Science, Faculty of
Earth, Ocean and Atmospheric Sciences, Department of
DSpace
UBCV
Zivanovic, Jelena
Master of Science - MSc
University of British Columbia
The Timok Magmatic Complex (TMC) is a well-endowed mineral district in Serbia that hosts world-class Cu-Au porphyry (Majdanpek, Veliki Krivelj, Borska Reka) and high-sulfidation deposits (Bor, Čukaru Peki). Recent exploration activities on the northwestern margin of the TMC have led to the discovery of the Bigar Hill sediment-hosted disseminated gold deposit (SHDG). It represents a previously unrecognized style of gold mineralization within the TMC and the Cretaceous metallogenic province of the western Tethyan orogenic belt - although they share many characteristics with the Carlin-type and distal disseminated gold deposits of Nevada, US. Gold distribution at Bigar Hill and associated hydrothermal mineralogical, geochemical and stable isotope alteration features were examined to reconstruct the structural and stratigraphic controls on hydrothermal fluid flow. The Bigar Hill stratigraphy encompasses Late Jurassic to Early Cretaceous limestone unconformably overlain by a calcareous clastic sedimentary sequence (unit S1). Late Cretaceous volcanic detritus-rich sandstone package (unit S2) unconformably overlies unit S1. Primary sparry carbonate cement, mainly ferroan calcite is characteristic features of both S1 and S2 units. Marl lies conformably over the S2 unit, and the andesitic sill intruded it. Gold mineralization is principally stratabound, located along two stratigraphic contacts. The contact zone between units S1 and S2 is a major mineralized horizon. The other mineralized corridor lies along the unconformable contact between limestone and the S1 siliciclastic rocks. Acidic hydrothermal fluids likely exploited the enhanced porosity and permeability of preserved weathering crusts, brecciated zones, and karst along the unconformities, further creating secondary porosity by dissolving host rock carbonate cement. Although stratigraphic features are considered highly influential on the spatial distribution of ore, the regional structural framework and syn-mineralization faults reactivations are thought to be necessary to allow mineralizing fluids to permeate favorable stratigraphic horizons. A 3D spatial analysis of stratigraphic contacts and changes in the thickness of sedimentary packages suggests that the controls of the ore body geometry are previously unrecognized sub-vertical structures that channeled upwelling metal-bearing fluids. Fluids then spread laterally along the contact zones between the sedimentary packages. Two recognized structural trends, NW and NE match the major gold mineralization trends.
Structural, Stratigraphic and Temporal Constraints of Gold Mineralization in the Bigar Hill Deposit, Timok Region, Serbia by Jelena Zivanovic BSc., Belgrade University, 2009 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in The Faculty of Graduate and Postdoctoral Studies (Geological Sciences) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) May 2019 © Jelena Zivanovic, 2019 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, a thesis/dissertation entitled: Structural, Stratigraphic and Temporal Constraints of Gold Mineralization in the Bigar Hill Deposit, Timok Region, Serbia submitted by Jelena Zivanovic in partial fulfillment of the requirements for the degree of Master of Science in Geological Sciences Examining Committee: Dr. Craig Hart, Geological Sciences Supervisor Dr. Kenneth Hickey, Geological Sciences Supervisory Committee Member Dr. Gregory Dipple, Geological Sciences Additional Examiner iii ABSTRACT The Timok Magmatic Complex (TMC) is a well-endowed mineral district in Serbia that hosts world-class Cu-Au porphyry (Majdanpek, Veliki Krivelj, Borska Reka) and high-sulfidation deposits (Bor, Čukaru Peki). Recent exploration activities on the northwestern margin of the TMC have led to the discovery of the Bigar Hill sediment-hosted disseminated gold deposit (SHDG). It represents a previously unrecognized style of gold mineralization within the TMC and the Cretaceous metallogenic province of the western Tethyan orogenic belt - although they share many characteristics with the Carlin-type and distal disseminated gold deposits of Nevada, US. Gold distribution at Bigar Hill and associated hydrothermal mineralogical, geochemical and stable isotope alteration features were examined to reconstruct the structural and stratigraphic controls on hydrothermal fluid flow. The Bigar Hill stratigraphy encompasses Late Jurassic to Early Cretaceous limestone unconformably overlain by a calcareous clastic sedimentary sequence (unit S1). Late Cretaceous volcanic detritus-rich sandstone package (unit S2) unconformably overlies unit S1. Primary sparry carbonate cement, mainly ferroan calcite is characteristic features of both S1 and S2 units. Marl lies conformably over the S2 unit, and the andesitic sill intruded it. Gold mineralization is principally stratabound, located along two stratigraphic contacts. The contact zone between units S1 and S2 is a major mineralized horizon. The other mineralized corridor lies along the unconformable contact between limestone and the S1 siliciclastic rocks. Acidic hydrothermal fluids likely exploited the enhanced porosity and permeability of preserved weathering crusts, brecciated zones, and karst along the unconformities, further creating secondary porosity by dissolving host rock carbonate cement. Although stratigraphic features are considered highly influential on the spatial distribution of ore, the regional structural framework and syn-mineralization faults reactivations are thought to be necessary to allow mineralizing fluids to permeate favorable stratigraphic horizons. A 3D spatial analysis of stratigraphic contacts and changes in the thickness of sedimentary packages suggests that the controls of the ore body geometry are previously unrecognized sub-vertical structures that channeled upwelling metal-bearing fluids. Fluids then spread laterally along the contact zones between the sedimentary packages. Two recognized structural trends, NW and NE match the major gold mineralization trends. iv LAY SUMMARY Bigar Hill is sediment-hosted disseminated gold deposit located on the margin of the Cretaceous magmatic province of the Tethyan orogenic belt; it represents the previously unclassified style of mineralization in the region explored for porphyry and epithermal deposits. Main objectives of this thesis are to establish geological features and critical processes necessary for gold deposition and to determine the timing of the key geological events relevant to the formation of the deposit. An ideal combination of structural and stratigraphic features provided favorable conditions for the circulation of Au-bearing hydrothermal fluids, their interaction with sedimentary rocks and finally gold precipitation. The most favorable mineralization host rocks were the Cretaceous calcareous sedimentary units with reactive iron, primarily permeable and porous, disturbed by processes of weathering, erosion, karstification, and structural deformations that additionally decreased rock competence. Geochronological analysis indicates that deposit-scale hydrothermal and magmatic activities were largely contemporaneous processes during the Late Cretaceous. v PREFACE This MSc. thesis is defined and coordinated by Dr. Craig Hart and Dr. Aleksandar Mišković, within the Western Tethyan Metallogeny Project. The location of the research area is in Eastern Serbia, at the Bigar Hill deposit, discovered by Avala Resources Ltd. in 2011. Avala Resource Ltd. provided logistical assistance during the two field seasons (summer 2013, 2014), as well as the drilling and lithogeochemical database for use in this study. The sampling, observations, analyses, and interpretations were performed by Jelena Živanović unless otherwise noted. The geological map of the Bigar Hill and northwestern Timok Magmatic Complex (shown in figures 2.5, 2.6, 4.1, 5.2, 5.4, and 6.1) is based on geological mapping and data collection performed by the geologists from Avala Resources. The completion of the thesis included contributions from thesis supervisor Dr. Craig Hart, and the committee members, Dr. Kenneth Hickey and Dr. Andreas Beinlich. vi TABLE OF CONTENTS ABSTRACT ..................................................................................................................................................... iii LAY SUMMARY ............................................................................................................................................. iv PREFACE ........................................................................................................................................................ v TABLE OF CONTENTS .................................................................................................................................... vi LIST OF TABLES .............................................................................................................................................. x LIST OF FIGURES ........................................................................................................................................... xi LIST OF ABBREVIATIONS ............................................................................................................................ xvii ACKNOWLEDGMENTS ................................................................................................................................. xix DEDICATION ................................................................................................................................................. xx CHAPTER 1 – INTRODUCTION ....................................................................................................................... 1 1.1 Rationale for Study.......................................................................................................................... 1 1.2 Overview of Sediment-hosted Disseminated Gold Deposits .......................................................... 3 1.2.1 Carlin-type Deposits in the Great Basin ................................................................................... 4 1.2.1.1 Magmatic History .............................................................................................................. 5 1.2.1.2 Deposit-hosting Sedimentary Units .................................................................................. 5 1.2.1.3 Mineralization Controls and Fluid Characteristics ............................................................ 6 1.2.2 Distal Disseminated Gold Deposits .......................................................................................... 7 1.3 Thesis Objectives ............................................................................................................................. 7 1.4 Methodology ................................................................................................................................... 9 1.4.1 Core Logging ............................................................................................................................. 9 1.4.2 Petrography ............................................................................................................................. 9 1.4.3 Lithogeochemistry ................................................................................................................. 10 1.4.4 Short-wave Infrared Spectroscopy (SWIR) ............................................................................. 10 1.4.5 Carbon and Oxygen Isotopic Analysis .................................................................................... 11 1.4.6 Geochronology ....................................................................................................................... 11 1.5 Thesis Organization ....................................................................................................................... 13 CHAPTER 2 – GEOLOGY, HYDROTHERMAL ALTERATION, AND MINERALIZATION OF THE BIGAR HILL GOLD DEPOSIT ....................................................................................................................................................... 14 2.1 Introduction .................................................................................................................................. 14 2.2 Regional Geology .......................................................................................................................... 16 vii 2.2.1 Tectonic Evolution and Metallogeny of the Apuseni-Banat-Timok-Srednogorie Belt ........... 17 2.2.2 Geology and Tectonic Setting of the Timok Magmatic Complex ........................................... 19 2.2.3 Metallogeny of the TMC ........................................................................................................ 22 2.2.3.1 Bor - Veliki Krivelj – Majdanpek Cu-Au Porphyry, High-Sulfidation Trend ..................... 23 2.2.3.2 Kuruga High-Sulfidation Cu-Au Trend ............................................................................. 23 2.2.3.3 Western Porphyry Trend................................................................................................. 24 2.2.3.4 The Sediment-hosted Disseminated Gold Trend ............................................................ 24 2.3 Host Rock Lithology and Stratigraphic Sequence ......................................................................... 26 2.3.1 Paleozoic Metamorphic Rocks (MPH) .................................................................................... 26 2.3.2 Late Jurassic Limestone (JLS) ................................................................................................. 28 2.3.3 Early Cretaceous Limestone (KLS) .......................................................................................... 29 2.3.4 Carbonate-siliciclastic unit (S1) .............................................................................................. 30 2.3.5 Carbonate and volcanic detritus-rich siliciclastic unit (S2) .................................................... 32 2.3.6 Marl (SMR) ............................................................................................................................. 32 2.3.7 Andesite (VOL) ....................................................................................................................... 33 2.3.8 Other Intrusive and accompanying Metamorphic Rocks....................................................... 33 2.4 Hydrothermal Alteration ............................................................................................................... 33 2.4.1 Carbonate Dissolution ............................................................................................................ 33 2.4.2 Silicification ............................................................................................................................ 35 2.4.3 Clay Alteration ........................................................................................................................ 36 2.4.3.1 Clay Identification ........................................................................................................... 37 2.4.3.2 Illite Crystallinity as a Mineralization Vectoring Parameter ........................................... 38 2.4.4 Sulfidation and Gold Mineralization ...................................................................................... 40 2.4.4.1 Metal distribution on the Bigar Hill ................................................................................ 43 CHAPTER 3 – STRATIGRAPHIC AND STRUCTURAL CONTROLS ON THE BIGAR HILL GOLD MINERALIZATION .................................................................................................................................................................... 46 3.1 Introduction .................................................................................................................................. 46 3.2 Stratigraphic Control on Gold Distribution ................................................................................... 46 3.2.1 Petrographic Characterization of the S1 Sub-Unit and S2 Unit ............................................. 46 3.2.1.1 Sub-Unit S1 Characterization .......................................................................................... 46 3.2.1.2 Unit S2 Characterization ................................................................................................. 48 3.2.2 Petrographic Analysis of Iron Precipitation ........................................................................... 49 3.2.3 Enhanced Weathering along Depositional Contacts ............................................................. 51 viii 3.3 Structural Control on Gold Distribution ........................................................................................ 52 CHAPTER 4 – DECIPHERING FLUID FLOW THROUGH THE APPLICATION OF OXYGEN AND CARBON STABLE ISOTOPES..................................................................................................................................................... 56 4.1 Introduction .................................................................................................................................. 56 4.2 Methodology ................................................................................................................................. 57 4.3 Results ........................................................................................................................................... 58 4.3.1 C and O Stable Isotopes ......................................................................................................... 58 4.3.1.1 Global and Local Background Values .............................................................................. 58 4.3.1.2 Stable Isotope Values of the Bigar Hill Deposit ............................................................... 60 4.3.2 Gold and Trace Elements Distribution ................................................................................... 62 4.3.3 Correlation between Isotope Ratios and Metal Concentrations ........................................... 67 4.4 Stable isotope ratios, metal concentrations, and zones of increased permeability ..................... 70 4.4.1 Spatial relation between isotope ratios, metal concentrations, tectonic and stratigraphic features ........................................................................................................................................... 72 CHAPTER 5 – GEOCHRONOLOGY OF THE MAGMATIC, HYDROTHERMAL AND SEDIMENTARY PROCESSES AT BIGAR HILL AND THE TMC...................................................................................................................... 75 5.1 Introduction .................................................................................................................................. 75 5.1.1 Geochronology of the TMC .................................................................................................... 76 5.2 Methodology ................................................................................................................................. 77 5.2.1 U-Pb Zircon Dating ................................................................................................................. 77 5.2.2 K-Ar Illite Dating ..................................................................................................................... 80 5.3 Results and Interpretation ............................................................................................................ 82 5.3.1 U-Pb zircon ages and interpretation ...................................................................................... 82 5.3.2 K-Ar illite age .......................................................................................................................... 85 CHAPTER 6 – DISCUSSION ........................................................................................................................... 88 6.1 Depositional Environment and Alteration of the Gold-Hosting Sedimentary Package ................ 88 6.2 Structural Control on Mineralizing Fluids ..................................................................................... 91 6.3 Deposit Formation – Favorable Host Environments, Critical Processes, Hydrothermal Alteration, and Metal Association ...................................................................................................... 95 6.3.1 Gold-hosting Environments ................................................................................................... 95 6.3.2 Hydrothermal Alteration ........................................................................................................ 97 6.4 Exploration Tools for Hydrothermal Gold Deposits ...................................................................... 99 6.4.1 Hydrothermal Alteration ........................................................................................................ 99 6.4.2 Oxygen and Carbon Stable Isotopes ...................................................................................... 99 ix 6.5 Temporal Constraints on Geological Processes Relevant to the Bigar Hill Deposit Formation .. 101 6.6 Deposit Model ............................................................................................................................. 102 CHAPTER 7 – CONCLUSION, EXPLORATION IMPLICATIONS, AND RECOMMENDATIONS FOR FUTURE WORK ........................................................................................................................................................ 105 7.1. Conclusion .................................................................................................................................. 105 7.2 Exploration Implications and Recommendations for Future Work ............................................ 107 References ................................................................................................................................................ 109 Appendix A: Samples from the Bigar Hill – locations, descriptions .......................................................... 117 Appendix B: Lithogeochemical data ......................................................................................................... 133 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features .......................... 154 Appendix D: Isocon diagrams for limestone, S1, S2 and andesite units representing the mass transfer during the rock alteration ......................................................................................................................... 161 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks 165 Appendix E.2: The spatial variability of O isotope in each stratigraphic unit in drill holes along the A-B cross section .............................................................................................................................................. 183 Appendix F: K-Ar Radiometric Age Dating ................................................................................................ 184 Appendix G: Bigar Hill, Korkan, Korkan West, Rakita, and Crna Reka drill hole collar locations and orientation data ........................................................................................................................................ 187 x LIST OF TABLES Table 4.1: Compilation of δ13C and δ18O global and local background values, and values from the Bigar Hill for each rock unit .................................................................................................................................. 59 Table 4.2: Spearman correlation matrix for O and C isotopes, gold and selected trace elements ............ 64 Table 4.3: Downhole depth (m) of the intersections of holes with inferred and established faults (F1-F9) .................................................................................................................................................................... 70 Table 5.1: Summary of age dates of magmatic and hydrothermal activity in eastern and central TMC. Localities are shown in Figure 2.1 and Figure 5.2. ...................................................................................... 76 Table 5.2: Summary of the U-Pb SHRIMP-RG ages of the intrusive rocks from the west-central TMC. Localities are shown in Figure 5.2. .............................................................................................................. 77 Table 5.3: Summary of the U-Pb LA-ICP-MS ages from this study with the location of samples in drill holes. Collar locations and orientations of the drill holes are in Appendix G. ........................................... 83 Table 5.4: The results of the K-Ar analyses, for two illite fractions (<2 µm and <5 µm) and the whole rock samples (w.r.) with the location of samples in drill holes. Collar locations and orientations of the drill holes are in Appendix G. ............................................................................................................................. 86 xi LIST OF FIGURES Figure 1.1: Diagrammatic model of Carlin-type and distal disseminated deposits (modified from Setijadji, 2002; Sillitoe and Humbolt, 1990; Peters et al., 2004). ................................................................................ 3 Figure 1.2: Hill-shaded digital elevation model of northern Nevada with the locations of mineral belts and districts, Carlin-type gold deposits (circles), and other significant deposits (crosses). Upper right box shows the northern Carlin trend with the principal Carlin-type deposits (Hofstra, 2002 and the references therein). ...................................................................................................................................... 4 Figure 2.1: Simplified geologic map of the Timok Magmatic Complex with the most significant ore deposits including the Bigar Hill. ................................................................................................................. 15 Figure 2.2: Simplified map of magmatic provinces within the western section of the Tethyan orogenic belt including the locations of the significant base and precious metal deposits. The red line contour shows the Timok Magmatic Complex. (Modified from MDRU, Jenkins, 2017). ......................................... 16 Figure 2.3: Generalized tectonic element map of the Balkan Peninsula with the location of the TMC (modified from Schmid et al., 2008). .......................................................................................................... 18 Figure 2.4: Simplified tectonic map of the TMC with the position of mineral deposits and major deposits trends (modified from Knaak et al., 2016). ................................................................................................. 22 Figure 2.5: Geologic map of the NW part of the TMC, with the position of the SHDG deposits (Bigar Hill, Korkan and Kraku Pešter), adjacent porphyry Cu-Au deposits (Kraku Riđi, Dumitru Potok, Čoka Rakita, Valja Strž) and Potaj Čuka monzonite pluton. Geolines from Avala Resources, 2012. .............................. 25 Figure 2.6: Geologic map of the Bigar Hill area with the locations of drill holes sampled for this study, including the holes from non-mineralized prospects Korkan West and Korkan South (inset, right). Grey line outlines 0.5 ppm Au mineralization shell. Geolines from Avala Resources, 2012. .............................. 26 Figure 2.7: Stratigraphic column of the Bigar Hill deposit area. ................................................................. 27 Figure 2.8: Bigar Hill lithologic units: (a) Jurassic (Tithonian) limestone; (b) Early Cretaceous “dirty” limestone with black chert; (c) Basal breccia with limestone fragments and very fine-grained groundmass rich in pyrite or oxidized; (d) Alternation of siltstone/mudstone with fine-grained sandstone; (e) S1 carbonate sandstone with stylolite seams parallel or perpendicular to bedding; (f) S2 volcanic detritus-rich sandstone to granulite; (g) Marl with laminas of organic matter; (h) Hornblende-plagioclase phyric andesite intruded as sill in marl. ................................................................................... 28 xii Figure 2.9: Background values for major and immobile elements in non-altered JLS (215 samples) and KLS (466 samples) with Au<0.01ppm; Avala Resources data set. .............................................................. 30 Figure 2.10: Carbonate dissolution in mineralized rocks: (a) hand sample with complete carbonate cement removal from the S1 sandstone, showing secondary porosity; this sample also exhibits silica addition; (b) hand sample of the S2 sandstone that underwent complete carbonate dissolution, with quartz grain framework and hydrothermal pyrite remaining; (c) transmitted light photomicrograph of completely dissolved sparry calcite cement, with quartz (qz) and clay minerals (cy) remaining in S1 sandstone; (d) partially dissolved sparry calcite cement (ca) of basal breccia (outlined with a green line). .................................................................................................................................................................... 34 Figure 2.11: Silica replacement: (a) and (b) hand sample and the transmitted light photomicrograph showing the replacement of carbonate cement or fragments with microcrystalline silica (si cement) in sandstone from the S1/S2 contact zone; (c) and (d) hand sample and the transmitted light photomicrograph of cryptocrystalline silica spatially associated with clay minerals (cy) and pyrite (py) in completely decarbonatized S2 sandstone. ................................................................................................. 35 Figure 2.12: Clay alteration of alumino-silicate minerals: (a) and (b) hand sample and the transmitted light photomicrograph of clay alteration (cy) in andesite with relicts of plagioclase (pk); (c) and (d) hand sample and the transmitted light photomicrograph of clay alteration (cy) in S2 sandstone, showing a visibly altered volcanic fragment with remnant hornblende (hb) and plagioclase (pk). ............................ 36 Figure 2.13: General element ratio diagram indicates the correlation of gold mineralization with illite alteration; Correlation is based on approximately 4,000 samples from the S2 unit and andesite; Avala Resources data set. ..................................................................................................................................... 38 Figure 2.14: Box plots representation of the illite crystallinity index ranges depending on the gold grade. .................................................................................................................................................................... 39 Figure 2.15: Box plots of illite crystallinity and gold grade ranges in samples from drill holes from the Bigar Hill ore and distal, non-mineralized zone, and distal, non-mineralized Korkan West and Korkan South areas. Drill hole locations are shown in Figure 2.6. .......................................................................... 40 Figure 2.16: Photomicrographs of pyrite morphology in mineralized rocks: (a) pyrite replacing hornblende in altered andesite; (b) pyrite associated with clay (illite?) alteration in the S2 sandstone; (c) pyrite disseminated in the S2 sandstone, replacing altered volcanic fragments; (d) distribution of pyrite of different grain sizes in decarbonatized S1 sandstone; (e) pyrite formed on the calcite from the S1 sandstone cement; (f) abundant pyrite in the fine-grained BBX breccia matrix. ....................................... 41 xiii Figure 2.17: Scatter plot of Fe vs. S from the Bigar Hill samples with Au content > 1ppm. Samples with gold hosted by pyrite are plotted near the x=y line (1 to 1 ratio corresponds to the ratio of Fe and S in pyrite). Samples with gold hosted by goethite are aligned along the y=0 line. Avala Resources data set. 42 Figure 2.18: Mineralized rocks from the Bigar Hill deposit (samples from drill core): (a) “Dirty” Cretaceous limestone, with fractures filled with secondary calcite; (b) Karst formed on the top of the Cretaceous limestone, with secondary porosity resulting from the carbonate dissolution; (c) Basal breccia with pyrite rich fine-grained matrix; (d) Decarbonatized S1 sandstone; (e) S2 coarse-grained clastic rock, located just above the contact with the S1; exposed to carbonate dissolution, clay alteration and sulfidation; (f) Strongly clay altered S2 sandstone, with visible pyrite nests; (g) Strongly decarbonatized and oxidized S2 sandstone; (h) Strongly clay altered andesite with pyrite accumulations. .................................................................................................................................................................... 44 Figure 2.19: NW-SE geological cross-section through the Bigar Hill deposit, with the 0.4 grade shell outline in black line. .................................................................................................................................... 45 Figure 3.1: Lithotypes of the S1 clastic sub-unit: (a) carbonate sandstone with dominant quartz and terrigenous detritus and subordinate carbonate cement; (b) sandy limestone (intra-biosparite) with principal carbonate components, microfossils, carbonate mud lumps, and calcite cement; quartz in this facies is subordinate. .................................................................................................................................. 47 Figure 3.2: Lithotypes of the S2 clastic unit: (a) litharenite with visibly altered phenocrysts of hornblende and plagioclase and minor calcite cement; (b) sub-litharenite from the lower level of the unit, with dominant quartz and carbonate cement, and subordinate volcanic detrital clasts. .................................. 48 Figure 3.3: Carbonate staining of rock slabs to identify iron-bearing carbonate minerals: (a) Ferroan calcite is the dominant component in mineralized S1 sandstone; (b) Ferroan calcite (f ca) is most abundant carbonate component in mineralized S1 sandstone, also minor calcite (ca) and dolomite (do) fragments; (c) Ferroan calcite (f ca) builds breccia cement; clasts are non-stained, most likely of dolomite composition, cut with calcite veins; (d) Mineralized breccia with calcite fragments cemented by ferroan carbonate. ................................................................................................................................................... 49 Figure 3.4: Isocon diagram represents the mass transfer of components during the fluid-rock interaction. The diagram includes the samples from all the Bigar Hill lithologic units. ................................................. 50 Figure 3.5: Phases in building the 3D structural model using the 2D cross-sections across the deposit: (a) Observations of the changes in thickness and orientation of the stratigraphic units on 2D cross-sections, and definition of structural blocks; (b) Inferring a fault network by connecting them in successive cross-sections; (c) Implementation of 2D observations in the 3D model (cross-section exported from the 3D xiv Leapfrog model); (d) Refining the interpretation further in a 3D model (cross-section exported into 2D). .................................................................................................................................................................... 54 Figure 3.6: Bigar Hill block model with the newly developed structural framework. All the faults are labeled with F1-F12. Structures inferred during this study are inferred in several common orientations, including (1) WNW (F1, F3); (2) NE (F4, F5, and F6); (3) NNW (F2); and (4) E (F12). .................................. 55 Figure 4.1: Locations of the sampled Bigar Hill drill holes (bounded by northing coordinates 4898157 and 4898187); The upper right box shows the locations of sampled Korkan West and Korkan South drill holes; Structures scrutinized in this study are labeled with F mark. Geolines from Avala Resources, 2012. .................................................................................................................................................................... 58 Figure 4.2: Plot of δ18O vs. δ13C for samples from all carbonate-bearing stratigraphic units, altered and least-altered, in relation to Global Phanerozoic marine carbonate background (Veizer et al., 1999) and local background ranges. ............................................................................................................................ 60 Figure 4.3: Box plot representation of the ranges of δ18O and δ13C for each stratigraphic unit, including all samples, altered to least-altered from Bigar Hill. .................................................................................. 61 Figure 4.4: Cross-sections are showing the spatial distribution of δ18O (top section) and δ13C (bottom section) values and their spatial relation with stratigraphic units, and the gold mineralization (0.4 ppm Au grade shell outlined with purple line). The position of the cross-section is shown on the map in Figure 4.1. .............................................................................................................................................................. 63 Figure 4.5: Cross-sections showing the spatial distribution of Sb, Tl, Hg and As values and their relation with stratigraphic units, and the gold mineralization (0.4 ppm Au grade shell outlined with purple line). The position of the cross-section is shown on the map in Figure 4.1. ....................................................... 65 Figure 4.6: XY plot of δ18O vs. δ13C for samples taken from all the carbonate-bearing stratigraphic units, color-coded by Au (top plot), Sb (bottom plot), Hg (next page top plot) and Tl (next page bottom plot) concentrations from the appropriate intervals. ......................................................................................... 