0.11 1.29 0.52 0.02 54.04 96.99 DS139 30.4 20.0 3.9 167 34.8 11.71 3.76 11.93 0.25 14.51 0.12 0.01 0.02 0.69 1.10 0.34 52.44 96.89 DS172 123.1 B 1.1 20.4 98 51.3 16.13 2.62 18.20 3.08 3.20 0.71 0.24 0.08 0.88 0.07 0.04 51.57 96.83 DS172 123.1 C 1.3 23.6 101 46.0 15.41 4.83 21.41 0.49 3.66 0.86 0.07 0.07 0.79 0.25 0.04 48.75 96.65 DS173 499.6 0.3 34.7 101 67.9 18.12 8.31 17.43 0.99 5.55 0.63 0.46 0.13 1.24 1.12 0.02 42.23 96.22 DS174 708.4 0.3 32.3 173 74.5 17.72 11.89 17.62 0.65 4.96 0.79 2.01 0.10 1.38 0.22 0.02 38.63 95.98 DS177 1500.8 0.5 29.7 315 61.7 19.17 6.20 13.82 0.20 4.41 0.68 0.98 0.06 1.29 1.22 0.03 48.55 96.63 DS180 400.2 0.4 22.8 89 142.0 16.13 7.46 8.33 1.01 3.75 0.14 1.98 0.22 1.18 0.17 0.00 56.79 97.17 DS358 132 0.4 17.0 193 169.0 16.36 6.87 6.65 1.12 5.67 0.11 3.88 0.44 0.98 0.52 0.02 54.39 97.02 DS358 1215 5.9 8.5 67 16.9 5.57 13.26 11.90 0.14 7.78 0.48 0.04 0.02 0.23 0.80 0.02 56.94 97.18 DS615 1905.1 7.8 10.1 204 61.0 11.64 4.77 24.82 2.54 2.45 0.67 0.27 0.04 0.17 0.27 0.00 49.01 96.66 GC01018 85.3 0.4 39.0 268 58.6 16.83 9.32 14.21 0.27 2.97 0.67 1.16 0.07 1.12 0.70 0.03 49.34 96.69 GC01018 691.7 1.5 20.9 62 50.1 14.15 1.58 30.74 2.66 2.34 2.02 0.23 0.00 0.08 1.37 0.01 40.96 96.14 GC04003 1716 0.1 6.1 29 28.9 15.17 13.40 2.42 0.31 0.56 0.11 1.79 0.04 0.54 0.30 0.01 62.91 97.57 GC04007 3890 2.0 18.7 195 19.3 5.04 8.24 23.34 0.08 8.95 1.40 0.04 0.03 0.26 2.20 0.12 46.82 96.52 GC04007 134ES 1.1 6.1 89 37.6 9.45 0.41 18.65 0.98 3.51 0.51 0.04 0.06 0.67 0.12 0.67 62.47 97.54 R87105 699.8 <0.1 16.2 161 47.2 13.79 6.48 10.94 0.29 8.80 0.29 3.76 0.07 0.70 0.07 0.02 51.60 96.83 R87107 482.3 1.4 24.7 72 78.4 15.45 8.79 9.68 1.12 5.72 0.24 0.73 0.13 1.36 0.07 0.02 53.66 96.97 R87108 629.5 6.9 22.5 119 57.5 13.02 12.76 12.69 0.34 6.91 0.45 0.73 0.05 0.89 2.82 0.02 45.78 96.45 RL338261AO 7.0 6.2 294 35.4 7.29 1.69 4.77 1.47 0.96 0.02 0.16 0.01 0.26 5.47 0.02 76.32 98.45 RL34875SO 158.0 8.1 71 21.4 12.35 5.67 12.19 0.34 2.60 0.22 0.19 0.02 0.79 19.83 0.02 41.99 96.20 RL35FW 38.3 15.1 345 12.7 2.19 14.27 16.33 0.12 9.05 0.52 0.07 0.01 0.15 6.37 0.01 47.47 96.56 RL422VG 3.2 3.2 498 8.2 1.79 5.11 18.97 0.36 2.74 0.07 0.07 0.01 0.06 21.75 0.02 45.49 96.43 BAS-1 0.2 13.6 93 76.8 15.60 7.82 9.14 0.52 7.15 0.14 3.28 0.23 1.28 0.10 0.02 51.55 96.83 BAS-1 0.2 16.5 97 84.4 15.43 8.06 8.91 0.53 7.03 0.14 3.36 0.23 1.26 0.10 0.02 51.77 96.84 BAS-1 0.2 15.6 101 90.3 16.30 8.37 9.77 0.55 7.39 0.14 3.41 0.24 1.33 0.05 0.02 49.08 96.67 592 B.9 Lithium borate fusion data This appendix consists of Table B.10 which refers to the complete lithium borate fusion whole rock geochemical data collected as part of this study. This data was derived from pulp sample of the RLGM and surrounding area along the cross sections, but all taken from the ‘Western Vol- canic Belt’ as referred by MacGeehan et al. (1982). The individual columns identify the sample with corresponding element concentrations in wt%. The molar ratio of Fe2+/Fetotal and the total FeOgrams is also provided. For the sample’s scale, lithology, complex, X-Y co-ordinates, depth from surface and ore zones, and metamorphic grade please refer to Appendix A.2 to limit re- peated data. 593 Table B.10 Complete lithium borate fusion whole rock geochemistry data Hole ID Depth SiO2 wt% Al2O3 wt% Fe2O3 wt% FeO wt% CaO wt% MgO wt% Na2O wt% K2O wt% Cr2O3 wt% TiO2 wt% MnO wt% P2O5 wt% SrO wt% BaO wt% LOI Total FeO total Molar Fe2/Fetot 06L337 186 42.26 4.87 10.79 9.23 13.15 6.65 0.12 0.60 0.02 0.28 0.42 0.02 0.01 <0.01 19.1 98.3 9.71 0.951 DS358 132 50.38 16.38 9.37 6.48 7.23 3.70 1.81 1.13 0.01 1.23 0.12 0.18 0.03 0.04 7.72 99.34 8.43 0.769 DS358 132 D 50.76 16.43 9.42 6.42 7.50 3.73 1.97 1.01 0.01 1.16 0.13 0.19 0.03 0.03 7.73 100.1 8.48 0.757 34L235 944 B 36.00 5.84 7.06 6.08 16.20 8.74 0.24 1.03 0.13 0.53 0.21 0.04 0.01 0.02 22.5 98.56 6.35 0.957 34L235 944 C 48.33 7.06 10.57 7.94 14.68 10.41 0.31 0.38 0.22 0.58 0.20 0.04 0.01 0.01 6.34 99.15 9.51 0.835 19L547 495.8 42.17 16.62 26.25 21.00 2.62 5.54 0.15 0.56 0.08 0.91 0.30 0.10 <0.01 0.01 3.42 98.74 23.62 0.889 34L814 2333.3 53.46 14.10 12.64 9.20 3.54 5.23 2.62 0.82 0.01 1.28 0.09 0.09 0.01 0.03 4.58 98.51 11.37 0.809 R87108 629.5 44.10 13.41 17.26 11.95 11.05 7.21 0.68 0.51 0.02 0.81 0.40 0.04 0.01 0.01 2.72 98.24 15.53 0.769 R87108 629.5 D 40.43 13.81 18.49 14.15 11.92 6.83 0.93 0.79 0.02 1.06 0.43 0.06 0.01 0.01 3.39 98.19 16.64 0.850 BK0510 376.12 52.77 13.95 9.39 7.83 10.57 5.64 0.96 1.23 0.06 0.66 0.18 0.06 0.01 0.01 3.18 98.68 8.45 0.927 CR4610 947 53.49 16.93 14.22 11.65 5.44 2.60 1.84 1.47 0.04 1.44 0.29 0.09 0.02 0.02 0.62 98.52 12.80 0.910 CR4611 581.4 40.51 15.48 22.14 17.25 8.76 5.56 0.69 2.17 0.02 2.14 0.51 0.18 0.01 0.03 1.81 100 19.92 0.866 CR4612 360.3 50.01 18.92 13.39 11.35 7.43 4.34 1.11 1.06 0.03 1.53 0.32 0.11 0.02 0.01 0.54 98.83 12.05 0.942 37L482 2057 42.21 20.64 13.98 11.25 5.39 9.74 0.52 4.38 0.06 0.55 0.23 0.02 0.01 0.05 1.94 99.73 12.58 0.894 37L726 836.6 43.62 18.34 18.82 15.40 2.94 7.71 0.17 0.04 0.04 1.09 0.20 0.15 <0.01 <0.01 5.43 98.56 16.93 0.909 37L726 836.6 D 46.56 18.28 17.73 14.90 3.40 6.73 0.14 0.03 0.03 1.14 0.61 0.15 <0.01 <0.01 4.17 98.98 15.95 0.934 D2253 75 56.84 15.58 11.70 10.25 4.15 4.43 0.16 0.40 0.05 1.10 0.18 0.07 0.01 <0.01 3.72 98.4 10.53 0.974 D39200 3241 53.64 18.04 11.96 10.45 6.53 4.64 0.25 0.05 0.03 1.29 0.28 0.11 0.01 <0.01 2.12 98.96 10.76 0.971 DS139 30.4 45.60 11.89 13.22 11.00 2.52 13.46 0.01 0.24 0.37 0.83 0.10 0.02 <0.01 <0.01 10.25 98.51 11.90 0.925 CR467 86.3 54.61 11.93 16.70 13.30 4.89 3.21 1.71 2.00 0.05 0.46 0.24 0.09 0.02 0.01 2.59 98.52 15.03 0.885 CR466 145 53.90 16.11 12.57 10.60 7.10 4.22 0.21 0.09 0.03 1.48 0.25 0.13 0.01 <0.01 2.75 98.86 11.31 0.937 CR466 145 D 54.00 16.97 14.92 12.40 5.23 4.09 0.20 0.07 0.03 1.62 0.24 0.15 0.01 <0.01 2.37 99.9 13.43 0.924 DS172 123.1 B 45.86 14.48 25.86 21.80 3.77 3.63 0.13 2.50 0.05 0.81 0.92 0.07 0.01 0.04 1.88 100 23.27 0.937 DS172 123.1 C 43.81 14.42 26.89 22.80 4.09 3.67 0.07 0.44 0.05 0.80 0.93 0.07 0.01 <0.01 3.06 98.32 24.20 0.942 DS173 499.6 44.97 17.15 20.29 17.30 6.79 4.96 0.38 1.42 0.03 1.21 0.66 0.11 0.01 0.03 0.64 98.66 18.26 0.948 DS177 1500.1 44.98 17.69 17.46 14.45 9.77 4.73 0.68 0.22 0.03 1.13 0.79 0.07 0.01 <0.01 1.16 98.73 15.71 0.920 GC01018 85.3 47.96 17.29 16.42 13.95 9.33 2.95 0.91 0.53 0.03 1.12 0.74 0.08 0.01 <0.01 0.97 98.35 14.77 0.944 GC04007 134 51.10 11.27 21.76 17.75 0.23 3.93 0.02 1.17 0.76 0.88 0.48 0.08 <0.01 0.01 7.06 98.76 19.58 0.907 D39018 43 56.19 17.25 3.95 3.23 8.94 4.32 0.35 2.55 0.03 1.04 0.19 0.03 0.01 0.04 3.81 98.71 3.55 0.909 D = duplicated sample, C = Chlorite is dominant in the sample, B = Biotite is dominant in the sample 594 B.10 Carbonate mineral identification using cathodoluminescence, scanning electron mi- croscopy and reactivity with acid This appendix consists of Table B.11which provides the identified carbonate mineral using elec- tron dispersion spectra (EDS), acid testing (reactivity with dilute (10%) HCl; effervesces = cal- cite, non-effervesce = dolomite/ankerite) and cathodoluminescence (CL) (bright red = calcite, dull orange red = dolomite/ankerite). For additional information on samples (e.g. location, altera- tion, etc) please refer to Appendix A.2. Table B.11 Carbonate mineral identification using SEM-EDS, CL and reactivity with acid Sample Depth SEM-EDS Acid CL Carbonate type 06L337 40 Ankerite microcrystalline carbonate 06L337 186 Ankerite Ankerite carbonate-quartz 06L337 448 Ankerite microcrystalline carbonate 11L086 266 Ankerite microcrystalline carbonate 11L086 417 Ankerite microcrystalline carbonate 11L086 1038 Ankerite microcrystalline carbonate 13L833 55 Ankerite Calcite carbonate-quartz 13L833 681.4 Ankerite carbonate-quartz 13L833 1237.8 Ankerite Ankerite coarse carbonate 16L1067 400.8 Ankerite amygdule and vein 16L1067 1208.1 Ankerite Micro=calcite, Coarse = Ankerite Textured vein 17L1437 152 No reaction pink dolomite 17L1437 556 Ankerite Calcite quartz-carbonate 17L1437 913 Ankerite carbonate 19L547 52.4 Ankerite Ankerite carbonate 19L547 495.8 Ankerite with minor calcite Ankerite carbonate-pyrrhotite 19L547 866.2 Calcite Calcite microcrystalline carbonate 24L755 64 Calcite quartz-carbonate 24L755 186 Calcite coarse carbonate 24L755 769 Ankerite Coarse - calcite, Fine = Ankerite Textured vein 30L1162 24.7 Ankerite Calcite amygdule and vein 30L1162 695 Ankerite microcrystalline carbonate 30L1162 1419 Ankerite microcrystalline carbonate and coarse carbonate 30L1268 25.7 No reaction carbonate-pyrrhotite 30L1268 327.9 Ankerite Calcite carbonate-chlorite 30L1268 574 Calcite Calcite quartz-carbonate-brown biotite 34L006 25 Ankerite Younger calcite vein deformed carbonate 34L006 706 No reaction microcrystalline carbonate 34L006 1235.1 Ankerite Ankerite microcrystalline carbonate 34L1352 28 Ankerite Ankerite carbonate 34L1352 315 Ankerite microcrystalline carbonate 34L1352 814 Calcite Calcite carbonate-chlorite 34L235 23.2 Calcite carbonate-quartz-chlorite 34L235 909.7 Ankerite microcrystalline carbonate 34L235 944 Ankerite Ankerite carbonate-brown biotite 34L235 1961 Ankerite carbonate-chlorite 595 Table B.11 (Continued) Sample Depth SEM-EDS Acid CL Carbonate type 34L814 195.7 Calcite and Ankerite Calcite microcrystalline carbonate 34L814 1147.4 Ankerite Calcite carbonate-chlorite 34L814 2333.4 Ankerite with minor calcite Calcite microcrystalline carbonate 37L482 91 Ankerite carbonate-quartz 37L482 1019 Ankerite with minor calcite Ankerite Recrystallized calcite carbonate-quartz-chlorite 37L482 2057 Ankerite Ankerite carbonate-chlorite 37L594 299 Ankerite coarse carbonate and pervasive 37L594 815 Ankerite Ankerite Calcite quartz-carbonate 37L594 1581 Ankerite Ankerite Green feld-spar microcrystalline carbonate 37L594 1609 Ankerite microcrystalline carbonate 37L667 25 Ankerite No reaction none 37L667 1067 Ankerite Calcite carbonate-chlorite 37L667 2054 Ankerite quartz-carbonate 37L726 400.7 Ankerite microcrystalline carbonate 37L726 836.6 No reaction none 37L768 66 Ankerite microcrystalline carbonate 37L768 98 Ankerite Ankerite Ankerite massive carbonate 37L768 1108 Ankerite quartz-carbonate 37L768 2005 Ankerite Calcite Calcite carbonate-chlorite BK0510 376.12 Calcite with minor ankerite Calcite carbonate-chlorite CB1925V1 Ankerite Ankerite Calcite and Ankerite quartz-carbonate CB302561 Ankerite Ankerite Calcite and Ankerite quartz-carbonate CB4043FV Ankerite with minor calcite Calcite Calcite and Ankerite carbonate-biotite CR4610 947 Calcite Calcite carbonate CR4611 581.4 Calcite Calcite Recrystallized calcite carbonate-pyrrhotite CR4612 360.3 No reaction none CR4613 1.3 Calcite with minor ankerite Calcite Calcite carbonate-chlorite-pyrrhotite CR464 31.2 No reaction microcrystalline carbonate CR466 145 None No reaction none CR467 86.3 Calcite No reaction microcrystalline carbonate CR468 629 Calcite Calcite Late calcite carbonate CR469 41.6 Fe-calcite Calcite Late calcite carbonate D14391 191 Ankerite carbonate-quartz D14391 1025 Ankerite pink dolomite D14391 1810 Ankerite carbonate-pyrrhotite D14391 2922 Ankerite Calcite Calcite microcrystalline carbonate D14981 3.2 Ankerite carbonate-quartz D14981 1045.2 Calcite microcrystalline carbonate D14981 1798.8 Ankerite with minor calcite Calcite Ankerite and calcite breccia carbonate D15367 85.3 Ankerite microcrystalline carbonate D15367 371.1 Ankerite Calcite Ankerite Textured vein D15367 793 Ankerite microcrystalline carbonate D16355 431 Ankerite carbonate-pyrite vine D16355 925.8 Ankerite microcrystalline carbonate D21708 139.3 Ankerite with minor calcite Calcite Ankerite and calcite microcrystalline carbonate 596 Table B.11 (Continued) Sample Depth SEM-EDS Acid CL Carbonate type D21708 1340 No reaction none D21708 2760 Calcite No reaction quartz-carbonate D22203 79 Ankerite microcrystalline carbonate D22203 908 Ankerite Coarse = calcite, Finer = Ankerite Ankerite breccia veins, textured vein D22203 1604 Ankerite microcrystalline carbonate D22223 38 Ankerite quartz-carbonate D22223 975 Ankerite with minor calcite Calcite Calcite Textured vein D22223 1932 Ankerite amygdules and pervasive D2252 162 Calcite amygdules and pervasive D2252 309 Calcite microcrystalline carbonate D2252 491 Ankerite microcrystalline carbonate D2253 75 Ankerite Ankerite microcrystalline carbonate D2253 252 Ankerite with minor calcite Ankerite microcrystalline carbonate D2253 495 Ankerite carbonate-quartz D239 95 Ankerite microcrystalline carbonate D239 217 Ankerite microcrystalline carbonate D2435 361 Ankerite microcrystalline carbonate D2435 454 Ankerite carbonate D27343 88 Calcite amygdules and veins D27343 501.3 Calcite Calcite Calcite microcrystalline carbonate D27343 1181.7 Ankerite carbonate-chlorite-pyrrhotite D27943 314 Ankerite carbonate-quartz D27943 933.8 Ankerite Ankerite coarse carbonate D27943 1779.5 Calcite carbonate-chlorite D27943 2104.2 Calcite with minor ankerite Calcite Ankerite and calcite carbonate-quartz D27943 2607.6 Calcite microcrystalline carbonate D27943 3389.5 Ankerite Calcite textured vein D33003 532 Ankerite carbonate-magnetite D33003 1106 Ankerite Ankerite Ankerite coarse carbonate D33003 2004 Ankerite with minor calcite Ankerite Ankerite and calcite textured vein D33003 3210 Ankerite Ankerite Ankerite coarse carbonate D39018 43 Ankerite Calcite Ankerite and calcite amygdules and veins D39018 635 No reaction none D39018 1325 Ankerite carbonate D39018 1820 Calcite Calcite Calcite carbonate-quartz D39018 2555 Calcite carbonate D39018 3050 Calcite No reaction pervasive D39018 3113 Calcite microcrystalline carbonate D39018 3562 Calcite Calcite Calcite carbonate-chlorite-quartz D39018 4848 Calcite Calcite Calcite carbonate-chlorite D39200 109 Ankerite carbonate-chlorite D39200 1469 None Ankerite microcrystalline carbonate D39200 3241 Calcite Calcite carbonate-chlorite D39204 19 Ankerite carbonate D39204 1032 Calcite Calcite pervasive and vein D39204 1333 Coarse = calcite, Finer = Ankerite carbonate-quartz D39357 37 Ankerite microcrystalline carbonate D39357 1287 No reaction microcrystalline carbonate D39357 1308 Ankerite Calcite Ankerite carbonate-chlorite D39357 2029 Ankerite microcrystalline carbonate D39357 2066 Ankerite amygdules DS11 103.4 No reaction none DS139 30.4 Ankerite Ankerite Ankerite textured veins 597 Table B.11 (Continued) Sample Depth SEM-EDS Acid CL Carbonate type DS139 323.3 Ankerite DS172 123.1 Calcite Calcite Calcite microcrystalline carbonate DS173 499.6 Calcite No reaction none DS174 708.4 Calcite Ankerite with calcite breccia DS177 460.5 No reaction quartz-carbonate DS177 613 Calcite Calcite quartz-carbonate DS177 1500.8 Calcite No reaction none DS180 400.2 No reaction none DS340 35.6 Ankerite carbonate-quartz DS340 297.3 Ankerite textured vein DS340 694.7 Ankerite microcrystalline carbonate DS343 90 Ankerite carbonate DS343 395 Ankerite microcrystalline carbonate DS343 696 Ankerite amygdules and veins DS352 25 Ankerite breccia DS352 341 Ankerite with minor calcite Calcite Ankerite carbonate-quartz DS352 512 No reaction quartz-carbonate DS358 132 Ankerite Ankerite Ankerite quartz-carbonate DS358 624 Ankerite carbonate-chlorite-pyrrhotite DS358 1215 Ankerite Ankerite Ankerite carbonate-quartz DS360 124 Ankerite microcrystalline carbonate DS360 528 Ankerite Ankerite Ankerite textured vein DS360 751 Ankerite carbonate DS615 1214.5 Ankerite quartz-tourmaline-carbonate DS615 1905.1 Calcite microcrystalline carbonate DS615 3001.1 Calcite carbonate DS615 4032.2 Calcite with minor ankerite Calcite Calcite carbonate ES09-AP-10 Ankerite Ankerite coarse and cryptocrystalline ES09-AP-20 Ankerite Ankerite Ankerite coarse and cryptocrystalline ES09-AP-23 Ankerite Ankerite Ankerite coarse carbonate ES09-AP-27 Ankerite Ankerite Ankerite coarse and cryptocrystalline ES09-AP-35 Ankerite Ankerite Ankerite coarse and cryptocrystalline ES09-AP-37 Ankerite Ankerite Ankerite coarse carbonate ES09-AP-49 Ankerite Ankerite Ankerite coarse and cryptocrystalline ES09-AP-6A Ankerite with minor calcite Ankerite Ankerite with minor calcite coarse carbonate GC01018 85.3 Calcite No reaction Calcite vein none GC01018 691.7 Ankerite coarse carbonate GC01018 1382.7 No reaction microcrystalline carbonate GC04002 239 No reaction textured vein GC04002 688 Calcite with ankerite GC04002 1522 Calcite microcrystalline carbonate GC04003 338 Ankerite Calcite Ankerite pervasive and vein GC04003 786.75 Ankerite Ankerite Ankerite coarse carbonate GC04003 1716 Calcite Calcite Calcite carbonate-quartz GC04007 134 Ankerite textured veins GC04007 911 Ankerite carbonate GC04007 2000 Calcite carbonate GC04007 2859 Calcite carbonate GC04007 3890 Ankerite Ankerite Ankerite coarse carbonate GC04007 4421 Ankerite and minor calcite Ankerite Ankerite microcrystalline carbonate GC95-010 350 No reaction carbonate-quartz GC95-010 939 Ankerite microcrystalline carbonate R87105 699.8 Calcite Calcite Calcite vein microcrystalline carbonate R87107 482.3 Calcite Calcite Calcite vein carbonate-quartz R87108 629.5 Calcite Calcite carbonate-chlorite-quartz RL434741B Ankerite and minor calcite Calcite Ankerite quartz-carbonate-brown biotite 598 B.11 Least altered samples and mass balance data This subset of four acid digestion whole rock geochemical data was used to calculate the mass balance difference (using the Gresens 1967 method) and the propagation area (Table B.12). Samples were chosen as those that contained one main alteration assemblage, e.g. for biotite-Ti- magnetite ± carbonate alteration no younger mineralization or veins were included. All samples selected are included: samples from this study combined with the subset of four acid digestion whole rock geochemistry from Bouzari (2009). For reference the X-Y co-ordinates and the main alteration assemblage information is included. The samples are arranged in paragenetic order of alteration assemblages (refer to Fig. 3.2). The samples of basalt, argillite and chert from Bouzari (2009) were referred to as the least altered and used as comparisons with the altered samples from the RLGM. Details of the least altered samples can be found in Bouzari (2009). Mass bal- ance for gold (Au) was not calculated as so few samples (From Bouzari, 2009) contained assay information. Note: For the least altered samples, no mass balance or propagation error was calculated as these were the reference samples 599 Table B.12 Subset of representative samples for mass balance calculations. Hole ID Depth (ft) Lithology Publication Loc X Loc Y Alteration 37L482 926 Basalt Bouzari (2009) 2854.1 3790.2 biotite-Ti-magnetite ± carbonate D27943 3389.5 Basalt Stock (2012) -2359.9 6720.1 biotite-Ti-magnetite ± carbonate D39204 481 Basalt Bouzari (2009) 2024.1 4155.8 biotite-Ti-magnetite ± carbonate D39018 43 Basalt Stock (2012) 2604.5 4233.7 biotite-Ti-magnetite ± carbonate D2253 75 Basalt Stock (2012) 2678.0 6725.2 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite R87107 482.3 Basalt Stock (2012) 17235.7 9626.8 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS172 123.1 B Basalt Stock (2012) 11736.5 9855.9 biotite-chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-calcite DS173 499.60 Basalt Stock (2012) 12840.8 9647.7 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L667 4 Basalt Bouzari (2009) 2542.3 4582.2 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L667 152 Basalt Bouzari (2009) 2660.7 4494.0 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L667 194 Basalt Bouzari (2009) 2694.1 4468.7 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D39200 3115 Basalt Bouzari (2009) -259.4 2809.2 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS352 134 Basalt Bouzari (2009) 3001.9 9942.5 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS358 32 Basalt Bouzari (2009) 718.0 9701.0 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite GC04007 2000 Basalt Bouzari (2009) 3349.7 8557.8 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite R87105 699.8 Basalt Stock (2012) 19181.7 9365.9 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 30L1268 25.7 Basalt Stock (2012) 5425.1 5605.5 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L726 836.6 Basalt Stock (2012) 4972.9 3937.0 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite CR466 145 Basalt Stock (2012) 19062.9 9843.9 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D14391 1810 Basalt Stock (2012) 4695.6 7982.9 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D39200 3241 Basalt Stock (2012) -380.3 2774.5 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D39357 1287 Basalt Bouzari (2009) 1251.0 3922.1 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS172 123.1 C Basalt Stock (2012) 11736.5 9855.9 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 19L547 495.8 Basalt Stock (2012) 7141.2 7210.2 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L482 118 Basalt Bouzari (2009) 2432.3 4477.7 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite CR4610 947 Basalt Stock (2012) 24961.1 9294.5 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D21708 2760 Basalt (two) Stock (2012) 4422.7 6725.1 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS177 1500.8 Basalt Stock (2012) 8420.4 9039.4 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS615 1905.1 Basalt (two) Stock (2012) 10395.2 8228.7 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite D33003 2004 Basalt Stock (2012) 670.8 5060.3 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite DS360 124 Basalt Bouzari (2009) 1752.8 9865.1 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite GC04007 2859 Basalt (two) Bouzari (2009) 3990.7 7991.4 chlorite-amphibole-garnet-epidote/clinozoisite-magnetite-biotite-calcite 37L667 1061 Basalt Bouzari (2009) 2423.4 3544.6 quartz-muscovite ± andalusite D39018 635 Basalt Bouzari (2009) 3194.6 4274.8 quartz-muscovite ± andalusite D39200 843 Basalt Bouzari (2009) 1789.7 3765.6 plagioclase D39200 1318 Basalt Bouzari (2009) 1380.1 3525.8 plagioclase CB4043HR Basalt Stock (2012) brown biotite-quartz ± carbonate ± sulfides D15367 5.5 Basalt Bouzari (2009) 2235.7 7817.2 brown biotite-quartz ± carbonate ± sulfides Abbreviations, B = biotite and C = chlorite, PE = Propagation error 600 Table B.12 (Continued) Hole ID Depth (ft) Lithology Publication Loc X Loc Y Alteration D39357 2067 Basalt Bouzari (2009) 472.1 3893.5 brown biotite-quartz ± carbonate ± sulfides D14391 2922 Basalt Bouzari (2009) 5786.4 7799.7 brown biotite-quartz ± carbonate ± sulfides CB25510LZ Basalt Bouzari (2009) brown biotite-quartz ± carbonate ± sulfides CB302561 Basalt Stock (2012) brown biotite-quartz ± carbonate ± sulfides 37L768 66 Basalt Bouzari (2009) 2225.9 4515.5 carbonate-quartz vein ± chlorite ± biotite selvage DS360 528 Basalt Bouzari (2009) 1914.7 9499.5 carbonate-quartz vein ± chlorite ± biotite selvage 17L1437 556 Basalt Bouzari (2009) 5891.0 7438.3 carbonate-quartz vein ± chlorite ± biotite selvage 24L755 64 Basalt Bouzari (2009) 6158.6 6483.4 carbonate-quartz vein ± chlorite ± biotite selvage 37L482 91 Basalt Bouzari (2009) 2419.4 4501.4 carbonate-quartz vein ± chlorite ± biotite selvage 37L594 299 Basalt Bouzari (2009) 1442.1 4289.5 carbonate-quartz vein ± chlorite ± biotite selvage 37L594 815 Basalt Bouzari (2009) 1527.4 3781.0 carbonate-quartz vein ± chlorite ± biotite selvage 37L768 98 Basalt Bouzari (2009) 2230.8 4484.1 carbonate-quartz vein ± chlorite ± biotite selvage D22203 908 Basalt Bouzari (2009) 1008.9 7140.9 carbonate-quartz vein ± chlorite ± biotite selvage D22223 975 Basalt Bouzari (2009) 3491.1 6859.2 carbonate-quartz vein ± chlorite ± biotite selvage D2435 454 Basalt Bouzari (2009) 2473.6 6417.6 carbonate-quartz vein ± chlorite ± biotite selvage D33003 3210 Basalt Bouzari (2009) -502.3 5324.3 carbonate-quartz vein ± chlorite ± biotite selvage D39018 1820 Basalt Bouzari (2009) 4379.0 4277.8 carbonate-quartz vein ± chlorite ± biotite selvage D39204 1333 Basalt Bouzari (2009) 1174.5 4126.6 carbonate-quartz vein ± chlorite ± biotite selvage GC04003 786.75 Basalt Bouzari (2009) 8615.1 9401.2 carbonate-quartz vein ± chlorite ± biotite selvage BK0510 376.12 Basalt Stock (2012) 18121.8 9676.8 carbonate-quartz vein ± chlorite ± biotite selvage D27943 2104.2 Basalt Stock (2012) -1150.4 6308.3 carbonate-quartz vein ± chlorite ± biotite selvage D39018 3562 Basalt Stock (2012) 6110.5 4143.8 carbonate-quartz vein ± chlorite ± biotite selvage GC04007 911 Basalt (two) Bouzari (2009) 2557.9 9301.4 carbonate-quartz vein ± chlorite ± biotite selvage RL422VG Basalt Stock (2012) quartz-sulfide ± carbonate vein D39200 1001 Basalt Bouzari (2009) 1654.5 3684.0 quartz-sulfide ± carbonate vein D39200 1064 Basalt Bouzari (2009) 1600.4 3651.8 quartz-sulfide ± carbonate vein 37L482 1347 Basalt (two) Bouzari (2009) 3673.4 3874.2 quartz-sulfide ± carbonate vein D39200 1406 Basalt Bouzari (2009) 1303.3 3483.2 quartz-sulfide ± carbonate vein DS352 390 Basalt Bouzari (2009) 3173.5 9752.8 quartz-sulfide ± carbonate vein 37L768 1108 Basalt Bouzari (2009) 2435.8 3499.4 quartz-sulfide ± carbonate vein DS352 305 Basalt Bouzari (2009) 3116.5 9815.8 quartz-sulfide ± carbonate vein 16L1067 267.9 Basalt Stock (2012) 3020.0 7220.0 quartz-sulfide ± carbonate vein CB1812M Basalt Stock (2012) 6188.8 7633.7 quartz-sulfide ± carbonate vein RL338261AO Basalt Stock (2012) 5911.5 5155.9 quartz-sulfide ± carbonate vein RL34875SO Basalt Stock (2012) 5568.6 4999.7 quartz-sulfide ± carbonate vein 5565.00 Basalt Bouzari (2009) 450037.0 5660331.0 least altered (basalt) 601 Table B.12 (Continued) Hole ID Depth (ft) Lithology Publication Loc X Loc Y Alteration CR-04-30 9.84 Basalt Bouzari (2009) 451748.5 5655648.2 least altered (basalt) DS196 396 Basalt Bouzari (2009) 445857.8 5657096.1 least altered (basalt) MB01-031 16.4 Basalt Bouzari (2009) 444876.1 5659239.2 least altered (basalt) CR-04-28 16.4 Basalt Bouzari (2009) 451160.5 5655579.2 least altered (basalt) GC01-015 49.87 Basalt Bouzari (2009) 450053.2 5657726.4 least altered (basalt) AB01196 65.62 Basalt Bouzari (2009) 446798.5 5661861.8 least altered (basalt) DS122 175.85 Basalt Bouzari (2009) 445173.5 5656929.0 least altered (basalt) MC02021 103.35 Basalt Bouzari (2009) 446520.1 5660246.8 least altered (basalt) MC-01-012 16.4 Basalt Bouzari (2009) 446549.2 5659890.9 least altered (basalt) IN8728 29.53 Basalt Bouzari (2009) 446983.4 5662082.5 least altered (basalt) 5554.00 Argillite Bouzari (2009) 449438.0 5656183.0 least altered (sediment) 5555.00 Argillite Bouzari (2009) 449612.0 5656336.0 least altered (sediment) CR-03-07 Argillite Bouzari (2009) 450748.5 5656728.2 least altered (sediment) CW06012 Argillite Bouzari (2009) 442790.0 5659040.0 least altered (sediment) CW06015 Argillite Bouzari (2009) 442720.0 5658860.0 least altered (sediment) CW06026 Argillite Bouzari (2009) 444050.0 5656413.0 least altered (sediment) CW06025 Argillite Bouzari (2009) 443271.0 5655594.0 least altered (sediment) CW02002 Argillite Bouzari (2009) 442704.5 5657518.6 least altered (sediment) SC99005 Argillite Bouzari (2009) 443531.2 5659047.5 least altered (sediment) CR-04-17 Argillite Bouzari (2009) 449824.5 5656118.2 least altered (sediment) CR-04-14 Argillite Bouzari (2009) 449674.5 5656058.2 least altered (sediment) GC98-006 Argillite Bouzari (2009) 449017.2 5654728.2 least altered (sediment) GC02-012 Argillite Bouzari (2009) 449096.7 5655078.5 least altered (sediment) GC02-013 Argillite Bouzari (2009) 449299.6 5655061.6 least altered (sediment) 5572.00 Argillite Bouzari (2009) 445881.0 5655929.0 least altered (sediment) GC98-005 Argillite Bouzari (2009) 449166.0 5655198.7 least altered (sediment) GC98-004 Argillite Bouzari (2009) 449132.0 5654994.9 least altered (sediment) GC02-011 Argillite Bouzari (2009) 449175.0 5655025.5 least altered (sediment) GC02-014 Argillite Bouzari (2009) 449235.0 5655041.5 least altered (sediment) 5540.00 Chert Bouzari (2009) 444868.0 5657966.0 least altered (sediment) 5545.00 Chert Bouzari (2009) 451172.0 5657765.0 least altered (sediment) 5546.00 Chert Bouzari (2009) 449393.0 5656658.0 least altered (sediment) 602 Table B.12 (Continued) Hole ID Depth (ft) Au_p pb Ag_ppm Al_pct As_ppm Ba_ppm Be_ppm Bi_ppm Ca_pct Cd_ppm Ce_ppm Co_pp m Cr_pp m Cs_pp m Cu_pp m 37L482 926 0.02 0.02 8.07 23.90 380 0.59 0.01 5.14 0.12 10.7 53.7 515 7.71 26.9 D27943 3389.5 0.02 8.32 3.40 1060 0.43 0.02 3.48 0.06 3.28 39.1 279 4.91 35.1 D39204 481 0.14 0.36 8.19 205.0 140 0.37 4.24 0.14 11.3 42.5 222 5.16 135.5 D39018 43 0.02 0.03 9.06 7.30 360 0.18 7.92 0.04 5.65 30.6 195 2.40 21.7 D2253 75 0.26 8.51 100.5 30 0.35 0.08 4.30 0.21 9.90 37.9 328 6.41 187.5 