68 Figure 4.7: Spatial representation of stable isotopic and gold ratios in drill holes along the A-B cross-section is shown as box plots. Box plots are formed based on the δ18O, δ13C and Au values from all the analyzed samples within respective drill holes. .......................................................................................... 71 Figure 5.1: Photographs of rocks sampled for U-Pb zircon dating: (a) 14JZBH285, a propylitic-altered andesitic sill from the Bigar Hill; (b) 14JZBH286, plagioclase-hornblende phyric diorite intruded in andesite from east of the Bigar Hill; (c) 14JZRA001, diorite from the Čoka Rakita Au-porphyry system; (d) 14JZCR003, plagioclase-hornblende diorite from the Crna Reka prospect; (e) 14JZCR002 - Coarse-grained xv K feldspar-plagioclase-biotite monzonite from the Crna Reka prospect; (f) S2 volcaniclastic-derived carbonate sandstone. ................................................................................................................................. 78 Figure 5.2: West and Central TMC geology with the location of the samples collected for U-Pb dating, and the obtained ages. Also, the locations of the previously obtained ages (Tosdal, 2012) shown using different symbols. Geolines from Avala Resources, 2012. ......................................................................... 79 Figure 5.3: Photographs of samples collected for K-Ar illite dating: (a-c) 14JZBH295, 14JZBH298, 14JZBH299 are intensively illite-altered and mineralized S2 sandstone; (d-f) 14JZBH292, 14JZBH294, 14JZBH296 are illite-altered and sulfidized andesite. ................................................................................. 80 Figure 5.4: Locations of sandstone and andesite samples collected for K-Ar illite dating from the Bigar Hill drill holes. Geolines from Avala Resources, 2012. ................................................................................ 81 Figure 5.5: Photomicrographs of highly mineralized samples (transmitted light, X-polar, left; reflected light, right) collected for illite dating illustrate the association between gold-bearing pyrite and illite: (a-b) S2 sandstone sample 14JZBH295, with illite (il) replacing volcanic detritus, minor quartz (qz) and calcite cement (ca); and (c-d) andesite sample 14JZBH296, with moderately disseminated pyrite (py) in illite dominant groundmass. ....................................................................................................................... 82 Figure 5.6: U-Pb Concordia plots showing data for zircons separated from samples (a) 14JZBH286; (b) 14JZCR002; (c) 14JZCR003 and (d) 14JZBH302; and (e) probability density plot for detrital zircon ages from the sample 14JZBH302. ...................................................................................................................... 84 Figure 5.7: Summary of the geochronology of the magmatic, sedimentary and mineralization in the TMC, with an emphasis on the Bigar Hill deposit (compiled from Janković et al., 1981; Banješević et al., 2001; von Quadt et al., 2002; Clark and Ullrich, 2004; Zimmerman et al., 2008; Tosdal, 2012; this study). ....... 87 Figure 6.1: Pathfinder metal associations from soil (defined using the weighted sums technique) over the geological map of the northwestern Timok magmatic complex (modified from Knaak et al., 2016). . 93 Figure 6.2: Trace elements distribution in (a) limestone, along NW-trend, and (b) all the units above the limestone, along NE-trend; Avala Resources data set. ............................................................................... 94 Figure 6.3: Schematic diagrams of the formation and modification of the Bigar Hill deposit (not to scale): (a) Formation of the sedimentary package and its structural modification, karstification and formation of the weathering crust; (b) Magmatic activity affecting the sedimentary package – diorite intrusion in the vicinity of the deposit and andesite sub-volcanic sill intrusion within the deposit; (c) hydrothermal activity within the Bigar Hill region, porphyry deposit formation in the vicinity of the deposit and SHDG deposit within Bigar Hill; (d) burial of the deposit along graben forming faults. ....................................... 97 xvi Figure 6.4: Distribution of δ18O (grid data), As (downhole data), and illite crystallinity (point data) and their spatial relationship with gold, and structural and stratigraphic controls. ....................................... 100 Figure 6.5: Simplified NW long section across the Bigar Hill, Bigar and Čoka Rakita, showing the spatial distribution of different magmatic-hydrothermal mineralization types. ................................................. 104 xvii LIST OF ABBREVIATIONS AAS = Atomic Absorption Spectrometry ABTS = Apuseni-Banat-Timok-Srednogorie magmatic-metallogenic belt BBX = Basal breccia sub-unit, part of the S1 unit ca = Calcite cy = Clay minerals f ca = Ferroan calcite g/t = Grams per tonne hb = Hornblende IB = Siltstone/mudstone interbedded sub-unit, part of the S1 unit il = Illite ICP-MS = Inductively Coupled Plasma Mass Spectroscopy JLS = Late Jurassic limestone unit KLS = Early Cretaceous limestone unit LA-ICP-MS = Laser Ablation Inductively Coupled Mass Spectroscopy Ma = Millions of years MDRU = Mineral Deposit Research Unit mu = Muscovite PCIGR = Pacific Center for Isotopic and Geochemical Research at the University of British Columbia Pk = Plagioclase ppb = Parts per billion ppm = Parts per million py = Pyrite qz = Quartz RC = Reverse Circulation (drilling) S1 = Early Cretaceous carbonate siliciclastic unit xviii S2 = Late Cretaceous volcanic detritus-rich, carbonate, siliciclastic unit SHDG = sediment-hosted disseminated gold si = Silica SMR = Late Cretaceous marl unit SWIR = Short-Wave Infrared Spectroscopy TMC = Timok Magmatic Complex TSG = The Spectral Geologist© interpretative software UBC = University of British Columbia VOL = Late Cretaceous andesite sill VPDB = Versus Peedee Belemnite (international standard for carbon isotope) VSMOW = Versus Standard Mean Ocean Water (international standard for oxygen isotopes) XRF = X-ray Fluorescence δ = Ratio of the heavy isotope (13C or 18O) vs. the light isotope (12C or 16O) xix ACKNOWLEDGMENTS This MSc. thesis is part of the Western Tethyan Metallogeny Project coordinated by Dr. Craig Hart, and Dr. Aleksandar Mišković. For financial and academic support for the project, I like to express sincere thanks to the sponsoring companies and organizations: Alamos Gold Inc., AngloAmerican, AngloGold Ashanti, Avala Resources Ltd., Centerra Gold, Dunav Resources Ltd., Dundee Precious Metals, Eldorado Gold Corporation, First Quantum Minerals Ltd., Kinross Gold, Pilot Gold Inc., Silver Standard Resources Inc., Teck Ltd., Muğla University, Turkey, University of Geneva, Switzerland, Aristotle University of Thessaloniki, and University of Athens, Greece. Dr. Richard Tosdal, Dr. István Márton, Justin van der Toorn, and Dr. Alex Mišković provided help in defining the theme and objectives of this thesis, and I am indebted to them. For significant help and support, I would like to thank Justin van der Toorn, Sean Hasson, István Márton, Dragana Davidović, Dragan Milošević, and Ivica Milojević from Avala Resources Ltd. Sincere thanks are offered to my supervisor Dr. Craig J.R. Hart. His assistance was much appreciated. Also, sincere thanks to Dr. Alex Mišković for his valuable support. Many thanks to the committee members, Dr. Kenneth Hickey and Dr. Andreas Beinlich for their questions and suggestions during the committee meetings. I am particularly grateful for the assistance from Dr. Beinlich who helped with the stable isotopes work, and also had to face the early drafts of my chapters. Sincere thanks go to Sara Jenkins who greatly improved the quality of the thesis draft. Richard Friedman and Vivian Lai provided valuable help at every step during my work on the U-Pb geochronology. I wish to thank Paula Brunetti, Raja Yarra, Kaleb Boucher, Fabien Rabayrol, Graham Leroux and Craig Richardson for being good friends and great geologists. Our fine Western-Eastern Tethyan group was my family for a while. I like to thank my parents for the continuous, unconditional love and support. Above all, I want to thank Miki who was an exceptional person in challenging times. xx DEDICATION To Miki 1 CHAPTER 1 – INTRODUCTION 1.1 Rationale for Study Sediment-hosted disseminated gold (SHDG) deposits are hydrothermal replacement bodies that typically form in calcareous rock sequences typical of passive continental margins. The passive margin basin geometries were shaped by continental rifting and long-lived, deep crustal structures. These structures controlled sedimentation and deformation as well as localization of calc-alkaline magmatism, and most SHDG deposits are structurally and stratigraphically controlled (Hofstra and Cline, 2000; Cline et al., 2005). SHDG deposit host rocks are mostly reactive and permeable sedimentary rocks, including limestone, dolomite, and calcareous siliciclastic rocks (i.e., Bagby and Berger, 1985; Sillitoe and Bonham, 1990; Berger et al., 2014). Hydrothermal host rock alteration can be variable and visually subtle, but is dominated by carbonate dissolution with clay formation, sulfidization and silicification (Li and Peters, 1998; Hofstra and Cline, 2000; Cline et al., 2005). Gold mineralization is frequently termed “invisible gold” since it occurs as structurally bound Au+1 or as sub-micron native gold in pyrite or arsenic-rich pyrite (Radtke et al. 1980; Muntean et al., 2011). Such deposits were mined during the first half of the 20th century but it was only after the discovery of the Carlin deposit in Nevada in the early 1960s that SHDG deposits were recognized as economically significant and became subject of academic research interest (Li and Peters, 1998; Muntean et al., 2004; Berger et al., 2014). Since 1961, over 100 geologically similar deposits have been discovered in the Great Basin physiographic province of the southwestern U.S. (Muntean et al. 2004). With gold production, reserves, and resources amounting more than 6,000 tons, SHDG deposits of northern Nevada represent the second largest Au concentration globally (Muntean et al., 2011; Ressel and Henry, 2006; Frimmel, 2008). Mining of these systems dominates gold production in the U.S. and accounts for 6% of the annual global production (Cline et al., 2005; Frimmel, 2008; Muntean et al., 2011). As such, SHDG deposits are economically significant, but their value has mostly been exploited in technologically-advanced mining districts and the emerging regions remain underexplored and undeveloped. Beyond Nevada, SHDG deposits are suggested to occur in western and southwestern China (Shuiyndong, Lannigou, Nibao, Zimudang etc.), Indonesia (Mesel, Lobongan Alason), Iran (Zarshurian, Agd), Malaysia (Bau), South Korea (Taebaegsan), Peru (Purisma Conception, Cajabamba), Chile (El-Hueso, Potrerillos, Jeronimo), Canada (Racla, Brewery), Spain (Salamon, Sant Bernat), Russia (Aldan, Zdiha etc.) and 2 Macedonia (Alšar) (Daglioglu, 1996; Berger, 2014; Feebrey, 2014; Hofstra, 2015). SHDG deposits have been recognized and discovered in Serbia at Bigar Hill, Korkan and Kraku Pešter in 2010 (Avala Resources Ltd, 2013; Knaak at all., 2016). These deposits and their recognition as SHDG systems represent an opportunity to reconsider significant potential from deposits that were previously considered uneconomical. These Serbian deposits share many classic features with SHDG deposits of Nevada which are crucial for delineating geological processes and features that were critical for gold deposition. The SHDG deposits of Serbia occur on the margin of the Timok Magmatic Complex (TMC), which is well-known for its world-class porphyry and epithermal Cu-Au deposits. Calcareous siliciclastic rocks rich in volcanic detritus, transitional calcareous sandstone to sandy limestone, basal breccia overlying the limestone unit, and Cretaceous limestone with high organic and clastic contents all host mineralization. Deposition of sub-µm sized gold accompanies pyrite formation and an association with low-temperature metals such as Tl, Hg, Sb, and Te. Mineralization forms with subtle hydrothermal host rock alteration, including carbonate dissolution, illite ± smectite, and kaolinite alteration, and local silicification. Bigar Hill is a gold deposit in the advanced stage of exploration. Since 2010, a significant amount of geological and geochemical data has been collected. These data enabled a general understanding of the deposit stratigraphy as well as the mineralization distribution within particular stratigraphic units. However, the exact controls on gold deposition remained unexplained. The lack of a clear understanding of the deposit structural setting made it difficult to determine feeder faults and the other structures that acted as conduits for hydrothermal fluids. The compositional variations and textural characteristics of the sedimentary host rocks that controlled gold deposition were not analyzed in details. Also, an unequivocal genetic link between mineralization and surrounding magmatic activities was not established. Listed unknowns will be addressed in this thesis. The significance of structural and stratigraphic controls on gold mineralization at Bigar Hill will be evaluated through the application of geological mapping, core logging, major, minor and trace element geochemistry, stable isotope geochemistry, petrography, short-wave spectroscopy, and 3D structural modeling. New geochronological data will be obtained for the Bigar Hill host rocks and nearby magmatic intrusions to directly and indirectly constrain the timing of mineralization. Lastly, a new Bigar Hill genetic model will be constructed in the context of new bracketing ages on regional magmatic, sedimentary and hydrothermal events. 3 1.2 Overview of Sediment-hosted Disseminated Gold Deposits In order to appreciate the significance of SHDG and its importance within this thesis, an overview of this deposit type is provided. Several classifications of SHDG deposits have been established based on their geological and geochemical characteristics. The most typical division is based on genetic links with shallow plutonic complexes and porphyry systems (Tosdal, 1998; Johnston and Ressel, 2004; Cline et al., 2005). In this classification, there are two subsets of the SHDG deposits: (1) Carlin-type and (2) Carlin-like or distal disseminated (Hofstra and Christensen, 2002; Cline et al., 2005; Theodore, 1998). Although the two subsets share many physicochemical characteristics, Carlin-type deposits lack the genetic link with igneous activity, whereas distal Carlin-like disseminated deposits are linked chemically, spatially and temporally with magmatism (Cline et al., 2005; Ressel, 2015) (Figure 1.1). Figure 1.1: Diagrammatic model of Carlin-type and distal disseminated deposits (modified from Setijadji, 2002; Sillitoe and Humbolt, 1990; Peters et al., 2004). 4 1.2.1 Carlin-type Deposits in the Great Basin Carlin-type deposits derive their name from the first deposit of its type, the “Carlin deposit,” discovered in 1961 in northeastern Nevada. Since then, many geologically similar deposits have been discovered in the Great Basin province - primarily in Nevada but also in adjacent southern Idaho and western Utah (Cline and Hofstra, 2000; Berger et al., 2014). The Carlin deposit (s.s.) has become the type example of a genetic class of previously undocumented, sediment-hosted, hydrothermal gold deposits. The majority of the Great Basin Carlin-type deposits are aligned along three regionally-significant structural lineaments, known as the Carlin, Battle Mountain-Eureka, and Getchell trends, and the Jerritt Canyon and Alligator Ridge districts (Muntean et al. 2004; Berger et al. 2014) (Figure 1.2). Figure 1.2: Hill-shaded digital elevation model of northern Nevada with the locations of mineral belts and districts, Carlin-type gold deposits (circles), and other significant deposits (crosses). Upper right box shows the northern Carlin trend with the principal Carlin-type deposits (Hofstra, 2002 and the references therein). 5 1.2.1.1 Magmatic History Several stages of magmatic activity accompanied regional deformations. Paleozoic basaltic volcanism was deposited within the allochthon of the Roberts Mountains thrust but was not associated with the Carlin trend and its deposits. According to Ressel and Henry (2006), magmatic episodes affecting the rocks of the Carlin trend occurred in the Late Jurassic, Cretaceous, Eocene, and Miocene. Subduction-related magmatism prevailed from the Late Jurassic through the Cretaceous to Late Eocene. Jurassic magmatism produced diorite to granodiorite, rhyolite and lamprophyre intrusions and associated volcanic rocks, while Cretaceous intrusions were primarily granitic. After a gap in magmatic activity during Paleocene, magmatism resumed in the Eocene with calc-alkaline volcanism and shallow intrusions. Eocene magmatism occurred contemporaneously and in response to Farallon plate subduction and the initiation of crustal extension. Rift-related bimodal basalt-rhyolite lavas extruded during the Miocene (Cline et al., 2005). The Jurassic intrusions have spatial relation with gold mineralization. However, Eocene intrusions have both spatial and temporal association with the majority of the Carlin-type gold deposits. Cretaceous and Miocene intrusions are not associated with gold mineralization (Ressel and Henry, 2006). 1.2.1.2 Deposit-hosting Sedimentary Units Paleozoic sedimentary rocks of north-central Nevada include three main sequences: (1) autochthonous, “lower plate” Silurian to Devonian continental margin carbonate facies; (2) allochthonous, “upper plate” Ordovician deep-water terrigenous clastic rocks; and (3) Late Mississippian to Early Permian overlap sequence located east of the Roberts Mountains allochthon (Teal and Jackson, 1997; Yigit et al. 2003). Autochthonous sequence hosts the majority of Carlin-type deposits (Teal and Jackson, 1997; Hofstra and Cline, 2000). This sequence encompasses three deposit-hosting formations: (i) Roberts Mountains; (ii) Popovich; and (iii) Rodeo Creek (Teal and Jackson, 1997). The Silurian-Devonian Roberts Mountains formation consists of medium- to thin-bedded, laminated, silty limestone and dolomitic siltstone. Stratigraphically higher sections exhibit relatively high permeability, which created a favorable environment for gold mineralization and host the Carlin, Betze, West Leeville, Pete, Screamer, Deep Post, and Goldbug-Post deposits. The Devonian Popovich formation is highly variable with sharp vertical and lateral facies changes, from thin-bedded silty limestone and micrite to massive, fossiliferous, sparry limestone. The Popovich formation hosts the Betze-Post, Genesis-Blue Star, Gold Quarry, Griffen, Rodeo, 6 Deep Star, Bootstrap-Capstone and Dee-Storm deposits. The Late Devonian Rodeo Creek unit represents the upper transitional zone immediately beneath the Roberts Mountains allochthon. Occurrences typical of this unit have abrupt lateral and vertical facies changes, thick sequences of debris flow and syn-sedimentary slumping. The rocks comprise calcareous siltstone, siliceous mudstone, and chert. The upper part of Gold Quarry and Upper Betze-Post deposits are hosted in Rodeo Creek siltstone (Teal and Jackson, 1997; Emsbo et al., 2003). Low-permeable, fine-grained siliciclastic rocks within the Roberts Mountains allochthon form a regional aquitard and lack any significant Carlin-type mineralization (Cline et al., 2005; Teal and Jackson, 1997). 1.2.1.3 Mineralization Controls and Fluid Characteristics Deposition of passive margin sedimentary sequences and the pre-Eocene deformation events established the pre-mineralization architecture for the Nevada SHDG deposits and created a favorable environment for the hydrothermal fluid circulation and deposition of disseminated gold. The majority of the Carlin-type deposits are adjacent to steeply-dipping faults through reactive and permeable mid-Paleozoic carbonate rocks (Teal and Jackson, 1997; Cline et al., 2005; Hickey et al., 2014). However, feeder structures of some Carlin-type deposits were low-angle thrusts, focusing lateral fluid flow underneath and up into the ore zone (e.g., Pipeline gold deposit) (Hickey et al., 2014). Multi-phase fluid inclusion data and geologic reconstructions suggest that Carlin-type deposits formed a few kilometers below the paleo-surface. Ore fluids where characterized by low temperature (~180-240°C), low salinity (mostly <6 wt.% NaCl equivalent), moderate acidity (pH~4), CO2 content <4 mol%, CH4 content <0.4 mol%, and H2S content (10-1 – 10-2 mol%) which were sufficient to transport Au and other metals as bisulfide-complexes (Cline et al., 2005; Muntean et al., 2011). Carlin host rock alteration is usually subtle and varies with the size of the hydrothermal system, host rock composition, and permeability. Visible alteration halo extents may be exceeded by larger zones showing an isotopic modification of the limestone host rocks and these indicate fluid circulation on the km-scale (Barker et al., 2013). Visible alteration is manifested as carbonate dissolution, clay alteration of primary silicate minerals and local silicification, particularly proximal to structural conduits (Teal and Jackson, 1997). Sulfidation of reactive iron in host rocks is the primary mineralization process. Sulfur from the fluid reacts with the reduced iron to form pyrite and destabilize aqueous Au-bisulfide complexes. Pyrite is an efficient scavenger of Au by adsorbing Au1+ onto its negatively charged surfaces from AuHS0 complexes in acidic fluids that are under-saturated in native Au (Muntean, 2015). Elevated concentrations of As, Sb, 7 Hg, Tl, ±Te occur along with gold in pyrite, the Au/Ag ratio is generally >1, and base metal abundances are very low (Radtke et al. 1980; Hofstra and Cline, 2000; Muntean et al., 2011). Rb-Sr dating of rare Hg-sulfosalt – galkhaite provided the only direct age of mineralization, indicating an age of 40-39 Ma (Arehart et al., 2003). Although considerable effort has been made to integrate geological, geochemical and isotopic data, a full understanding and a widely accepted genetic model of Carlin-type deposits have yet to be established (Hofstra and Cline, 2000). In particular, the sources of fluids, metals and heat-driving hydrothermal convection systems remain debated (Arehart, 1996; Ressel and Henry, 2006). Two end-member models determining the origin of gold in Carlin-type deposits include (1) magmatic-hydrothermal models, which suggest a magmatic origin of Au, and (2) amagmatic models favoring Au mobilization from the crust by meteoric and metamorphic waters (Muntean et al., 2011). 1.2.2 Distal Disseminated Gold Deposits Distal disseminated Au deposits share many features with Carlin-type deposits. They formed in the same regional tectonic and depositional environment of the continental margin, within carbonate and clastic sedimentary host rocks (Cox and Singer, 1990). For both types, structurally and stratigraphically controlled mineralization is disseminated and associated with the weakly developed hydrothermal host rock alteration. Distal disseminated deposits have higher Ag and base metal concentrations than Carlin-type deposits, but lower concentrations of Au, and are thought to form from fluids of higher temperature and salinity (Cline et al., 2005). The main distinction from Carlin-type deposits is their genetic and spatial relation to magmatic intrusions (Theodore, 1998; Tosdal, 1998), porphyry, skarn, polymetallic veins, and polymetallic replacement deposits (Cox and Singer, 1990). The distal disseminated deposits of north-central Nevada are proximal to Jurassic, Cretaceous and mid-Tertiary granitoid bodies and exhibit isotopic signatures that indicate formation from magmatic fluids (Hofstra, 1997; Hofstra and Cline, 2000). The most economically essential deposits (e.g., Lone Tree, Marigold) are located in the Battle Mountain-Eureka trend and are proximal to a cluster of established and inferred porphyry Cu-Mo systems of Late Eocene age (Hofstra and Cline, 2000). 1.3 Thesis Objectives The Bigar Hill SHDG deposit represents a thrilling opportunity to study a previously unrecognized and unclassified mineralization style in the Timok Magmatic Complex (TMC) and wider in the Cretaceous metallogenic province of the western sector of the Tethyan orogenic belt. A full characterization of the 8 deposit is challenging due to the lack of surficial manifestation of faults, the heterogeneity of the sedimentary units, and their mineralogical and physicochemical features. Of particular importance are the geological features and processes that facilitated the formation of economically significant gold mineralization, i.e., what structures facilitated primary hydrothermal fluid flow, and what stratigraphic features favor gold deposition? As well, new geochronological data can define the relative sequence of magmatic and hydrothermal events at Bigar Hill that can constrain the timing of the sources of thermal energy, gold, and fluids? How does this deposit compare to the classic Carlin-type and disseminated gold models in a global context? To address these questions, the central thesis objectives are to: (1) Establish the structural and stratigraphic controls on gold deposition formation; (2) Identify the critical processes that facilitated gold deposition; (3) Determine the timing of the key magmatic and hydrothermal events; (4) Develop a refined Bigar Hill deposit model. The objectives were reached through the application of several methods. (1) Core logging, petrography including carbonate staining, geochemical and stable isotope data were used to define stratigraphic features that controlled the deposition and distribution of gold. The approach to establishing structural controls was through the observations of the 3D spatial distribution of lithology data recorded by core logging. Geochemical and stable isotopic data were used for further support and enabled a better understanding of the timing of structural events. (2) Core logging, petrography, short-wave infrared spectroscopy, and C-O isotopic data provided the basis for the identification of chemical processes that led to the deposition of gold. (3) The timing of the major geological events relevant to the formation of the Bigar Hill deposit was deciphered by the use of data from two geochronological techniques. U-Pb zircon technique provided the age of the major magmatic events spatially or genetically linked to the ore formation as well as the indirect age of the main sedimentary host rocks. K-Ar dating of illite was used to determine the age of hydrothermal activity and the indirect age of mineralization. (4) The refined geological model of the Bigar Hill deposit was built as a synthesis of all available data and observations and as such can be compared with the SHDG deposit model. 9 1.4 Methodology 1.4.1 Core Logging A database of rock lithology, alteration observations, mineralization, vein properties, weathering characteristics, and structural features for 87 diamond drill holes was obtained from the Avala Resources Ltd., from their previous work at the deposit. Fifteen drill holes located along the NW-SE deposit cross-section were selected for further analysis. Characteristics of siliciclastic rocks such as grain size, composition, and distribution of clasts and cement were recorded in details. The previous classification of sedimentary units was refined into sub-facies according to their composition and grain-size. These steps helped to determine the importance of rock features for fluid transport and gold mineralization. Sample locations and descriptions are listed in Appendix A. 1.4.2 Petrography Sixty samples were petrographically analyzed under transmitted and reflected light. The selection of 52 samples collected at the Bigar Hill represents mineralized and barren examples of all significant sedimentary and volcanic units. Eight samples are from the barren Korkan West and Korkan South prospects, collected from the same stratigraphy as in the case of the Bigar Hill deposit. The petrographic analysis focused on determining texture, mineral assemblage, and alteration, and in the case of siliciclastic rocks, also fabric characteristics (homogeneity, packing, porosity, clast orientation), grain size, grain shape, textural maturity, matrix, and cement composition. The carbonate staining method enabled the identification and discrimination of carbonate minerals in calcareous siliciclastic sedimentary rocks from the Bigar Hill. Staining was applied on 27 samples from the S1 and S2 clastic units. The alizarin red (sodium alizarine sulfonate C14O2H5(OH)2SO3) - potassium ferri-cyanide (K3[Fe(CN)6]) composite test allowed the distinction of ferroan carbonates. Non-ferroan dolomite, siderite, and magnesite do not stain, while calcite and aragonite become pink to scarlet red. Ferroan calcite stains dark purple to royal blue and ferroan dolomite stains pale to turquoise blue and blue. Before staining, samples were etched in diluted HCl for 5 seconds and then thoroughly washed with distilled water. The samples were then placed in the staining solution, prepared as a mixture of 250 ml of 2% HCl and 2 g of each alizarin red and potassium ferricyanide. After 2 minutes, the stained samples were removed from the solution, washed with distilled water and air dried (Hitzman, 1999). This procedure was conducted at the Mineral Deposit Research Unit (MDRU, UBC) laboratory under the fume hood. 10 1.4.3 Lithogeochemistry Avala Resources Ltd provided lithogeochemistry data for approximately 50,000 samples from 87 diamond and 333 reverse circulations (RC) drill holes used in this thesis. Samples were prepared and analyzed at the SGS facility in Bor, Serbia. Gold concentration analysis was performed by conventional fire assay, with an atomic absorption spectrometry (AAS) finish. Silver and trace metal analyses were performed using a 0.3 g charge, aqua regia digestion, and AAS or inductively coupled plasma mass spectrometry (ICP-MS). Gold, silver, and sulfur analyses were performed on one-meter intervals of the split core or RC chip samples, while the remaining element suite analyses were done on five-meter composite samples. The 5 m composite samples were not available from all drill holes. One in twenty samples represented internationally-certified standard material, covering the grade range, along with blank and duplicate analyses. An additional 59 samples were analyzed to constrain mineralization and alteration on a scale larger than that covered by samples contained in the Avala Recourses database. These samples were prepared at UBC and processed by Acme Analytical Laboratories Ltd, Vancouver, using the total whole rock characterization package. Major and trace elements were digested using a lithium borate fusion and analyzed by X-ray fluorescence (XRF) and ICP-MS, respectively. Base and precious metals were digested in aqua regia and analyzed by ICP-MS. Additionally, gold concentrations were determined by fire assay with the detection limit of 30 ppb. Total carbon and sulfur were determined using a LECO elemental analyzer and direct combustion and non-dispersive infrared detection of CO2 and SO2 gas. Data quality control included five duplicates and five internal standards with known chemical composition. Lithogeochemical data for analyzed samples are listed in Appendix B. 1.4.4 Short-wave Infrared Spectroscopy (SWIR) Short-wave infrared spectra were collected from 250 core samples from volcanic and siliciclastic rocks to determine the presence and distribution of clay and carbonate minerals. The reflectance spectra resulting from the absorption of characteristic wavelengths due to sub-molecular vibrations during bending and stretching of molecular bonds in minerals were obtained using the TerraSpec® analytical spectral device (ASD Inc.). Spectra were processed both automatically by the interpretative software The Spectral Geologist© (TSG) and manually with the SPECMIN™, comparing obtained spectra with the extensive library examples. Spectral analysis was conducted at MDRU laboratory. 11 1.4.5 Carbon and Oxygen Isotopic Analysis Carbonate oxygen and carbon isotope ratios of the host rocks to mineralization changed due to isotope exchange between the host rock and alteration fluid. This method was used to delineate hydrothermal fluid flow pathways within the Bigar Hill system. For that purpose, 629 samples from sedimentary carbonate rocks (marl, sandstone, sandy limestone, siltstone, breccia, and limestone) collected at 5 m intervals from 22 diamond and RC drill holes that comprise an E-W section that crosses the Bigar Hill mineralization and also from the surrounding barren area. The amount of carbonate material used in the analysis ranged from 17 to 100 mg depending on carbonate concentration. Sample powders were obtained by a hand-drilling homogeneous rock or carbonate cement using a handheld Dremel tool or by crushing the RC chips. The sample powder was placed in glass vials, sealed with rubber septa. Approximately 0.2 ml of 85% H3PO4 was injected into each vial and left to react at 70°C for at least one hour in a heated aluminum block. Further processing of the samples and measurement of C and O isotope composition of CO2 gas produced from the acidification of carbonate minerals was carried out using Los Gatos Research (LGR) CCIA-43r-EP carbon-dioxide isotope off-axis integrated cavity output laser spectrometer (OA-ICOS) instrument at MDRU. The sample vial connected with the instrument inlet via a series of Swagelok compression fittings, stainless steel tubing, and a cold glass trap. The measured volume fractions of several isotopologues of CO2 (12C16O16O, 13C16O16O, and 12C16O18O) were converted to the conventional δ notation (δ13CVPDB and δ18OVSMOW) (Beinlich et al. 2017). Instrumental drift was monitored on an hourly basis and corrected using the 2000 ppm CO2 gas sample of constant isotopic composition. Each analytical session commenced and ended with at least three UBC in-house reference materials (BN13, Sigma, BDH). These reference materials were also run after at least the 8th to 10th unknown for quality control and to establish the analytical reproducibility of known values. 1.4.6 Geochronology Six samples were collected for U-Pb zircon geochronology analysis by laser ablation ICP-MS (LA-ICP-MS). These included samples from volcanic detritus-rich sandstone, andesite, and diorite from the Bigar Hill, two samples from the nearby Au and Cu-Au porphyry Čoka Rakita and Crna Reka deposits, and one sample from the Crna Reka monzonite. LA-ICP-MS U/Pb age determinations were conducted at the Pacific Center for Isotopic and Geochemical Research (PCIGR) at UBC. Zircon grains from the samples were isolated using standard heavy mineral separation processes, then hand-picked under a binocular and embedded in epoxy resin. Puck were then ground, polished, cleaned with HNO3, and carbon coated. Several grains of the Plešovice and Temora zircon standards of known age were also mounted together 12 with the unknowns. Cathodoluminescence (CL) imagery preceded the zircon analysis to identify inherited cores, inclusions, and physical defects (Kolb et al., 2012). Analyses were performed using a New Wave UP-213 laser ablation system and a ThermoFinnigan Element2 single collector, double-focusing, magnetic sector ICP-MS. The laser operated along approximately 100 μm long line scans at a beam width of 25 μm and 20 Hz repetition rate. Each analytical sequence commenced and ended with the measurement of at least three zircon standards, which were also analyzed after every five unknowns. The resulting signals were analyzed using Iolite™, an application extension of the Igor Pro™ software. Corrections for mass and elemental fractionation were made by bracketing analyses of unknown grains with replicate analyses of both Plešovice and Temora zircon standards. Data reduction was performed using MS Excel add-in Isoplot. K-Ar dating of hydrothermal illite was performed to constrain the age of hydrothermal alteration and gold mineralization. Clay minerals were separated from six drill core samples collected from intensively altered and highly mineralized volcanic detritus-rich sandstone and andesite from Bigar Hill. Sample preparation and K-Ar dating were carried out at the Institute of Nuclear Research at the Hungarian Academy of Science (ATOMKI). In order to avoid contamination, the <2 μm fraction was separated from each sample according to the standard clay separation procedure. The <5 μm and <10 μm fractions were also separated from 2 andesitic samples to test the effect of grain size on the radiometric age. The effect of the rock host minerals was tested by dating the whole rock samples. The purity of the separated clay fraction was checked with X-ray powder diffraction at the Mineralogical Department of the Eötvös Loránd University, Budapest, using a Philips PW 1710 diffractometer with CuKα radiation at 45 kV and 35 mA. For the calculation of the K/Ar age, it was necessary to determine the concentrations of 40K and radiogenic 40Ar. For 40K measurement, approximately 0.05 g of finely-grounded samples were digested in HF, HNO3, and H2SO4 and finally dissolved in 0.2 M HCl. Potassium was determined by flame photometry with a Na buffer and Li internal standard using Sherwood M420 type flame photometer. For 40Ar, approximately 0.8 g of whole-rock sample and 0.2 g of mineral fraction were preheated for about 24 h at 150–180°C in a vacuum. Argon was extracted under ultra-high vacuum conditions by RF induction heating and fusion of rock samples in Mo crucibles. The extraction line was linked directly to a mass spectrometer using in-static mode. Argon isotope ratios were measured by a 38Ar isotope dilution mass spectrometric method, previously calibrated with atmospheric argon and international rock standards (Pécskay and Benkó, 2015). 13 1.5 Thesis Organization This thesis includes seven chapters. Chapter 1 is an introductory explanation of the rationale and objectives of this thesis. This chapter also provides an overview of sediment-hosted disseminated gold deposits, their characteristics and classification, and a literature review of Carlin-type and distal disseminated gold systems. The first part of chapter 2 focuses on the regional geological background, geodynamic setting and metallogeny of southeastern Europe, particularly the Cretaceous magmatic belt and Timok Magmatic Complex. The second part of chapter 2 focuses on the geology of the Bigar Hill deposit and provides an overview of the host rocks stratigraphy. It also addresses critical processes that facilitated the ore formation such as hydrothermal alteration, and gold deposition. Chapter 3 provides a hypothesis on the structural and stratigraphic factors that may have controlled the precipitation of the significant economic concentrations of gold. Chapter 4 evaluates the applicability of stable carbon and oxygen isotopes as an exploration tool. Generally, deviations in C and O isotopic composition are observable in a broader area than visible alteration and other geochemical indicators. Isotopic shifts were used to establish the extent of the fluid interaction with carbonate rock, to differentiate pervasive from structurally controlled alteration and to delineate fluid flow pathways. Chapter 5 provides a geochronological overview of the collected data on the magmatic and hydrothermal events in the Bigar Hill region and explores possible links between gold mineralization and nearby magmatic activity. Chapter 6 represents a synthesis of the obtained results and observations, giving the interpretation of the main topics set out in this study. Chapter 7 outlines the main conclusions and proposes an outlook on future applications of the obtained knowledge to future exploration and suggestions for future work. 14 CHAPTER 2 – GEOLOGY, HYDROTHERMAL ALTERATION, AND MINERALIZATION OF THE BIGAR HILL GOLD DEPOSIT 2.1 Introduction The Bigar Hill is sediment-hosted disseminated gold (SHDG) deposit discovered in 2010 within the exploration license of Avala Resources Ltd in Serbia. The Bigar Hill is emplaced on the northwestern margin of the Timok Magmatic Complex (TMC) which had previously been known only for its porphyry and epithermal Cu-Au deposits (Figure 2.1). Therefore, the discovery of the Bigar Hill has wide range implications because this SHDG deposit represents a previously unrecognized genetic type within the TMC. Indicated mineral resources of Bigar Hill are 1.48 Moz Au at an average grade of 1.19 g/t (Avala Resources Ltd., 2014). The Bigar Hill mineralization is characterized by micron to submicron scale gold within pyrite disseminated in carbonate-rich sedimentary and less in sub-volcanic rocks. The main controls of gold precipitation and its distribution are both structural and stratigraphic. The primary porosity and permeability of the host rocks as well as the secondary porosity and permeability caused by faulting, weathering or erosion were critical in the formation of the deposit. These features controlled the ore fluid flow and its interaction with reactive iron-bearing rocks. Weakly acidic gold-bearing fluids caused carbonate dissolution, clay and local silica alteration of the host rocks and reacted with liberated iron that led to the deposition of pyrite with gold (Cline et al., 2005). Within the stratigraphic sequence, only two calcareous siliciclastic S1 and S2 units had characteristics that made them the overall favorable mineralization host rocks. Particularly important were the two depositional contact zones with high secondary porosity and permeability, one between the S1 and S2 units, and the other between the S1 unit and the underlying limestone. Other rock units had a somewhat limited capacity for hosting mineralization either due to the unfavorable composition or low porosity and permeability. This chapter will provide the review of the regional geology, geodynamic and metallogeny. Afterward, the focus will be on the Bigar Hill stratigraphy through the detailed description of the rock units as well as critical processes – alterations that were crucial for the gold deposition. The characterization of the rocks and hydrothermal alterations is based on the core logging, petrographic observations and whole rock and trace element geochemistry. 15 Figure 2.1: Simplified geologic map of the Timok Magmatic Complex with the most significant ore deposits including the Bigar Hill. 16 2.2 Regional Geology The Bigar Hill deposit is hosted primarily in Cretaceous strata of the westernmost component of the Tethyan orogenic belt (Figure 2.2) that spans from the western Mediterranean via the Alps and Balkan Peninsula through Turkey and the Caucasus, and into south-central Iran, Afghanistan, Pakistan, the Himalayas, and Indochina (Janković, 1997; Zimmerman et al., 2008). The Tethyan orogenic belt formed during the closure of the Tethyan Ocean in Mesozoic and Cenozoic. The arcuate, double-verging orogenic system includes temporally and spatially distinct Cretaceous and Tertiary magmatic provinces (Neubauer, 2002). The belt hosts numerous small to world-class porphyry Cu±Mo±Au and related Au±Cu epithermal and base metal deposits. Richards (2015) linked Mesozoic deposits with the subduction of the oceanic lithosphere and suggested that the majority of Tertiary deposits formed during or after the continental collision. Figure 2.2: Simplified map of magmatic provinces within the western section of the Tethyan orogenic belt including the locations of the significant base and precious metal deposits. The red line contour shows the Timok Magmatic Complex. (Modified from MDRU, Jenkins, 2017). 17 2.2.1 Tectonic Evolution and Metallogeny of the Apuseni-Banat-Timok-Srednogorie Belt The Late Cretaceous magmatic province of the western Tethyan belt is named Apuseni-Banat-Timok-Srednogorie belt (ABTS) (Figure 2.2). It represents one of the European most productive ore provinces and is well-known for its mining activities since pre-Roman times (Ciobanu et al., 2002; von Quadt et al., 2002; Drew, 2005; Chamberfort and Moritz; 2006; Richards 2015). Despite the gaps in the exposure of magmatic rocks and irregularly clustered ore deposits, the L-shaped ABTS belt is largely continuous for 1,500 km and has a width of 30 to 70 km (von Quadt et al., 2002). It extends through southeastern Europe, running southward from the North Apuseni Mountains and the Banat region in Romania to Timok area in Serbia and then eastward through the Srednogorie zone in Bulgaria where the Panagyurishte is the central metallogenic district (Ciobanu et al., 2002; von Quadt et al., 2002; Zimmerman et al., 2008). The belt continues through Turkey further to the east. The ABTS was formed from the interaction of multiple micro-plates that were between the African and Eurasian plates during the closure of the Tethyan Ocean (Neugebauer et al., 2001; Heinrich and Neubauer, 2003). A divergence of Africa and Eurasia terminated in the Early Jurassic. Continental fragments (such as Dacia, Tisza, and Rhodopian micro-plates) migrated northwards and interacted with the Moesian platform – a promontory of the stable Eurasian plate (Zimmerman et al., 2008; Schmid et al., 2008, Kolb et al., 2012) (Figure 2.3). During the Late Cretaceous, continual continent convergence initiated the closure of the Vardar Ocean (a branch of the former Tethys Ocean) by subducting the oceanic slab beneath the Dacia micro-plate (Drew, 2005; Zimmerman et al., 2008; Kolb et al., 2012). Several geodynamic models have been proposed to explain the formation and evolution of the Cretaceous magmatic and metallogenic belt, including slab roll back as the most accepted model (Zimmerman et al., 2005; Kolb et al., 2012). The model implies a gradual steepening of the north-dipping subduction slab resulting in an inversion from compressional to extensional tectonic regimes (Kolb et al., 2012). Subducting slab dehydration triggered the melt generation, which was enhanced by asthenosphere upwelling (Neubauer, 2002; Lips et al., 2004). Extension of the upper crust allowed melt access to high crustal levels, ultimately leading to widespread calc-alkaline magmatism and formation of the ABTS magmatic belt (Kolb et al., 2012). Subduction ceased in the region at the very beginning of the Cenozoic but continued in the Aegean region and Alps. 18 Figure 2.3: Generalized tectonic element map of the Balkan Peninsula with the location of the TMC (modified from Schmid et al., 2008). The ABTS belt hosts numerous hydrothermal metal deposits in eastern Serbia, the Southern Carpathians in Romania, and the Panagyurishte zone in Bulgaria. Porphyry and high-sulfidation deposits are in the central segments of the belt in southernmost Banat, Serbia, and northwestern Bulgaria. These deposits are copper dominated but also represent significant gold resources. Anomalous molybdenum is registered, though generally in small quantities (Janković, 1997; Ciobanu et al., 2002). Some porphyry deposits contain notable PGE abundances (Zimmerman et al. 2008). Major Cu-Au deposits are Rosia 19 Montana in Romania, Majdanpek, Veliki Krivelj, and Bor in Serbia, Elatsite and Chelopech in Bulgaria (Figure 2.2). Re-Os molybdenite ages constrain the timing of mineralization in the Apuseni-Banat, Timok, and Panagyrishte districts to 83-72 Ma, 88-80 Ma, and 92-87 Ma respectively (Ciobanu et al., 2002; Zimmerman et al., 2008). The data indicates an increasing mineralization age from the northwestern to the southeastern part of the ABTS belt. Sediment-hosted gold deposits discovered in Serbia in 2010 at the northwestern margin of the TMC are a previously unrecognized genetic type within the ABTS. 2.2.2 Geology and Tectonic Setting of the Timok Magmatic Complex The Late Cretaceous magmatism in the Serbian part of the ABTS belt occurred along the TMC. The northerly-oriented, elongated, lozenge-shaped TMC is about 85 km x 25 km and is one of the most prolific mining areas in Europe. Volcanic rocks dominate the TMC. They are intercalated with the Late Cretaceous, calcareous sedimentary, volcaniclastic and epiclastic rocks (Banješević, 2006, 2010), and are intruded by numerous dikes, sills and large plutons emplaced mainly at shallow crustal levels (Figure 2.1). The TMC is formed on the edge of the Moesian platform, on Proterozoic to Early Cretaceous continental crust of Dacia micro-plate (Figure 2.3). Basement rocks of the TMC comprise Proterozoic gneiss, amphibolite, greenschist, gabbro, metasediments, and Paleozoic schist, phyllite, and metasediments. (Dimitrijević et al., 1970; Banješević, 2006). Due to the late Paleozoic terrain uplift caused by Variscan orogeny, deposition of Triassic sedimentary rocks was sparse and had a local character (Dimitrijević et al., 1976). Transgressive basal conglomerate unit marked the beginning of the continuous carbonate sequence sedimentation in Late Jurassic and Early Cretaceous (Doger to Aptian). Approximately 800 m of limestone, dolomite and transitional varieties were deposited within the carbonate platform environment. Early, Austrian stage of the Alpine orogeny led to regression of sea level and cessation of carbonate precipitation. During the short hiatus in sedimentation, carbonate rocks were exposed to karstification processes. Further evolution of the area took place during middle Cretaceous (Albian-Cenomanian) in the environment with the frequent sea-level oscillations. Calcareous clastic rocks deposited during that time included conglomerate and breccia, sandstone, siltstone, mudstone, and sandy limestone (Banješević, 2006, 2010; Dimitrijević et al., 1976). The next break in sedimentation was caused by the Laramide phase of the Alpine orogeny. After the hiatus, Late Cretaceous, Turonian- Senonian, clastic sedimentary cycle commenced during which sequences of sandstone and conglomerate and younger marl and marly limestone were produced. Igneous activity in the TMC was synchronous with the Late Cretaceous sedimentation. TMC classically includes three successive phases 20 spanning over 30 Ma (Drovenik et al., 1960; Dimitrijević et al., 1976; Janković et al., 2002). However, new interpretations proposed only two phases (Milovanović et al., 2005; Banješević, 2010). Phase I rocks deposited in the eastern TMC during the Late Turonian to Santonian (von Quadt et al., 2002; Clark and Urllich, 2004), and resulted in shallow-marine hornblende ± biotite ± pyroxene andesite (“Timocites”) to trachyandesite (Clark and Ullrich, 2004; Milovanović et al., 2005; Banješević, 2010) that built to form large stratovolcanoes dominated by volcaniclastic rocks. Sub-volcanic to hypabyssal diorite and quartz-diorite were emplaced simultaneously, resulting in skarn and hornfels alteration of the country rocks. Intrusion was emplaced and have associated porphyry and epithermal-style mineralization (e.g., Bor and Veliki Krivelj Cu-Au deposits) (Zimmerman et al., 2008). Phase II commenced during the Campanian in the central and western TMC and was synchronous with the cessation of phase I in the east (Banješević, 2010). Phase II andesite-basalt and minor andesite magmatism are more voluminous and widespread than phase I. Phase II first occurred in the sub-aquatic environment and was followed with sub-areal activity (Banješević, 2005; Milovanović et al., 2005; Banješević, 2010). Phase II included Middle Campanian monzonite, monzodiorite, diorite, granodiorite, quartz-diorite and their porphyritic varieties. The most substantial intrusion - Potaj Čuka monzonite outcrops on over ~20 km2. Adjacent sedimentary country rocks are thermally altered to form skarn, hornfels, and marble (Milovanović et al., 2005). Several Cu-(Au) porphyry and epithermal deposits formed during this stage (e.g., Lipa, Čoka Kuruga, Valja Strž). Igneous activity in the TMC terminated with the emplacement of small, shallow latite dikes and sills in the western part of the complex (Banješević 2010, Zimmerman et al., 2008). Igneous rocks of the TMC dominantly have a calc-alkaline composition (Ciobanu et al., 2002; Janković et al. 2002; Kolb et al., 2012). Geochronological data suggests that Late Cretaceous magmatic activity in the TMC lasted for approximately 13 million years, from 90 Ma to 77 Ma, with a magmatic front moving from east to west, approaching the subduction zone (Banješević, 2001; Ciobanu et al., 2002; von Quadt et al., 2002; Clark and Ullrich, 2004; Kolb et al., 2012; Tosdal, 2012). Termination of Timok igneous activity in the Late Campanian corresponds with Laramide phase of Alpine orogeny. Carbonate reef sedimentation in the central and southern parts of the TMC and coarse-grained, regressive clastic deposition in the eastern parts followed. The gradual uplifting of the area led to a complete cessation of continual marine sedimentation by the end of the Cretaceous (Banješević, 2006). The youngest rocks within the TMC area are lacustrine and localized shallow-marine Tertiary and terrigenous Quaternary sediments (Dimitrijević et al., 1976). 21 Formation of the TMC and its subsequent modification into present-day elongate lozenge-shape are the consequences of a complex tectonic evolution and multiple compressional and extensional deformation episodes. Proterozoic to Early Paleozoic basement rocks underwent Late Paleozoic Variscan orogeny deformation during which deep-seated N- and NNW-trending faults such as Bor-Brestovac-Tupižnica, Todorova Reka, and Blagojev Kamen-Rudaria faults were initiated. These structures were repeatedly reactivated during the Late Mesozoic Alpine orogeny (Knaak et al., 2014). Tectonic evolution of the TMC is subject to different interpretations including formation in the extensional or transtensional regime associated with the subduction slab roll back (Zimmerman et al., 2008; Kolb et al., 2012). The lozenge-shaped geometry of the TMC, as well as the presence of the arc-parallel faults across the complex, suggest a model where the crustal-scale dextral transtention and the opening of the pull-apart basin are the main controls of the TMC emplacement (Drew, 2005; Knaak et al., 2016). The orientation of the porphyry clusters and the Potaj Čuka monzonite within TMC indicates the importance of the intermittent reactivations of the Paleozoic basement structures (Knaak et al., 2014). Furthermore, fault reactivation facilitated the infiltration of hydrothermal mineralization fluids into the Mesozoic sedimentary rocks. The TMC obtained its present-day shape in the Tertiary due to post-collisional escape tectonics accommodated by oroclinal bending of the Dacia block around the tip of the Moesian platform (Schmid et al., 2008; Knaak et al., 2014), and the segment containing TMC rotated ~30° clockwise. The rotation caused a dextral displacement more than 100 km along major strike-slip fault systems, East Serbo-Macedonian on the west and Timok and Cerna on the east (Knaak et al., 2016). During late phase oroclinal bending in the Early Miocene, orogen-parallel extension produced E-W striking normal faults. Such structures played a significant role in the preservation of the Bigar Hill deposit, within the graben. A simplified tectonic map of the TMC is shown in Figure 2.4. 22 2.2.3 Metallogeny of the TMC Prospecting for gold and copper in the region date back to the Bronze Age. In Roman times, people mined gold from placer deposits as well as from primary quartz veins down to 20 to 30 m deep in underground adits. Modern exploration and mining have been successful in this region for over 100 years (Janković et al., 2002). Figure 2.4: Simplified tectonic map of the TMC with the position of mineral deposits and major deposits trends (modified from Knaak et al., 2016). 23 Four temporally and spatially distinct metallogenic trends within the TMC distinguished based on the mineralization type include from east to west: (1) Bor-Veliki Krivelj-Majdanpek Cu-Au porphyry, high-sulfidation trend; (2) Kuruga high-sulfidation Cu-Au trend; (3) Western porphyry trend; and (4) sediment-hosted disseminated gold trend on the northwestern margin of the TMC (Knaak et al., 2016). The fourth sector constitutes a newly recognized mineralization type in Serbia (Figure 2.4). 2.2.3.1 Bor - Veliki Krivelj – Majdanpek Cu-Au Porphyry, High-Sulfidation Trend The easternmost trend comprises several porphyry deposits, including the world-class Majdanpek, Veliki Krivelj, Borska Reka and Cerovo deposits as well as the recently discovered Čukaru Peki deposit. Some porphyry deposits occur with massive sulfide ores, e.g., Bor and Čukaru Peki deposits. Mineralization is typically hosted by hydrothermally-altered coherent and volcaniclastic hornblende-biotite andesite that have been intruded by porphyritic dikes of granodioritic, quartz-dioritic to dioritic composition (Janković, 1990; Koželj, 1999). The porphyry ore bodies consist of stockwork, stockwork-disseminated and disseminated sulfide mineralization. The mineral paragenesis comprises pyrite and chalcopyrite as dominant sulfide phases. Molybdenite is a minor phase, sporadically containing anomalously high Re concentrations (up to 3,000 ppm in Majdanpek). The copper grade of most of the deposits is up to 0.8% Cu. Gold occurs in pyrite and chalcopyrite, with typical grades of <0.25 ppm. Molybdenum grade is usually <150 ppm (Janković, 1990). Massive sulfide ore in telescoping porphyry deposits is mainly composed of chalcocite, covellite, and enargite with 3-6% Cu and 1-3 ppm Au. Zimmerman et al. (2008) constrained the mineralization ages of these deposits to 87.9 – 83.4 Ma, using Re-Os molybdenite technique. The mineralization age at the easternmost Veliki Krivelj deposit is the oldest (87.9 ± 0.5 Ma), while the Majdanpek mineralization is the youngest (83.8 ± 0.5 to 83.4 ± 0.5 Ma). The mineralization age at Bor is between 86.2 ± 0.5 and 85.9 ± 0.4 Ma. The mineralization ages coincide with the end phase of Late Turonian-Santonian magmatic activity (phase I) of the TMC. 2.2.3.2 Kuruga High-Sulfidation Cu-Au Trend The Kuruga high-sulfidation Cu-Au trend of the TMC includes the economically important Čoka Kuruga, and Lipa deposits. Deposits formed within hydrothermally-altered hornblende-phyric andesite. Mineralization occurs as massive, stockwork, disseminated, transitional stockwork-disseminated, local veins and veinlets (Janković, 1990). Pyrite is the most abundant mineral in these epithermal deposits, while enargite is the primary source of copper (Koželj, 1999). Gold is a significant ore constituent and is present in pyrite, copper-bearing sulfides, barite or quartz. The diorite porphyry beneath the Čoka 24 Kuruga deposit has a U-Pb zircon age of 83.6 ± 0.4 Ma (Tosdal, 2012), consistent with the second magmatic phase of the TMC (phase II). 2.2.3.3 Western Porphyry Trend The western porphyry trend is at the western end of the TMC and contains Au and Cu-Au deposits and occurrences along the northeastern, eastern and southern edges of the Potaj Čuka monzonite pluton. The most significant porphyry deposits are Valja Strž, Dumitru Potok, Kraku Riđi, Crna Reka (all Cu-Au deposits) and Čoka Rakita (the only Au-only bearing system). Dikes and sills associated with the deposits have mainly dioritic but also quartz-dioritic and granodioritic compositions and intrude andesite and andesitic agglomerates, breccia and epiclastic rocks of phase II. Mineralization has low to moderate Cu-Au or Au grades and occurs in quartz and quartz-pyrite stockwork veins. Pyrite and chalcopyrite are the major sulfide minerals, while molybdenite, bornite, galena, and sphalerite are present in the less significant quantities. Au occurs with pyrite and chalcopyrite; its grade is higher where these minerals form dense stockwork systems, particularly within the potassic core. In the Au-only deposit, gold is associated with pyrite and alloyed with silver (Avala Resources Ltd., 2010-2014). 2.2.3.4 The Sediment-hosted Disseminated Gold Trend The westernmost mineralization trend is located on the NW margin of the TMC and contains three Au deposits: Bigar Hill, Korkan, and Kraku Pešter. The Bigar Hill deposit is positioned north of the Potaj Čuka pluton at the margin of the thermal contact aureole. The Korkan deposit is located farther north from Bigar Hill, and the Kraku Pešter deposit is within the thermal aureole of the Potaj Čuka monzonite pluton at the northwestern tip of the intrusion. Au mineralization at the Bigar Hill and Korkan deposits are dominantly in the Cretaceous sedimentary sequence. At the Kraku Pešter deposit, mineralization is in brittle deformed rocks composed of sulfidized fault breccia formed in both thermally metamorphosed sedimentary rocks and monzonite (Avala Resources, 2014). Late Cretaceous magmatic features, including porphyry Cu-Au deposit clusters (Kraku Riđi, Dumitru Potok, Čoka Rakita, Valja Strž) occur in proximity to SHDG deposits, a few kilometers to the east within the TMC (Figure 2.5). Geologic map of the Bigar Hill area is shown in Figure 2.6. 25 Figure 2.5: Geologic map of the NW part of the TMC, with the position of the SHDG deposits (Bigar Hill, Korkan and Kraku Pešter), adjacent porphyry Cu-Au deposits (Kraku Riđi, Dumitru Potok, Čoka Rakita, Valja Strž) and Potaj Čuka monzonite pluton. Geolines from Avala Resources, 2012. 26 2.3 Host Rock Lithology and Stratigraphic Sequence Rock descriptions for the Bigar Hill lithostratigraphy are based on drill core logging, petrographic studies on selected thin sections and geochemical data. The stratigraphic column of the lithologies for the Bigar Hill area is in Figure 2.7. The main rock units are described in details below. 2.3.1 Paleozoic Metamorphic Rocks (MPH) The Paleozoic crystalline basement is the oldest unit (Dimitrijević et al., 1970). Basement occurs immediately west and southwest of Bigar Hill and does not outcrop, but several drill holes intersected it. The unit is truncated in the east by steeply-dipping, normal faults, that juxtapose the unit against younger, Jurassic limestone. The depth of the transgressional basement and limestone contact is uncertain but must be >300 m. The unit consists of Paleozoic phyllites and subordinate meta-sedimentary sequence composed of sandstone, shale, and conglomerate. When fresh, phyllite is Figure 2.6: Geologic map of the Bigar Hill area with the locations of drill holes sampled for this study, including the holes from non-mineralized prospects Korkan West and Korkan South (inset, right). Grey line outlines 0.5 ppm Au mineralization shell. Geolines from Avala Resources, 2012. 27 dominantly grey to black, locally green, but in the weathering conditions it obtained tan or red color. Main components are fine-grained mica minerals, quartz, feldspar, and chlorite. Phyllite is foliated with the parallel, flat or wavy alignment of muscovite or sericite. Figure 2.7: Stratigraphic column of the Bigar Hill deposit area. 28 2.3.2 Late Jurassic Limestone (JLS) The Late Jurassic carbonate sequence has a large areal extent but does not outcrop within the deposit domain. However, the carbonate sequence has an erosional exposure to the north and south of the deposit which is buried along E- trending faults. Drill holes indicate the thickness of the unit to be >300 m. Except for tectonic contact with older basement unit, registered in the southwestern part of the deposit, the character of the depositional contact between the two units is uncertain. Regionally, the deposition of carbonate sequence was preceded by transgressive sedimentation of basal conglomerate Figure 2.8: Bigar Hill lithologic units: (a) Jurassic (Tithonian) limestone; (b) Early Cretaceous “dirty” limestone with black chert; (c) Basal breccia with limestone fragments and very fine-grained groundmass rich in pyrite or oxidized; (d) Alternation of siltstone/mudstone with fine-grained sandstone; (e) S1 carbonate sandstone with stylolite seams parallel or perpendicular to bedding; (f) S2 volcanic detritus-rich sandstone to granulite; (g) Marl with laminas of organic matter; (h) Hornblende-plagioclase phyric andesite intruded as sill in marl. 29 and sandstone (Dimitrijević et al., 1970; Banješević, 2006). The Late Jurassic sequence encompasses the Oxford-Kimmeridgian and Tithonian carbonate rocks whose age is defined paleontologically (Dimitrijević et al., 1970; 1976). Due to their compositional and textural similarities as well as the negligible importance as mineralization host rocks these two units are grouped and studied together. The Oxfordian-Kimmeridgian carbonate rocks dominantly contain micritic limestone, and subordinately dolomite and limestone-dolomite. Rocks are grey to pink, with chert nodules of similar color. The conformably overlying Tithonian unit is dominantly composed of massive or bedded reef limestone that varies from white, light gray, yellow to pink (Figure 2.8a). Limestone with coarse-grained sparite cement dominates over the fine-grained micritic-cemented limestone. Depending on the different components such as carbonate fragments (intraclasts), fossils or pellets, the Tithonian limestone occurs as intrasparite, intrabiosparite, pelsparite and pelbiosparite (Folk, 1959; Vasić, 2012). X-ray powder diffraction indicates that the Tithonian limestone is pure, with CaCO3 content from 97-100% (Vasić, 2012). Non-carbonate constituents include clay minerals and organic matter. Non-carbonate components, as well as terrigenous quartz, pyrite or Fe-hydroxides, are present in stylolite seams, which are characteristic of these rocks. 2.3.3 Early Cretaceous Limestone (KLS) The Early Cretaceous limestone underlies the Bigar Hill deposit and extends regionally. The unit is up to 100 m thick and lies unconformably on top of Jurassic carbonate rocks. Regionally, the KLS contains Valangian-Hauterivian and Barremian-Aptian limestones dated by fossil fauna (Dimitrijević et al., 1970; 1976). The older, Valanginian-Hauterivian or “dirty” limestone comprises bedded, black to grey limestone (Figure 2.8b). Micritic limestone dominates, such as biomicrite and intrabiomicrite, while dolomite has a minor abundance. Layers rich in organic and very fine-grained clastic material are black and very prominent, several centimeters to several tens of meters thick. CaCO3 content in limestone ranges from 70-97% (Vasić, 2012). Geochemical differences between the Jurassic and Cretaceous limestone is in figure 2.9. Chert concretions and nodules are black, dark gray or brown, ranges from cm to dm size, and are characteristic features of this unit. Stylolite seams contain organic matter, clay or very fine-grained pyrite. A younger Barremian-Aptian limestone is a significant component of the Early Cretaceous carbonate sequence in the wider TMC region forming several hundred-meter-thick packages (Dimitrijević, 1976), however it occurs only in the eastern part of the Bigar Hill and is otherwise eroded, or present as fragments in the overlying breccia from the younger, clastic S1 unit. Barremian-Aptian 30 limestone is grey to light grey, massive to bedded, and highly stylolitized. It contains sparite varieties such as intrabiosparite and biosparite. Both Jurassic and Cretaceous limestone were exposed to karstification. Dissolution primarily affected their respective upper unconformities or developed along fault and fracture zones or bedding planes. Karstification process increases porosity and permeability of the otherwise compact limestones with tightly packed components. Figure 2.9: Background values for major and immobile elements in non-altered JLS (215 samples) and KLS (466 samples) with Au<0.01ppm; Avala Resources data set. 2.3.4 Carbonate-siliciclastic unit (S1) The carbonate-siliciclastic unit, informally named the S1, is a basal clastic sequence continuously deposited within the Bigar Hill area. It is up to 200 m thick. The S1 was deposited unconformably on the limestone and commenced with the Albian transgression. The Albian age of the unit is determined paleontologically (Dimitrijević, 1976). The S1 outcrops in the western area of the deposit. This unit is divided into three sub-units: (1) basal breccia (BBX), (2) siltstone to mudstone member (IB), and dominant (3) calcareous sandstone to sandy limestone member (S1). 31 Basal breccia (BBX) forms the base of the Albian S1 sequence. Breccia is laterally discontinuous and is not present along the entire basal contact with the underlying limestone. The thickness of this sub-unit varies from a few meters to approximately 50 meters. It is the thickest in the central part of the deposit, and it is not formed in the northwestern part. The breccia is heterogeneous and poorly sorted, includes both matrix- and clast-dominated facies (Figure 2.8c). It comprises fragments of the bioclastic Barremian-Aptian limestone and, to a lesser extent, of the older, Valenginian-Hauterivian limestone, with quartz and other metamorphic rock-derived pebbles (e.g., schists, gneiss) embedded in a carbonate cement. Limestone clasts have a wide variation in size, from mm-scale pebbles to decimeter-scale cobbles and boulders which are primarily angular or weakly rounded. Well-rounded quartzite pebbles of various size originate from the crystalline basement. The breccia matrix is heterogeneous and highly variable in both grain-size and composition. It includes fine- to very coarse-grained sandy, as well as sandy-gravel to gravel or silt fraction. Interbedded siltstone to mudstone member (IB) lies unconformably on top of the KLS, BBX, or in the form of a laterally-variable, discontinuous lens within or below the S1 sandstone. Thickness ranges from a few centimeters to 30 meters, irregularly distributed within the deposit stratigraphy. The IB sub-unit is not developed in the northwestern part of the deposit stratigraphy and generally is very thin in the northern area. The stratigraphic transition to the upper S1 sandstone member is gradational, with decreasing silty and increasing sandy fraction. The most abundant lithologies are black, laminated siltstone or mudstone that alternate with fine- to medium-grained calcareous sandstone (Figure 2.8d). Breccia bodies with limestone fragments in siltstone matrix occur locally. The IB member is composed of terrigenous quartz grains and phyllosilicate minerals, predominantly sericite and muscovite, with lesser biotite and chlorite. Phyllosilicate laths are sub-parallel with the lamination planes. Coarser interbeds contain more carbonate cement than siltstone or mudstone; organic matter and diagenetic pyrite are abundant in fine-grained interbeds. Diagenetic pyrite occurs either as individual grains or as several mm-scale accumulations. The IB member was locally affected by the soft sediment deformations. The S1 calcareous sandstone-sandy limestone is the most abundant member within the S1 sequence, laterally continuous but with variable thickness, ranging from 30 to 150 m going from southeast to northwest. The S1 sub-unit lies unconformably over the Cretaceous limestone, basal breccia (BBX) or has a gradational transition to IB lenses. The rocks vary from well bedded to locally cross-bedded sandy limestone, to calcareous sandstone (Figure 2.8e). The main constituents are: terrigenous material including quartz and other fragments of metamorphic rocks, white mica, also carbonate components - 32 limestone fragments and carbonate fossils. Detrital material is cemented by calcite, or to a lesser extent by dolomite. Terrigenous components vary in granulometry from fine- to medium-grained size. Coarse-grained clastic material occurs locally. Stylolites are a notable feature of the S1 sub-unit, and in addition to pyrite, also contains clay, organic matter, or iron hydroxides. They occur as seams that are (sub-) parallel to bedding planes and likely formed under lithostatic pressure dissolution. They also occur oblique to the bedding planes and likely formed during deformation related stress (Vasić, 2012). 2.3.5 Carbonate and volcanic detritus-rich siliciclastic unit (S2) The volcanic detritus-rich, calcareous siliciclastic unit, informally named S2, has a continual distribution within the Bigar Hill stratigraphic sequence. Unit S2 is 15 to 70 m thick sequence deposited unconformably on the erosional surface of the S1. The S2 outcrops in the western area of the deposit. The Late Cretaceous age of the unit is indirectly determined by U-Pb dating of detrital zircons done for this study. The S2 unit is composed of reddish, green or light grey, bedded, coarse- to medium-grained sandstone. The conglomerate occurs locally as basal beds up to 5 meters thick (Figure 2.8f). Sandstone and conglomerate typically comprise dominant quartz, detrital volcanic fragments of andesite and its groundmass or phenocrysts (plagioclase and hornblende), limestone fragments, hematite, and subordinate fragments of quartzite, schists, re-deposited S2 sandstone or detrital phyllosilicates (muscovite, clay minerals). Detrital magnetite is locally concentrated in the form of the thin laminae. Cement is mainly composed of calcite or, rarely of dolomite. Detrital pyrite is present within the carbonate cement. Chapter 3 provides a more detailed characterization of the S1 and S2 sandstones. 2.3.6 Marl (SMR) Marl (SMR) conformably overlies S2 unit or alternates with it within the transitional zone. The overall unit thickness ranges from a few meters to 150 m. Sub-volcanic andesitic sill intruded and caused weak thermal alteration on marl. In the central and partly eastern area of the deposit, marl above the andesite is eroded. Santonian age of the unit is defined by paleontological data (Dimitrijević et al., 1970; 1976; Vasić, 2012). Marl is finely-laminated, light grey, light green, or red with laminations differing in color, thickness, and composition. The main constituents are terrigenous or calcareous (Figure 2.8g). Terrigenous components are part of clayey, silty or very fine-grained sandy fraction. Quartz is the most abundant constituent of the sandy fraction while volcanic and metamorphic rock fragments or minerals (i.e., plagioclase) are represented to a lesser degree. Phyllosilicate minerals, particularly white mica abundance is notable; their general orientation is (sub-) parallel to the lamination planes. Carbonate 33 materials are with debris and carbonate cement. X-ray diffraction results indicate that CaCO3 content varies from 35 to 65% (Vasić, 2012). 2.3.7 Andesite (VOL) Andesitic sill (VOL) is a sub-volcanic intrusion that cuts the marl unit. Sill intruded towards west within the eastern section of the deposit. Andesite is exposed over the area of ~300 x 100 m at the top of the Bigar Hill, due to the erosion of marl. Locally, in the southeastern section, lower intrusive contact is with the S2 unit. Andesite is dark grey to grey-green, medium-grained, and porphyritic, with amphibole (hornblende) ≥ intermediate plagioclase (andesine) phenocrysts (Figure 2.8h). Accessory minerals include quartz (up to 2%), apatite, zircon, Fe-Ti oxide, and Fe-sulfide. Andesite contains veins of calcite, or rarely gypsum or zeolite. 2.3.8 Other Intrusive and accompanying Metamorphic Rocks Several, few meters wide diorite dikes (GDI) cut the deeper parts of limestone, below the deposit. The dikes occur along the NW and NE trends. The dikes are typically strongly clay altered. Locally, the host rocks are altered to marble (MLS) or calc-silicate rocks (MSC) due to the thermal or metasomatic impact of the small dikes. Kraku Riđi, Čoka Rakita, and Dumitru Potok swarms of hornblende-plagioclase-phyric diorite porphyry are proximal to the deposit, located 1-5 km to the east or southeast (Figure 2.5). Porphyry clusters are aligned along NW to N trends (Knaak et al., 2012). 2.4 Hydrothermal Alteration Circulating hydrothermal fluids introduced chemical, thermodynamic and physical changes to the host rocks that resulted in the degradation of primary minerals, the formation of new alteration minerals and the deposition of gold. Unlike high-temperature hydrothermal deposits, alteration haloes around the low-temperature Bigar Hill deposit are subtle, often coinciding with the gold mineralization. Dominant types of host rock alteration at the Bigar Hill include carbonate dissolution which results in decarbonatization, silica addition (silicification), clay alteration of primary silicate minerals, and sulfidation which accompanied gold deposition. 