R87107 482.3 0.17 8.18 2.50 220 0.76 0.10 6.28 0.08 8.64 37.5 153 2.19 79.1 DS172 123.1 B 0.07 8.54 38.60 430 1.13 0.02 1.87 0.03 12.6 45.0 249 11.05 52.0 DS173 499.6 0.13 9.59 14.30 210 0.62 0.02 5.94 0.13 13.8 81.5 153 1.29 440 37L667 4 0.17 0.07 8.29 14.30 20 0.35 0.01 3.51 0.13 9.39 39.5 248 3.90 99.1 37L667 152 0.05 8.66 2.00 300 0.48 0.05 3.18 0.07 4.21 61.7 355 9.96 164 37L667 194 0.08 7.72 2.10 160 0.18 0.01 5.88 0.10 4.74 50.6 371 0.40 90.3 D39200 3115 0.07 0.14 7.65 72.9 350 0.41 0.02 6.32 0.29 9.99 54.1 121 5.23 138 DS352 134 0.02 0.10 8.00 7.10 290 0.34 0.01 5.80 0.12 11.25 39.2 253 7.02 172 DS358 321 0.02 0.20 8.53 44.9 190 0.45 0.01 4.65 0.78 6.50 31.3 396 7.49 62.8 GC04007 2000 0.07 9.96 4.20 130 0.39 0.01 2.19 0.07 13.1 48.5 255 13.85 211 R87105 699.8 0.42 7.30 5.10 50 0.42 0.10 4.63 0.09 11.9 54.6 164 0.59 151 30L1268 25.7 0.15 6.73 8.00 60 0.32 0.03 1.05 0.09 13.2 44.5 189 0.60 112 37L726 836.6 0.08 10.60 63.6 40 0.22 0.02 3.91 0.06 11.0 54.8 254 0.81 136 CR466 145 0.11 8.51 3.00 10 0.50 0.01 3.82 0.11 13.4 38.5 152 0.15 161 D14391 1810 0.02 0.08 9.24 54.1 20 0.22 <0.01 2.70 0.06 7.36 71.0 193 0.51 115 D39200 3241 0.12 9.69 196.5 30 0.72 0.01 5.10 0.15 11.6 66.9 156 0.13 104 D39357 1287 0.02 0.09 7.75 167.5 90 0.23 0.73 0.51 7.37 42.2 172 3.27 142 DS172 123.1 C 0.14 8.16 19.2 70 1.11 0.06 3.45 0.04 13.8 55.4 276 4.28 90.0 19L547 495.8 0.28 8.58 251.0 50 0.39 0.04 2.21 0.14 12.6 48.6 221 2.38 237 37L482 118 0.16 4.50 118.5 230 0.48 0.02 1.98 0.44 13.0 65.0 187 6.76 139 CR4610 947 0.14 8.78 3.40 180 0.52 0.06 4.11 0.08 6.6 58.9 181 2.45 236 D21708 2760 0.15 7.73 4.50 140 0.67 0.05 2.25 0.06 62.2 17.1 47 5.58 25.7 DS177 1500.8 0.14 10.15 59.50 70 0.35 0.07 4.43 0.22 14.5 90.3 239 8.73 401 DS615 1905.1 0.09 6.16 217.0 150 0.97 0.15 3.41 0.07 18.6 14.7 20 18.50 24.7 D33003 2004 0.15 8.36 30.3 100 1.32 0.02 7.48 0.17 20.4 49.1 39 9.66 94.0 DS360 124 0.23 7.24 48.9 30 0.24 0.01 8.70 0.15 5.18 34.6 245 1.31 190.5 GC04007 2859 0.06 7.45 1.90 80 1.20 0.02 4.88 0.08 63.3 27.8 61 1.66 59.7 37L667 1061 0.11 8.61 108.0 180 0.49 0.02 0.09 0.07 8.14 64.2 311 1.34 210 D39018 635 0.02 0.06 9.86 65.4 360 0.56 0.17 0.09 11.9 28.3 185 2.88 197 D39200 843 0.02 0.17 8.84 54.1 90 0.38 0.02 4.29 0.14 13.8 62.2 196 3.74 237 D39200 1318 0.02 0.07 9.62 38.9 60 0.27 0.01 2.15 0.07 9.59 28.8 151 5.26 52.2 CB4043HR 5.94 7.61 362.0 90 0.55 0.15 7.77 0.23 7.50 52.0 295 3.76 283 D15367 5.5 1.12 6.97 742.0 200 1.21 0.19 7.91 0.15 6.77 41.1 226 5.17 95.6 603 Table B.12 (Continued) Hole ID Depth (ft) Au_pp b Ag_pp m Al_pc t As_ppm Ba_pp m Be_pp m Bi_pp m Ca_pc t Cd_pp m Ce_pp m Co_pp m Cr_pp m Cs_pp m Cu_pp m D39357 2067 1.87 7.75 10.8 80 1.01 0.55 6.84 0.24 12.1 49.6 262 5.54 248 D14391 2922 0.02 0.04 7.79 90.1 190 0.31 0.01 5.09 0.10 9.45 22.0 138 2.88 72.3 CB25510LZ 1.43 5.71 185.5 180 0.75 0.20 9.40 0.26 5.57 147.0 264 4.36 155 CB302561 6.35 5.81 10000 100 0.52 0.06 5.89 0.14 11.4 59.2 332 3.73 296 37L768 66 0.02 0.07 1.79 638.0 0.10 6.51 0.16 7.89 48.7 77 0.48 83.8 DS360 528 0.09 0.98 7140.0 0.21 0.03 10.90 0.27 4.03 28.0 39 0.23 100 17L1437 556 0.02 0.04 1.69 39.0 20 0.21 0.04 14.20 0.24 3.93 12.1 69 0.68 31.8 24L755 64 0.02 0.09 4.68 43.0 30 0.28 0.01 8.00 0.09 5.22 29.5 52 2.43 76.5 37L482 91 0.02 0.25 4.33 12.5 20 0.23 0.01 7.01 0.28 11.8 23.5 141 1.00 90.1 37L594 299 0.02 0.05 1.52 27.0 30 0.28 0.05 15.40 0.16 4.45 22.3 36 1.39 32.2 37L594 815 0.10 0.03 1.77 16.0 30 0.26 0.03 12.10 0.23 4.54 19.7 76 2.21 14.7 37L768 98 0.02 0.01 0.36 2.5 0.16 17.50 0.15 1.85 9.2 13 0.32 5.3 D22203 908 0.02 0.02 1.63 16.0 20 0.34 0.01 13.10 0.06 7.70 12.5 13 0.94 6.0 D22223 975 0.07 2.06 100.0 10 0.18 15.35 0.43 8.39 39.8 52 0.32 221 D2435 454 0.21 0.40 1.37 395.0 20 0.48 0.08 13.30 0.14 2.60 34.2 662 1.31 30.3 D33003 3210 0.03 0.02 0.15 5.00 10 0.66 19.75 0.18 3.08 3.3 1 0.08 2.9 D39018 1820 0.02 0.02 1.80 82.0 70 0.19 0.03 27.30 0.06 3.43 19.1 199 1.10 34.3 D39204 1333 0.02 0.04 1.31 156.0 10 0.59 12.85 0.13 3.84 10.0 36 0.44 18.0 GC04003 787 0.02 0.03 0.21 9.00 10 0.01 18.50 0.38 2.56 24.2 119 0.40 66.5 BK0510 376 0.21 7.41 1.50 70 0.81 0.06 5.61 0.20 8.53 24.2 86 1.79 14.6 D27943 2104 0.07 9.12 1.40 410 0.94 0.01 6.06 0.07 8.15 37.2 331 4.74 109 D39018 3562 0.09 9.68 37.5 170 0.45 0.01 8.86 0.10 7.79 62.7 164 10.25 35.3 GC04007 911 0.02 0.07 8.13 4.40 460 0.92 0.04 4.51 0.10 71.2 23.9 9 8.09 44.5 RL422VG 106.00 0.95 10000 50 0.30 7.37 3.65 2.46 4.20 91.6 151 0.53 1415 D39200 1001 2.51 2.96 22.8 80 0.22 0.17 6.81 1.26 5.12 29.5 53 1.40 265 D39200 1064 0.02 2.45 3.76 167.5 80 0.36 0.08 0.76 0.58 16.1 85.6 122 4.94 197 37L482 1347 0.99 4.70 241.0 70 0.36 0.58 1.01 0.97 20.0 46.5 53 1.26 172 D39200 1406 0.02 0.12 8.69 55.2 50 0.20 0.02 0.33 0.07 8.85 10.9 169 1.03 135 DS352 390 0.02 0.04 7.72 18.70 30 0.38 0.01 4.78 0.06 11.8 47.8 497 0.88 24.9 37L768 1108 3.98 1.44 4.94 5.90 220 0.54 0.11 2.42 0.26 8.70 64.9 195 1.76 178 DS352 305 0.07 0.66 5.75 51.0 150 0.60 0.27 10.30 0.41 8.12 40.4 170 2.87 183 16L1067 268 2.90 6.09 10000 240 0.49 0.18 1.11 3.23 5.11 45.2 173 5.92 303 CB1812M 0.52 7.60 298.0 110 1.33 0.18 1.77 0.06 7.11 57.1 253 5.10 107 RL338261A O 6.97 3.86 10000 100 0.71 0.20 1.21 1.13 5.40 25.9 161 2.70 24.1 RL34875SO 2.44 6.54 1120.0 40 0.42 0.03 4.05 0.20 6.83 45.8 144 2.04 86.9 5565.00 0.14 7.72 0.80 40 0.24 0.03 8.79 0.13 8.21 43.0 115 0.07 191 604 Table B.12 (Continued) Hole ID Depth (ft) Au_pp b Ag_pp m Al_pc t As_ppm Ba_pp m Be_pp m Bi_pp m Ca_pc t Cd_pp m Ce_pp m Co_pp m Cr_pp m Cs_pp m Cu_pp m CR-04-30 10 0.08 8.92 2.20 30 0.26 7.29 0.14 8.10 55.2 211 0.16 148 DS196 396 0.05 8.38 3.10 50 0.25 0.01 7.31 0.06 7.17 52.6 293 0.30 137 MB01- 031 16 0.04 7.18 8.30 30 0.16 0.01 8.16 0.11 7.30 55.5 353 3.90 151 CR-04-28 16 0.10 7.77 51.1 90 0.21 0.02 7.56 0.10 6.16 57.7 140 1.80 161 GC01-015 50 0.08 8.57 4.70 20 0.26 7.52 0.14 11.3 54.9 131 0.28 152 AB01196 66 0.06 8.10 7.00 10 0.33 0.01 6.53 0.12 10.1 52.7 159 0.24 120 DS122 176 0.03 7.81 34.2 30 0.39 0.01 6.64 0.07 12.3 52.1 186 1.37 150 MC02021 103 0.04 7.93 2.60 10 0.22 0.01 4.06 0.05 10.2 47.6 201 1.15 77.3 MC-01- 012 16 0.08 8.23 18.0 30 0.31 0.17 7.10 0.05 10.9 44.5 256 0.18 99.0 IN8728 30 0.06 7.43 4.30 220 0.32 0.01 6.42 0.04 10.1 48.0 115 0.15 140 5554.00 0.02 8.00 10.1 1050 1.28 0.22 0.57 0.04 49.1 2.1 7 4.58 11.9 5555.00 0.05 11.35 45.2 1060 1.12 0.67 0.64 0.09 58.1 23.4 150 4.55 38.1 CR-03-07 0.16 8.61 12.7 770 1.40 0.90 1.42 0.33 52.3 22.9 85 4.15 53.1 CW06012 0.15 8.15 37.0 300 1.45 0.36 1.03 0.08 27.4 39.6 125 4.18 93.5 CW06015 0.07 6.67 22.1 470 0.93 0.23 1.80 0.05 42.6 15.7 31 2.12 17.1 CW06026 0.08 6.48 27.8 290 0.68 0.17 3.85 0.16 29.7 17.4 50 4.30 59.6 CW06025 0.14 8.31 18.7 560 1.17 0.20 2.40 0.14 57.8 24.6 85 3.71 51.2 CW02002 0.27 6.81 78.4 150 1.45 0.16 0.54 1.00 36.3 22.9 34 6.14 82.0 SC99005 0.07 9.73 19.9 330 2.20 0.16 0.31 52.9 15.2 94 13.40 26.1 CR-04-17 0.08 7.08 2.10 1420 1.24 1.48 0.43 0.26 77.3 10.4 42 2.23 33.6 CR-04-14 0.08 9.13 6.70 1080 1.31 0.24 0.44 0.35 45.8 25.3 126 5.79 50.4 GC98-006 0.05 8.19 27.2 760 1.68 0.23 0.78 0.05 85.8 19.2 67 3.47 32.5 GC02-012 0.07 9.48 11.20 740 1.39 0.32 0.34 0.10 60.8 16.0 55 4.21 34.3 GC02-013 0.03 9.42 2.30 650 0.98 0.39 0.24 0.21 68.2 12.3 68 5.33 19.3 5572.00 0.03 6.90 29.7 90 0.26 0.01 2.07 0.19 7.55 29.9 198 3.24 95.8 GC98-005 0.01 7.47 3.10 590 1.36 0.05 1.07 0.05 70.4 13.1 30 3.71 22.1 GC98-004 0.05 7.91 7.80 490 1.22 0.17 1.72 0.09 33.3 9.9 20 2.59 26.5 GC02-011 0.05 9.24 7.00 1060 1.25 0.07 0.74 0.03 67.9 4.0 15 3.51 8.2 GC02-014 0.06 7.22 5.00 1030 0.86 0.04 1.43 0.09 78.2 8.1 27 3.16 17.3 5540.00 0.12 4.90 32.1 80 0.39 0.09 0.07 0.03 36.4 12.3 10 0.55 95.0 5545.00 0.09 0.08 159.5 30 0.48 0.02 0.13 0.10 2.63 1.7 19 0.20 57.4 5546.00 0.04 0.10 34.8 50 0.37 0.02 0.13 0.05 1.74 1.6 22 0.11 5.5 605 Table B.12 (Continued) Hole ID Depth (ft) Fe_pc t Ga_pp m Ge_pp m Hf_pp m In_pp m K_pc t La_pp m Li_pp m Mg_pc t Mn_pp m Mo_pp m Na_pc t Nb_pp m Ni_pp m 37L482 926 9.22 19.0 0.15 1.2 0.068 1.06 3.8 72.0 3.23 1570 0.19 0.68 3.4 237 D27943 3389.5 5.14 18.1 0.05 1.3 0.045 3.07 1.2 42.8 3.10 510 0.11 0.65 1.2 95 D39204 481 8.93 15.4 0.16 1.8 0.103 1.11 3.9 58.8 3.33 1320 0.48 0.12 2.7 103 D39018 43 3.63 16.5 0.11 2.3 0.017 2.55 2.1 45.7 3.31 1830 0.29 0.24 1.1 103 D2253 75 8.34 18.8 0.18 2.0 0.076 0.28 3.8 12.1 3.14 2020 0.19 0.15 3.3 146 R87107 482.3 7.53 22.5 0.14 2.2 0.085 0.93 3.2 61.8 3.45 1820 0.42 0.54 4.4 103 DS172 123.1 B 14.15 21.5 0.20 1.7 0.067 2.56 6.2 90.6 1.93 5500 0.21 0.18 2.0 133 DS173 499.6 13.6 22.1 0.24 2.0 0.110 0.82 5.4 16.8 3.35 4860 0.32 0.34 3.9 144 37L667 4 8.96 18.7 0.13 1.4 0.070 0.14 3.1 38.6 2.71 2120 0.94 0.22 2.7 102 37L667 152 9.07 20.6 0.11 1.7 0.085 1.10 1.4 137 2.83 1370 0.30 1.32 2.7 147 37L667 194 7.70 14.4 0.12 1.1 0.045 0.07 1.8 124 6.04 1340 0.31 1.51 1.6 111 D39200 3115 7.05 16.1 0.12 1.3 0.071 0.69 3.9 77.3 2.84 1505 0.48 0.74 3.3 117 DS352 134 8.85 16.8 0.14 1.9 0.067 1.26 4.4 77.9 3.83 1455 0.38 0.85 3.4 83 DS358 321 5.84 14.8 0.11 1.0 0.044 1.21 2.7 131.5 3.39 1370 1.01 0.19 1.2 143 GC04007 2000 10.1 20.4 0.17 2.0 0.070 1.10 5.5 69.0 1.97 1010 0.31 1.04 3.6 207 R87105 699.8 8.51 15.9 0.13 1.3 0.054 0.24 4.6 80.3 5.31 2260 0.21 2.79 3.1 100 30L1268 25.7 16.2 15.7 0.25 1.4 0.065 0.14 6.2 31.9 2.39 4170 0.30 0.06 2.3 112 37L726 836.6 9.62 24.4 0.22 2.4 0.147 0.12 3.8 93.4 3.70 2050 0.15 0.24 3.5 167 CR466 145 10.1 22.4 0.20 1.9 0.111 0.08 4.9 15.9 2.47 1610 0.33 0.17 4.8 52 D14391 1810 10.7 19.8 0.12 2.0 0.048 0.06 2.9 63.1 3.04 3110 0.61 0.07 4.2 220 D39200 3241 8.04 22.6 0.09 1.2 0.080 0.03 4.2 26.3 2.79 2180 0.27 0.21 4.0 141 D39357 1287 9.90 16.0 0.20 1.9 0.062 0.74 2.7 32.2 2.29 1340 0.35 0.07 2.7 85 DS172 123.1 C 16.7 21.4 0.25 1.4 0.072 0.41 7.0 69.3 2.21 6670 0.24 0.05 1.8 152 19L547 495.8 18.4 21.1 0.31 1.6 0.053 0.37 5.8 39.3 3.40 2910 0.31 0.11 3.6 177 37L482 118 30.3 13.1 1.30 0.6 0.047 0.63 5.8 44.1 2.93 7430 0.46 0.12 1.6 209 CR4610 947 8.95 23.2 0.20 2.5 0.093 1.29 2.2 27.2 1.48 1600 0.50 1.59 4.7 111 D21708 2760 11.80 19.0 0.25 2.9 0.027 0.91 34.6 54.8 1.44 3670 0.95 1.33 6.6 53 DS177 1500.8 10.8 25.1 0.18 1.8 0.092 0.17 4.8 60.6 2.66 5220 0.27 0.73 3.8 267 DS615 1905.1 19.3 16.6 0.26 1.5 0.015 2.11 9.7 45.8 1.48 5210 1.18 0.20 2.6 23 D33003 2004 10.3 20.9 0.15 2.9 0.115 0.91 8.2 156.5 3.71 3030 0.41 0.45 5.8 64 DS360 124 5.62 12.4 0.11 0.9 0.048 0.14 2.0 33.8 3.95 2270 0.34 0.18 0.9 87 GC04007 2859 4.93 19.6 0.11 3.3 0.043 0.07 29.0 54.6 2.22 781 0.15 3.76 6.2 75 37L667 1061 0.97 22.3 0.07 1.8 0.050 0.46 3.7 12.3 0.08 95 0.44 0.12 2.2 207 D39018 635 0.79 23.9 0.08 2.6 0.093 4.74 4.3 9.20 0.14 56 0.23 0.19 3.5 60 D39200 843 8.04 17.9 0.12 2.3 0.092 0.51 5.6 65.5 2.33 1860 0.35 0.08 4.2 168 D39200 1318 3.60 22.2 0.07 2.3 0.066 0.66 3.8 48.4 1.20 571 0.32 0.08 3.6 58 CB4043H R 8.70 16.9 0.09 1.5 0.066 1.03 3.0 86.5 4.26 1800 0.42 0.19 2.6 160 D15367 5.5 7.87 16.8 0.11 1.3 0.045 1.44 2.7 41.1 3.23 1270 5.58 0.23 1.6 131 606 Table B.12 (Continued) Hole ID Depth (ft) Fe_pc t Ga_pp m Ge_pp m Hf_pp m In_pp m K_pc t La_pp m Li_pp m Mg_pc t Mn_pp m Mo_pp m Na_pc t Nb_pp m Ni_pp m D39357 2067 10.3 20.6 0.20 1.8 0.053 0.38 4.8 35.1 2.95 1365 72.80 0.54 2.9 181 D14391 2922 2.86 19.3 0.10 1.6 0.117 3.58 4.1 12.1 2.06 788 0.17 0.21 2.8 136 CB25510LZ 10.1 13.6 0.17 0.8 0.054 1.39 2.2 111.5 5.29 2120 0.11 0.48 0.8 283 CB302561 7.72 16.0 0.12 1.4 0.058 0.85 4.2 40.6 2.73 1260 0.54 0.24 1.7 234 37L768 66 31.6 3.63 0.38 0.3 0.024 0.01 3.3 8.50 7.23 8460 0.66 0.02 0.6 165 DS360 528 18.8 2.74 0.19 0.2 0.038 0.01 1.8 2.90 6.85 4860 0.11 0.01 0.3 68 17L1437 556 6.11 3.88 0.09 0.4 0.022 0.16 1.5 50.7 6.54 2920 0.26 0.07 0.6 62 24L755 64 6.15 9.05 0.10 0.8 0.044 0.24 2.2 57.4 3.89 2160 0.56 0.13 1.3 85 37L482 91 5.13 8.21 0.10 0.5 0.044 0.06 4.7 15.4 2.78 1695 0.27 0.08 1.3 56 37L594 299 6.20 3.54 0.10 0.3 0.015 0.29 1.7 21.3 7.15 2360 0.13 0.14 0.4 53 37L594 815 6.02 5.07 0.09 0.4 0.016 0.34 1.9 24.1 5.31 3340 0.19 0.20 0.5 65 37L768 98 6.06 1.01 0.09 0.1 0.008 0.02 0.8 5.80 8.58 2740 0.29 0.03 0.2 19 D22203 908 6.17 4.68 0.10 0.6 0.034 0.26 3.8 6.00 5.98 3090 0.50 0.03 1.2 24 D22223 975 7.73 4.53 0.10 0.6 0.039 0.02 3.6 24.3 6.84 3550 1.20 0.02 1.1 235 D2435 454 5.43 4.66 0.11 0.3 0.022 0.23 1.1 27.6 6.22 2160 2.93 0.17 0.4 304 D33003 3210 4.47 0.72 0.07 0.1 0.014 0.02 1.3 6.30 10.30 1855 0.17 0.02 0.2 9 D39018 1820 3.30 4.28 0.06 0.5 0.021 0.30 1.6 15.9 0.51 5670 0.15 0.19 0.8 75 D39204 1333 6.65 5.75 0.10 0.1 0.011 0.08 1.8 15.6 5.87 2030 0.52 0.02 0.4 35 GC04003 787 2.70 0.66 0.05 0.005 0.01 1.1 12.4 12.20 5080 0.34 0.04 0.1 159 BK0510 376 4.36 18.7 0.17 1.8 0.042 0.70 3.5 21.7 2.62 988 0.66 0.89 1.6 53 D27943 2104 7.25 17.8 0.05 1.2 0.064 2.29 3.1 78.6 2.99 1680 0.13 0.49 2.4 101 D39018 3562 8.89 20.3 0.13 1.3 0.065 1.72 2.8 68.0 4.43 1660 0.15 0.68 3.0 129 GC04007 911 5.54 22.3 0.10 4.3 0.059 1.46 30.8 85.0 1.72 848 0.93 2.49 5.2 32 RL422VG 14.8 3.82 0.72 0.2 0.220 0.30 2.6 17.0 1.65 557 0.33 0.05 0.3 500 D39200 1001 24.5 7.69 0.34 0.7 0.059 0.45 2.1 19.9 3.09 2270 1.33 0.08 1.4 1170 D39200 1064 31.4 9.30 0.44 1.0 0.061 1.23 6.9 53.3 2.44 4090 1.03 0.08 1.9 172 37L482 1347 20.3 12.4 0.31 2.1 0.215 0.75 10.0 71.9 2.02 2550 3.24 0.09 3.6 159 D39200 1406 0.91 18.9 1.9 0.032 0.32 3.5 7.40 0.11 91 0.45 0.02 1.6 24 DS352 390 8.95 17.7 0.14 1.3 0.067 0.08 4.4 64.4 3.38 1755 0.27 0.12 3.6 235 37L768 1108 7.24 14.0 0.16 1.3 0.037 1.52 3.7 28.6 1.31 768 1.74 0.13 1.7 183 DS352 305 8.53 12.9 0.14 1.5 0.050 0.93 3.2 22.9 4.49 1780 5.40 0.12 1.4 101 16L1067 268 5.27 13.7 0.05 0.9 0.075 1.45 2.7 50.5 0.64 175 0.18 0.18 1.3 94 CB1812M 7.47 15.4 0.13 0.9 0.050 1.16 2.8 111.0 1.18 704 0.90 0.38 2.1 108 RL338261A O 3.71 14.6 0.05 0.9 0.083 1.22 2.2 24.9 0.58 136 0.13 0.12 0.7 78 RL34875SO 9.48 13.5 0.18 0.8 0.063 0.28 2.6 37.2 1.57 1710 2.74 0.14 1.8 108 5565.00 9.50 19.4 0.27 0.8 0.060 0.10 3.4 16.7 4.44 2560 0.23 1.85 2.4 61 607 Table B.12 (Continued) Hole ID Depth (ft) Fe_pc t Ga_pp m Ge_pp m Hf_pp m In_pp m K_pc t La_pp m Li_pp m Mg_pc t Mn_pp m Mo_pp m Na_pc t Nb_pp m Ni_pp m CR-04-30 10 8.43 18.5 0.10 0.6 0.067 0.10 3.0 39.2 4.62 1470 0.33 1.49 2.3 172 DS196 396 8.35 16.7 0.12 0.8 0.063 0.09 2.8 22.5 4.91 1550 0.31 2.01 2.3 92 MB01-031 16 8.32 13.9 0.11 0.7 0.057 0.20 2.8 91.3 5.80 1480 0.13 0.65 1.7 177 CR-04-28 16 8.53 16.3 0.10 0.7 0.058 0.29 2.4 32.1 4.35 1445 0.36 1.91 1.6 102 GC01-015 50 8.94 19.0 1.1 0.072 0.07 4.4 44.8 3.37 1050 0.29 1.28 3.2 118 AB01196 66 8.82 17.2 0.11 1.3 0.074 0.09 3.7 36.1 4.44 1500 0.27 1.50 2.5 150 DS122 176 8.16 16.0 0.10 1.6 0.061 0.04 5.2 27.5 4.37 1490 0.26 2.65 2.6 107 MC02021 103 9.66 19.6 0.14 1.9 0.060 0.10 4.0 57.7 4.51 1330 0.15 2.64 3.4 105 MC-01- 012 16 6.74 14.0 0.08 1.4 0.057 0.07 5.1 18.8 4.91 1375 0.18 1.53 1.9 104 IN8728 30 8.46 16.9 0.10 0.9 0.066 0.08 4.0 61.5 3.83 1330 0.23 1.80 2.8 110 5554.00 0.99 20.9 0.14 5.2 0.029 1.98 27.1 16.1 0.17 82 0.48 3.10 8.5 3 5555.00 3.33 28.8 0.21 4.2 0.109 3.76 30.3 21.2 0.58 645 1.88 1.14 7.8 58 CR-03-07 3.43 22.1 0.09 3.4 0.051 2.78 28.0 36.3 0.82 577 2.72 1.02 7.6 98 CW06012 6.81 20.9 0.20 3.1 0.074 1.96 12.7 58.0 1.20 1320 1.07 1.56 4.8 83 CW06015 1.74 16.8 0.11 2.5 0.020 1.61 22.4 24.1 0.87 265 1.27 1.17 3.9 23 CW06026 5.39 15.9 0.17 2.4 0.038 1.10 14.4 68.9 1.43 1190 0.78 1.09 3.2 45 CW06025 4.02 23.5 0.17 3.7 0.063 2.24 27.2 51.0 1.12 725 1.42 1.32 3.4 68 CW02002 5.38 19.1 0.15 5.3 0.124 1.36 17.1 149 0.55 649 2.14 0.66 5.1 66 SC99005 3.45 25.4 0.15 5.4 0.081 2.93 26.3 101 0.72 907 2.88 0.58 4.4 135 CR-04-17 1.09 19.7 0.10 5.1 0.056 2.86 40.6 17.2 0.27 77 2.92 0.41 8.9 30 CR-04-14 6.23 24.0 0.15 4.5 0.161 4.04 24.9 26.3 0.51 1260 3.02 0.77 7.2 76 GC98-006 1.69 22.1 0.16 7.0 0.035 2.83 47.0 25.3 0.39 232 2.42 1.42 9.8 45 GC02-012 2.50 24.8 5.0 0.044 2.93 31.6 57.1 0.95 130 1.58 0.80 8.0 42 GC02-013 4.08 24.4 0.05 4.6 0.087 2.72 35.5 33.8 0.54 963 1.67 0.48 7.2 27 5572.00 10.3 15.2 0.27 1.5 0.057 0.53 3.0 34.8 1.53 3290 0.21 1.13 2.2 100 GC98-005 1.66 20.1 0.15 4.9 0.028 2.18 38.3 27.9 0.39 182 0.84 1.71 8.2 44 GC98-004 2.26 21.5 0.13 3.4 0.015 1.84 17.4 37.3 0.50 585 0.53 2.35 5.9 15 GC02-011 1.58 23.6 5.3 0.026 3.18 34.5 33.9 0.35 208 2.02 1.61 6.7 15 GC02-014 1.75 16.1 3.8 0.023 2.19 42.2 20.7 0.35 356 1.13 2.28 6.1 21 5540.00 10.6 11.8 0.24 6.2 0.101 0.40 16.7 43.5 1.75 1470 0.60 0.06 5.1 40 5545.00 9.11 0.96 0.16 0.005 0.01 1.5 1.20 0.34 1015 0.23 0.01 0.2 8 5546.00 12.1 0.65 0.21 0.1 0.011 0.01 1.0 0.90 0.23 1550 0.30 0.01 0.3 4 608 Table B.12 (Continued) Hole ID Depth (ft) P_pp m Pb_pp m Rb_pp m Re_pp m S_pc t Sb_pp m Sc_pp m Se_pp m Sn_pp m Sr_pp m Ta_pp m Te_pp m Th_pp m Ti_pc t 37L482 926 380 4.4 39.3 0.06 12.9 49.1 2 0.9 120 0.2 0.5 0.615 D27943 3389.5 250 2.1 36.5 0.23 2.58 39.7 2 0.4 89.1 0.08 0.2 0.346 D39204 481 390 3.5 34.2 0.002 0.30 90.0 77.2 2 0.6 137 0.15 0.06 0.4 0.526 D39018 43 170 1.1 42.4 0.005 0.01 1.88 37.6 2 0.2 25.3 0.08 0.4 0.473 D2253 75 360 2.6 14.6 0.002 0.31 32.6 42.6 2 0.6 66.3 0.21 0.06 0.6 0.658 R87107 482.3 550 5.1 12.6 0.003 0.03 3.04 38.1 2 0.9 174 0.26 0.08 0.5 0.818 DS172 123.1 B 360 2.2 103.5 0.03 4.48 63.8 3 0.5 182 0.13 0.5 0.530 DS173 499.6 550 0.8 14.1 0.003 0.45 3.54 58.0 4 1.0 49.6 0.21 0.05 0.4 0.741 37L667 4 290 1.9 3.2 0.002 0.20 23.8 46.6 2 0.7 32.1 0.17 0.4 0.540 37L667 152 190 2.3 15.6 0.002 0.25 10.6 60.4 2 0.8 116.5 0.17 0.05 0.3 0.555 37L667 194 220 1.3 1.2 0.02 8.92 48.1 2 0.6 254 0.1 0.2 0.341 D39200 3115 420 2.3 23.1 0.15 12.1 42.9 2 0.7 224 0.2 0.3 0.623 DS352 134 340 4.2 49.3 0.09 13.0 38.3 2 0.6 159 0.21 0.5 0.605 DS358 321 220 2.0 35.6 0.14 19.75 41.8 1 0.3 58.4 0.09 0.11 0.3 0.173 GC04007 2000 400 1.1 27.2 0.03 5.80 34.1 0.8 93.1 0.22 0.7 0.580 R87105 699.8 310 8.8 4.1 0.03 2.04 30.5 2 0.5 380 0.18 0.1 0.6 0.422 30L1268 25.7 210 1.1 5.8 0.003 0.66 19.25 65.5 3 0.3 52.5 0.16 0.11 0.3 0.463 37L726 836.6 670 2.2 4.1 0.007 0.26 16.0 67.5 3 0.8 108 0.22 0.4 0.755 CR466 145 650 1.4 0.7 0.003 0.08 1.87 47.5 3 1.1 32.6 0.32 0.4 0.887 D14391 1810 420 1.5 1.7 0.003 0.28 28.9 42.4 3 0.3 34.0 0.25 0.6 0.698 D39200 3241 500 3.5 0.5 0.003 0.21 12.1 62.6 4 0.7 83.9 0.23 0.3 0.773 D39357 1287 340 1.4 17.9 0.002 0.12 60.3 30.9 2 0.4 42.3 0.19 0.4 0.561 DS172 123.1 C 320 1.5 15.6 0.10 9.32 60.8 3 0.6 332 0.11 0.06 0.4 0.474 19L547 495.8 380 2.3 10.5 0.002 0.73 57.1 46.8 3 0.8 31.9 0.24 0.6 0.531 37L482 118 80 1.4 26.2 0.48 34.1 43.8 3 0.5 22.9 0.09 0.06 0.2 0.286 CR4610 947 420 2.4 31.2 0.003 0.29 0.67 48.3 3 1.0 198 0.29 0.1 0.4 0.852 D21708 2760 400 10.1 47.9 0.77 1.13 10.4 2 0.9 133.5 0.54 9.2 0.297 DS177 1500.8 270 1.3 5.0 0.003 0.49 3.90 60.4 5 0.7 85.1 0.23 0.08 0.3 0.775 DS615 1905.1 180 4.2 60.2 0.11 3.29 3.8 1 0.5 86.9 0.18 0.07 1.8 0.100 D33003 2004 760 3.3 38.4 0.002 0.11 17.45 57.6 4 1.2 228 0.34 0.05 0.9 0.943 DS360 124 190 1.6 3.9 0.05 12.85 49.4 1 0.2 39.3 0.07 0.2 0.181 GC04007 2859 940 7.0 2.4 0.002 0.24 1.88 16.7 2 1.0 352 0.39 4.2 0.505 37L667 1061 130 3.6 21.0 0.28 26.3 18.4 2 0.7 72.8 0.16 0.6 0.453 D39018 635 620 0.9 79.4 0.002 0.16 3.38 37.0 2 0.9 29.9 0.24 0.4 0.771 D39200 843 520 7.3 18.9 0.002 0.48 35.3 42.5 2 0.6 59.3 0.27 0.7 0.678 D39200 1318 520 5.9 18.9 0.60 18.3 23.6 2 0.8 52.0 0.24 0.6 0.739 CB4043HR 330 5.0 38.9 1.36 18.55 38.2 2 1.1 164 0.17 0.78 0.4 0.523 D15367 5.5 260 3.9 40.9 0.002 4.78 13.45 30.8 3 0.6 160 0.1 1.76 0.3 0.378 609 Table B.12 (Continued) Hole ID Depth (ft) P_pp m Pb_pp m Rb_pp m Re_pp m S_pct Sb_pp m Sc_pp m Se_pp m Sn_pp m Sr_pp m Ta_pp m Te_pp m Th_pp m Ti_pc t D39357 2067 280 6.9 14.2 0.004 3.12 11.95 41.6 3 1.3 142.5 0.22 1.72 0.5 0.584 D14391 2922 460 0.8 72.9 0.02 3.49 46.8 2 1.0 53.2 0.2 0.3 0.590 CB25510LZ 30 7.9 46.8 4.24 7.85 58.6 5 0.4 140.5 0.05 0.8 0.2 0.238 CB302561 180 9.1 28.7 0.002 2.92 60.9 26.8 8 1.1 84.4 0.11 8.36 0.4 0.341 37L768 66 80 0.5 0.5 0.69 53.2 61.6 1 24.7 0.05 0.101 DS360 528 80 1.1 0.1 1.76 8.10 32.4 2 52.5 1.27 0.053 17L1437 556 80 1.5 4.2 0.07 13.9 24.2 2 0.2 77.5 0.110 24L755 64 170 1.7 9.3 0.10 16.3 40.7 2 0.3 65.4 0.08 0.2 0.276 37L482 91 120 1.5 2.8 0.07 9.20 25.8 2 0.3 37.3 0.07 0.244 37L594 299 70 1.3 9.8 0.01 30.6 18.8 3 0.2 71.9 0.080 37L594 815 60 1.6 13.9 0.03 2.91 33.4 3 0.2 95.6 0.105 37L768 98 40 0.7 0.01 1.91 11.5 37.3 0.014 D22203 908 130 1.6 6.1 0.08 4.58 22.3 2 0.7 47.2 0.07 0.2 0.185 D22223 975 120 2.2 0.6 0.10 22.7 22.2 2 200 0.06 0.2 0.154 D2435 454 50 4.2 8.4 0.36 6.21 14.7 3 0.2 144 2.49 0.082 D33003 3210 40 1.5 0.5 1.68 13.1 3 76.3 0.016 D39018 1820 110 1.7 15.4 0.19 0.87 10.2 2 0.2 105 0.3 0.125 D39204 1333 60 0.6 3.1 0.12 14.5 10.9 98.2 0.046 GC04003 787 30 2.7 0.3 0.01 1.40 3.7 3 139 0.006 BK0510 376 270 16.2 21.0 0.002 0.05 3.60 16.0 2 0.6 105 0.11 0.4 0.276 D27943 2104 300 1.6 64.4 0.002 0.03 3.18 61.0 3 0.5 236 0.15 0.4 0.534 D39018 3562 340 2.1 38.4 0.002 0.02 3.39 48.1 3 0.6 141.5 0.17 0.3 0.653 GC04007 911 940 7.0 37.5 0.18 6.66 17.6 2 1.2 350 0.4 5.3 0.549 RL422VG 30 51.9 12.2 8.71 525 6.0 101 1.4 24.4 101.5 0.038 D39200 1001 100 14.3 12.0 0.002 10.00 23.5 19.4 5 0.5 81.9 0.08 0.89 0.3 0.200 D39200 1064 140 22.8 38.4 0.002 10.00 18.3 60.2 7 0.6 56.4 0.12 1 0.5 0.208 37L482 1347 340 51.5 22.9 0.003 10.00 8.52 10.9 4 1.9 64.3 0.25 0.91 2.7 0.223 D39200 1406 490 1.2 9.6 0.002 0.16 15.35 22.9 3 0.5 30.2 0.11 0.4 0.327 DS352 390 460 2.3 1.1 0.08 14.25 42.7 2 0.6 71.6 0.23 0.5 0.670 37L768 1108 220 4.1 50.6 2.63 9.30 21.0 3 0.6 59.2 0.12 1.03 0.4 0.356 DS352 305 340 4.8 36.6 3.56 19.2 29.4 4 0.6 307 0.1 1.77 0.3 0.315 16L1067 268 130 39.8 42.6 2.63 589 20.3 2 0.4 62.6 0.08 0.3 0.286 CB1812M 210 7.3 39.5 0.002 5.94 42.0 33.9 4 0.5 108 0.11 1.71 0.3 0.458 RL338261A O 30 8.1 40.4 2.19 240 18.4 9 3.6 49.1 0.05 5.59 0.3 0.158 RL34875SO 70 5.1 3.1 0.004 7.94 67.30 50.2 4 0.5 85.0 0.12 1.75 0.3 0.474 5565.00 290 0.8 1.1 0.002 0.10 0.35 41.0 1 0.8 114.5 0.15 0.4 0.507 610 Table B.12 (Continued) Hole ID Depth (ft) P_pp m Pb_pp m Rb_pp m Re_pp m S_pct Sb_pp m Sc_pp m Se_pp m Sn_pp m Sr_pp m Ta_pp m Te_pp m Th_pp m Ti_pc t CR-04-30 10 350 0.7 0.6 0.002 0.04 1.11 55.8 0.4 152 0.18 0.3 0.532 DS196 396 290 1.3 1.0 0.002 0.04 1.45 49.6 1 0.5 164.5 0.14 0.3 0.480 MB01-031 16 290 1.1 11.3 0.10 10.65 48.2 0.4 122.5 0.14 0.2 0.482 CR-04-28 16 200 1.4 8.1 0.07 1.91 49.0 0.4 125 0.12 0.2 0.400 GC01-015 50 350 1.3 1.0 0.002 0.04 1.30 45.0 0.8 214 0.19 0.4 0.621 AB01196 66 420 1.3 0.9 0.002 0.07 21.7 45.4 0.5 175.5 0.2 0.3 0.610 DS122 176 290 1.8 0.7 0.04 2.42 44.5 2 0.5 330 0.12 0.5 0.460 MC02021 103 480 1.4 5.2 0.002 0.09 1.78 44.8 0.5 72.4 0.22 0.5 0.682 MC-01- 012 16 270 1.5 0.7 0.02 4.23 50.7 0.4 107 0.17 1.1 0.388 IN8728 30 360 1.8 1.7 0.10 3.10 41.1 2 0.6 71.9 0.19 0.3 0.561 5554.00 180 17.3 91.9 0.002 0.04 0.90 4.5 1 1.6 235 0.69 11.8 0.192 5555.00 510 16.9 160.0 0.004 0.12 0.59 23.3 1 2.2 189 0.71 0.18 11.8 0.425 CR-03-07 360 21.1 117.5 0.58 1.40 13.2 2 1.4 177 0.70 0.05 14.8 0.244 CW06012 470 6.3 119.5 0.002 0.75 3.03 31.1 2 1.0 146.5 0.41 0.23 4.1 0.448 CW06015 340 9.3 44.9 0.09 1.86 6.8 1 0.5 291 0.32 0.2 6.1 0.177 CW06026 340 10.1 46.5 0.41 3.29 14.0 2 0.6 157.5 0.24 0.06 3.2 0.165 CW06025 530 16.3 72.4 0.51 6.04 16.8 2 1.1 335 0.27 0.10 5.7 0.201 CW02002 400 13.0 69.8 0.004 2.79 11.55 10.6 5 3.2 193.5 0.41 0.96 5.3 0.120 SC99005 550 7.7 136.0 0.007 0.37 8.48 18.6 2 2.4 163.5 0.38 0.16 6.5 0.223 CR-04-17 200 15.1 112.5 0.23 1.57 10.2 2.4 109.0 0.94 0.11 16.3 0.157 CR-04-14 400 12.6 120.0 0.65 5.46 12.5 1 2.3 95.2 0.76 0.1 11.0 0.345 GC98-006 400 16.4 100.0 0.13 3.32 10.3 1.3 200 0.76 13.6 0.470 GC02-012 150 17.1 112.0 0.002 0.13 3.78 13.0 1.4 218 0.73 12.6 0.347 GC02-013 480 13.9 125.0 0.005 0.16 1.03 13.5 2.0 103.5 0.60 0.07 11.0 0.350 5572.00 350 1.3 16.2 0.002 0.34 4.80 51.2 1 0.5 91.1 0.13 0.3 0.488 GC98-005 230 15.7 83.2 0.17 3.63 8.0 1.3 213 0.68 12.1 0.258 GC98-004 340 11.4 66.2 0.04 2.30 4.7 0.8 239 0.55 7.3 0.220 GC02-011 20 23.1 93.9 0.07 2.49 5.4 1 2.0 174.5 1.02 28.1 0.075 GC02-014 200 14.7 63.0 0.20 0.65 5.8 1.0 171.5 0.53 11.7 0.193 5540.00 190 3.0 14.6 1.83 9.85 10.6 1 1.3 18.5 0.45 0.18 7.2 0.117 5545.00 150 2.7 0.4 0.002 0.61 3.67 0.4 1 0.2 4.7 0.06 5546.00 290 2.0 0.2 0.002 0.25 10.55 0.6 0.2 6.4 0.005 611 Table B.12 (Continued) Hole ID Depth (ft) Tl_pp m U_pp m V_pp m W_pp m Y_pp m Zn_pp m Zr_pp m Al2O3 wt% CaO wt% FeO wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% 37L482 926 0.42 0.1 335 0.8 18.5 88 40.3 15.24 7.19 11.86 1.28 5.36 0.20 0.92 0.09 D27943 3389.5 0.31 0.1 291 12.9 5.2 53 41.9 15.72 4.87 6.61 3.70 5.14 0.07 0.88 0.06 D39204 481 0.83 0.1 351 18.6 12 109 59.1 15.47 5.93 11.48 1.34 5.52 0.17 0.16 0.09 D39018 43 0.16 0.2 428 7 11.5 24 63.3 17.11 11.08 4.67 3.07 5.49 0.24 0.32 0.04 D2253 75 0.20 0.2 315 20.6 8.6 105 71 16.08 6.02 10.73 0.34 5.21 0.26 0.20 0.08 R87107 482.3 0.30 0.2 416 1.4 24.7 72 78.4 15.45 8.79 9.68 1.12 5.72 0.24 0.73 0.13 DS172 123.1 B 0.43 0.1 344 1.1 20.4 98 51.3 16.13 2.62 18.20 3.08 3.20 0.71 0.24 0.08 DS173 499.6 0.12 0.1 376 0.3 34.7 101 67.9 18.12 8.31 17.43 0.99 5.55 0.63 0.46 0.13 37L667 4 0.07 0.1 315 10.1 11.3 70 46.6 15.66 4.91 11.52 0.17 4.49 0.27 0.30 0.07 37L667 152 0.33 0.1 374 13.4 8.6 104 46.2 16.36 4.45 11.66 1.33 4.69 0.18 1.78 0.04 37L667 194 0.02 0.1 247 0.2 12.6 80 30.1 14.58 8.23 9.90 0.08 10.01 0.17 2.04 0.05 D39200 3115 0.30 0.1 291 0.7 24.5 98 36.9 14.45 8.84 9.07 0.83 4.71 0.19 1.00 0.10 DS352 134 0.43 0.1 288 1 10.9 93 64.8 15.11 8.11 11.38 1.52 6.35 0.19 1.15 0.08 DS358 321 0.37 228 4.7 6.5 111 32.2 16.11 6.51 7.51 1.46 5.62 0.18 0.26 0.05 GC04007 2000 0.06 0.2 320 0.5 9.1 123 65.3 18.81 3.06 12.92 1.33 3.27 0.13 1.40 0.09 R87105 699.8 0.04 0.2 238 16.2 161 47.2 13.79 6.48 10.94 0.29 8.80 0.29 3.76 0.07 30L1268 25.7 0.14 0.1 333 17.4 38.7 114 53.1 12.71 1.47 20.77 0.17 3.96 0.54 0.08 0.05 37L726 836.6 0.17 0.2 490 21.6 9.2 70 87.2 20.02 5.47 12.37 0.14 6.13 0.27 0.32 0.15 CR466 145 0.02 0.1 386 0.5 31.9 108 68.8 16.08 5.34 12.92 0.10 4.10 0.21 0.23 0.15 D14391 1810 0.08 0.2 313 50.1 11.4 84 71.6 17.45 3.78 13.70 0.07 5.04 0.40 0.09 0.10 D39200 3241 0.06 0.1 399 21.8 20.2 94 42.2 18.30 7.13 10.34 0.04 4.63 0.28 0.28 0.11 D39357 1287 1.69 0.1 294 19.7 8.2 245 52.4 14.64 1.02 12.73 0.89 3.80 0.17 0.09 0.08 DS172 123.1 C 0.09 0.1 329 1.3 23.6 101 46 15.41 4.83 21.41 0.49 3.66 0.86 0.07 0.07 19L547 495.8 0.33 0.2 315 52.8 25.1 52 65.1 16.21 3.09 23.66 0.45 5.64 0.38 0.15 0.09 37L482 118 0.30 0.1 222 5.6 51.0 184 20.2 8.50 2.77 38.97 0.76 4.86 0.96 0.16 0.02 CR4610 947 0.35 0.2 473 0.8 17.4 102 81.9 16.59 5.75 11.51 1.55 2.45 0.21 2.14 0.10 D21708 2760 0.24 2.6 68 0.6 18.5 162 115 14.60 3.15 15.17 1.10 2.39 0.47 1.79 0.09 DS177 1500.8 0.30 0.1 360 0.5 29.7 315 61.7 19.17 6.20 13.82 0.20 4.41 0.68 0.98 0.06 DS615 1905.1 0.25 0.7 31 7.8 10.1 204 61 11.64 4.77 24.82 2.54 2.45 0.67 0.27 0.04 D33003 2004 0.61 0.2 395 8 34.5 106 102.5 15.79 10.46 13.25 1.10 6.15 0.39 0.61 0.17 DS360 124 0.05 0.1 310 6 7 47 31.5 13.68 12.17 7.23 0.17 6.55 0.29 0.24 0.04 GC04007 2859 0.04 0.8 122 0.4 19.8 83 116.5 14.07 6.83 6.34 0.08 3.68 0.10 5.07 0.22 37L667 1061 0.36 0.1 320 6.3 3.9 16 49 16.26 0.13 1.25 0.55 0.13 0.01 0.16 0.03 D39018 635 0.17 0.1 373 0.4 6.9 37 78.7 18.63 0.24 1.02 5.71 0.23 0.01 0.26 0.14 D39200 843 0.29 0.2 314 11.1 10 52 76.2 16.70 6.00 10.34 0.61 3.86 0.24 0.11 0.12 D39200 1318 0.87 0.3 314 51.9 4.7 45 73.5 18.17 3.01 4.63 0.80 1.99 0.07 0.11 0.12 CB4043H R 0.43 0.1 317 11 19.6 81 53.5 14.38 10.87 11.19 1.24 7.06 0.23 0.26 0.08 D15367 5.5 0.72 0.1 277 47.0 6.8 64 44.7 13.17 11.07 10.12 1.74 5.36 0.16 0.31 0.06 612 Table B.12 (Continued) Hole ID Depth (ft) Tl_ppm U_pp m V_pp m W_p pm Y_pp m Zn_pp m Zr_pp m Al2O3 wt% CaO wt% FeO wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% D39357 2067 0.29 0.1 208 77.9 15.7 63 53.1 14.64 9.57 13.25 0.46 4.89 0.18 0.73 0.06 D14391 2922 0.09 0.1 355 0.5 10.4 32 47.9 14.72 7.12 3.68 4.31 3.42 0.10 0.28 0.11 CB25510LZ 0.61 255 10 6.5 60 24.5 10.79 13.15 12.92 1.67 8.77 0.27 0.65 0.01 CB302561 0.39 0.1 332 35.5 6.9 48 44.7 10.98 8.24 9.93 1.02 4.53 0.16 0.32 0.04 37L768 66 209 5.7 15.3 194 12.5 3.38 9.11 40.64 0.01 11.99 1.09 0.03 0.02 DS360 528 114 5.7 3.5 97 8.9 1.85 15.25 24.18 0.01 11.36 0.63 0.01 0.02 17L1437 556 0.08 0.1 114 5.2 7.4 108 14.5 3.19 19.87 7.86 0.19 10.84 0.38 0.09 0.02 24L755 64 0.16 0.1 212 20.9 9.4 47 28.3 8.84 11.19 7.91 0.29 6.45 0.28 0.18 0.04 37L482 91 0.03 127 9.3 7.8 44 13 8.18 9.81 6.60 0.07 4.61 0.22 0.11 0.03 37L594 299 0.12 85 2.8 7.3 59 17.1 2.87 21.54 7.97 0.35 11.85 0.31 0.19 0.02 37L594 815 0.09 97 6.5 12.2 60 14.7 3.34 16.93 7.74 0.41 8.80 0.43 0.27 0.01 37L768 98 34 26.5 5.7 48 3.2 0.68 24.48 7.79 0.02 14.23 0.35 0.04 0.01 D22203 908 0.04 92 5.6 6.9 34 20 3.08 18.33 7.93 0.31 9.91 0.40 0.04 0.03 D22223 975 0.1 174 6.4 7.7 115 21.8 3.89 21.47 9.94 0.02 11.34 0.46 0.03 0.03 D2435 454 0.13 94 12.1 6.7 51 8.8 2.59 18.61 6.98 0.28 10.31 0.28 0.23 0.01 D33003 3210 28 20.7 4.2 48 4.9 0.28 27.63 5.75 0.02 17.08 0.24 0.03 0.01 D39018 1820 0.12 0.1 63 0.6 5.9 30 16.1 3.40 38.19 4.24 0.36 0.85 0.73 0.26 0.03 D39204 1333 0.29 75 24.1 12.1 52 8.7 2.47 17.98 8.55 0.10 9.73 0.26 0.03 0.01 GC04003 787 8 0.3 3.6 10 0.5 0.40 25.88 3.47 0.01 20.23 0.66 0.05 0.01 BK0510 376 0.29 0.3 133 16.9 13.1 135 60.3 14.00 7.85 5.61 0.84 4.34 0.13 1.20 0.06 D27943 2104 0.32 0.1 338 2.3 18.2 74 40.9 17.23 8.48 9.32 2.76 4.96 0.22 0.66 0.07 D39018 3562 0.21 0.1 316 6.3 13.9 139 41.1 18.29 12.40 11.43 2.07 7.34 0.21 0.92 0.08 GC04007 911 0.32 1.2 165 2.3 22.6 84 136.5 15.36 6.31 7.12 1.76 2.85 0.11 3.36 0.22 RL422VG 0.14 166 3.2 3.2 498 8.2 1.79 5.11 18.97 0.36 2.74 0.07 0.07 0.01 D39200 1001 0.41 0.1 153 29.8 9.5 168 23.5 5.59 9.53 31.51 0.54 5.12 0.29 0.11 0.02 D39200 1064 2.43 0.1 375 53.4 26.8 263 38.3 7.10 1.06 40.38 1.48 4.05 0.53 0.11 0.03 37L482 1347 0.54 0.7 89 14.8 8.7 458 72.6 8.88 1.41 26.11 0.90 3.35 0.33 0.12 0.08 D39200 1406 0.35 0.1 276 3.4 7.1 15 59.4 16.42 0.46 1.17 0.39 0.18 0.01 0.03 0.11 DS352 390 0.03 0.1 326 20.4 9.7 89 42.4 14.58 6.69 11.51 0.10 5.60 0.23 0.16 0.11 37L768 1108 0.72 0.1 277 22.9 6.6 99 41.7 9.33 3.39 9.31 1.83 2.17 0.10 0.18 0.05 DS352 305 0.31 0.1 268 21.4 9 72 52 10.86 14.41 10.97 1.12 7.44 0.23 0.16 0.08 16L1067 268 1.08 0.1 221 36.6 12.7 661 35.9 11.50 1.55 6.78 1.75 1.06 0.02 0.24 0.03 CB1812M 2.18 0.1 281 79.2 3.8 36 30.6 14.36 2.48 9.61 1.40 1.96 0.09 0.51 0.05 RL338261AO 0.64 0.1 730 7.0 6.2 294 35.4 7.29 1.69 4.77 1.47 0.96 0.02 0.16 0.01 RL34875SO 0.40 0.1 269 158 8.1 71 21.4 12.35 5.67 12.19 0.34 2.60 0.22 0.19 0.02 5565.00 0.1 288 0.1 18.5 99 21.6 14.58 12.30 12.22 0.12 7.36 0.33 2.49 0.07 613 Table B.12 (Continued) Hole ID Depth (ft) Tl_pp m U_pp m V_pp m W_pp m Y_pp m Zn_pp m Zr_pp m Al2O3 wt% CaO wt% FeO wt% K2O wt% MgO wt% MnO wt% Na2O wt% P2O5 wt% CR-04-30 10 0.1 282 0.5 20.0 93 10.7 16.85 10.20 10.84 0.12 7.66 0.19 2.01 0.08 DS196 396 0.1 292 0.2 19.5 94 19 15.83 10.23 10.74 0.11 8.14 0.20 2.71 0.07 MB01-031 16 0.08 0.1 241 0.5 18.1 80 21.5 13.56 11.42 10.70 0.24 9.62 0.19 0.88 0.07 CR-04-28 16 0.1 232 0.9 14.9 82 18.4 14.68 10.58 10.97 0.35 7.21 0.19 2.57 0.05 GC01-015 50 0.1 281 0.2 23.1 104 33.8 16.19 10.52 11.50 0.08 5.59 0.14 1.73 0.08 AB01196 66 0.1 282 0.4 22.8 94 37 15.30 9.14 11.34 0.11 7.36 0.19 2.02 0.10 DS122 176 0.1 267 0.2 17.4 97 47.3 14.75 9.29 10.49 0.05 7.25 0.19 3.57 0.07 MC02021 103 0.05 0.1 320 19.5 13.1 97 69.6 14.98 5.68 12.42 0.12 7.48 0.17 3.56 0.11 MC-01- 012 16 0.3 242 1.4 16.3 65 40.9 15.55 9.93 8.67 0.08 8.14 0.18 2.06 0.06 IN8728 30 0.1 260 0.6 20.7 79 30.6 14.04 8.98 10.88 0.10 6.35 0.17 2.43 0.08 5554.00 0.48 3.0 21 1.1 11.9 37 173.5 15.11 0.80 1.27 2.39 0.28 0.01 4.18 0.04 5555.00 0.79 3.1 152 1.7 14.1 52 131 21.44 0.90 4.28 4.53 0.96 0.08 1.54 0.12 CR-03-07 0.63 4.1 81 1.7 12.6 114 102.5 16.26 1.99 4.41 3.35 1.36 0.07 1.37 0.08 CW06012 0.60 1.3 214 4.9 18.4 119 102 15.40 1.44 8.76 2.36 1.99 0.17 2.10 0.11 CW06015 0.26 1.9 48 0.5 6.1 46 85.3 12.60 2.52 2.24 1.94 1.44 0.03 1.58 0.08 CW06026 0.36 1.0 90 0.3 9.7 108 86.1 12.24 5.39 6.93 1.33 2.37 0.15 1.47 0.08 CW06025 0.66 1.7 114 0.4 15.1 83 125 15.70 3.36 5.17 2.70 1.86 0.09 1.78 0.12 CW02002 2.85 1.4 48 0.9 13 418 205 12.86 0.76 6.92 1.64 0.91 0.08 0.89 0.09 SC99005 3.90 2.0 106 2.5 17.4 35 191.5 18.38 0.43 4.44 3.53 1.19 0.12 0.78 0.13 CR-04-17 0.55 4.5 45 1.2 17.3 75 144.5 13.37 0.60 1.40 3.45 0.45 0.01 0.55 0.05 CR-04-14 0.75 2.9 92 3.1 13 193 147.5 17.25 0.62 8.01 4.87 0.85 0.16 1.04 0.09 GC98-006 0.68 3.7 82 2.0 15.6 42 269 15.47 1.09 2.17 3.41 0.65 0.03 1.91 0.09 GC02-012 0.80 3.8 79 1.1 14.1 100 164.5 17.91 0.48 3.22 3.53 1.58 0.02 1.08 0.03 GC02-013 0.92 2.8 89 1.4 14.5 68 151.5 17.79 0.34 5.25 3.28 0.90 0.12 0.65 0.11 5572.00 0.09 0.1 290 0.5 7.6 140 48.6 13.03 2.90 13.18 0.64 2.54 0.43 1.52 0.08 GC98-005 0.59 2.8 40 0.6 15.2 52 175 14.11 1.50 2.13 2.63 0.65 0.02 2.31 0.05 GC98-004 0.42 2.3 38 0.7 7.9 51 127 14.94 2.41 2.91 2.22 0.83 0.08 3.17 0.08 GC02-011 0.57 5.8 7 1.1 10.5 33 131.5 17.45 1.04 2.03 3.83 0.58 0.03 2.17 0.00 GC02-014 0.44 2.6 34 0.7 12.1 47 122 13.64 2.00 2.25 2.64 0.58 0.05 3.07 0.05 5540.00 0.28 1.8 36 3.7 20.9 73 227 9.26 0.10 13.63 0.48 2.90 0.19 0.08 0.04 5545.00 0.03 2 0.4 1.7 16 2.2 0.15 0.18 11.72 0.01 0.56 0.13 0.01 0.03 5546.00 0.03 4 0.6 2.3 14 2.7 0.19 0.18 15.56 0.01 0.38 0.20 0.01 0.07 614 Table B.12 (Continued) Hole ID Depth (ft) TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total Δ Ca_pct Δ Cr_ppm Δ Fe_pct Δ K_pct Δ Mg_pct Δ Mn_ppm Δ Na_pct Δ P_ppm Δ S_pct 37L482 926 1.03 0.15 0.08 53.58 96.96 -1.94 314.4 0.61 0.94 -1.30 49.82 -1.08 50.51 -0.01 D27943 3389.5 0.58 0.57 0.04 59.10 97.32 -3.69 72.0 -3.59 2.84 -1.52 -1016.67 -1.13 -85.87 0.16 D39204 481 0.88 0.75 0.03 55.25 97.07 -2.89 20.6 0.19 0.97 -1.25 -217.31 -1.64 54.76 0.23 D39018 43 0.79 0.02 0.03 54.13 97.00 -0.04 -24.1 -5.33 2.14 -1.58 109.36 -1.54 -176.19 -0.06 D2253 75 1.10 0.77 0.05 56.32 97.14 -0.95 21.4 1.51 -1.67 -0.14 688.76 -0.27 58.27 0.16 R87107 482.3 1.36 0.07 0.02 53.66 96.97 1.26 -145.4 1.01 -0.99 0.30 563.67 0.13 267.96 -0.12 DS172 123.1 B 0.88 0.07 0.04 51.57 96.83 -3.35 -57.5 7.20 0.57 -1.34 4108.78 -0.25 57.02 -0.12 DS173 499.6 1.24 1.12 0.02 42.23 96.22 0.01 -168.6 5.15 -1.23 -0.30 2954.50 -0.12 184.83 0.24 37L667 4 0.90 0.50 0.04 58.45 97.28 -1.63 -51.2 2.36 -1.81 -0.49 843.19 -0.20 -3.30 0.05 37L667 152 0.93 0.62 0.05 54.96 97.05 -2.11 42.0 2.08 -0.88 -0.49 22.95 0.86 -112.98 0.09 37L667 194 0.57 0.05 0.05 51.06 96.80 1.21 101.4 1.66 -1.87 3.34 152.27 1.22 -57.84 -0.13 D39200 3115 1.04 0.37 0.02 56.54 97.16 1.75 -169.7 1.02 -1.19 -0.12 347.02 0.39 164.23 0.01 DS352 134 1.01 0.22 0.04 51.68 96.84 0.90 -36.8 2.57 -0.62 0.78 222.07 0.47 59.93 -0.06 DS358 321 0.29 0.35 0.06 58.93 97.31 -0.61 87.7 -0.97 -0.75 0.10 43.23 -0.24 -80.59 -0.01 GC04007 2000 0.97 0.07 0.04 54.96 97.05 -3.35 -87.4 1.76 -1.02 -1.58 -454.68 0.46 40.25 -0.12 R87105 699.8 0.70 0.07 0.02 51.60 96.83 0.14 -113.8 3.07 -1.67 2.87 1296.14 2.79 59.64 -0.12 30L1268 25.7 0.77 1.65 0.03 54.85 97.05 -3.88 -66.6 13.45 -1.77 -0.26 3903.45 -0.35 -35.08 0.67 37L726 836.6 1.26 0.65 0.04 49.89 96.72 -2.09 -101.2 0.90 -1.85 -0.31 318.96 -0.23 234.08 0.06 CR466 145 1.48 0.20 0.02 56.32 97.14 -1.42 -152.5 3.20 -1.87 -0.80 283.58 -0.25 344.86 -0.07 D14391 1810 1.16 0.70 0.03 54.50 97.02 -2.74 -127.1 2.96 -1.89 -0.48 1523.14 -0.36 84.77 0.10 D39200 3241 1.29 0.52 0.02 54.04 96.99 -0.77 -167.4 0.25 -1.92 -0.82 584.53 -0.24 136.45 0.03 D39357 1287 0.94 0.30 0.03 62.88 97.57 -4.40 -116.1 4.01 -1.14 -0.76 146.62 -0.35 71.45 -0.02 DS172 123.1 C 0.79 0.25 0.04 48.75 96.65 -1.64 -18.3 10.43 -1.52 -0.96 5566.85 -0.37 32.30 -0.05 19L547 495.8 0.89 1.82 0.03 43.93 96.33 -3.03 -86.1 11.31 -1.58 0.09 1544.84 -0.31 74.97 0.57 37L482 118 0.48 1.20 0.03 37.19 95.89 -1.49 46.7 49.90 -0.77 2.23 12578.34 -0.20 -147.99 0.75 CR4610 947 1.42 0.72 0.03 54.56 97.03 -1.26 -129.4 1.84 -0.71 -1.82 225.07 1.10 104.80 0.13 D21708 2760 0.50 1.92 0.01 55.92 97.12 -2.75 -251.6 6.11 -0.96 -1.68 2685.35 1.02 137.69 0.69 DS177 1500.8 1.29 1.22 0.03 48.55 96.63 -1.52 -104.7 2.18 -1.81 -1.04 3017.64 0.18 -73.79 0.26 DS615 1905.1 0.17 0.27 0.00 49.01 96.66 -0.54 -275.4 19.62 0.93 -1.22 5805.50 -0.15 -51.75 0.00 D33003 2004 1.57 0.27 0.01 46.74 96.52 2.33 -263.5 3.63 -1.03 0.49 1740.62 0.03 467.05 -0.04 DS360 124 0.30 0.12 0.04 56.31 97.14 4.91 -18.2 -0.20 -1.78 1.35 1329.34 -0.21 -76.80 -0.09 GC04007 2859 0.84 0.60 0.01 59.51 97.35 0.31 -233.9 -1.16 -1.87 -0.74 -425.86 3.82 763.63 0.12 37L667 1061 0.76 0.70 0.05 78.57 98.60 -5.11 1.0 -5.78 -1.50 -3.16 -1214.71 -0.31 -170.52 0.12 D39018 635 1.29 0.40 0.03 70.10 98.04 -5.05 -145.0 -6.06 2.10 -3.12 -1259.74 -0.26 231.32 -0.01 D39200 843 1.13 1.20 0.03 56.83 97.18 -0.10 -20.2 -3.62 -0.19 -0.79 -1120.34 -0.61 93.66 0.21 D39200 1318 1.23 1.50 0.02 66.14 97.78 -2.26 -73.5 -8.03 -0.10 -1.94 -2364.14 -0.62 54.38 0.27 CB4043HR 0.87 3.40 0.04 46.91 96.53 4.31 116.4 -1.69 0.45 1.65 -905.23 -0.48 -33.64 1.23 D15367 5.5 0.63 11.94 0.03 41.60 96.18 5.25 64.2 -1.81 1.04 0.85 -1352.53 -0.41 -83.55 5.41 615 Table B.12 (Continued) Hole ID Depth (ft) TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total Δ Ca_pct Δ Cr_ppm Δ Fe_pct Δ K_pct Δ Mg_pct Δ Mn_ppm Δ Na_pct Δ P_ppm Δ S_pct D39357 2067 0.97 7.79 0.04 43.74 96.32 3.17 75.6 -0.16 -0.26 0.17 -1402.60 -0.11 -93.22 3.08 D14391 2922 0.98 0.05 0.02 62.78 97.56 1.28 -56.9 -8.08 3.12 -0.79 -2019.95 -0.46 95.52 -0.22 CB25510LZ 0.40 10.59 0.04 36.59 95.85 9.46 177.9 3.39 1.34 4.67 204.32 0.01 -347.45 5.87 CB302561 0.57 7.29 0.05 53.85 96.98 4.25 267.7 -0.17 0.54 0.91 -1067.14 -0.35 -135.61 3.90 37L768 66 0.17 1.72 0.01 27.06 95.23 2.64 -42.3 16.84 -0.63 4.01 4112.45 -0.87 -136.94 0.27 DS360 528 0.09 4.39 0.01 38.16 95.95 12.01 -46.4 18.76 -0.63 7.70 4404.03 -0.87 -90.70 2.03 17L1437 556 0.18 0.17 0.01 54.19 97.00 8.60 -45.1 -0.73 -0.52 3.79 359.01 -0.83 -133.63 -0.16 24L755 64 0.46 0.25 0.01 61.60 97.49 0.23 -82.3 -3.61 -0.57 -0.01 -1226.10 -0.85 -147.42 -0.19 37L482 91 0.41 0.17 0.02 67.66 97.88 0.11 -55.4 -3.78 -0.62 -0.25 -1313.83 -0.86 -158.20 -0.20 37L594 299 0.13 0.02 0.01 51.56 96.83 10.77 -66.5 -0.15 -0.40 4.84 139.72 -0.77 -135.24 -0.21 37L594 815 0.18 0.07 0.01 59.12 97.33 6.64 -42.4 -1.00 -0.40 2.71 558.29 -0.74 -150.46 -0.20 37L768 98 0.02 0.02 0.00 49.00 96.66 58.94 -51.0 15.81 -0.57 28.78 7723.69 -0.78 -53.80 -0.18 D22203 908 0.31 0.20 0.00 56.61 97.16 8.15 -86.2 -0.52 -0.44 3.54 569.18 -0.86 -93.05 -0.16 D22223 975 0.26 0.25 0.01 48.96 96.66 7.41 -64.6 -0.56 -0.63 3.11 353.37 -0.87 -119.97 -0.16 D2435 454 0.14 0.90 0.10 56.75 97.17 10.24 508.7 -0.30 -0.43 4.63 169.78 -0.73 -147.20 0.11 D33003 3210 0.03 0.00 0.00 45.36 96.43 162.90 -87.8 32.04 -0.47 84.91 13676.67 -0.71 140.92 -0.22 D39018 1820 0.21 0.47 0.03 47.82 96.59 17.07 42.2 -2.96 -0.43 -0.69 2139.30 -0.75 -116.39 -0.08 D39204 1333 0.08 0.30 0.01 57.72 97.23 10.36 -61.8 1.10 -0.56 4.56 135.95 -0.86 -135.56 -0.10 GC04003 787 0.01 0.02 0.02 45.69 96.45 108.36 613.2 10.84 -0.58 71.67 28477.64 -0.64 -14.06 -0.16 BK0510 376 0.46 0.12 0.01 62.95 97.58 -0.97 -81.7 -4.52 -0.52 -0.61 -1636.94 -0.73 -147.28 -0.21 D27943 2104 0.89 0.07 0.05 52.16 96.87 -1.08 -50.8 -4.26 -0.32 -0.64 -1573.26 -0.81 -151.71 -0.21 D39018 3562 1.09 0.05 0.02 42.32 96.23 -0.77 -75.0 -4.11 -0.42 -0.48 -1589.18 -0.79 -148.92 -0.21 GC04007 911 0.92 0.45 0.00 58.86 97.31 -1.22 -94.8 -4.41 -0.41 -0.78 -1673.28 -0.50 -48.16 -0.19 RL422VG 0.06 21.75 0.02 45.49 96.43 27.54 1106.0 116.74 1.94 11.34 1975.00 -0.25 -130.68 75.26 D39200 1001 0.33 24.97 0.01 16.51 94.54 14.85 -55.3 57.05 0.59 5.63 3461.91 -0.46 -112.53 27.58 D39200 1064 0.35 24.97 0.02 14.32 94.39 -2.43 64.4 57.66 2.03 2.38 6104.08 -0.51 -84.12 21.66 37L482 1347 0.37 24.97 0.01 28.82 95.34 -2.33 -109.9 24.46 0.65 0.58 1614.65 -0.53 204.96 17.28 D39200 1406 0.55 0.40 0.02 78.88 98.62 -3.79 -42.6 -10.25 -0.36 -2.86 -2766.67 -0.67 73.59 -0.09 DS352 390 1.12 0.20 0.07 56.81 97.17 1.00 327.3 -1.56 -0.58 0.64 -980.98 -0.56 99.93 -0.15 37L768 1108 0.59 6.57 0.03 64.11 97.65 -0.06 122.3 0.96 1.87 -0.78 -1572.74 -0.47 -24.01 4.14 DS352 305 0.53 8.89 0.02 41.45 96.17 10.65 40.7 1.11 0.67 3.47 -303.84 -0.51 96.18 4.86 16L1067 268 0.48 6.57 0.03 67.89 97.90 -2.60 31.1 -3.98 1.30 -2.10 -2616.28 -0.44 -214.94 3.32 CB1812M 0.76 14.83 0.04 50.70 96.77 -2.18 71.3 -3.01 0.59 -1.68 -2090.14 -0.27 -163.19 6.20 RL338261AO 0.26 5.47 0.02 76.32 98.45 -1.52 140.7 -3.19 1.94 -1.73 -2562.77 -0.43 -326.72 4.43 RL34875SO 0.79 19.83 0.02 41.99 96.20 1.00 -21.5 0.83 -0.31 -0.99 -699.89 -0.51 -302.58 9.76 5565.00 0.85 0.25 0.02 45.88 96.46 616 Table B.12 (Continued) Hole ID Depth (ft) TiO2 wt% SO3 wt% Cr2O3 wt% SiO2 wt% Total Δ Ca_pct Δ Cr_ppm Δ Fe_pct Δ K_pct Δ Mg_pct Δ Mn_ppm Δ Na_pct Δ P_ppm Δ S_pct CR-04-30 10 0.89 0.10 0.03 47.61 96.57 DS196 396 0.80 0.10 0.04 47.61 96.57 MB01-031 16 0.80 0.25 0.05 48.88 96.66 CR-04-28 16 0.67 0.17 0.02 49.22 96.68 GC01-015 50 1.04 0.10 0.02 49.74 96.71 AB01196 66 1.02 0.17 0.02 49.95 96.73 DS122 176 0.77 0.10 0.03 50.19 96.74 MC02021 103 1.14 0.22 0.03 50.87 96.79 MC-01-012 16 0.65 0.05 0.04 51.41 96.82 IN8728 30 0.94 0.25 0.02 52.68 96.90 5554.00 0.32 0.10 0.00 73.78 98.28 5555.00 0.71 0.30 0.02 62.68 97.56 CR-03-07 0.41 1.45 0.01 67.08 97.85 CW06012 0.75 1.87 0.02 62.59 97.55 CW06015 0.30 0.22 0.00 75.44 98.39 CW06026 0.28 1.02 0.01 66.55 97.81 CW06025 0.34 1.27 0.01 65.34 97.73 CW02002 0.20 6.97 0.00 66.48 97.81 SC99005 0.37 0.92 0.01 67.57 97.88 CR-04-17 0.26 0.57 0.01 77.83 98.55 CR-04-14 0.58 1.62 0.02 62.45 97.54 GC98-006 0.78 0.32 0.01 72.24 98.18 GC02-012 0.58 0.32 0.01 69.24 97.99 GC02-013 0.58 0.40 0.01 68.52 97.94 5572.00 0.81 0.85 0.03 61.47 97.48 GC98-005 0.43 0.42 0.00 74.05 98.30 GC98-004 0.37 0.10 0.00 71.01 98.10 GC02-011 0.13 0.17 0.00 70.64 98.08 GC02-014 0.32 0.50 0.00 73.14 98.24 5540.00 0.20 4.57 0.00 66.35 97.80 5545.00 0.00 1.52 0.00 84.67 99.00 5546.00 0.01 0.62 0.00 81.55 98.79 Mass balance differences were not calculated for the least altered samples as these were the references. Consequently, the remaining data tables are for the al- tered samples where mass balance and propagation errors were calculated. 617 Table B.12 (Continued) Hole ID Depth (ft) Δ Ti_pct Δ Ag_ ppm Δ As_ ppm Δ Ba_ppm Δ Be_ppm Δ Bi_ppm Δ Cd_ppm Δ Ce_ppm Δ Co_ppm Δ Cs_ppm Δ Cu_ppm Δ Ga_ppm Δ Ge_p pm Δ Hf_ppm 37L482 926 0.09 -0.05 11.31 325.97 0.32 -0.02 0.03 1.37 2.01 6.77 -111.85 1.77 0.03 0.1 D27943 3389.5 -0.19 -0.05 -9.12 968.78 0.15 -0.01 -0.03 -6.09 -13.64 3.85 -104.76 0.34 -0.07 0.2 D39204 481 -0.01 0.28 187.94 85.91 0.09 -0.03 0.04 1.80 -9.72 4.17 -6.11 -1.97 0.03 0.7 D39018 43 -0.10 -0.04 -5.94 267.12 -0.11 -0.03 -0.06 -4.25 -24.22 1.25 -119.36 -2.45 -0.03 1.0 D2253 75 0.16 0.15 39.42 -455.35 -0.05 0.06 0.12 2.05 -4.02 1.29 130.50 1.30 0.06 0.3 R87107 482.3 0.35 0.07 -57.33 -258.81 0.39 0.09 -0.01 1.15 -2.92 -2.79 26.52 5.91 0.03 0.6 DS172 123.1 B 0.03 -0.04 -21.89 -61.55 0.72 0.00 -0.06 4.63 2.84 5.84 -3.59 3.95 0.08 0.0 DS173 499.6 0.16 0.01 -47.36 -300.84 0.15 0.00 0.02 4.33 30.00 -3.91 331.06 2.16 0.09 0.1 37L667 4 0.06 -0.04 -45.39 -464.71 -0.04 0.00 0.04 1.79 -1.40 -1.09 45.73 1.75 0.01 -0.2 37L667 152 0.05 -0.06 -57.96 -193.66 0.07 0.03 -0.02 -3.64 18.44 4.63 103.98 2.78 -0.01 0.0 37L667 194 -0.12 -0.02 -57.61 -310.70 -0.20 0.00 0.02 -2.57 13.65 -4.61 43.57 -1.54 0.01 -0.5 D39200 3115 0.19 0.05 20.24 -100.23 0.06 0.01 0.23 3.25 18.00 0.70 96.36 0.47 0.01 -0.2 DS352 134 0.15 0.00 -52.44 -180.14 -0.04 0.00 0.04 4.09 -0.27 2.33 125.49 0.44 0.03 0.3 DS358 321 -0.32 0.09 -15.63 -297.67 0.05 -0.01 0.68 -1.32 -10.62 2.34 7.12 -2.68 -0.01 -0.7 GC04007 2000 0.00 -0.05 -56.35 -375.23 -0.06 -0.01 -0.03 3.33 -0.52 6.65 123.36 0.00 0.03 0.0 R87105 699.8 0.00 0.38 -54.02 -427.40 0.09 0.10 0.01 5.98 21.43 -4.37 119.16 1.09 0.03 -0.2 30L1268 25.7 0.09 0.08 -49.90 -410.02 0.01 0.02 0.02 8.76 14.13 -4.30 84.53 2.33 0.19 0.1 37L726 836.6 0.11 -0.04 -9.44 -453.26 -0.22 0.00 -0.04 0.99 2.00 -4.40 53.10 2.13 0.06 0.3 CR466 145 0.39 0.00 -56.94 -475.12 0.10 -0.01 0.02 5.46 -3.43 -4.90 104.31 4.91 0.08 0.2 D14391 1810 0.15 -0.03 -10.66 -466.80 -0.19 -0.04 -1.03 23.15 -4.58 49.41 0.75 -0.01 0.2 D39200 3241 0.18 0.00 110.64 -458.96 0.23 -0.01 0.04 2.29 16.59 -4.93 35.46 2.39 -0.04 -0.6 D39357 1287 0.12 -0.01 121.86 -387.34 -0.14 -0.02 0.46 0.27 4.32 -1.50 99.29 0.08 0.10 0.4 DS172 123.1 C 0.00 0.04 -40.11 -412.86 0.75 0.05 -0.05 6.44 15.62 -0.63 37.96 4.83 0.14 -0.2 19L547 495.8 0.03 0.17 186.13 -435.99 -0.01 0.02 0.05 4.62 6.16 -2.71 177.50 3.46 0.19 -0.1 37L482 118 0.04 0.19 161.56 -55.16 0.50 0.02 0.73 16.47 80.00 7.59 204.04 7.26 2.31 -0.5 CR4610 947 0.33 0.03 -56.64 -312.59 0.11 0.04 -0.01 -1.44 14.94 -2.70 171.25 5.00 0.07 0.7 D21708 2760 -0.17 0.06 -55.00 -332.68 0.34 0.04 -0.02 59.94 -22.87 1.03 -26.84 3.45 0.15 1.5 DS177 1500.8 0.15 0.01 -10.60 -427.00 -0.10 0.04 0.09 4.28 33.35 2.19 277.46 3.57 0.03 -0.2 DS615 1905.1 -0.35 0.02 236.36 -280.21 0.93 0.19 0.01 17.59 -21.41 20.21 -21.08 5.37 0.24 0.4 D33003 2004 0.46 0.04 -29.42 -384.40 0.94 0.01 0.08 12.79 7.92 4.67 39.76 3.80 0.03 1.3 DS360 124 -0.28 0.16 -3.10 -450.15 -0.11 0.00 0.08 -1.72 -1.28 -3.52 166.49 -2.82 0.01 -0.6 GC04007 2859 0.08 -0.04 -57.76 -394.69 0.96 0.01 0.00 63.72 -10.09 -3.17 12.59 4.90 0.01 2.1 37L667 1061 0.21 0.00 45.59 -309.18 0.09 0.00 -0.02 0.22 21.23 -3.74 150.32 4.56 -0.05 0.1 D39018 635 -0.03 -0.06 -4.12 -177.94 0.09 -0.02 -0.01 2.37 -17.34 -2.59 112.80 3.16 -0.05 0.6 D39200 843 -0.27 0.02 -5.16 -49.38 -0.19 -0.02 -0.03 -1.78 9.34 -1.38 73.93 -2.46 -0.10 0.4 D39200 1318 -0.41 -0.08 -22.25 -81.86 -0.32 -0.03 -0.10 -6.43 -23.95 -0.36 -102.15 -0.13 -0.15 0.2 CB4043HR 0.01 6.29 336.15 -35.83 0.05 0.12 0.09 -6.52 7.67 -0.79 159.38 -0.84 -0.12 -0.2 D15367 5.5 -0.11 1.18 821.04 103.06 0.88 0.19 0.02 -6.64 -0.04 1.24 -33.89 0.72 -0.08 -0.2 618 Table B.12 (Continued) Hole ID Depth (ft) Δ Ti_pct Δ Ag_pp m Δ As_ppm Δ Ba_ppm Δ Be_p pm Δ Bi_pp m Δ Cd_p pm Δ Ce_ppm Δ Co_ppm Δ Cs_ppm Δ Cu_ppm Δ Ga_ppm Δ Ge_pp m Δ Hf_pp m D39357 2067 0.06 1.85 -44.08 -48.22 0.53 0.55 0.09 -1.83 4.10 1.02 116.66 2.76 0.00 0.1 D14391 2922 0.06 -0.10 39.69 67.62 -0.22 -0.03 -0.06 -4.64 -25.35 -1.82 -70.41 1.27 -0.11 -0.1 CB25510LZ -0.22 1.92 211.96 126.36 0.53 0.25 0.21 -6.60 163.39 1.42 76.69 0.41 0.03 -0.6 CB302561 -0.08 8.86 14117.06 8.51 0.19 0.05 0.04 1.52 35.30 0.42 272.67 3.48 -0.04 0.2 37L768 66 -0.15 -0.03 374.64 -110.76 -0.25 -0.04 -0.05 -8.60 16.83 -4.31 -37.46 -0.92 0.05 -0.4 DS360 528 -0.16 0.03 9048.69 -110.76 -0.05 0.00 0.18 -8.97 18.54 -4.35 31.67 0.04 0.02 -0.4 17L1437 556 -0.14 -0.05 -42.64 -95.94 -0.17 -0.01 0.01 -11.21 -8.26 -4.14 -72.51 -0.58 -0.15 -0.3 24L755 64 -0.15 -0.06 -60.03 -102.73 -0.25 -0.03 -0.14 -12.72 -9.33 -3.99 -75.60 -1.04 -0.19 -0.4 37L482 91 -0.15 -0.01 -67.91 -104.97 -0.26 -0.03 -0.08 -10.72 -10.43 -4.35 -70.01 -1.08 -0.19 -0.5 37L594 299 -0.16 -0.04 -49.29 -86.05 -0.09 0.00 -0.03 -10.45 1.14 -3.50 -69.54 -0.54 -0.14 -0.4 37L594 815 -0.15 -0.06 -60.21 -89.54 -0.14 -0.02 0.00 -10.91 -3.29 -3.08 -85.67 0.13 -0.16 -0.3 37L768 98 -0.17 -0.05 -62.83 -110.76 0.23 -0.04 0.36 -7.68 14.77 -3.53 -77.63 0.06 0.09 -0.3 D22203 908 -0.08 -0.06 -59.24 -95.40 -0.06 -0.03 -0.12 -8.20 -7.63 -3.92 -91.45 0.14 -0.14 -0.2 D22223 975 -0.13 -0.04 -10.76 -104.68 -0.21 -0.04 0.10 -9.02 6.96 -4.45 38.23 -0.70 -0.16 -0.3 D2435 454 -0.15 0.29 289.39 -92.48 0.12 0.04 -0.04 -11.74 14.02 -3.45 -68.38 0.80 -0.12 -0.4 D33003 3210 -0.09 0.09 -29.80 -27.30 5.18 -0.04 1.34 11.59 10.31 -3.98 -71.86 2.55 0.36 0.2 D39018 1820 -0.14 -0.07 -14.50 -62.08 -0.19 -0.02 -0.12 -11.73 -3.94 -3.88 -72.21 -0.48 -0.18 -0.3 D39204 1333 -0.18 -0.04 77.54 -101.20 0.24 -0.04 -0.04 -10.45 -7.67 -4.22 -78.86 2.04 -0.13 -0.5 GC04003 787 -0.19 0.10 -17.88 -51.15 -0.32 0.02 2.10 1.14 127.03 -2.26 300.34 0.48 0.08 -0.6 BK0510 376 -0.18 -0.04 -71.27 -98.93 -0.19 -0.03 -0.13 -12.68 -13.14 -4.34 -93.60 -0.30 -0.19 -0.3 D27943 2104 -0.15 -0.07 -71.33 -54.48 -0.19 -0.03 -0.16 -13.00 -12.12 -3.99 -81.17 -1.02 -0.21 -0.5 D39018 3562 -0.14 -0.07 -66.68 -88.77 -0.26 -0.03 -0.15 -13.11 -9.12 -3.32 -91.50 -0.83 -0.20 -0.5 GC04007 911 -0.14 -0.07 -70.85 -39.93 -0.18 -0.03 -0.15 -3.15 -13.54 -3.40 -89.21 -0.02 -0.21 0.0 RL422VG -0.23 918.63 86621.14 300.17 2.05 63.84 21.16 21.77 745.36 -0.27 12117.92 13.98 6.03 0.0 D39200 1001 0.00 6.84 7.88 89.33 0.06 0.43 3.34 -0.39 33.46 -0.97 590.36 2.26 0.73 0.2 D39200 1064 -0.10 5.23 311.27 41.98 0.24 0.14 1.11 20.62 138.86 5.96 284.59 1.24 0.75 0.4 37L482 1347 -0.17 1.59 366.68 -10.58 0.08 0.98 1.54 20.41 32.87 -2.66 154.50 2.60 0.33 1.9 D39200 1406 -0.25 -0.03 -3.24 -85.84 -0.36 -0.02 -0.10 -6.25 -38.27 -3.89 -19.39 -1.22 -0.21 0.0 DS352 390 0.16 -0.10 -35.60 -101.22 -0.14 -0.03 -0.10 -2.05 2.38 -3.92 -120.28 -0.25 -0.06 -0.4 37L768 1108 0.03 2.26 -45.72 233.49 0.35 0.14 0.27 -0.13 59.58 -1.93 149.87 4.12 0.05 0.4 DS352 305 -0.11 0.80 17.48 81.59 0.31 0.35 0.43 -3.01 9.25 -0.75 114.51 -0.66 -0.01 0.4 16L1067 268 -0.17 3.78 13465.44 191.29 0.11 0.20 4.21 -7.72 12.51 3.14 262.85 -0.60 -0.15 -0.6 CB1812M -0.06 0.42 267.32 -14.03 0.89 0.16 -0.10 -6.93 13.27 0.66 -31.45 -2.44 -0.07 -0.8 RL338261AO -0.22 14.73 21276.80 80.11 0.97 0.39 2.25 -3.11 6.65 0.90 -95.42 11.91 -0.11 0.1 RL34875SO 0.04 2.93 1354.60 -82.85 -0.02 0.00 0.09 -6.03 9.07 -2.29 -37.42 -2.19 0.01 -0.8 619 Table B.12 (Continued) Hole ID Depth (ft) Δ In_ppm Δ La_ppm Δ Li_ppm Δ Mo_ppm Δ Nb_p pm Δ Ni_ppm Δ Pb_ppm Δ Rb_ppm Δ Re_ppm Δ Sb_ppm Δ Sc_ppm Δ Se_pp m Δ Sn_pp m Δ Sr_ppm 37L482 926 0.004 0.06 30.66 -0.06 0.9 117.21 3.1 36.04 -0.002 8.25 1.87 0 0.4 -30.92 D27943 3389.5 -0.020 -2.55 0.43 -0.14 -1.3 -26.64 0.7 32.18 -0.002 -2.06 -8.64 0 -0.1 -64.22 D39204 481 0.037 0.10 16.72 0.22 0.2 -17.67 2.1 30.49 0.000 83.41 28.62 0 0.1 -16.05 D39018 43 -0.048 -1.85 -0.37 0.01 -1.5 -26.85 -0.3 34.52 0.002 -2.88 -13.61 0 -0.4 -127.59 D2253 75 0.017 1.01 -42.87 -0.08 1.2 9.96 -0.2 -23.67 -0.002 5.38 -8.80 0 0.1 -27.33 R87107 482.3 0.029 0.54 8.71 0.16 2.4 -28.43 2.5 -25.15 0.000 -23.71 -11.73 0 0.4 86.04 DS172 123.1 B 0.008 3.36 34.40 -0.06 -0.1 -3.35 -0.6 63.82 -0.004 -22.43 11.93 1 0.0 86.38 DS173 499.6 0.038 1.99 -40.09 0.01 1.3 -8.04 -2.1 -25.73 -0.001 -23.74 -0.04 2 0.4 -49.35 37L667 4 0.013 0.39 -15.67 0.69 0.6 -30.85 -0.8 -34.85 -0.001 -2.70 -3.63 0 0.2 -60.29 37L667 152 0.024 -1.39 78.22 0.02 0.5 7.95 -0.5 -22.95 -0.002 -16.55 7.76 0 0.3 20.29 37L667 194 -0.009 -0.79 79.71 0.07 -0.4 -13.40 -1.4 -36.79 -0.004 -17.12 1.50 0 0.1 183.85 D39200 3115 0.020 1.54 30.15 0.26 1.5 -5.70 -0.2 -12.71 -0.004 -13.59 -3.74 0 0.2 153.40 DS352 134 0.012 1.88 27.07 0.13 1.5 -47.18 1.6 13.73 -0.004 -13.23 -10.64 0 0.1 74.30 DS358 321 -0.015 -0.09 74.83 0.73 -0.9 6.66 -0.8 -3.00 -0.004 -7.37 -9.69 -1 -0.2 -35.27 GC04007 2000 0.001 1.89 3.44 -0.01 0.9 40.46 -1.8 -15.13 -0.004 -21.94 -22.11 -2 0.2 -14.24 R87105 699.8 0.004 2.55 37.69 -0.03 1.5 -19.12 7.4 -33.38 -0.004 -24.49 -15.76 0 0.1 344.93 30L1268 25.7 0.023 5.00 -14.96 0.11 0.8 5.63 -1.4 -30.85 0.000 -2.78 30.95 2 -0.2 -27.24 37L726 836.6 0.058 0.26 19.28 -0.15 0.7 -2.22 -1.0 -34.85 0.002 -14.15 2.65 0 0.1 -7.16 CR466 145 0.051 2.09 -39.11 0.06 2.6 -82.54 -1.4 -37.41 -0.001 -24.99 -3.96 1 0.6 -60.63 D14391 1810 -0.015 -0.11 2.61 0.29 1.7 65.91 -1.4 -36.55 -0.001 -0.54 -12.31 1 -0.3 -61.90 D39200 3241 0.011 0.90 -32.00 -0.03 1.4 -11.95 0.3 -37.67 -0.001 -16.34 3.43 1 0.1 -20.03 D39357 1287 0.009 0.18 -19.88 0.11 0.8 -42.30 -1.3 -18.68 -0.001 38.60 -17.37 0 -0.1 -46.95 DS172 123.1 C 0.016 4.46 16.60 -0.02 -0.2 21.82 -1.2 -22.02 -0.004 -17.23 11.76 1 0.1 249.32 19L547 495.8 -0.006 2.94 -16.30 0.04 1.4 38.68 -0.5 -27.81 -0.002 29.13 -5.03 1 0.3 -61.58 37L482 118 0.030 8.09 27.59 0.59 0.9 256.27 -0.2 10.86 -0.004 36.89 30.96 4 0.4 -50.05 CR4610 947 0.031 -0.64 -28.77 0.21 2.4 -28.48 -0.5 -8.21 -0.001 -26.20 -4.64 1 0.4 96.81 D21708 2760 -0.029 34.89 4.80 0.77 5.1 -76.88 8.2 14.01 -0.004 -25.61 -39.59 0 0.5 52.39 DS177 1500.8 0.018 1.23 -4.61 -0.04 1.0 86.90 -1.7 -33.96 -0.001 -23.61 -0.85 2 0.1 -22.34 DS615 1905.1 -0.038 10.49 7.70 1.34 1.4 -103.47 3.0 44.09 -0.004 -22.35 -45.71 -1 0.2 25.79 D33003 2004 0.057 5.50 102.61 0.14 3.7 -69.64 0.5 0.53 -0.001 -9.29 7.04 2 0.7 136.51 DS360 124 -0.002 -0.43 -15.56 0.13 -1.1 -33.03 -0.9 -33.57 -0.004 -11.91 6.48 -1 -0.3 -47.20 GC04007 2859 -0.010 29.99 6.81 -0.10 4.9 -49.89 5.1 -35.39 -0.001 -24.72 -32.05 0 0.6 304.51 37L667 1061 -0.009 0.86 -42.81 0.16 0.0 67.87 0.7 -17.59 -0.004 -1.15 -32.93 0 0.2 -21.74 D39018 635 0.021 0.92 -46.98 -0.07 0.9 -83.32 -2.0 29.62 -0.002 -23.96 -19.34 0 0.2 -67.35 D39200 843 0.016 -1.21 -2.03 -0.10 0.5 30.48 3.9 -2.97 -0.001 17.89 -5.40 -1 -0.1 -75.19 D39200 1318 -0.014 -3.17 -21.61 -0.15 -0.3 -76.62 2.2 -4.40 -0.003 0.68 -24.79 -1 0.0 -85.92 CB4043HR 0.001 -3.18 30.55 0.03 -0.6 47.11 2.5 21.52 -0.003 5.08 -3.65 0 0.5 47.03 D15367 5.5 -0.017 -3.23 -14.49 6.17 -1.5 28.16 1.7 27.74 0.000 0.90 -8.60 1 0.0 58.60 620 Table B.12 (Continued) Hole ID Depth (ft) Δ In_pp m Δ La_pp m Δ Li_pp m Δ Mo_pp m Δ Nb_pp m Δ Ni_pp m Δ Pb_pp m Δ Rb_pp m Δ Re_pp m Δ Sb_pp m Δ Sc_pp m Δ Se_pp m Δ Sn_pp m Δ Sr_pp m D39357 2067 -0.014 -1.32 -25.75 76.92 -0.3 66.30 4.4 -5.49 0.001 -2.29 -0.79 1 0.7 20.98 D14391 2922 0.054 -2.09 -50.25 -0.25 -0.4 17.22 -2.0 56.48 -0.003 -11.30 4.48 0 0.4 -74.19 CB25510LZ 0.008 -3.25 97.75 -0.27 -2.2 282.10 8.5 46.91 -0.003 -3.67 39.52 5 -0.1 72.19 CB302561 0.012 -0.47 -5.50 0.34 -1.0 205.63 10.0 20.10 0.000 71.32 -7.00 9 0.9 -10.81 37L768 66 -0.012 -5.15 -32.23 0.19 -1.0 59.20 -2.0 -22.82 -0.001 21.60 26.93 0 -0.3 -86.63 DS360 528 0.020 -5.16 -34.47 -0.13 -1.1 30.76 -0.9 -23.05 -0.001 -5.26 25.24 2 -0.3 -36.84 17L1437 556 -0.012 -6.35 -0.62 -0.08 -1.0 -10.21 -1.2 -20.06 -0.001 -5.31 1.78 1 -0.1 -46.50 24L755 64 -0.017 -6.87 -22.82 -0.12 -1.1 -33.08 -1.9 -20.69 -0.001 -11.24 -5.26 0 -0.2 -86.41 37L482 91 -0.016 -6.10 -33.73 -0.19 -1.1 -39.57 -1.9 -22.36 -0.001 -12.94 -8.69 0 -0.2 -93.12 37L594 299 -0.016 -6.06 -20.64 -0.16 -1.1 -12.52 -1.2 -15.10 -0.001 9.60 -0.66 1 -0.1 -44.69 37L594 815 -0.017 -6.12 -21.13 -0.14 -1.1 -10.08 -1.2 -13.34 -0.001 -13.54 7.48 1 -0.1 -36.29 37L768 98 -0.001 -4.68 -18.01 0.74 -0.7 10.23 -2.3 -20.74 -0.001 -8.96 23.84 -1 -0.3 25.80 D22203 908 -0.002 -4.54 -33.57 0.11 -0.5 -37.56 -1.1 -18.49 -0.001 -12.08 0.98 1 0.3 -67.66 D22223 975 -0.005 -5.28 -23.41 0.46 -0.8 86.96 -1.0 -22.81 -0.001 -1.81 -2.65 0 -0.3 17.63 D2435 454 -0.008 -6.46 -12.96 2.41 -1.1 221.93 1.5 -15.50 -0.001 -9.93 -2.71 2 -0.1 27.67 D33003 3210 0.088 3.39 14.40 1.15 0.2 18.43 10.2 -19.00 -0.001 -1.58 93.18 24 -0.3 532.84 D39018 1820 -0.014 -6.35 -27.12 -0.17 -0.9 -3.75 -1.1 -12.46 -0.001 -15.00 -9.05 0 -0.1 -30.88 D39204 1333 -0.018 -5.74 -23.27 0.23 -1.1 -22.49 -1.7 -20.21 -0.001 -1.75 -5.73 -1 -0.3 -10.07 GC04003 787 0.001 -0.91 35.74 1.76 -0.8 888.96 13.8 -21.39 -0.001 -7.26 5.91 17 -0.3 724.66 BK0510 376 -0.021 -6.87 -34.51 -0.16 -1.2 -46.92 0.4 -19.63 -0.001 -14.99 -13.44 -1 -0.2 -86.17 D27943 2104 -0.020 -7.04 -27.39 -0.25 -1.1 -42.05 -2.1 -14.33 -0.001 -15.17 -7.77 -1 -0.2 -71.51 D39018 3562 -0.020 -7.10 -29.38 -0.25 -1.0 -39.22 -2.0 -18.21 -0.001 -15.16 -9.92 -1 -0.2 -85.61 GC04007 911 -0.019 -2.72 -25.09 -0.13 -0.6 -50.96 -1.2 -17.40 -0.001 -14.58 -13.44 -1 -0.1 -50.01 RL422VG 1.837 16.11 84.31 2.44 -0.8 4207.8 2 447.0 85.17 -0.003 4535.5 4 7.02 873 11.5 81.07 D39200 1001 0.094 -0.58 -7.68 3.27 0.5 3128.7 6 36.9 12.81 0.003 50.38 8.98 11 0.7 97.41 D39200 1064 0.064 8.69 53.68 1.83 0.8 249.57 47.0 63.52 0.002 25.09 86.85 13 0.6 -6.91 37L482 1347 0.307 11.10 62.92 5.25 2.9 152.55 87.3 19.55 0.002 -0.06 -25.89 4 2.7 -17.77 D39200 1406 -0.040 -3.10 -56.03 0.00 -1.9 -103.27 -1.7 -11.48 -0.001 -0.44 -23.29 0 -0.2 -101.81 DS352 390 0.001 -1.73 5.65 -0.14 0.5 124.64 -0.4 -19.40 -0.003 0.21 0.56 0 0.0 -54.06 37L768 1108 -0.008 -0.25 -15.37 2.48 -0.5 178.19 3.9 63.77 -0.003 0.51 -9.98 2 0.3 -31.75 DS352 305 0.002 -1.84 -30.25 7.31 -1.4 18.63 4.0 31.84 -0.003 12.51 -2.88 3 0.2 309.21 16L1067 268 0.031 -2.77 5.24 -0.18 -1.6 1.09 50.9 37.02 -0.003 781.40 -17.54 0 -0.1 -45.78 CB1812M -0.016 -3.39 57.22 0.55 -1.1 -9.54 5.0 22.22 -0.001 30.52 -8.26 2 -0.1 -13.41 RL338261A O 0.107 -1.73 -9.93 -0.15 -1.9 40.17 14.4 65.61 -0.003 496.99 -5.73 17 7.0 -25.68 RL34875SO 0.009 -3.15 -16.21 3.02 -1.1 9.34 3.5 -16.67 0.002 69.75 18.22 2 0.0 -23.40 621 Table B.12 (Continued) Hole ID Depth (ft) Δ Ta_ppm Δ Th_ppm Δ Tl_ppm Δ U_ppm Δ V_ppm Δ W_ppm Δ Y_ppm Δ Zn_ppm Δ Zr_ppm Δ Mass CaO Δ Mass Cr2O3 Δ Mass FeO Δ Mass K2O Δ Mass MgO 37L482 926 0.03 0.1 0.35 0.0 60.70 -1.43 -0.23 -2.18 8.11 -2.71 0.05 0.78 1.13 -2.16 D27943 3389.5 -0.09 -0.2 0.23 0.0 8.39 10.18 -13.58 -38.47 8.45 -5.16 0.01 -4.62 3.42 -2.52 D39204 481 -0.02 0.0 0.75 0.0 71.47 15.95 -6.85 17.07 25.90 -4.04 0.00 0.24 1.17 -2.07 D39018 43 -0.09 -0.1 0.08 0.1 106.55 3.96 -8.42 -68.25 24.06 -0.05 0.00 -6.86 2.58 -2.62 D2253 75 0.08 0.2 -0.23 0.1 -39.95 10.53 -3.30 35.27 19.02 -1.32 0.00 1.94 -2.01 -0.23 R87107 482.3 0.14 0.1 -0.12 0.1 76.45 -8.39 13.59 5.52 29.45 1.76 -0.02 1.30 -1.19 0.50 DS172 123.1 B 0.00 0.1 -0.01 0.0 -12.49 -8.74 8.29 28.01 -0.63 -4.69 -0.01 9.27 0.69 -2.22 DS173 499.6 0.06 0.0 -0.32 0.0 -21.51 -9.56 18.63 20.07 8.40 0.02 -0.02 6.63 -1.48 -0.51 37L667 4 0.04 0.0 -0.36 0.0 -31.69 0.42 -0.34 2.51 -3.88 -2.29 -0.01 3.03 -2.18 -0.82 37L667 152 0.04 -0.1 -0.11 0.0 11.95 3.19 -3.45 32.50 -6.28 -2.95 0.01 2.67 -1.06 -0.82 37L667 194 -0.02 -0.2 -0.41 0.0 -82.17 -9.61 1.93 18.65 -18.36 1.69 0.01 2.13 -2.25 5.53 D39200 3115 0.09 0.0 -0.10 0.0 -31.34 -9.06 15.13 39.24 -10.58 2.45 -0.02 1.31 -1.43 -0.20 DS352 134 0.09 0.2 0.02 0.0 -48.49 -8.77 -0.34 29.27 16.97 1.26 -0.01 3.31 -0.75 