2.4.1 Carbonate Dissolution Carbonate dissolution or decarbonatization is a typical alteration feature of Carlin-type deposits (e.g., Radtke et al., 1972; Stenger et al., 1998; Cail and Cline, 2001). It is a process of partial to complete dissolution and redistribution of the host rock carbonate components, primarily calcite cement, by acidic 34 fluids. Fluid acidity, temperature and the degree of fluid-rock interaction control the extent of alteration (Cline et al., 2005). Carbonate dissolution causes a wall rock volume decrease and the formation of secondary porosity and permeability that leads to the secondary enrichment of insoluble minerals such as quartz, clay minerals, and organic matter. Drill core samples subjected to hydrochloric acid reaction tests, along with petrographic analyses, indicate that the most intensive calcite dissolution affected rocks at the immediate contact of the S1 and S2 sedimentary units (Figure 2.10). Dissolved carbonate material was redistributed and precipitated in fractures within and around the primary zone of intensive alteration. Calcite veins appear in stockworks or as individual veins, with thickness up to several tens of cm, and increase towards the mineralization. Decarbonatization occurs with the extensive hydrothermal pyrite deposition in high-grade gold zones. Carbonate dissolution zones also, to a various degree, contain the products of clay alteration and silicification. Figure 2.10: Carbonate dissolution in mineralized rocks: (a) hand sample with complete carbonate cement removal from the S1 sandstone, showing secondary porosity; this sample also exhibits silica addition; (b) hand sample of the S2 sandstone that underwent complete carbonate dissolution, with quartz grain framework and hydrothermal pyrite remaining; (c) transmitted light photomicrograph of completely dissolved sparry calcite cement, with quartz (qz) and clay minerals (cy) remaining in S1 sandstone; (d) partially dissolved sparry calcite cement (ca) of basal breccia (outlined with a green line). 35 2.4.2 Silicification Silica addition (silicification) is a typical but not ubiquitous alteration feature of the low-temperature SHDG deposits. In Carlin-type deposits it is manifested as jasperoid or fine-grained, drusy quartz lining vugs; ore-stage quartz veins are relatively uncommon (Cline et al. 2005). At the Bigar Hill, low-intensity silicification is spatially discontinuous and not observed outside of the high-grade gold zones. Silica addition was challenging to identify microscopically due to the prominence of other primary quartz minerals, quartzite fragments and diagenetic silica occurrences in sedimentary host rocks. Some of the non-hydrothermal silica occurrences that complicated the identification of silicification include chalcedony in the kidney-shaped or irregular form within microfossil chambers, also chalcedony irregularly present within carbonate cement. Their origin is assumed to be organogenic or diagenetic (Vasić, 2012). Silicification related to hydrothermal alteration includes cryptocrystalline Figure 2.11: Silica replacement: (a) and (b) hand sample and the transmitted light photomicrograph showing the replacement of carbonate cement or fragments with microcrystalline silica (si cement) in sandstone from the S1/S2 contact zone; (c) and (d) hand sample and the transmitted light photomicrograph of cryptocrystalline silica spatially associated with clay minerals (cy) and pyrite (py) in completely decarbonatized S2 sandstone. 36 quartz replacing calcite cement or carbonate fragments such as fossils, limestone or carbonate mud clasts (Figure 2.11). In intensely altered rocks, hydrothermal silica co-exists with other alteration minerals as a fill in secondary pores created by carbonate dissolution. In these highly mineralized zones, very fine-grained silica intergrows with hydrothermal illite and pyrite. Quartz veins are uncommon at the Bigar Hill. 2.4.3 Clay Alteration The interaction between circulating hydrothermal fluids and the alumino-silicate minerals in Bigar Hill host rocks produced a clay minerals assemblage. This argillic alteration is typical in the andesitic sill, diorite dikes, or in volcanic detritus-rich S2 siliciclastic rocks (Figure 2.12). In the andesite, the degree of clay alteration depends on the cohesion and permeability of the rocks. Pervasive clay alteration is limited to zones of secondary permeability along fault and fracture zones. Clay alteration in calcareous S1 sediments and limestone is low due to rare primary alumino-silicate minerals. Figure 2.12: Clay alteration of alumino-silicate minerals: (a) and (b) hand sample and the transmitted light photomicrograph of clay alteration (cy) in andesite with relicts of plagioclase (pk); (c) and (d) hand sample and the transmitted light photomicrograph of clay alteration (cy) in S2 sandstone, showing a visibly altered volcanic fragment with remnant hornblende (hb) and plagioclase (pk). 37 2.4.3.1 Clay Identification Clay minerals were identified using short-wave infrared spectroscopy (SWIR) on 302 drill-core samples (Appendix C). Samples were collected from Bigar Hill and also from the non-mineralized Korkan West and Korkan South prospects, which are located near Bigar Hill and share the same stratigraphy. Drill hole collars for analyzed samples are shown in Figure 2.6. Barren prospects were also sampled to establish the background clay mineralogy (i.e., clays that have not resulted from hydrothermal alteration). Samples are collected from each lithologic unit and in the case of the Bigar Hill from both non-mineralized and mineralized rocks. SWIR spectra reveal that illite is the dominant clay species at the Bigar Hill. Other clays, in various proportions, include kaolinite and montmorillonite, with infrequent dickite, nacrite, halloysite, and palygorskite. The main clay species in non-mineralized samples (<0.1 g/t Au) from Bigar Hill are illite, kaolinite, and montmorillonite. In mineralized samples (>0.1 g.t Au), illite dominates, with or without minor kaolinite (Figure 2.13). Montmorillonite is present in samples with low grade (0.1 – 1 g/t Au) but is absent in highly mineralized samples (>1 g/t Au). Detrital muscovite or sericite occurs in non- or weakly altered siliciclastic rocks. Samples from the Korkan West and Korkan South prospects contain montmorillonite, illite+montmorillonite and illite. At these prospects, the montmorillonite proportion is higher overall than at Bigar Hill. Other minerals such as kaolinite, palygorskite or muscovite are sparse and isolated. 38 Figure 2.13: General element ratio diagram indicates the correlation of gold mineralization with illite alteration; Correlation is based on approximately 4,000 samples from the S2 unit and andesite; Avala Resources data set. 2.4.3.2 Illite Crystallinity as a Mineralization Vectoring Parameter Hydrothermally-formed clay minerals and their variable characteristics reflect changes in the alteration system of the host rocks. For example, the progression from smectite (montmorillonite) to illite-smectite and illite is generally attributed to increasing temperature (Hofstra and Cline, 2000) because illite crystallinity is higher temperature-dependent (Ji, Browne, 2000). Illite can thus be used as a vector towards mineralization by indicating pathways of higher temperature fluid movement. The illite crystallinity index is defined as a ratio of the depths of 2200 nm and 1900 nm absorption features in the mineral SWIR spectra, as calculated using The Spectral Geologist© (TSG) interpretative software on data obtained with the TerraSpec® analytical spectral device. The crystallinity index for illite from the Korkan West and Korkan South prospects is relatively low, up to 0.6. Illite from the Bigar Hill exhibits a wide range of index values, from 0.1 up to 2.2. In non-mineralized samples (<0.1 g/t Au) crystallinity index varies from 0.1 to 2.2 and in mineralized samples (>0.1 g/t Au) it ranges from 0.3 to 2.2. 39 Although the increase in crystallinity index with gold mineralization is subtle, it shows higher values in relation to non-mineralized prospects (Figures 2.14 and 2.15). The link between the increasing illite crystallinity index with gold grades emphasizes the hydrothermal origin of illite and its formation as an alteration product of feldspar, muscovite or montmorillonite. However, particularly in clastic rocks, illite could also be the product of supergene or diagenetic processes or could have a detrital origin (Ruiz Cruz, 2006). The highest crystallinity index values (>2) might be related to high-temperature hydrothermal processes and the increasing illite crystallinity with increasing temperature (Gharrabi et al., 1998). However, the more extreme high index values are likely associated with detrital muscovite or illite-muscovite transition varieties likely originating from the Proterozoic metamorphic complex that, in addition to limestone and andesite rocks, is the main protolith for clastic rock units. Figure 2.14: Box plots representation of the illite crystallinity index ranges depending on the gold grade. 40 Figure 2.15: Box plots of illite crystallinity and gold grade ranges in samples from drill holes from the Bigar Hill ore and distal, non-mineralized zone, and distal, non-mineralized Korkan West and Korkan South areas. Drill hole locations are shown in Figure 2.6. 2.4.4 Sulfidation and Gold Mineralization Pyrite is the dominant sulfide mineral in the deposit. Pyrite occurs in the form of individual grains, from 1 mm to couple of μm in diameter, to aggregates disseminated throughout host rock. Pyrite morphology varies from euhedral to anhedral, often porous or framboidal. Pre-ore pyrite is coarse-grained, of brassy 41 color and is mostly in the S2 sandstone. Fine-grained diagenetic pyrite is in organic-rich stratigraphic units, such as marl or mudstone. Pyrite is abundant in mineralized zones, but its μm size and dark sooty color make it difficult to recognize it in hand samples. In highly mineralized domains, sulfide minerals are typically concentrated Figure 2.16: Photomicrographs of pyrite morphology in mineralized rocks: (a) pyrite replacing hornblende in altered andesite; (b) pyrite associated with clay (illite?) alteration in the S2 sandstone; (c) pyrite disseminated in the S2 sandstone, replacing altered volcanic fragments; (d) distribution of pyrite of different grain sizes in decarbonatized S1 sandstone; (e) pyrite formed on the calcite from the S1 sandstone cement; (f) abundant pyrite in the fine-grained BBX breccia matrix. 42 with hydrothermal illite in secondary pore spaces that formed through carbonate dissolution. Thin sections show pyrite replacing sparry calcite or dolomite cement, Fe-bearing alumino-silicates such as hornblende (and its alteration product – chlorite), microfossils and carbonate mud fragments. Pyrite also occurs in stylolites, fractures, and micro-fractures in structurally deformed zones (Figure 2.16). Rarely, pyrite occurs within calcite veins. Sulfidation reaction is the major mineralization mechanism (Hofstra and Cline 2000; Cline et al., 2005). Gold is “invisible,” and present as structurally bound Au1+ in the lattice of pyrite. Also, gold occurs as sub-μm to 50 μm inclusions within pyrite crystals, mainly as native gold, or rarely as electrum, kustellite or calaverite (Pačevski, 2012). In surficial weathering oxidized conditions, gold is in goethite formed on pyrite. Distribution of gold in pyrite and its oxide is shown in Figure 2.17. At Bigar Hill gold is part of the low-temperature metal assemblage which includes Sb, Tl, Hg, Te and As, similar to most Carlin-type deposits (e.g., Stenger et al., 1998; Hofstra and Cline, 2000; Muntean et al., 2011). There is a moderate correlation between Au and Se, Ag and W. Elements enriched with gold do not form economically interesting concentrations or minerals but represent trace level pathfinder elements. Figure 2.17: Scatter plot of Fe vs. S from the Bigar Hill samples with Au content > 1ppm. Samples with gold hosted by pyrite are plotted near the x=y line (1 to 1 ratio corresponds to the ratio of Fe and S in pyrite). Samples with gold hosted by goethite are aligned along the y=0 line. Avala Resources data set. 43 2.4.4.1 Metal distribution on the Bigar Hill The spatial distribution of gold, its correlation with the other pathfinder elements, and their distribution within Bigar Hill was evaluated using data from the geochemical database from Avala Resources Ltd. The database comprises data for approximately 50,000 1 m samples from 87 diamond and 125 reverse circulations (RC) drill holes. Gold and sulfur concentrations were obtained from 1 m samples while 52 additional elements were analyzed on 5 m samples of the split core or RC chip samples. Samples were digested by aqua regia and analyzed by fire assay with atomic absorption spectrometry finish for gold grade determination, or by atomic absorption or inductively coupled plasma mass spectrometry for the other elements. Chapter 1 provided a detailed overview of the analytical process (Section 1.5.3). The distribution of gold within the Bigar Hill deposit is complex; it occurs in all lithological environments in various quantities. However, gold is concentrated principally along two contact zones within the Cretaceous sedimentary rock sequence. The major mineralized horizon extends laterally along the contact between the S1 and overlying S2 unit, outcropping along the western part of the deposit and dipping towards the east. A discontinuous, lower gold-bearing horizon occurs along the unconformable contact between the Cretaceous (or Jurassic) limestone and overlying S1 calcareous siliciclastic unit, mainly where there is basal breccia in the S1 or karst features in limestone. Minor gold precipitation also occurs along steeply-dipping fault and fracture zones that cut through the deposit. Structurally-controlled mineralization is in the otherwise barren andesite. Stylolite fractures in limestone and calcareous clastic rocks of the S1 are also favorable locations for gold concentration. Siltstone and mudstone from the IB sub-unit are generally poor host rocks, with sparse mineralization only in fault zones. Similarly, the marl, which is considered to be an aquiclude, may represent a “cap-rock” to the hydrothermal system and thus a poor mineralization host. Examples of mineralized rocks are shown in Figure 2.18, and geological cross-section illustrating the distribution of gold mineralization is shown in Figure 2.19. At Bigar Hill, gold occurs along the two orthogonal mineralized trends, NW and NE (in map view). In cross-section, however, gold is not well distributed vertically across the section and is absent from some lithologic units. The highest grades in andesite are in the SE part of the deposit, along the NW-trend. Mineralization in marl and S2 extends along the NE direction, while the S1 unit host gold along both trends. Gold in limestone is primarily concentrated at the intersection of two trends, as well as in the SE part of the Bigar Hill. 44 Trace metals are also concentrated along NW and NE trends. Prominent NW alignment of increased values of Bi, W, Pb, Zn, In, Cd, Se, Te occurs in limestone. In the upper, clastic units, the NE trend has elevated values of the low-temperature elemental association As, Hg, Tl, Sb, Te. In volcanic rocks, Figure 2.18: Mineralized rocks from the Bigar Hill deposit (samples from drill core): (a) “Dirty” Cretaceous limestone, with fractures filled with secondary calcite; (b) Karst formed on the top of the Cretaceous limestone, with secondary porosity resulting from the carbonate dissolution; (c) Basal breccia with pyrite rich fine-grained matrix; (d) Decarbonatized S1 sandstone; (e) S2 coarse-grained clastic rock, located just above the contact with the S1; exposed to carbonate dissolution, clay alteration and sulfidation; (f) Strongly clay altered S2 sandstone, with visible pyrite nests; (g) Strongly decarbonatized and oxidized S2 sandstone; (h) Strongly clay altered andesite with pyrite accumulations. 45 anomalous concentrations of As, Sb, Te, and Ag occur with gold mineralization in the SE part of the NW trend. Figure 2.19: NW-SE geological cross-section through the Bigar Hill deposit, with the 0.4 grade shell outline in black line. 46 CHAPTER 3 – STRATIGRAPHIC AND STRUCTURAL CONTROLS ON THE BIGAR HILL GOLD MINERALIZATION 3.1 Introduction Gold mineralization distribution at Bigar Hill emphasizes the likely combined influences of structural and stratigraphic features. The geological architecture of the area encompasses: (1) Carbonate sedimentary sequence, with domains of physical and chemical characteristics that favorably facilitated gold deposition, such as increased porosity and permeability, as well as high carbonate content and sufficient concentrations of reactive iron. These features enabled circulation of gold-bearing hydrothermal fluids and reactions between fluids and the host rocks; (2) Structural framework with intersecting fault planes of varying significance, including first-order feeder faults that channeled Au-bearing fluids from the source region; second-order faults that provided pathways for fluids infiltration to favorable horizons; and post-mineral faults that changed the shape of the ore body. 3.2 Stratigraphic Control on Gold Distribution The composition, textural characteristics of the gold-hosting rock units, and their depositional contact zones with each other all represent stratigraphic features that control the spatial distribution of gold mineralization. A detailed review of these features is provided below. 3.2.1 Petrographic Characterization of the S1 Sub-Unit and S2 Unit The erosional contact zone between S1 and S2 units hosts the most continuous gold-bearing zone and also hosts the highest gold grades. Petrography of these units evaluated their textural and structural features and composition. 3.2.1.1 Sub-Unit S1 Characterization The composition of the S1 sub-unit ranges from sandy limestone to carbonate sandstone. The constituents of these rocks are: (1) terrigenous clasts such as: quartz (5-75% of the rock), metamorphic lithoclasts, dominantly quartzite with lesser schists and gneiss (up to 5%), muscovite (up to 10% in finer-grained rocks); (2) allochemical clasts (up to 50% of the sediment), including bioclasts (remains of whole 47 or fragmented calcareous fossils such as algae, bryozoans, bivalves, foraminifera) and intraclasts (lumps of carbonate mud); and (3) carbonate cement, usually composed of very fine to very coarse-grained sparry calcite, seldom of dolomite; in a hydrothermally-altered rock, carbonate cement is dissolved, locally replaced with silica. Sorting of clastic material in sandstone varies from poor to moderate. Terrigenous clasts have a wide range of shapes (dominantly spherical to sub-prismoidal) and different degree of roundness (usually sub-angular to sub-rounded). Clastic components are mainly medium to fine-grained (0.125 to 0.5 mm). Influxes of coarse-grained material produced relatively frequent but thin layers, up to several centimeters. Gravel and pebble-sized grains are sparse. Although sediments of different grain size alternate, the overall grain size in these rocks generally increase up section. Depending on the abundance of terrigenous and carbonate material, sedimentary facies are classified as bio- to intra-biosparite and calcareous sandstone (Figure 3.1). Rocks with >50% of terrigenous components are sandstones, and >50% of calcite defines limestone. If the content of the sandy component is >10%, limestone is sandy. Visual identification of these lithotypes is a difficult task, but according to microscopic analysis, clastic varieties generally occur in the lower part of the S1 sub-unit. Samples from this part of the sub-unit contain below 35% of calcite and correspond to calcareous sandstone. In the samples from the upper part, calcite content exceeds 65% of calcite, which determines these rocks as sandy limestone (Vasić, 2012). Stylolite seams are abundant in the sandy limestone. Figure 3.1: Lithotypes of the S1 clastic sub-unit: (a) carbonate sandstone with dominant quartz and terrigenous detritus and subordinate carbonate cement; (b) sandy limestone (intra-biosparite) with principal carbonate components, microfossils, carbonate mud lumps, and calcite cement; quartz in this facies is subordinate. 48 3.2.1.2 Unit S2 Characterization The S2 unit is composed of conglomerate, sandstone-conglomerate transitional rocks, and sandstone which is predominant lithotype and represents approximately 90% of the unit (Figure 3.2). Sandstone composition is variable and, depending on the ratio of mineral or rock fragments, quartz and rock matrix, sub-litharenite, volcanic and plagioclase litharenite lithotypes are differentiated. Main forming constituents are: (1) terrigenous clasts: quartz (5-75% of the rock), fragments of andesite (5-60%), fragments of phenocrysts – plagioclase and hornblende (1-30%), metamorphic lithoclasts of quartzite, rarely schists or gneiss (up to 10%), re-deposited S2 sandstone and limestone fragments (up to 5%); detrital phyllosilicates – muscovite, sericite (up to 3%); magnetite; hematite; (2) allochemical clasts: bio- and intraclasts, similar as in a case of the S1 unit, but less abundant (up to 10%); (3) carbonate cement, less abundant than in S1 unit; mainly composed of very fine to very coarse-grained sparry calcite or rarely dolomite. In hydrothermally-altered rocks, carbonate cement is dissolved and locally replaced with silica. Sorting of clastic material in the unit is poor to moderate. Similar to the S1 unit, terrigenous clasts are mainly spherical or sub-prismoidal and sub-angular to sub-rounded. The S2 sandstone has variable grain-size but is principally medium to coarse-grained. Grain size decreases up section. A conglomerate of the same composition as sandstone formed beds up to 5 m thick, mainly in the lower parts of the unit. Quartz and volcanic detritus are the major constituents. Quartz and carbonate material is dominant in the lower levels of the unit, while volcanic material prevails in the upper horizons. The transition between them is gradual. Figure 3.2: Lithotypes of the S2 clastic unit: (a) litharenite with visibly altered phenocrysts of hornblende and plagioclase and minor calcite cement; (b) sub-litharenite from the lower level of the unit, with dominant quartz and carbonate cement, and subordinate volcanic detrital clasts. 49 3.2.2 Petrographic Analysis of Iron Precipitation Combined alizarin red and potassium ferri-cyanide carbonate staining methods are used to determine the presence and distribution of the iron required to precipitate hydrothermal pyrite in calcareous clastic rocks by identifying the iron-bearing carbonates. The carbonate staining procedure is described in Chapter 1. Twenty-seven mineralized and non-mineralized slab samples from the S2 and S1 sandstone, and breccia from the Bigar Hill were stained to differentiate between calcite (red to pink), ferroan calcite (purple to royal blue) and ferroan dolomite (pale to turquoise blue). Staining affected cement, carbonate fragments and veins in sandstone and breccia (Figure 3.3). Slab surfaces mainly obtained uniform color, but different colorations also affected the various carbonate components – cement, clasts or veins. All three types of stained rocks show the variability in the composition of carbonate components. Cement generally has a uniform character, whether it is composed of calcite, ferroan calcite or rarely ferroan dolomite. Clasts are of diverse composition, non-related with the composition of rock cement. Figure 3.3: Carbonate staining of rock slabs to identify iron-bearing carbonate minerals: (a) Ferroan calcite is the dominant component in mineralized S1 sandstone; (b) Ferroan calcite (f ca) is most abundant carbonate component in mineralized S1 sandstone, also minor calcite (ca) and dolomite (do) fragments; (c) Ferroan calcite (f ca) builds breccia cement; clasts are non-stained, most likely of dolomite composition, cut with calcite veins; (d) Mineralized breccia with calcite fragments cemented by ferroan carbonate. 50 Spatially close occurrences of fragments of all carbonate varieties are not uncommon. Carbonate veins are dominantly composed of calcite or rarely of ferroan calcite. Distribution of stained components indicates that the S1 sandstone contains more carbonate than the S2 sandstone which is richer in terrigenous components. Mineralized rocks contain ferroan calcite or, rarely, dolomite. Both ferroan calcite and dolomite were also observed together with non-ferroan calcite. Non-mineralized rocks mostly contain non-ferroan calcite, or rarely, ferroan calcite. Figure 3.4: Isocon diagram represents the mass transfer of components during the fluid-rock interaction. The diagram includes the samples from all the Bigar Hill lithologic units. Study of mass transfer between non-altered and mineralized rocks during the fluid-rock interaction has been conducted using the data set from 59 samples processed by the total whole rock characterization. Isocon diagram (Gresens, 1967; Grant, 1986; Hofstra and Cline, 2000) was defined by immobile elements Zr, Hf, Nb, and Ti and it indicates that the iron is also an immobile component in the Bigar Hill stratigraphic units and its concentration remained the same during the fluid-rock interaction. Isocon 51 diagram that represents the ratio of non-altered (Au<0.01 ppm) and mineralized rocks (Au>0.1 ppm) for all the stratigraphic units and andesite sill is in Figure 3.4. Isocon diagrams for mass transfer in limestone, andesite, S1, and S2 units are in Appendix D. In the units where the iron is an immobile component, carbonate staining confirmed that the ferroan carbonates are the source of reactive iron necessary for hydrothermal sulfidation and associated gold precipitation. To determine the spatial distribution of facies with different iron content in carbonates, more systematic analysis is required. 3.2.3 Enhanced Weathering along Depositional Contacts Within the lower auriferous horizon between limestone and overlying clastic units, gold mineralization occurs in basal breccia of the S1 unit, and in karstified zones near limestone upper unconformity. Breccia and karst features are only locally developed. Karst features in the upper limestone are variable and include favorable high porosity and permeability gold-hosting features such as collapse breccia, limestone dissolution features, and sinkholes that are filled with reactive clastic material. The S2/S1 contact is unconformable as indicated by the S1 paleosurface weathering and erosion where rocks were fractured, brecciated and re-deposited. Physical weathering is evident in the deformed or broken laminae in not fully consolidated fine-grained clastic rocks. Chemical weathering and the formation of an intermittent, red iron-weathering crust on the surface of the S1 is sporadic. Rare occurrences of hematite-rich, altered sandstone are developed to a depth of a few meters. The intermittent presence of the iron-rich crust likely reflects erosion and further transport, particularly since hematite fragments that may represent eroded and re-deposited crust are present in the overlying S2 unit. Combined chemical and physical weathering processes acting upon the S1 surface likely created a favorable zone for the circulation of hydrothermal fluids and gold precipitation by reducing rock stability and increasing porosity and permeability. In contrast, oxidation along the S1/S2 contact zone in the western part of the deposit is linked to post-mineralization weathering process. Iron-hydroxide formed in the reaction of meteoric water and atmospheric oxygen with Fe2+ from hydrothermal pyrite. Oxidation is pervasive, affecting the entire rock or is restricted to the fractures. Intense oxidation affected the part of the deposit where the S1/S2 contact was near the surface, where it was not covered with thick sequences of marl and andesitic sill. 52 3.3 Structural Control on Gold Distribution On the heavily-vegetated surface in the Bigar Hill region, the identification of faults is difficult. Recognized and inferred faults, based on the data from the drill core, have N or E orientations and were observed on the deposit margins. However, the overall structural setting was uncertain. A new structural model was constructed from 2D and 3D spatial analysis of stratigraphic information from the extensive diamond and RC drilling data sets. Stratigraphic contacts, their orientations, and changes in unit thickness and the differing elevations of sedimentary unit contacts were the primary data sources for the model. Stratigraphic information from the drill holes were integrated into a series of stacked sections (Figure 3.5). Since the general dip direction of the sedimentary rocks within the deposit was to the east, and thus most drill hole azimuths are to the west, stacked sections were made in the E-W direction. The distance between parallel sections ranged from 20 to 40 m. Following the 2D analyses, stacked section observations were incorporated into a Leapfrog® 3D model as guides for defining structural blocks. Tracing the changes in thickness and orientation of contact surfaces between the lithologic units was applicable only to the sedimentary units. Importantly, processes and features apart from faulting that could change unit thicknesses were also considered. For example, the shape of a unit’s lower bedding plane could depend on the shape of the upper surface of the underlying rock unit that may differ from the horizontal due to weathering or erosion. As well, primary depositional features and location within a depositional basin could also affect sedimentary unit thickness. Changes in thickness or orientation were used as the indicators of structural discontinuities if they could be traced with lateral continuity and through several sedimentary units. All fault indicators were observed in the drill core to confidently incorporate them into the model. The most prominent changes in the elevation of the Jurassic limestone paleo-surface occur along E-trending, graben-forming faults, along which the entire block hosting the deposit dropped down. On the eastern edge of the deposit area, in a northerly direction, the dip of limestone and the overlying clastic units becomes significantly steeper (~40°) compared to the dip of sedimentary units in the west. This dip change occurs along a previously inferred fault on the margins of the deposit. Within the deposit area, calcareous clastic units had variable thicknesses, elevation, and bedding-plane orientations over short distances, but the magnitude of the dip changes was minor. 53 Basal breccia from the S1 unit is not laterally continuous in the deposit area, varying considerably across short intervals. The thickest breccia (up to 50 m) occurs in the central part of the deposit. A less prominent breccia zones, with a thickness <30 m, occurs in the southeastern part of the deposit area, and as NE-elongated zone across the deposit. In the northwestern deposit area, breccia is thin (up to a few meters) or is not developed. The S1 sub-unit is up to 150 m thick but highly variable. The most prominent feature is the NE-trending break in thickness that decreases from up to 150 m in the northwestern to approximately 30 m in the southeastern part of the deposit. Within the northwestern deposit area, there are numerous subtle changes in the upper surface dip. The elevation of the S1/S2 contact decreases towards NW. Changes in the S2 thickness are opposite to the S1 thickness changes. In the northwestern area of the deposit, the S2 unit is the thinnest, up to a few meters, thickening up to 70 m towards the southeast. Marl is completely, and the S2 unit is partly eroded in the western part of the deposit. Changes in marl’s thickness are obscured by the intrusion of the andesitic sill. Discontinuities in the thicknesses of sedimentary units and the position of their contact surfaces are traced across several additional faults. Newly inferred structures have four orientations: WNW (faults F1 and F3), NE (faults F4, F5, and F6), NNW (fault F2), and E (fault F12). The new fault network interpretation at Bigar Hill with labeled faults is shown in Figure 3.6. 54 Figure 3.5: Phases in building the 3D structural model using the 2D cross-sections across the deposit: (a) Observations of the changes in thickness and orientation of the stratigraphic units on 2D cross-sections, and definition of structural blocks; (b) Inferring a fault network by connecting them in successive cross-sections; (c) Implementation of 2D observations in the 3D model (cross-section exported from the 3D Leapfrog model); (d) Refining the interpretation further in a 3D model (cross-section exported into 2D). 55 Figure 3.6: Bigar Hill block model with the newly developed structural framework. All the faults are labeled with F1-F12. Structures inferred during this study are inferred in several common orientations, including (1) WNW (F1, F3); (2) NE (F4, F5, and F6); (3) NNW (F2); and (4) E (F12). 56 CHAPTER 4 – DECIPHERING FLUID FLOW THROUGH THE APPLICATION OF OXYGEN AND CARBON STABLE ISOTOPES 4.1 Introduction Interactions between carbonate-bearing sedimentary rocks and percolating hydrothermal fluids can lead to mineral replacements and isotope exchange reactions. Thus, hydrothermally-altered rocks may have distinct stable isotope ratios compared to their pristine precursor rocks. The shift in stable isotope ratios of the altered rocks proceeds through to carbonate recrystallization and the formation of additional carbonate veins. Stable isotope alteration of the host rocks to hydrothermal ore deposits has been widely documented in Carlin-type, carbonate replacement, Mississippi Valley-type and skarn deposits (Barker et al., 2013; Vaughan, 2013; Arehart and Donelick, 2006; Levresse et al., 2004; Shanks, 2014). Carbonate minerals and limestone are relatively rich in the 18O isotope (high δ18O) compared to most natural fluids (low δ18O) (Stenger et al., 1998; White, 2015). Consequently, the hydrothermal alteration is mostly accompanied by depletion of the rock in 18O that results in distinct alteration zones characterized by low δ18O values (Stenger et al., 1998; Hickey et al., 2014). The shift to lower δ18O values is typically more pronounced along fluid flow paths that have experienced higher fluid flux and pervasive alteration (Arehart and Donelick, 2006). In contrast, the carbon isotope composition is generally less affected by fluid-rock interaction due to the much lower carbon (CO2 and CH4) concentration of hydrothermal fluids compared to volumetrically more significant carbonate-bearing clastic sedimentary and limestone of rock-buffered system. The complexity of the stable isotope systematics increases with the presence of organic carbon and low alteration temperature which results in strong fluid-solid fractionation and potentially non-equilibrium effects that can yield both apparent depletion and enrichment in 13C (Barker et al. 2013; Beinlich et al., 2017; Arehart and Donelick, 2006). Depending on the amount of fluid involved in ore deposition, 18O isotope alteration (depletion) halos can develop on scales of up to several kilometers from the ore body. These altered depletion zones can be larger than zones of visible alteration and other geochemical haloes and thus can be used as an exploration tool for hydrothermal deposits. This method may be complementary to other, more traditional approaches such as pathfinder element and geophysical studies (Barker et al., 2013). The 57 stable isotope data can be used to delineate fluid flow pathways, establish the extent of its interactions with carbonate host rocks, and to discriminate structurally-controlled from pervasive alteration. This study utilizes the results of 18O and 13C isotopic analyses of the carbonate-bearing rocks from the Bigar Hill deposit to delineate pathways of hydrothermal fluid flow, primarily along (sub-) vertical up-flow zones through high-angle faults, but also laterally along stratigraphically-controlled high porosity and permeability zones. Additionally, the results will be tested against the inferred location of sub-vertical faults that have been established using the 3D deposit model. 4.2 Methodology Six hundred and six samples from 19 drill holes were collected for stable oxygen and carbon isotope footprint analysis. Samples comprise all of the calcareous stratigraphic units (limestone, S1 – basal breccia, sandstone and mudstone, S2 – sandstone, marl). Drill holes were sampled along a ~1100 m long E-W section in the southern part of the Bigar Hill deposit (bounded by northing coordinates 4898157 and 4898187 (WGS 84/ UTM Zone 34N), that transects inferred faults F1, F2, F4, and F5. The location of the analyzed drill holes is in Figure 4.1. Samples were collected after every 5 m interval and included both reverse circulation (RC) chips and pieces of diamond drill core. Samples were collected from the carbonate rock matrix, avoiding calcite veins, to investigate the intensity of wall rock isotope alteration. Twenty additional samples from three drill holes from Korkan West and Korkan South prospects, from the northwest and north of Bigar Hill were also analyzed. Rock units of the Korkan prospects are identical to those of the Bigar Hill but are considered to be relatively unaltered and were therefore collected to establish local δ18O and δ13C isotope background values. The stable oxygen and carbon isotope dataset were complemented with the corresponding gold and trace element data in order to delineate hydrothermal fluid pathways and to constrain the role of structural permeability on mineralization. The gold and sulfur dataset is from 1 m samples, and trace element data are from 5 m composite samples that were obtained from Avala Resources Ltd. Gold values were available for all the analyzed drill holes, while trace element data were available only for 9 of 22 drill holes. Additional whole rock chemical analysis was carried out on 11 samples in order to determine trace element background concentrations of the least-altered rocks. The complete δ18O and δ13C dataset along with corresponding gold and trace element values are listed in Appendix E.1. 58 4.3 Results 4.3.1 C and O Stable Isotopes 4.3.1.1 Global and Local Background Values Stable isotope ratios of the Bigar Hill carbonate rocks are compared to the global background values for Jurassic and Cretaceous carbonate-bearing sedimentary rocks as compiled from the global Phanerozoic marine carbonate rocks database (Veizer et al., 1999), and to the local background values established from least-altered Korkan West and Korkan South prospects samples. Global background δ13C values for the Jurassic limestone range from 5‰ to -1.5‰ VPDB, δ18O background values range between 33.5‰ and 26.8‰ VSMOW (95% of all data, Veizer et al., 1999). The global background in Cretaceous δ13C values ranges between 5.5‰ and -1.5‰ VPDB, and δ18OVSMOW ranges from 32.5‰ to 26.8‰ (95% of all data, Veizer et al., 1999). Figure 4.1: Locations of the sampled Bigar Hill drill holes (bounded by northing coordinates 4898157 and 4898187); The upper right box shows the locations of sampled Korkan West and Korkan South drill holes; Structures scrutinized in this study are labeled with F mark. Geolines from Avala Resources, 2012. 59 Carbonate rocks from Korkan West and Korkan South prospect define a local stable isotope background. The samples lack visible evidence of hydrothermal alteration and contain negligible concentrations of gold. Twenty samples from three drill holes: KWDD005, KWDD008, and KODD028 represent all of the stratigraphic units. The range of average isotope values of all units is from 4.2‰ to – 1.0‰ for δ13C, and 29.6‰ to 24.2‰ for δ18O. δ13C values are consistent with the global range of Jurassic and Cretaceous marine carbonate, while δ18O is offset to somewhat lower values. The difference between the global and the local δ18O background may be caused by weak hydrothermal alteration of the Korkan rocks, or reflect local primary seawater carbonate deposition from fluids that were isotopically different from global Jurassic and Cretaceous seawater. All background values for the different stratigraphic units are summarized in Table 4.1. Table 4.1: Compilation of δ13C and δ18O global and local background values, and values from the Bigar Hill for each rock unit Lithology Global Jurassic and Cretaceous marine carbonate background (Veizer et al., 1999) Local background values Values from the Bigar Hill δ13C (‰) δ18O (‰) δ13C (‰) δ18O (‰) δ13C (‰) δ18O (‰) Jurassic limestone 5 to -1.5 33.5 to 26.8 2.4 to 1.9 27.1 to 26.6 3.2 to -1.7 27.8 to 14.7 Cretaceous Limestone 5.5 to -1.5 32.5 to 26.8 2.2 25.4 3.7 to -4.6 28.4 to 8.9 S1 Basal breccia 3.2 to -5.9 25.2 to 12.6 Siltstone/mudstone 1.5 to 1 25.3 to 24.2 2.8 to -3.9 23.6 to 11.8 Carbonate sandstone 2.9 to 2 29.6 to 25.9 3.6 to -2.3 29.1 to 12.9 S2 carbonate clastic rocks 4.2 to 1.5 29 to 24.5 3.6 to -3.5 25.6 to 13.8 Marl 3.7 to 1.2 27.1 to 25.1 4.3 to -1.0 26.0 to 14.5 60 Figure 4.2: Plot of δ18O vs. δ13C for samples from all carbonate-bearing stratigraphic units, altered and least-altered, in relation to Global Phanerozoic marine carbonate background (Veizer et al., 1999) and local background ranges. 4.3.1.2 Stable Isotope Values of the Bigar Hill Deposit Oxygen isotope ratios of 606 samples from the Bigar Hill range from 29.1‰ to 8.9‰ and 98% of the data are within a narrower range from 28‰ to 12‰. Approximately 3% of the samples are consistent with the range defined by global Jurassic to Cretaceous marine limestone (Veizer et al. 1999), and 13% of the samples are in the range of the local background values. δ13C values of all samples range between 4.3‰ and -5.9‰. The majority of samples have a somewhat restricted range in δ13C between 3.5‰ and -3.0‰. Unlike the oxygen isotope ratios, most δ13C values are consistent with the global marine carbonate background, and 93% of samples fall within that interval. Approximately 60% of the samples are consistent with the local δ13C background (Figure 4.2). δ18O and δ13C values are moderately correlated (correlation coefficient R = 0.62). δ 18O depletion is frequently accompanied by δ 13C depletion but not with the same intensity. Even though δ13C values are dispersed in the narrower range, their 61 variations are more erratic than in a case of oxygen. The range in isotope ratios of all stratigraphic units are summarized in Table 4.1 and presented as box plots in Figure 4.3. Figure 4.3: Box plot representation of the ranges of δ18O and δ13C for each stratigraphic unit, including all samples, altered to least-altered from Bigar Hill. Box plots provide information on the interquartile range (range between 25th and 75th percentiles) that defines the size of the box, and median and mean values, as well as whisker values (1.5 times the interquartile range), outliers (up to 3 times the length of the box) and far outliers. The median and mean δ18O values provide the most obvious indication for compositional differences between the different stratigraphic units. The median represents the average value for all the samples, fresh to altered, and reflects the various proportion of various samples in each unit. The δ18O median for the S1 sub-unit equals ~22.4‰ and is close to the local background and higher than that of all other stratigraphic units. The overall range in δ18O of the S1 sub-unit is from 29.1‰ to 12.9‰. Marl (SMR), S2 and Jurassic 62 limestone (JLS) have median δ18O values between 20.5‰ and 19.0‰. IB mudstone, basal breccia (BBX) and Cretaceous limestone have the lowest median values ranging between 16.9‰ and 16.1‰. The IB sub-unit is characterized by relatively low variability, δ18O = 19.8 – 11.8‰ (up to 23.6‰ including outliers), the basal breccia has the interquartile range of 21.5‰ to 14‰, while the KLS has the overall highest variability δ18O = 25.3‰ – 8.9‰ (up to 28.4‰ including outliers). Values of δ13C exhibit less variability than δ18O. The SMR and S1 have the highest median δ13C values of 1.6‰ and 1.8‰ respectively. The S2, KLS and JLS units have median δ13C values in the range of 1.2‰ to 0.9‰. The lowest values are present in the BBX and IB sub-units with δ13C = 0.5‰ and -0.8‰, respectively. These two sub-units are characterized by the broadest interquartile ranges, from 1.3‰ to -0.8‰ in BBX, and from 0.9‰ to -2.1‰ in IB. The different carbon and oxygen isotope ratios in the different (sub-) units may be the result of variable lithologic composition. According to Hofstra and Cline (2000), higher δ18O and δ13C values are typical of ordinary marine limestone while the lower values are characteristic of calcite in calcareous shales. Low isotopic values in the IB sub-unit, which is composed of mudstone to siltstone with variable amounts of organic matter, are partially caused by the typically low δ13C values of organic carbon (Ohmoto, 1986; Arehart and Donelick, 2006). The same reason may apply to the BBX sub-unit, which partially contains mudstone as a matrix. In addition to rock composition, isotopic variability could reflect the intensity of alteration (Stenger et al., 1998). 4.3.2 Gold and Trace Elements Distribution Cross-sections show the spatial distribution of δ18O and δ13C values and their spatial relationships to the Bigar Hill mineralization (0.4 ppm Au grade shell) and stratigraphic units (Figure 4.4). For the following discussion and correlation with Au grades, ranges in δ18O values are grouped into: (1) within the range of the global background values; (2) slightly depleted (>22‰); (3) moderately depleted (22‰ – 15‰); (4) strongly depleted (<15‰); and (5) very strongly depleted (<10‰). Gold and sulfur concentration data from 1 m core sample intervals are available for all 22 drill holes used in this study, while trace metals concentration integrating over core lengths of 5 m were obtained for nine drill holes. Correlation analysis shows that gold best correlates with Sb, Tl, Hg, As and Te. The correlation matrix for gold, trace metals, and oxygen and carbon isotope ratios is presented in Table 4.2. 63 Figure 4.4: Cross-sections are showing the spatial distribution of δ18O (top section) and δ13C (bottom section) values and their spatial relation with stratigraphic units, and the gold mineralization (0.4 ppm Au grade shell outlined with purple line). The position of the cross-section is shown on the map in Figure 4.1. 64 Association of gold with As, Sb, Hg, Tl, and Te is one of the characteristic features of Carlin-type gold deposits indicating their transport and deposition from the same mineralizing fluid (Bagby and Berger, 1985; Hofstra and Cline, 2000; Hickey et al. 2014). This low-temperature element association, along with the oxygen and carbon isotopes was therefore used to constrain hydrothermal flow along zones of structural permeability and within favorable stratigraphic units. Correlation coefficients (R) for the concentration of gold and low-temperature trace elements range between 0.6 and 0.74. Cross-sections showing the spatial distribution of Sb, Tl, Hg and As concentrations are in Figure 4.5. Table 4.2: Spearman correlation matrix for O and C isotopes, gold and selected trace elements δ18O (‰) δ13C (‰) Au (ppm) As (ppm) Sb (ppm) Hg (ppm) Tl (ppm) Te (ppm) Se (ppm) Ag (ppm) δ18O (‰) 1 0.62 -0.32 -0.34 -0.45 -0.43 -0.41 -0.44 -0.36 -0.11 δ13C (‰) 0.62 1 -0.2 -0.24 -0.3 -0.25 -0.21 -0.2 -0.15 -0.064 Au (ppm) -0.32 -0.2 1 0.69 0.73 0.7 0.72 0.6 0.54 0.33 As (ppm) -0.34 -0.24 0.69 1 0.77 0.69 0.83 0.75 0.58 0.3 Sb (ppm) -0.45 -0.3 0.73 0.77 1 0.73 0.79 0.65 0.62 0.25 Hg (ppm) -0.43 -0.25 0.7 0.69 0.73 1 0.77 0.66 0.6 0.26 Tl (ppm) -0.41 -0.21 0.72 0.83 0.79 0.77 1 0.74 0.62 0.37 Te (ppm) -0.44 -0.2 0.6 0.75 0.65 0.66 0.74 1 0.63 0.41 Se (ppm) -0.36 -0.15 0.54 0.58 0.62 0.6 0.62 0.63 1 0.34 Ag (ppm) -0.11 -0.064 0.33 0.3 0.25 0.26 0.37 0.41 0.34 1 Pb (ppm) -0.29 -0.16 0.21 0.27 0.27 0.23 0.3 0.34 0.34 0.39 Cu (ppm) -0.22 -0.11 -0.012 0.22 0.043 -0.032 0.19 0.34 0.22 0.26 W (ppm) -0.24 -0.16 0.27 0.26 0.33 0.42 0.27 0.28 0.32 0.058 Bi (ppm) -0.11 -0.12 0.14 0.27 0.082 -0.016 0.23 0.31 0.14 0.34 Mn (ppm) -0.57 -0.31 0.51 0.32 0.5 0.52 0.5 0.49 0.44 0.37 Mg (ppm) -0.47 -0.25 0.08 0.069 0.16 0.17 0.23 0.19 0.21 0.23 S (%) -0.37 -0.32 0.6 0.77 0.68 0.59 0.68 0.67 0.5 0.42 65 Figure 4.5: Cross-sections showing the spatial distribution of Sb, Tl, Hg and As values and their relation with stratigraphic units, and the gold mineralization (0.4 ppm Au grade shell outlined with purple line). The position of the cross-section is shown on the map in Figure 4.1. 66 Local background concentrations of gold and trace elements are established using the lithogeochemical dataset for the Korkan West and Korkan South prospects. Gold grades in all the assayed samples (n = 10) are below the detection limit (Au <0.01 ppm). In further work, these values were replaced by half of the limit of detection values. Tl concentrations are mainly below the detection limit (Tl <0.1 ppm); only two Figure 4.5 (Cont.) 67 samples had concentrations of 0.2 ppm. Hg ranges from the detection limit (Hg <0.01 ppm) to 0.03 ppm, Sb values vary between the detection limit (<0.1 ppm) and 0.8 ppm. Arsenic shows the highest variability, ranging between the detection limit (As <0.5 ppm) and 33.8 ppm. 4.3.3 Correlation between Isotope Ratios and Metal Concentrations Values of δ18O and δ13C were correlated against all of the analyzed element concentrations. A positive correlation exists only for δ18O and δ13C (R = 0.62) indicating that isotopic depletion generally applies to both δ18O and δ13C, and that metal concentrations are elevated in zones of isotopic depletion. δ18O have the strongest inverse correlation with manganese (R = -0.57). Depletion of isotope values lacks a strong correlation with gold mineralization; their correlation coefficients are R = -0.32 and R = -0.2 for oxygen or carbon versus gold respectively. Values of δ18O exhibit slightly stronger correlations with Sb (R = -0.45), Te (R = - 0.44), Hg (R = -0.43), Tl (R = -0.41) and As (R = -0.35). Carbon isotope ratios have a weaker correlation with trace element concentrations, ranging from -0.2 (vs. Tl) to -0.3 (vs. Sb) (Figure 4.6). It is important to emphasize that the samples for different types of analyses were collected on a different scale, with different amount of material. Gold analyses were performed on the 1 m interval drill core or crushed RC chips. Trace element concentrations were analyzed from the 5 m composite samples. On the other hand, isotope analyses involved significantly smaller amounts of material (17 mg to 100 mg), obtained by spot drilling of selected areas of selected rock core pieces or by crushing of RC chips from the 1 m interval. Due to the discrepancy in the sample size, isotope depletion may not precisely match gold and trace elements enrichment on the sample scale. For this reason, trends of isotope depletion and metal enrichment should be the point of interest (Ahmed, 2010; Arehart and Donelick, 2006). 68 Figure 4.6: XY plot of δ18O vs. δ13C for samples taken from all the carbonate-bearing stratigraphic units, color-coded by Au (top plot), Sb (bottom plot), Hg (next page top plot) and Tl (next page bottom plot) concentrations from the appropriate intervals. 69 Figure 4.6 (Cont.) 70 4.4 Stable isotope ratios, metal concentrations, and zones of increased permeability Depletion of stable isotopic ratios can be linked to zones of gold mineralization and the inferred location of hydrothermal fluid flow paths, in particular, proximity to inferred faults F1, F2, F4, and F5. Depths of inferred intersections of drill holes with F1, F2, F4, and F5 faults, as well as with confirmed faults (F7, F8, and F9) are shown in Table 4.3. Spatial representation of stable isotopic ratios in drill holes along the A-B cross-section is shown as box plots in Figure 4.7. From the west to the east, the ore zone spans between drill holes BHRC222 and BHRC283. The proximal ore zone is intersected with drill holes BHRC159 to BHRC221 in the west, and BHDD076 in the east, while the holes BHDD058 and BHDD053 are considered distal to the ore zone. Median and mean δ18O values exhibit a continuous decrease from the westernmost drill hole (BHRC159) towards drill hole BHRC297 that is located within the ore body and contains the highest gold grade. Median values range from 23.5‰ in the west to 15.0‰ in the ore zone. A distinct decrease of median δ18O values from 20.7‰ to 18.8‰ occurs between drill holes BHRC221 and BHRC222 and correlates with an increase in gold grade from the detection limit to 1.65 ppm in BHRC222. The strongest depletion of δ18O, with median values below 20‰, is observed between drill holes BHRC222 and BHRC046. δ18O increases strongly between BHRC046 and the neighboring hole BHDD068 from 15.9‰ to 20.3‰. Towards the east, oxygen isotopic values irregularly increase and show a sudden drop in drill hole BHRC283, which has been crosscut by the F7 fault. Gold values are significantly higher within the ore zone bounded by F4 and F7 faults. Within the ore zone, the gold grades are variable, with median values ranging between the detection limit and up to 0.41 ppm (in BHRC297). The highest gold grade of 4.97 ppm recorded in BHRC297, occurs along with the most intensive strongest oxygen depletion. Outside the ore zone, gold median values do not exceed 0.01 ppm in most drill holes; however, easternmost holes contain outliers up to 1.05 ppm Au. Table 4.3: Downhole depth (m) of the intersections of holes with inferred and established faults (F1-F9) BHRC 159 BHRC 143 BHRC 222 BHRC 105 BHRC 229 BHDD 056 BHRC 297 BHRC 130 BHDD 084 BHRC 283 BHDD 076 BHDD 058 F1 92 302 F2 41 124 206 262 F4 34 134 F5 65 F7 30 306 F8 335 F9 65 144 71 Figure 4.7: Spatial representation of stable isotopic and gold ratios in drill holes along the A-B cross-section is shown as box plots. Box plots are formed based on the δ18O, δ13C and Au values from all the analyzed samples within respective drill holes. 72 Even though carbon isotope ratios show less per mill variation than oxygen isotope ratios (median 2.24‰ to 0.11‰) both show consistent trends of depletion. Drill hole BHRC130, located in the central part of the ore zone, exhibits the lowest median and mean δ13C values (0.11‰ and -0.29‰) and the lowest individual value (-5.91‰). The spatial variability of oxygen isotopes in each stratigraphic unit in drill holes along the A-B cross section is shown in Appendix E.2. 4.4.1 Spatial relation between isotope ratios, metal concentrations, tectonic and stratigraphic features The presented data show that changes in oxygen isotope ratios and the correlation with metal concentrations have greater per mill shift than for carbon isotope ratios. Therefore, oxygen isotope ratios are the most sensitive proxy for hydrothermal fluid/host rock interaction. Variations in δ18O and metal concentration in the drill holes and their spatial relationship with the observed and inferred faults, as well as stratigraphic zones of increased porosity are apparent along a W-E trending transect. The transect encompasses the distal zone in the east (intersected with BHDD053 and BHDD058), proximal zone (BHRC159 to BHRC221 in the west and BHDD076 in the east) and the ore zone of the Bigar Hill deposit (between BHRC222 and BHRC283). Distal zone  The easternmost drill holes BHDD058, and BHDD053 are located outside of the ore zone and show generally high δ18O values, with rare moderately-depleted δ18O values, especially in narrow intervals in S1, S2 and marl units. These depletion zones may reflect the distal flow of the hydrothermal fluid without mineralization. The inferred intersection of fault F8 with the BHDD058 is coupled with isotopic depletion of the S2 clastic rocks. Proximal zone  The westernmost drill hole BHRC159 intersected rocks with high δ18O values that are mostly >22‰, i.e., only slightly depleted relative to the global and local background values. The only significant deviation to lower δ18O values occurs in the non-mineralized IB mudstone rock, directly above the contact with limestone. Although this deviation to lower δ18O values may be a feature related to the mudstone’s lower background values, it matches spatially with the intersection of inferred fault F5 and established fault F9, which might represent a preferred pathway for hydrothermal fluids even in the absence of mineralization. Oxygen values are lower in the S2 unit than in S1, and there is a slight decrease of isotopic values on the contact of these two units. 73  Adjacent drill holes to the east (BHRC143, BHRC147, and BHRC221) show low gold grades that oscillate between the detection limit and 0.06 ppm. Zones of oxygen isotopic depletion correlate with zones of increased gold values even though individual gold concentration peaks are generally not associated with isotopic lows. The S2 unit and marl underwent moderate depletion (22‰ – 16‰), while δ18O values of the S1 unit are within the global background range. Oxygen isotopic depletion in drill hole BHRC221 may be the consequence of hydrothermal fluids circulation through the fault F4 which is assumed to intersect the stratigraphy in the vicinity of the hole. The contact zone between S1 and S2 in BHRC147 and BHRC221 shows only subtle depletion in δ18O.  BHDD076 is located in the proximal zone, east from the deposit. Its oxygen values are highly variable, ranging from 27.9 to 14.8‰. Oxygen ratios in the S1 unit approach background values. Strong depletion is recorded at the contact of marl and S2 and within the S2. Increased gold and trace elements show a weak correlation with isotope depletion. Depletion in the breccia zone matches with the inferred intersection with the fault F7. Ore zone  The westernmost drill hole in the ore zone BHRC222 is moderately to strongly depleted in 18O (δ18O <22‰) relative to the local and global background. The most depleted interval is associated with the basal breccia – limestone contact and fractured limestone at a deeper level and coincides with the gold grades of up to 1.6 ppm. The inferred intersection with the fault F4 does not have any notable O isotope depletion, but only a slight decrease in marl.  The next drill hole to the east, BHRC105 shows highly variable values of δ18O, ranging from 22.7‰ to 14.5‰. The most robust depletion is in marl (14.5‰) and basal breccia (14.9‰). Strong depletion in the marl coincides with its contact zone with the andesitic sill in the vicinity of F2 and F4 faults, while moderate depletion in the S2 unit matches the projected intersection depth of the F4 fault. Mineralization is absent in both zones. However, elevated concentrations of gold (up to 6.6 ppm) and trace elements in the S1 unit correlate with moderate δ18O depletion.  δ18O is moderately to strongly depleted in hole BHRC229. Strong δ18O depletion is recorded in a broad zone around the S1/S2 contact (~25 m), while gold enrichment occurs in the narrow contact interval. Strong depletion in the S2 occurs at the projected depth of intersection with the F2 fault.  Drill hole BHDD056 shows highly variable δ18O values that are well-correlated with gold and trace element increased concentrations. 18O depletion zones are spatially consistent with the contact zone of S2 and andesite units, as well as S1 and S2 units, the basal breccia, and a few intervals in 74 limestone. Intersection with the F2 fault in basal breccia had a significant decrease in δ18O and increase in gold and associated metals.  Rocks from the drill hole BHRC297 mostly have strong 18O depletions. The lowest value (δ18O = 8.9‰) appears at the intersection of the F2 fault with limestone where the gold grade is up to 2.5 ppm. The strong O depletion affected the S1 unit more than the upper S2 unit. The S1 also contains higher gold grades. 75 CHAPTER 5 – GEOCHRONOLOGY OF THE MAGMATIC, HYDROTHERMAL AND SEDIMENTARY PROCESSES AT BIGAR HILL AND THE TMC 5.1 Introduction Although there are geochronological constraints for several deposits and prospects in the TMC region, dates presented here are the first to constrain Bigar Hill geology and mineralizing processes. Constraining the age of host rock sedimentation and local igneous and associated hydrothermal activities provides insight into the timing and evolution of ore genesis at Bigar Hill. However, dating sediment-hosted disseminated gold mineralization remains a scientific challenge (Hofstra, 1999; Hofstra and Cline, 2000). Absolute dating is hindered by the very fine-grained nature of the mineralization while the limitations of indirect dating lie in a small number of datable materials that are co-genetic with gold (Hofstra and Cline, 2000; Arehart, 2003). Numerous age dates from Carlin-type deposits in the Great Basin region of the US, obtained by different isotopic dating techniques, provided highly variable results. Rb-Sr dating of galkhaite [(Cs,Tl)(Hg,Cu,Zn)6(As,Sb)4S12] provides the only direct age of mineralization. This sulfosalt is recognized in only a few locations in Nevada (Getchell, Rodeo, Carlin, SSX), and rarely worldwide. At the Getchell and Rodeo deposits, mineral associations and detailed observations of its occurrence, distribution, and chemistry indicate that galkhaite is part of the Au stage mineralization (Arehart, 2003). Several other techniques for direct or indirect dating have had limited success. Some of those techniques include: Re-Os dating on realgar, orpiment, and pyrite; Sm-Nd dating on fluorite; Rb-Sr on sphalerite; U-Th-Pb techniques on various minerals (post-ore calcite, apatite, and late ore-stage pyrite); and K-Ar or 40Ar-39Ar on sericite, biotite, feldspar, alunite (Hofstra and Cline, 2000; Arehart, 2003). At Bigar Hill, the K-Ar ages of hydrothermal illite are considered to best represent the timing of gold mineralization. Moderate to strong clay alteration developed during mineralization in the andesite and S2 clastic rocks and formed widespread but fine-grained illite. The K-Ar dating technique was chosen over the 40Ar-39Ar method because the very fine-grained illite would likely suffer recoil effects during irradiation which makes meaningful dates difficult or impossible to interpret (Lovera et al., 1989; Foland et al., 1992). To further constrain the understanding of the timing of mineralization, a U-Pb dating study of magmatic and sedimentary rocks was designed to better indicate the timing of igneous activity in the 76 northwestern Timok area, thus further constraining the timing of hydrothermal activity associated with gold mineralization of the Bigar Hill deposit. 5.1.1 Geochronology of the TMC Previous geochronology of the igneous events within the broader TMC provided K-Ar, Ar-Ar and U-Pb ages of volcanic and plutonic rocks. The Re-Os molybdenite dating technique provided the age of the porphyry mineralization. The age data of magmatic and hydrothermal activities was constrained to a period of approximately 13 million years, from 90 to 77 Ma (von Quadt et al., 2002; Clark and Ullrich, 2004; Banješević, 2001, 2010; Tosdal, 2012), showing a general younging of magmatism from east to west. A summary of the known radiometric dates of plutonism, volcanism, and mineralization in eastern and central Timok is provided in Table 5.1. In the northwestern portion of the TMC, results from SHRIMP-RG ion microprobe analyses on U-Pb in zircons from the diorite porphyry stocks and dikes indicated that magmatism spanned about 5-6 million years (Tosdal, 2012). The Dumitru Potok and Valja Strž porphyry Cu-Au systems, located 2 km and 5 km SE of Bigar Hill, formed roughly contemporaneously, before 82.5 - 81.3 Ma. A late, poorly mineralized diorite porphyry from the Kraku Riđi Cu-Au system, located immediately east of Bigar Hill, has been dated at 80.6 ± 0.6 Ma. The emplacement of the Potaj Čuka monzonite pluton, south of Bigar Hill, is interpreted to have occurred at 79.9 ± 0.5 Ma, after the intrusion of porphyry systems (Table 5.2). Table 5.1: Summary of age dates of magmatic and hydrothermal activity in eastern and central TMC. Localities are shown in Figure 2.1 and Figure 5.2. Locality Lithology/ Mineralization Fraction Isotopic System Interpreted Age (Ma) Reference Veliki Krivelj Andesite Amphibole K-Ar 91.0 ± 4.0 Janković et al. (1981) Andesite Zircon U-Pb 86.29 ± 0.3 to 86.17 ± 0.2 von Quadt et al. (2002) Diorite Zircon U-Pb 86.6 ± 0.6 von Quadt et al. (2002) Mineralization Molybdenite Re-Os 87.88 ± 0.5 Zimmerman et al. (2008) Bor Andesite Amphibole K-Ar 89.7 ± 3.6 to 89.6 ± 3.6 Banješević et al. (2001) Andesite Biotite Ar-Ar 89.0 ± 0.6 Clark and Ullrich (2004) Mineralization Molybdenite Re-Os 86.24 ± 0.5 to 85.94 ± 0.4 Zimmerman et al. (2008) Majdanpek Andesite Biotite Ar-Ar 84.0 ± 0.4 to 83.6 ± 0.5 Clark and Ullrich (2004) Andesite Zircon U-Pb 82.73 ± 0.5 von Quadt et al. (2002) Diorite Zircon U-Pb 83.1 ± 0.1 von Quadt et al. (2002) Mineralization Molybdenite Re-Os 83.77 ± 0.5 to 83.37 ± 0.5 Zimmerman et al. (2008) Dumitru Potok Mineralization Molybdenite Re-Os 80.82 ± 0.5 to 80.69 ± 0.4 Zimmerman et al. (2008) 77 5.2 Methodology 5.2.1 U-Pb Zircon Dating Six samples were selected for U-Pb dating with the intention to establish the age of local sedimentary and igneous processes and to indirectly constrain the timing of hydrothermal activity at the Bigar Hill. Samples were collected from the Bigar Hill S2 sandstone, andesite, and diorite, but also from the adjacent intrusions which could provide a better understanding of the broader magmatic-hydrothermal activities. Samples and rationale include: (1) A sample from a propylitic-altered andesitic sill at Bigar Hill (14JZBH285) was collected to indirectly provide the maximum age of the gold mineralization since the andesite is the youngest gold-bearing unit within the deposit (Figure 5.1a); (2) Non-mineralized, plagioclase-hornblende-phyric diorite (sample 14JZBH286) intruded into andesite on the eastern margin of the deposit was sampled to constrain the minimum age on the andesite. This sample also indirectly constrains the maximum age of mineralization (Figure 5.1b); (3) Diorite from the Čoka Rakita Au-porphyry prospect (sample 14JZRA001), is located 3 km SE from the Bigar Hill. It is essential to constrain the age of this porphyry, as it may have been a source of fluids, heat or gold for the SHDG deposit (Figure 5.1c); (4) Coarse-grained, K-feldspar-plagioclase-biotite monzonite (14JZCR002) from Crna Reka (see a sample (5) for rationale); (5) Porphyritic, plagioclase-hornblende diorite (14JZCR003) from Crna Reka, along with sample (4), was analyzed to distinguish the timing of these two intrusions in the broader temporal framework of the Table 5.2: Summary of the U-Pb SHRIMP-RG ages of the intrusive rocks from the west-central TMC. Localities are shown in Figure 5.2. Locality Lithology/ Mineralization Fraction Isotopic System Interpreted Age (Ma) Reference Čoka Kuruga Diorite Zircon U-Pb 83.6 ± 0.5 Tosdal (2012) Valja Strž Diorite Zircon U-Pb 82.5 ± 0.6 Tosdal (2012) Diorite Zircon U-Pb 81.3 ± 0.7 Tosdal (2012) Dumitru Potok Diorite Zircon U-Pb 82.0 ± 0.6 Tosdal (2012) Diorite Zircon U-Pb 81.4 ± 0.4 Tosdal (2012) Kraku Riđi Diorite Zircon U-Pb 80.6 ± 0.6 Tosdal (2012) Kraku Pešter Monzonite Zircon U-Pb 79.9 ± 0.5 Tosdal (2012) Valja Strž South Monzonite Zircon U-Pb 78.5 ± 1.3 Tosdal (2012) 78 Bigar Hill deposit evolution, and to test the assumption that diorite is younger than the Potaj Čuka monzonite batholith, as suggested by the cross-cutting relationship and soil geochemical data (Figure 5.1d, e); and (6) S2 volcanic detritus-rich sandstone (14JZBH302) was sampled for detrital zircon dating. The sample provides a maximum age for the deposition of the S2 unit by providing an age on the volcanic protolith that was eroded and redeposited as S2, one of the key gold-hosting units. Locations of selected samples and the results of U-Pb analyses are shown in Figure 5.2, along with the previous geochronology data for comparison. Figure 5.1: Photographs of rocks sampled for U-Pb zircon dating: (a) 14JZBH285, a propylitic-altered andesitic sill from the Bigar Hill; (b) 14JZBH286, plagioclase-hornblende phyric diorite intruded in andesite from east of the Bigar Hill; (c) 14JZRA001, diorite from the Čoka Rakita Au-porphyry system; (d) 14JZCR003, plagioclase-hornblende diorite from the Crna Reka prospect; (e) 14JZCR002 - Coarse-grained K feldspar-plagioclase-biotite monzonite from the Crna Reka prospect; (f) S2 volcaniclastic-derived carbonate sandstone. 79 Figure 5.2: West and Central TMC geology with the location of the samples collected for U-Pb dating, and the obtained ages. Also, the locations of the previously obtained ages (Tosdal, 2012) shown using different symbols. Geolines from Avala Resources, 2012. 80 5.2.2 K-Ar Illite Dating Illite ages can be a proxy for mineralization ages, based on the assumption that illite formed during and from the same hydrothermal process that led to coupled gold and pyrite precipitation. Figure 5.3: Photographs of samples collected for K-Ar illite dating: (a-c) 14JZBH295, 14JZBH298, 14JZBH299 are intensively illite-altered and mineralized S2 sandstone; (d-f) 14JZBH292, 14JZBH294, 14JZBH296 are illite-altered and sulfidized andesite. Six samples from moderately to highly mineralized and strongly to moderately clay-altered S2 sandstone (14JZBH295, 14JZBH298, 14JZBH299) and andesite (14JZBH292, 14JZBH294, 14JZBH296) were selected. Photographs of the sampled rocks are shown in Figure 5.3, and their locations in the Bigar Hill drill holes are shown in Figure 5.4. SWIR spectral analysis using the TerraSpec® (ADS, Inc.) enabled the identification of illite in the rock samples. Identified minerals are listed in Appendix C. Gold grades in the andesite samples are from 1.5 to 7.4 ppm, and illite is the only mineral identified by spectral analysis. In sandstone samples, gold grades are somewhat lower, from 0.5 to 2.05 ppm. All three samples contain illite, but 14JZBH295 also has kaolinite, and 14JZBH299 has kaolinite and muscovite. The petrographic study confirmed the intergrowth of illite and gold-bearing pyrite (Figure 5.5). In the andesite, clay alteration destroyed original rock texture and replaced primary minerals. Only rare occurrences of plagioclase phenocrysts relicts remained. Pyrite is formed after the primary femic minerals (hornblende or chlorite) and is disseminated as fine-grained anhedral crystalline masses or rarely occurs in veins. In the S2 81 sandstone, clay altered volcanic detritus material intimately intergrows with partially to intensively dissolved calcite cement. Anhedral pyrite is disseminated in the rock mass. Two illite fractions, <2 μm and <5 μm, were separated and analyzed. The <2 μm fraction is separated to avoid contamination by rock-forming minerals. The <5 μm fraction provides a measure of the effect of a grain-size on the radiometric age; it was collected from three samples (andesite samples 14JZBH294, 14JZBH296, and S2 sample 14JZBH298). Additional age dating of the whole rock samples tests the influence of rock-forming minerals on the age (Pécskay and Benkó, 2015). Before analysis, illite purity was quantified using X-ray diffraction (XRD) on powdered illite. The XRD analysis also registered small quantities of illite/smectite, smectite, quartz, chlorite and kaolinite and traces of calcite, dolomite, and gypsum (Pécskay and Benkó, 2015). XRD analysis results are presented in Appendix F. Figure 5.4: Locations of sandstone and andesite samples collected for K-Ar illite dating from the Bigar Hill drill holes. Geolines from Avala Resources, 2012. 82 5.3 Results and Interpretation 5.3.1 U-Pb zircon ages and interpretation Results of U-Pb analyses are presented in Table 5.3. Results and interpretation of individual samples include: (1) Andesite sample 14JZBH285 yielded no zircons, so the rock age remained undefined; (2) Nineteen zircons from diorite sample 14JZBH286 were analyzed. Seventeen zircons yielded a mean age of 80.16 ± 0.77 Ma with an MSWD of 0.51 (Figure 5.6a). Two crystals yielded significantly older ages (approx. 570-540 Ma) and were excluded from magmatic activity interpretations. These were assumed to be zircons from Paleozoic basement rocks xenocrysts incorporated into the diorite during the intrusion. The 80.16 ± 0.77 Ma mean age is interpreted as the minimum age of the host Figure 5.5: Photomicrographs of highly mineralized samples (transmitted light, X-polar, left; reflected light, right) collected for illite dating illustrate the association between gold-bearing pyrite and illite: (a-b) S2 sandstone sample 14JZBH295, with illite (il) replacing volcanic detritus, minor quartz (qz) and calcite cement (ca); and (c-d) andesite sample 14JZBH296, with moderately disseminated pyrite (py) in illite dominant groundmass. 83 andesite. Because this unit is the youngest gold bearing unit of the deposit, this age also provides a bounding maximum age on mineralization. (3) The plagioclase-hornblende-phyric diorite (sample 14JZRA001) from the Rakita Au-porphyry system did not yield any zircons. (4) The monzonite sample (14JZCR002) provided six zircons. One crystal exhibited poor analytical quality and was excluded; the remaining five zircon crystals yielded an average age of 80.0 ± 1.2 Ma with the MSWD of 1.4. (5) Eleven zircons from the porphyritic diorite sample 14JZCR003 yielded an average age of 77.66 ± 0.75 Ma with slightly elevated MSWD of 2.0 (Figure 5.6b, c). These data confirm the assumption that the porphyritic diorite is younger than the monzonite batholith and raise the possibility of a genetic link between intrusion and the Kraku Pešter deposit. (6) Detrital zircons separated from S2 sandstone sample 14JZBH302 exhibit typical zoning and melt inclusions. Seventeen zircons yielded a well-distributed range of ages between 93.3 ± 3.1 Ma to 87.5 ± 3.1 Ma (Figure 5.6d, e). This age distribution indicates that the zircons derived from weathering of various igneous protoliths before deposition in the S2 clastic sequence. Without the constraints on Late Cretaceous erosion rates and duration of local sediment transport and storage, it can only be concluded that the S2 sequence is younger than the zircons and older than the marls whose age is paleontologically determined to be Santonian (Dimitrijević et al., 1970; 1976; Vasić, 2012) from 86.3 to 83.6 Ma (Cohen et al., 2013). Table 5.3: Summary of the U-Pb LA-ICP-MS ages from this study with the location of samples in drill holes. Collar locations and orientations of the drill holes are in Appendix G. Sample Lithology U-Pb Interpreted Age (Ma) Hole ID From (m) To (m) Locality 14JZBH286 Diorite 80.16 ± 0.77 BHDD081 53.8 58.5 Bigar Hill 14JZBH302 S2 Sandstone 93.3 to 87.5 ± 3.1 BHDD084 151.6 160.7 Bigar Hill 14JZCR002 Monzonite 80.0 ± 1.2 CRDD005 395.4 399.6 Crna Reka 14JZCR003 Diorite 77.66 ± 0.75 CRDD005 408.1 416.6 Crna Reka 14JZBH285 Andesite No zircons BHDD083 38.0 41.4 Bigar Hill 14JZRA001 Diorite No zircons RADD001 231.4 235.9 Rakita 84 Figure 5.6: U-Pb Concordia plots showing data for zircons separated from samples (a) 14JZBH286; (b) 14JZCR002; (c) 14JZCR003 and (d) 14JZBH302; and (e) probability density plot for detrital zircon ages from the sample 14JZBH302. 85 5.3.2 K-Ar illite age Age of the <2 μm illite fraction from the andesitic sample 14JZBH292 is 79.55 ± 2.95 Ma and coincides with the whole rock age for that sample. The 40Arrad (%) for illite separate is relatively low, indicating that the rock is not entirely altered. Therefore, the measured radiometric age of the whole rock most likely approximates the real age of the andesite. Given the relatively pure character of <2 μm fraction, with a trace amount of illite/smectite and chlorite, it is assumed that this sample also provides the age of the alteration (Pécskay and Benkó, 2015). Ages for <2 μm and <5 μm fractions of andesite sample 14JZBH294 do not coincide. The age of the <2 μm is 81.90 ± 2.62 Ma, while the age of the <5 μm fraction is 77.68 ± 2.59 Ma, which agrees with radiometric age of the whole rock (78.24 ± 3.41 Ma). The finer-grained fraction contains less K (5.13%) than the <5 μm fraction (5.4%). A similar discrepancy occurs in andesite sample 14JZBH296, where the <2 μm fraction yields an anomalously old radiometric age of 89.65 ± 3.28 Ma, whereas the age of the <5 μm fraction is considerably younger, at 75.31 ± 2.93 Ma. Also, the smaller fraction has lower K content (4.5%) compared with the coarser one (5.3%). In both samples, the <2 μm fraction contains higher amounts of smectite and lower K content relative to the coarser fraction. The K loss is assumed to be related to the formation of smectite that retains Ar but no K (Pécskay and Benkó, 2015). For that reason, further interpretation used the radiometric age of the <5 μm fraction. Age of the <2 μm illite fraction of the 14JZBH295 sandstone sample is 78.79 ± 2.49 Ma which is consistent with the age obtained for 14JZBH298 sandstone sample. Ages for fractions <2 and <5 μm of the 14JZBH298 are 78.86 ± 2.82 Ma and 80.42 ± 2.87 Ma, respectively, although they overlap within the error ranges. Both fractions are characterized with relatively homogeneous composition, with dominant illite and low smectite abundance, indicating that the mineralogy has not affected the radiometric age. Sample 14JZBH299 from the S2 sandstone yielded an anomalously old radiometric age of 96.96 ± 3.6 Ma. Even though the <2 μm fraction is dominantly illite, there is contamination with detrital mica which is identified by spectral analysis. Muscovite is preserved either in weakly altered parts of the sample or remobilized and deposited in the fracture system after the mineralization process. This age is older than the oldest known magmatic phase in the TMC. Based on the selected K-Ar ages, the average age of 79 Ma with an average error of 2.78 Ma is a reasonable estimate for the age of the mineralization. A summary of the K-Ar radiometric age results is provided in Table 5.4. A summary of the TMC and the Bigar Hill geochronology is shown in Figure 5.7. 