1.30 DS358 321 -0.04 -0.1 -0.07 -0.1 -126.46 -5.19 -5.39 40.94 -19.40 -0.85 0.01 -1.25 -0.91 0.17 GC04007 2000 0.06 0.2 -0.38 0.0 -81.05 -9.40 -4.12 35.36 3.99 -4.68 -0.01 2.26 -1.23 -2.62 R87105 699.8 0.08 0.3 -0.38 0.1 -77.06 -9.83 6.86 116.98 3.23 0.19 -0.02 3.95 -2.01 4.77 30L1268 25.7 0.07 0.0 -0.26 0.0 64.88 11.92 36.56 73.96 15.21 -5.43 -0.01 17.30 -2.14 -0.42 37L726 836.6 0.05 -0.1 -0.30 0.0 37.51 7.31 -4.50 -12.96 18.03 -2.93 -0.01 1.16 -2.23 -0.51 CR466 145 0.19 0.0 -0.41 0.0 30.21 -9.33 19.73 38.23 16.84 -1.99 -0.02 4.12 -2.25 -1.33 D14391 1810 0.10 0.2 -0.36 0.1 -66.37 35.77 -1.42 7.95 14.02 -3.83 -0.02 3.81 -2.28 -0.79 D39200 3241 0.07 -0.1 -0.38 0.0 -4.96 9.10 5.73 13.08 -14.52 -1.08 -0.02 0.32 -2.32 -1.36 D39357 1287 0.08 0.1 1.40 0.0 -32.21 11.55 -2.90 197.36 5.71 -6.16 -0.02 5.16 -1.38 -1.26 DS172 123.1 C -0.01 0.0 -0.34 0.0 -12.17 -8.49 12.52 35.59 -3.74 -2.29 0.00 13.41 -1.84 -1.60 19L547 495.8 0.11 0.2 -0.11 0.1 -42.49 41.93 12.80 -17.53 12.66 -4.24 -0.01 14.54 -1.91 0.15 37L482 118 0.04 0.0 0.13 0.1 63.64 0.64 83.51 275.38 -13.40 -2.09 0.01 64.17 -0.93 3.70 CR4610 947 0.15 0.0 -0.09 0.1 101.82 -9.06 4.87 29.20 27.30 -1.76 -0.02 2.37 -0.86 -3.03 D21708 2760 0.46 9.6 -0.17 2.7 -277.27 -9.17 8.33 107.75 73.97 -3.84 -0.04 7.85 -1.15 -2.78 DS177 1500.8 0.06 -0.1 -0.18 0.0 -52.96 -9.41 12.81 192.50 -0.03 -2.13 -0.02 2.80 -2.18 -1.72 DS615 1905.1 0.12 2.1 -0.09 0.8 -308.93 0.82 1.99 210.01 32.13 -0.75 -0.04 25.23 1.12 -2.03 D33003 2004 0.21 0.5 0.18 0.1 46.11 -1.78 22.91 38.13 51.96 3.26 -0.04 4.67 -1.24 0.81 DS360 124 -0.05 -0.1 -0.37 0.0 8.85 -2.86 -3.67 -13.90 -14.56 6.87 0.00 -0.26 -2.15 2.23 GC04007 2859 0.31 4.4 -0.38 0.8 -213.53 -9.37 10.55 25.20 80.36 0.44 -0.03 -1.50 -2.25 -1.22 37L667 1061 0.03 -0.1 -0.05 -0.1 -0.03 -38.68 -3.67 -7.99 -52.87 -7.14 0.00 -7.44 -1.81 -5.25 D39018 635 0.08 -0.1 0.17 -0.3 -0.04 -33.10 -9.48 -5.91 -36.94 -7.06 -0.02 -7.79 2.53 -5.18 D39200 843 0.04 -0.1 0.07 0.0 -0.09 -14.37 0.38 -10.13 -68.96 -0.14 0.00 -4.65 -0.23 -1.31 D39200 1318 -0.01 -0.1 0.07 0.5 -0.02 -38.09 34.46 -15.42 -78.87 -3.16 -0.01 -10.32 -0.12 -3.21 CB4043HR -0.03 -0.5 0.20 -0.2 36.15 1.94 1.77 -29.75 -3.35 6.03 0.02 -2.18 0.54 2.73 D15367 5.5 -0.10 -0.6 0.59 -0.2 20.39 45.57 -11.41 -41.78 -8.43 7.34 0.01 -2.33 1.25 1.41 622 Table B.12 (Continued) Hole ID Depth (ft) Δ Ta_ppm Δ Th_pp m Δ Tl_pp m Δ U_pp m Δ V_ppm Δ W_ppm Δ Y_ppm Δ Zn_ppm Δ Zr_ppm Δ Mass CaO Δ Mass Cr2O3 Δ Mass FeO Δ Mass K2O Δ Mass MgO D39357 2067 0.02 -0.4 0.04 -0.2 -85.86 72.81 -2.76 -50.46 -4.82 4.43 0.01 -0.21 -0.31 0.28 D14391 2922 0.00 -0.6 -0.17 -0.2 68.39 -9.43 -8.45 -83.57 -10.60 1.79 -0.01 -10.40 3.76 -1.30 CB25510LZ -0.14 -0.6 0.62 -0.3 60.87 4.46 -10.07 -30.87 -25.90 13.23 0.03 4.35 1.62 7.74 CB302561 -0.06 -0.4 0.29 -0.1 163.67 40.35 -9.66 -49.36 2.12 5.94 0.04 -0.21 0.65 1.50 37L768 66 -0.10 -1.8 -0.32 -0.5 40.66 -10.13 -0.59 76.68 -15.48 36.16 0.02 172.66 -0.74 50.23 DS360 528 -0.10 -1.8 -0.32 -0.5 40.12 -6.84 -6.82 64.92 -12.85 122.39 0.02 188.86 -0.70 90.52 17L1437 556 -0.10 -1.8 -0.26 -0.4 -21.06 -10.26 -5.81 21.01 -13.48 91.06 0.02 24.00 0.14 47.92 24L755 64 -0.08 -1.7 -0.28 -0.5 -48.79 -8.53 -8.77 -46.42 -16.65 13.96 -0.02 -0.37 -0.29 6.44 37L482 91 -0.08 -1.8 -0.31 -0.5 -68.78 -11.43 -9.03 -46.27 -20.46 12.92 0.01 -1.74 -0.66 3.85 37L594 299 -0.10 -1.8 -0.22 -0.5 -35.50 -11.81 -5.28 -10.40 -10.14 110.98 0.00 28.91 1.09 59.31 37L594 815 -0.10 -1.8 -0.25 -0.5 -36.90 -9.52 -2.66 -16.55 -13.82 73.02 0.02 21.73 1.11 36.05 37L768 98 -0.10 -1.8 -0.32 -0.5 12.73 78.03 8.53 107.92 -13.09 554.25 0.01 163.97 -0.25 320.47 D22203 908 -0.05 -1.6 -0.29 -0.5 -34.84 -9.82 -5.99 -32.88 -8.86 86.85 -0.02 25.80 0.78 45.18 D22223 975 -0.06 -1.7 -0.32 -0.4 0.24 -10.23 -6.61 10.89 -10.97 80.11 0.00 25.45 -0.70 40.42 D2435 454 -0.10 -1.8 -0.20 -0.5 -19.61 -3.06 -5.17 -12.39 -16.18 106.10 0.55 27.69 0.87 57.07 D33003 3210 -0.10 -1.8 -0.32 -0.5 128.17 158.63 23.76 341.59 16.67 1511.04 -0.02 301.28 0.52 932.56 D39018 1820 -0.10 -1.6 -0.24 -0.4 -61.68 -13.70 -7.18 -38.12 -13.02 168.98 0.10 5.13 0.85 -1.04 D39204 1333 -0.10 -1.8 -0.04 -0.5 -33.83 8.91 0.27 -9.30 -15.91 107.27 0.00 39.47 -0.19 56.26 GC04003 787 -0.10 -1.8 -0.32 -0.5 -57.81 -12.33 10.17 0.62 -21.24 1009.10 0.65 121.86 -0.33 788.23 BK0510 376 -0.08 -1.7 -0.27 -0.4 -83.03 -11.26 -9.07 -36.18 -14.03 2.99 -0.02 -8.05 0.14 -0.08 D27943 2104 -0.08 -1.7 -0.27 -0.5 -59.10 -13.80 -8.79 -48.83 -18.61 1.92 0.01 -5.87 1.69 -0.44 D39018 3562 -0.08 -1.8 -0.29 -0.5 -64.63 -13.30 -9.49 -41.01 -18.91 4.81 -0.01 -4.56 0.96 1.34 GC04007 911 -0.04 -1.0 -0.27 -0.3 -80.09 -13.76 -7.81 -46.05 -3.20 0.66 -0.03 -7.07 0.98 -2.02 RL422VG -0.21 -0.9 0.95 -0.3 1131.98 17.78 8.29 4199.11 9.84 38.53 0.16 150.13 2.33 18.80 D39200 1001 0.01 -0.1 0.88 0.0 118.77 72.94 6.98 349.96 4.14 20.77 -0.01 73.36 0.71 9.34 D39200 1064 0.05 0.2 5.06 -0.1 514.38 106.99 39.25 458.57 22.64 -3.41 0.01 74.15 2.45 3.95 37L482 1347 0.22 3.8 0.68 1.0 -150.93 15.97 -4.20 685.01 65.96 -3.26 -0.02 31.45 0.78 0.96 D39200 1406 -0.11 -0.5 0.07 -0.2 -45.33 -6.74 -12.72 -103.18 -4.95 -5.30 -0.01 -13.18 -0.43 -4.74 DS352 390 0.03 -0.4 -0.23 -0.2 40.86 11.80 -9.10 -22.46 -16.01 1.40 0.05 -2.01 -0.70 1.07 37L768 1108 -0.01 -0.3 0.94 -0.1 154.86 28.21 -8.44 47.63 8.27 -0.09 0.02 1.24 2.25 -1.29 DS352 305 -0.07 -0.5 0.18 -0.1 76.93 20.69 -6.55 -14.29 13.23 14.90 0.01 1.42 0.81 5.75 16L1067 268 -0.11 -0.5 1.20 -0.1 -8.04 39.53 -2.27 776.34 -12.70 -3.63 0.00 -5.12 1.56 -3.48 CB1812M -0.10 -0.6 2.10 -0.2 -2.41 75.85 -15.33 -78.39 -28.08 -3.05 0.01 -3.88 0.71 -2.79 RL338261AO -0.11 -0.3 1.10 -0.1 1250.40 4.97 -6.22 509.78 14.28 -2.12 0.02 -4.11 2.34 -2.86 RL34875SO -0.06 -0.5 0.24 -0.1 31.83 188.97 -9.24 -28.00 -34.29 1.40 0.00 1.07 -0.37 -1.63 623 Table B.12 (Continued) Hole ID Depth (ft) Δ Mass MnO Δ Mass Na2O Δ Mass P2O5 Δ Mass SO3 Δ Mass SiO2 Δ Mass TiO2 PE Al2O3 PE CaO PE FeO PE K2O PE MgO PE MnO PE Na2O PE P2O5 37L482 926 0.01 -1.46 0.01 -0.01 3.68 0.15 0.95 0.98 1.19 0.38 0.46 0.05 0.39 0.02 D27943 3389.5 -0.13 -1.52 -0.02 0.39 7.39 -0.31 0.95 0.34 -0.23 0.99 0.36 0.01 0.38 0.01 D39204 481 -0.03 -2.21 0.01 0.57 4.53 -0.01 0.95 0.63 1.05 0.39 0.48 0.04 0.20 0.02 D39018 43 0.01 -2.08 -0.04 -0.14 -1.63 -0.17 0.95 1.68 -0.82 0.76 0.33 0.05 0.23 0.01 D2253 75 0.09 -0.37 0.01 0.39 0.14 0.27 0.84 2.38 4.07 0.72 0.11 0.10 0.29 0.03 R87107 482.3 0.07 0.18 0.06 -0.30 -0.35 0.59 0.84 3.16 3.90 0.93 0.30 0.09 0.43 0.04 DS172 123.1 B 0.53 -0.33 0.01 -0.30 -4.73 0.05 0.84 1.53 5.92 1.40 -0.39 0.21 0.30 0.03 DS173 499.6 0.38 -0.17 0.04 0.61 -18.48 0.27 0.84 2.72 5.25 0.85 0.05 0.17 0.34 0.04 37L667 4 0.11 -0.27 0.00 0.13 3.78 0.10 0.84 2.13 4.34 0.68 -0.03 0.10 0.32 0.02 37L667 152 0.00 1.16 -0.03 0.23 -2.14 0.08 0.84 1.97 4.25 0.96 -0.03 0.07 0.68 0.02 37L667 194 0.02 1.65 -0.01 -0.32 0.10 -0.20 0.84 3.14 4.11 0.66 1.57 0.08 0.80 0.02 D39200 3115 0.04 0.53 0.04 0.04 6.64 0.33 0.84 3.33 3.91 0.86 0.12 0.09 0.52 0.03 DS352 134 0.03 0.63 0.01 -0.14 -1.19 0.24 0.84 3.03 4.41 1.04 0.50 0.08 0.54 0.03 DS358 321 0.01 -0.32 -0.02 -0.03 2.58 -0.53 0.84 2.50 3.26 1.00 0.21 0.08 0.30 0.02 GC04007 2000 -0.06 0.61 0.01 -0.31 -9.11 0.00 0.84 1.53 4.15 0.92 -0.49 0.06 0.54 0.03 R87105 699.8 0.17 3.76 0.01 -0.29 3.93 -0.01 0.84 2.76 4.57 0.72 1.38 0.12 1.34 0.03 30L1268 25.7 0.50 -0.47 -0.01 1.68 13.02 0.15 0.84 1.34 7.95 0.69 0.07 0.20 0.27 0.02 37L726 836.6 0.04 -0.31 0.05 0.14 -15.93 0.18 0.84 1.97 3.87 0.66 0.04 0.08 0.30 0.04 CR466 145 0.04 -0.34 0.08 -0.18 0.14 0.64 0.84 2.21 4.62 0.66 -0.16 0.08 0.30 0.04 D14391 1810 0.20 -0.48 0.02 0.26 -5.91 0.24 0.84 1.74 4.54 0.65 -0.03 0.12 0.26 0.03 D39200 3241 0.08 -0.32 0.03 0.08 -8.62 0.30 0.84 2.44 3.66 0.64 -0.17 0.09 0.30 0.03 D39357 1287 0.02 -0.47 0.02 -0.05 12.73 0.20 0.84 1.16 4.88 0.88 -0.14 0.08 0.27 0.03 DS172 123.1 C 0.72 -0.50 0.01 -0.12 -5.27 0.00 0.84 2.13 6.97 0.76 -0.23 0.26 0.26 0.03 19L547 495.8 0.20 -0.42 0.02 1.41 -12.45 0.05 0.84 1.64 7.25 0.74 0.21 0.12 0.28 0.03 37L482 118 1.63 -0.27 -0.03 1.87 14.00 0.07 0.84 2.18 19.80 0.99 1.11 0.49 0.32 0.02 CR4610 947 0.03 1.48 0.02 0.32 -3.26 0.54 0.84 2.27 4.17 1.01 -0.59 0.08 0.76 0.03 D21708 2760 0.35 1.38 0.03 1.72 5.33 -0.28 0.84 1.74 5.56 0.94 -0.53 0.16 0.73 0.03 DS177 1500.8 0.39 0.25 -0.02 0.64 -15.29 0.25 0.84 2.17 4.28 0.68 -0.26 0.17 0.45 0.02 DS615 1905.1 0.75 -0.20 -0.01 0.00 11.40 -0.59 0.84 2.52 9.96 1.51 -0.34 0.26 0.33 0.02 D33003 2004 0.23 0.04 0.11 -0.10 -8.50 0.77 0.84 3.54 4.76 0.91 0.38 0.13 0.39 0.05 DS360 124 0.17 -0.29 -0.02 -0.23 9.89 -0.47 0.84 4.45 3.51 0.68 0.74 0.12 0.31 0.02 GC04007 2859 -0.06 5.15 0.17 0.30 11.66 0.13 0.84 2.82 3.20 0.66 -0.14 0.06 1.69 0.07 37L667 1061 -0.16 -0.41 -0.04 0.31 21.23 -0.08 0.84 0.91 1.69 0.77 -1.15 0.03 0.28 0.01 D39018 635 -0.16 -0.35 0.05 -0.03 4.28 0.28 0.84 0.93 1.60 1.87 -1.14 0.03 0.29 0.04 D39200 843 -0.14 -0.82 0.02 0.52 0.26 0.12 2.36 2.63 5.12 0.69 1.28 0.18 0.90 0.05 D39200 1318 -0.31 -0.83 0.01 0.68 3.93 0.12 2.36 1.57 3.13 0.73 0.61 0.13 0.89 0.05 CB4043HR -0.12 -0.65 -0.01 3.08 -1.91 0.01 2.36 4.80 6.00 0.96 2.70 0.19 0.96 0.04 D15367 5.5 -0.17 -0.56 -0.02 13.50 -3.53 -0.19 2.36 5.26 5.94 1.21 2.24 0.17 0.99 0.04 624 Table B.12 (Continued) Hole ID Depth (ft) Δ Mass MnO Δ Mass Na2O Δ Mass P2O5 Δ Mass SO3 Δ Mass SiO2 Δ Mass TiO2 PE Al2O3 PE CaO PE FeO PE K2O PE MgO PE MnO PE Na2O PE P2O5 D39357 2067 -0.18 -0.15 -0.02 7.68 -6.20 0.10 2.36 4.24 6.69 0.66 1.84 0.17 1.13 0.04 D14391 2922 -0.26 -0.63 0.02 -0.55 13.68 0.11 2.36 3.31 3.10 2.09 1.28 0.14 0.97 0.05 CB25510LZ 0.03 0.01 -0.08 14.67 0.10 -0.36 2.36 7.34 8.30 1.34 4.46 0.24 1.19 0.02 CB302561 -0.14 -0.47 -0.03 9.73 23.65 -0.13 2.36 4.77 6.69 1.00 2.27 0.18 1.02 0.03 37L768 66 4.66 -0.80 -0.01 7.33 71.81 -0.16 2.36 15.41 67.54 0.51 19.42 1.88 0.91 0.04 DS360 528 4.91 -0.81 0.06 36.33 267.95 -0.19 2.36 45.76 73.24 0.52 33.60 1.96 0.90 0.07 17L1437 556 1.47 -0.47 0.00 0.25 211.37 -0.04 2.36 34.73 15.21 0.82 18.61 0.75 1.02 0.04 24L755 64 0.12 -0.62 -0.02 -0.16 55.70 -0.12 2.36 7.59 6.63 0.67 4.01 0.28 0.97 0.04 37L482 91 0.05 -0.72 -0.04 -0.27 76.00 -0.16 2.36 7.23 6.15 0.54 3.10 0.25 0.93 0.03 37L594 299 1.28 0.10 0.00 -0.46 226.66 -0.21 2.36 41.75 16.94 1.15 22.62 0.69 1.22 0.04 37L594 815 1.64 0.33 -0.03 -0.25 222.37 -0.12 2.36 28.38 14.41 1.16 14.43 0.81 1.30 0.04 37L768 98 7.74 0.00 0.12 -0.03 1068.20 -0.40 2.36 197.79 64.48 0.68 114.55 2.96 1.19 0.09 D22203 908 1.65 -0.72 0.06 0.41 233.32 0.63 2.36 33.25 15.84 1.04 17.64 0.81 0.93 0.07 D22223 975 1.47 -0.82 0.02 0.40 143.04 0.09 2.36 30.88 15.72 0.52 15.97 0.75 0.90 0.05 D2435 454 1.31 0.45 -0.02 4.80 288.42 -0.11 2.36 40.03 16.51 1.07 21.83 0.69 1.35 0.04 D33003 3210 12.80 0.56 0.41 -0.60 2437.31 0.53 2.36 534.60 112.82 0.95 330.02 4.74 1.38 0.19 D39018 1820 2.99 0.25 0.03 1.57 166.06 0.02 2.36 62.16 8.57 1.07 1.37 1.28 1.27 0.05 D39204 1333 1.28 -0.76 0.00 1.28 310.11 -0.45 2.36 40.44 20.66 0.70 21.55 0.68 0.92 0.04 GC04003 787 25.39 1.19 0.18 0.38 1738.73 -0.54 2.36 357.91 49.66 0.65 279.21 9.17 1.61 0.11 BK0510 376 -0.23 0.41 -0.02 -0.46 17.28 -0.42 2.36 3.73 3.93 0.82 1.71 0.15 1.33 0.04 D27943 2104 -0.17 -0.33 -0.03 -0.53 -5.58 -0.13 2.36 3.35 4.70 1.36 1.59 0.17 1.07 0.03 D39018 3562 -0.19 -0.15 -0.02 -0.56 -16.67 -0.01 2.36 4.37 5.16 1.11 2.21 0.17 1.14 0.04 GC04007 911 -0.26 2.47 0.13 -0.14 6.94 -0.01 2.36 2.91 4.27 1.11 1.03 0.14 2.06 0.09 RL422VG 0.26 -0.34 -0.03 187.90 341.60 -0.38 2.36 16.24 59.61 1.59 8.36 0.32 1.07 0.03 D39200 1001 0.45 -0.62 -0.03 68.86 -6.74 -0.01 2.36 9.99 32.59 1.02 5.03 0.39 0.97 0.04 D39200 1064 0.79 -0.69 -0.02 54.08 -21.32 -0.17 2.36 1.48 32.86 1.63 3.13 0.51 0.94 0.04 37L482 1347 0.21 -0.71 0.05 43.15 -2.19 -0.28 2.36 1.53 17.83 1.04 2.08 0.31 0.94 0.06 D39200 1406 -0.36 -0.90 0.02 -0.22 22.07 -0.42 2.36 0.81 2.12 0.62 0.07 0.11 0.87 0.05 DS352 390 -0.13 -0.75 0.02 -0.39 7.92 0.26 2.36 3.17 6.06 0.52 2.12 0.19 0.92 0.05 37L768 1108 -0.20 -0.63 -0.01 10.35 54.18 0.06 2.36 2.65 7.20 1.56 1.29 0.16 0.96 0.04 DS352 305 -0.04 -0.69 0.02 12.13 6.69 -0.18 2.36 7.92 7.26 1.05 3.76 0.22 0.94 0.05 16L1067 268 -0.34 -0.60 -0.05 8.28 39.12 -0.29 2.36 1.40 4.96 1.32 0.52 0.11 0.98 0.03 CB1812M -0.27 -0.37 -0.04 15.47 2.25 -0.11 2.36 1.60 5.40 1.02 0.76 0.14 1.06 0.03 RL338261AO -0.33 -0.58 -0.07 11.07 110.14 -0.37 2.36 1.93 5.32 1.59 0.73 0.12 0.98 0.02 RL34875SO -0.09 -0.69 -0.07 24.36 0.19 0.06 2.36 3.17 7.14 0.64 1.16 0.20 0.95 0.02 625 Table B.12 (Continued) Hole ID Depth (ft) PE TiO2 PE SO3 PE Cr2O3 PE SiO2 PE Ag_ppm PE Al_pct PE As_ppm PE Ba_ppm PE Be_ppm PE Bi_ppm PE Ca_pct PE Cd_pp m PE Ce_p pm PE Co_ppm 37L482 926 0.19 0.07 0.02 2.90 0.02 0.50 19.09 162.29 0.15 0.05 0.70 0.05 2.31 5.34 D27943 3389.5 0.07 0.18 0.01 3.87 0.02 0.50 13.71 363.54 0.10 0.05 0.24 0.03 0.35 1.22 D39204 481 0.15 0.22 0.01 3.12 0.11 0.50 65.56 87.14 0.09 0.45 0.05 2.43 2.25 D39018 43 0.11 0.04 0.01 1.50 0.02 0.50 14.55 143.87 0.04 1.20 0.02 0.84 -1.56 D2253 75 0.26 0.44 0.02 2.52 0.21 0.45 107.11 260.51 0.16 0.02 1.70 0.08 4.42 8.55 R87107 482.3 0.34 0.27 0.02 2.40 0.19 0.45 82.64 320.05 0.27 0.03 2.26 0.05 4.19 8.83 DS172 123.1 B 0.20 0.27 0.02 1.29 0.16 0.45 91.60 379.81 0.35 0.01 1.09 0.03 5.07 10.28 DS173 499.6 0.26 0.50 0.02 -2.19 0.17 0.45 85.16 307.32 0.21 0.01 1.94 0.05 5.00 17.15 37L667 4 0.21 0.38 0.02 3.44 0.16 0.45 85.66 257.68 0.16 0.01 1.53 0.06 4.36 9.21 37L667 152 0.21 0.40 0.02 1.95 0.15 0.45 82.48 339.79 0.19 0.02 1.41 0.04 2.98 14.23 37L667 194 0.14 0.26 0.03 2.51 0.16 0.45 82.57 304.33 0.12 0.01 2.25 0.05 3.25 13.02 D39200 3115 0.27 0.35 0.02 4.17 0.18 0.45 102.26 368.09 0.18 0.01 2.38 0.11 4.72 14.12 DS352 134 0.25 0.31 0.02 2.19 0.17 0.45 83.88 343.89 0.16 0.01 2.17 0.06 4.94 9.50 DS358 321 0.05 0.34 0.02 3.14 0.19 0.45 93.19 308.28 0.18 0.01 1.78 0.22 3.57 6.88 GC04007 2000 0.19 0.26 0.02 0.18 0.16 0.45 82.89 284.78 0.15 0.01 1.09 0.04 4.74 9.43 R87105 699.8 0.19 0.27 0.02 3.48 0.26 0.45 83.48 268.98 0.19 0.03 1.97 0.05 5.41 14.98 30L1268 25.7 0.22 0.77 0.02 5.78 0.19 0.45 84.52 274.24 0.17 0.01 0.96 0.05 6.12 13.14 37L726 836.6 0.23 0.38 0.02 -1.54 0.16 0.45 94.75 261.15 0.11 0.01 1.41 0.04 4.15 10.07 CR466 145 0.35 0.30 0.02 2.52 0.17 0.45 82.74 254.52 0.20 0.01 1.58 0.05 5.28 8.70 D14391 1810 0.25 0.41 0.02 0.99 0.16 0.45 94.44 257.05 0.12 0.01 1.25 0.04 3.64 15.42 D39200 3241 0.26 0.36 0.02 0.31 0.17 0.45 125.13 259.42 0.23 0.01 1.74 0.06 4.48 13.76 D39357 1287 0.24 0.33 0.02 5.71 0.17 0.45 127.96 281.12 0.13 0.83 0.16 3.97 10.66 DS172 123.1 C 0.19 0.31 0.02 1.15 0.18 0.45 87.00 273.39 0.36 0.02 1.52 0.04 5.53 13.52 19L547 495.8 0.20 0.70 0.02 -0.66 0.21 0.45 144.22 266.38 0.17 0.01 1.17 0.06 5.07 11.12 37L482 118 0.21 0.81 0.02 6.03 0.22 0.45 138.01 381.75 0.30 0.01 1.56 0.23 8.07 29.80 CR4610 947 0.33 0.42 0.02 1.66 0.18 0.45 82.81 303.76 0.20 0.02 1.62 0.04 3.54 13.34 D21708 2760 0.12 0.78 0.01 3.84 0.18 0.45 83.23 297.67 0.25 0.02 1.24 0.04 19.06 3.78 DS177 1500.8 0.25 0.50 0.02 -1.38 0.17 0.45 94.46 269.10 0.14 0.02 1.55 0.07 4.99 18.00 DS615 1905.1 0.04 0.34 0.01 5.37 0.17 0.45 156.93 313.57 0.41 0.06 1.80 0.05 8.35 4.15 D33003 2004 0.38 0.32 0.01 0.34 0.18 0.45 89.70 282.01 0.41 0.01 2.53 0.07 7.14 11.57 DS360 124 0.07 0.28 0.02 4.99 0.21 0.45 96.36 262.09 0.14 0.01 3.18 0.07 3.47 9.24 GC04007 2859 0.22 0.42 0.01 5.44 0.16 0.45 82.53 278.89 0.41 0.01 2.02 0.05 20.02 7.01 37L667 1061 0.17 0.42 0.02 7.86 0.17 0.45 108.67 304.79 0.19 0.01 0.65 0.04 3.96 14.93 D39018 635 0.26 0.33 0.02 3.57 0.15 0.45 96.10 344.55 0.19 0.66 0.04 4.50 5.18 D39200 843 0.41 0.72 0.01 5.65 0.09 1.25 69.71 90.90 0.25 0.03 1.88 0.15 13.49 20.51 D39200 1318 0.41 0.78 0.01 6.94 0.05 1.25 63.69 77.85 0.21 0.03 1.12 0.13 11.85 8.79 CB4043HR 0.38 1.62 0.02 4.88 2.29 1.25 189.86 96.35 0.34 0.08 3.43 0.20 11.82 19.92 D15367 5.5 0.31 5.29 0.02 4.31 0.50 1.25 360.55 152.19 0.63 0.10 3.76 0.17 11.78 17.21 626 Table B.12 (Continued) Hole ID Depth (ft) PE TiO2 PE SO3 PE Cr2O3 PE SiO2 PE Ag_ppm PE Al_pct PE As_ppm PE Ba_ppm PE Be_ppm PE Bi_ppm PE Ca_pct PE Cd_ppm PE Ce_ppm PE Co_ppm D39357 2067 0.41 3.24 0.02 3.37 0.73 1.25 56.01 91.37 0.51 0.23 3.03 0.20 13.47 18.67 D14391 2922 0.41 0.35 0.01 10.37 0.05 1.25 85.50 137.94 0.25 0.03 2.37 0.15 12.48 8.30 CB25510LZ 0.24 5.70 0.02 5.59 0.76 1.25 146.14 161.56 0.51 0.12 5.24 0.24 11.79 74.74 CB302561 0.33 3.97 0.03 13.88 3.20 1.25 5041.04 114.18 0.39 0.05 3.41 0.18 14.65 29.65 37L768 66 0.32 3.12 0.02 30.83 0.07 1.25 203.41 0.23 2.84 0.15 11.09 23.15 DS360 528 0.30 13.33 0.02 99.88 0.09 1.25 3256.87 0.30 0.04 6.14 0.23 10.96 23.75 17L1437 556 0.36 0.63 0.02 79.96 0.06 1.25 56.52 72.19 0.26 0.03 4.94 0.17 10.17 14.32 24L755 64 0.33 0.49 0.01 25.16 0.06 1.25 50.40 69.46 0.24 0.02 1.99 0.12 9.64 13.94 37L482 91 0.32 0.45 0.02 32.31 0.08 1.25 47.62 68.55 0.23 0.02 1.95 0.14 10.34 13.55 37L594 299 0.30 0.38 0.01 85.35 0.07 1.25 54.18 76.16 0.29 0.04 5.71 0.15 10.44 17.63 37L594 815 0.33 0.45 0.02 83.83 0.06 1.25 50.33 74.76 0.27 0.03 4.25 0.16 10.28 16.07 37L768 98 0.23 0.53 0.02 381.58 0.06 1.25 49.41 0.41 22.66 0.29 11.41 22.42 D22203 908 0.59 0.69 0.01 87.69 0.06 1.25 50.67 72.40 0.30 0.03 4.78 0.12 11.23 14.54 D22223 975 0.40 0.68 0.01 55.91 0.07 1.25 67.74 68.67 0.25 4.52 0.20 10.94 19.68 D2435 454 0.33 2.23 0.21 107.09 0.18 1.25 173.40 73.58 0.36 0.05 5.52 0.15 9.98 22.16 D33003 3210 0.56 0.00 0.01 863.54 0.11 1.25 61.04 99.78 2.15 59.26 0.64 18.20 20.86 D39018 1820 0.38 1.09 0.05 64.01 0.06 1.25 66.42 85.80 0.26 0.03 7.92 0.12 9.99 15.84 D39204 1333 0.21 0.99 0.02 114.72 0.07 1.25 98.82 70.07 0.41 5.56 0.15 10.44 14.53 GC04003 787 0.18 0.68 0.24 617.63 0.11 1.25 65.23 90.19 0.04 40.06 0.90 14.52 61.94 BK0510 376 0.22 0.38 0.01 11.64 0.06 1.25 46.44 70.98 0.26 0.03 1.57 0.12 9.65 12.60 D27943 2104 0.33 0.35 0.02 3.59 0.06 1.25 46.42 88.85 0.25 0.02 1.53 0.11 9.54 12.96 D39018 3562 0.37 0.35 0.01 -0.31 0.06 1.25 48.06 75.07 0.23 0.02 1.64 0.11 9.50 14.02 GC04007 911 0.37 0.49 0.00 8.00 0.06 1.25 46.59 94.70 0.26 0.03 1.49 0.11 13.01 12.46 RL422VG 0.24 66.69 0.07 125.81 323.46 1.25 30564.09 231.43 1.05 25.70 11.61 7.61 21.78 279.61 D39200 1001 0.37 24.78 0.01 3.18 2.49 1.25 74.30 146.67 0.35 0.21 7.14 1.34 13.98 29.01 D39200 1064 0.31 19.58 0.02 -1.95 1.92 1.25 181.10 127.63 0.41 0.09 1.06 0.55 21.38 66.11 37L482 1347 0.27 15.73 0.01 4.78 0.64 1.25 200.61 106.50 0.35 0.43 1.09 0.71 21.30 28.79 D39200 1406 0.23 0.46 0.01 13.32 0.07 1.25 70.38 76.25 0.20 0.03 0.58 0.13 11.92 3.75 DS352 390 0.46 0.41 0.03 8.34 0.05 1.25 58.99 70.07 0.27 0.03 2.27 0.13 13.40 18.06 37L768 1108 0.39 4.18 0.02 24.63 0.88 1.25 55.43 204.63 0.45 0.09 1.89 0.26 14.07 38.20 DS352 305 0.31 4.81 0.02 7.91 0.36 1.25 77.68 143.56 0.43 0.16 5.66 0.31 13.06 20.48 16L1067 268 0.27 3.46 0.02 19.33 1.41 1.25 4811.66 187.66 0.36 0.11 1.00 1.65 11.40 21.63 CB1812M 0.33 5.99 0.02 6.35 0.23 1.25 165.63 105.11 0.64 0.09 1.15 0.13 11.68 21.89 RL338261AO 0.24 4.44 0.02 44.33 5.26 1.25 7561.43 142.96 0.66 0.17 1.38 0.96 13.02 19.57 RL34875SO 0.39 9.12 0.01 5.62 1.11 1.25 548.38 77.45 0.32 0.04 2.27 0.20 11.99 20.42 627 Table B.12 (Continued) Hole ID Depth (ft) PE Cr_ppm PE Cs_ppm PE Cu_ppm PE Fe_pct PE Ga_pp m PE Ge_ppm PE Hf_ppm PE In_ppm PE K_pct PE La_ppm PE Li_ppm PE Mg_p ct PE Mn_ppm PE Mo_ppm 37L482 926 160.08 2.95 1.30 0.93 2.44 0.06 0.5 0.01 0.32 1.0 30.33 0.28 388.05 0.06 D27943 3389.5 96.32 2.18 3.16 -0.18 2.07 0.03 0.5 0.00 0.82 0.3 22.38 0.22 107.50 0.04 D39204 481 82.78 2.26 29.11 0.82 1.46 0.06 0.6 0.02 0.33 1.0 26.66 0.29 317.78 0.13 D39018 43 71.03 1.49 -0.68 -0.63 1.33 0.05 0.7 -0.01 0.63 0.4 22.17 0.20 403.72 0.08 D2253 75 151.18 2.50 87.09 3.16 1.91 0.07 0.6 0.04 0.60 1.6 2.56 0.07 745.20 0.14 R87107 482.3 108.98 1.46 60.79 3.04 3.08 0.06 0.7 0.04 0.77 1.5 15.60 0.18 713.56 0.20 DS172 123.1 B 131.21 3.65 53.17 4.60 2.58 0.07 0.5 0.04 1.16 2.2 22.10 -0.24 1610.25 0.14 DS173 499.6 103.13 1.18 137.82 4.08 2.13 0.07 0.5 0.05 0.71 1.8 3.26 0.03 1318.29 0.16 37L667 4 132.83 1.89 65.65 3.38 2.02 0.05 0.4 0.04 0.56 1.4 9.44 -0.02 784.26 0.33 37L667 152 156.39 3.34 80.38 3.31 2.29 0.05 0.5 0.04 0.80 1.0 33.18 -0.02 576.79 0.17 37L667 194 171.42 1.00 65.10 3.20 1.19 0.05 0.4 0.03 0.55 1.1 33.56 0.95 609.50 0.18 D39200 3115 102.84 2.35 78.46 3.04 1.70 0.05 0.5 0.04 0.72 1.7 21.03 0.07 658.76 0.23 DS352 134 136.46 2.76 85.82 3.43 1.69 0.06 0.6 0.04 0.86 1.8 20.25 0.30 627.16 0.19 DS358 321 167.95 2.76 55.88 2.53 0.90 0.05 0.3 0.03 0.83 1.3 32.33 0.13 581.92 0.34 GC04007 2000 123.65 3.85 85.29 3.22 1.58 0.06 0.5 0.04 0.76 1.8 14.27 -0.30 455.98 0.16 R87105 699.8 116.98 1.07 84.22 3.56 1.86 0.06 0.5 0.04 0.60 2.0 22.93 0.83 898.83 0.15 30L1268 25.7 128.93 1.08 75.46 6.18 2.17 0.10 0.5 0.04 0.57 2.6 9.62 0.04 1558.31 0.19 37L726 836.6 120.16 1.06 67.51 3.01 2.12 0.06 0.6 0.05 0.55 1.4 18.28 0.03 651.66 0.12 CR466 145 107.19 0.93 80.47 3.59 2.82 0.07 0.6 0.05 0.55 1.9 3.51 -0.10 642.71 0.17 D14391 1810 113.62 1.01 66.58 3.53 1.77 0.05 0.5 0.03 0.54 1.3 14.06 -0.02 956.24 0.23 D39200 3241 103.44 0.92 63.05 2.84 2.19 0.04 0.4 0.04 0.53 1.5 5.31 -0.10 718.84 0.15 D39357 1287 116.40 1.79 79.20 3.79 1.60 0.08 0.6 0.04 0.73 1.4 8.37 -0.09 608.07 0.19 DS172 123.1 C 141.14 2.01 63.68 5.42 2.80 0.09 0.5 0.04 0.63 2.5 17.60 -0.14 1979.05 0.15 19L547 495.8 123.98 1.48 98.98 5.64 2.46 0.10 0.5 0.03 0.62 2.1 9.28 0.13 961.73 0.17 37L482 118 157.59 4.09 105.69 15.40 3.42 0.63 0.4 0.04 0.82 3.4 20.38 0.67 3752.51 0.31 CR4610 947 113.04 1.49 97.40 3.25 2.85 0.07 0.7 0.04 0.84 1.2 6.12 -0.36 627.92 0.21 D21708 2760 82.13 2.43 47.29 4.32 2.45 0.09 0.9 0.03 0.78 10.1 14.61 -0.32 1250.21 0.35 DS177 1500.8 119.28 2.72 124.26 3.33 2.49 0.06 0.5 0.04 0.56 1.6 12.23 -0.16 1334.26 0.15 DS615 1905.1 76.10 7.28 48.75 7.74 2.94 0.11 0.6 0.03 1.25 4.0 15.35 -0.20 2039.41 0.50 D33003 2004 79.11 3.35 64.14 3.70 2.54 0.06 0.8 0.05 0.76 2.7 39.35 0.23 1011.25 0.20 DS360 124 141.18 1.28 96.19 2.73 0.87 0.05 0.4 0.04 0.57 1.2 9.46 0.44 907.22 0.19 GC04007 2859 86.61 1.37 57.27 2.48 2.82 0.05 1.0 0.03 0.55 8.9 15.12 -0.08 463.27 0.13 37L667 1061 146.03 1.23 92.10 1.32 2.74 0.04 0.5 0.03 0.64 1.5 2.57 -0.70 263.74 0.20 D39018 635 109.10 1.52 82.61 1.25 2.38 0.04 0.7 0.04 1.55 1.6 1.52 -0.69 252.35 0.14 D39200 843 89.07 4.16 122.09 3.98 2.59 0.18 0.8 0.03 0.57 7.0 37.46 0.77 1409.47 0.24 D39200 1318 70.30 4.52 60.10 2.43 3.41 0.17 0.7 0.02 0.60 6.3 30.57 0.37 971.62 0.22 CB4043HR 137.17 4.36 152.17 4.66 3.16 0.18 0.6 0.03 0.80 6.3 48.93 1.63 1485.19 0.28 D15367 5.5 118.79 5.08 84.13 4.62 3.71 0.19 0.5 0.02 1.00 6.3 33.08 1.35 1327.73 2.44 628 Table B.12 (Continued) Hole ID Depth (ft) PE Cr_ppm PE Cs_ppm PE Cu_ppm PE Fe_pct PE Ga_pp m PE Ge_p pm PE Hf_ppm PE In_ppm PE K_pct PE La_ppm PE Li_ppm PE Mg_pct PE Mn_ppm PE Mo_ppm D39357 2067 122.79 5.00 137.13 5.20 4.43 0.22 0.7 0.02 0.55 7.0 29.11 1.11 1310.11 27.35 D14391 2922 76.15 4.00 71.28 2.41 3.90 0.18 0.6 0.05 1.74 6.7 20.49 0.77 1092.78 0.18 CB25510LZ 158.82 5.14 123.06 6.45 3.60 0.23 0.4 0.03 1.11 6.3 72.59 2.69 1875.78 0.18 CB302561 190.44 4.79 192.05 5.20 4.68 0.21 0.7 0.03 0.83 7.3 36.24 1.37 1428.19 0.39 37L768 66 81.28 3.13 82.88 11.19 3.13 0.24 0.5 0.02 0.42 5.6 26.83 2.46 3251.52 0.34 DS360 528 79.86 3.11 107.21 11.86 3.47 0.23 0.5 0.04 0.42 5.6 26.04 3.76 3354.17 0.23 17L1437 556 80.32 3.19 70.54 5.00 3.25 0.17 0.5 0.02 0.46 5.2 37.96 2.39 1930.23 0.24 24L755 64 67.22 3.24 69.45 3.99 3.09 0.15 0.5 0.02 0.44 5.0 30.14 1.05 1372.24 0.23 37L482 91 76.68 3.11 71.42 3.93 3.08 0.15 0.5 0.02 0.42 5.3 26.31 0.96 1341.35 0.20 37L594 299 72.76 3.41 71.58 5.20 3.27 0.17 0.5 0.02 0.50 5.3 30.91 2.75 1853.04 0.21 37L594 815 81.25 3.56 65.91 4.91 3.50 0.17 0.5 0.02 0.50 5.3 30.74 2.00 2000.38 0.22 37L768 98 78.24 3.40 68.73 10.83 3.48 0.25 0.5 0.03 0.44 5.8 31.84 11.18 4522.76 0.53 D22203 908 65.84 3.26 63.87 5.08 3.50 0.17 0.6 0.03 0.48 5.9 26.36 2.30 2004.22 0.31 D22223 975 73.45 3.08 109.52 5.06 3.21 0.16 0.5 0.03 0.42 5.6 29.94 2.14 1928.24 0.43 D2435 454 275.26 3.43 71.99 5.15 3.74 0.18 0.5 0.03 0.49 5.2 33.62 2.68 1863.62 1.12 D33003 3210 65.26 3.24 70.77 16.54 4.35 0.35 0.7 0.06 0.47 8.7 43.25 30.94 6618.34 0.68 D39018 1820 111.04 3.28 70.64 4.22 3.29 0.16 0.5 0.02 0.49 5.2 28.63 0.80 2556.93 0.21 D39204 1333 74.44 3.16 68.30 5.64 4.17 0.18 0.4 0.02 0.44 5.4 29.99 2.65 1851.71 0.35 GC04003 787 312.03 3.85 201.79 9.07 3.62 0.25 0.03 0.43 7.1 50.76 26.28 11828.61 0.89 BK0510 376 67.44 3.12 63.11 3.67 3.35 0.15 0.5 0.02 0.46 5.0 26.03 0.84 1227.61 0.21 D27943 2104 78.32 3.24 67.49 3.76 3.10 0.15 0.5 0.02 0.52 5.0 28.54 0.82 1250.03 0.18 D39018 3562 69.79 3.48 63.85 3.81 3.16 0.15 0.5 0.02 0.49 5.0 27.83 0.88 1244.42 0.18 GC04007 911 62.81 3.45 64.66 3.71 3.45 0.15 0.6 0.02 0.49 6.5 29.35 0.77 1214.82 0.23 RL422VG 485.53 4.55 4361.84 46.35 8.38 2.34 0.6 0.68 1.32 13.1 67.86 5.04 2499.09 1.13 D39200 1001 76.70 4.30 303.88 25.34 4.25 0.48 0.7 0.06 0.85 7.3 35.47 3.03 3022.52 1.42 D39200 1064 118.85 6.74 196.24 25.56 3.89 0.48 0.8 0.05 1.35 10.5 57.08 1.89 3952.62 0.92 37L482 1347 57.49 3.71 150.45 13.87 4.37 0.34 1.3 0.14 0.87 11.4 60.33 1.25 2372.24 2.12 D39200 1406 81.17 3.27 89.24 1.65 3.03 0.6 0.01 0.51 6.4 18.45 0.04 829.92 0.27 DS352 390 211.41 3.26 53.72 4.71 3.37 0.20 0.5 0.03 0.43 6.9 40.17 1.28 1458.52 0.22 37L768 1108 139.22 3.96 148.82 5.60 4.91 0.24 0.8 0.03 1.30 7.4 32.77 0.78 1250.21 1.14 DS352 305 110.50 4.38 136.37 5.65 3.23 0.22 0.8 0.03 0.87 6.8 27.53 2.27 1696.89 2.84 16L1067 268 107.14 5.75 188.59 3.86 3.24 0.17 0.4 0.04 1.09 6.5 40.02 0.31 882.86 0.21 CB1812M 121.30 4.88 84.99 4.20 2.60 0.19 0.3 0.02 0.85 6.3 58.32 0.46 1068.08 0.46 RL338261AO 145.70 4.96 62.47 4.13 7.65 0.18 0.7 0.07 1.32 6.9 34.68 0.44 901.70 0.22 RL34875SO 88.62 3.84 82.89 5.55 2.68 0.23 0.4 0.03 0.53 6.4 32.47 0.70 1557.47 1.34 629 Table B.12 (Continued) Hole ID Depth (ft) PE Na_pct PE Nb_ppm PE Ni_ppm PE P_ppm PE Pb_ppm PE Rb_ppm PE Re_ppm PE S_pct PE Sb_ppm PE Sc_ppm PE Se_ppm PE Sn_ppm PE Sr_ppm 37L482 926 0.29 0.8 65.59 90.13 1.2 13.14 0.03 8.93 4.87 0.7 0.2 65.33 D27943 3389.5 0.28 0.2 27.75 54.26 0.5 12.12 0.07 5.70 2.10 0.7 0.1 56.57 D39204 481 0.14 0.6 30.11 91.25 0.9 11.68 0.000 0.09 32.46 11.90 0.7 0.2 69.24 D39018 43 0.17 0.2 27.70 30.50 0.3 12.74 0.001 0.02 5.44 0.79 0.6 0.1 39.90 D2253 75 0.22 1.4 71.07 121.00 1.4 -2.44 0.002 0.18 43.77 16.01 0.0 0.3 42.29 R87107 482.3 0.32 1.7 61.36 174.04 2.1 -2.82 0.002 0.11 36.41 15.27 0.0 0.4 70.97 DS172 123.1 B 0.22 1.1 67.71 120.68 1.3 19.69 0.11 36.73 21.25 0.2 0.3 71.05 DS173 499.6 0.25 1.5 66.52 153.01 0.9 -2.96 0.002 0.20 36.40 18.22 0.4 0.4 36.72 37L667 4 0.23 1.3 60.75 105.43 1.2 -5.27 0.002 0.15 41.73 17.32 0.0 0.3 33.96 37L667 152 0.50 1.3 70.56 77.68 1.3 -2.26 0.002 0.16 38.22 20.19 0.0 0.4 54.34 37L667 194 0.59 1.0 65.16 91.63 1.1 -5.76 0.10 38.08 18.61 0.0 0.3 95.71 D39200 3115 0.38 1.5 67.11 147.80 1.4 0.33 0.14 38.97 17.29 0.1 0.4 88.01 DS352 134 0.40 1.5 56.62 121.42 1.9 7.02 0.12 39.06 15.54 0.0 0.3 68.00 DS358 321 0.23 0.9 70.24 85.88 1.3 2.79 0.13 40.54 15.78 -0.3 0.2 40.28 GC04007 2000 0.40 1.4 78.79 116.44 1.0 -0.28 0.11 36.86 12.64 0.3 45.60 R87105 699.8 0.99 1.5 63.72 121.35 3.3 -4.90 0.11 36.21 14.25 0.1 0.3 136.45 30L1268 25.7 0.20 1.3 69.98 97.39 1.1 -4.26 0.002 0.31 41.70 26.06 0.4 0.3 42.31 37L726 836.6 0.23 1.3 67.99 165.47 1.2 -5.27 0.003 0.15 38.83 18.90 0.1 0.3 47.39 CR466 145 0.22 1.8 47.68 193.49 1.1 -5.92 0.002 0.12 36.09 17.23 0.2 0.4 33.87 D14391 1810 0.19 1.6 85.22 127.70 1.1 -5.70 0.002 0.16 42.27 15.12 0.2 0.2 33.55 D39200 3241 0.22 1.5 65.53 140.78 1.5 -5.98 0.002 0.15 38.27 19.10 0.4 0.3 44.14 D39357 1287 0.20 1.3 57.85 124.34 1.1 -1.18 0.002 0.13 52.17 13.84 0.0 0.3 37.33 DS172 123.1 C 0.19 1.1 74.07 114.43 1.2 -2.03 0.13 38.05 21.21 0.3 0.3 112.27 19L547 495.8 0.20 1.5 78.34 125.23 1.3 -3.49 0.002 0.28 49.77 16.96 0.2 0.4 33.63 37L482 118 0.23 1.4 133.37 68.83 1.4 6.29 0.33 51.74 26.06 0.9 0.4 36.54 CR4610 947 0.56 1.7 61.35 132.77 1.3 1.47 0.002 0.17 35.78 17.06 0.2 0.4 73.69 D21708 2760 0.54 2.4 49.11 141.09 3.5 7.09 0.31 35.93 8.22 0.0 0.4 62.46 DS177 1500.8 0.33 1.4 90.53 87.60 1.0 -5.04 0.002 0.20 36.44 18.02 0.5 0.3 43.55 DS615 1905.1 0.25 1.5 42.38 93.17 2.2 14.70 0.14 36.75 6.67 -0.2 0.3 55.73 D33003 2004 0.29 2.1 50.94 224.40 1.6 3.68 0.002 0.13 40.06 20.01 0.5 0.5 83.73 DS360 124 0.23 0.9 60.20 86.84 1.2 -4.95 0.11 39.39 19.87 -0.2 0.2 37.27 GC04007 2859 1.25 2.4 55.93 299.41 2.8 -5.41 0.002 0.17 36.15 10.13 0.1 0.5 126.23 37L667 1061 0.21 1.1 85.72 63.13 1.7 -0.90 0.17 42.06 9.90 0.0 0.3 43.71 D39018 635 0.22 1.4 47.48 164.77 1.0 11.04 0.002 0.13 35.15 13.34 -0.1 0.4 32.17 D39200 843 0.67 1.6 66.57 225.86 3.7 22.13 0.001 0.29 22.79 14.24 0.7 0.2 77.44 D39200 1318 0.66 1.3 28.87 212.03 3.1 21.63 0.31 15.87 7.42 0.7 0.3 73.66 CB4043HR 0.71 1.2 72.43 181.05 3.2 30.75 0.65 17.65 14.86 0.8 