86 Table 5.4: The results of the K-Ar analyses, for two illite fractions (<2 µm and <5 µm) and the whole rock samples (w.r.) with the location of samples in drill holes. Collar locations and orientations of the drill holes are in Appendix G. Sample ID Lithology Dated fraction K (%) 40Arrad (ccSTP/g) 40Arrad (%) K/Ar age (Ma) Hole ID From To 14JZBH292 Andesite w.r. 01.-0.25 2.682 8.5245×10-6 63.2 79.96 ± 2.63 BHDD032 100.0 117.4 illite ˂2µm 5.532 1.7490×10-5 47.3 79.55 ± 2.95 14JZBH294 Andesite w.r. 01.-0.25 2.745 8.5322×10-6 35.5 78.24 ± 3.41 BHDD017 136.1 142.0 illite ˂2µm 5.130 1.6709×10-5 70.2 81.90 ± 2.62 illite ˂5µm 5.399 1.6659×10-5 60.7 77.68 ± 2.59 14JZBH296 Andesite w.r. 01.-0.25 2.788 8.9206×10-6 54.9 80.49 ± 2.78 BHDD083 51.6 64.8 illite ˂2µm 4.511 1.6083×10-5 48.3 89.65 ± 3.28 illite ˂5µm 5.254 1.5707×10-5 42.8 75.31 ± 2.93 14JZBH295 Sandstone illite ˂2µm 5.137 1.6083×10-5 72.1 78.79 ± 2.49 BHDD084 192.5 202.0 14JZBH298 Sandstone illite ˂2µm 4.791 1.5315×10-5 50.8 80.42 ± 2.87 BHDD063 211.0 212.8 illite ˂5µm 4.806 1.5059×10-5 50.8 78.86 ± 2.82 14JZBH299 Sandstone illite ˂2µm 4.631 1.7932×10-5 46.9 96.96 ± 3.60 BHDD085 192.0 195.0 87 Figure 5.7: Summary of the geochronology of the magmatic, sedimentary and mineralization in the TMC, with an emphasis on the Bigar Hill deposit (compiled from Janković et al., 1981; Banješević et al., 2001; von Quadt et al., 2002; Clark and Ullrich, 2004; Zimmerman et al., 2008; Tosdal, 2012; this study). 88 CHAPTER 6 – DISCUSSION 6.1 Depositional Environment and Alteration of the Gold-Hosting Sedimentary Package Deposition of the sedimentary package hosting the Bigar Hill mineralization took place from Late Jurassic until Late Cretaceous time. Several stratigraphic units, interpreted from surficial mapping and drill hole logs, were deposited during that time: Late Jurassic (Oxfordian-Kimmeridgian and Tithonian) limestone (JLS), Early Cretaceous (Valanginian-Hautrivian and Barremian-Aptian) limestone (KLS), calcareous siliciclastic rocks of Albian age (S1), Late Cretaceous volcanic detritus-rich calcareous siliciclastic rocks (S2), and Santonian marl (SMR). Deposition of the sedimentary package was episodic, with several notable unconformities recorded between JLS and KLS, KLS and S1, S1 and S2, that span up to several million years. Regionally, in the western margin of the TMC, the sedimentary package was deposited transgressively over the paleorelief composed of the Paleozoic crystalline basement rocks (Dimitrijević et al., 1970). The limestone sequence of the Bigar Hill sedimentary package is part of the carbonate platform that developed during the Late Jurassic and Early Cretaceous (Grubić and Jankičević, 1973). The limestone sequence encompasses four carbonate facies of different ages: Oxfordian-Kimmeridgian micritic limestone and dolomite, Tithonian bioclastic and oolitic limestone, Valanginian-Hauterivian “dirty” micritic limestone and Barremian-Aptian bioclastic limestone. Each of the carbonate units exhibits textural differences that indicate distinct depositional environments. Reef limestone is formed on the peripheral parts of the platform, while micritic limestone is deposited in the deeper parts, contains chert concretions characteristic of a deep-marine environment (Vasić, 2012). Over time, primary sedimentary features in the limestone sequence were altered to a varying extent by tectonic activities, karstification, pressure dissolution, and thermal and chemical alteration related to localized intrusions and percolating fluids. Fault and fracture zones, karst features, brecciation, stylolite seams, skarn alteration, re-crystallization, or silicification are regular features in the preserved rocks. The chemical and mineralogical composition of the Jurassic platform carbonate sequence is generally homogeneous with negligible input of non-carbonate material. In contrast, the Valanginian-Hauterivian “dirty” limestone contains variable proportions of organic or clastic matter, and consequently, its chemical composition differs from the other limestone facies. This 89 limestone facies contains higher background values of lithophile and siderophile elements (e.g., K, Rb, Cs, Be, Mg, Sr, Fe, Sc, Cr, Al). Elevated iron content makes this limestone facies more reactive in contact with acidic gold-bearing fluids than the other limestone facies. The Cretaceous limestone is not laterally-continuous in the deposit area due to the tectonic complexity of the area and variable erosion rates for discrete structural blocks. Organic material-rich black limestone facies of the Valangian-Hauterivian limestone has a variable thickness over the deposit area, from a few to several tens of meters. The Barremian-Aptian limestone is only sporadically observed in the eastern part of the Bigar Hill area, even though it is a large regional unit. However, clasts of this limestone facies represent one of the dominant components of the overlying basal breccia of the S1 unit. Abundant evidence for exposed surface weathering of the carbonate platform during regressive cycles includes collapsed sinkholes and caves, fissure enlargement due to preferential dissolution along fracture system, the formation of terra rossa, laminated clastic rocks infilling caves, and fissures. Karstification has most strongly developed on the surface and sub-surficial part of Tithonian and black Valanginian-Hauterivian limestone, particularly along NW- and NE-oriented fault and fracture systems. Deposition of the sedimentary package S1 started in the Albian, following the Austrian deformation phase of the Alpine orogeny (Knaak et al., 2016). The unit S1 is heterogeneous, composed of various calcareous siliciclastic rocks. The basal breccia (BBX) is present at the lower levels of the S1 unit, lying unconformably over the limestone. The distribution of the breccia is not continuous and displays frequent, abrupt variations in thickness. In the northwestern part of the deposit area, the breccia is thin or not developed (potentially eroded); in the central part of the deposit, it reaches up to 50 m, preferentially in the zone of intersection of NW- and NE-faults. This poorly-sorted breccia contains limestone fragments and quartz pebbles in silty to very coarse-grained matrix cemented by calcite or Fe-calcite. Variability in breccia composition, textural characteristics and its spatial distribution implies a complex genesis from several processes. Partly, the basal breccia formed during regional tectonic activity and represents fault scarp-derived deposits that are characterized by large angular dropstone clasts. Other sections appear to preserve debris flow deposits of terrestrial alluvium mixing with coarse limestone fragments derived from eroding shorelines (Vasić, 2012; Knaak et al., 2016) or intense karst activity at the surface of the underlying limestone. Black, laminated, very fine-grained clastic rocks (IB) is another facies deposited within the S1 unit. The main constituent of the IB sub-unit is clastic detritus with low carbonate components. The abundance of clay and silt-size fraction, along with clay minerals contributed to the low porosity and permeability of 90 the rock. The IB mudstone and siltstone have a pronounced spatial variability, not formed in the northwestern part of the deposit area, and with scatter occurrences in the northern area. The IB overlies basal breccia or Cretaceous limestone, or it can appear in the form of the lenses within the S1 sandstone. Mudstone/siltstone upper boundary with the S1 clastic rocks is transitional, and it extends up section to a few tens of meters. The S1 sub-unit sensu stricto represents the dominant part of the S1 unit. Unlike the basal breccia and IB, the S1 shows lateral continuity. However, its thickness is variable, exceeding 100 m in the northwestern part of the deposit. Deposition of the S1 and IB sub-units is interpreted to have been contemporaneous, as products of a continuous process in transitional and marine environments, where they developed laterally adjacent to each other. Based on changes in the thickness of the unit, the possible direction of detrital material transport is from the northwest. However, the precise detritus movements are difficult to ascertain due to the structural complexity of the area. The S1 sub-unit is composed of the transitional varieties from calcareous sandstone to sandy limestone. Its principal constituents are detrital material originating from the metamorphic complex, and carbonate components, which are partly clastic, but mainly form a rock cement. Cement is composed of sparry calcite to iron-bearing calcite. Clastic-rich varieties are typical for the lower parts of the sub-unit, while the carbonate-rich facies are more abundant in the upper horizons. One of the pronounced textural characteristics of the rocks is the abundant occurrence of stylolite fractures, preferentially developed in the carbonate-rich facies. Before the deposition of the overlying S2 unit, the surface of the S1 was exposed to weathering and erosion, in some cases to a depth of several meters. Rocks were fractured, brecciated, likely transported and re-deposited. Chemical weathering did not appear to be widespread – red iron crusts resulting from chemical weathering occurs sporadically. Disruptions of the rock coherency by the weathering and erosion increased primary porosity and permeability, making the S1/S2 contact zone favorable environment for subsequent hydrothermal fluid circulation. The overlying volcanic detritus-rich, calcareous siliciclastic S2 unit is compositionally complex, with distinct vertical variations from carbonate-rich at the bottom to volcaniclastics dominated at the top. In both cases, calcite or iron-bearing calcite cemented the detrital material. The thickness of the unit is relatively constant, except in the northwestern part of the deposit where it decreases due to erosion of its upper levels. The source of the volcanic detritus in the S2 and direction of this material transport is not unequivocally established. However, the ages of the detrital zircons in the S2 (93.3± 3.1 Ma – 87.5 ± 91 3.1 Ma) coincide with the age of the oldest magmatic rocks in TMC, and therefore it is assumed that the protolithic sources of the S2 are in the east of the deposit. Marl lies conformably over the S2 unit. Their contact is transitional, with the alternation of sandstone and marlstone for a few meters in the contact zone. The ratio of the clastic and carbonate components in marl is variable. Clay and white mica minerals have a significant share in the detrital material. These minerals along with the other very fine-grained components result in marl having a low porosity and permeability. In the area of the Bigar Hill, marl is intruded by a Late Cretaceous andesite sub-volcanic sill. In their contact zone, weak contact thermal metamorphic alteration affected the marl. The Bigar Hill calcareous sedimentary sequence is heterogeneous, comprising rocks of different composition, grain size, and textural features, characterized by rapid lateral facies and thickness changes. Lithofacies exhibit a variable potential for fluid circulation and gold mineralization. The basal breccia, S1, and S2 sandstones are the most favorable environments for gold deposition, particularly their contact zones (BBX/limestone, and S1/S2). 6.2 Structural Control on Mineralizing Fluids Stratigraphy exerts substantial control over the spatial distribution of mineralization. However, deposition of gold was primarily conditioned by structures that enhanced local permeability and porosity in the host rocks. The resulting pathways allowed gold-bearing fluids to reach horizons favorable for deposition. A regional structural network formed through a series of tectonic events since the Paleozoic Era. Late Paleozoic Variscan orogeny produced N- and NW-oriented faults (present-day orientation). Weak extension dominated during the Late Jurassic to Early Cretaceous. Subsequent mid-Cretaceous Austrian compressional phase of the Alpine orogeny re-activated the old NW-oriented basement structures and formed a series of NE-oriented faults (Schmidt et al., 2008; Knaak et al., 2016). Intermittent extensional and compressional phases continued throughout the Late Cretaceous accompanied by arc magmatism and subsequent hydrothermal activities. During the transition to the Cenozoic Era, the region underwent the Laramide deformational phase of the Alpine orogeny. Significant deformation occurred along normal, reverse and strike-slip faults during oroclinal bending in the Oligocene and Miocene. The extension during the Miocene caused E-W normal faulting, forming grabens and half-grabens (Schmidt et al., 2008; Knaak et al., 2016 and the references therein; Shaw and Johnston, 2012). 92 In the broader Bigar Hill region, N- to NW- trending structures are evident in the orientation of the large Potaj Čuka monzonite pluton (south of the Bigar Hill), and also in the alignment of porphyry clusters (east of the deposit). Anomalously high gold and chalcophile pathfinder elements in soils also align with these trends (Knaak et al., 2014). Narrow, elongated anomaly zones are particularly well-developed east of the Bigar Hill, over the porphyry clusters and volcanic complex, and also south of the deposit, in soils developed over limestone (Figure 6.1). The surface manifestations of the NE-oriented structures are evident as aligned sinkholes in the limestone karst, particularly north of the Bigar Hill. E-trending structures are also inferred from karst features, but to a lesser extent. This E-W structural trend is most apparent in the orientation of the horst-and-graben systems. Bigar Hill is bounded by parallel E-W faults, which ultimately preserved the mineralization from the erosional processes in the down-dropped graben. Although the main regional structures are well-understood, detailed field mapping and core logging did not provide a clear understanding of the Bigar Hill structural framework. In addition to the E-trending structures, several N-trending faults were identified before this study. However, the presence of highly fractured rocks, notable facies changes, and NW- and NE-trending orientations of gold distribution suggested a more complex structural network. To visualize this framework, a 3D model was developed using lithologic information logged from the Bigar Hill diamond and reverse circulation drill holes (Figure 3.6). During the modeling process, special attention was given to the rapid facies changes (i.e., bed thickness and spatial orientation). Matching orientations and bed thicknesses provided a reconstruction of the original morphology of the sedimentary units. Comparing that model with the current lithologic information suggests that a series of faults have broken and reoriented the host rocks into discrete, fault-bounded blocks. The orientations of the newly defined faults are WNW to NW, NE, and E. The WNW- and NE-trending faults generally coincide with the gold mineralization trends. The distribution of accompanying trace elements also supports the orientations of the inferred faults. At the local scale of the Bigar Hill deposit, elements exhibit both horizontal and vertical zoning along differently oriented trends. Geochemical anomalies of Bi, W, Pb, Zn, In, Cd, Se, Te can be traced along the NW-trend in limestone, decreasing towards the northwest. At higher stratigraphic levels, the dominant trace element assemblage is different, reflecting precipitation from low-temperature fluids. This assemblage includes Au, As, Sb, Tl, Hg, Te, and Ag (Figure 6.2). In the S1 unit, the trace elements are evenly distributed along both NW- and NE-trends, while in the upper S2 unit, they occur along the NE-trend. 93 Figure 6.1: Pathfinder metal associations from soil (defined using the weighted sums technique) over the geological map of the northwestern Timok magmatic complex (modified from Knaak et al., 2016). 94 Figure 6.2: Trace elements distribution in (a) limestone, along NW-trend, and (b) all the units above the limestone, along NE-trend; Avala Resources data set. Trace element zoning suggests that the mineralizing hydrothermal fluids arrived from the southeast, first utilizing the NW-trending fault zone at its deeper levels. At the intersection with the NE-trending structures, fluids partly utilized these new corridors, while generally moving upward into the stratigraphically higher, clastic sedimentary units. The NW and NE faults served as first and second order fluid corridors to favorable gold-hosting horizons in the sedimentary package. The sequence of events indicates that these structural trends formed before mineralization. Details of structural controls at the scale of mineralization are discussed further in section 6.3. The role of the E- and N-oriented structures as the fluid corridors is not clear. There is no continuity in either gold or trace element distribution along these faults, but several anomalous zones near their 95 intersections with the primary fluid pathways suggest that they could also be pre-mineralizing structures, re-activated by subsequent tectonic activity. 6.3 Deposit Formation – Favorable Host Environments, Critical Processes, Hydrothermal Alteration, and Metal Association 6.3.1 Gold-hosting Environments Gold enrichments are present in all lithologic units, to variable extents. Fault and fracture zones represent one of the two main loci for the ore deposition. These structurally disturbed zones represent environments with increased permeability and porosity contrary to the undisturbed surrounding rocks and therefore provide important pathways for gold-bearing fluids. Gold mineralization deposited in marl or andesite is entirely structurally controlled, as the porosity and permeability of the undisturbed rocks are generally very low and gold-bearing fluids cannot infiltrate these rocks from fractures (Yoo et al., 2013). Similarly, the limestone is generally impermeable, however, beside fault and fracture zones, specific rock disturbances such as stylolites or karst modifications or particularly reactive clastic infill, can produce a local increase in porosity and permeability. The S1 and S2 clastic units represent the most favorable host rocks, where in addition to structural factors, their stratigraphic features play a significant role in controlling the spatial distribution of fluid flow and gold deposition. During a hiatus in sedimentation, weathering and erosional processes affected the surfaces of the limestone and the S1. Limestone/S1 and S1/S2 contacts, as disturbed zones, enabled lateral spreading of the fluids. These clastic units have higher permeability relative to the other units, specifically the S1 and S2 sandstone and conglomerate, and particularly the basal breccia sub-unit developed at the bottom of the S1 unit. Acidic fluids in the contact zones infiltrated the pores of the surrounding rocks and dissolved calcite cement, creating secondary porosity. Gold-bearing fluids infiltrated several tens of meters from the contact zones, utilizing pore space in sandstone, conglomerate, breccia, stylolites and karst features in limestone. In the S1 upper horizons and S2 lower horizons, carbonate material that dominates over the clastic detritus was exposed to dissolution. Schematic model of the formation and modifications of the Bigar Hill deposit are shown in Figure 6.3. 96 97 Figure 6.3: Schematic diagrams of the formation and modification of the Bigar Hill deposit (not to scale): (a) Formation of the sedimentary package and its structural modification, karstification and formation of the weathering crust; (b) Magmatic activity affecting the sedimentary package – diorite intrusion in the vicinity of the deposit and andesite sub-volcanic sill intrusion within the deposit; (c) hydrothermal activity within the Bigar Hill region, porphyry deposit formation in the vicinity of the deposit and SHDG deposit within Bigar Hill; (d) burial of the deposit along graben forming faults. The iron content required for sulfidation varied in different hosting units, in the Cretaceous limestone from 0.1 to 0.4%, in the S1 from 0.6 to 1.3%, and in the S2 unit from 2 to 3.5% (all ranges are interquartile). Iron in the host rocks originated from multiple sources. In the S1 unit and Cretaceous limestone, iron mainly derived from the iron-bearing carbonates. In the S2 unit, major iron-bearing minerals are hematite, magnetite, ferromagnesian minerals from the volcanic detritus, and Fe-carbonates. It is assumed that the major source of iron for the mineralization process derived from carbonates that are easily dissolved by acidic fluids. 6.3.2 Hydrothermal Alteration Hydrothermal fluid-rock interactions result in chemical alteration of both interacting agents. The pervasiveness and intensity of alteration vary depending upon volume, composition and thermodynamic changes of the circulating fluids, including temperature, pH and Eh changes, but also upon host rocks composition, and its mechanical properties including permeability and porosity (Teal and Jackson, 1985). Four main rock alteration types include carbonate dissolution, clay alteration, silica addition, and sulfidation. Decarbonatization is the result of the reactions of acidic fluids with calcite mainly from the cement of the clastic host rocks. The most intensive effects of dissolution, with the removal of all the carbonate components, develop locally at the S1/S2 contact, affecting the narrow zones of few meters. 98 To a lesser degree, decarbonatization effects are noticed to affect the calcite cement in the basal breccia, and also in the fracture zones of “dirty” Cretaceous limestone. In all the cases, the alteration is accompanying by gold enrichment, indicating the intensive fluid-rock interactions. Hydrothermal silica replacement of calcite cement and carbonate fragments is sparse and of low intensity, noted only in the areas with strong carbonate dissolution and high gold grades. The absence of intensive silicification indicates the relatively low temperature of ore formation since silica precipitation is significantly reduced below ~180°C, and diminishes with further cooling, while gold precipitation may continue (Hofstra and Cline, 2000; Emsbo et al., 2003; Cline et al., 2005). Clay alteration has the most substantial impact on the rocks containing alumino-silicate minerals, such as andesite, or volcanic detritus-rich clastic rocks of the S2. Due to the low porosity of andesite, clay alteration was confined in the fault zones, where fluids were able to flow and interact with the rock. Illite is the dominant clay species, identified using the SWIR analysis, while kaolinite and montmorillonite form to a lesser degree. Dickite, nacrite, halloysite are sparsely identified by SWIR (Appendix C). During the interaction between hydrothermal fluids and host rocks, along with the dissolution of carbonates and clay alteration of silicates, the iron released from these, and any other reactive Fe-bearing minerals, reacted with sulfur ions from the fluids, precipitating pyrite (Hofstra and Cline, 2000). Ferroan carbonates, dominantly calcite, and dolomite to a lesser degree, are the main iron source in the sedimentary rocks. Less soluble alumino-silicate minerals, hornblende, and chlorite, present in the volcanic detritus-rich S2 clastic rocks and magmatic rocks are the alternative providers of iron. The sulfidation process results in coupled precipitation of iron sulfides with gold. The assumption is that the transport and deposition of gold of the Bigar Hill deposit generally had a similar mechanism as in the Carlin-type deposits. In moderately acidic, H2S-rich fluids, gold was transported as AuHS0 or Au(HS)2-1 complexes (Hofstra and Cline, 2000; Emsbo et al., 1999). The interaction with calcareous rocks and the dissolution of carbonate minerals caused the neutralization of the acidic fluids. Increasing pH values of the fluids would destabilize the Au-bisulfide complexes, and result in sulfidation of reactive iron released from the Fe-bearing minerals. Liberated gold ions would linger near the newly formed pyrite, and eventually get structurally bound in the sulfide crystal lattice (Hofstra and Cline, 2000; Cline et al., 2005). Except for gold, ore-stage pyrite contains increased content of Sb, Tl, As, Hg and Te. These elements are typical for the low-temperature metal association, and exhibit high correlation with gold. 99 6.4 Exploration Tools for Hydrothermal Gold Deposits 6.4.1 Hydrothermal Alteration The alteration minerals are closely related to the increase in gold grades, and generally, do not extend beyond the mineralization zone. The effects of decarbonatization and silicification are visible only in zones affected by the intensive fluid flow, with high gold grades, and thus have a limited application as an exploration tool that can help to establish vectors towards the mineralization. The distribution of clay species and illite crystallization index were considered as the exploration indicators of ore proximity, particularly since clay mineralogy may indicate specific conditions during the fluid-rock interactions. The transition from smectite (montmorillonite) to illite suggests an increase in temperature (Hofstra and Cline, 2000), or similarly, the transition from kaolinite to its polytypes dickite and nacrite (Ruiz Cruz, 2006). Halloysite is an indicator for lower temperature (<60-75°C) solutions and a higher pH environment, whereas kaolinite forms in more acidic conditions (Drews-Armitage et al., 1996). Illite is a widely distributed clay mineral, present in both hydrothermally altered, and non-altered rocks. Unlike illite, montmorillonite is characteristic for non-altered rocks, and its content decreases with the intensity of the fluid-rock interaction. Kaolinite is not as abundant as illite, but it appears in both non-altered and mineralized rocks. Dickite, nacrite, and halloysite occur only sporadically, and it was not possible to establish zonation indicating the direction of the temperature gradient. The other parameter used in this study, illite crystallinity, was defined as a ratio of depths of 2200 nm and 1900 nm absorption features. This parameter is temperature dependent, its value rising with the temperature. Thus illite crystallinity could potentially be used to establish vectors of the thermal influence of hydrothermal fluids. However, this parameter did not prove to be a robust indicator of clay mineral formation temperature, and therefore cannot be employed to establish the temperature gradient in the hydrothermal system. The parameter could be roughly used to separate the areas not exposed to hydrothermal activities from the areas with weak to intensive fluid circulation. The reason for the limited benefit of using illite crystallinity is the presence in the same place of different genetic types of illite with different formational temperature. The other reason could be analytical, caused by the interference of absorption spectra from the different minerals present in a sample. 6.4.2 Oxygen and Carbon Stable Isotopes During the percolation of the hydrothermal fluids through the carbonate-bearing sedimentary package, changes of oxygen and carbon isotopic composition affected both the rocks and the fluid system. Rocks 100 interacting with fluids show depletion in both δ18O and δ13C values. Oxygen isotope ratios shift from the background values of 29.6-24.2‰ to the altered values of 8.9‰. Carbon shows a slightly lower degree of change, altering from 4.2-1.2‰ in fresh to -4.6‰ in mineralized rocks. When establishing the extent of isotopic depletion, it was essential to consider different background signatures appropriate to different carbonate units. Lower background values of both δ18O and δ13C (25.3-24.2‰ and 1.5-1‰ respectively) are noted in organic matter rich mudstone, while in the other sedimentary units these values are variable but higher. Isotopic depletion has a weak correlation with gold enrichment, while the correlation with gold accompanying trace elements (Hg, Tl, Sb, As, Te) is somewhat stronger. Even though changes in δ18O and δ13C do not correlate strongly with the distribution of gold mineralization, they clearly outline the domains around the feeder and main fluid conduit structures and highly porous and permeable discontinuities in sedimentary rocks. To a limited extent, isotopic shifts enable the identification of the inferred (sub-) vertical faults, as the zones with noticeable oxygen/carbon depletion. The halo formed during the isotopic exchange extends over a few hundred meters around mineralization, and it is broader than the distribution of alteration minerals or trace elements that formed during the same processes and generally coincided with the gold distribution (Figure 6.4). Figure 6.4: Distribution of δ18O (grid data), As (downhole data), and illite crystallinity (point data) and their spatial relationship with gold, and structural and stratigraphic controls. 101 The broader distribution of isotopic alteration can be effectively utilized in exploration. If accurate background values are established for the particular carbonate-bearing sedimentary rocks, tracking the changes in the isotopic composition can be a useful tool in vectoring towards blind deposits at depth or identifying structurally or stratigraphically controlled fluid pathways. 6.5 Temporal Constraints on Geological Processes Relevant to the Bigar Hill Deposit Formation To fully characterize the mechanism of the Bigar Hill deposit formation, it is crucial to establish the chronology of relevant sedimentary, magmatic and hydrothermal events. The geochronology data helps not only to understand better the processes that preceded or enabled the gold deposition but also to put those processes into the perspective of the deposit-forming activities in the TMC and the broader Cretaceous Carpathian-Balkanian belt. The ages of the stratigraphic units were defined mainly by characteristic fossils and superposition relationships. The age of the S2 unit was established indirectly using U-Pb geochronology on detrital zircons. The window of 93.3 ± 3.1 Ma to 87.5 ± 3.1 Ma defines the age range of igneous protolith rocks and indirectly suggest the maximum age of the clastic rocks. Taken together, these data constrain the period of regional sedimentary deposition between the Late Jurassic to Late Cretaceous. During that period sedimentation was not continuous, and the breaks between deposition of major stratigraphic units lasted for several millions of years. The rocks were subsequently exposed to weathering and erosional processes, resulting in increased porosity and permeability, and local iron enrichment, thus forming the favorable horizons along which the gold-bearing fluids were flowing into the sedimentary rocks. Determining the age of the gold mineralization proves to be a complex task. The very fine-grained character of mineralization, as well as the paucity of datable or separable minerals with a clear genetic association with gold, represent the main difficulties. Due to the inability to establish the direct age of the Bigar Hill disseminated mineralization, the K-Ar technique has been applied on illite that formed during hydrothermal alteration. Previous petrographic studies suggest a spatial relationship of illite and gold-bearing pyrite. Therefore, illites were separated from the intensively altered and highly mineralized S2 sandstone and andesite. Dating identified the ages for the illite formation at approximately 79 ± 3 Ma, excluding two older samples which are considered to partially represent detrital illite. The Campanian age of the dated clay minerals suggests that the hydrothermal activity within the 102 sedimentary package was largely contemporaneous with the Late Cretaceous magmatic activity in the northwestern TMC. Another approach used to indirectly determine the age of mineralization includes dating an andesite sill from the Bigar Hill and a younger diorite from the eastern margin of the deposit using the U-Pb in zircon technique. The idea of dating andesite sill was to establish the maximum age of the gold mineralization given that this is the youngest gold-bearing lithology unit, but the sample yield no zircons or any other datable mineral. However, the age of the plagioclase-hornblende porphyritic diorite that intruded the andesite sill is determined to be 80.2 ± 0.8 Ma, indirectly constraining the minimum age of the sill and the maximum age of the ore-forming processes. This age matches within the error with the K-Ar age of illite, thus increasing the credibility to the interpretational Campanian age of mineralization. Previous U-Pb zircon dating of the intrusive rocks in the northwestern part of the TMC (Tosdal, 2012), was conducted with the goal to establish the time frame of the magmatic activity, indicating a period of 2–6 million years from 82.5 ± 0.6 to 78.5 ± 2.0 Ma. Although temporal and spatial associations exist between the ore deposit and local diorite intrusions, their genetic link remains unproven. However, the geochemical footprint established by soil data, and the zonal distribution of chalcophile metals ranging from the high temperature assemblage (Cu, Mo, Au), intermediate (Pb, Zn, Ag, Au) to the low temperature assemblage (Au, As, Sb, Hg, Tl, Te) suggest a potential genetic relationship between the Bigar Hill mineralization and the Čoka Rakita gold porphyry system to the southeast (Figure 5.2 and Figure 6.1). The age of large Potaj Čuka monzonite batholith positioned south of Bigar Hill was determined to be between 80.0 ± 1.2 to 79.9 ± 0.5 Ma, but because its spatial and temporal relationship with the SHDG is unclear, a genetic link is not well-established. However, the impact of this sizeable magmatic body should not be neglected, at least as a thermal driver for the circulation of surface fluids and potentially as a source of gold-bearing magmatic-hydrothermal fluids. 6.6 Deposit Model A proposed metallogenic model suggests that the SHDG mineralization represents the distal extension of the porphyry Au system (Knaak et al., 2016). In that model, the porphyry system is considered to be a source of metal and heat. The origin of hydrothermal fluids, either from magmatic or meteoric water, remained unconstrained. “The perfect storm” of structural and stratigraphic features has provided favorable conditions for the circulation of gold-bearing fluids, their interaction with the sedimentary rocks, and ultimately gold precipitation. NW-oriented faults are recognized as the feeder structures that channeled fluids from the source towards the favorable stratigraphy. NE structures had a role in 103 increasing the permeability of sedimentary rocks that opened additional pathways for fluid flow. Within such structurally prepared, heterogeneous sedimentary package, its units had a different significance for fluid flow and the associated gold mineralization. Calcareous units with reactive iron, primarily permeable and porous, disturbed by processes like weathering, erosion, karstification, pressure dissolution and structural events that further increased permeability and porosity, proved to be the most favorable host rocks. For all these reasons, the S1 and S2 units, particularly the contact zones between S1 and S2, and also S1 (basal breccia) and the Cretaceous limestone served as the main mineralization hosts. The continental margin thick sequence of reactive calcareous sedimentary rocks, structurally modified by intermittent extensional and compressional deformation phases represents the ideal pre-mineral architecture that favored the deposition of the Bigar Hill gold mineralization, but also Carlin-type deposits. Apart from the stratigraphic and structural gold controls, Bigar Hill shares many key characteristics of the ore-forming processes with Carlin-type deposits, such as hydrothermal alteration, gold deposition mechanism, and the accompanied trace metals. In interaction with acidic fluids, calcareous host rocks were exposed to decarbonatization and silicification. Magmatic rocks that were part of the host rock package were exposed to argillization with illite and kaolinite as dominant minerals. Gold is hosted in pyrite or in its oxides. Trace metals associated with gold are As, Sb, Te, Tl, and Hg. Ore-fluids utilized the pathways within zones of increased permeability. However, genetic and spatial relation to magmatic intrusions, porphyry, skarn, and polymetallic replacement deposits classifies the Bigar Hill as the distal disseminated gold deposit (Figure 6.5). Its gold grade is relatively low compared to Carlin-type deposits. However, gold deposition from higher-temperature fluids (>250°C) and higher concentrations of silver and base metals that are typical for distal disseminated deposits but not for the Bigar Hill. Based on the characteristics that the Bigar Hill shares with the Carlin-type and distal disseminated gold deposits it can be defined as the transition between these two genetic types of gold mineralization. 104 Figure 6.5: Simplified NW long section across the Bigar Hill, Bigar and Čoka Rakita, showing the spatial distribution of different magmatic-hydrothermal mineralization types. 105 CHAPTER 7 – CONCLUSION, EXPLORATION IMPLICATIONS, AND RECOMMENDATIONS FOR FUTURE WORK 7.1. Conclusion The Bigar Hill is a sediment-hosted disseminated gold deposit hosted in calcareous rocks. The mineralization-hosting sedimentary package unconformably overlies metamorphic basement and is composed of a Late Jurassic and Early Cretaceous carbonate platform limestone sequence and Early to Late Cretaceous calcareous clastic rocks. The limestone sequence includes geochemically pure Jurassic limestone and “dirty” Cretaceous limestone with variably abundant organic and clastic components. The clastic sequence contains several calcareous units: (1) S1 siliciclastic unit, dominantly composed of sandstone to sandy limestone, but also mudstone and siltstone (IB sub-unit) and basal breccia (BBX), (2) S2 volcanic detritus-rich sandstone and conglomerate, and (3) marl. The youngest lithology is a sub-volcanic andesite sill that intruded the marls. All of the lithology units host gold enrichment in variable grades, mainly depending on their structural and stratigraphic features. The NW-trending, high-angle, long-lived fault system acted as a primary gold-bearing fluid corridor. Its increased permeability and porosity compared to the structurally-undisturbed country rock facilitated transportation of metals-bearing fluids from deeper sources. NE-trending faults are second-order structures that additionally increased permeability. These fault systems also enabled infiltration and subsequent lateral spreading of the gold-bearing fluids into favorable mineralization horizons. The locations of these faults are constrained by 3D modeling, by visualizing changes in thickness and by the orientations of the stratigraphic units. The distribution of gold and associated trace metals corroborates the presence of the main structural trends. The zonation of the trace metals supports the hierarchy of differently oriented faults in channeling fluid flow, where the high and moderate temperature fluids deposited elevated Bi, W, Pb, Zn, In, Cd, Se, Te along the NW-trend in the lower stratigraphic units (limestone), while the low-temperature assemblage with elevated As, Sb, Tl, Hg, Te, and Ag followed the NE-trend in the upper, clastic units. Gold-bearing acidic fluid flow along (sub-) vertical faults and fracture zones infiltrated sedimentary units laterally along zones of internal structural heterogeneity. The main discontinuities include unconformities between sedimentary units, comprising weathering crust, the karstification of former surfaces, and breccia bodies. Stylolites are another feature characteristic of the calcareous rocks that are 106 frequently utilized by fluids. In these conduits, acidic fluids would infiltrate surrounding rocks and react with carbonates, dissolving the calcite cement or carbonate fragments and creating secondary porosity and permeability. Gold precipitation occurs during the sulfidation that results from the reaction of sulfur in the hydrothermal fluids with iron in the host rocks, which destabilizes aqueous Au-bisulfide complexes (Muntean, 2016). Ferroan carbonates are the main iron-bearing minerals in the sedimentary sequence, while hornblende or chlorite represent the iron source in magmatic rocks or volcanic detritus-rich S2 clastic rocks. The highest gold concentrations occur along the S1/S2 and basal breccia/Cretaceous limestone contacts. Patchy and relatively low concentrations of gold precipitated along the karstified contact between Jurassic and Cretaceous limestone. Structurally-controlled mineralization, of relatively high importance but restricted distribution occurs in the fracture zones in the Cretaceous limestone and andesitic sill. The interaction between host rocks and low-temperature, acidic fluids caused compositional changes in both the rock and the fluid and eventually led to gold deposition. Carbonate dissolution, silica addition and clay alteration of silicate minerals are the most prominent consequences of hydrothermal alteration. The most intensive decarbonatization affected the S1 and S2 units, from their contact zone towards the undisturbed rocks. Pervasive clay alteration was the strongest in the fault/fracture zones in the andesite, but also affected the volcanic detritus of the S2 clastic rocks. The primary product of the clay alteration is illite and to a lesser extent kaolinite and montmorillonite. Silica addition occurs locally and is usually related to highly mineralized zones, where microcrystalline silica replaced calcite cement or carbonate fragments. The described alteration changes do not develop a substantial footprint which exceeds the domain of ore, as is often the case for higher temperature ore systems, but mainly coincide with the distribution of gold. The interaction of hydrothermal fluids with carbonate minerals results in changes in their oxygen and carbon isotopic composition. Stable isotope depletions occur further away from the mineralization and visible host rock alteration (e.g., decarbonatization), and also from the distribution of specific pathfinder elements such as Hg, Tl, Sb, As, Te. Zones of low stable isotope ratios outline the zones exposed to percolation of hydrothermal fluids. Previous U-Pb zircon age dating suggests that magmatism in the west and central TMC spanned about six million years during the Late Cretaceous (83.6-77.7 Ma). Diorite and monzonite ages generally fit into 107 the existing hypothesis of the westward younging of magmatism in the TMC. Available age data indicates that the Potaj Čuka monzonite batholith, although spatially associated, is generally younger than diorite intrusions, except in the cases of Valja Strž and Crna Reka porphyritic diorite whose emplacement happen after the monzonite pluton. The age of one of the main Bigar Hill gold hosting lithologies – the S2 sandstone, is constrained by U-Pb dating of detrital zircons which covers the period from 93.3 to 87.5 ± 3.1 Ma, thus also constraining the age of the sandstone’s protolith. Since the erosion rate of the magmatic protolith and the transport distance and duration are unknown, it can only be inferred that the S2 sandstone is younger than the dated zircons. Hydrothermal illite is used as a proxy for gold mineralization and is dated with the K-Ar technique at ca. 79 Ma. The radiometric ages of illite and zircons of the western TMC indicate that deposit-scale hydrothermal and magmatic activities were largely contemporaneous during the Late Cretaceous and that illite formation closely followed zircon crystallization. 7.2 Exploration Implications and Recommendations for Future Work The Bigar Hill distal disseminated gold deposit is a recent discovery of a previously unrecognized type of mineralization on the flanks of the TMC and the broader Cretaceous arc region. This study has contributed to a better understanding of the geological features and critical processes necessary for the formation of the deposit. The collected data set is significant and informative; it enabled the genetic type of the deposit to be established and evaluated against its global counterparts and also helped to establish targeting criteria for further exploration. Significant exploration implications that can be applied not only on the sedimentary package around the TMC but globally, are represented below:  Distal disseminated deposits exhibit spatial, chemical and temporal links with related porphyry deposits (e.g., Theodore, 1998; Hofstra and Cline, 2000, Johnston and Ressel, 2004). Exploration for this deposit type should involve the targeting of sedimentary rocks in the vicinity of felsic to intermediate calc-alkaline magmatic centers. The genetic link between the magmatic metal and/or heat source and low-temperature mineralization can be established based on the distribution of pathfinder trace metals, from the high-temperature assemblage of Cu, Mo, Au, through moderate Pb, Zn, Ag, towards low-temperature elements such as Au, As, Tl, Hg, Sb, Te.  Gold mineralization is present in all of the Bigar Hill lithologic units, including the sub-volcanic andesite sill. However, the main mineralization host rocks are carbonate-bearing sedimentary rocks. Gold exhibited a different susceptibility to the lithologic varieties within the sedimentary carbonate package, with lowest gold content in marls, variable concentrations in limestone, and 108 highest in siliciclastic S1 and S2 units. The conclusion may be that exploration efforts should focus on carbonate-rich targets, mainly calcareous siliciclastic rocks.  The structural network represents a first-order control on the spatial location of the mineralization. Therefore, understanding of the area’s structural framework is crucial for exploration. It is important to identify significant faults that have gone through several stages of activation and connected the metal source and trap zone. Second order structures that channeled fluids further into the host stratigraphy are equally essential to identify. These include smaller faults that created additional porosity and permeability of the rocks.  Within calcareous sedimentary units, mineralization lies along the contacts of limestone and S1, or S1 and S2. These contact zones have been modified by surface weathering and erosion (karstification), thus producing preferential pathways for the mineralization fluids. Focusing on contact zones narrows the target zone within the sedimentary package.  A better understanding of the alteration product assemblages, including clay minerals, could enable their successful use as exploration vectors in low-temperature hydrothermal systems. SWIR spectroscopy carried out in this study elucidated the spatial distribution of clay minerals and allowed calculation of the illite crystallinity index as the ratio of the depth of AlOH and water adsorption features. However, identification of illite crystallinity zonation patterns is hampered by the presence of different genetic varieties of illite that are indistinct from one another by SWIR spectroscopy (hydrothermal, diagenetic, or detrital). Further study on various clay characteristics such as chemical composition, textural features (size, morphology), polytypism, Kübler illite crystallinity index or formation temperature could help establish vectors to mineralization.  Variations in δ18O and δ13C values in carbonate host rocks acted as a tool to identify isotopic alteration and to delineate hydrothermal fluid flow pathways within the deposit. Oxygen and carbon isotope ratios have proven useful for identifying hydrothermally altered lithologies that did not develop visible secondary mineral assemblages. The extent of stable isotope alteration is larger than that of gold and other recognized pathfinder elements. 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L., Koželj, D., Bogdanov, K., Berza, T., 2008: Tectonic configuration of the Apuseni-Banat-Timok-Srednogorie belt, Balkans-South Carpathians, constrained by high precision Re-Os molybdenite ages: Mineralium Deposita, v. 43, p. 1-21. 117 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD083 13JZBH001 570704 4898132 UTM(WGS84)34N 785/-50.35 Propylitic altered andesitic sill VOL BHDD083 13JZBH002 570704 4898132 UTM(WGS84)34N 785/-62.25 Clay altered andesite with pyrite disseminations VOL + BHDD083 13JZBH003 570704 4898132 UTM(WGS84)34N 785/-71.8 Propylitic altered andesitic sill VOL + BHDD083 13JZBH004 570704 4898132 UTM(WGS84)34N 785/-77.6 Weakly clay altered andesite VOL BHDD083 13JZBH005 570704 4898132 UTM(WGS84)34N 785/-89 Propylitic altered andesitic sill VOL + BHDD084 13JZBH006 570652 4898169 UTM(WGS84)34N 785/-172.95 Green sandstone with dominant volcanic detritus S2 + BHDD084 13JZBH007 570652 4898169 UTM(WGS84)34N 785/-173.6 Gray, partially decarbonatized sandstone, with disseminate pyrite S2 + BHDD084 13JZBH008 570652 4898169 UTM(WGS84)34N 785/-175.6 Gray, partially decarbonatized sandstone, with disseminate pyrite S2 + + BHDD084 13JZBH009 570652 4898169 UTM(WGS84)34N 785/-191.62 Gray sandstone with pyrite disseminated and in veins S2 BHDD084 13JZBH010 570652 4898169 UTM(WGS84)34N 785/-200.52 Transition from non-altered to visibly decarbonatized sandstone S2 BHDD084 13JZBH011 570652 4898169 UTM(WGS84)34N 785/-201.2 Sandstone decarbonatized, clay altered and sulfidized with 8 ppm Au S2 BHDD084 13JZBH012 570652 4898169 UTM(WGS84)34N 785/-202.3 Sulfidized sandstone S1 BHDD084 13JZBH013 570652 4898169 UTM(WGS84)34N 785/-207.6 Carbonate sandstone with stylolites S1 + + BHDD084 13JZBH014 570652 4898169 UTM(WGS84)34N 785/-219.8 Alternation of sandstone with thin laminas of mudstone S1 BHDD084 13JZBH015 570652 4898169 UTM(WGS84)34N 785/-245.37 Alternation of siltstone, fine-grained sandstone, and diagenetic pyrite IB BHDD084 13JZBH016 570652 4898169 UTM(WGS84)34N 785/-250.4 Sulfidized, dolomitized breccia BBX + + BHDD084 13JZBH017 570697 4898213 UTM(WGS84)34N 775/-94.85 Clay altered, sulfidized andesite VOL BHDD085 13JZBH018 570697 4898213 UTM(WGS84)34N 775/-95.65 Chlorite, epidote altered andesite VOL BHDD085 13JZBH019 570697 4898213 UTM(WGS84)34N 775/-110.33 Chlorite, epidote altered andesite VOL BHDD085 13JZBH020 570697 4898213 UTM(WGS84)34N 775/-161 Hematite rich gravelite S2 118 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD085 13JZBH021 570697 4898213 UTM(WGS84)34N 775/-167.65 gray, sulfidized sandstone with abundant volcanic detritus S2 + BHDD085 13JZBH022 570697 4898213 UTM(WGS84)34N 775/-190.45 Alternation of sandy and gravelite clastic material S2 + BHDD085 13JZBH023 570697 4898213 UTM(WGS84)34N 775/-193.55 Conglomerate, volcanic material rich S2 BHDD085 13JZBH024 570697 4898213 UTM(WGS84)34N 775/-194.73 Strongly carbonate dissolved and silicified sandstone S1 + BHDD085 13JZBH025 570697 4898213 UTM(WGS84)34N 775/-195.2 Strongly carbonate dissolved and silicified sandstone with 3.42 ppm Au S1 BHDD085 13JZBH026 570697 4898213 UTM(WGS84)34N 775/-196.35 Brecciated, clay altered sandstone S1 BHDD085 13JZBH027 570697 4898213 UTM(WGS84)34N 775/-209.6 Oxidized, brecciated sandstone S1 BHDD085 13JZBH028 570697 4898213 UTM(WGS84)34N 775/-258.55 Basal breccia, with sulfidized fine-grained matrix BBX BHDD086 13JZBH029 570431 4898382 UTM(WGS84)34N 723/-17.45 Skarn altered marl from the contact with andesite SMR BHDD086 13JZBH030 570431 4898382 UTM(WGS84)34N 723/-53.5 Laminated marl SMR BHDD086 13JZBH031 570431 4898382 UTM(WGS84)34N 723/-60.9 Fine-grained sandstone with disseminated diagenetic pyrite S2 + + BHDD086 13JZBH032 570431 4898382 UTM(WGS84)34N 723/-67.6 Coarse-grained sandstone with abundant volcanic material S2 BHDD086 13JZBH033 570431 4898382 UTM(WGS84)34N 723/-74.4 Fine-grained sandstone with disseminated pyrite S2 + BHDD086 13JZBH034 570431 4898382 UTM(WGS84)34N 723/-82.35 Contact between non-altered and decarbonatized sandstone S2 + + BHDD086 13JZBH035 570431 4898382 UTM(WGS84)34N 723/-84.6 Strongly oxidized and brecciated sandstone S1 BHDD086 13JZBH036 570431 4898382 UTM(WGS84)34N 723/-90.2 Sandstone exposed to carbonate dissolution S1 BHDD086 13JZBH037 570431 4898382 UTM(WGS84)34N 723/-103.6 Partially oxidized, decarbonatized sandstone S1 BHDD086 13JZBH038 570431 4898382 UTM(WGS84)34N 723/-125 Sandy limestone S1 BHDD086 13JZBH039 570431 4898382 UTM(WGS84)34N 723/-144.45 Laminated mudstone/siltstone IB BHDD086 13JZBH040 570431 4898382 UTM(WGS84)34N 723/-176.55 Faulted breccia-conglomerate BBX 119 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD087 13JZBH041 570521 4898327 UTM(WGS84)34N 761/-30 Chlorite, epidote altered andesite VOL BHDD087 13JZBH042 570521 4898327 UTM(WGS84)34N 761/-45.8 Clay altered andesite VOL BHDD087 13JZBH043 570521 4898327 UTM(WGS84)34N 761/-54 Strongly clay and carbonate altered andesite VOL BHDD087 13JZBH044 570521 4898327 UTM(WGS84)34N 761/-56 Clay altered andesite VOL BHDD087 13JZBH045 570521 4898327 UTM(WGS84)34N 761/-94.55 Carbonate veins in andesite VOL BHDD087 13JZBH046 570521 4898327 UTM(WGS84)34N 761/-95.15 Chlorite, epidote altered andesite VOL BHDD087 13JZBH047 570521 4898327 UTM(WGS84)34N 761/-122.9 Coarse-grained sandstone with abundant volcanic material S2 + BHDD087 13JZBH048 570521 4898327 UTM(WGS84)34N 761/-141.37 Dark, volcanic material rich sandstone S2 BHDD087 13JZBH049 570521 4898327 UTM(WGS84)34N 761/-150.7 Green, fine-grained sandstone S2 BHDD087 13JZBH050 570521 4898327 UTM(WGS84)34N 761/-151.7 Decarbonatized and clay-altered sandstone S2 BHDD087 13JZBH051 570521 4898327 UTM(WGS84)34N 761/-152.1 Decarbonatized and clay-altered sandstone S2 + + BHDD087 13JZBH052 570521 4898327 UTM(WGS84)34N 761/-156.6 Greenish, decarbonatized sandstone S2 BHDD087 13JZBH053 570521 4898327 UTM(WGS84)34N 761/-158.2 Faulted sandstone S2 BHDD087 13JZBH054 570521 4898327 UTM(WGS84)34N 761/-163.1 Strongly decarbonitized sandstone with sooty pyrite S2 + BHDD087 13JZBH055 570521 4898327 UTM(WGS84)34N 761/-166.65 Strongly decarbonitized sandstone with sooty pyrite with 9.7 ppm Au S2 BHDD087 13JZBH056 570521 4898327 UTM(WGS84)34N 761/-168.75 Brecciated sandy limestone S1 BHDD087 13JZBH057 570521 4898327 UTM(WGS84)34N 761/-170.3 Partially oxidized, brecciated sandstone S1 BHDD087 13JZBH058 570521 4898327 UTM(WGS84)34N 761/-175.63 Sandy limestone S1 BHDD087 13JZBH059 570521 4898327 UTM(WGS84)34N 761/-191.3 Carbonate sandstone S1 BHDD087 13JZBH060 570521 4898327 UTM(WGS84)34N 761/-209.25 Polymictic breccia, with pyrite in fine-grained matrix BBX BHDD026 13JZBH061 570220 4898565 UTM(WGS84)34N 685/-13.55 Green, volcanic material rich sandstone S2 + 120 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD026 13JZBH062 570220 4898565 UTM(WGS84)34N 685/-19.15 Contact between oxidized and non-oxidized sandstone S2 BHDD026 13JZBH063 570220 4898565 UTM(WGS84)34N 685/-23.85 Oxidized, clay altered sandstone from the fault zone S2 BHDD026 13JZBH064 570220 4898565 UTM(WGS84)34N 685/-34.8 Strongly oxidized, decarbonatized sandstone S2 BHDD026 13JZBH065 570220 4898565 UTM(WGS84)34N 685/-48.7 Skarn altered sandstone S1 BHDD026 13JZBH066 570220 4898565 UTM(WGS84)34N 685/-58.15 Contact between oxidized zone in conglomerate and fresh in sandstone S1 BHDD026 13JZBH067 570220 4898565 UTM(WGS84)34N 685/-75.8 Brecciated, skarn altered sandstone S1 BHDD026 13JZBH068 570220 4898565 UTM(WGS84)34N 685/-80.2 Sandstone with pyrite disseminations S1 BHDD026 13JZBH069 570220 4898565 UTM(WGS84)34N 685/-82.25 Brecciated, skarn altered sandstone S1 + BHDD026 13JZBH070 570220 4898565 UTM(WGS84)34N 685/-101 Brecciated sandstone with fine-grained matrix S1 BHDD026 13JZBH071 570220 4898565 UTM(WGS84)34N 685/-157.6 Carbonate sandstone S1 BHDD020 13JZBH072 570373 4898559 UTM(WGS84)34N 691/-6.1 Oxidized, strongly decarbonatized granulite S2 BHDD020 13JZBH073 570373 4898559 UTM(WGS84)34N 691/-13.5 Oxidized, fine-grained sandstone rich in volcanic material S2 BHDD020 13JZBH074 570373 4898559 UTM(WGS84)34N 691/-16.7 Strongly oxidized sandstone, decalcified, with 10.66 ppm Au S2 BHDD020 13JZBH075 570373 4898559 UTM(WGS84)34N 691/-16.85 From the same interval, less oxidized sandstone S2 BHDD020 13JZBH076 570373 4898559 UTM(WGS84)34N 691/-17.9 Weakly oxidized, brecciated sandstone S2 BHDD020 13JZBH077 570373 4898559 UTM(WGS84)34N 691/-21.85 Weakly oxidized sandstone S2 BHDD020 13JZBH078 570373 4898559 UTM(WGS84)34N 691/-22.9 Strongly oxidized, decarbonatized sandstone S2 BHDD020 13JZBH079 570373 4898559 UTM(WGS84)34N 691/-24.05 Strongly oxidized, brecciated, decarbonatized sandstone S2 BHDD020 13JZBH080 570373 4898559 UTM(WGS84)34N 691/-30.95 Brecciated sandstone with oxide infill in stylolites S1 BHDD020 13JZBH081 570373 4898559 UTM(WGS84)34N 691/-36.4 Dacarbonatized, sulfidized sandstone S1 121 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD020 13JZBH082 570373 4898559 UTM(WGS84)34N 691/-51 Brecciated sandy limestone S1 BHDD020 13JZBH083 570373 4898559 UTM(WGS84)34N 691/-124.35 Carbonate sandstone with finer-grained laminas S1 BHDD020 13JZBH084 570373 4898559 UTM(WGS84)34N 691/-153.9 Oxidation front in carbonate sandstone S1 + BHDD020 13JZBH085 570373 4898559 UTM(WGS84)34N 691/-185.15 Breccia with oxidized sandy matrix and limestone clasts BBX BHDD020 13JZBH086 570373 4898559 UTM(WGS84)34N 691/-196.3 Oxidized sandstone breccia matrix BBX BHDD020 13JZBH087 570373 4898559 UTM(WGS84)34N 691/-197.85 Breccia with oxidized granulite size matrix BBX BHDD004 13JZBH088 570364 4898444 UTM(WGS84)34N 701/-17.8 Green, hematite clasts rich sandstone S2 + BHDD004 13JZBH089 570364 4898444 UTM(WGS84)34N 701/-20.9 Clay altered sandstone with disseminated pyrite S2 + BHDD004 13JZBH090 570364 4898444 UTM(WGS84)34N 701/-37.5 Strongly decarbonitized conglomerate-sandstone S2 + BHDD004 13JZBH091 570364 4898444 UTM(WGS84)34N 701/-49.3 Fine-grained, skarn altered sandstone S1 + + BHDD004 13JZBH092 570364 4898444 UTM(WGS84)34N 701/-49.7 Clastite with zones of different alteration S1 BHDD004 13JZBH093 570364 4898444 UTM(WGS84)34N 701/-63.3 Brecciated, dolomitized sandstone S1 BHDD004 13JZBH094 570364 4898444 UTM(WGS84)34N 701/-69.5 Oxidized, brecciated sandstone S1 BHDD004 13JZBH095 570364 4898444 UTM(WGS84)34N 701/-81.7 Brecciated sandy limestone S1 BHDD004 13JZBH096 570364 4898444 UTM(WGS84)34N 701/-89.35 Brecciated, partially decarbonatized sandstone S1 BHDD004 13JZBH097 570364 4898444 UTM(WGS84)34N 701/-125.25 Laminated mudstone-siltstone IB BHDD004 13JZBH098 570364 4898444 UTM(WGS84)34N 701/-135.45 Breccia, partially decarbonatized BBX BHDD004 13JZBH099 570364 4898444 UTM(WGS84)34N 701/-137 Breccia with partially oxidized and sulfidized matrix and 4.66 ppm Au BBX BHDD004 13JZBH100 570364 4898444 UTM(WGS84)34N 701/-147 Breccia-conglomerate with sandy matrix BBX BHDD004 13JZBH101 570364 4898444 UTM(WGS84)34N 701/-195.8 Gray Cretaceous limestone, fractured, with calcite veins KLS 122 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD005 13JZBH102 570533 4898412 UTM(WGS84)34N 747/-9.2 Oxidized , thermally altered marl at the contact with andesite SMR BHDD005 13JZBH103 570533 4898412 UTM(WGS84)34N 747/-18.25 Strongly clay altered, and partially oxidized andesite from the fault zone VOL BHDD005 13JZBH104 570533 4898412 UTM(WGS84)34N 747/-45.92 Thermally altered marl SMR BHDD005 13JZBH105 570533 4898412 UTM(WGS84)34N 747/-106.6 Conglomerate-sandstone transition, rich in volcanic material S2 BHDD005 13JZBH106 570533 4898412 UTM(WGS84)34N 747/-126.45 Green-reddish sandstone rich in volcanic detritus S2 + BHDD005 13JZBH107 570533 4898412 UTM(WGS84)34N 747/-131 Light gray to gray sandstone with diagenetic pyrite S2 + BHDD005 13JZBH108 570533 4898412 UTM(WGS84)34N 747/-139.2 Partially oxidized carbonate sandstone S1 BHDD005 13JZBH109 570533 4898412 UTM(WGS84)34N 747/-144.5 Brecciated sandstone filled with calcite S1 BHDD005 13JZBH110 570533 4898412 UTM(WGS84)34N 747/-158.7 Brecciated sandstone with finer-grained material between clasts S1 + BHDD005 13JZBH111 570533 4898412 UTM(WGS84)34N 747/-163.55 Bedded sandstone with disseminated pyrite S1 BHDD005 13JZBH112 570533 4898412 UTM(WGS84)34N 747/-175.15 Siltstone-mudstone alternation with diagenetic pyrite IB BHDD005 13JZBH113 570533 4898412 UTM(WGS84)34N 747/-185 Breccia-conglomerate with sandy matrix, with disseminated pyrite BBX BHDD005 13JZBH114 570533 4898412 UTM(WGS84)34N 747/-197.9 Sandy matrix of the polymictic breccia BBX BHDD041 13JZBH115 570221 4898488 UTM(WGS84)34N 686/-11.8 Oxidation front in coarse-grained sandstone S2 BHDD041 13JZBH116 570221 4898488 UTM(WGS84)34N 686/-15.8 Fractured sandy limestone, with calcite veins S1 BHDD041 13JZBH117 570221 4898488 UTM(WGS84)34N 686/-45.2 Thermally altered sandstone S1 BHDD041 13JZBH118 570221 4898488 UTM(WGS84)34N 686/-55.6 Sandstone with pyrite filled stylolites S1 + BHDD041 13JZBH119 570221 4898488 UTM(WGS84)34N 686/-57 Skarn altered sandstone S1 BHDD041 13JZBH120 570221 4898488 UTM(WGS84)34N 686/-79.1 Skarn altered sandstone S1 BHDD041 13JZBH121 570221 4898488 UTM(WGS84)34N 686/-100.85 Calcite-pyrite veins in carbonate sandstone S1 123 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD041 13JZBH122 570221 4898488 UTM(WGS84)34N 686/-123.3 Sandstone-skarn altered siltstone contact S1 BHDD041 13JZBH123 570221 4898488 UTM(WGS84)34N 686/-134.45 Breccia with pyrite filled stylolite BBX BHDD007 13JZBH124 570534 4898248 UTM(WGS84)34N 776/-157.6 Conglomerate with re-deposited S2 sandstone S2 BHDD007 13JZBH125 570534 4898248 UTM(WGS84)34N 776/-180 Contact of green and light gray sandstone S2 BHDD007 13JZBH126 570534 4898248 UTM(WGS84)34N 776/-180.45 Sandstone oxidized along laminas S2 + BHDD007 13JZBH127 570534 4898248 UTM(WGS84)34N 776/-181.65 Clay altered, sulfidized sandstone S2 BHDD007 13JZBH128 570534 4898248 UTM(WGS84)34N 776/-185.4 Oxidized, brecciated sandstone S1 BHDD007 13JZBH129 570534 4898248 UTM(WGS84)34N 776/-190.95 Brecciated sandstone, with calcite infill S1 + BHDD007 13JZBH130 570534 4898248 UTM(WGS84)34N 776/-193.2 Contact of sandy limestone with stylolites and finer-grained fraction S1 + BHDD007 13JZBH131 570534 4898248 UTM(WGS84)34N 776/-233.35 Brecciated sandstone with pyrite matrix infill and 12.08 ppm Au BBX BHDD068 13JZBH132 570761 4898166 UTM(WGS84)34N 769/-40.9 Strongly clay altered andesite with pyrite nests and calcite-pyrite veins VOL BHDD068 13JZBH133 570761 4898166 UTM(WGS84)34N 769/-48.2 Clay, pyrite altered andesite VOL + BHDD068 13JZBH134 570761 4898166 UTM(WGS84)34N 769/-49.8 Chlorite, clay altered andesite VOL BHDD068 13JZBH135 570761 4898166 UTM(WGS84)34N 769/-136 Brecciated marl SMR BHDD068 13JZBH136 570761 4898166 UTM(WGS84)34N 769/-136.6 Laminated marl SMR BHDD068 13JZBH137 570761 4898166 UTM(WGS84)34N 769/-153.55 Dark green, volcanic material rich sandstone S2 BHDD068 13JZBH138 570761 4898166 UTM(WGS84)34N 769/-160.6 Clay altered sandstone with pyrite concentrations along lamination S2 BHDD068 13JZBH139 570761 4898166 UTM(WGS84)34N 769/-173.45 Clay and pyrite altered sandstone S2 + BHDD068 13JZBH140 570761 4898166 UTM(WGS84)34N 769/-174.35 Coarse-grained sandstone with abundant volcanic material S2 BHDD068 13JZBH141 570761 4898166 UTM(WGS84)34N 769/-187.6 Reddish sandstone with pyrite disseminations S2 + 124 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD068 13JZBH142 570761 4898166 UTM(WGS84)34N 769/-211.6 Sandy limestone S1 + + BHDD068 13JZBH143 570761 4898166 UTM(WGS84)34N 769/-214.6 Sandy limestone alternating with finer clastic fractions S1 + BHDD017 13JZBH144 570854 4898097 UTM(WGS84)34N 742/-14 Skarn altered marl at the contact with andesite SMR BHDD017 13JZBH145 570854 4898097 UTM(WGS84)34N 742/-17.2 Tuffaceous marl SMR BHDD017 13JZBH146 570854 4898097 UTM(WGS84)34N 742/-34.5 Clay alteration front in andesite VOL BHDD017 13JZBH147 570854 4898097 UTM(WGS84)34N 742/-39.9 Propylitic altered andesitic sill VOL BHDD017 13JZBH148 570854 4898097 UTM(WGS84)34N 742/-49.1 Enclaves within andesite VOL BHDD017 13JZBH149 570854 4898097 UTM(WGS84)34N 742/-147.3 Transition between S2 sandstone and marl SMR BHDD017 13JZBH150 570854 4898097 UTM(WGS84)34N 742/-164.45 Coarse-grained reddish sandstone with abundant volcanic material S2 BHDD017 13JZBH151 570854 4898097 UTM(WGS84)34N 742/-182.45 Contact of reddish and greenish sandstone S2 + BHDD017 13JZBH152 570854 4898097 UTM(WGS84)34N 742/-192.85 Clay altered gray sandstone with pyrite disseminations S2 BHDD017 13JZBH153 570854 4898097 UTM(WGS84)34N 742/-194.45 Altered conglomerate with pyrite rich matrix S2 BHDD017 13JZBH154 570854 4898097 UTM(WGS84)34N 742/-195.5 Strongly decarbonatized, vuggy clastite with 4.33 ppm Au S1 + + BHDD017 13JZBH155 570854 4898097 UTM(WGS84)34N 742/-197.55 Brecciated sandstone with 4.97 ppm Au S1 BHDD017 13JZBH156 570854 4898097 UTM(WGS84)34N 742/-210 Sandy limestone with stylolite S1 + + BHDD017 13JZBH157 570854 4898097 UTM(WGS84)34N 742/-224.6 Carbonate siliciclastic rock S1 + BHDD017 13JZBH158 570854 4898097 UTM(WGS84)34N 742/-236.38 Carbonate siliciclastics alternating with finer fraction S1 + BHDD017 13JZBH159 570854 4898097 UTM(WGS84)34N 742/-241.2 Coarser influx in S1 sandstone S1 + BHDD017 13JZBH160 570854 4898097 UTM(WGS84)34N 742/-244.3 Laminated siltstone IB KWDD008 13JZBH161 568862 4900428 UTM(WGS84)34N 737/45.5 Very coarse-grained, non-altered sandstone S2 125 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining KWDD005 13JZBH162 568862 4900428 UTM(WGS84)34N 737/44.6 Coarse red sandstone S2 KWDD008 13JZBH163 569494 4899763 UTM(WGS84)34N 739/31.95 Coarse red sandstone S2 KWDD005 13JZBH164 569494 4899763 UTM(WGS84)34N 739/32 Red-dark green coarse-grained non-altered sandstone S2 BHDD067 13JZBH165 570927 4898011 UTM(WGS84)34N 724/-32.15 Laminated gray marl SMR BHDD067 13JZBH166 570927 4898011 UTM(WGS84)34N 724/-36.2 Volcanic material rich marl SMR BHDD067 13JZBH167 570927 4898011 UTM(WGS84)34N 724/-115.15 Epidote-chlorite altered andesite VOL BHDD067 13JZBH168 570927 4898011 UTM(WGS84)34N 724/-213.85 Gray sandstone with pyrite disseminated S2 BHDD067 13JZBH169 570927 4898011 UTM(WGS84)34N 724/-214.75 Clay altered and sulfidized, brecciated sandstone S2 + + BHDD067 13JZBH170 570927 4898011 UTM(WGS84)34N 724/-219.5 Grey, sulfidized sandstone S2 BHDD067 13JZBH171 570927 4898011 UTM(WGS84)34N 724/-223.75 Strongly clay altered sandstone, with pyrite laminas S2 BHDD067 13JZBH172 570927 4898011 UTM(WGS84)34N 724/-235.3 Clastic dominated sandstone S1 + BHDD067 13JZBH173 570927 4898011 UTM(WGS84)34N 724/-243 Fault breccia with pyrite rich fine-grained matrix and 3.47 ppm Au BBX BHDD067 13JZBH174 570927 4898011 UTM(WGS84)34N 724/-244.5 Polymictic breccia with pyrite rich matrix BBX BHDD063 13JZBH175 570925 4898075 UTM(WGS84)34N 718/-195.1 Strongly clay altered and sulfidized andesite VOL BHDD063 13JZBH176 570925 4898075 UTM(WGS84)34N 718/-197.45 Light gray sandstone S2 + + BHDD063 13JZBH177 570925 4898075 UTM(WGS84)34N 718/-212.47 Sulfidized gray sandstone S2 BHDD063 13JZBH178 570925 4898075 UTM(WGS84)34N 718/-215.95 Contact of conglomerate and fine-grained sandstone S2 + BHDD063 13JZBH179 570925 4898075 UTM(WGS84)34N 718/-217.45 Alternation of fine-grained sandstone with silty/muddy fraction S1 + BHDD063 13JZBH180 570925 4898075 UTM(WGS84)34N 718/-217.8 Sandy limestone with stylolites S1 + + BHDD063 13JZBH181 570925 4898075 UTM(WGS84)34N 718/-233.9 Fine-grained, sulfidized sandstone S1 BHDD063 13JZBH182 570925 4898075 UTM(WGS84)34N 718/-248.8 Clastic rich sandstone S1 126 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD063 13JZBH183 570925 4898075 UTM(WGS84)34N 718/-256 Mudstone with calcite veins IB BHDD057 13JZBH184 570864 4898154 UTM(WGS84)34N 734/-3.5 Partially oxidized marl SMR BHDD057 13JZBH185 570864 4898154 UTM(WGS84)34N 734/-19.5 Laminated marl SMR BHDD057 13JZBH186 570864 4898154 UTM(WGS84)34N 734/-43.8 Weakly clay, chlorite altered andesite VOL BHDD057 13JZBH187 570864 4898154 UTM(WGS84)34N 734/-50 Strongly clay altered andesite with calcite-pyrite veins VOL + BHDD057 13JZBH188 570864 4898154 UTM(WGS84)34N 734/-51.35 Strongly clay altered andesite from the fault gauge VOL BHDD057 13JZBH189 570864 4898154 UTM(WGS84)34N 734/-120.75 Weakly clay, chlorite altered andesite VOL BHDD057 13JZBH190 570864 4898154 UTM(WGS84)34N 734/-138.5 Light gray sandstone with pyrite lenses along bedding S2 BHDD057 13JZBH191 570864 4898154 UTM(WGS84)34N 734/-144.57 Strongly clay altered and sulfidized andesite S2 BHDD057 13JZBH192 570864 4898154 UTM(WGS84)34N 734/-161.85 Breccia with limestone and S2 sandstone re-deposited clasts S2 BHDD057 13JZBH193 570864 4898154 UTM(WGS84)34N 734/-169.2 Reddish-gray sandstone with calcite veins S2 BHDD057 13JZBH194 570864 4898154 UTM(WGS84)34N 734/-185.95 Green, coarse sandstone with pyrite disseminations S2 BHDD057 13JZBH195 570864 4898154 UTM(WGS84)34N 734/-189.65 Conglomerate-sandstone contact, clay altered and decarbonatized S2 + BHDD057 13JZBH196 570864 4898154 UTM(WGS84)34N 734/-192.5 Brecciated, strongly decarbonatized sandstone with 9.65 ppm Au S1 BHDD057 13JZBH197 570864 4898154 UTM(WGS84)34N 734/-198.1 Sandy limestone with stylolites S1 BHDD057 13JZBH198 570864 4898154 UTM(WGS84)34N 734/-226.2 Fine-grained sandstone and finer fractions S1 BHDD057 13JZBH199 570864 4898154 UTM(WGS84)34N 734/-264.95 Laminated siltstone IB BHDD057 13JZBH200 570864 4898154 UTM(WGS84)34N 734/-271.6 Siltstone from the fault gauge IB BHDD057 13JZBH201 570864 4898154 UTM(WGS84)34N 734/-273.2 Breccia with fine-grained, pyrite rich matrix BBX BHDD057 13JZBH202 570864 4898154 UTM(WGS84)34N 734/-276.6 Gray limestone and calcite vein KLS 127 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD084 13JZBH206 570652 4898169 UTM(WGS84)34N 785/-186.3 Red-green, medium to coarse-grained sandstone S2 BHDD084 13JZBH207 570652 4898169 UTM(WGS84)34N 785/-193 Grey, medium to coarse-grained sandstone, with pyrite disseminations S2 BHDD084 13JZBH208 570652 4898169 UTM(WGS84)34N 785/-204.05 Light grey, fine to medium-grained sandstone, with pyrite dissemination S2 BHDD085 13JZBH209 570697 4898213 UTM(WGS84)34N 775/-172.73 Red-green, medium to coarse-grained sandstone S2 BHDD086 13JZBH210 570431 4898382 UTM(WGS84)34N 723/-47 Grey, laminated, very fine-grained marl SMR BHDD086 13JZBH211 570431 4898382 UTM(WGS84)34N 723/-60.7 Light grey, medium-grained sandstone, with pyrite dissemination S2 BHDD086 13JZBH212 570431 4898382 UTM(WGS84)34N 723/-70.1 Green-red, medium-grained sandstone, with pyrite dissemination S2 BHDD005 13JZBH213 570533 4898412 UTM(WGS84)34N 747/-113.81 Green-red, coarse-grained sandstone S2 BHDD005 13JZBH214 570533 4898412 UTM(WGS84)34N 747/-130.69 Grey-green, medium-grained sandstone, with pyrite dissemination S2 BHDD068 13JZBH215 570761 4898166 UTM(WGS84)34N 769/-176.3 Green, medium-grained sandstone S2 BHDD068 13JZBH216 570761 4898166 UTM(WGS84)34N 769/-228.5 Light grey, stylolitized, sandy limestone S1 BHDD087 13JZBH217 570521 4898327 UTM(WGS84)34N 761/-133.3 Red-green, medium to fine-grained sandstone S2 BHDD087 13JZBH218 570521 4898327 UTM(WGS84)34N 761/-141.5 Red-green, coarse-grained sandstone, rich in volcanic material S2 BHDD087 13JZBH219 570521 4898327 UTM(WGS84)34N 761/-189.8 Light grey, medium to coarse-grained sandstone S1 BHDD007 13JZBH220 570534 4898248 UTM(WGS84)34N 776/-85.62 Green-grey, non-altered, plagioclase-hornblende-phyric andesite VOL BHDD007 13JZBH221 570534 4898248 UTM(WGS84)34N 776/-176.1 Green-red, medium to coarse-grained sandstone S2 BHDD007 13JZBH222 570534 4898248 UTM(WGS84)34N 776/-181.55 Ochre-grey, coarse-grained sandstone with pyrite dissemination S2 BHDD007 13JZBH223 570534 4898248 UTM(WGS84)34N 776/-195 Light grey, fine to medium-grained, stylolitized sandstone S1 BHDD007 13JZBH224 570534 4898248 UTM(WGS84)34N 776/-213.5 Light grey, medium to coarse grained, stylolitized sandstone S1 128 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD057 13JZBH225 570864 4898154 UTM(WGS84)34N 734/-247.15 Grey, medium to fine-grained sandstone S1 + BHDD057 13JZBH226 570864 4898154 UTM(WGS84)34N 734/-203.29 Gray, sandy limestone S1 + + BHDD017 13JZBH227 570854 4898097 UTM(WGS84)34N 742/-153.48 Volcanic material rich green, medium to coarse-grained sandstone S2 BHDD017 13JZBH228 570854 4898097 UTM(WGS84)34N 742/-182.55 Green, medium-grained sandstone S2 BHDD063 13JZBH229 570925 4898075 UTM(WGS84)34N 718/-218.43 Light grey, stylolitized, sandy limestone S1 BHDD026 13JZBH230 570220 4898565 UTM(WGS84)34N 685/-4.93 Green-grey, medium-grained sandstone S2 BHDD026 13JZBH231 570220 4898565 UTM(WGS84)34N 685/-113.75 Light grey, stylolitized, sandy limestone S1 BHDD020 13JZBH232 570373 4898559 UTM(WGS84)34N 691/-72.8 Grey, medium-grained sandstone S1 BHDD020 13JZBH233 570373 4898559 UTM(WGS84)34N 691/-153.96 Grey, medium-grained, sandstone S1 BHDD020 13JZBH234 570373 4898559 UTM(WGS84)34N 691/-167.09 Oxidation front in medium-grained sandstone S1 KWDD005 14JZBH235 569494 4899763 UTM(WGS84)34N 739/-6 Red laminated marl SMR + KWDD005 14JZBH236 569494 4899763 UTM(WGS84)34N 739/-16 Grey marlstone with laminas of organic material SMR KWDD005 14JZBH237 569494 4899763 UTM(WGS84)34N 739/-21.5 Red, fine-grained sandstone on the basis of the marl formation SMR KWDD005 14JZBH238 569494 4899763 UTM(WGS84)34N 739/-22 Gray, medium-grained sandstone, on the contact with marl S2 KWDD005 14JZBH239 569494 4899763 UTM(WGS84)34N 739/-45 Red to light grey sandstone with alternations of different size fractions S2 KWDD005 14JZBH240 569494 4899763 UTM(WGS84)34N 739/-65 Red-green sandstone, with cc.0.2 mm thick magnetite laminas S2 KWDD005 14JZBH241 569494 4899763 UTM(WGS84)34N 739/-100 Weakly oxidized, medium-grained sandstone S2 KWDD005 14JZBH242 569494 4899763 UTM(WGS84)34N 739/-108 Contact of sandstone richer in carbonate and richer in clastic detritus S1 KWDD005 14JZBH243 569494 4899763 UTM(WGS84)34N 739/-114 Light grey sandstone to gravelite richer in carbonate component S1 KWDD005 14JZBH244 569494 4899763 UTM(WGS84)34N 739/-130 Fine-grained sandstone with glauconite S1 129 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining KWDD005 14JZBH245 569494 4899763 UTM(WGS84)34N 739/-274 Light grey, fine to very coarse grained sandstone S1 + KWDD005 14JZBH246 569494 4899763 UTM(WGS84)34N 739/-291 Fresh to partially weakly oxidized, light grey, biogenic limestone JLS KWDD005 14JZBH247 569494 4899763 UTM(WGS84)34N 739/-306 Fresh, grey limestone, with pyrite filled stylolites JLS KWDD008 14JZBH248 568862 4900428 UTM(WGS84)34N 737/-55.3 Alternation of coarse grained sandstone and conglomerate S2 KWDD008 14JZBH249 568862 4900428 UTM(WGS84)34N 737/-59.9 Weakly oxidized, red, coarse to very coarse grained sandstone S2 KWDD008 14JZBH250 568862 4900428 UTM(WGS84)34N 737/-60.7 Weakly oxidized sandstone with interbeds of finer grained fraction S1 KWDD008 14JZBH251 568862 4900428 UTM(WGS84)34N 737/-80 Weakly oxidized, coarse-grained carbonate rich sandstone S1 KWDD008 14JZBH252 568862 4900428 UTM(WGS84)34N 737/-81.8 Calcareous sandstone alternating with different grain sizes S1 KWDD008 14JZBH253 568862 4900428 UTM(WGS84)34N 737/-200.4 Interbedding of siltstone and very fine-grained sandstone IB KWDD008 14JZBH254 568862 4900428 UTM(WGS84)34N 737/-241.5 Grey, medium to coarse-grained sandstone S1 KWDD008 14JZBH255 568862 4900428 UTM(WGS84)34N 737/-245.5 Partially oxidized, cream, fractured limestone JLS KWDD008 14JZBH256 568862 4900428 UTM(WGS84)34N 737/-85.4 Fresh, poorly sorted conglomerate (clasts ranging from 0.5-10 cm) S1 KODD028 14JZBH257 570882 4899188 UTM(WGS84)34N 708/-120 Green, coarse-grained plag-hornblende phyric diorite GDI KODD028 14JZBH258 570882 4899188 UTM(WGS84)34N 708/-174 Green, plag-hornblende phyric andesite, chlorite and epidote altered VOL KODD028 14JZBH259 570882 4899188 UTM(WGS84)34N 708/-203 Light grey, very fine-grained marl, with laminas of organic material SMR KODD028 14JZBH260 570882 4899188 UTM(WGS84)34N 708/-239 Dark green-grey, medium-grained sandstone, rich in volcanic material S2 + KODD028 14JZBH261 570882 4899188 UTM(WGS84)34N 708/-283 Fresh, dark grey, fine-grained sandstone, near contact with S1 S2 KODD028 14JZBH262 570882 4899188 UTM(WGS84)34N 708/-294 Light grey, coarse-grained carbonate rich, stylolitized sandstone S1 + KODD028 14JZBH263 570882 4899188 UTM(WGS84)34N 708/-374 Dark grey, fine-grained sandstone interbedded with siltstone S1 130 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining KODD028 14JZBH264 570882 4899188 UTM(WGS84)34N 708/-444.5 Mudstone interbedded with thin layers of fine-grained sandstone IB KODD028 14JZBH265 570882 4899188 UTM(WGS84)34N 