0.4 120.46 D15367 5.5 0.73 0.9 65.75 163.48 2.9 32.94 0.001 2.12 15.96 13.12 1.3 0.3 124.53 630 Table B.12 (Continued) Hole ID Depth (ft) PE Na_pct PE Nb_ppm PE Ni_ppm PE P_ppm PE Pb_ppm PE Rb_ppm PE Re_ppm PE S_pct PE Sb_ppm PE Sc_ppm PE Se_ppm PE Sn_ppm PE Sr_ppm D39357 2067 0.84 1.3 79.18 160.08 3.9 21.24 0.002 1.30 14.68 15.87 1.2 0.5 111.29 D14391 2922 0.72 1.3 61.90 226.52 1.6 43.06 0.14 11.06 17.72 0.8 0.4 77.79 CB25510LZ 0.88 0.7 155.15 70.58 5.3 39.69 2.28 14.13 30.06 2.6 0.2 129.32 CB302561 0.76 1.1 128.23 145.15 5.8 30.25 0.001 1.59 44.27 13.68 4.1 0.6 100.10 37L768 66 0.58 1.1 76.68 144.68 1.6 15.14 0.31 24.29 25.63 0.9 73.41 DS360 528 0.58 1.1 66.67 160.96 2.0 15.06 0.93 13.49 25.03 1.5 90.93 17L1437 556 0.59 1.1 52.25 145.85 1.9 16.11 0.16 13.47 16.77 1.2 0.2 87.54 24L755 64 0.58 1.1 44.20 141.00 1.7 15.89 0.15 11.08 14.29 0.8 0.2 73.49 37L482 91 0.58 1.1 41.91 137.20 1.7 15.30 0.15 10.40 13.09 0.8 0.2 71.12 37L594 299 0.61 1.0 51.43 145.28 1.9 17.86 0.14 19.46 15.91 1.5 0.2 88.17 37L594 815 0.62 1.1 52.29 139.93 1.9 18.48 0.15 10.16 18.78 1.4 0.2 91.13 37L768 98 0.61 1.2 59.44 173.95 15.87 0.15 12.00 24.54 112.99 D22203 908 0.58 1.3 42.62 160.13 1.9 16.67 0.16 10.74 16.49 1.2 0.4 80.09 D22223 975 0.57 1.2 86.45 150.66 2.0 15.14 0.16 14.87 15.21 1.1 110.11 D2435 454 0.63 1.1 133.97 141.07 2.9 17.72 0.26 11.61 15.19 1.6 0.2 113.65 D33003 3210 0.63 1.5 62.33 242.50 5.9 16.49 14.97 48.95 9.4 291.48 D39018 1820 0.62 1.1 54.52 151.92 1.9 18.79 0.19 9.57 12.96 1.1 0.2 93.03 D39204 1333 0.58 1.1 47.92 145.17 1.7 16.06 0.18 14.90 14.13 100.36 GC04003 787 0.65 1.1 368.78 187.94 7.2 15.65 0.16 12.68 18.23 6.9 359.00 BK0510 376 0.62 1.0 39.32 141.05 2.5 16.27 0.001 0.14 9.57 11.41 0.8 0.2 73.57 D27943 2104 0.59 1.0 41.04 139.48 1.6 18.13 0.001 0.14 9.50 13.41 0.8 0.2 78.73 D39018 3562 0.60 1.1 42.03 140.47 1.6 16.76 0.001 0.14 9.51 12.65 0.8 0.2 73.77 GC04007 911 0.71 1.2 37.90 175.94 1.9 17.05 0.15 9.74 11.42 0.7 0.2 86.30 RL422VG 0.79 1.2 1537.09 146.89 159.7 53.16 26.71 1838.99 18.62 308.2 4.3 132.44 D39200 1001 0.72 1.6 1157.23 153.28 15.3 27.68 0.002 9.93 35.86 19.31 5.0 0.5 138.19 D39200 1064 0.70 1.7 143.70 163.28 18.9 45.53 0.002 7.84 25.69 46.72 5.5 0.5 101.47 37L482 1347 0.69 2.5 109.54 265.04 33.1 30.05 0.002 6.30 15.58 7.03 2.5 1.2 97.65 D39200 1406 0.65 0.8 19.49 218.80 1.7 19.13 0.001 0.19 15.42 7.95 1.1 0.2 68.07 DS352 390 0.68 1.6 99.72 228.07 2.2 16.34 0.16 15.69 16.34 0.8 0.2 84.88 37L768 1108 0.72 1.2 118.57 184.44 3.7 45.62 1.68 15.81 12.63 1.8 0.4 92.73 DS352 305 0.70 1.0 62.40 226.75 3.7 34.38 1.93 20.63 15.13 2.1 0.3 212.75 16L1067 268 0.72 0.9 56.22 117.23 20.2 36.21 1.38 329.74 9.97 1.0 0.2 87.79 CB1812M 0.78 1.0 52.48 135.45 4.1 31.00 0.001 2.40 27.87 13.24 1.6 0.2 99.18 RL338261AO 0.73 0.8 69.98 77.88 7.4 46.27 1.78 215.40 14.13 6.8 2.7 94.86 RL34875SO 0.70 1.0 59.13 86.38 3.6 17.31 0.002 3.65 43.64 22.56 1.8 0.2 95.67 631 Table B.12 (Continued) Hole ID Depth (ft) PE Ta_ppm PE Th_ppm PE Ti_pct PE Tl_ppm PE U_ppm PE V_ppm PE W_ppm PE Y_ppm PE Zn_ppm PE Zr_ppm 37L482 926 0.04 0.27 0.12 0.13 0.1 42.18 5.29 3.04 10.93 19.22 D27943 3389.5 0.01 0.19 0.04 0.09 0.1 28.42 8.93 -0.47 1.38 19.33 D39204 481 0.03 0.25 0.09 0.25 0.1 45.01 10.73 1.30 15.99 24.79 D39018 43 0.01 0.24 0.07 0.05 0.1 54.24 6.98 0.88 -6.45 24.22 D2253 75 0.08 0.31 0.17 0.04 0.3 -10.06 60.30 6.82 14.35 43.36 R87107 482.3 0.09 0.29 0.21 0.08 0.3 19.39 54.57 11.10 6.83 46.52 DS172 123.1 B 0.06 0.28 0.13 0.11 0.3 -3.11 54.46 9.75 12.52 37.41 DS173 499.6 0.07 0.24 0.17 0.01 0.3 -5.39 54.21 12.37 10.51 40.14 37L667 4 0.07 0.26 0.14 0.00 0.3 -7.97 57.24 7.57 6.07 36.42 37L667 152 0.07 0.23 0.14 0.08 0.3 3.07 58.08 6.78 13.65 35.70 37L667 194 0.05 0.21 0.10 -0.01 0.3 -20.73 54.20 8.14 10.15 32.04 D39200 3115 0.08 0.24 0.18 0.08 0.3 -7.88 54.37 11.48 15.36 34.39 DS352 134 0.08 0.29 0.16 0.12 0.3 -12.21 54.45 7.57 12.84 42.74 DS358 321 0.05 0.23 0.05 0.09 0.3 55.54 6.29 15.79 31.72 GC04007 2000 0.07 0.31 0.13 0.00 0.3 -20.45 54.26 6.62 14.38 38.81 R87105 699.8 0.08 0.33 0.12 0.00 0.3 -19.44 54.13 35.02 38.58 30L1268 25.7 0.08 0.25 0.15 0.04 0.3 16.46 60.72 16.90 24.14 42.20 37L726 836.6 0.07 0.24 0.15 0.02 0.3 9.54 59.33 6.52 2.16 43.06 CR466 145 0.11 0.26 0.22 -0.01 0.3 7.69 54.28 12.65 15.10 42.70 D14391 1810 0.08 0.30 0.16 0.00 0.3 -16.74 67.95 7.30 7.45 41.85 D39200 3241 0.08 0.22 0.17 0.00 0.3 -1.20 59.87 9.11 8.74 33.20 D39357 1287 0.08 0.27 0.16 0.54 0.3 -8.10 60.61 6.92 55.35 39.33 DS172 123.1 C 0.05 0.26 0.13 0.01 0.3 -3.03 54.54 10.82 14.44 36.47 19L547 495.8 0.09 0.31 0.13 0.08 0.3 -10.70 69.81 10.90 1.00 41.43 37L482 118 0.07 0.25 0.14 0.15 0.3 16.15 57.30 28.78 75.09 33.54 CR4610 947 0.10 0.25 0.21 0.08 0.3 25.80 54.37 8.89 12.82 45.87 D21708 2760 0.17 2.79 0.08 0.06 1.0 -70.08 54.33 9.76 32.69 60.01 DS177 1500.8 0.07 0.22 0.16 0.06 0.3 -13.35 54.26 10.90 54.12 37.59 DS615 1905.1 0.09 0.80 0.04 0.09 0.5 -78.09 57.36 8.16 58.55 47.33 D33003 2004 0.11 0.39 0.24 0.17 0.3 11.71 56.57 13.45 15.08 53.34 DS360 124 0.05 0.21 0.06 0.00 0.3 2.29 56.25 6.73 1.92 33.19 GC04007 2859 0.14 1.40 0.15 0.00 0.5 -53.96 54.27 10.33 11.81 61.94 37L667 1061 0.07 0.24 0.17 0.27 0.0 57.10 -4.06 4.51 35.58 -4.27 D39018 635 0.08 0.24 0.10 0.34 0.0 57.10 -2.37 3.04 36.10 0.56 D39200 843 0.11 1.77 0.13 0.35 0.5 105.47 8.34 11.42 55.42 -3.50 D39200 1318 0.10 1.77 0.08 0.35 0.7 105.49 -1.20 23.42 53.56 -7.49 CB4043HR 0.09 1.62 0.23 0.40 0.4 118.22 14.90 11.91 48.51 22.88 D15367 5.5 0.07 1.59 0.18 0.55 0.4 112.67 32.43 7.27 44.28 20.83 632 Table B.12 (Continued) Hole ID Depth (ft) PE Ta_ppm PE Th_ppm PE Ti_pct PE Tl_ppm PE U_ppm PE V_ppm PE W_ppm PE Y_ppm PE Zn_ppm PE Zr_ppm D39357 2067 0.11 1.65 0.24 0.34 0.4 75.27 43.39 10.32 41.23 22.28 D14391 2922 0.10 1.58 0.25 0.25 0.4 129.57 10.32 8.31 29.57 19.96 CB25510LZ 0.05 1.57 0.15 0.57 126.93 15.91 7.74 48.12 13.81 CB302561 0.08 1.67 0.20 0.43 0.4 163.11 30.34 7.89 41.61 25.07 37L768 66 0.17 119.81 10.04 11.08 85.98 18.00 DS360 528 0.17 119.62 11.37 8.89 81.84 19.05 17L1437 556 0.17 0.21 0.3 98.09 9.99 9.24 66.38 18.80 24L755 64 0.07 1.18 0.17 0.21 0.3 88.32 10.69 8.20 42.65 17.53 37L482 91 0.07 0.17 0.19 81.28 9.52 8.11 42.70 15.99 37L594 299 0.17 0.23 93.00 9.37 9.43 55.33 20.15 37L594 815 0.17 0.22 92.51 10.29 10.35 53.16 18.66 37L768 98 0.16 109.98 45.49 14.29 96.98 18.96 D22203 908 0.08 1.22 0.19 0.20 93.23 10.17 9.18 47.41 20.66 D22223 975 0.08 1.20 0.18 0.3 105.58 10.00 8.96 62.82 19.81 D2435 454 0.17 0.24 98.60 12.89 9.47 54.63 17.72 D33003 3210 0.19 150.62 77.89 19.65 179.23 30.92 D39018 1820 1.24 0.18 0.22 0.3 83.78 8.61 8.76 45.57 18.98 D39204 1333 0.16 0.30 93.59 17.70 11.38 55.71 17.83 GC04003 787 0.16 85.15 9.16 14.87 59.21 15.68 BK0510 376 0.07 1.19 0.16 0.21 0.3 76.27 9.59 8.09 46.25 18.58 D27943 2104 0.07 1.18 0.17 0.21 0.3 84.69 8.57 8.19 41.80 16.74 D39018 3562 0.07 1.18 0.17 0.20 0.3 82.75 8.77 7.95 44.55 16.62 GC04007 911 0.09 1.45 0.17 0.21 0.4 77.30 8.58 8.54 42.78 22.93 RL422VG 0.14 0.70 503.98 21.26 14.21 1537.17 28.18 D39200 1001 0.10 1.76 0.22 0.67 0.5 147.31 43.44 13.75 182.18 25.88 D39200 1064 0.12 1.85 0.19 2.35 0.5 286.57 57.13 25.10 220.41 33.32 37L482 1347 0.18 3.13 0.16 0.59 0.8 52.37 20.54 9.81 300.13 50.74 D39200 1406 0.06 1.60 0.13 0.35 0.4 89.54 11.41 6.81 22.67 22.23 DS352 390 0.11 1.66 0.28 0.23 0.4 119.88 18.86 8.09 51.08 17.78 37L768 1108 0.09 1.70 0.23 0.69 0.5 160.01 25.46 8.32 75.75 27.55 DS352 305 0.07 1.62 0.18 0.39 0.4 132.58 22.43 8.98 53.96 29.54 16L1067 268 0.06 1.61 0.16 0.80 0.4 102.67 30.01 10.49 332.28 19.12 CB1812M 0.07 1.58 0.20 1.16 0.4 104.65 44.61 5.89 31.39 12.93 RL338261AO 0.06 1.69 0.14 0.76 0.5 545.67 16.12 9.10 238.44 29.96 RL34875SO 0.08 1.60 0.24 0.41 0.4 116.70 90.09 8.03 49.13 10.43 633 Appendix C for Chapter 5 C.1 Quality control for carbon and oxygen isotope data This appendix consists of Tables C.1 and C.2 which contains the quality control data (values, mean and standard deviation (±1σ)) for the carbon and oxygen isotopes analyzed at the Univer- sity of British Columbia and the GNS Stable Isotope Laboratory, New Zealand respectively. Figures C.1 and C.2 graphically compare the data for each laboratory. For sample locations, lithology, and other details please refer to appendix Table A.1. Table C.1 Duplicated samples assessed for carbon and oxygen isotopes collected at the University of British Co- lumbia with calculated mean and standard deviation. Sample Name d13C VPDB d18O SMOW* d13C mean d13C stan- dard devia- tion d18O mean d18O stan- dard devia- tion D33003-1106 3.35 17.65 3.27 0.22 17.70 0.19 D33003-1106 3.45 17.91 D33003-1106 3.02 17.54 ES09_AP_6A 0.36 16.08 0.40 0.03 15.52 0.57 ES09_AP_6A 0.40 15.54 ES09_AP_6A 0.43 14.95 17L1437-556 1.55 22.34 1.38 0.15 21.35 1.12 17L1437-556 1.33 20.13 17L1437-556 1.27 21.57 24L755-769 0.83 21.36 0.98 0.13 20.35 0.96 24L755-769 1.08 20.23 24L755-769 1.04 19.44 D33003-3210 1.51 18.32 1.51 0.03 18.28 0.53 D33003-3210 1.54 18.79 D33003-3210 1.48 17.73 The d18O smow has been recalculated to account for fractionation correction using Rosenbaum and Sheppard (1986) 634 Table C.2 Duplicated samples assessed for carbon and oxygen isotopes collected at the GNS Stable Isotope Labora- tory, New Zealand with calculated mean and standard deviation. Sample Mineral δ13C VDP δ13C VDP mean δ13C VDP standard deviation δ18O VDP δ18O VDP mean δ18O VDP standard deviation δ18O smow δ18O smow mean δ18O smow standard deviation BN13 Calcite 1.77 1.76 0.05 -15.96 - 15.9967 0.04 14.46 14.42 0.05 BN13 Calcite 1.72 0.02 -16.05 0.03 14.36 BN13 Calcite 1.78 0.05 -15.98 0.09 14.44 D33003- 3210 Ankerite 1.67 1.74 0.06 -11.58 -11.565 0.11 18.97 18.99 0.02 D33003- 3210 Ankerite 1.81 0.02 -11.55 0.01 19.00 GC04003- 786 Ankerite 1.57 1.49 0.01 -14.49 -14.505 0.09 15.97 15.96 0.02 GC04003- 786 Ankerite 1.4 0 -14.52 0.15 15.94 D33003- 1106 Ankerite 3.41 0.03 -12.68 0.02 17.84 24L755-769 Ankerite 1.16 0 -11.5 0.03 19.05 D27943- 3389.5 Ankerite -1.14 0.05 -15.34 0.14 15.10 Figure C.1 Graphical comparison of δ18C (VDP) data collected at the University of British Columbia (UBC) and at GNS Stable Isotope Laboratory, New Zealand. Error bars for used the mean of all data (0.11) for each datum. Errors for the GNS data used the averaged reported value (0.02). The geological variation between samples is greater than the analytical error from Barker et al. (2011) as the same instrument, setup and sample was used as in this thesis. 635 Figure C.2 Graphical comparison of δ18O (smow) data collected at the University of British Columbia (UBC) and at GNS Stable Isotope Laboratory, New Zealand. The data from GNS was reported as VPD values and converted to SMOW values using the method outlined by Coplen et al. (1983). Error bars for used the mean of all data (0.67) for each datum. Errors for the GNS data used the averaged reported value (0.07). The geological variation between samples is greater than the analytical error. The UBC δ18O values were derived. 636 C.2 Quality control for sulfur isotope data This appendix consists of Table C.3 which contains the quality control data (values, mean and standard deviation (±1σ)) for the sulfur isotopes samples analyzed at the Central Science Labora- tory at the University of Tasmania, Australia. For sample locations, lithology, and other details please refer to appendix Table A.1. Table C.3 Assessment of duplicated sulfur isotope samples for quality control Sample Sulfide type Mineral Δ34S* Mean Standard deviation (± 1σ) CB25-21LZ replacement pyrrhotite pyrrhotite 3.82 3.965 0.21 CB25-51LZ replacement pyrrhotite pyrrhotite 4.11 CB4143 py replacement pyrite pyrite 2.74 2.985 0.35 CB4143 py replacement pyrite pyrite 3.23 D33003-93 massive rep. pyrite 17.82 16.85 1.37 D33003-93 massive rep. pyrite 15.88 DS174-605.9 massive rep. pyrite -6.07 -5.875 0.28 DS174-605.9 massive rep. pyrite -5.68 DS340-403.4 carbonate-pyrite vein pyrite 4.04 4.01 0.04 DS340-403.4 carbonate-pyrite vein pyrite 3.98 GC01018-68.7 carbonate-pyrrhotite vein pyrrhotite 8.26 8.195 0.09 GC01018-68.7 carbonate-pyrrhotite vein pyrrhotite 8.13 RL42-2 sub replacement pyrrhotite pyrrhotite 3.49 3.515 0.04 RL42-2 Sub replacement pyrrhotite pyrrhotite 3.54 Standard-BAS- 1 pyrite 4.33 5.0466 67 0.78 Standard-BAS- 1 pyrite 4.93 Standard-BAS- 1 pyrite 5.88 *δ34Ssulfide mineral (per mil CDT) Average standard deviation for all samples is ±0.4 per mil 637 C.3 Carbon and oxygen isotope data This appendix contains Table C.4 which contains all the carbon and oxygen isotope data col- lected from the University of British Columbia. Data was collected using an OA-ICOS technique which is outlined by Barker et al., (2011). This data was used in the dissertation. The GNS car- bon and oxygen data was only used for comparative review. For sample locations, lithology, and other details please refer to appendix Table A.1. 638 Table C.4 Carbon and oxygen isotope data Sample Name Depth (ft) Metamorphic grade Lithology Carbonate mineral Carbonate type (in paragenetic sequence) Complex δ13C (VDP) δ18O (SMOW) CR469 41.6 Transition Ultramafic Fe-calcite Pervasive carbonate Red Lake -10.3 11.47 ES09-AP-6B 0 Transition Basalt Ankerite Cryptocrystalline-microcrystalline ankerite Mapped outcrop 1.6 16.89 ES09-AP-20 0 Transition Carbonate-quartz vein Ankerite Cryptocrystalline-microcrystalline ankerite Mapped outcrop 1.34 16.99 ES09-AP-27 0 Transition Carbonate-quartz vein Ankerite Cryptocrystalline-microcrystalline ankerite Mapped outcrop 1.23 15.73 ES09-AP-35 0 Transition Carbonate-quartz vein Ankerite Cryptocrystalline-microcrystalline ankerite Mapped outcrop -0.05 13.57 ES09-AP-49 0 Transition Carbonate-quartz vein Ankerite Cryptocrystalline-microcrystalline ankerite Mapped outcrop 0.73 15.15 D27343 501.4 Greenschist Basalt Calcite Medium-coarse ankerite-calcite Campbell 0.0 13.21 D33003 1106 Greenschist Basalt Ankerite Medium-coarse ankerite-calcite Campbell 3.34 16.96 DS177 613 Amphibolite Basalt Calcite Medium-coarse ankerite-calcite Campbell 0.9 19.29 ES09-AP-23 0 Transition Carbonate-quartz vein Ankerite Medium-coarse ankerite-calcite Mapped outcrop 1.4 17.29 ES09-AP-6A 0 Transition Basalt Ankerite Medium-coarse ankerite-calcite Mapped outcrop 0.8 17.64 ES09-AP-6A 0 Transition Basalt Ankerite Medium-coarse ankerite-calcite Mapped outcrop 0.36 16.08 ES09-AP-6A 0 Transition Basalt Ankerite Medium-coarse ankerite-calcite Mapped outcrop 0.40 15.54 ES09-AP-6A 0 Transition Basalt Ankerite Medium-coarse ankerite-calcite Mapped outcrop 0.43 14.95 ES09-AP-10A 0 Transition Carbonate-quartz vein Ankerite Medium-coarse ankerite-calcite Mapped outcrop -1.44 17.09 ES09-AP-27 0 Transition Carbonate-quartz vein Ankerite Medium-coarse ankerite-calcite Mapped outcrop 2.71 15.95 ES09-AP-37 0 Transition Carbonate-quartz vein Ankerite Medium-coarse ankerite-calcite Mapped outcrop 2.00 14.75 ES09-AP-49 0 Transition Carbonate-quartz vein Ankerite Medium-coarse ankerite-calcite Mapped outcrop -0.10 14.55 GC04003 786.75 Greenschist Basalt Ankerite Medium-coarse ankerite-calcite Red Lake 1.78 17.69 GC04007 3890 Transition Ultramafic Ankerite Medium-coarse ankerite-calcite Red Lake 1.91 13.20 D14981 1798.8 Transition Basalt Ankerite Breccia ankerite-calcite-quartz Campbell 0.66 18.81 D22203 908 Greenschist Basalt Ankerite Breccia ankerite-calcite-quartz Campbell 1.9 17.65 16L1067 1208.1 Greenschist Basalt Ankerite Colloform-crustiform ankerite-calcite Red Lake 0.21 14.06 24L755 769 Greenschist Basalt Ankerite Colloform-crustiform ankerite-calcite Red Lake 0.64 20.46 D15367 371.1 Greenschist Ultramafic Ankerite Colloform-crustiform ankerite-calcite Campbell -0.82 20.34 D22223 975 Greenschist Basalt Ankerite Colloform-crustiform ankerite-calcite Campbell 1.47 16.42 D27943 3389.5 Greenschist Basalt Ankerite Colloform-crustiform ankerite-calcite Campbell -1.62 14.90 D39018 43 Amphibolite Basalt Ankerite Colloform-crustiform ankerite-calcite Campbell 2.54 19.79 DS139 30.4 Greenschist Ultramafic Ankerite Colloform-crustiform ankerite-calcite Campbell -1.0 19.86 DS360 528 Greenschist Basalt Ankerite Colloform-crustiform ankerite-calcite Campbell 1.41 18.30 639 Table C.4 (Continued) Sample Name Depth (ft) Metamorphic grade Lithology Carbonate mineral Carbonate type (in paragenetic sequence) Complex δ13C (VDP) δ18O (SMOW) 30L1268 372.4 Transition Basalt Ankerite Medium-coarse ankerite-calcite Red Lake -1.0 12.15 34L814 1147.4 Amphibolite Basalt Ankerite Medium-coarse ankerite-calcite Red Lake 2.65 20.67 37L482 2057 Amphibolite Basalt Ankerite Medium-coarse ankerite-calcite Red Lake -3.55 17.39 37L768 2005 Amphibolite Rhyolite Ankerite Medium-coarse ankerite-calcite Red Lake -0.49 17.22 CR4613 1.3 Amphibolite Basalt Calcite Medium-coarse ankerite-calcite Red Lake -3.4 18.13 D39357 1308 Transition Basalt Ankerite Medium-coarse ankerite-calcite Campbell 2.5 20.41 06L337 186 Greenschist Basalt Ankerite ankerite-calcite-quartz Red Lake 2.18 17.76 19L547 495.8 Amphibolite Basalt Ankerite ankerite-calcite-quartz Red Lake 0.36 4.27 34L006 1235 Amphibolite Basalt Ankerite ankerite-calcite-quartz Red Lake -4.6 17.55 34L814 2333.4 Greenschist Diorite Ankerite ankerite-calcite-quartz Red Lake -2.3 15.41 37L482 1019 Amphibolite Basalt Ankerite ankerite-calcite-quartz Red Lake 4.03 19.19 37L594 1581 Amphibolite Basalt Ankerite ankerite-calcite-quartz Red Lake 1.69 19.57 CR468 629 Amphibolite Basalt Calcite ankerite-calcite-quartz Red Lake 2.11 14.06 D14931 2992 Greenschist Basalt Ankerite ankerite-calcite-quartz Campbell 2.5 18.72 D21708 139.3 Greenschist Basalt Ankerite ankerite-calcite-quartz Campbell 1.58 20.76 D2253 252 Greenschist Basalt Ankerite ankerite-calcite-quartz Campbell 0.93 19.05 D27943 2104.2 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell 1.1 18.05 D39018 1820 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell -0.53 15.49 D39018 1820 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell -2.94 -2.67 DS352 341 Greenschist Basalt Ankerite ankerite-calcite-quartz Campbell 1.2 16.10 DS615 4032.2 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell -2.15 6.11 GC04007 4421 Greenschist Basalt Ankerite ankerite-calcite-quartz Red Lake -0.1 19.78 R87105 699.8 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell -4.6 13.72 R87107 402.3 Amphibolite Basalt Calcite ankerite-calcite-quartz Campbell -1.9 15.57 37L768 98 Amphibolite Basalt Ankerite ankerite-calcite-quartz Red Lake 3.46 21.44 D33003 3210 Transition Basalt Ankerite ankerite-calcite-quartz Campbell 1.46 18.32 17L1437 556 Greenschist Basalt Ankerite quartz-ankerite Red Lake 1.3 20.90 37L594 815 Amphibolite Basalt Ankerite quartz-ankerite Red Lake -1.00 9.95 34L235 944 Amphibolite Ultramafic Ankerite quartz-ankerite with brown biotite selvage Red Lake -1.10 14.27 640 C.4 Sulfur isotope data This appendix contains Table C.5 which includes all the sulfur isotope data collected in this study. Sulfur isotopes were analyzed at the Central Science Laboratory at the University of Tas- mania, Australia. For sample locations, lithology, and other details please refer to appendix Ta- ble A.1. Table C.5 Sulfur isotope data. Sample Sulfide Mineral Mineralization Style pre/syn/post δ34SCDT (permil) δ34SH2S (permil) CR4612-273.2 pyrite qtz-mus-py vein post 1.03 0 11L086-853 pyrite banded pre -5.34 -6.37 37L667-1891 pyrrhotite banded pre 3.48 3.22 37L667-1891 pyrite banded pre 3.8 2.77 CR466-572.1 pyrite banded pre 3.37 2.34 CR467-117.3 pyrite banded pre -3.36 -4.39 D33003-94 pyrite massive pyrite pre 16.85 15.82 D39018-173 pyrrhotite banded pre 1.26 1 DS174-606.4 pyrite layered pre -5.875 -6.905 DS177-119.6 pyrite banded pre 1.47 0.44 GC01018-1171.8 pyrrhotite banded pre 1.37 1.11 GCO4007-167 pyrite massive pyrite pre -2.25 -3.28 R87105-523.6 pyrrhotite banded pre 5.82 5.56 34L814-348.2 pyrrhotite Pyrrhotite cut by ankerite- calcite vein pre 4.18 3.92 06L337-191 pyrrhotite replacement pyrrhotite syn 6.85 6.59 13L833-1144.3 pyrite replacement pyrite syn -3.89 -4.92 13L833-138.5 pyrite pyrite vein syn 4.77 3.74 16L1067-267.4 arsenopyrite arsenopyrite + quartz syn 2.7 17L1437-763 pyrite replacement pyrite syn 5.08 4.05 19L547-495.8 pyrrhotite replacement pyrrhotite syn 5.17 4.91 30L1162-1419 pyrrhotite replacement pyrrhotite syn 3.24 2.98 30L1268-25.7 pyrrhotite replacement pyrrhotite syn 5.34 5.08 34L1352-238 pyrrhotite replacement pyrrhotite syn 8.29 8.03 34L235-1961 pyrrhotite replacement pyrrhotite syn 4.67 4.41 37L482-1137 pyrrhotite replacement pyrrhotite syn 6.99 6.73 37L667-157 pyrrhotite replacement pyrrhotite syn 8.48 8.22 37L667-2058 pyrrhotite replacement pyrite syn 5.29 5.03 CB15-56 pyrrhotite replacement pyrrhotite syn 3.98 3.72 CB1812M pyrite replacement pyrite syn 6.87 5.84 CB1925V1 pyrite replacement pyrite syn 3.99 2.96 CB25-21LZ pyrrhotite replacement pyrrhotite syn 3.965 3.705 CB302561 pyrrhotite replacement pyrrhotite syn 3.92 3.66 CB33451M pyrite replacement pyrite syn 5.44 4.41 CB39-2 pyrrhotite replacement pyrrhotite syn 4.09 3.83 CB4143 po pyrrhotite quartz-pyrite vein syn 2.36 2.1 641 Table C.5 (Continued) Sample Sulfide Mineral Mineralization Style pre/syn/post d 34SCDT (permil) d34S H2S CB4143 py pyrite replacement pyrite syn 2.985 1.955 CB4143W pyrrhotite replacement pyrrhotite syn 4.72 4.46 D21708-139.3 pyrite replacement pyrite syn 4.09 3.06 D22203-1544 pyrrhotite replacement pyrrhotite syn 4.13 3.87 D22203-1545 pyrrhotite replacement pyrrhotite syn 3.92 3.66 D22223-1399 pyrite replacement pyrite syn 4.52 3.49 D2435-361 pyrrhotite replacement pyrrhotite syn 6.37 6.11 D27343-232.4 pyrrhotite replacement pyrrhotite syn 4.87 4.61 D27943-351.2 pyrite replacement pyrite syn 6.16 5.13 D39018-2555 pyrrhotite replacement pyrrhotite syn 8.43 8.17 D39018-4844 pyrrhotite replacement pyrrhotite syn 1.88 1.62 D39200-1469 pyrrhotite replacement pyrrhotite syn 6.51 6.25 D39204-1165 pyrrhotite replacement pyrrhotite syn 2.4 2.14 D39357-2029 pyrrhotite replacement pyrrhotite syn 5.09 4.83 DS340-403.4 pyrite replacement pyrrhotite syn 4.01 2.98 DS343-264 pyrite quartz-pyrite vein syn 2.91 1.88 DS343-455 pyrite replacement pyrite syn 2.55 1.52 DS352-243 pyrite replacement pyrite syn 5.73 4.7 DS360-329 pyrite replacement pyrrhotite syn 5.32 4.29 GC01018-68.2 pyrrhotite replacement pyrrhotite syn 8.195 7.935 GC95-010-1173 pyrite replacement pyrite syn 5.16 4.13 GCO4007-3606 pyrrhotite quartz-pyrite vein syn 5.35 5.09 RL33-806-B pyrite replacement pyrite syn 4.19 3.16 RL33-826-1AO pyrite quartz-pyrite vein syn 3.82 2.79 RL34-875-So pyrite replacement pyrite syn 7.35 6.32 RL35-746-2 pyrite replacement pyrite syn 5.08 4.05 RL35-826-1 arsenopyrite replacement arsenopyrite syn 2.91 RL35-FW pyrrhotite quartz-pyrrhotite vein syn 4.26 4 RL38-746-2 sphalerite replacement sphalerite syn 3.4 3.14 RL42-2 Sub pyrrhotite replacement pyrrhotite syn 3.515 3.255 RL44-746-1SV sphalerite replacement sphalerite syn 4.26 4 642 Appendix D for Chapter 7 D.1 SWIR data This appendix consists of Table D.1 which contains all the shortwave infrared data collected dur- ing this study. Each column identifies the sample, which mineral was identified using the auto- mated software The Spectral Geologist© and by manual interpretation of the spectra. Following the mineral identification the absorption features position, depth and widths correlating to spe- cific minerals are provided. The mineral abbreviations are: MUS = muscovite, BIO = biotite, CHL = chlorite, CARB = carbonate, AMP = amphibole. SWIR abbreviations are: wlm = wave- length minimum, d = depth, w = width. For additional information such as location, lithology, distance from mineralization and main alteration assemblage please refer to Appendix A.2. 643 Table D.1. Complete shortwave infrared data. Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefringence Colour Manual Mineral ID 1 Manual Mineral ID 2 Manual Mineral ID 3 Manual Mineral ID 4 TSA_S Mineral1 TSA_S Mineral2 TSA_S Weight1 06L337 40 Unknown Black Unknown Grey carbonate Int chlorite Siderite Montmoril- lonite 0.764 06L337 186 Black Ankerite Blue dolomite clay (dickite?) Dolomite 1 06L337 448 Black Unknown Brown Fe-chlorite Fe- carbonate Dolomite 1 06L337 488 Black Unknown Grey IntChlorite Siderite 0.556 11L086 266 Unknown Unknown Grey Mg-chlorite biotite talc Actinolite 1 11L086 417 Black Unknown Grey amphibole carbonate talc Hornblende MgChlorite 0.603 11L086 1038 Unknown Grey Mg-chlorite Ankerite Hornblende 0.523 13L833 55 Black Grey dolomite muscovite chlorite Siderite Opal 0.778 13L833 681.4 Unknown Unknown Grey dolomite Int-chlorite illite? IntChlorite Illite 0.793 13L833 1237.8 Unknown Black Unknown Blue Fe-chlorite muscovite alunite IntChlorite Muscovite 0.567 16L1067 400.8 Unknown Black Unknown Blue Mg-chlorite carbonate FeChlorite 1 16L1067 1208.1 Unknown Black Ankerite Blue Mg-chlorite carbonate IntChlorite 1 17L1437 152 Unknown Unknown Grey talc Mg-chlorite alunite calcite Talc MgChlorite 0.595 17L1437 556 Black Ankerite Grey dolomite Fe-chlorite Dolomite Illite 0.718 17L1437 913 Black Unknown Grey chlorite corderite? carbonate Dolomite Muscovite 0.533 17L1437 913 Black Unknown Grey Fe-chlorite clay (dickite?) carbonate FeChlorite Ankerite 0.684 19L547 52.4 Black Ankerite Brown biotite Fe-chlorite IntChlorite 1 19L547 52.4 Black Ankerite Brown biotite Fe-chlorite MgChlorite 1 19L547 866.2 Unknown Black Calcite Grey carbonate Mg-chlorite lizardite IntChlorite Siderite 0.504 24L755 64 Unknown Grey carbonate Mg- chlorite? Siderite 1 24L755 186 Unknown Grey Int-chlorite carbonate biotite Calcite 1 24L755 769 Unknown Black Ankerite Grey carbonate Siderite 1 30L1162 24.7 Brown Unknown Grey low Ca- orthopyroxene calcite muscovite Fe- chlorite Biotite Hornblende 0.751 30L1162 695 Unknown Grey biotite chlorite Ankerite 1 30L1162 695 Unknown Grey natrolite carbonate Mg- chlorite Dolomite 1 30L1162 1419 Unknown Black Unknown Blue Fe-chlorite FeChlorite 1 30L1268 25.7 Unknown Black Unknown Blue amphibole Int-chlorite FeChlorite 1 30L1268 327.9 Unknown Black Ankerite Blue Mg-chlorite FeChlorite 1 Int = interrmediate. Wlm = wavelength minimum. D = depth. W = width. ID = identification. ? = unsure mineral name. For other abbreviations seen list of abbreviations 644 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w 06L337 40 0.236 90.365 0.324 2263.6 0.0677 2334 0.105 20.792 1855.7 0.0936 10.901 1942.9 0.0739 11.779 06L337 186 169.24 0.243 0.0349 9.255 2326.6 0.0697 18.28 0.0428 11.721 1949.6 0.0324 15.643 06L337 448 1548.37 1406.4 0.28 14.36 2259 0.132 13.066 2343.7 0.168 20.397 1891.9 0.029 14.088 1959.6 0.0428 11.966 06L337 488 0.444 41.759 1407 0.28 14.384 2261 0.127 2338.7 0.17 23.523 1879.7 0.0315 13.357 0.0437 11L086 266 417.73 1392 0.345 13.98 0.0865 9.743 2312.7 0.0905 12.706 1857.1 0.12 11.96 1947.5 0.0996 9.176 11L086 417 0.397 110.89 1392.4 0.356 14.66 2263 0.119 12.553 2314.9 0.177 1864.1 0.103 1951.9 0.084 10.853 11L086 1038 0.477 199.76 1392.6 0.328 16.363 0.146 11.071 2316.7 0.157 1868.6 0.15 10.615 1954.4 0.145 13.536 13L833 55 0.222 39.439 0.33 18.994 2262.8 0.0732 12.981 2328.5 0.117 20.145 1855.2 0.0685 15.146 1946.5 0.0617 13.064 13L833 681.4 0.207 53.83 1408.1 0.22 19.592 2253.8 0.126 14.521 2339.3 0.142 15.728 1890.2 0.0408 11.347 1949.2 0.0508 8.844 13L833 1237.8 0.433 101.87 1409.4 0.363 15.06 2259.5 0.249 2351.3 0.274 15.102 1890.8 0.217 14.311 1958.7 0.214 7.374 16L1067 400.8 257.17 1407.4 0.3 14.634 2254.8 0.113 13.544 2341.8 0.107 13.574 0.17 1942.8 0.15 12.31 16L1067 1208.1 290.03 1407.8 0.366 15.795 2253.6 0.202 14.29 2326.3 0.193 15.353 1856.6 0.248 15.719 1953.7 0.228 9.355 17L1437 152 0.405 150.03 1392.3 0.312 13.943 0.0879 10.512 2312.3 0.0928 1857.7 0.0469 9.935 1952.9 0.0379 11.229 17L1437 556 0.282 120.43 0.368 23.984 2264.6 0.0849 2329.3 0.194 20.999 1867.7 0.0115 12.322 1958.8 0.0205 11.489 17L1437 913 0.467 189.66 1408.8 0.0764 16.36 2257.8 0.0948 13.903 2338.7 0.11 20.132 0.0779 10.434 1958.3 0.0939 9.32 17L1437 913 0.316 48.638 1406.4 0.195 18.138 2257.7 0.0995 13.329 2334.7 0.102 18.93 1858.3 0.0889 1948.1 0.0838 10.545 19L547 52.4 270.64 1387.6 0.299 19.368 2252.5 0.116 12.217 2332.7 0.114 16.368 1860.1 0.161 12.731 1942.6 0.144 10.404 19L547 52.4 694.39 0.306 2253.6 0.0893 14.523 2327.5 0.0936 19.731 1857.3 0.136 1941.9 0.117 8.286 19L547 866.2 0.496 108.17 1405 0.23 20.74 2254.4 0.0751 13.641 2328 0.0975 18.662 1856.8 0.12 13.87 1945 0.101 9.927 24L755 64 881.78 1400.3 0.281 16.801 2252.3 0.157 9.862 2312.9 0.15 17.73 1862.6 0.149 1949.6 0.148 13.351 24L755 186 679.34 1402.1 0.354 19.111 2246.1 0.145 14.102 2330.7 0.154 19.946 1856.9 0.197 0.182 24L755 769 78.085 0.35 2263.5 0.0494 2326.2 0.117 20.87 1859.2 0.0399 13.062 1946 0.0334 9.931 30L1162 24.7 0.249 47.992 1387.3 0.134 17.191 2252.8 0.0569 13.591 2331.4 0.0742 19.946 1860.7 0.0465 13.266 1941.9 0.0414 9.874 30L1162 695 361.41 1380.6 0.212 2251.5 0.0748 14.101 2318.9 0.0695 19.272 1857.6 0.0904 13.882 1949.5 0.0835 13.695 30L1162 695 410.71 0.233 19.587 2253.1 0.113 11.252 2324.4 0.112 1869.6 0.124 10.576 1953.4 0.118 11.349 30L1162 1419 24.164 1406.8 0.283 14.997 2257.2 0.111 12.913 2353 0.122 20.831 1864.3 0.0453 1959.1 0.0432 11.454 30L1268 25.7 198.39 1408.2 0.317 12.761 2253.3 0.148 12.443 2348.6 0.123 13.696 0.211 0.189 30L1268 327.9 183.34 0.352 21.654 2261.1 0.191 11.973 2313.1 0.169 20.365 1857.2 0.255 1942.4 0.236 11.301 645 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d 06L337 40 0.0178 2334 15.667 13.944 0.0146 2334 0.106 15.678 2407.6 0.0242 06L337 186 0.0049 2326.6 0.0894 21.222 2259 13.651 2114.5 0.0045 7.209 2326.6 0.0894 20.793 2401.3 0.0115 06L337 448 2159.8 0.0023 9.788 2328 0.21 18.514 2250.2 13.477 2111.9 0.002 12.294 2328 0.21 17.44 0.0138 06L337 488 ###### 2338.7 16.743 14.056 2115.1 0.0023 10.443 2338.5 17.679 2392.3 0.0193 11L086 266 0.0122 2313 16.34 2257.8 0.0711 19.359 2114.7 0.0297 2396 0.0787 11L086 417 2142.1 0.0075 9.85 2313.9 17.257 2259.4 20.349 2133.8 0.0155 8.815 2392.8 0.159 11L086 1038 2154 0.108 8.398 2312.8 17.796 2257.8 0.0909 2123.5 0.117 9.348 2322.2 17.386 2394.7 0.103 13L833 55 2155.3 0.0117 11.757 2328.5 0.135 16.683 2257.3 0.0124 10.488 2328.5 0.135 20.643 2406.4 0.0058 13L833 681.4 0.0067 2339.3 0.126 15.47 2253.8 14.229 2114.4 0.0035 2339.2 0.135 17.939 2392.8 0.046 13L833 1237.8 0.193 2346.9 15.932 2124 0.187 9.258 0.271 16.262 2390.1 0.235 16L1067 400.8 2145.5 0.0751 13.215 2341.8 0.104 2254.8 0.115 14.078 0.0809 9.638 0.104 12.486 2398.3 0.0712 16L1067 1208.1 2142.2 0.163 8.23 2326.3 0.2 17.695 2253.6 13.422 2112.6 0.169 8.632 2326.3 0.2 18.647 2393.6 0.133 17L1437 152 0.0134 2312.2 2257.3 2134.2 0.0274 2391.7 0.114 17L1437 556 0.0036 2329.3 18.413 2133.2 0.0009 8.055 2329.3 0.212 21.639 2405.7 0.0049 17L1437 913 0.0497 2331.6 19.639 2257 0.0519 2331.6 0.139 17.209 2394.7 0.0177 17L1437 913 2159.7 0.0281 8.989 2334.7 17.738 2257.7 0.03 2334.7 19.327 2392.1 0.0143 19L547 52.4 2156.1 0.0922 11.666 2332.7 0.121 15.437 2252.5 0.116 13.945 2110.3 0.0986 9.205 2332.7 0.123 17.163 0.0757 19L547 52.4 2144.6 0.0616 11.992 2327.5 0.105 17.353 2253.6 14.069 0.0661 9.584 2327.5 0.105 17.821 2404.1 0.0563 19L547 866.2 2147.1 0.0378 9.089 2328 0.104 19.666 2254.4 12.846 0.0457 2328 0.104 20.562 2409 0.0374 24L755 64 0.136 2312.9 0.161 16.574 2252.3 12.764 2134 0.137 2334.4 18.405 2397.5 0.127 24L755 186 0.121 2332.4 19.93 2253.5 0.0941 14.147 2116.9 0.127 9.769 2332.4 0.0927 21.984 2400.8 0.112 24L755 769 2151.8 0.0018 8.645 2326.2 0.14 20.307 2118.1 0.0026 9.419 2326.2 0.14 19.399 2402.4 0.0021 30L1162 24.7 2151.4 0.0196 10.823 2327.3 0.103 20.389 2251.3 16.134 0.0206 2327.3 0.103 20.301 0.0588 30L1162 695 2151 0.0401 7.942 2318.9 21.767 2251.5 0.0639 2111.5 0.0423 0.0804 2393.3 0.0115 30L1162 695 0.078 2324.4 0.125 18.508 2253.1 0.0822 8.798 2324.4 13.482 2401.3 0.0674 30L1162 1419 2155.9 0.0033 11.647 2342 13.433 2257.2 2111.3 0.0027 9.752 2335.5 0.123 15.102 2392.4 0.036 30L1268 25.7 2141.6 0.116 11.03 2343.9 0.13 11.465 0.123 10.914 2340 0.13 14.582 2402.3 0.0838 30L1268 327.9 0.174 2313.1 14.681 2258 0.191 2112.3 0.186 12.223 2322.4 14.665 2405.4 0.125 646 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w 06L337 40 11.723 2263.6 0.0677 20.022 2324.5 0.096 12.058 0.0253 14.246 06L337 186 8.693 0.0349 2326.6 0.0864 14.296 0.0069 06L337 448 2259 0.132 19.686 2327.2 0.163 9.75 0.0647 2357.3 0.145 06L337 488 8.764 2261 0.127 20.265 0.153 2365 0.0679 10.075 0.075 11L086 266 11.219 0.0865 2312.7 0.192 12.173 2381.7 0.0799 6.859 2383 14.244 11L086 417 12.322 2263 0.119 19.595 2314.9 0.303 14.177 2383.4 0.159 11.251 2391.2 0.138 13.893 11L086 1038 11.078 0.146 2316.7 0.212 12.364 0.121 2391.7 13.327 13L833 55 12.367 2262.8 0.0732 19.283 2328.5 0.125 10.835 2366.8 0.0262 10.218 13L833 681.4 9.577 2253.8 0.126 20.998 2327.7 0.118 10.249 2365.7 0.0888 9.539 0.0916 13L833 1237.8 6.992 2259.5 0.249 19.141 2324 0.254 10.583 2367.3 0.258 10.1 2356.1 0.261 15.383 16L1067 400.8 11.12 2254.8 0.113 18.737 2326.1 0.0926 9.11 0.0932 2364.5 0.0984 19.025 16L1067 1208.1 12.168 2253.6 0.202 20.071 2326.3 0.183 9.925 2366.5 0.158 8.052 0.168 17.398 17L1437 152 11.952 0.0879 2312.3 0.29 13.271 0.113 2391.6 17L1437 556 8.764 2264.6 0.0849 16.752 2329.4 0.203 12.775 0.0217 17L1437 913 11.173 2257.8 0.0948 20.228 2320.5 0.106 10.537 0.0322 0.0392 11.897 17L1437 913 10.577 2257.7 0.0995 18.92 2329.2 0.0912 9.379 0.0412 2356.5 19L547 52.4 2252.5 0.116 18.438 2327 0.113 11.925 2366.8 0.0866 12.456 2357.8 19L547 52.4 14.835 2253.6 0.0893 21.307 2327.5 0.0945 9.922 2374 0.0618 9.143 2358.3 0.0626 19L547 866.2 11.733 2254.4 0.0751 18.733 2328 0.1 13.306 2365.6 0.052 9.663 0.057 16.877 24L755 64 8.077 2252.3 0.157 14.952 2312.9 0.158 10.897 2373.9 0.142 10.222 2373.9 0.144 15.19 24L755 186 11.463 2246.1 0.145 18.247 2327.5 0.15 7.291 0.109 2357.8 0.0573 24L755 769 11.85 2263.5 0.0494 16.372 2326.2 0.133 12.002 2367.8 0.008 8.285 2355.4 10.225 30L1162 24.7 2252.8 0.0569 19.335 0.069 2374.1 0.0603 8.925 13.964 30L1162 695 11.761 2251.5 0.0748 18.788 2318.9 0.0818 14.408 2367.8 0.0203 9.923 12.332 30L1162 695 10.807 2253.1 0.113 17.553 2324.4 0.122 9.938 2367 0.0759 10.75 2356.2 0.0759 30L1162 1419 7.188 2257.2 0.111 19.685 2325.1 0.106 9.526 2366.8 0.0944 10.686 30L1268 25.7 10.873 2253.3 0.148 19.064 2325.4 0.123 9.043 2370.8 0.109 11.827 2357.4 0.122 14.538 30L1268 327.9 11.488 2261.1 0.191 15.975 2313.1 0.174 12.633 2372.3 0.159 11.333 2360.1 0.165 15.388 647 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefringence Colour Manual Mineral ID 1 Manual Mineral ID 2 Manual Mineral ID 3 Manual Min- eral ID 4 TSA_S Min- eral1 TSA_S Mineral2 TSA_S Weight1 30L1268 574 Brown Calcite Blue Fe-carbonate Fe-chlorite dickite? FeChlorite 1 34L006 25 Black Unknown Brown amphibole Int-chlorite Siderite Opal 0.792 34L006 1235.1 Unknown Black Ankerite Blue dolomite Fe-chlorite Ankerite 1 34L1352 28 Unknown Unknown Grey and Blue chlorite natrolite MgChlorite 1 34L1352 28 Unknown Unknown Grey and Blue chlorite IntChlorite 1 34L1352 315 Unknown Black Unknown Grey Fe-chlorite Siderite IntChlorite 0.541 34L1352 814 Unknown Unknown Unknown Brown alunite clay? Dolomite 1 34L235 23.2 Unknown olivine clay? Opal 1 34L235 909 Unknown Black Unknown Grey Mg-chlorite talc Talc MgChlorite 0.506 34L235 944 Unknown Brown Ankerite Grey Mg-chlorite biotite MgChlorite 1 34L235 944 Unknown Brown Ankerite Grey biotite Mg-chlorite amphibole IntChlorite Hornblende 0.539 34L235 1961 Unknown Black Unknown Brown dolomite Fe-chlorite Jarosite? IntChlorite Dolomite 0.509 34L814 92 Unknown Black Unknown Brown Int-Fe-chlorite carbonate IntChlorite Siderite 0.557 34L814 195.7 Unknown Brown Calcite Brown carbonate Fe-chlorite biotite amphibole Biotite MgChlorite 0.687 34L814 195.7 Unknown Brown Calcite Brown carbonate amphibole Fe-chlorite biotite IntChlorite 1 34L814 1147.7 Unknown Black Ankerite Blue carbonate Dolomite 1 34L814 2333.4 Unknown Black Ankerite Brown dolomite epidote Mg-chlorite FeChlorite Calcite 0.537 34L814 2333.4 Unknown Black Ankerite Brown gibbsite carbonate Mg-chlorite IntChlorite Siderite 0.694 37L482 91 Unknown Black Unknown Grey Int-Fe-chlorite muscovite Ankerite Phlogopite2 0.789 37L482 1019 Unknown Black Ankerite Blue aragonite illite? Dolomite 1 37L482 2057 Calcic and non-calcic Black Ankerite Grey Zoisite Mg-chlorite IntChlorite 1 37L594 299 Unknown Black Unknown Grey dolomite Dolomite IntChlorite 0.56 37L594 815 Unknown Black Ankerite Grey carbonate Int-Fe- chlorite IntChlorite Siderite 0.514 37L594 1581 Black Ankerite Grey and Brown biotite Mg-chlorite tremolite talc MgChlorite 1 37L594 1581 Black Unknown Grey and Brown carbonate Fe-chlorite IntChlorite Dolomite 0.669 37L594 1609 Unknown Black Unknown Grey Int-Fe-chlorite Zoisite 1 37L667 25 Unknown Black Ankerite Grey chlorite chlorite chlorite chlorite Dolomite IntChlorite 0.517 37L667 1067 Unknown Black Unknown Grey chlorite Siderite 1 37L667 2054 Unknown Black Unknown Brown carbonate actinolite alunite? Hornblende Dolomite 0.592 37L726 400.7 Unknown Black Grey Mg-chlorite amphibole biotite alunite? FeTourmaline 1 37L726 836.6 Unknown Black Unknown Grey Mg-chlorite carbonate IntChlorite 1 37L726 836.6 Unknown Black Unknown Grey Mg-chlorite gibbsite muscovite? FeChlorite 1 648 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w 30L1268 574 22.296 1408.8 0.265 16.671 2256.7 0.149 13.277 2351.6 0.16 18.909 1865.3 0.084 1952.4 0.0712 9.049 34L006 25 0.208 32.19 0.289 0.0484 2324.4 0.0958 19.821 1865.7 0.0516 9.795 1944.2 0.0447 11.533 34L006 1235.1 565.53 1414.2 0.229 9.969 2258.2 0.0833 12.419 2322.4 0.178 19.769 1893.8 0 10.231 1959.9 0.0044 10.136 34L1352 28 230.33 1384.9 0.379 2252.3 0.265 13.614 2334.6 0.274 20.377 1860.9 0.24 11.718 1943.4 0.238 12.39 34L1352 28 529.55 1383.4 0.334 2253.6 0.154 13.698 2318.7 0.172 21.912 1877.9 0.153 12.305 1942.1 0.145 8.012 34L1352 315 0.459 75.476 1392.3 0.203 21.748 2257.8 0.0853 14.018 2322.7 0.093 20.312 1892.8 0.0555 1958.1 0.0696 12.469 34L1352 814 1204.67 1399.9 0.291 16.981 0.13 8.79 2322.7 0.151 18.889 1881.7 0.0563 10.612 1958.7 0.072 10.392 34L235 23.2 1716.54 1400.9 0.0904 15.535 0.0608 13.697 2326.6 0.063 9.625 1878.1 0.012 14.192 1959 0.0175 7.991 34L235 909 0.494 221.16 1392.2 0.2 12.968 2253.9 0.0954 15.634 2313.1 0.089 0.121 1951 0.109 13.444 34L235 944 241.36 1381.5 0.258 2252 0.0759 12.474 2329 0.0643 17.513 0.123 12.116 0.115 34L235 944 0.461 70.45 1381.2 0.257 2251.5 0.067 12.837 2327.1 0.0666 16.568 1862.8 0.111 12.331 1942 0.0955 9.907 34L235 1961 0.491 127.71 1399.6 0.39 18.524 2261.1 0.101 12.555 2325.7 0.143 17.58 1864.7 0.0077 0.0161 34L814 92 0.443 28.233 1381.8 0.316 2259.6 0.11 12.749 2342.8 0.157 18.863 1861.2 0.0849 10.523 1956.9 0.0696 10.304 34L814 195.7 0.313 58.309 1387.3 0.265 18.751 2251.6 0.106 15.485 2332.7 0.132 17.441 1882.4 0.0337 9.681 0.0312 34L814 195.7 227.26 1387.6 0.226 18.424 2252.8 0.0831 15.573 2333.7 0.0999 18.536 1887.5 0.0167 0.022 34L814 1147.7 493.69 1407.7 0.304 12.656 2262.6 0.0917 9.314 2319.6 0.135 19.03 1884.8 0.0025 1959.9 0.0078 9.497 34L814 2333.4 0.463 44.358 1404.2 0.342 18.78 0.134 2336.2 0.307 21.899 1871.1 0.115 14.247 0.0733 34L814 2333.4 0.306 26.052 1405.5 0.35 17.445 2256.5 0.155 13.514 2342.5 0.194 17.119 1859.8 0.144 14.918 1946.5 0.112 14.964 37L482 91 0.211 125.76 1402.9 0.326 17.863 2257.1 0.164 14.136 2328.1 0.157 15.685 1856.6 0.2 1940.9 0.186 10.72 37L482 1019 147.25 1400.4 0.268 18.845 2244.2 0.0591 8.771 0.0529 18.035 0.0641 9.802 1955.1 0.0624 12.892 37L482 2057 253.26 1403.4 0.24 19.433 2253.8 0.24 13.761 2314.5 0.214 15.981 1876.3 0.137 9.631 1942.3 0.133 10.702 37L594 299 0.44 99.508 0.422 0.0935 2327.8 0.187 20.484 1864.7 0.0374 1959.8 0.0315 9.553 37L594 815 0.486 98.345 1382.4 0.37 2259.2 0.0904 2334.1 0.187 20.724 1859.7 0.0429 10.909 1958.1 0.0278 10.076 37L594 1581 1119.88 0.309 18.527 2253.5 0.0777 12.802 2333.6 0.093 20.173 1859.1 0.106 11.822 1943.9 0.0914 8.489 37L594 1581 0.331 139.24 0.369 21.51 2261.4 0.0778 13.471 2324.5 0.14 20.092 1862.6 0.0085 14.417 1958.2 0.0041 12.067 37L594 1609 1276.8 1400.6 0.211 15.657 2257.3 0.0561 9.771 2315.3 0.0693 16.644 1890.4 0.0028 1950.7 0.0063 14.208 37L667 25 0.483 121.98 0.282 22.218 0.0571 2324.3 0.105 1863.2 0.0262 11.788 1946.3 0.0153 8.716 37L667 1067 2072.76 1399.9 0.243 18.129 2257.4 0.12 11.205 2317.6 0.114 1865 0.105 1950 0.11 9.762 37L667 2054 0.408 92.561 1393.8 0.33 15.176 0.0414 2319.5 0.106 1862.6 0.0474 1942.1 0.032 7.573 37L726 400.7 426.75 1383.5 0.197 20.969 2250.8 0.0656 8.439 0.0471 19.129 1857.6 0.114 1954.8 0.101 16.122 37L726 836.6 167.87 1408.4 0.177 16.393 2255.3 0.136 12.776 2352.1 0.122 13.575 1867 0.14 13.246 1952.6 0.132 11.53 37L726 836.6 88.443 1408.6 0.156 16.013 2256.7 0.0918 13.334 2339 0.0812 18.94 1867.7 0.0976 11.68 1944.4 0.0889 11.127 649 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d 30L1268 574 2149.7 0.0048 7.432 2346.5 17.536 2256.7 2117 0.0058 6.275 0.156 13.383 0.033 34L006 25 2146.3 0.0183 8.659 2324.4 0.112 19.693 0.0176 2324.4 0.112 21.937 2397.1 0.0034 34L006 1235.1 2158.1 0.0214 11.08 2317.4 16.255 2257.8 2126.2 0.0138 10.69 2323.6 15.164 2395.5 0.129 34L1352 28 0.205 2334.6 0.273 15.581 2252.3 13.513 2115 0.207 2334.6 0.277 17.862 2393 0.206 34L1352 28 0.0966 2318.7 18.949 2253.6 12.798 0.107 16.645 2392.9 0.102 34L1352 315 2149 0.0327 9.22 2322.7 0.104 16.993 2257.9 14.466 2112.4 0.0347 11.298 2322.7 0.104 16.736 0.0311 34L1352 814 0.101 2322.7 0.162 18.393 2258.3 0.132 21.38 2134.2 0.097 7.062 2322.7 0.162 18.036 2398.4 0.105 34L235 23.2 0.034 2326.6 0.089 12.627 2230.5 15.081 2113.1 0.0288 2326.6 0.089 13.868 2399.9 0.0742 34L235 909 0.0709 2313.1 14.678 2253.9 0.0961 18.791 2113.2 0.0722 2391.3 0.069 34L235 944 0.0612 2329 19.42 2252 16.214 2110.4 0.0683 9.091 2329 0.0825 18.883 2390.5 0.0194 34L235 944 2142.9 0.0417 10.358 2327.1 0.0828 20.923 2251.5 15.23 0.0499 10.55 2327.1 0.0828 21.103 2392.6 0.0323 34L235 1961 0.0352 2325.7 0.171 17.063 2257.8 2137.7 0.0245 10.414 2325.7 0.171 17.535 2392 0.0175 34L814 92 0.0118 2342.8 16.621 2259.9 2114.8 0.0177 10.017 2339.3 17.152 2400.7 0.0684 34L814 195.7 2140.9 0.0016 9.936 2332.7 19.23 2251.6 16.275 2112.9 0.0061 9.794 2332.7 0.142 17.469 2391.8 0.0665 34L814 195.7 2158.1 0.0015 6.107 2331 0.183 20.82 2253.9 15.922 2112.1 0.0034 10.06 2331 0.186 21.949 2391.3 0.0295 34L814 1147.7 0.0457 2319.6 0.147 19.439 2257.4 0.0925 2133.7 0.0382 9.074 2329.9 0.149 21.156 2396 0.0758 34L814 2333.4 2158 0.0082 10.628 2336.2 20.132 0.0018 8.587 2336.2 13.04 2391.2 0.0219 34L814 2333.4 2142.3 0.004 8.796 2342.5 0.189 2256.5 2114.6 0.009 2335.5 12.521 2396.1 0.0427 37L482 91 2141.9 0.122 10.436 2328.4 19.055 0.131 11.94 2328.4 0.147 22.496 2392.5 0.0889 37L482 1019 0.0456 2324.9 0.209 22.558 2123.2 0.0476 8.727 2324.9 0.209 14.917 2399.2 0.0357 37L482 2057 2143 0.106 11.155 0.211 13.681 0.211 0.209 2138.2 0.102 0.211 0.209 2407.7 0.166 37L594 299 0.0031 2327.8 0.212 19.893 2111.7 0.0005 5.742 2327.8 0.212 15.299 2399.6 0.0104 37L594 815 0.0011 2334.1 0.192 17.655 0.0005 10.07 2334.1 11.513 0.0781 37L594 1581 2154.1 0.0388 11.091 2333.6 0.1 17.143 2253.5 0.0655 0.0462 9.318 2333.6 0.104 11.479 2396.4 0.0555 37L594 1581 2152 0.0012 8.932 2324.5 0.158 18.509 2258 0.0035 9.896 2324.5 0.158 14.364 2396 0.026 37L594 1609 2157.5 0.026 11.006 2315.3 19.784 2257.3 0.0563 10.677 2129.6 0.0234 9.349 2323.1 0.0789 13.463 2402.5 0.0405 37L667 25 0.0022 2324.3 21.844 2112.1 0.0009 8.824 2324.3 22.254 2406.8 0.0081 37L667 1067 2159 0.0967 8.898 2317.6 0.13 21.418 2257.4 0.116 2113.6 0.1 2325.6 12.582 2397 0.0858 37L667 2054 2143.4 0.0028 7.43 2319.5 20.355 2116.3 0.0072 10.719 2392.7 0.0366 37L726 400.7 2145.5 0.057 9.598 2308.9 0.0535 16.631 2250.8 11.943 2111.6 0.0622 2333.6 0.0546 10.4 2403.4 0.0337 37L726 836.6 2157.3 0.0912 12.55 21.283 2252 0.235 0.0964 11.186 2331.8 0.224 12.706 2390.7 0.0757 37L726 836.6 0.0362 2343.9 0.139 13.572 2256 0.149 10.359 2112.6 0.0408 10.489 2336.1 8.856 2391.4 0.0252 650 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w 30L1268 574 2256.7 0.149 19.807 2329.3 0.132 12.029 0.109 15.037 34L006 25 11.063 0.0484 2324.4 0.109 14.414 0.0066 34L006 1235.1 9.29 2258.2 0.0833 19.123 2322.4 0.183 13.217 2366.9 0.135 9.828 2356.3 0.079 34L1352 28 13.752 2252.3 0.265 17.413 2326.3 0.273 10.256 0.221 2357.2 34L1352 28 9.842 2253.6 0.154 19.547 2318.7 0.174 11.29 0.108 2357.4 34L1352 315 2257.8 0.0853 19.352 2322.7 0.105 12.004 0.036 2356.2 0.0399 13.702 34L1352 814 14.305 0.13 2322.7 0.162 10.083 2369.9 0.0932 12.763 2358.9 34L235 23.2 11.161 0.0608 2326.6 0.0828 10.291 2368 0.055 9.013 2368 0.0601 16.27 34L235 909 10.706 2253.9 0.0954 20.753 2313.1 0.144 12.621 0.0706 2390.7 0.0747 12.766 34L235 944 11.797 2252 0.0759 19.291 0.078 0.0278 0.0312 11.873 34L235 944 10.969 2251.5 0.067 18.663 2327.1 0.0778 11.719 2382.1 0.033 10.785 0.0359 34L235 1961 9.323 2261.1 0.101 18.791 2325.7 0.16 9.919 0.037 0.0503 34L814 92 10.473 2259.6 0.11 20.068 2324 0.147 13.121 2367.7 0.0829 9.327 34L814 195.7 8.747 2251.6 0.106 21.445 2327.6 0.123 11.003 2365.7 0.0748 7.932 10.794 34L814 195.7 8.851 2252.8 0.0831 20.794 2326.6 0.0968 12.851 2367.6 0.0446 10.887 12.165 34L814 1147.7 12.53 2262.6 0.0917 16.501 2319.6 0.148 11.437 2365.9 0.072 9.542 2356.7 0.0907 34L814 2333.4 8.186 0.134 0.28 0.119 34L814 2333.4 9.413 2256.5 0.155 20.428 2326.7 0.172 13.3 0.103 2357.4 37L482 91 7.458 2257.1 0.164 19.858 2327.8 0.161 10.207 2368.1 0.112 11.487 0.0307 37L482 1019 11.52 2244.2 0.0591 13.151 0.0618 2378.9 0.0266 13.998 37L482 2057 7.5 2253.8 0.24 20.152 2314.5 0.208 8.101 2366 0.187 9.393 0.191 18.772 0.187 37L594 299 8.145 0.0935 2327.8 0.208 14.066 0.0199 37L594 815 2259.2 0.0904 19.976 2326.7 0.186 10.601 2366.4 0.082 8.382 37L594 1581 14.075 2253.5 0.0777 17.576 2328.3 0.0942 11.105 0.0497 2356.1 0.0512 13.926 37L594 1581 9.452 2261.4 0.0778 20.285 2324.5 0.15 11.84 0.0195 2355.4 37L594 1609 10.577 2257.3 0.0561 18.443 2315.3 0.0762 11.974 2377.6 0.0461 9.942 2377.6 0.0581 14.965 37L667 25 11.577 0.0571 2324.3 0.118 13.673 2365.2 0.0161 8.058 2357.5 0.0193 37L667 1067 10.755 2257.4 0.12 17.201 2317.6 0.127 10.708 2375 0.105 10.761 2359 0.105 37L667 2054 10.936 0.0414 2319.5 0.204 15.186 2383.6 0.0159 9.236 2388.1 13.23 37L726 400.7 10.853 2250.8 0.0656 16.679 0.047 0.0319 2361 0.0403 13.236 37L726 836.6 8.401 2255.3 0.136 18.095 2325.6 0.118 10.889 2366.6 0.0965 11.334 2356.4 37L726 836.6 10.522 2256.7 0.0918 19.6 2329 0.0724 9.601 0.0585 0.121 15.604 651 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefringence Colour Manual Mineral ID 1 Manual Mineral ID 2 Manual Mineral ID 3 Manual Mineral ID 4 TSA_S Mineral1 TSA_S Mineral2 TSA_S Weight1 37L768 66 Unknown Black Unknown Grey carbonate Mg-chlorite Epidote 1 37L768 98 Ankerite Grey Fe-dolomite Dolomite 1 37L768 1108 Unknown Unknown Grey Fe-chlorite calcite IntChlorite Muscovite 0.696 37L768 2005 Unknown Black Ankerite Grey dolomite biotite amphibole Dolomite Hornblende 1 BK05010 376.12 Calcic Black Calcite Grey and Blue carbonate amphibole Fe-chlorite Hornblende Ankerite 0.65 CB1912V1 Unknown Brown Ankerite Grey biotite Fe-chlorite IntChlorite Siderite 1 CB302561 Unknown Brown Ankerite Grey biotite MgChlorite 1 CB4043FV Unknown Brown Ankerite Grey Mg-chlorite biotite IntChlorite 1 CR4610 947 Calcic Black Calcite Blue and Late blue Mg-chlorite clay (kaolinite?) IntChlorite 1 CR4611 581.4 Unknown Black Calcite Blue calcite Mg-chlorite biotite Dark CR4612 360.3 Unknown Black Unknown Brown alunite clay (illite?) Dark 1 CR4613 1.3 Unknown Black Calcite Blue Fe-chlorite epidote illite? FeChlorite CR464 31.2 Unknown Black Unknown Blue Fe-chlorite Dark 1 CR466 145 Unknown Black Unknown Blue Int-chlorite carbonate Illite? IntChlorite 1 CR467 86.3 Unknown Black Calcite Blue serpentine Tourmaline 1 CR468 629 Unknown Black Calcite Blue olivine (996) chlorite illite Palygorskite 0.558 CR469 41.6 Unknown Black Calcite Blue and Brown Int-Fe- chlorite amphibole carbonate? Serpentine MgChlorite 0.527 D14391 191 Brown Unknown Grey (Fe) carbon- ate Fe-chlorite dickite? Siderite IntChlorite 0.708 D14391 1025 Black Unknown Grey Mg-chlorite tremolite dickite? Dolomite D14391 1810 Unknown Black Unknown Blue Mg-chlorite carbonate Dark 0.706 D14391 2922 Brown Ankerite Grey carbonate Fe-chlorite IntChlorite Muscovite 0.76 D14981 3.2 Unknown Brown Unknown Grey Fe-chlorite calcite IntChlorite 1 D14981 1045.2 Brown Unknown Blue Fe-chlorite Epidote 1 D14981 1798.8 Unknown Black Ankerite Brown dolomite Fe-chlorite FeChlorite Ankerite 0.644 D14981 1798.8 Unknown Black Unknown Brown dolomite Fe-chlorite Siderite IntChlorite 1 D15367 5.5 Brown Unknown Grey Int-chlorite calcite brucite IntChlorite 0.517 D15367 371.1 Unknown Ankerite Grey dolomite Int-Fe-chlorite muscovite IntChlorite Ankerite 0.8 D15367 793 Unknown Black Unknown Blue Int-chlorite IntChlorite 0.774 D16355 85.3 Unknown Black Unknown Grey dolomite chlorite quartz? IntChlorite Talc 0.522 D16355 85.3 Unknown Black Unknown Grey Mg-chlorite Ankerite Hornblende 0.823 D16355 431 Black Unknown Grey natrolite (zeo- lie) dolomite Int-Fe- chlorite IntChlorite Dolomite 1 D16355 925.8 Black Unknown Grey dolomite Dolomite 1 652 Table D.1 (Continued) Sample Depth (ft) TSA_ S Weig ht2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w 37L768 66 1355.94 0.307 20.82 2250.8 0.118 11.935 2334.7 0.109 14.297 1860.7 0.141 10.447 1945.7 0.128 9.398 37L768 98 64.565 0.544 0.108 2325.4 0.275 20.476 1863.9 0.0394 0.0306 37L768 1108 0.304 47.241 1393.9 0.229 23.956 2255.6 0.0664 14.053 2333.3 0.0881 20.023 1866.8 0.0244 10.718 1952.5 0.0266 13.302 37L768 2005 642.76 1400.4 0.259 19.169 2253.6 0.0791 13.218 2320.4 0.164 16.284 1874.1 0.0152 11.017 1941.6 0.0153 8.336 BK05010 376.12 0.35 39.522 1393.4 0.277 22.494 2252.1 0.0835 15.114 2332.6 0.0903 21.611 1869.1 0.0853 12.141 1942.5 0.0717 13.437 CB1912V1 344.77 0.316 2250.1 0.128 13.639 2319.3 0.104 18.257 1855.5 0.205 11.35 0.189 CB302561 477.19 1382.1 0.289 20.276 2251.8 0.103 14.527 2328.1 0.0951 16.513 1857.4 0.167 12.138 0.149 CB4043FV 336.22 1385 0.299 2252.1 0.116 11.662 2345.7 0.0957 19.494 1867.7 0.206 8.975 1949.7 0.188 12.672 CR4610 947 336.22 1385 0.299 2252.1 0.116 11.662 2345.7 0.0957 19.494 1867.7 0.206 8.975 1949.7 0.188 12.672 CR4611 581.4 10000 1404.9 0.265 17.634 2253 0.171 10.455 2324.4 0.161 12.913 1876.4 0.202 8.217 1957.2 0.19 10.734 CR4612 360.3 91.355 1405.7 0.306 16.659 2257.5 0.131 12.779 2350.1 0.152 14.919 1868 0.107 12.573 1960 0.0872 9.084 CR4613 1.3 10000 1407.4 0.272 15.489 2255.3 0.17 10.698 2320 0.209 17.365 1871.9 0.133 8.194 1952.7 0.13 11.227 CR464 31.2 357.92 1411 0.34 17.351 2258.2 0.191 12.434 2340 0.24 10.666 1872.1 0.176 10.057 1954.1 0.151 10.768 CR466 145 2242.09 1399.5 0.222 17.041 2238.9 0.124 11.555 2326.1 0.119 15.663 1869 0.162 10.824 1947.1 0.148 12.427 CR467 86.3 2893.27 1406.9 0.225 13.314 2247 0.151 9.873 2325.2 0.163 13.679 0.127 10.373 1940.9 0.117 9.758 CR468 629 0.442 117.6 1393.7 0.376 22.264 0.163 15.655 2324.9 0.216 0.0566 9.335 0.126 CR469 41.6 0.473 17.666 1399.3 0.325 22.947 2255.2 0.15 14.351 2327.6 0.199 21.372 1865.6 0.0211 13.165 1956.4 0.0288 11.985 D14391 191 0.292 45.517 1399.3 0.325 22.947 2255.2 0.15 14.351 2327.6 0.199 21.372 1865.6 0.0211 13.165 1956.4 0.0288 11.985 D14391 1025 10000 1410 0.385 14.968 2256.7 0.293 11.451 2352.9 0.293 17.815 1872.3 0.324 10.319 1952.1 0.307 10.602 D14391 1810 0.294 77.066 1397.5 0.386 23.076 2250.8 0.141 13.238 2335.8 0.211 21.998 1857.1 0.0336 12.096 1940.8 0.0274 11.148 D14391 2922 0.24 64.443 1397.5 0.386 23.076 2250.8 0.141 13.238 2335.8 0.211 21.998 1857.1 0.0336 12.096 1940.8 0.0274 11.148 D14981 3.2 757.68 1406.2 0.179 18.314 2255.2 0.148 13.037 2342.6 0.176 14.838 1874.5 0.0342 8.873 1958.3 0.0364 11.576 D14981 1045.2 130.53 1409.5 0.306 15.428 2260.6 0.121 2353.2 0.11 18.318 1857.9 0.194 11.202 1947.8 0.162 12.626 D14981 1798.8 0.356 32.822 0.319 0.0972 12.568 2331.4 0.161 20.424 1866.4 0.0399 14.397 1949.3 0.0362 15.107 D14981 1798.8 290.79 1393.3 0.22 22.22 2257.7 0.0712 12.301 2342.6 0.0782 12.284 0.108 10.409 1952.5 0.0969 12.19 D15367 5.5 0.483 101.33 1403.6 0.197 19.903 2257.9 0.109 13.249 2342.2 0.133 19.978 1881.9 0.0615 10.722 1948.3 0.0578 12.951 D15367 371.1 0.2 34.49 1403.6 0.197 19.903 2257.9 0.109 13.249 2342.2 0.133 19.978 1881.9 0.0615 10.722 1948.3 0.0578 12.951 D15367 793 0.226 51.359 1411.8 0.389 16.181 2257.9 0.23 11.818 2353.7 0.212 21.886 0.299 9.807 1947.5 0.277 11.486 D16355 85.3 0.478 57.419 1392.3 0.293 16.732 2253.2 0.096 12.715 2312.2 0.117 13.546 1863.7 0.115 1948.6 0.0986 11.205 D16355 85.3 0.177 81.1 1401.1 0.26 20.604 2255.9 0.115 14.578 2323.5 0.125 1876.2 0.0697 11.131 1951.7 0.0609 7.871 D16355 431 298.76 0.193 2263.2 0.066 13.756 2327.1 0.0873 15.804 1874.3 0.0293 7.899 1949.3 0.038 11.006 653 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d 37L768 66 2156.4 0.0918 10.198 2334.4 0.184 13.927 2253.2 0.189 13.528 2111.6 0.0933 10.57 2334.4 0.198 13.029 2396.8 0.0851 37L768 98 2148.7 0.0085 13.999 2325.4 0.316 23.016 2139.7 0.0015 2325.4 0.316 23.245 2399.9 0.0051 37L768 1108 0.0014 2336.8 19.955 2253.4 2113.5 0.0006 9.813 2336.8 0.0978 13.195 2396.7 0.0052 37L768 2005 2158 0.0169 9.637 2322.5 0.362 22.901 2124.2 0.019 8.372 2322.5 14.217 2391.2 0.117 BK05010 376.12 2158.4 0.0106 10.008 2320.4 19.752 2253.6 0.0684 2112.4 0.0163 2320.6 0.188 12.16 2390.3 0.0112 CB1912V1 2145.4 0.131 9.523 2332.6 0.0948 20.462 2252.1 0.137 2332.6 0.0953 13.702 2393.1 0.0675 CB302561 2146.2 0.0929 12.376 2310 0.143 20.503 0.163 14.305 0.0997 9.924 2328.5 0.143 14.431 2397.7 0.0607 CB4043FV 2158.4 0.106 10.855 2328.1 0.1 15.199 2251.8 2113.3 0.116 2328.1 0.1 11.424 2400.8 0.0688 CR4610 947 2158.4 0.106 10.855 2345.4 16.328 2252.1 0.116 12.402 2113.3 0.116 2324.8 2400.8 0.0688 CR4611 581.4 2149.6 0.165 13.457 2315.6 0.181 14.225 2245.5 0.168 10.237 2110.6 0.166 8.921 2330.8 0.181 9.164 2399.3 0.153 CR4612 360.3 0.0021 2324.4 0.183 14.419 2257.5 2122.7 0.0101 12.069 2324.4 0.183 13.272 2396.8 0.0504 CR4613 1.3 2150.1 0.144 12.512 2338.8 0.14 19.758 2255.3 16.584 2114 0.136 10.837 2339.2 20.303 2398.4 0.204 CR464 31.2 2156.1 0.0926 10.6 2320 0.218 17.421 2258.2 2118.7 0.0955 9.615 0.221 17.561 2393.1 0.172 CR466 145 2151.2 0.118 11.516 2340 15.723 2222.2 0.126 19.372 0.115 7.397 13.956 2391.6 0.0959 CR467 86.3 2158.5 0.125 10.172 2326.1 0.123 12.353 2247 0.157 11.644 2122.1 0.12 9.069 2326.1 0.123 12.962 2401.2 0.152 CR468 629 2141.8 0.0446 10.713 2325.2 0.169 13.984 2251.6 19.483 2112.5 0.0689 2325.2 0.169 13.992 2392.4 0.101 CR469 41.6 2154.1 0 8.054 2323.5 0.331 20.201 2255.2 15.209 2126.5 0.0021 11.315 2323.5 0.331 20.493 2391.6 0.0099 D14391 191 2154.1 0 8.054 2327.6 0.209 15.221 2257.1 2126.5 0.0021 11.315 2327.6 0.209 21.429 2391.6 0.0099 D14391 1025 2140.3 0.248 9.252 2311.3 0.0829 2256.7 2123.9 0.257 10.384 2327.3 0.0829 17.827 2392.8 0.237 D14391 1810 2155 0.0002 7.408 2346 14.603 2250.8 15.206 2111 0.0111 12.313 2339.8 0.285 16.689 0.0434 D14391 2922 2155 0.0002 7.408 2335.8 21.905 2251.7 17.031 2111 0.0111 12.313 2335.8 21.946 0.0434 D14981 3.2 2156.4 0.002 12.073 2342.6 0.0741 14.338 2115.7 0.0046 10.575 2334.1 0.178 14.723 2397 0.0613 D14981 1045.2 2140.5 0.0663 11.784 2335.9 0.174 13.146 2112.6 0.0743 2335.9 14.409 2395.1 0.0427 D14981 1798.8 2148.6 0.0027 10.085 2338.7 13.057 2259.4 2120.9 0 9.428 2338.5 0.179 14.767 2404.3 0 D14981 1798.8 0.0419 2331.4 16.444 2257.7 0.0712 13.082 0.0499 9.916 2331.4 0.181 20.694 2401.8 0.0394 D15367 5.5 2155.4 0.0013 8.912 2342.6 0.0715 15.02 2115.7 0.0048 9.941 0.0741 11.491 2392.1 0.0243 D15367 371.1 2155.4 0.0013 8.912 2330.8 16.641 2258 2115.7 0.0048 9.941 2330.8 0.153 17.191 2392.1 0.0243 D15367 793 2159.7 0.193 10.847 2339.8 14.578 2257.6 13.191 2113.6 0.201 10.222 0.159 14.896 0.136 D16355 85.3 2142.3 0.0317 9.813 2312.5 0.166 18.654 2259.7 2124.2 0.0427 12.168 0.166 16.64 2391.9 0.0708 D16355 85.3 2159.8 0.0052 9.461 2314.2 19.697 2255.9 2113.8 0.0104 10.808 18.134 2391.8 0.0207 D16355 431 2143.1 0.015 12.827 2323.5 17.36 2257.4 15.41 2112.5 0.0203 2323.5 11.545 2392.6 0.0123 654 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w 37L768 66 8.367 2250.8 0.118 16.067 2327.4 0.116 10.251 0.097 2369.1 16.981 37L768 98 8.851 0.108 2325.4 0.311 14.374 0.007 37L768 1108 13.527 2255.6 0.0664 21.079 2327.1 0.0892 12.223 2365 0.0233 7.651 2357.6 37L768 2005 8.496 2253.6 0.0791 19.506 2320.4 0.192 11.848 2383 0.123 9.074 BK05010 376.12 8.803 2252.1 0.0835 21.226 2329.5 0.0859 11.235 0.0235 2390.9 0.123 12.424 CB1912V1 9.736 2250.1 0.128 18.849 2319.3 0.113 14.136 2366.9 0.078 9.762 CB302561 10.676 2251.8 0.103 18.406 2328.2 0.0974 11.251 2367.2 0.0632 7.887 13.382 CB4043FV 12.52 2252.1 0.116 15.676 2324.8 0.094 6.226 2366.3 0.0663 10.636 CR4610 947 12.52 2252.1 0.116 15.676 2324.8 0.094 6.226 2366.3 0.0663 10.636 2359.6 CR4611 581.4 12.039 2253 0.171 15.196 2324.4 0.166 10.054 2375.1 0.161 12.065 2355.8 0.162 17.593 CR4612 360.3 9.977 2257.5 0.131 19.739 2324.8 0.138 12.709 2367 0.112 12.71 0.161 17.556 CR4613 1.3 8.147 2255.3 0.17 15.433 2320 0.223 12.826 2372.9 0.191 12.189 2357.4 CR464 31.2 10.732 2258.2 0.191 18.582 2321.4 0.233 12.59 0.203 2355.8 0.196 17.773 CR466 145 10.694 2238.9 0.124 15.034 2326.1 0.117 8.562 2367.1 0.105 11.044 2357.7 0.213 CR467 86.3 12.08 2247 0.151 13.944 2325.2 0.163 9.934 2368.7 0.147 8.397 2357.1 0.109 18.177 CR468 629 13.135 0.163 2324.9 0.247 9.471 2379.1 0.0932 11.615 2368.7 11.388 CR469 41.6 9.324 2255.2 0.15 21.389 2327.6 0.205 11.508 0.0475 0.189 19.043 D14391 191 9.324 2255.2 0.15 21.389 2327.6 0.205 11.508 0.0475 D14391 1025 9.413 2256.7 0.293 19.027 2316.9 0.271 9.602 0.269 2358.9 0.0391 D14391 1810 2250.8 0.141 18.449 2329.2 0.184 11.61 0.0612 2357 0.278 D14391 2922 2250.8 0.141 18.449 2329.2 0.184 11.61 0.0612 0.0641 D14981 3.2 11.315 2255.2 0.148 20.24 2327.8 0.162 11.362 0.106 D14981 1045.2 10.036 2260.6 0.121 19.511 2329 0.102 9.909 2367.2 0.1 13.996 2356.9 0.159 D14981 1798.8 11.757 0.0972 2327.1 0.173 11.119 0.0283 2357.7 D14981 1798.8 14.207 2257.7 0.0712 17.278 2325.4 0.0692 11.574 2367.7 0.0573 11.913 D15367 5.5 8.178 2257.9 0.109 19.42 2328.2 0.117 11.066 0.0716 2357.4 0.0576 D15367 371.1 8.178 2257.9 0.109 19.42 2328.2 0.117 11.066 0.0716 2356.2 D15367 793 2257.9 0.23 19.651 2328.2 0.201 11.128 2366.1 0.184 13.049 2360 13.977 D16355 85.3 12.874 2253.2 0.096 20.333 2312.2 0.173 15.389 2368.5 0.0693 12.208 0.078 16.971 D16355 85.3 9.841 2255.9 0.115 20.451 2323.5 0.13 12.675 0.0611 0.0331 D16355 431 11.217 2263.2 0.066 19.826 2327.1 0.0996 11.488 2367 0.0307 13.678 0.0721 16.403 655 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefrin- gence Colour Manual Mineral ID 1 Manual Min- eral ID 2 Manual Mineral ID 3 Manual Mineral ID 4 TSA_S Min- eral1 TSA_S Min- eral2 TSA_S Weight 1 D16355 925.8 Black Unknown Grey dolomite Dolomite 1 D21708 139.3 Black Ankerite Brown Int-chlorite Ankerite 1 D21708 139.3 Black Ankerite Brown muscovite Int-chlorite MgChlorite 1 D21708 1340 Unknown Black Unknown Grey Mg-chlorite MgChlorite 1 D21708 2760 Unknown Black Calcite Brown Fe-chlorite carbonate Zoisite 1 D22203 79 Unknown Black Unknown Grey dolomite Fe-chlorite Ankerite FeTourmaline 0.525 D22203 908 Unknown Black Ankerite Grey Fe-chlorite augite IntChlorite Opal 0.798 D22203 1604 Unknown Black Unknown Brown dolomite Fe-chlorite IntChlorite Illite 0.718 D22203 1604 Unknown Black Unknown Brown dolomite Fe-chlorite FeChlorite Dolomite 0.604 D22223 38 Black Unknown Grey dolomite Int-Fe-chlorite IntChlorite Dolomite 0.524 D22223 975 Unknown Ankerite Grey carbonate OH- Ankerite Hornblende 1 D22223 1932 Black Unknown Grey Mg-chlorite alunite Siderite 0.841 D2252 162 Unknown Grey Fe-chlorite dolomite amphibole muscovite IntChlorite Muscovite 0.813 D2252 309 Unknown Brown Unknown Grey carbonate illite? Ankerite Phlogopite2 1 D2252 491 Unknown Black Unknown Grey and Brown Mg-chlorite Epidote 1 D2253 75 Unknown Black Ankerite Grey and Blue Int-Mg chlorite Dolomite IntChlorite 1 D2253 252 Unknown Black Ankerite Grey and Brown Mg-chlorite Epidote 1 D2253 495 Black Unknown Grey Fe-chlorite biotite Biotite MgChlorite 0.741 D2253 495 Black Unknown Grey (Fe) carbonate Fe-chlorite muscovite IntChlorite Muscovite 1 D239 95 Unknown Black Unknown Grey carbonate Dolomite 0.589 D239 217 Brown Unknown Grey dolomite Int-chlorite amphibole MgChlorite Dolomite 0.602 D2435 182 Brown Unknown Grey and Brown Fe-chlorite carbonate clay? Dolomite Halloysite 1 D2435 361 Unknown Brown Unknown Grey epidote carbonate Fe-chlorite muscovite Ankerite Nacrite 0.657 D2435 454 Unknown Black Unknown Grey dolomite Int-Fe-chlorite dickite? IntChlorite Dolomite 1 D27343 88 Unknown Unknown Grey, Blue and Brown carbonate clinozoisite clay? FeChlorite 1 D27343 501.3 Black Calcite Blue Fe-chlorite (Fe) carbonate FeChlorite 0.826 D27343 1181.7 Unknown Black Unknown Grey (Fe) carbonate Fe-chlorite epidote amphibole IntChlorite Muscovite 1 D27943 314 Unknown Black Unknown Brown Fe-chlorite calcite FeChlorite 1 D27943 314 Unknown Black Unknown Brown Fe-chlorite calcite IntChlorite 1 D27943 933.8 Unknown Black Unknown Blue dolomite Calcite 1 D27943 1779.5 Unknown Black Unknown Blue Fe-chlorite amphibole carbonate? Siderite IntChlorite 1 D27943 2104.2 Unknown Black Calcite Grey and Brown Mg-chlorite amphibole? FeChlorite Ankerite 0.541 D27943 2607.6 Unknown Black Unknown Grey (Fe) carbonate Fe-chlorite amphibole Hornblende Calcite 0.628 D27943 3389.5 Unknown Black Ankerite Grey (Fe) carbonate Fe-chlorite IntChlorite Calcite 0.842 656 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w D16355 925.8 119.14 1393.5 0.326 21.923 2255.3 0.152 12.833 2322.9 0.164 19.741 1855.2 0.184 9.031 0.169 D21708 139.3 190.62 1392.4 0.27 19.282 2255.9 0.101 15.343 2332.6 0.0867 11.872 1864.7 0.15 1940.4 0.13 8.493 D21708 139.3 361.88 1408.4 0.136 15.754 2257.8 0.0585 11.301 2330.6 0.0651 20.641 1865.1 0.0637 1953.6 0.0637 13.183 D21708 1340 329.39 1408.4 0.136 15.754 2257.8 0.0585 11.301 2330.6 0.0651 20.641 1865.1 0.0637 1953.6 0.0637 13.183 D21708 2760 200.43 0.258 16.639 2252.6 0.107 12.28 2350.7 0.113 14.582 0.135 13.434 1942.7 0.118 11.675 D22203 79 0.475 229.22 1408.5 0.358 16.932 2256.8 0.0774 13.349 2344.5 0.0866 15.372 0.168 0.113 D22203 908 0.202 80.294 1409.6 0.282 14.157 2258.8 0.116 12.443 2341.2 0.172 19.215 1858.6 0.106 13.916 1945.7 0.0825 12.093 D22203 1604 0.282 52.907 1407.5 0.339 13.578 2262.2 0.0994 2327.2 0.147 19.94 1870 0.0876 10.724 1942 0.072 8.252 D22203 1604 0.396 168.68 1390.8 0.254 20.869 2254.1 0.0669 14.701 2332.1 0.0995 20.54 1856.1 0.0227 12.92 1956.4 0.0224 10.575 D22223 38 0.476 180.58 1390.8 0.254 20.869 2254.1 0.0669 14.701 2332.1 0.0995 20.54 1856.1 0.0227 12.92 1956.4 0.0224 10.575 D22223 975 593.14 1399 0.216 21.935 2251.8 0.0659 9.172 2323.8 0.0487 13.815 1877.1 0.104 7.479 1944.7 0.0963 9.741 D22223 1932 0.159 25.62 1402.2 0.183 20.283 2251.8 0.148 14.645 2335.6 0.185 21.009 1876.6 0.0163 11.538 1957.9 0.0185 11.296 D2252 162 0.187 86.963 0.432 0.0657 2326.7 0.169 19.544 1860.6 0.0402 12.099 1942.2 0.0373 12.526 D2252 309 2653.56 1408.5 0.349 18.081 2258.9 0.184 12.188 2334.6 0.16 19.639 1858 0.27 11.02 1941.8 0.249 10.113 D2252 491 345.97 1408.5 0.349 18.081 2258.9 0.184 12.188 2334.6 0.16 19.639 1858 0.27 11.02 1941.8 0.249 10.113 D2253 75 192.1 1411 0.353 16.134 2260.9 0.186 13.399 2344.3 0.153 14.762 1863.3 0.255 12.22 0.234 D2253 252 183.73 1407.8 0.362 15.309 2258.5 0.202 2333 0.199 15.583 1857.4 0.223 11.859 1941.6 0.208 9.52 D2253 495 0.259 45.649 1398.1 0.339 21.969 2251.6 0.234 14.194 2333.4 0.274 22.549 1860.6 0.0073 10.613 1957.8 0.0207 10.968 D2253 495 160.11 0.469 0.097 2325.2 0.222 19.973 1863.7 0.0398 1957.7 0.0313 11.892 D239 95 0.411 95.399 1392.7 0.359 17.123 2258.4 0.167 12.967 2316.8 0.205 13.432 1856.8 0.171 1953.7 0.149 9.364 D239 217 0.398 405.13 1383.7 0.258 21.602 2254.4 0.0899 14.5 2335.4 0.112 18.271 0.0584 13.109 1943.5 0.0463 11.446 D2435 182 123.44 1383.7 0.258 21.602 2254.4 0.0899 14.5 2335.4 0.112 18.271 0.0584 13.109 1943.5 0.0463 11.446 D2435 361 0.343 199.64 1395.6 0.0267 21.818 2251.6 0.0405 8.465 2328.2 0.0454 15.522 1871.5 0.0175 10.229 1949.5 0.0192 14.483 D2435 454 235.68 1394 0.343 19.966 2255.6 0.147 13.518 2324 0.122 17.56 1857.3 0.248 8.989 1942.3 0.22 9.435 D27343 88 16.221 1411.5 0.361 14.649 2258.6 0.205 13.072 2345.2 0.186 17.13 1867.8 0.137 9.353 1958.1 0.11 9.639 D27343 501.3 0.174 39.603 1408.8 0.283 18.134 2255.1 0.377 15.203 2343.6 0.359 20.159 1881.6 0.0638 14.604 0.0968 D27343 1181.7 284.69 1409.4 0.393 16.39 2256.3 0.278 13.885 2348 0.264 17.557 1857.7 0.319 12.578 1948.2 0.305 11.314 D27943 314 316.85 1407.6 0.324 14.719 2256.8 0.124 13.486 2348.7 0.104 14.227 1860.6 0.204 12.087 1951.2 0.179 11.796 D27943 314 355.48 1380.6 0.378 0.0666 11.687 2326.3 0.119 20.616 1863.5 0.0602 10.779 1946 0.0459 11.359 D27943 933.8 53.403 0.321 19.706 2260.7 0.105 2334.8 0.139 14.892 1856.4 0.0771 12.823 1956.7 0.0578 10.552 D27943 1779.5 185.85 1408.7 0.346 18.242 2254 0.193 15.136 2345.2 0.191 14.357 1870.9 0.221 10.796 1940.5 0.198 7.9 D27943 2104.2 0.459 117.55 1398.9 0.274 17.882 2255.5 0.113 14.41 2328.9 0.27 21.883 1873.6 0.0068 10.405 1954.2 0.0081 11.716 D27943 2607.6 0.372 50.986 1398.9 0.274 17.882 2255.5 0.113 14.41 2328.9 0.27 21.883 1873.6 0.0068 10.405 1954.2 0.0081 11.716 D27943 3389.5 0.158 66.677 1397.7 0.334 23.185 2254.2 0.172 15.305 2332.3 0.237 22.915 1872.7 0.0738 12.66 1958.3 0.0523 12.852 657 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d D16355 925.8 0.109 2327.1 0.106 18.38 2259.9 14.824 0.115 2327.1 0.106 21.82 2407.8 0.107 D21708 139.3 0.0686 2329.4 18.037 2255.9 2112.8 0.0774 12.559 2329.4 0.145 18.792 2391.5 0.0592 D21708 139.3 0.0288 2322.9 14.923 2257.7 14.736 0.0315 11.559 2322.9 15.467 0.0323 D21708 1340 0.0288 2330.6 0.0686 17.637 2252.9 13.48 0.0315 11.559 2330.6 0.0695 17.658 0.0323 D21708 2760 2151.9 0.0726 10.278 2325.1 22.026 2252.6 13.242 2110.5 0.0752 10.627 2325.1 20.159 2400.5 0.0877 D22203 79 2152.5 0.001 8.87 2327.1 0.121 17.075 2254 13.147 0.01 2327.1 0.121 20.927 2391.1 0.0051 D22203 908 2145.9 0.0013 7.895 2344.5 0.0734 14.165 2258.6 2116 0.0016 7.542 2339.9 0.0784 2400.9 0.053 D22203 1604 2151.1 0.0044 11.083 2341.2 15.351 2122.3 0.0081 10.695 15.605 2396.8 0.0094 D22203 1604 0.0005 2327.2 0.159 16.8 2254.1 2113.8 0.002 2327.2 0.159 17.219 2392 0.0115 D22223 38 0.0005 2332.1 17.976 2255.5 2113.8 0.002 2332.1 0.119 19.256 2392 0.0115 D22223 975 2155 0.0597 8.616 2323.4 22.305 2251.8 16.388 2112.7 0.0664 2323.4 21.349 0.0282 D22223 1932 2157.2 0.0033 12.185 2323.8 0.0712 15.519 2251.8 15.259 2114.6 0.004 2323.8 0.0712 13.595 2391.9 0.0801 D2252 162 0.0101 2335.6 0.178 18.967 2127.4 0.001 8.423 2335.6 20.914 2392.7 0.0071 D2252 309 2146.2 0.177 13.103 2326.7 0.199 20.373 2259.3 13.805 2111.8 0.185 2326.7 0.199 21.927 0.0908 D2252 491 2146.2 0.177 13.103 2334.6 0.162 16.103 2260 14.689 2111.8 0.185 2334.6 0.165 16.172 0.0908 D2253 75 0.138 2326.3 0.259 21.221 2256.7 0.15 2326.3 0.259 22.56 2393.1 0.0806 D2253 252 2141.5 0.146 13.584 2324.1 0.164 14.438 2257.6 2112.2 0.153 11.465 2324.1 0.164 13.75 2395 0.134 D2253 495 2150.7 0.002 8.955 2335.1 20.913 2251.6 15.933 2116.5 0.0113 12.147 2335.1 21.548 0.093 D2253 495 2151.8 0.0068 8.279 2333.4 21.596 2138.3 0.0006 2333.4 0.28 21.963 2400.8 0.0083 D239 95 2143.3 0.0737 9.973 2325.2 0.263 22.234 2258.1 16.67 2110.8 0.0804 10.037 2325.2 0.263 22.368 2392.8 0.133 D239 217 2152.3 0.0077 13.701 2315.5 20.359 2258.2 0.0281 15.533 2116 0.0112 2322 19.211 2403.4 0.0452 D2435 182 2152.3 0.0077 13.701 2318.9 20.518 2254.4 15.483 2116 0.0112 2324.9 21.125 2403.4 0.0452 D2435 361 2158.4 0.0049 11.854 2325.9 0.0603 16.754 2251.6 12.459 2111.1 0.0075 9.936 2325.9 0.0603 18.615 0.0181 D2435 454 0.148 2329.4 19.129 2255.6 0.147 2116.3 0.155 13.145 2329.4 0.253 22.194 2391.2 0.0594 D27343 88 2156.8 0.0022 11.613 2324 14.436 2258.1 2120 0.0059 8.476 2324 15.297 0.0382 D27343 501.3 2147.6 0.0028 12.521 2345 0.177 2255.1 16.188 2115.2 0.0032 2337.6 2394.2 0.122 D27343 1181.7 2159 0.242 11.536 2343.6 12.428 2256.3 0.278 2114.5 0.249 14.991 0.196 D27943 314 2140.8 0.0895 12.736 0.262 14.831 2256.8 13.82 2112.2 0.0999 9.603 2336.6 15.692 2399.8 0.0418 D27943 314 2141.8 0 10.282 2344.3 0.101 15.289 2257.4 2111.4 0.0024 10.663 2334.1 17.068 2392.4 0.0055 D27943 933.8 2151.3 0.0042 10.421 2326.3 0.138 15.323 2116.2 0.0074 10.362 2326.3 0.138 14.599 2391.4 0.0655 D27943 1779.5 2144.4 0.126 11.214 2323 14.497 2254 0.193 14.221 2112.3 0.136 11.853 2323 0.0855 14.67 2393.4 0.111 D27943 2104.2 2141.6 0.0014 13.616 2333.8 0.132 18.093 2256 2129.2 0.0038 12.945 2333.8 0.135 19.879 2391.2 0.109 D27943 2607.6 2141.6 0.0014 13.616 2327.2 0.258 19.08 2255.5 14.107 2129.2 0.0038 12.945 2327.2 0.258 20.384 2391.2 0.109 D27943 3389.5 2152.2 0.0013 8.853 2332.3 20.095 2114.1 0.0054 2332.3 0.242 19.636 2390 0.0286 658 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w D16355 925.8 11.865 2255.3 0.152 18.161 2322.9 0.161 9.079 0.107 0.0321 D21708 139.3 7.484 2255.9 0.101 19.061 2328.5 0.0947 11.893 2368 0.0698 9.128 D21708 139.3 2257.8 0.0585 16.847 2327.4 0.0648 12.865 2372.7 0.0432 10.686 2356.6 18.979 D21708 1340 2257.8 0.0585 16.847 2327.4 0.0648 12.865 2372.7 0.0432 10.686 0.0495 15.107 D21708 2760 7.566 2252.6 0.107 18.976 2327.4 0.112 10.133 2367.1 0.0908 11.647 15.932 D22203 79 9.737 2256.8 0.0774 19.909 2327.7 0.0672 11.566 0.0383 11.892 D22203 908 8.07 2258.8 0.116 19.609 2327.5 0.137 11.001 0.0796 0.0466 D22203 1604 8.945 2262.2 0.0994 18.458 2327.2 0.146 10.845 2366.6 0.0487 8.277 2355.3 D22203 1604 10.92 2254.1 0.0669 20.095 0.106 2367 0.0145 8.818 16.165 D22223 38 10.92 2254.1 0.0669 20.095 0.106 2367 0.0145 8.818 0.017 D22223 975 2251.8 0.0659 17.802 2323.8 0.0633 7.517 2376.4 0.0377 14.634 D22223 1932 12.017 2251.8 0.148 20.527 2327.7 0.16 9.784 0.101 2358.7 0.04 D2252 162 14.317 0.0657 2326.7 0.191 13.085 0.0104 D2252 309 2258.9 0.184 17.555 2328.2 0.157 8.553 2366 0.125 12.581 D2252 491 2258.9 0.184 17.555 2328.2 0.157 8.553 2366 0.125 12.581 2357.6 0.13 D2253 75 9.696 2260.9 0.186 19.726 2327.4 0.149 5.448 2366.8 0.134 11.615 0.0442 D2253 252 12.116 2258.5 0.202 20.065 2329.6 0.204 9.984 2366.3 0.152 8.199 2355.9 D2253 495 2251.6 0.234 20.123 0.249 0.129 0.197 D2253 495 7.246 0.097 2325.2 0.257 13.881 0.0082 D239 95 9.791 2258.4 0.167 20.816 2316.8 0.238 10.186 2376.7 0.155 11.577 D239 217 12.587 2254.4 0.0899 21.778 2325.9 0.102 10.806 0.0619 D2435 182 12.587 2254.4 0.0899 21.778 2325.9 0.102 10.806 0.0619 2355.2 0.0069 11.596 D2435 361 2251.6 0.0405 15.98 2328.4 0.051 11.169 0.0192 D2435 454 8.911 2255.6 0.147 17.466 2324 0.116 8.841 2367.9 0.101 13.33 D27343 88 2258.6 0.205 20.033 2326.2 0.165 11.846 0.161 2359.4 0.11 18.391 D27343 501.3 13.626 2255.1 0.377 21.843 0.306 0.218 2355.8 16.878 D27343 1181.7 2256.3 0.278 19.585 2315.1 0.262 10.814 0.236 D27943 314 12.837 2256.8 0.124 18.165 2320.7 0.104 11.846 2369.7 0.0574 10.693 2356 17.078 D27943 314 11.245 0.0666 2326.3 0.126 10.215 0.0251 2356.8 0.0831 D27943 933.8 11.942 2260.7 0.105 18.306 2328.4 0.129 10.176 0.0983 12.094 D27943 1779.5 11.474 2254 0.193 21.133 2319.2 0.186 11.766 0.151 2357.6 0.0443 D27943 2104.2 12.083 2255.5 0.113 20.871 2328.7 0.269 12.819 0.127 2356.9 0.0584 11.412 D27943 2607.6 12.083 2255.5 0.113 20.871 2328.7 0.269 12.819 0.127 D27943 3389.5 11.421 2254.2 0.172 22.276 0.217 0.072 659 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Min- eral Chl Birefrin- gence Colour Manual Mineral ID 1 Manual Mineral ID 2 Manual Mineral ID 3 Manual Mineral ID 4 TSA_S Mineral1 TSA_S Mineral2 TSA_S Weight1 D33003 532 Black Unknown Blue amphibole Int-chlorite illite? Illite 1 D33003 1106 Black Ankerite Grey dolomite Fe-chlorite Dolomite 0.73 D33003 2004 Calcic and non-calcic Black Ankerite Grey calcite Ankerite Phlogopite2 1 D33003 3210 Ankerite Grey and Blue Int-chlorite carbonate clay? Ankerite 1 D39018 43 Biotite + carbonate Ankerite (Fe) carbonate Fe-phlogopite Fe-chlorite IntChlorite Phlogopite1 0.786 D39018 635 Black Grey muscovite gibbsite alunite pyrophyllite Illite D39018 1820 Unknown Black Calcite Blue carbonate Calcite Hornblende 1 D39018 2555 Unknown Black Unknown Blue Fe-chlorite low Ca- orthopyroxene carbonate dickite? FeChlorite 1 D39018 3050 Unknown Black Unknown Grey hornblende biotite Biotite 1 D39018 3113 Unknown Unknown Grey amphibole Actinolite 0.809 D39018 3562 Unknown Black Calcite Grey dolomite Int-chlorite dickite? IntChlorite Calcite 1 D39018 4848 Calcic and non-calcic Black Calcite Blue dolomite Int-chlorite amphibole Dolomite 0.0897 D39200 109 Unknown Black Unknown Grey biotite Dolomite 1 D39200 1469 Unknown Black Unknown Grey amphibole biotite Muscovite 0.534 D39200 3241 Unknown Black Unknown Grey and Brown amphibole calcite Hornblende Zoisite 1 D39204 19 Unknown Black Unknown Grey monzonite (Fe) carbonate Dolomite 1 D39204 1032 Unknown Black Unknown Grey dolomite chlorite tremolite Dolomite Epidote 0.679 D39204 1333 Unknown Black Unknown Grey carbonate amphibole hallyosite dickite? Dolomite Halloysite 0.53 D39357 37 Unknown Black Unknown Grey Fe-chlorite talc carbonate Dolomite Talc 1 D39357 1287 Unknown Black Unknown Blue Mg-chlorite rhodochrosite Gibbsite 1 D39357 1308 Unknown Black Ankerite Grey olivine hornblende Brucite Zoisite 0.561 D39357 2029 Black Unknown Grey Fe-chlorite muscovite IntChlorite Halloysite 1 D39357 2066 Unknown Black Unknown Grey amphibole zunyite? Hornblende 0.843 DS11 103.4 Unknown Black Grey amphibole Fe-chlorite Hornblende Epidote 0.702 DS139 30.4 Black Ankerite Grey carbonate Fe-chlorite amphibole IntChlorite Siderite 1 DS139 323.3 Black Ankerite Brown Fe-chlorite FeChlorite 1 DS172 123.1 Calcic Black Calcite Blue Fe-chlorite epidote FeChlorite 1 DS173 499.6 Unknown Black Calcite Brown Fe-chlorite amphibole FeChlorite 1 DS174 708.4 Unknown Black Unknown Blue Mg-chlorite carbonate Dark 1 DS177 460.5 Unknown Black Unknown Grey Fe-chlorite amphibole carbonate Riebeckite 1 DS177 613 Unknown Black Calcite Grey biotite muscovite Muscovite 1 660 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w D33003 532 66.394 1392.5 0.362 21.359 2253.3 0.172 14.577 2332.5 0.206 20.612 1870.8 0.0262 12.709 1953.3 0.038 13.528 D33003 1106 0.27 71.558 1392.5 0.362 21.359 2253.3 0.172 14.577 2332.5 0.206 20.612 1870.8 0.0262 12.709 1953.3 0.038 13.528 D33003 2004 1264.33 1408.6 0.358 16.679 2260.6 0.206 2344.3 0.178 12.584 0.284 13.304 1945.6 0.265 15.311 D33003 3210 111.2 1408.6 0.358 16.679 2260.6 0.206 2344.3 0.178 12.584 0.284 13.304 1945.6 0.265 15.311 D39018 43 0.214 26.796 1387.8 0.518 18.361 2250.5 0.285 14.079 2329.9 0.334 20.968 0.104 0.0769 D39018 635 10000 1389.4 0.211 19.292 2255 0.0887 10.993 2323.7 0.0822 20.536 0.11 9.566 1944.1 0.106 13.079 D39018 1820 23.733 1409.6 0.3 15.565 2259.4 0.1 13.247 2350.4 0.125 18.143 1857.3 0.162 1944.4 0.124 12.423 D39018 2555 132.88 1395.1 0.388 20.329 2253.6 0.264 12.34 2343 0.272 12.616 1856.6 0.315 1945.9 0.293 11.435 D39018 3050 196.47 1396.9 0.258 16.982 2250.8 0.134 13.839 2313.9 0.166 15.322 1892.4 0.124 14.641 1955.2 0.143 14.689 D39018 3113 0.191 89.64 1399.9 0.363 21.118 2261.1 0.172 13.924 2334.6 0.232 20.232 1866.8 0.0721 13.321 1958.8 0.0455 8.351 D39018 3562 433.33 0.262 21.392 2260.2 0.0816 2320.3 0.109 21.343 1871.1 0.0686 10.567 1945.3 0.061 12.755 D39018 4848 8.503 486.86 1395.6 0.236 17.681 2263.6 0.0974 12.643 2319.8 0.119 19.761 1862 0.0433 9.787 1952.3 0.0494 12.438 D39200 109 3846.62 1381.7 0.257 21.504 2252 0.111 11.153 2341 0.105 15.339 1868.8 0.151 12.314 1942.1 0.131 12.468 D39200 1469 0.466 371.24 1399.9 0.368 17.095 2260.3 0.11 2314.2 0.166 1871.2 0.0056 10.622 1953.6 0.0019 13.207 D39200 3241 425.64 1397.2 0.175 18.521 2259.1 0.102 9.181 2324.6 0.106 1890.5 0.0228 12.207 1958.7 0.0439 10.91 D39204 19 294.89 1382.4 0.241 2260 0.0546 2327.4 0.084 20.366 0.0538 12.214 1950.5 0.0391 14.055 D39204 1032 0.321 336.24 1406.6 0.326 20.974 2262.4 0.0562 11.827 2328.1 0.116 20.392 1871.9 0.0047 8.462 1948.4 0.0157 6.991 D39204 1333 0.47 133.14 1392.3 0.325 14.897 0.0858 11.912 2312.7 0.105 1869.5 0.0433 13.566 1947.2 0.0318 12.56 D39357 37 1444.17 1405.5 0.297 18.888 2254.2 0.103 11.082 2349.9 0.0882 14.728 1861.7 0.184 9.437 1944 0.164 11.679 D39357 1287 696.91 1400.5 0.156 14.555 2258.5 0.0777 10.499 2314.8 0.0973 16.014 1866.9 0.0011 9.194 1958.5 0.0094 12.721 D39357 1308 0.439 172.46 1411.5 0.16 19.456 2256.5 0.0623 13.449 2332.4 0.0752 19.222 0.0122 11.204 1947.5 0.0309 9.163 D39357 2029 418.01 1396.9 0.176 17.735 2262.2 0.0208 9.419 2313.8 0.0593 0.0423 1945.6 0.0287 7.999 D39357 2066 0.157 95.541 1393.9 0.484 17.591 2251.5 0.179 14.27 2328 0.37 21.257 0.175 0.154 DS11 103.4 0.298 39.742 1395.2 0.317 19.644 2255.4 0.156 14.798 2318.3 0.179 19.602 1871.3 0.0793 12.44 1956.6 0.0707 12.69 DS139 30.4 193.41 1409.7 0.318 17.055 2255.1 0.169 13.315 2347.7 0.16 15.784 0.228 11.847 1940.1 0.209 7.048 DS139 323.3 25.338 1404.6 0.321 17.31 2259.3 0.157 2344.8 0.184 20.454 1856.9 0.112 11.024 1959 0.0876 9.846 DS172 123.1 75.22 1407.8 0.272 14.038 2258.2 0.105 12.221 2351 0.119 16.56 0.069 12.048 1950.6 0.0554 10.353 DS173 499.6 75.22 1407.8 0.272 14.038 2258.2 0.105 12.221 2351 0.119 16.56 0.069 12.048 1950.6 0.0554 10.353 DS174 708.4 1464.08 0.325 19.521 2259.6 0.139 12.319 2352 0.131 13.435 0.219 12.303 1953.7 0.195 12.714 DS177 460.5 437.84 1408.4 0.357 18.171 2252.6 0.0511 7.903 2347.8 0.0812 18.614 1857.1 0.164 10.185 0.119 DS177 613 63.451 1409.6 0.308 15.609 2259 0.0916 10.534 2343.1 0.0895 15.534 1871.5 0.172 12.132 1941.6 0.137 8.093 661 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d D33003 532 2141.6 0.0028 10.378 0.17 16.592 2253.3 16.46 2117.7 0.0073 11.169 2337.4 14.849 2390.7 0.0302 D33003 1106 2141.6 0.0028 10.378 2332.5 0.227 17.206 2117.7 0.0073 11.169 2332.5 0.233 18.317 2390.7 0.0302 D33003 2004 2148 0.195 12.36 2327.7 0.148 19.069 2254.7 0.139 0.202 8.895 2327.7 0.148 19.422 2395.4 0.125 D33003 3210 2148 0.195 12.36 2318.1 19.061 10.73 0.202 8.895 2334.6 17.371 2395.4 0.125 D39018 43 2155.6 0.0016 9.196 2329.9 21.918 2250.5 17.654 0.0088 10.624 2329.9 0.355 20.465 2390.8 0.156 D39018 635 2150.7 0.0754 11.468 2346 2116.1 0.076 7.215 2401.4 0.076 D39018 1820 2154.7 0.0007 11.02 2334.1 0.243 19.398 0.0139 10.581 2334.1 0.246 11.159 2390.1 0.0264 D39018 2555 2157.9 0.237 11.67 2345.2 0.0891 15.658 2258.6 0.244 12.618 2334.8 0.0977 9.663 2403.9 0.239 D39018 3050 2141.7 0.117 9.001 2346.9 0.171 20.995 2251.1 0.168 2113.8 0.129 9.71 2338.8 0.171 12.687 2391.9 0.114 D39018 3113 2157.5 0.0076 11.923 2320.4 20.485 2251.3 2116.2 0.0049 11.408 2320.2 11.628 0.127 D39018 3562 0.0534 2334.6 0.241 20.665 2257.8 2114.2 0.054 2334.6 9.705 0.0547 D39018 4848 0.0457 14.893 0.0909 2325.2 15.935 0.121 2258.2 0.0444 2325.2 0.0529 D39200 109 2142.6 0.0931 12.463 2310.6 0.104 18.793 2252.6 0.0726 2114.4 0.0964 11.615 2323.9 0.103 11.7 2391 0.0812 D39200 1469 0.0576 2345.5 0.0974 14.837 2220.4 0.107 10.812 2136.7 0.0479 6.676 2333.7 0.0983 11.903 0.103 D39200 3241 2159.6 0.07 9.217 2314.2 19.946 2132.1 0.0682 12.103 2322 13.078 2399.7 0.0812 D39204 19 2159.2 0.0017 9.169 2327 0.162 15.484 2121.6 0.0054 11.02 2327 0.162 14.204 2391.7 0.0185 D39204 1032 0.0097 2327.4 0.0972 17.581 2134.9 0.0006 2327.4 0.0972 13.277 2393.9 0.0219 D39204 1333 2141.7 0.0057 10.019 2328.1 0.13 18.697 2255.6 0.0495 2135.2 0.0143 2328.1 0.13 9.701 2394.1 0.0908 D39357 37 2158.4 0.0818 11.187 2313.1 17.814 2110.5 0.0941 11.326 2395.9 0.0477 D39357 1287 2160 0.0423 11.635 2332.7 0.1 14.318 2254.2 0.101 10.868 0.0333 2332.7 0.102 8.819 2390.5 0.0639 D39357 1308 0.0171 2307 0.148 19.97 2249.8 0.102 0.0026 11.403 2331 0.148 11.09 0.0177 D39357 2029 2146.4 0.0035 10.033 2332.4 20.927 2256.5 0.0061 7.815 2332.4 0.0799 14.003 2390.9 0.0409 D39357 2066 0.0118 19.029 0.129 8.74 2116.9 0.0549 13.245 2321.2 0.142 9.465 2391.3 0.208 DS11 103.4 2153.1 0.0028 8.428 2328 0.398 18.2 2255.4 2132.9 0.0042 8.831 2328 0.398 20.68 2393.2 0.0229 DS139 30.4 0.13 2318.3 0.192 20.984 2255.1 0.169 2111.7 0.14 9.832 0.192 21.731 2390.7 0.0903 DS139 323.3 2152 0.0027 10.851 2344.1 0.147 10.97 2124.7 0.0069 12.456 2339.7 13.355 2390.4 0.0641 DS172 123.1 2143 0.0003 9.729 2344.5 17.272 2258.4 13.197 2117.7 0.0051 8.866 2338.5 17.436 2402.1 0.0791 DS173 499.6 2143 0.0003 9.729 2334.2 12.654 2258.4 13.197 2117.7 0.0051 8.866 2334.2 14.807 2402.1 0.0791 DS174 708.4 0.14 2319.4 0.181 13.542 2259.4 0.146 13.31 0.144 8.802 2320.4 0.185 16.078 0.112 DS177 460.5 2158.1 0.0134 6.632 2340.9 0.13 18.24 0.0589 2115.7 0.0271 10.876 0.13 18.25 2391.7 0.0259 DS177 613 0.0269 15.545 2259.5 2113.2 0.0378 2337.2 2396.2 0.0084 662 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w D33003 532 8.908 2253.3 0.172 21.006 2327.3 0.209 11.825 2367.9 0.044 7.025 2359.7 0.169 D33003 1106 8.908 2253.3 0.172 21.006 2327.3 0.209 11.825 2367.9 0.044 7.025 D33003 2004 11.117 2260.6 0.206 16.981 2317 0.183 9.651 0.155 D33003 3210 11.117 2260.6 0.206 16.981 2317 0.183 9.651 0.155 2356.4 15.286 D39018 43 11.463 2250.5 0.285 20.283 0.32 0.182 0.184 D39018 635 11.009 2255 0.0887 15.929 2323.7 0.0836 11.374 2366.9 0.0747 12.182 D39018 1820 8.775 2259.4 0.1 19.873 2327 0.0932 12.761 2366.7 0.0892 10.9 D39018 2555 12.52 2253.6 0.264 18.678 0.255 2368.3 0.254 10.16 2359.8 D39018 3050 12.38 2250.8 0.134 19.477 2313.9 0.239 16.349 2382.6 0.105 6.649 2357.6 0.161 13.992 D39018 3113 2261.1 0.172 21.467 2323.9 0.234 13.391 0.157 2387.4 11.896 D39018 3562 2260.2 0.0816 13.296 2320.3 0.119 8.837 2375.2 0.0798 12.427 2357.2 0.166 12.422 D39018 4848 2263.6 0.0974 18.884 2319.8 0.13 12.303 2366.8 0.0642 9.874 0.084 D39200 109 8.69 2252 0.111 17.858 2323.9 0.0991 10.773 2379.2 0.0891 9.081 2358.6 14.242 D39200 1469 2260.3 0.11 20.415 2314.2 0.208 13.845 0.094 2360 D39200 3241 10.86 2259.1 0.102 12.894 2324.6 0.119 11.526 2367.8 0.0811 8.547 0.101 D39204 19 11.629 2260 0.0546 20.132 2327.4 0.0922 12.265 0.0223 2363.3 0.101 16.822 D39204 1032 8.911 2262.4 0.0562 17.015 2328.2 0.121 11.371 2367 0.019 9.875 2357.9 0.0224 D39204 1333 11.467 0.0858 2312.7 0.238 13.189 2384.9 0.0755 9.669 2357 D39357 37 12.168 2254.2 0.103 18.617 2327.5 0.0937 13.181 0.0758 2385.6 13.414 D39357 1287 10.491 2258.5 0.0777 15.285 2314.8 0.117 12.285 2381.7 0.067 12.036 0.078 D39357 1308 2256.5 0.0623 18.908 2327.8 0.0679 11.593 2367 0.0442 8.477 2359.6 0.104 D39357 2029 9.022 2262.2 0.0208 12.483 2313.8 0.0715 14.082 2384.8 0.0243 6.891 0.0529 D39357 2066 10.665 2251.5 0.179 20.341 2328 0.39 13.479 0.216 2387.1 15.82 DS11 103.4 11.502 2255.4 0.156 21.746 2318.3 0.196 13.86 2367.1 0.065 10.108 13.776 DS139 30.4 8.714 2255.1 0.169 19.476 2310.5 0.143 12.306 2366.6 0.13 12.385 DS139 323.3 9.803 2259.3 0.157 21.748 0.158 2367.9 0.141 12.109 2358 0.14 15.899 DS172 123.1 7.731 2258.2 0.105 19.169 2318.2 0.114 13.51 2366.5 0.0831 8.457 2356.8 DS173 499.6 7.731 2258.2 0.105 19.169 2318.2 0.114 13.51 2366.5 0.0831 8.457 DS174 708.4 2259.6 0.139 16.553 2325.1 0.124 13.602 2365.8 0.119 11.664 2356.6 0.164 13.634 DS177 460.5 10.454 2252.6 0.0511 20.496 0.0435 0.055 2390 0.122 DS177 613 10.003 2259 0.0916 17.119 2315.8 0.0872 12.12 2367.7 0.0734 10.365 2359.4 0.055 663 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefringence Colour Manual Mineral ID 1 Manual Min- eral ID 2 Manual Mineral ID 3 Manual Mineral ID 4 TSA_S Mineral1 TSA_S Mineral2 TSA_S Weight1 DS177 1500.8 Unknown Black Calcite Blue Int-Mg chlorite clay? IntChlorite 1 DS177 1500.8 Unknown Black Calcite Brown Fe-chlorite Epidote 1 DS180 400.2 Unknown Black Unknown Grey biotite Fe-chlorite Hornblende 1 DS340 35.6 Black Unknown Grey Mg-chlorite carbonate IntChlorite 0.846 DS340 35.6 Black Unknown Grey Mg-chlorite FeChlorite Brucite 0.539 DS340 297.3 Black Unknown Grey Fe-chlorite carbonate clay? Siderite Diaspore 0.632 DS340 694.7 Black Unknown Grey dolomite Fe-chlorite Dolomite IntChlorite 0.842 DS343 90 Unknown Black Unknown Grey Int-Fe-chlorite pyrophyllite smectite talc IntChlorite Talc 1 DS343 90 Unknown Black Unknown Grey Int-Fe-chlorite apatite brucite MgChlorite 0.667 DS343 395 Black Unknown Grey chlorite carbonate atacamite? MgChlorite Illite 1 DS343 696 Unknown Black Unknown Grey (Fe) carbonate chlorite Ankerite 0.599 DS352 25 Black Brown Fe-chlorite carbonate illite/smectite FeChlorite Dolomite 0.752 DS352 341 Unknown Black Ankerite Grey and Brown Mg-chlorite IntChlorite Opal 0.774 DS352 512 Unknown Grey Fe-chlorite dolomite Ankerite Muscovite 0.695 DS352 512 Unknown Grey (Fe) carbonate Fe-chlorite sepiolite IntChlorite Muscovite 0.735 DS358 132 Ankerite Brown Fe-chlorite dickite? FeChlorite 0.71 DS358 132 Ankerite Brown Fe-chlorite carbonate illite? Dolomite Epidote 0.727 DS358 624 Black Unknown Blue chlorite (Fe) carbonate diaspore? clay? FeChlorite Dolomite 1 DS358 1215 Unknown Black Ankerite Blue (Fe) carbonate brucite Ankerite 0.805 DS360 124 Black Ankerite Grey carbonate Fe-chlorite hallyosite IntChlorite Muscovite 1 DS360 124 Black Unknown Brown calcite Fe-chlorite illite FeChlorite 1 DS360 528 Ankerite dolomite dickite? Dolomite 0.845 DS360 751 Black Unknown Blue carbonate muscovite FeChlorite Illite 0.766 DS360 751 Black Unknown Brown biotite muscovite carbonate chlorite IntChlorite Illite 1 DS615 1214.5 Unknown Black Unknown Grey Fe-chlorite amphibole Biotite DS615 3001.1 Unknown Black Unknown Blue calcite phlogopite alunite Riebeckite 1 DS615 4032.2 Unknown Black Calcite Blue carbonate epidote Fe-chlorite FeChlorite 1 GC01018 85.3 Calcic Black Calcite Blue Fe-chlorite biotite amphibole IntChlorite 1 GC01018 691.7 Unknown Black Unknown Blue biotite chlorite lithiophilite Biotite 1 GC01018 1382.7 Unknown Black Unknown Brown Int-chlorite tremolite FeChlorite 1 GC04002 239 Black Unknown gibbsite kaolinite? Riebeckite 1 GC04002 688 Black Calcite Grey Int-Fe-chlorite calcite FeChlorite 1 GC04002 1522 Black Mg-chlorite silica dickite? FeChlorite 0.566 GC04003 338 Ankerite Grey talc Talc MgChlorite 0.605 664 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w DS177 1500.8 2861.04 1411.7 0.308 14.048 2259.1 0.0838 12.612 2339.8 0.124 16.18 1856.1 0.155 1941.3 0.116 11.387 DS177 1500.8 700.37 1394.9 0.317 19.9 2251.9 0.0807 14.293 2316.9 0.0901 17.315 0.18 11.444 0.152 DS180 400.2 69.029 1405.5 0.316 16.743 2253.9 0.12 13.635 2335.3 0.126 15.997 1860.9 0.142 11.843 1943.7 0.122 11.75 DS340 35.6 0.154 86.165 1405.5 0.353 17.899 2255.7 0.217 13.862 2346.1 0.224 13.852 1865.8 0.212 10.875 1944.9 0.2 12.425 DS340 35.6 0.461 53.435 1407.7 0.116 16.446 2240 0.276 6.941 2316.5 0.251 19.236 1894.8 0.274 1953.2 0.308 11.41 DS340 297.3 0.368 48.955 0.265 22.437 0.121 2325.1 0.182 1865.6 0.0171 11.868 0.0251 DS340 694.7 0.158 74.757 1393 0.321 18.049 2254.7 0.11 15.01 2312.6 0.132 16.045 0.0907 1945.8 0.0738 14.688 DS343 90 161.45 1392.7 0.334 17.677 2254.2 0.143 13.502 2314.4 0.178 1871.7 0.0927 10.89 1953.4 0.0738 10.362 DS343 90 0.333 178.1 1403.7 0.119 17.807 2257.4 0.0995 15.24 2327.8 0.12 22.056 0.0794 11.051 1946.1 0.0845 12.07 DS343 395 297.76 1403.7 0.119 17.807 2257.4 0.0995 15.24 2327.8 0.12 22.056 0.0794 11.051 1946.1 0.0845 12.07 DS343 696 0.401 67.361 1408.3 0.404 13.256 2261.5 0.145 2334 0.255 22.596 1871.1 0.0131 10.804 1959.2 0.0348 12.195 DS352 25 0.248 57.025 1408.9 0.291 14.524 2258.4 0.107 12.947 2334.6 0.11 17.002 0.166 13.249 1947.6 0.143 12.809 DS352 341 0.226 44.712 1408.9 0.297 13.562 2257.5 0.116 12.409 2339.7 0.123 14.74 1857.7 0.174 0.151 DS352 512 0.305 52.664 1408.5 0.22 17.417 2256.5 0.123 13.452 2336 0.16 18.996 1876.6 0.0159 11.684 1959.5 0.0314 13.435 DS352 512 0.265 135.32 1408.4 0.319 16.101 2262 0.118 12.547 2337.6 0.145 13.661 1857.2 0.125 12.383 1948 0.108 12.095 DS358 132 0.29 355.7 1407.9 0.309 16.158 2256.1 0.0919 12.201 2332.1 0.109 17.942 0.1 10.487 1953.9 0.0821 14.308 DS358 132 0.273 33.106 1409 0.411 13.65 2261.7 0.196 2327.5 0.256 21.689 1878.3 0.0263 16.827 1957.9 0.0522 11.821 DS358 624 67.072 0.586 0.119 2326.5 0.306 21.141 1868.9 0.04 13.32 1959.9 0.0294 12.946 DS358 1215 0.195 54.948 1409.5 0.332 14.457 2258.2 0.258 13.415 2340.9 0.3 18.613 1883.9 0.0356 13.885 1957.3 0.0621 12.424 DS360 124 43.883 1409.5 0.323 14.432 2257.9 0.259 13.344 2341.4 0.296 18.694 1892.3 0.0345 14.586 0.0594 DS360 124 176.56 0.449 0.0824 2324.7 0.195 19.38 1860.4 0.04 12.325 1953.1 0.0343 11.607 DS360 528 0.155 43.813 1409.2 0.275 14.012 2258 0.141 13.214 2342.6 0.191 20.447 1872.5 0.0706 11.437 1953 0.0653 9.702 DS360 751 0.234 80.753 1409.2 0.279 13.994 2257.9 0.143 13.105 2344.2 0.184 18.638 1871.7 0.0715 11.389 1953.2 0.0647 12.936 DS360 751 979.74 1392.7 0.244 20.452 2258.9 0.157 2358.6 0.156 20.677 0.186 12.159 1947.1 0.169 8.997 DS615 1214.5 10000 1394.9 0.233 18.294 2259.1 0.0926 11.792 2346.1 0.112 15.543 1855.5 0.141 11.445 1950.8 0.126 14.204 DS615 3001.1 58.694 1409.9 0.2 16.124 2254.1 0.0955 13.288 2352 0.117 16.41 1891.7 0.0517 12.693 1957.8 0.0702 10.109 DS615 4032.2 263.85 1414.5 0.246 8.521 2261.4 0.0476 12.638 2315 0.117 18.851 1857.3 0.119 11.137 0.0915 GC01018 85.3 163.06 0.194 18.864 2256.1 0.0245 12.171 2353.7 0.0617 16.038 1860.1 0.0619 10.292 1944.6 0.0486 12.205 GC01018 691.7 439.26 1400.6 0.183 17.985 2257.9 0.0549 11.127 2355.3 0.0746 0.0723 12.72 1951.2 0.0649 9.667 GC01018 1382.7 439.26 1400.6 0.183 17.985 2257.9 0.0549 11.127 2355.3 0.0746 0.0723 12.72 1951.2 0.0649 9.667 GC04002 239 4731.39 1383.4 0.256 17.633 2246.4 0.138 7.138 2314.1 0.118 17.493 1864.3 0.192 1951.6 0.186 12.285 GC04002 688 112.38 1405.8 0.259 18.811 2255.4 0.101 14.178 2345 0.0972 15.744 0.0998 10.49 1941.1 0.0918 12.248 GC04002 1522 0.434 119.09 1391.7 0.153 11.51 0.0531 7.694 2313.1 0.0724 1868.9 0.0704 12.501 1949.2 0.0643 14.395 GC04003 338 0.395 108.96 1391.7 0.153 11.51 0.0531 7.694 2313.1 0.0724 1868.9 0.0704 12.501 1949.2 0.0643 14.395 665 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d DS177 1500.8 2147.6 0.0202 10.075 2339.8 0.118 15.122 2118.3 0.0233 9.579 2339.7 0.118 16.683 2394.6 0.0528 DS177 1500.8 2142.4 0.0626 10.204 2340.8 16.039 2251.9 14.527 2118.9 0.0792 11.102 0.176 16.016 2390.3 0.0438 DS180 400.2 2159.4 0.0209 9.636 2316.9 0.106 15.7 2253.9 13.429 0.0251 2325 0.106 14.398 2392.1 0.0204 DS340 35.6 0.119 2335.3 14.678 2255.7 2111.1 0.122 11.276 2335.3 16.07 2395.1 0.13 DS340 35.6 2147.9 0.282 10.138 0.221 15.451 0.283 13.385 0.287 8.929 2337.2 0.227 17.887 2395.8 0.205 DS340 297.3 2140.4 0.0017 9.438 2316.5 0.267 17.94 0.0014 8.506 2321.7 17.974 2397 0.0015 DS340 694.7 2140.9 0.0012 8.317 2325.1 22.405 2254.7 2118.1 0.0092 9.698 2325.1 22.162 2392.4 0.0511 DS343 90 2151 0.0065 11.465 2312.6 0.16 2254.2 16.872 2112.1 0.0117 0.16 16.782 2394.4 0.0974 DS343 90 0.057 2314.4 17.442 2257.4 0.0995 16.05 2111.5 0.0606 9.972 14.867 0.0755 DS343 395 0.057 2327.8 0.12 21.064 0.0443 2111.5 0.0606 9.972 2327.8 0.12 18.542 0.0755 DS343 696 2146.4 0.0036 9.272 2324.1 16.015 0 6.467 2324.1 18.301 2403.1 0.0056 DS352 25 2142.9 0.0457 9.091 2334 20.009 2258.5 0.0519 2334 0.263 18.101 0.0163 DS352 341 2144.6 0.057 10.225 2334.6 0.108 15.802 2257.5 2112.4 0.0628 12.649 2334.6 0.113 15.957 2392.2 0.0288 DS352 512 0.0058 2340.9 20.299 2256.5 0.005 11.543 2334.5 22.003 2404.2 0 DS352 512 2154.8 0.0507 11.321 2336 0.158 17.166 2255 2126 0.0585 11.391 2336 16.937 0.0743 DS358 132 0.0186 2332.1 14.724 2258.1 2117.3 0.0229 10.262 2332.1 0.12 16.046 0.0316 DS358 132 2145.8 0.0048 11.801 2325.8 18.943 0.0008 8.499 2325.8 16.351 0.0119 DS358 624 2147 0.0064 13.171 2327.5 0.268 19.796 0.0016 2327.5 0.268 22.705 2409.6 0.0004 DS358 1215 2146.7 0.0053 10.026 2326.5 0.336 18.69 0.0017 4.878 2326.5 0.336 21.37 0.0353 DS360 124 2146.5 0.0036 13.073 2342.5 0.29 2258.4 2125.8 0.0019 7.603 2337.7 10.684 0.0382 DS360 124 2142.2 0.0043 8.598 2342 14.845 2137 0.0006 2408.5 0.0048 DS360 528 0.0077 2324.7 0.239 22.094 2257.8 2113.2 0.0008 7.443 2324.7 0.239 21.932 2391.1 0.0129 DS360 751 0.0077 2340.5 12.751 2257 2138 0.0005 6.877 14.181 2391.5 0.0323 DS360 751 2150.2 0.128 7.964 2340.8 13.169 13.456 0.133 12.018 14.083 2399.2 0.151 DS615 1214.5 2154.8 0.0822 12.361 2332.9 17.139 2260 0.0931 0.087 2332.9 0.158 18.814 2400.5 0.117 DS615 3001.1 2158.1 0.002 11.09 2325.6 0.185 18.944 2254.1 2135.8 0.0043 2325.6 0.185 18.678 0.0476 DS615 4032.2 2143.7 0.0188 10.204 2340.2 0.11 13.771 2259 2110.8 0.0243 2338.1 13.661 2400.3 0.0509 GC01018 85.3 2153 0.0015 8.81 2315 14.578 2256.1 0.0245 2111.3 0.0025 8.773 2337.8 0.115 2399 0.0485 GC01018 691.7 2141.5 0.0133 10.108 2343 0.0921 2257.9 0.0221 11.992 2338 14.481 2407.9 0.046 GC01018 1382.7 2141.5 0.0133 10.108 2343.7 11.938 2257.9 0.0221 11.992 2337.3 0.0714 12.112 2407.9 0.046 GC04002 239 2150.6 0.147 9.853 2325.9 0.0841 17.113 0.144 0.146 9.594 2325.9 0.0841 15.904 2405.9 0.113 GC04002 688 2144.5 0.0029 14.635 2335.3 16.301 2255.4 0.0063 2335.3 18.739 0.0251 GC04002 1522 2141.9 0.03 9.957 0.0372 2114.2 0.0353 2391.5 0.0786 GC04003 338 2141.9 0.03 9.957 2313.1 15.183 2259.8 0.0539 2114.2 0.0353 2391.5 0.0786 666 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w DS177 1500.8 9.641 2259.1 0.0838 18.604 2316.7 0.12 11.131 0.0832 DS177 1500.8 7.574 2251.9 0.0807 19.063 2316.9 0.103 9.356 2377.5 0.0575 13.357 2358.6 0.131 DS180 400.2 8.61 2253.9 0.12 19.45 2322.2 0.124 12.961 0.0715 0.06 16.152 DS340 35.6 11.254 2255.7 0.217 19.662 2327.9 0.219 12.277 2366.9 0.167 9.978 DS340 35.6 13.24 2240 0.276 10.774 2316.5 0.267 10.603 2366.3 0.211 10.004 0.181 DS340 297.3 10.324 0.121 2325.1 0.227 12.041 0.0059 0.212 DS340 694.7 12.684 2254.7 0.11 21.482 2312.6 0.171 12.115 0.0746 DS343 90 12.275 2254.2 0.143 21.685 2314.4 0.228 13.095 0.11 2356.5 0.0746 DS343 90 2257.4 0.0995 19.971 2327.8 0.109 12.577 0.0797 2357.4 0.111 DS343 395 2257.4 0.0995 19.971 2327.8 0.109 12.577 0.0797 0.0814 11.035 DS343 696 10.118 2261.5 0.145 19.467 2328.7 0.246 11.927 0.0398 0.0209 DS352 25 2258.4 0.107 19.052 2327.2 0.0995 8.596 0.0498 DS352 341 11.144 2257.5 0.116 19.31 2327.9 0.11 12.687 0.0526 0.0633 DS352 512 14.196 2256.5 0.123 18.69 2327.9 0.145 10.561 0.0542 0.0807 DS352 512 2262 0.118 20.236 2327.9 0.132 10.86 0.0835 14.858 DS358 132 2256.1 0.0919 17.626 0.097 0.0625 16.037 DS358 132 2261.7 0.196 19.614 2327.5 0.262 13.562 0.0657 0.0387 DS358 624 7.154 0.119 2326.5 0.326 13.483 0.0214 DS358 1215 2258.2 0.258 20.054 0.247 0.134 DS360 124 2257.9 0.259 20.026 2327.1 0.247 10.08 0.144 DS360 124 11.138 0.0824 2324.7 0.235 14.201 0.0062 DS360 528 8.069 2258 0.141 19.756 0.14 0.087 DS360 751 12.915 2257.9 0.143 19.62 2327.8 0.146 10.311 0.0883 2357.7 DS360 751 14.071 2258.9 0.157 18.866 2324.6 0.14 10.419 2376 0.162 8.838 DS615 1214.5 11.412 2259.1 0.0926 16.475 2315.4 0.11 13.826 2366.6 0.108 10.739 2376 0.164 13.13 DS615 3001.1 2254.1 0.0955 19.65 2328.4 0.104 9.152 2367.4 0.0922 12.913 2365 0.154 13.68 DS615 4032.2 13.553 2261.4 0.0476 17.728 2315 0.116 10.481 2366.3 0.0607 8.335 2360.5 0.0997 15.848 GC01018 85.3 10.429 2256.1 0.0245 18.755 0.0493 0.0573 2357.6 GC01018 691.7 11.472 2257.9 0.0549 17.651 2319 0.07 13.588 2369.2 0.0747 12.182 2360.5 0.101 15.52 GC01018 1382.7 11.472 2257.9 0.0549 17.651 2319 0.07 13.588 2369.2 0.0747 12.182 GC04002 239 9.29 2246.4 0.138 15.21 2314.1 0.124 10.855 2379.3 0.102 9.316 2365.1 0.0641 13.832 GC04002 688 2255.4 0.101 20.205 2326.7 0.0838 10.077 2367.6 0.0586 9.025 GC04002 1522 10.931 0.0531 2313.1 0.161 12.661 0.0745 GC04003 338 10.931 0.0531 2313.1 0.161 12.661 0.0745 2391.3 667 Table D.1 (Continued) Sample Depth (ft) Amp Type Bio type Carb Mineral Chl Birefrin- gence Colour Manual Mineral ID 1 Manual Mineral ID 2 Manual Mineral ID 3 Manual Min- eral ID 4 TSA_S Min- eral1 TSA_S Mineral2 TSA_S Weight1 GC04003 786.75 Ankerite Grey dolomite gibbsite Dolomite 0.637 GC04003 1716 Calcite Blue calcite FeTourmaline Calcite 0.746 GC04007 911 Unknown Blue (Fe) car- bonate Fe-chlorite muscovite IntChlorite Muscovite 0.808 GC04007 911 Unknown Blue Fe-chlorite muscovite FeChlorite Illite 1 GC04007 2000 Unknown Black Blue (Fe) car-bonate Fe-chlorite FeChlorite 1 GC04007 2859 Unknown Grey Fe-chlorite (Fe) car- bonate paragosite IntChlorite 1 GC04007 3890 Unknown Black Ankerite Blue Int-chlorite gibbsite alunite clay? FeChlorite Brucite 0.663 GC04007 4421 Unknown Brown Ankerite Grey chlorite muscovite calcite Dolomite Illite 0.795 GC04007 134ES Unknown Black Unknown Late Blue chlorite illite? FeChlorite 1 GC95010 350 Black Unknown Blue muscovite Fe-chlorite FeChlorite Illite 0.722 GC95010 939 Black Unknown Grey Fe-chlorite muscovite IntChlorite Illite 0.633 R87105 699.8 Unknown Black Calcite Grey Fe-chlorite amphibole carbonate Hornblende IntChlorite 0.573 R87107 482.3 Unknown Black Calcite Grey amphibole lizardite Hornblende Ankerite 1 R87108 629.5 Unknown Black Calcite Grey and Brown Mg-chlorite amphibole dickite? talc? IntChlorite Hornblende 1 RL437461B Unknown Brown Ankerite Grey biotite Mg-chlorite Siderite Phlogopite1 1 668 Table D.1 (Continued) Sample Depth (ft) TSA_S Weight2 TSA_S Error CHL 1400 wlm CHL 1400 d CHL 1400 w CHL 2250 wlm CHL 2250 d CHL 2250 w CHL 2340 wlm CHL 2340 d CHL 2340 w CARB 1870 wlm CARB 1870 d CARB 1870 w CARB 1950 wlm CARB 1950 d CARB 1950 w GC04003 786.75 0.363 97.042 1410.2 0.119 12.472 2263.5 0.0374 11.989 2339.4 0.179 19.513 1876.6 0.0576 12.058 1943.2 0.0532 11.529 GC04003 1716 0.254 120.16 1410.2 0.119 12.472 2263.5 0.0374 11.989 2339.4 0.179 19.513 1876.6 0.0576 12.058 1943.2 0.0532 11.529 GC04007 911 0.192 34.116 1409.5 0.393 16.738 2256.3 0.136 12.778 2349.1 0.167 19.195 1856.5 0.168 12.922 1946.8 0.124 13.582 GC04007 911 16.646 1412.5 0.374 14.261 2260.1 0.213 12.185 2352.1 0.201 14.762 1876.4 0.143 9.238 1952.5 0.113 13.491 GC04007 2000 60.184 1403.8 0.296 19.09 2256.3 0.14 14.919 2344.9 0.171 20.704 1873.3 0.128 9.862 1942.1 0.108 14.395 GC04007 2859 320.8 1380.4 0.232 2260.5 0.0497 2336.6 0.0633 15.457 1870.4 0.0584 12.128 1951.6 0.0423 13.186 GC04007 3890 0.337 131.25 1400.4 0.0986 19.766 2252.3 0.132 12.827 2327.2 0.144 17.705 1874 0.087 13.099 1942.7 0.0968 9.703 GC04007 4421 0.205 112.06 1410.3 0.0443 15.175 2257.9 0.174 12.194 2343.2 0.154 11.505 0.164 15.482 1957.4 0.179 13.016 GC04007 134ES 709.97 1382.1 0.27 18.11 2263.7 0.158 12.801 2327.9 0.142 18.268 1873.5 0.191 10.397 1941.4 0.176 10.2 GC95010 350 0.278 133.46 1409 0.134 15.244 2254.7 0.0583 14.697 2349.2 0.0671 18.217 1872.9 0.0335 10.136 1953.7 0.0281 11.397 GC95010 939 0.367 85.173 1393.3 0.399 19.61 2255.7 0.0825 14.082 2325.7 0.283 1856.6 0.0781 14.134 1940.1 0.0365 8.866 R87105 699.8 0.427 270.87 1399.4 0.255 18.371 2260.9 0.0369 13.109 2325.5 0.112 17.76 0.0284 10.349 1941.4 0.0266 8.872 R87107 482.3 632.32 1400.2 0.294 20.541 2252.9 0.0691 10.961 0.0927 19.026 1859.5 0.128 10.859 1947.2 0.107 14.253 R87108 629.5 119.9 1399.9 0.374 21.213 2250.5 0.21 13.226 2325.6 0.236 15.199 1865.8 0.239 1943 0.226 11.986 RL437461B 893.07 1382.6 0.258 2244.7 0.09 13.65 2325 0.0662 1858.8 0.165 12.833 1942.6 0.151 10.756 669 Table D.1 (Continued) Sample Depth (ft) CARB 2150 wlm CARB 2150 d CARB 2150 w CARB 2330 wlm CARB 2330 d CARB 2330 w CARB 2240 wlm CARB 2240 d CARB 2240 w AMP 2125 wlm AMP 2125 d AMP 2125 w AMP 2330 wlm AMP 2230 d AMP 2330 w AMP 2400 wlm AMP 2400 d GC04003 786.75 2158.1 0.0121 11.86 2323.2 23.335 2246.6 0.081 15.789 0.0015 10.798 2323.2 22.709 2399.6 0.0172 GC04003 1716 2158.1 0.0121 11.86 15.057 2258.8 0.038 15.19 0.0015 10.798 2339.9 0.117 17.225 2399.6 0.0172 GC04007 911 2150.1 0.0025 11.171 2346.6 15.191 2256.3 2114.9 0.0108 10.146 0.0272 GC04007 911 2157.3 0.0012 6.899 2258.9 2119.3 0.0046 6.731 2390.5 0.0527 GC04007 2000 2142.9 0.0008 11.623 2346.1 0.181 2256.3 15.175 0.0092 11.939 0.191 0.0507 GC04007 2859 0.0041 2344.8 0.154 15.47 2255.4 2111.5 0.0051 10.049 2338.5 16.844 2391.6 0.0121 GC04007 3890 2158.5 0.0764 9.426 2336.6 0.0731 14.026 2252.3 13.395 2123.8 0.0771 10.611 2336.6 0.0732 14.218 2396.2 0.0933 GC04007 4421 0.146 2327.2 0.167 18.709 0.153 12.426 2327.2 0.167 20.198 2391.8 0.0935 GC04007 134ES 2147.1 0.135 13.292 2327.9 0.155 16.232 2255.5 12.017 0.137 2327.9 0.155 16.739 2401.5 0.133 GC95010 350 2151.1 0.01 13.047 2343.2 0.152 2257.9 0.162 0.0017 10.808 2337.2 0.152 11.999 2398.1 0.0114 GC95010 939 2149.5 0.0152 11.697 2338.1 14.985 2254.7 2116.7 0.018 9.507 2338.1 0.0663 11.534 2392.9 0.16 R87105 699.8 2151 0.0052 9.334 2325.7 0.297 16.244 2255.7 2117.5 0.0026 9.072 2325.7 11.91 2404.4 0.0728 R87107 482.3 2159.5 0.0376 10.383 0.141 18.936 2258.1 0.0449 10.071 2325.5 0.141 11.677 2393.1 0.0557 R87108 629.5 2158.7 0.171 11.172 2309.3 0.11 21.834 2252.9 0.0605 2115 0.172 2335.6 0.111 14.869 2399.8 0.202 RL437461B 2140.1 0.0931 11.757 2327.9 20.161 2251.9 15.582 0.0989 10.359 2327.9 0.114 21.786 0.0354 670 Table D.1 (Continued) Sample Depth (ft) AMP 2400 w BIO 2250 wlm BIO 2250 d BIO 2250 w BIO 2320 wlm BIO 2320 d BIO 2320 w BIO 2375 wlm BIO 2375 d BIO 2375 w BIO 2375 wlm BIO 2375 d BIO 2375 w GC04003 786.75 11.686 2263.5 0.0374 20.208 0.131 0.0364 0.0043 GC04003 1716 11.686 2263.5 0.0374 20.208 0.131 0.0364 15.415 GC04007 911 2256.3 0.136 18.1 0.115 2366.9 0.117 11.928 16.378 GC04007 911 7.07 2260.1 0.213 19.275 2328.3 0.161 11.935 0.17 15.524 GC04007 2000 2256.3 0.14 21.731 2328.4 0.143 11.245 0.098 2357 16.491 GC04007 2859 11.969 2260.5 0.0497 20.054 2326.6 0.061 8.191 2367.9 0.0311 11.107 GC04007 3890 9.862 2252.3 0.132 17.132 2327.2 0.137 10.454 2366.7 0.105 8.224 0.0344 GC04007 4421 9.309 2257.9 0.174 17.339 2328.5 0.152 12.757 2369.3 0.124 14.444 GC04007 134ES 8.602 2263.7 0.158 16.376 2327.8 0.146 9.895 2365 0.129 8.896 2365.7 16.188 GC95010 350 9.115 2254.7 0.0583 19.737 0.054 0.0316 2355.1 GC95010 939 13.531 2255.7 0.0825 19.513 2325.7 0.289 9.846 2382.5 0.166 9.865 2356.9 15.199 R87105 699.8 11.045 2260.9 0.0369 18.811 2325.5 0.133 12.01 0.06 0.172 R87107 482.3 10.839 2252.9 0.0691 16.295 0.11 0.0559 2359.2 0.0744 R87108 629.5 12.637 2250.5 0.21 19.88 2325.6 0.243 10.127 2378 0.198 10.125 2358.8 0.0559 RL437461B 2244.7 0.09 19.122 2325 0.0722 12.31 2365.8 0.0435 7.969 0.063 671 D.2 Magnetic susceptibility data This appendix consists of Table D.2 which contains all the magnetic susceptibility data col- lected. The reported magnetic susceptibility (in 10^-3 SI units) has been recalculated to account for odd diameter core (2.2., 3.6 and 4.7 cm) and whole vs. split core. For sample location, lithol- ogy, distance from ore zone, metamorphic facies, main alteration and other details please refer to Appendix A.2.Abbreviations Au = gold, ppb = parts per billion, opt = ounces per ton, data from Bouzari (2009), Table D.2 Complete magnetic susceptibility data. Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* 06L337-186 2.2 Split 46.30 0.69 06L337-40 2.2 Split 5.99 0.69 06L337-478 2.2 Whole 1.52 11L086-1038 2.54 Split 8.75 0.03 11L086-266 2.54 Split 39.10 11L086-417 2.54 Split 18.90 0.02 13L833-55 3.6 Split 9.24 13L833-681.4 3.6 Split 13.00 16L1067-1008.3 2.54 Whole 6.17 16L1067-1208.1 2.54 Split 0.86 16L1067-400.8 2.54 Split 5.54 17L1437-152 3.6 Split 42.80 0.02 17L1437-556 3.6 Split 0.80 0.02 17L1437-913 3.6 Split 0.28 0.02 19L547-124.5 3 Whole 58.90 19L547-17.1 3 Whole 48.50 19L547-195.6 3 Whole 479.80 19L547-282.4 3 Whole 0.21 19L547-303.4 3 Whole 0.35 19L547-495.3 3 Split 60.00 19L547-52.4 3 Split 2.13 19L547-548.5 3 Whole 7.27 19L547-592.4 3 Whole 29.20 19L547-866.2 3 Split 0.99 24L755-186 2.54 Split 0.69 1.17 24L755-64 2.54 Split 1.22 0.02 24L755-769 2.54 Split 1.03 24L755-775.5 2.54 Whole 65.60 30L1162-1419 3.6 Split 11.60 30L1162-24.7 3.6 Split 4.04 30L1162-695 3.6 Split 3.02 30L1268-106.2 3 Split 78.80 30L1268-106.7 3 Whole 78.80 0.02 0.001 30L1268-124.9 3 Split 1.11 30L1268-175.2 3 Split 151.00 30L1268-198.5 3 Split 44.30 0.02 0.001 30L1268-215.2 3 Split 45.78 0.02 0.001 30L1268-221 3 Split 62.65 0.02 0.001 30L1268-25.7 3 Whole 5.68 1.98 0.099 30L1268-301.5 3 Split 4.87 0.02 0.001 30L1268-327.4 3 Whole 131.00 672 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* 30L1268-399.3 3 Split 0.03 30L1268-403.2 3 Split 0.53 30L1268-42.7 3 Split 1.99 30L1268-448.2 3 Split 0.07 30L1268-524.5 3 Split 0.02 0.001 0.001 30L1268-533.4 3 Split 1.26 0.001 0.001 30L1268-546.3 3 Split 2.34 0.001 0.001 30L1268-574 3 Whole 0.05 0.02 0.001 30L1268-66.2 3 Split 6.06 34L006-1235.1 3.6 Split 0.66 34L006-25 3.6 Split 90.70 34L006-706 3.6 Split 136.00 0.59 34L1352-28 3.6 Split 1.34 34L1352-315 3.6 Split 0.98 34L1352-814 3.6 Split 56.60 34L235-1961 2.54 Split 1.45 34L235-23.2 2.54 Split 4.16 34L235-648.3 2.54 Whole 1.59 34L235-909.7 2.54 Whole 16.00 34L235-944 2.54 Split 1.22 34L814-1147.7 3.6 Split 3.00 34L814-195.7 3.6 Split 1.37 34L814-2125.4 3.6 Whole 18.20 34L814-2333.4 3.6 Split 49.40 37L482-1019 3 Split 4.60 37L594-1074.5 4.7 Whole 0.66 37L594-1218.5 4.7 Whole 19.50 37L594-1581 4.7 Split 0.81 37L594-1609 4.7 Split 1.66 0.02 37L594-299 4.7 Split 0.60 0.02 37L594-815 4.7 Split 1.22 0.1 37L726-400.7 4.7 Split 174.00 37L726-532.1 4.7 Whole 82.10 37L726-836.6 4.7 Split 3.44 37L768-1108 4.7 Split 2.38 3.98 37L768-2005 4.7 Split 0.31 0.21 37L768-66 4.7 Spilt 679.00 0.02 37L768-98 4.7 Split 0.35 0.02 BK05010-376.12 4.7 Split 0.93 BK05010-42-.18 4.7 Whole 28.50 CB1556B Hand sample Hand sample 0.80 CB1812Min Hand sample Hand sample 1.09 CB1812Min2 Hand sample Hand sample 10.03 CB1912V1 Hand sample Hand sample 1.64 CB25-25 Sub Hand sample Hand sample 1.82 CB25-51 L zone Hand sample Hand sample 10.15 CB3025161 Hand sample Hand sample 3.10 CB33451AM Hand sample Hand sample 3.74 CB33451LP Hand sample Hand sample 43.67 CB33451LPQ Hand sample Hand sample 0.05 CB33451Min Hand sample Hand sample 0.88 CB33451V Hand sample Hand sample 1.30 CB39-2 Hand sample Hand sample 1.10 CB4043_0W Hand sample Hand sample 0.26 CB4143 PO Hand sample Hand sample 0.32 CB4143 PY Hand sample Hand sample 1.05 CB4143-0E Hand sample Hand sample 1.61 CB41432W Hand sample Hand sample 2.15 673 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* CB4143W Hand sample Hand sample 1.19 CR410-941.1 2.2 Whole 0.82 CR410-947 2.2 Split 4.70 CR411-185.6 2.2 Whole 0.75 CR411-581.4 2.2 Split 1.93 CR412-1170 2.2 Whole 0.62 CR412-360.3 2.2 Split 0.97 CR413-1.3 2.2 Split 2.06 CR464-31.2 2.2 Split 13.50 CR464-431.5 2.2 Whole 3.08 CR466-145 2.2 Split 0.80 CR467-86.3 2.2 Split 0.81 CR468-601.1 2.2 Whole 0.93 CR468-629 2.2 Split 23.20 CR469-41.6 2.2 Split 8.37 D14391-1025 2.54 Split 8.70 D14391-1810 2.54 Split 25.30 0.02 D14391-191 2.54 Split 0.88 0.02 D14391-2922 2.54 Split 0.25 0.02 D14981-1045.2 3.6 Split 1.99 0.02 D14981-1727.9 3.6 Whole 39.50 D14981-1798.8 3.6 Split 0.89 D14981-3.2 3.6 Split 47.90 D15367-371.1 2.54 Split 0.93 D15367-413.5 2.54 Whole 1.77 D15367-5.5 2.54 Split 3.94 D15367-671.7 2.54 Whole 5.85 D15367-793 2.54 Split 58.70 D16355-431 2.54 Split 3.22 D16355-800.5 2.54 Whole 0.52 D16355-85.3 2.54 Split 2.07 D16355-856.2 2.54 Whole 106.00 D16355-925.8 2.54 Split 3.40 D21708-1118 3.6 Whole 92.00 D21708-1340 3.6 Split 42.00 D21708-139.3 3.6 Split 16.10 D21708-1762.8 3.6 Whole 29.20 D21708-2760 3.6 Split 84.00 D22203-1604 2.54 Split 0.49 0.02 D22203-79 2.54 Split 0.45 0.02 D22203-908 2.54 Split 0.80 0.02 D22223-1932 2.54 Split 16.20 D22223-38 2.54 Split 1.22 0.1 D22223-975 2.54 Split 1.54 D2252-162 2.54 Split 0.20 D2252-309 2.54 Split 3.52 D2252-491 2.54 Split 1.92 0.1 D2253-252 2.54 Split 1.34 D2253-495 2.54 Split 0.09 0.02 D2253-75 2.54 Split 1.26 1.26 D239-217 2.54 Split 1.97 0.07 D239-95 2.54 Split 11.50 0.07 D2435-361 2.54 Split 3.36 D2435-454 2.54 Split 1.08 D27343-1181.7 2.54 Split 0.18 D27343-232.8 2.54 Whole 66.50 D27343-501.3 2.54 Split 0.60 D27343-88 2.54 Split 4.91 674 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* D27943-1779.5 5 Split 32.90 D27943-2104.2 5 Split 39.90 D27943-2607.6 5 Split 1.58 D27943-314 5 Split 4.79 D27943-933.8 5 Split 3.96 D33003-1290 5 Whole 24.70 D33003-2004 5 Split 0.94 D33003-2625 5 Whole 0.07 D33003-2823 5 Whole 44.20 D33003-2888 5 Whole 1.52 D33003-2923 5 Whole 2.09 D33003-672 5 Whole 0.30 D33003-782 5 Whole 1.32 D39018-1325 5 Split 0.22 0.02 D39018-1820 5 Split 0.63 0.02 D39018-2555 5 Split 0.53 D39018-3113 5 Whole 0.48 D39018-43 5 Split 0.30 0.03 D39018-4819 5 Whole 0.90 D39018-4848 5 Split 57.00 D39018-635 5 Split 0.04 0.02 D39200-1001 5 Split 1.79 D39200-1002 5 Split 3.44 D39200-1033 5 Split 36.69 D39200-1044 5 Split 173.85 D39200-1063 5 Split 25.89 D39200-1064 5 Split 484.70 0.02 D39200-109 5 Split 11.30 D39200-1118 5 Split 20.84 D39200-1208 5 Split 9.62 D39200-1210 5 Split 5.41 D39200-1211 5 Split 22.14 D39200-1228 5 Split 2.00 D39200-1263 5 Split 73.98 D39200-1267 5 Split 0.12 D39200-1289 5 Split 5.54 D39200-1318 5 Split 1.61 0.02 D39200-1358 5 Split 3.73 D39200-1395 5 Split 36.53 D39200-1406 5 Split 0.15 0.02 D39200-1434 5 Split 180.90 D39200-1455 5 Split 141.43 D39200-1464 5 Split 50.53 D39200-1509 5 Split 18.05 0.175 D39200-1532 5 Split 3.90 0.001 D39200-1586 5 Split 47.58 0.001 D39200-1600 5 Split 19.91 0.001 D39200-1618 5 Split 47.47 7.85 0.116 D39200-1634 5 Split 6.75 0.001 D39200-1663 5 Split 702.60 0.001 D39200-1702 5 Split 28.62 0.001 D39200-1704 5 Split 14.99 0.001 D39200-1726 5 Split 1.10 0.001 D39200-1756 5 Split 264.41 0.001 D39200-1804 5 Split 79.13 D39200-1846 5 Split 164.62 0.97 D39200-1850 5 Split 82.47 0.39 D39200-1881 5 Split 127.03 0.34 0.001 675 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* D39200-1884 5 Split 3.32 0.72 0.001 D39200-1886 5 Split 49.55 0.001 D39200-1921 5 Split 10.32 0.17 0.001 D39200-1958 5 Split 1060.55 0.001 D39200-1978 5 Split 65.93 0.001 D39200-1989 5 Split 64.47 0.001 D39200-2035 5 Split 7.13 0.001 D39200-208 5 Split 6.45 D39200-2090 5 Split 1.61 0.02 0.001 D39200-2106 5 Split 24.16 0.039 D39200-2127 5 Split 6.31 0.001 D39200-2133 5 Split 24.12 0.001 D39200-2169 5 Split 15.96 0.213 D39200-2214 5 Split 0.34 0.0001 D39200-2228 5 Split 0.88 0.001 D39200-2251 5 Split 0.66 0.001 D39200-2284 5 Split 33.70 D39200-2288 5 Split 1.00 0.001 D39200-2304 5 Split 0.81 0.02 0.078 D39200-2366 5 Split 1.36 0.001 D39200-2397 5 Split 131.61 0.001 D39200-2402 5 Split 1.08 0.1 0.0227451 D39200-2436 5 Split 1.34 0.001 D39200-244 5 Split 0.86 0.02 D39200-2452 5 Split 1.47 0.001 D39200-249 5 Split 0.85 D39200-2514 5 Split 57.17 D39200-2556 5 Split 107.86 D39200-2579 5 Split 0.97 D39200-2586 5 Split 3.17 D39200-2608 5 Split 34.96 D39200-263 5 Split 5.29 0.02 D39200-2641 5 Split 1.59 D39200-2652 5 Split 4.72 0.72 0.16376471 D39200-2665 5 Split 0.69 D39200-268 5 Split 0.60 D39200-2695 5 Split 5.94 D39200-2749 5 Split 3.44 D39200-280 5 Split 0.69 0.02 D39200-2800 5 Split 21.93 0.832 D39200-2801 5 Split 28.39 0.832 D39200-2813 5 Split 10.52 11.863 D39200-2824 5 Split 6.66 0.136 D39200-2827 5 Split 4.32 D39200-2858 5 Split 1.61 0.175 D39200-2862 5 Split 1.63 D39200-2880 5 Split 24.27 0.001 D39200-2906 5 Split 54.54 0.001 D39200-2935 5 Split 0.89 0.07 0.01592157 D39200-2954 5 Split 1.99 D39200-298 5 Split 13.71 D39200-2983 5 Split 1.55 D39200-3029 5 Split 6.66 D39200-3058 5 Split 0.58 D39200-309 5 Split 1.41 D39200-3115 5 Split 0.94 0.07 0.01592157 D39200-315 5 Split 1.30 D39200-3171 5 Split 1.65 676 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* D39200-3212 5 While 37.55 0.116 D39200-3216 5 Split 0.66 0.51 0.116 D39200-3239 5 Split 93.48 D39200-325 5 Split 0.56 D39200-3288 5 Split 1.80 D39200-3291 5 Split 370.99 D39200-3317 5 Split 3.36 D39200-336 5 Split 2.51 D39200-347 5 Split 0.74 D39200-396 5 Split 0.68 0.02 D39200-415 5 Split 1.06 D39200-438 5 Split 11.30 D39200-467 5 Split 19.47 0.02 D39200-469 5 Split 1.03 D39200-483 5 Split 7.96 D39200-52 5 Split 12.95 D39200-539 5 Split 4.91 D39200-575 5 Split 1.08 D39200-610 5 Split 5.16 D39200-651 5 Split 3.33 D39200-695 5 Split 38.85 D39200-750 5 Split 18.66 D39200-775 5 Split 27.28 D39200-791 5 Split 3.66 D39200-843 5 Split 15.04 0.02 D39200-878 5 Split 14.66 D39200-906 5 While 8.26 D39200-969 5 Split 134.58 0.02 D39204-1032 5 Split 36.50 D39204-1333 5 Split 2.99 0.02 D39204-19 5 Whole 3.92 0.1 D39357-104 5 Whole 0.68 D39357-1236 5 Whole 516.00 D39357-1287 5 Split 2.79 0.02 D39357-1308 5 Split 1.71 D39357-2029 5 Split 2.44 0.1 D39357-2066 5 Split 11.80 0.79 D39357-37 5 Split 6.67 0.07 D39357-741 5 Whole 65.60 DS11-103.4 3 Split 0.29 DS139-30.4 2.54 Split 1.74 DS172-123.1 2.54 Split 2.26 DS172-501 2.54 Whole 21.20 DS173-499.6 2.54 Split 1.57 DS173-518 2.54 Whole 8.11 DS174-708.4 2.54 Split 6.43 DS177-1500.8 2.54 Split 3.48 DS177-460.5 2.54 Split 191.00 DS177-613.5 2.54 Split 0.90 DS180-400.7 2.54 Split 0.81 DS340-505.6 4.7 Split 0.56 DS343-696 4.7 Split 53.20 DS358-1215 4.7 Split 13.20 0.02 DS358-162 4.7 Split 0.60 DS358-624 4.7 Split 5.50 DS360-124 4.7 Split 0.44 DS360-751 4.7 Split 0.42 DS615-1214.5 4.7 Whole 0.50 677 Table D.2 (Continued) Sample† Core Diameter (cm) Whole or Split core Magnetic Susceptibility (x10^-3 SI units) Au ppb* Au opt* DS615-1692.8 4.7 Whole 9.78 DS615-1905.2 4.7 Split 103.00 DS615-3001.1 3.6 Split 0.53 DS615-4032.2 3.6 Split 71.00 GC01-018-1382.2 3.6 Split 3.37 GC01-018-691.2 3.6 Split 325.00 GC01-018-85.3 3.6 Split 1.35 GC04-002-688 4.7 Split 0.30 GC04-003-1716 4.7 Split 0.08 GC04-003-1729.5 4.7 Split 0.19 GC04-003-338 4.7 Split 52.90 GC04-003-786.75 4.7 Split 1.56 GC04-007-134 4.7 Split 0.71 GC04-007-2000 4.7 Split 0.66 GC04-007-2859 4.7 Spilt 0.42 GC04-007-3890 4.7 Split 25.70 GC04-007-4421 4.7 Split 0.43 GC04-007-911 4.7 Spilt 0.55 GC95-010-350 3.6 Split 0.56 GC95-010-939 3.6 Split 5.37 R87105-699.3 3.6 Split 0.71 R87105-749.7 3.6 Whole 0.87 R87107-482.8 3.6 Split 0.84 R87108-629.5 3.6 Split 60.50 RL16A Hand sample Hand sample 12.21 RL33806B Hand sample Hand sample 1.85 RL338261AO Hand sample Hand sample 0.02 RL348651T Hand sample Hand sample 120.74 RL34865-3 Hand sample Hand sample 209.06 RL34875SO Hand sample Hand sample 1.93 RL35-2 Hand sample Hand sample 1.54 RL352806 Hand sample Hand sample 1.48 RL352806 Hand sample Hand sample 0.33 RL352FW Hand sample Hand sample 1.06 RL357462 Hand sample Hand sample 5.95 RL358066 Hand sample Hand sample 19.01 RL35FW Hand sample Hand sample 4.81 RL387462 Hand sample Hand sample 0.93 RL387462breccia Hand sample Hand sample 0.56 RL417461 Hand sample Hand sample 1.30 RL417461ASP Hand sample Hand sample 2.03 RL42-2Sub Min Hand sample Hand sample 0.67 RL437461B Hand sample Hand sample 0.85 RL437461FucM Hand sample Hand sample 0.30 RL447461 Hand sample Hand sample 0.29
Thesis/Dissertation
eng
Geological Sciences
Vancouver : University of British Columbia Library
Attribution-NoDerivs 3.0 Unported
Graduate
The mineralogical, geochemical and isotope characteristics of alteration, mineralization and metamorphism of the Red Lake Gold Mines, Ontario
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