708/-473.7 Dark grey, cherty limestone KLS KODD028 14JZBH266 570882 4899188 UTM(WGS84)34N 708/-592.7 Light grey, biogenic limestone JLS BHDD056 14JZBH267 570468 4898171 UTM(WGS84)34N 775/-151 Dark red, coarse-grained sandstone S2 BHDD056 14JZBH268 570468 4898171 UTM(WGS84)34N 775/-175 Light grey-green, medium grained sandstone S2 BHDD056 14JZBH269 570468 4898171 UTM(WGS84)34N 775/-186.5 Moderately oxidized, grey-brown sandstone from the fault zone S2 BHDD056 14JZBH270 570468 4898171 UTM(WGS84)34N 775/-214.5 Black siltstone with laminas of organic material IB BHDD056 14JZBH271 570468 4898171 UTM(WGS84)34N 775/-216.4 Sandstone from fault zone, with 5.8 ppm Au, and carbonate removed S1 + + BHDD056 14JZBH272 570468 4898171 UTM(WGS84)34N 775/-224 Fresh, light grey, limestone KLS BHDD056 14JZBH273 570468 4898171 UTM(WGS84)34N 775/-260.7 Carbonate dissolution texture in karstified limestone, partially oxidized KLS BHDD056 14JZBH274 570468 4898171 UTM(WGS84)34N 775/-279 Recrystallized carbonate related with karstification KLS BHDD056 14JZBH275 570468 4898171 UTM(WGS84)34N 775/-373 Massive pyrite from the fault zone within limestone, weak silica addition JLS + BHDD056 14JZBH276 570468 4898171 UTM(WGS84)34N 775/-413 Dark grey-reddish, partially oxidized, fine-grained meta-sandstone MPH BHDD047 14JZBH277 570599 4898502 UTM(WGS84)34N 723/-95 Fresh, grey, very fine-grained marl with blebs of organic material SMR + BHDD047 14JZBH278 570599 4898502 UTM(WGS84)34N 723/-124 Grey, partially oxidized, medium-grained sandstone S2 BHDD047 14JZBH279 570599 4898502 UTM(WGS84)34N 723/-126 Grey-ochre, partially oxidized, medium-grained sandstone S2 BHDD047 14JZBH280 570599 4898502 UTM(WGS84)34N 723/-157 Grey, partially oxidized, medium-grained sandstone S1 BHDD047 14JZBH281 570599 4898502 UTM(WGS84)34N 723/-263 Dark grey, cherty, stylolitized limestone KLS BHDD047 14JZBH282 570599 4898502 UTM(WGS84)34N 723/-297 White, partially oxidized, biogenic limestone JLS 131 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD047 14JZBH283 570599 4898502 UTM(WGS84)34N 723/-216 Basal breccia from the fault, with fine-grained, sulfidized matrix BBX + BHDD047 14JZBH284 570599 4898502 UTM(WGS84)34N 723/-231 Breccia with limestone clasts and partially oxidized sandy matrix BBX BHDD083 14JZBH285 570704 4898132 UTM(WGS84)34N 785/-41.4 Dark green, clay, chlorite altered andesite VOL + BHDD081 13JZBH286 571331 4898419 UTM(WGS84)34N 677/-58.5 Green-grey, coarse-grained plag-hornblende phyric diorite GDI BHDD049 13JZBH287 570455 4898400 UTM(WGS84)34N 730/-103 Brecciated sandstone with calcite infill and sulfidation S1 + + BHDD080 13JZBH288 571521 4898384 UTM(WGS84)34N 661/-313.5 Volcanic polymictic breccia VOL BHDD021 13JZBH289 570394 4898251 UTM(WGS84)34N 749/-187 Fractured limestone with thick calcite-sulfide vein, and 5.3 ppm Au JLS + BHDD065 13JZBH290 570700 4898012 UTM(WGS84)34N 787/-197.7 Breccia with carbonate fragments and fine-grained, pyrite rich matrix BBX + BHDD009 13JZBH291 570540 4898087 UTM(WGS84)34N 780/-212 Medium-grained sandstone to siltstone karst infill within KLS limestone KLS + + BHDD032 13JZBH292 570781 4897931 UTM(WGS84)34N 771/-117.4 Partially oxidized, strongly clay altered and sulfidized andesite VOL BHDD010 13JZBH293 570700 4898243 UTM(WGS84)34N 771/-199 Grey to light grey, moderately oxidized, medium-grained sandstone S2 BHDD017 13JZBH294 570854 4898097 UTM(WGS84)34N 742/-142 Strongly clay altered and sulfidized andesite VOL BHDD084 13JZBH295 570652 4898169 UTM(WGS84)34N 785/-202 Medium-grained, brecciated sandstone, decarbonatized S2 + BHDD083 13JZBH296 570704 4898132 UTM(WGS84)34N 785/-64.8 Intensively clay altered andesite, with pyrite disseminations VOL + BHDD068 13JZBH297 570761 4898166 UTM(WGS84)34N 769/-169.76 Strongly clay altered sandstone, with pyrite disseminations S2 + BHDD063 13JZBH298 570925 4898075 UTM(WGS84)34N 718/-212.8 Reddish , clay altered sandstone S2 BHDD085 13JZBH299 570697 4898213 UTM(WGS84)34N 775/-195 Sandstone with thin beds of conglomerate, partially decarbonatized S2 BHDD047 13JZBH300 570599 4898502 UTM(WGS84)34N 723/-130.3 Sandstone-conglomerates, clay altered, decarbonatized, with 3 ppm Au S2 + + 132 Appendix A: Samples from the Bigar Hill – locations, descriptions Hole ID Sample ID Easting Northing UTM Zone Elevation/Depth (m) Sample Description Lithology Unit Thin Section Carbonate Staining BHDD068 13JZBH301 570761 4898166 UTM(WGS84)34N 769/-185.2 Green, coarse-grained sandstone, rich in volcanic material S2 BHDD084 13JZBH302 570652 4898169 UTM(WGS84)34N 785/-160.7 Green-red, coarse-grained sandstone S2 + RADD001 14JZRA001 572785 4896010 UTM(WGS84)34N 889/-235.9 Dark grey, coarse grained plag-hornblende diorite GDI CRDD002 14JZCR001 574479 4888711 UTM(WGS84)34N 812/-442.5 Grey, medium to coarse-grained plag-hornblende diorite-porphyry GDI CRDD005 14JZCR002 574327 4888084 UTM(WGS84)34N 510/-399.6 Light grey, very coarse-grained plagioclase-biotite phyric monzonite GMO CRDD005 14JZCR003 574327 4888084 UTM(WGS84)34N 510/-416.6 Grey, coarse-grained plag-hornblende diorite-porphyry GDI 133 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH035 13JZBH076 13JZBH092 13JZBH230 13JZBH235 13JZBH238 13JZBH242 13JZBH245 Au (ppb) FA130 1 >1000 955 >1000 15 14 6 6 5 SiO2 (%) LF700 0.1 86 10.8 26.3 47 45.7 42.6 30.2 46.4 Al2O3 (%) LF700 0.01 4.89 3.15 4.93 12.04 10.17 8.7 2.3 1.14 Fe2O3 (%) LF700 0.01 2.39 1.78 3.6 3.11 5.16 1.82 0.9 0.74 CaO (%) LF700 0.01 2.29 45.95 33.65 17.19 17.07 24.61 35.57 28.08 MgO (%) LF700 0.01 0.06 0.15 0.14 1.7 1.42 0.7 0.56 0.34 Na2O (%) LF700 0.01 <0.01 <0.01 <0.01 2.17 1.21 2.01 0.17 0.02 K2O (%) LF700 0.01 0.07 <0.01 0.05 1.62 2.03 0.68 0.52 0.27 MnO (%) LF700 0.01 0.1 0.13 0.23 0.07 0.04 0.04 0.02 0.01 TiO2 (%) LF700 0.01 0.27 0.14 0.24 0.29 0.6 0.16 0.11 0.05 P2O5 (%) LF700 0.01 0.13 0.15 0.08 0.13 0.07 0.11 0.07 0.07 Cr2O3 (%) LF700 0.001 0.002 0.002 0.005 0.001 0.007 <0.001 <0.001 <0.001 Ba (%) LF700 0.01 0.04 <0.01 <0.01 0.03 0.04 0.02 <0.01 <0.01 LOI (%) LF700 -5.11 3.44 36.61 24.72 13.64 15.95 18.99 28.61 21.8 Cu (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Ni (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Pb (%) LF700 0.01 0.04 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 SO3 (%) LF700 0.002 1.02 0.07 5.808 0.497 0.04 0.022 0.356 0.853 Sr (%) LF700 0.002 <0.002 <0.002 <0.002 0.039 0.014 0.042 <0.002 <0.002 V2O5 (%) LF700 0.002 0.009 0.007 0.009 0.015 0.015 0.008 0.005 0.004 Zn (%) LF700 0.001 0.027 0.004 0.004 0.003 0.006 0.002 <0.001 <0.001 Zr (%) LF700 0.002 0.008 0.003 0.005 0.003 0.02 <0.002 0.003 <0.002 SUM (%) LF700 0.01 100.75 99.01 99.77 99.51 99.55 100.47 99.4 99.74 TOT/C (%) TC000 0.02 0.36 10.15 7.52 3.49 3.73 5.11 7.97 6.28 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 134 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH035 13JZBH076 13JZBH092 13JZBH230 13JZBH235 13JZBH238 13JZBH242 13JZBH245 TOT/S (%) TC000 0.02 0.4 0.05 2.9 0.24 <0.02 0.03 0.11 0.37 Ba (ppm) LF100 1 19 8 65 270 395 187 64 25 Be (ppm) LF100 1 <1 2 <1 1 2 2 2 <1 Co (ppm) LF100 0.2 6.7 3.1 5.3 7.8 8.6 2.9 1.2 0.7 Cs (ppm) LF100 0.1 0.4 0.3 0.4 4.4 3.6 0.6 1.2 1 Ga (ppm) LF100 0.5 2.5 3.8 6.7 10.9 11.5 7.2 1.5 <0.5 Hf (ppm) LF100 0.1 2.3 1.4 1.6 1.3 6.2 1.1 1.3 0.9 Nb (ppm) LF100 0.1 4.5 2.7 4.3 3.1 9.7 1.7 2.1 1.1 Rb (ppm) LF100 0.1 1.9 0.8 1.5 25.9 94.7 17.2 22.3 9.8 Sn (ppm) LF100 1 <1 <1 <1 <1 2 <1 <1 <1 Sr (ppm) LF100 0.5 22.3 168.9 74.7 569.5 328.2 731.1 314.7 139.8 Ta (ppm) LF100 0.1 0.3 0.2 0.2 0.2 0.8 0.1 0.2 <0.1 Th (ppm) LF100 0.2 3.5 2.5 3.6 2.7 9.2 1.8 1.9 0.9 U (ppm) LF100 0.1 2.8 1 2.7 0.5 1.4 0.4 0.7 0.5 V (ppm) LF100 8 60 42 71 91 84 45 27 19 W (ppm) LF100 0.5 2.4 7.6 23 <0.5 1.5 <0.5 <0.5 0.5 Zr (ppm) LF100 0.1 87 54.5 59.7 45 229.8 39.4 49.4 34.3 Y (ppm) LF100 0.1 5.9 14 8.6 10.2 22.3 9.1 7.3 3.5 La (ppm) LF100 0.1 10.3 14.7 11.1 13.4 26.2 10.9 10 5.5 Ce (ppm) LF100 0.1 18.3 19 19.8 23.7 51.2 16.7 15.5 8.8 Pr (ppm) LF100 0.02 2.32 2.78 2.26 2.76 5.71 2.01 1.94 1.01 Nd (ppm) LF100 0.3 10.1 11.3 8.9 11.4 22.6 8.5 7.7 4.5 Sm (ppm) LF100 0.05 1.69 2.32 1.65 2.28 4.18 1.66 1.31 0.85 Eu (ppm) LF100 0.02 0.37 0.53 0.39 0.71 0.83 0.51 0.33 0.18 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 135 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH035 13JZBH076 13JZBH092 13JZBH230 13JZBH235 13JZBH238 13JZBH242 13JZBH245 Gd (ppm) LF100 0.05 1.51 2.27 1.48 2.16 3.96 1.63 1.4 0.7 Tb (ppm) LF100 0.01 0.21 0.34 0.23 0.31 0.6 0.24 0.19 0.1 Dy (ppm) LF100 0.05 1.16 2.02 1.37 1.88 3.54 1.48 1.17 0.61 Ho (ppm) LF100 0.02 0.24 0.45 0.28 0.39 0.76 0.29 0.24 0.12 Er (ppm) LF100 0.03 0.58 1.27 0.75 1.06 2.18 0.88 0.69 0.31 Tm (ppm) LF100 0.01 0.1 0.2 0.11 0.17 0.35 0.12 0.09 0.05 Yb (ppm) LF100 0.05 0.6 1.11 0.68 1 2.31 0.79 0.57 0.31 Lu (ppm) LF100 0.01 0.1 0.18 0.12 0.15 0.37 0.12 0.1 0.04 Mo (ppm) AQ200 0.1 0.3 1.2 0.4 0.1 <0.1 <0.1 <0.1 0.1 Cu (ppm) AQ200 0.1 29.8 4.1 74.9 14.6 10.8 7.3 2.2 1.5 Pb (ppm) AQ200 0.1 360.9 35.5 78.9 8.3 14.5 4.7 4.7 4.5 Zn (ppm) AQ200 1 299 47 49 36 64 20 11 8 Ni (ppm) AQ200 0.1 14.3 5.3 18.2 6.5 26.9 4.4 3.1 4.5 As (ppm) AQ200 0.5 212.7 512.5 110.7 18 2.5 2.3 <0.5 33.8 Cd (ppm) AQ200 0.1 0.6 0.3 0.4 <0.1 <0.1 <0.1 <0.1 <0.1 Sb (ppm) AQ200 0.1 441.9 51.7 19.1 1.8 0.1 <0.1 <0.1 0.2 Bi (ppm) AQ200 0.1 0.2 <0.1 0.4 <0.1 0.2 <0.1 <0.1 <0.1 Ag (ppm) AQ200 0.1 11.8 1.7 9.6 <0.1 <0.1 <0.1 <0.1 <0.1 Au (ppb) AQ200 0.5 2094 1070 4808.4 41.1 5.5 0.7 2.3 1.7 Hg (ppm) AQ200 0.01 4 2.87 1.33 0.05 0.01 0.01 <0.01 0.01 Tl (ppm) AQ200 0.1 5.1 4 16.2 0.2 0.2 <0.1 <0.1 <0.1 Se (ppm) AQ200 0.5 6.6 0.8 6 <0.5 <0.5 <0.5 <0.5 <0.5 Sc (ppm) AQ200 0.1 5.5 5.2 3.1 5.3 4.7 3.2 2.3 1.4 Te (ppm) AQ200 0.2 5.1 5.4 1.3 <0.2 <0.2 <0.2 <0.2 <0.2 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 136 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH246 13JZBH247 14JZBH257 14JZBH260 14JZBH262 14JZBH264 14JZBH265 14JZBH267 Au (ppb) FA130 1 6 4 3 3 3 7 2 3 SiO2 (%) LF700 0.1 0.2 5.4 52 49.3 19.7 54.9 12.5 45.2 Al2O3 (%) LF700 0.01 0.03 0.04 18.58 12.49 1.13 17.8 0.88 7.94 Fe2O3 (%) LF700 0.01 0.08 0.35 6.14 4.75 0.54 7.13 0.3 2.91 CaO (%) LF700 0.01 55.56 52.28 8.71 13.59 42.71 4.28 47.75 21.34 MgO (%) LF700 0.01 0.42 0.48 3.34 3.03 0.68 2.46 0.56 1.42 Na2O (%) LF700 0.01 <0.01 <0.01 2.23 2.64 0.13 1.63 <0.01 1.13 K2O (%) LF700 0.01 <0.01 <0.01 1.02 1.15 0.22 3.32 0.13 0.73 MnO (%) LF700 0.01 <0.01 <0.01 0.12 0.12 0.04 0.05 <0.01 0.08 TiO2 (%) LF700 0.01 <0.01 <0.01 0.5 0.43 0.05 1.01 0.04 0.25 P2O5 (%) LF700 0.01 0.03 0.07 0.17 0.21 0.04 0.11 0.02 0.13 Cr2O3 (%) LF700 0.001 <0.001 <0.001 0.001 <0.001 <0.001 0.016 <0.001 0.001 Ba (%) LF700 0.01 <0.01 <0.01 0.02 0.03 <0.01 0.06 <0.01 0.03 LOI (%) LF700 -5.11 43.74 40.76 6.84 11.84 34.02 7.47 37.9 17.53 Cu (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Ni (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Pb (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 SO3 (%) LF700 0.002 0.031 0.607 0.057 0.019 0.003 0.911 0.131 0.02 Sr (%) LF700 0.002 <0.002 <0.002 0.05 0.084 <0.002 0.013 0.037 0.008 V2O5 (%) LF700 0.002 <0.002 <0.002 0.03 0.022 0.004 0.026 0.002 0.01 Zn (%) LF700 0.001 <0.001 <0.001 0.005 0.005 <0.001 0.01 <0.001 0.002 Zr (%) LF700 0.002 <0.002 <0.002 0.005 <0.002 <0.002 0.021 <0.002 <0.002 SUM (%) LF700 0.01 100.03 99.97 99.88 99.73 99.31 101.2 100.23 98.76 TOT/C (%) TC000 0.02 12.29 11.66 0.12 2.63 9.67 1.67 10.74 4.68 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 137 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH246 13JZBH247 14JZBH257 14JZBH260 14JZBH262 14JZBH264 14JZBH265 14JZBH267 TOT/S (%) TC000 0.02 <0.02 0.26 <0.02 <0.02 0.04 0.61 0.06 <0.02 Ba (ppm) LF100 1 2 3 247 359 43 553 29 353 Be (ppm) LF100 1 <1 <1 1 1 <1 5 <1 3 Co (ppm) LF100 0.2 <0.2 <0.2 17.4 11.1 1.7 17.8 0.9 5.7 Cs (ppm) LF100 0.1 <0.1 <0.1 1.4 0.5 0.4 5.6 0.6 2.9 Ga (ppm) LF100 0.5 <0.5 <0.5 15.8 12.6 <0.5 21.8 <0.5 7.4 Hf (ppm) LF100 0.1 <0.1 <0.1 2.1 1.7 0.8 7.2 0.3 1.1 Nb (ppm) LF100 0.1 <0.1 <0.1 4.8 2.8 1 15.6 0.7 2.1 Rb (ppm) LF100 0.1 0.2 0.3 21.3 21.4 10.1 133.3 9.1 19.8 Sn (ppm) LF100 1 <1 <1 <1 <1 <1 3 <1 <1 Sr (ppm) LF100 0.5 182.4 189.4 647.7 1147.6 401.2 177.3 1132 362.7 Ta (ppm) LF100 0.1 <0.1 <0.1 0.3 0.2 <0.1 1.1 <0.1 0.1 Th (ppm) LF100 0.2 <0.2 <0.2 3.3 3 0.9 12.6 0.6 1.9 U (ppm) LF100 0.1 0.3 1 1.1 0.3 1.1 3.6 1.1 0.4 V (ppm) LF100 8 15 11 199 135 16 156 17 79 W (ppm) LF100 0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2.2 0.6 <0.5 Zr (ppm) LF100 0.1 0.8 0.8 79.7 59.4 33.3 264.3 9.5 39.9 Y (ppm) LF100 0.1 0.6 0.7 13.3 16.6 4.2 35.4 1.9 12.9 La (ppm) LF100 0.1 1.4 0.6 12.7 16.1 5.1 37.3 2.7 11.4 Ce (ppm) LF100 0.1 0.4 0.4 24.8 31.1 7.3 76.9 3.2 17.7 Pr (ppm) LF100 0.02 0.02 <0.02 2.91 3.69 0.95 8.83 0.36 2.42 Nd (ppm) LF100 0.3 <0.3 <0.3 11.4 15.4 3.5 34.8 1.7 10.1 Sm (ppm) LF100 0.05 <0.05 <0.05 2.53 3.3 0.74 6.62 0.3 2 Eu (ppm) LF100 0.02 <0.02 <0.02 0.74 0.99 0.16 1.33 0.07 0.57 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 138 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH246 13JZBH247 14JZBH257 14JZBH260 14JZBH262 14JZBH264 14JZBH265 14JZBH267 Gd (ppm) LF100 0.05 0.06 <0.05 2.26 3.19 0.71 6.45 0.31 2.04 Tb (ppm) LF100 0.01 <0.01 <0.01 0.39 0.52 0.11 1.04 0.05 0.31 Dy (ppm) LF100 0.05 0.1 0.08 2.43 2.98 0.66 6.57 0.31 1.84 Ho (ppm) LF100 0.02 <0.02 <0.02 0.54 0.66 0.13 1.3 0.07 0.41 Er (ppm) LF100 0.03 0.05 0.04 1.54 1.77 0.38 3.91 0.22 1.17 Tm (ppm) LF100 0.01 <0.01 <0.01 0.24 0.26 0.07 0.62 0.03 0.17 Yb (ppm) LF100 0.05 <0.05 <0.05 1.52 1.72 0.35 3.76 0.18 1.06 Lu (ppm) LF100 0.01 <0.01 <0.01 0.27 0.27 0.05 0.61 0.03 0.16 Mo (ppm) AQ200 0.1 <0.1 0.2 <0.1 <0.1 <0.1 0.3 0.4 <0.1 Cu (ppm) AQ200 0.1 0.8 1.5 36.2 23.4 2 34.1 1.6 6.9 Pb (ppm) AQ200 0.1 1.6 1.2 2.5 6.7 2.9 17.2 1.9 5.8 Zn (ppm) AQ200 1 4 7 29 46 8 103 8 27 Ni (ppm) AQ200 0.1 2 3.4 3.7 6.1 3.8 48.8 6.5 4.3 As (ppm) AQ200 0.5 2.4 6.5 1.7 2.8 1.7 9.8 1.6 1.2 Cd (ppm) AQ200 0.1 0.2 0.3 <0.1 <0.1 <0.1 <0.1 <0.1 0.1 Sb (ppm) AQ200 0.1 0.2 0.8 <0.1 <0.1 <0.1 0.3 0.4 0.6 Bi (ppm) AQ200 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.4 <0.1 <0.1 Ag (ppm) AQ200 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Au (ppb) AQ200 0.5 <0.5 3.1 <0.5 1.3 <0.5 0.9 0.7 0.8 Hg (ppm) AQ200 0.01 0.03 0.03 <0.01 <0.01 <0.01 0.03 0.02 0.01 Tl (ppm) AQ200 0.1 <0.1 0.2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Se (ppm) AQ200 0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Sc (ppm) AQ200 0.1 0.7 0.8 2.1 5.4 1.6 7.6 1.3 4.5 Te (ppm) AQ200 0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 139 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH268 14JZBH269 14JZBH270 14JZBH271 14JZBH272 14JZBH273 14JZBH274 14JZBH275 Au (ppb) FA130 1 72 >1000 770 >1000 12 >1000 237 654 SiO2 (%) LF700 0.1 44.3 29.3 57.1 72.5 0.7 8.4 0.5 30.9 Al2O3 (%) LF700 0.01 9.44 19.1 17.74 7.07 0.39 3.06 0.28 7.5 Fe2O3 (%) LF700 0.01 2.73 8.89 6.01 8.35 0.48 2.36 2.59 19.07 CaO (%) LF700 0.01 19.84 10.51 1.6 1.35 52.93 32.57 40.89 14.91 MgO (%) LF700 0.01 1.7 6.45 1.78 0.74 1.61 12.5 10.46 1.02 Na2O (%) LF700 0.01 0.09 0.06 0.14 0.02 <0.01 0.06 <0.01 0.01 K2O (%) LF700 0.01 1.4 3.12 4.91 1.28 0.02 0.66 <0.01 0.25 MnO (%) LF700 0.01 0.1 0.73 0.15 0.11 0.04 0.1 0.39 0.07 TiO2 (%) LF700 0.01 0.25 0.82 0.93 0.34 0.02 0.17 0.02 0.26 P2O5 (%) LF700 0.01 0.12 0.38 0.1 0.36 0.14 0.32 0.05 0.16 Cr2O3 (%) LF700 0.001 <0.001 0.003 0.015 0.006 <0.001 0.002 <0.001 0.002 Ba (%) LF700 0.01 0.02 0.09 0.14 0.02 <0.01 <0.01 0.01 <0.01 LOI (%) LF700 -5.11 17.77 12.23 7.74 7.56 42.48 37.55 41.77 11.18 Cu (%) LF700 0.01 <0.01 <0.01 <0.01 0.02 <0.01 <0.01 <0.01 0.1 Ni (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Pb (%) LF700 0.01 <0.01 <0.01 <0.01 0.27 <0.01 <0.01 <0.01 <0.01 SO3 (%) LF700 0.002 1.895 7.992 1.429 0.634 0.759 2.368 2.975 14.459 Sr (%) LF700 0.002 <0.002 <0.002 <0.002 0.011 <0.002 <0.002 <0.002 <0.002 V2O5 (%) LF700 0.002 0.014 0.045 0.026 0.017 0.002 0.006 <0.002 0.017 Zn (%) LF700 0.001 0.004 0.003 0.026 0.502 <0.001 0.007 0.007 0.003 Zr (%) LF700 0.002 0.002 0.008 0.018 0.006 <0.002 <0.002 <0.002 <0.002 SUM (%) LF700 0.01 99.65 99.8 99.85 101.33 99.53 100.16 99.93 99.94 TOT/C (%) TC000 0.02 4.54 2.45 0.79 0.3 11.99 11 12.21 3.56 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 140 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH268 14JZBH269 14JZBH270 14JZBH271 14JZBH272 14JZBH273 14JZBH274 14JZBH275 TOT/S (%) TC000 0.02 1.41 6.66 4.48 6.98 0.38 1.9 1.78 14.82 Ba (ppm) LF100 1 241 1114 1523 232 11 107 113 39 Be (ppm) LF100 1 2 2 <1 <1 1 <1 <1 <1 Co (ppm) LF100 0.2 5 20.7 23.3 18.6 0.8 4.7 5.9 35 Cs (ppm) LF100 0.1 4.6 18.3 13.5 4.8 0.1 3.3 0.2 2.6 Ga (ppm) LF100 0.5 8.1 13.4 21.9 14.3 <0.5 2.6 <0.5 7.9 Hf (ppm) LF100 0.1 1.6 3.6 6 2.6 <0.1 1.1 <0.1 0.9 Nb (ppm) LF100 0.1 2.5 6.6 15 5.4 0.4 2.5 <0.1 1.8 Rb (ppm) LF100 0.1 33.2 79.3 165.4 37.8 1.4 28.4 0.7 5.7 Sn (ppm) LF100 1 <1 <1 3 2 <1 <1 <1 2 Sr (ppm) LF100 0.5 171.2 142.7 36.5 103.2 163.6 69.9 48.8 33.6 Ta (ppm) LF100 0.1 0.2 0.5 1 0.4 <0.1 0.2 <0.1 0.1 Th (ppm) LF100 0.2 2.7 5 13.4 5.6 <0.2 2.1 <0.2 1.6 U (ppm) LF100 0.1 0.5 1.9 5.5 3.5 0.4 2.8 0.8 1.7 V (ppm) LF100 8 87 312 164 112 19 49 21 115 W (ppm) LF100 0.5 <0.5 7.7 3.9 6.4 <0.5 1.3 0.6 3.2 Zr (ppm) LF100 0.1 55.7 138.2 217 93.5 4 39.4 3.8 36.5 Y (ppm) LF100 0.1 9.5 18.8 35.7 9.2 2.6 10.8 3.8 8.9 La (ppm) LF100 0.1 11.1 18 39.8 13 2.1 8.5 2.5 7.2 Ce (ppm) LF100 0.1 19.4 36.1 86.1 21.6 2.1 14.6 2.9 13.7 Pr (ppm) LF100 0.02 2.43 4.66 9.52 2.52 0.27 1.79 0.29 1.68 Nd (ppm) LF100 0.3 10 19.5 36.1 9.4 1.3 7.2 1.4 7.5 Sm (ppm) LF100 0.05 2.1 4.17 7.3 2.51 0.23 1.48 0.31 1.49 Eu (ppm) LF100 0.02 0.67 0.6 1.06 0.58 0.06 0.31 0.08 0.55 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 141 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH268 14JZBH269 14JZBH270 14JZBH271 14JZBH272 14JZBH273 14JZBH274 14JZBH275 Gd (ppm) LF100 0.05 1.93 3.89 6.7 2.4 0.25 1.55 0.42 1.52 Tb (ppm) LF100 0.01 0.3 0.6 1.09 0.32 0.05 0.26 0.06 0.25 Dy (ppm) LF100 0.05 1.85 3.47 6.45 1.55 0.31 1.56 0.43 1.4 Ho (ppm) LF100 0.02 0.34 0.73 1.36 0.31 0.07 0.35 0.1 0.31 Er (ppm) LF100 0.03 1 2.14 3.85 0.88 0.21 0.89 0.31 0.9 Tm (ppm) LF100 0.01 0.15 0.31 0.56 0.14 0.03 0.12 0.05 0.12 Yb (ppm) LF100 0.05 0.98 2.04 3.56 1.02 0.14 0.83 0.3 0.84 Lu (ppm) LF100 0.01 0.14 0.3 0.55 0.18 0.02 0.12 0.04 0.13 Mo (ppm) AQ200 0.1 0.2 0.4 1.4 5.7 0.3 2.7 1.9 6.6 Cu (ppm) AQ200 0.1 12.7 34.4 48 192.8 4.3 14.3 12.7 1044.7 Pb (ppm) AQ200 0.1 5.6 87.1 28.1 2816.8 3.2 10.9 11.1 38.8 Zn (ppm) AQ200 1 41 55 284 5320 14 76 59 44 Ni (ppm) AQ200 0.1 5.1 18.1 61.6 53.1 2.6 17.3 15.8 19.5 As (ppm) AQ200 0.5 155.7 431.3 242.3 452.9 18.3 152.8 156.8 926.4 Cd (ppm) AQ200 0.1 0.1 0.4 0.6 44.4 0.4 0.9 0.9 1 Sb (ppm) AQ200 0.1 1.3 34.8 14.1 111.7 1.8 25 17.6 4 Bi (ppm) AQ200 0.1 <0.1 <0.1 0.5 30.5 <0.1 0.1 <0.1 2.4 Ag (ppm) AQ200 0.1 0.2 >100.0 3.3 33.4 0.3 0.4 1.7 0.7 Au (ppb) AQ200 0.5 71 1524 160 9167.7 15.7 980 181 608.7 Hg (ppm) AQ200 0.01 0.17 1.2 2.21 50.54 0.15 6.24 1.73 1.36 Tl (ppm) AQ200 0.1 0.3 10.2 4.5 16.3 0.1 9.9 2.7 0.8 Se (ppm) AQ200 0.5 0.7 13.9 2.5 9.9 <0.5 4.5 4.1 7.2 Sc (ppm) AQ200 0.1 4.9 8.4 3.2 0.7 1.3 2.7 1.5 4 Te (ppm) AQ200 0.2 0.5 4.9 2.6 6.8 <0.2 1.4 1 1.5 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 142 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH276 14JZBH277 14JZBH279 14JZBH282 14JZBH285 14JZBH295 14JZBH296 14JZBH301 14JZBH302 Au (ppb) FA130 1 16 7 232 3 3 917 12 4 3 SiO2 (%) LF700 0.1 62.2 43 62.3 0.2 54 51.5 51.9 43.2 44.5 Al2O3 (%) LF700 0.01 17.37 10.04 9.77 0.06 16.89 9.17 16.06 11.72 7.8 Fe2O3 (%) LF700 0.01 7.96 4.3 3.99 0.07 7.06 4.69 6 4.66 2.9 CaO (%) LF700 0.01 0.57 19.47 9.25 55.49 5.99 13.72 5.7 17.67 22.77 MgO (%) LF700 0.01 0.76 1.67 0.2 0.3 3.51 1.32 2.91 2.12 1.16 Na2O (%) LF700 0.01 0.62 0.12 <0.01 <0.01 3.73 0.05 0.26 0.15 0.78 K2O (%) LF700 0.01 2.67 2.02 0.61 <0.01 1.36 1.94 3.61 2.16 1.16 MnO (%) LF700 0.01 0.06 0.06 0.04 0.01 0.12 0.18 0.2 0.11 0.07 TiO2 (%) LF700 0.01 1.39 0.52 0.3 <0.01 0.6 0.41 0.58 0.4 0.25 P2O5 (%) LF700 0.01 0.15 0.12 0.2 <0.01 0.16 0.23 0.15 0.14 0.13 Cr2O3 (%) LF700 0.001 0.022 0.007 0.001 <0.001 <0.001 0.003 0.003 <0.001 <0.001 Ba (%) LF700 0.01 0.06 0.04 <0.01 <0.01 0.02 <0.01 0.02 0.01 <0.01 LOI (%) LF700 -5.11 7.07 17.83 9.7 43.4 7.53 11.24 9.39 16.81 18.97 Cu (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Ni (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Pb (%) LF700 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 SO3 (%) LF700 0.002 0.044 0.081 3.326 0.014 0.019 5.277 3.958 0.02 0.014 Sr (%) LF700 0.002 0.01 0.006 <0.002 <0.002 0.038 <0.002 <0.002 <0.002 <0.002 V2O5 (%) LF700 0.002 0.04 0.013 0.019 <0.002 0.037 0.022 0.033 0.022 0.012 Zn (%) LF700 0.001 0.009 0.005 0.007 <0.001 0.005 0.007 0.004 0.003 0.003 Zr (%) LF700 0.002 0.021 0.014 <0.002 <0.002 0.002 0.005 0.003 0.002 <0.002 SUM (%) LF700 0.01 101.01 99.32 99.67 99.53 101.08 99.73 100.77 99.21 100.53 TOT/C (%) TC000 0.02 0.97 4.51 2.02 12.36 1.17 3.33 2.15 3.88 4.9 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 143 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH276 14JZBH277 14JZBH279 14JZBH282 14JZBH285 14JZBH295 14JZBH296 14JZBH301 14JZBH302 TOT/S (%) TC000 0.02 0.56 0.05 2.87 <0.02 <0.02 3.58 3 0.03 <0.02 Ba (ppm) LF100 1 588 427 40 5 220 80 69 116 116 Be (ppm) LF100 1 4 3 2 <1 <1 <1 2 <1 2 Co (ppm) LF100 0.2 22.7 8.3 8.2 <0.2 19.8 9.4 18.1 9.6 5 Cs (ppm) LF100 0.1 7.6 5.8 2.5 <0.1 2.5 8.5 8.7 8.5 4.8 Ga (ppm) LF100 0.5 19.7 11.8 9 <0.5 14.4 9.7 14.7 11.8 6.7 Hf (ppm) LF100 0.1 6.3 4 1.3 <0.1 1.7 1.8 1.7 1.7 1.1 Nb (ppm) LF100 0.1 10.1 8.4 2.3 <0.1 3.7 3.3 3.8 3.1 2.3 Rb (ppm) LF100 0.1 81.8 84.8 17.3 0.3 43.8 43.8 101 50.6 27.5 Sn (ppm) LF100 1 3 2 <1 <1 <1 <1 <1 <1 <1 Sr (ppm) LF100 0.5 70.2 337 53.4 94.6 455.1 81.1 96.6 157.4 175.8 Ta (ppm) LF100 0.1 0.7 0.5 0.2 <0.1 0.3 0.2 0.3 0.2 0.1 Th (ppm) LF100 0.2 5.8 7.7 1.9 <0.2 2.8 2.3 2.7 2.9 1.7 U (ppm) LF100 0.1 2.3 2.3 1 0.4 0.6 0.7 0.9 0.5 0.5 V (ppm) LF100 8 242 93 122 <8 227 151 209 142 75 W (ppm) LF100 0.5 1 1.6 2.2 <0.5 <0.5 1.2 1.5 <0.5 <0.5 Zr (ppm) LF100 0.1 247.2 148.3 43.9 0.8 66.6 57.3 62.4 59.4 39.3 Y (ppm) LF100 0.1 36.4 20.6 10.5 0.8 14.2 12.6 14.4 12.5 10.4 La (ppm) LF100 0.1 24.3 23.8 11.8 0.9 11.2 12.4 10.5 12.9 9.7 Ce (ppm) LF100 0.1 53.1 48.6 22.4 0.6 22.9 25.1 20.4 22.5 15.1 Pr (ppm) LF100 0.02 6.26 5.34 2.7 <0.02 2.69 3.18 2.62 2.95 2.2 Nd (ppm) LF100 0.3 25 21.3 11.5 <0.3 10.7 13.3 10.7 11.9 9 Sm (ppm) LF100 0.05 5.76 4.08 2.34 0.06 2.38 2.73 2.35 2.39 1.86 Eu (ppm) LF100 0.02 1.5 0.85 0.6 0.02 0.75 0.67 0.73 0.76 0.56 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 144 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 14JZBH276 14JZBH277 14JZBH279 14JZBH282 14JZBH285 14JZBH295 14JZBH296 14JZBH301 14JZBH302 Gd (ppm) LF100 0.05 6.1 3.74 2.24 0.1 2.64 2.52 2.41 2.32 1.88 Tb (ppm) LF100 0.01 1.03 0.62 0.33 0.01 0.41 0.38 0.39 0.34 0.28 Dy (ppm) LF100 0.05 6.52 3.39 1.89 0.07 2.65 2.17 2.42 2.02 1.66 Ho (ppm) LF100 0.02 1.44 0.74 0.36 <0.02 0.55 0.42 0.5 0.4 0.34 Er (ppm) LF100 0.03 4.11 2.12 1.04 0.06 1.66 1.26 1.45 1.25 0.92 Tm (ppm) LF100 0.01 0.63 0.31 0.16 <0.01 0.23 0.19 0.21 0.18 0.14 Yb (ppm) LF100 0.05 4.01 2.07 1.03 <0.05 1.51 1.27 1.44 1.14 0.85 Lu (ppm) LF100 0.01 0.63 0.33 0.14 <0.01 0.24 0.19 0.22 0.19 0.13 Mo (ppm) AQ200 0.1 0.2 <0.1 0.2 <0.1 <0.1 0.5 0.3 <0.1 <0.1 Cu (ppm) AQ200 0.1 9.4 22.7 31.8 0.9 28.7 16.8 42.8 8.8 2.2 Pb (ppm) AQ200 0.1 3.2 8.6 11.3 0.3 1.5 10.2 4.1 3.2 4 Zn (ppm) AQ200 1 87 64 84 8 59 75 47 32 24 Ni (ppm) AQ200 0.1 50.9 29 8.9 2 14.3 7 12 5 3 As (ppm) AQ200 0.5 12.3 2.6 326.7 2 2.7 235.4 446.9 5.2 3.4 Cd (ppm) AQ200 0.1 <0.1 <0.1 <0.1 0.1 <0.1 0.2 <0.1 <0.1 <0.1 Sb (ppm) AQ200 0.1 0.6 0.1 10.6 0.5 0.4 4 15 7.2 0.8 Bi (ppm) AQ200 0.1 <0.1 0.2 <0.1 <0.1 <0.1 0.1 <0.1 <0.1 <0.1 Ag (ppm) AQ200 0.1 <0.1 <0.1 0.4 <0.1 <0.1 1.2 0.2 <0.1 <0.1 Au (ppb) AQ200 0.5 12.4 1.6 239.2 1.5 <0.5 974.1 12.5 2.7 2.4 Hg (ppm) AQ200 0.01 0.15 0.01 1.42 0.02 0.01 0.5 0.04 0.02 <0.01 Tl (ppm) AQ200 0.1 <0.1 <0.1 6.5 <0.1 <0.1 1.5 0.8 <0.1 <0.1 Se (ppm) AQ200 0.5 <0.5 <0.5 1.1 <0.5 <0.5 1.6 <0.5 <0.5 <0.5 Sc (ppm) AQ200 0.1 6.1 4.6 5.5 0.7 11.9 6.6 14.6 4.2 3.1 Te (ppm) AQ200 0.2 <0.2 <0.2 2.4 <0.2 <0.2 1.1 <0.2 <0.2 <0.2 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 145 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH014 13JZBH030 13JZBH032 13JZBH033 13JZBH041 13JZBH050 13JZBH071 13JZBH083 13JZBH106 Au (ppb) FA130 0.5 21.6 9 11.1 7.2 4.2 2.6 11.9 0.7 2 SiO2 (%) LF700 0.10 49.10 46.90 51.40 45.50 54.40 49.20 35.50 57.70 49.00 Al2O3 (%) LF700 0.01 3.17 10.46 17.21 15.16 17.55 16.31 1.41 4.72 13.71 Fe2O3 (%) LF700 0.01 1.12 4.14 6.39 6.61 7.48 6.54 0.65 1.31 3.87 CaO (%) LF700 0.01 24.10 17.28 7.86 11.74 5.11 8.67 33.96 18.03 13.59 MgO (%) LF700 0.01 0.72 1.69 3.10 1.56 4.20 1.09 0.42 0.43 2.54 Na2O (%) LF700 0.01 0.01 0.61 3.05 0.42 4.79 0.35 0.01 0.02 1.83 K2O (%) LF700 0.01 0.76 2.07 1.17 1.28 1.66 1.06 0.25 1.19 1.82 MnO (%) LF700 0.01 0.05 0.05 0.13 0.15 0.13 0.09 0.02 0.01 0.08 TiO2 (%) LF700 0.01 0.21 0.57 0.67 0.68 0.63 0.79 0.09 0.31 0.33 P2O5 (%) LF700 0.01 0.04 0.09 0.19 0.16 0.17 0.20 0.06 0.06 0.13 Cr2O3 (%) LF700 0.001 0.01 0.01 <0.001 <0.001 0.01 <0.001 <0.001 <0.001 <0.001 LOI (%) LF700 -5.11 19.60 15.91 8.22 10.09 3.84 11.76 26.92 14.76 13.41 SO3 (%) LF700 0.002 1.08 0.29 0.21 6.99 0.03 3.41 0.53 1.11 0.09 V2O5 (%) LF700 0.002 0.01 0.02 0.03 0.03 0.04 0.04 <0.002 0.01 0.02 Total (%) LF700 0.01 99.96 100.09 99.64 100.38 100.04 99.51 99.82 99.66 100.42 TOT/C (%) TC000 0.02 5.50 3.93 1.31 2.79 0.15 1.94 7.54 4.08 2.73 TOT/S (%) TC000 0.02 0.80 0.11 0.03 4.58 0.01 4.21 0.22 0.83 0.01 Ba (%) LF700 0.01 0.01 0.04 0.14 0.05 0.02 0.03 0.01 0.02 0.03 Cu (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 Ni (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Pb (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 Sr (%) LF700 0.002 0.02 0.04 0.07 0.03 0.07 0.03 0.02 0.02 0.05 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 146 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH014 13JZBH030 13JZBH032 13JZBH033 13JZBH041 13JZBH050 13JZBH071 13JZBH083 13JZBH106 Zn (%) LF700 0.001 <0.001 0.01 0.01 0.01 <0.001 0.01 <0.001 <0.001 0.01 Zr (%) LF700 0.002 0.01 0.02 0.01 0.01 <0.002 0.01 <0.002 0.01 <0.002 Ba (ppm) LF100 1 148 457 1407 589 304 270 62 172 285 Be (ppm) LF100 1 0.5 3 0.5 3 0.5 0.5 0.5 0.5 2 Co (ppm) LF100 0.2 2.2 10.8 13.5 13.6 20.5 13.1 0.9 3.6 6.9 Cs (ppm) LF100 0.1 2.9 4 7 7.2 9.8 6.1 1 7.1 7.8 Ga (ppm) LF100 0.5 2.7 14 17.4 17.3 15.6 17.8 1.1 6.5 11.5 Hf (ppm) LF100 0.1 2 5 2.4 2.6 1.7 2.9 1.4 3.5 1.3 Nb (ppm) LF100 0.1 3.1 7.9 4.5 4.3 3.2 5 1.2 4.7 3 Rb (ppm) LF100 0.1 20.5 88.8 23.1 27.3 45.7 26.2 9.8 42.9 33.6 Sn (ppm) LF100 1 0.5 2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sr (ppm) LF100 0.5 190.4 438.5 649.9 236.6 646.4 224.9 254.9 208.1 472.1 Ta (ppm) LF100 0.1 0.3 0.7 0.4 0.3 0.2 0.3 0.2 0.3 0.2 Th (ppm) LF100 0.2 2.7 9.4 3.4 2.8 2.6 3 1.4 4.3 2.9 U (ppm) LF100 0.1 0.8 1.8 0.8 0.4 0.7 0.7 0.6 1.2 0.7 W (ppm) LF100 0.5 0.6 1.2 0.25 0.25 0.25 1.1 0.25 1.1 0.25 V (ppm) LF100 8 28 89 212 208 226 218 15 41 113 Zr (ppm) LF100 0.1 70 153.5 84.7 108.5 60.8 111.4 56.6 122.2 46 Y (ppm) LF100 0.1 7.1 20.5 17.2 16 14.1 15.8 4.8 11.9 10.4 La (ppm) LF100 0.1 8.9 23.2 16.5 10.9 10.5 13.2 8.9 16.1 13.1 Ce (ppm) LF100 0.1 22.1 51.5 33.3 32.2 24.5 28.3 17.3 27.6 23.6 Pr (ppm) LF100 0.02 2.56 5.88 4.55 4.24 2.85 3.75 2.01 3.39 3.04 Nd (ppm) LF100 0.3 9.5 21.4 20.8 18 11.5 16.9 7.1 12.4 12.3 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 147 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH014 13JZBH030 13JZBH032 13JZBH033 13JZBH041 13JZBH050 13JZBH071 13JZBH083 13JZBH106 Sm (ppm) LF100 0.05 1.64 3.97 4.27 3.6 2.63 3.59 1.11 2.41 2.27 Eu (ppm) LF100 0.02 0.33 0.84 1.23 1.1 0.75 1.01 0.29 0.51 0.67 Gd (ppm) LF100 0.05 1.41 4.09 3.57 3.51 2.75 3.01 0.94 1.84 2.15 Tb (ppm) LF100 0.01 0.24 0.59 0.57 0.5 0.42 0.46 0.14 0.33 0.34 Dy (ppm) LF100 0.05 1.28 4.11 3.12 3 2.34 2.45 0.86 1.85 1.82 Ho (ppm) LF100 0.02 0.26 0.87 0.72 0.67 0.57 0.61 0.14 0.37 0.41 Er (ppm) LF100 0.03 0.8 2.42 2.05 1.93 1.5 1.54 0.44 1.03 0.98 Tm (ppm) LF100 0.01 0.1 0.3 0.23 0.22 0.22 0.28 0.07 0.17 0.15 Yb (ppm) LF100 0.05 0.79 2.03 1.87 1.47 1.38 1.65 0.4 0.93 0.9 Lu (ppm) LF100 0.01 0.12 0.33 0.31 0.23 0.23 0.24 0.06 0.14 0.14 Mo (ppm) AQ200 0.1 0.2 0.05 0.05 0.05 0.2 0.05 0.1 0.1 0.05 Cu (ppm) AQ200 0.1 9.5 20.5 6 21.3 67.8 28.3 2.1 10.3 221 Pb (ppm) AQ200 0.1 4.8 7.6 3 6.7 1 7.5 2.9 5.6 2.3 Zn (ppm) AQ200 1 16 54 48 68 29 59 8 22 33 Ni (ppm) AQ200 0.1 4.7 27.6 3.4 4.9 10.2 4.7 1.9 10 4.4 As (ppm) AQ200 0.5 44.3 4.2 0.8 217.9 2 50.7 59.9 18.3 2.9 Cd (ppm) AQ200 0.1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Sb (ppm) AQ200 0.1 1.7 0.05 0.05 1.1 0.05 1.2 0.8 2.5 3.6 Bi (ppm) AQ200 0.1 0.05 0.2 0.05 0.05 0.05 0.1 0.05 0.05 0.05 Ag (ppm) AQ200 0.1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.1 Hg (ppm) AQ200 0.01 0.09 0.005 0.005 0.11 0.005 0.33 0.01 0.02 0.005 Tl (ppm) AQ200 0.1 0.1 0.05 0.05 0.3 0.05 0.9 0.05 0.05 0.05 Se (ppm) AQ200 0.5 0.5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 148 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH111 13JZBH118 13JZBH125 13JZBH133 13JZBH136 13JZBH140 13JZBH142 13JZBH143 13JZBH147 Au (ppb) FA130 0.5 4 1861.1 62.3 302.3 9.1 9.4 511.9 7 11.2 SiO2 (%) LF700 0.10 47.30 1.80 36.10 52.40 33.50 43.60 12.80 31.60 53.40 Al2O3 (%) LF700 0.01 2.02 1.02 5.18 16.78 9.77 10.45 0.59 1.60 17.09 Fe2O3 (%) LF700 0.01 1.02 0.77 2.46 5.94 5.88 4.61 0.58 0.52 7.13 CaO (%) LF700 0.01 26.22 36.55 28.75 6.53 16.89 18.24 47.62 36.50 7.30 MgO (%) LF700 0.01 0.48 14.74 1.67 2.86 7.27 0.72 0.47 0.57 3.97 Na2O (%) LF700 0.01 0.01 0.01 0.01 0.21 0.05 0.09 0.01 0.01 2.50 K2O (%) LF700 0.01 0.48 0.01 0.58 3.34 2.20 2.52 0.11 0.37 1.32 MnO (%) LF700 0.01 0.02 0.46 0.12 0.15 0.09 0.17 0.05 0.03 0.11 TiO2 (%) LF700 0.01 0.15 0.05 0.24 0.60 0.52 0.31 0.03 0.14 0.59 P2O5 (%) LF700 0.01 0.03 0.05 0.15 0.16 0.07 0.16 0.03 0.03 0.15 Cr2O3 (%) LF700 0.001 0.01 <0.001 0.01 0.01 0.01 <0.001 0.01 <0.001 <0.001 LOI (%) LF700 -5.11 20.34 43.38 23.58 8.98 23.55 13.76 37.23 28.74 6.80 SO3 (%) LF700 0.002 1.55 1.03 1.13 2.24 0.37 4.96 0.64 0.55 0.06 V2O5 (%) LF700 0.002 <0.002 0.01 0.01 0.04 0.02 0.02 <0.002 <0.002 0.04 Total (%) LF700 0.01 99.63 99.87 99.99 100.23 100.18 99.62 100.17 100.66 100.46 TOT/C (%) TC000 0.02 5.93 12.30 6.32 1.47 6.17 4.07 10.50 8.08 1.03 TOT/S (%) TC000 0.02 0.61 0.57 0.78 2.73 0.10 3.15 0.22 0.23 0.01 Ba (%) LF700 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.02 Cu (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ni (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Pb (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Sr (%) LF700 0.002 0.03 0.01 0.02 0.03 0.03 0.02 0.03 0.04 0.04 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 149 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH111 13JZBH118 13JZBH125 13JZBH133 13JZBH136 13JZBH140 13JZBH142 13JZBH143 13JZBH147 Zn (%) LF700 0.001 <0.001 <0.001 <0.001 <0.001 0.01 <0.001 <0.001 <0.001 0.01 Zr (%) LF700 0.002 0.01 <0.002 <0.002 <0.002 0.02 <0.002 <0.002 0.01 <0.002 Ba (ppm) LF100 1 101 4 85 96 141 98 17 69 132 Be (ppm) LF100 1 0.5 0.5 2 2 5 0.5 0.5 0.5 3 Co (ppm) LF100 0.2 1.1 1 6 23.2 8.3 8.4 1 0.6 21.4 Cs (ppm) LF100 0.1 1.5 1 4 5.6 3.6 11.1 0.3 1 4.5 Ga (ppm) LF100 0.5 2.1 0.25 5.3 14.2 12 9.6 0.6 1 16.1 Hf (ppm) LF100 0.1 1.6 1.2 1.3 1.7 4.1 1.5 0.4 1.4 1.7 Nb (ppm) LF100 0.1 2.6 0.9 1.8 3.8 7.7 2.1 0.2 1.9 3.7 Rb (ppm) LF100 0.1 18.7 0.6 16.6 85.1 75.8 54.8 5.3 13.1 48.4 Sn (ppm) LF100 1 0.5 0.5 0.5 0.5 1 0.5 0.5 0.5 0.5 Sr (ppm) LF100 0.5 196.6 75.2 153.3 162.6 320.3 129.3 330.5 369.2 377.2 Ta (ppm) LF100 0.1 0.2 0.05 0.3 0.2 0.6 0.3 0.05 0.2 0.3 Th (ppm) LF100 0.2 1.7 1.1 1.2 2.9 8.2 2.4 0.5 1.5 2.9 U (ppm) LF100 0.1 0.6 0.8 0.4 1.1 1.6 0.5 0.7 0.7 0.9 W (ppm) LF100 0.5 0.25 0.8 0.25 2 1.5 1.6 0.25 0.25 0.25 V (ppm) LF100 8 24 29 83 213 85 104 13 18 215 Zr (ppm) LF100 0.1 60.6 30.8 47.3 63.5 155.4 47.3 19.4 53.5 68.5 Y (ppm) LF100 0.1 6.4 8.5 12.2 13.1 23.1 11.6 5.4 6.7 13.9 La (ppm) LF100 0.1 8.3 7.6 11.6 10.2 21.3 13.1 4.2 7.7 11 Ce (ppm) LF100 0.1 14.5 11.9 21.6 21.4 44.5 24.6 6.2 12.8 22.4 Pr (ppm) LF100 0.02 1.62 1.58 2.98 2.56 5.53 3.16 0.87 1.59 2.69 Nd (ppm) LF100 0.3 6.3 6.9 12.4 10.2 22.1 12.9 4.2 6.3 11 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 150 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH111 13JZBH118 13JZBH125 13JZBH133 13JZBH136 13JZBH140 13JZBH142 13JZBH143 13JZBH147 Sm (ppm) LF100 0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 Eu (ppm) LF100 0.02 <0.02 <0.02 <0.02 <0.02 0.02 <0.02 <0.02 <0.02 <0.02 Gd (ppm) LF100 0.05 101 4 85 96 141 98 17 69 132 Tb (ppm) LF100 0.01 0.5 0.5 2 2 5 0.5 0.5 0.5 3 Dy (ppm) LF100 0.05 1.1 1 6 23.2 8.3 8.4 1 0.6 21.4 Ho (ppm) LF100 0.02 1.5 1 4 5.6 3.6 11.1 0.3 1 4.5 Er (ppm) LF100 0.03 2.1 0.25 5.3 14.2 12 9.6 0.6 1 16.1 Tm (ppm) LF100 0.01 1.6 1.2 1.3 1.7 4.1 1.5 0.4 1.4 1.7 Yb (ppm) LF100 0.05 2.6 0.9 1.8 3.8 7.7 2.1 0.2 1.9 3.7 Lu (ppm) LF100 0.01 18.7 0.6 16.6 85.1 75.8 54.8 5.3 13.1 48.4 Mo (ppm) AQ200 0.1 0.5 0.5 0.5 0.5 1 0.5 0.5 0.5 0.5 Cu (ppm) AQ200 0.1 196.6 75.2 153.3 162.6 320.3 129.3 330.5 369.2 377.2 Pb (ppm) AQ200 0.1 0.2 0.05 0.3 0.2 0.6 0.3 0.05 0.2 0.3 Zn (ppm) AQ200 1 1.7 1.1 1.2 2.9 8.2 2.4 0.5 1.5 2.9 Ni (ppm) AQ200 0.1 0.6 0.8 0.4 1.1 1.6 0.5 0.7 0.7 0.9 As (ppm) AQ200 0.5 0.25 0.8 0.25 2 1.5 1.6 0.25 0.25 0.25 Cd (ppm) AQ200 0.1 24 29 83 213 85 104 13 18 215 Sb (ppm) AQ200 0.1 60.6 30.8 47.3 63.5 155.4 47.3 19.4 53.5 68.5 Bi (ppm) AQ200 0.1 6.4 8.5 12.2 13.1 23.1 11.6 5.4 6.7 13.9 Ag (ppm) AQ200 0.1 8.3 7.6 11.6 10.2 21.3 13.1 4.2 7.7 11 Hg (ppm) AQ200 0.01 14.5 11.9 21.6 21.4 44.5 24.6 6.2 12.8 22.4 Tl (ppm) AQ200 0.1 1.62 1.58 2.98 2.56 5.53 3.16 0.87 1.59 2.69 Se (ppm) AQ200 0.5 6.3 6.9 12.4 10.2 22.1 12.9 4.2 6.3 11 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 151 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH156 13JZBH165 13JZBH167 13JZBH176 13JZBH181 13JZBH185 13JZBH190 13JZBH197 Au (ppb) FA130 0.5 9.1 1.3 2.2 0.7 1.5 0.8 2.2 0.25 SiO2 (%) LF700 0.10 15.20 39.30 54.10 27.20 14.60 52.00 30.40 9.30 Al2O3 (%) LF700 0.01 0.63 9.53 16.99 3.68 0.75 11.37 4.61 0.44 Fe2O3 (%) LF700 0.01 0.50 4.15 7.02 1.38 0.71 5.15 1.57 0.69 CaO (%) LF700 0.01 46.32 23.42 6.38 36.47 45.90 8.37 33.76 49.69 MgO (%) LF700 0.01 0.38 5.39 4.12 0.76 0.57 5.88 0.79 0.41 Na2O (%) LF700 0.01 0.01 1.47 3.35 0.04 0.01 2.04 0.06 0.01 K2O (%) LF700 0.01 0.11 2.17 1.38 0.62 0.15 2.04 0.74 0.07 MnO (%) LF700 0.01 0.03 0.09 0.13 0.06 0.03 0.13 0.07 0.03 TiO2 (%) LF700 0.01 0.03 0.51 0.58 0.21 0.05 0.60 0.24 0.02 P2O5 (%) LF700 0.01 0.03 0.10 0.15 0.07 0.03 0.08 0.08 0.02 Cr2O3 (%) LF700 0.001 <0.001 0.01 <0.001 <0.001 <0.001 0.01 <0.001 <0.001 LOI (%) LF700 -5.11 36.44 13.94 6.04 29.02 36.21 13.05 26.81 38.44 SO3 (%) LF700 0.002 0.33 0.06 0.09 0.53 0.79 0.05 0.87 1.01 V2O5 (%) LF700 0.002 <0.002 0.02 0.04 0.01 <0.002 0.02 0.01 <0.002 Total (%) LF700 0.01 100.01 100.15 100.37 100.04 99.80 100.79 100.01 100.13 TOT/C (%) TC000 0.02 10.20 3.57 0.65 7.97 10.10 3.02 7.33 10.90 TOT/S (%) TC000 0.02 0.14 0.01 0.04 0.09 0.27 0.01 0.40 0.32 Ba (%) LF700 0.01 0.01 0.06 0.02 0.01 0.01 0.04 0.01 0.01 Cu (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ni (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Pb (%) LF700 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Sr (%) LF700 0.002 0.03 0.06 0.05 0.02 0.03 0.04 0.02 0.03 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 152 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH156 13JZBH165 13JZBH167 13JZBH176 13JZBH181 13JZBH185 13JZBH190 13JZBH197 Zn (%) LF700 0.001 <0.001 0.01 0.01 <0.001 <0.001 <0.001 <0.001 <0.001 Zr (%) LF700 0.002 <0.002 0.01 <0.002 <0.002 <0.002 0.02 <0.002 <0.002 Ba (ppm) LF100 1 23 525 160 94 21 399 78 19 Be (ppm) LF100 1 0.5 2 2 0.5 0.5 0.5 2 0.5 Co (ppm) LF100 0.2 0.7 10.2 19.2 2.5 0.7 13.3 2.9 0.6 Cs (ppm) LF100 0.1 0.2 0.6 2.3 2.3 0.5 2.1 1.4 0.2 Ga (ppm) LF100 0.5 0.25 12 14.6 3.2 0.25 14.5 4.8 0.25 Hf (ppm) LF100 0.1 0.4 3.2 1.8 1.5 0.6 5.4 1.4 0.2 Nb (ppm) LF100 0.1 0.05 7.3 3.4 1.5 0.4 9.3 2.3 0.05 Rb (ppm) LF100 0.1 5.4 74.1 44.1 19.8 6.6 67.9 21.6 4.2 Sn (ppm) LF100 1 0.5 1 0.5 0.5 0.5 3 0.5 0.5 Sr (ppm) LF100 0.5 328.4 638.9 428.2 121.3 365 373.6 189.6 295.8 Ta (ppm) LF100 0.1 0.05 0.5 0.3 0.05 0.05 0.7 0.2 0.05 Th (ppm) LF100 0.2 0.5 8 3 1.8 0.8 9.6 2 0.3 U (ppm) LF100 0.1 0.5 1.8 0.8 1.1 0.8 2.4 0.8 0.7 W (ppm) LF100 0.5 0.25 0.7 0.25 0.25 0.25 1.9 0.6 0.25 V (ppm) LF100 8 9 94 196 32 12 102 45 4 Zr (ppm) LF100 0.1 20.3 129.5 69.9 53.2 33.8 203.5 58.7 12.5 Y (ppm) LF100 0.1 3.5 19.3 14.1 8.8 4.7 18 9.7 3 La (ppm) LF100 0.1 4.3 23.1 10.7 10.2 5.9 25.6 9 3.2 Ce (ppm) LF100 0.1 5.6 42.1 22 16.9 7.8 50.3 15.8 4.5 Pr (ppm) LF100 0.02 0.84 5.35 2.7 2.13 1.11 6.45 2.05 0.6 Nd (ppm) LF100 0.3 3.9 22.4 11.6 8.2 4.9 25.9 8.9 2.4 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 153 Appendix B: Lithogeochemical data Analyte Analytical Method* Detection Limit 13JZBH156 13JZBH165 13JZBH167 13JZBH176 13JZBH181 13JZBH185 13JZBH190 13JZBH197 Sm (ppm) LF100 0.05 0.64 4.59 2.32 1.41 0.89 5.05 1.85 0.44 Eu (ppm) LF100 0.02 0.13 0.95 0.7 0.33 0.2 0.83 0.39 0.09 Gd (ppm) LF100 0.05 0.62 3.64 2.62 1.54 0.76 3.79 1.54 0.43 Tb (ppm) LF100 0.01 0.08 0.56 0.39 0.23 0.14 0.64 0.24 0.08 Dy (ppm) LF100 0.05 0.55 3.18 2.74 1.51 0.73 3.55 1.38 0.43 Ho (ppm) LF100 0.02 0.13 0.64 0.6 0.27 0.14 0.67 0.28 0.09 Er (ppm) LF100 0.03 0.29 2.11 1.5 0.77 0.34 1.82 0.72 0.26 Tm (ppm) LF100 0.01 0.03 0.28 0.22 0.12 0.05 0.28 0.12 0.03 Yb (ppm) LF100 0.05 0.22 1.64 1.4 0.65 0.38 1.97 0.74 0.18 Lu (ppm) LF100 0.01 0.04 0.24 0.22 0.11 0.05 0.3 0.12 0.03 Mo (ppm) AQ200 0.1 0.2 0.05 0.2 0.1 0.05 0.2 0.5 0.3 Cu (ppm) AQ200 0.1 1.1 8.3 67 2.4 2.1 1.2 4.4 1 Pb (ppm) AQ200 0.1 1.7 4.8 1.2 2.4 1.8 3.9 3.8 1.8 Zn (ppm) AQ200 1 3 20 49 14 6 119 19 3 Ni (ppm) AQ200 0.1 0.5 10.7 10.5 2.9 2.5 33.4 4.5 3.1 As (ppm) AQ200 0.5 14.9 1.9 1.4 1.9 26.1 1.5 30.2 5.6 Cd (ppm) AQ200 0.1 0.05 0.05 0.05 0.05 0.05 0.2 0.05 0.05 Sb (ppm) AQ200 0.1 0.7 0.05 0.05 0.05 1.1 0.05 0.6 0.5 Bi (ppm) AQ200 0.1 0.05 0.05 0.05 0.2 0.05 0.05 0.05 0.05 Ag (ppm) AQ200 0.1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Hg (ppm) AQ200 0.01 0.03 0.005 0.005 0.005 0.01 0.005 0.005 0.01 Tl (ppm) AQ200 0.1 0.1 0.05 0.05 0.05 0.1 0.05 0.05 0.05 Se (ppm) AQ200 0.5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 * FA130 – fire assay/ICP-MS, LF700 –XRF – fusion - major oxides, TC000 - Leco - total C and S, LF100 - lithium fusion, AQ - aqua regia ICP-MS 154 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 Mineral 3 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 13JZBH001 VOL Illite 2196.04 0.27 31.81 0.34 0.78 13JZBH002 VOL Illite 2197.76 0.33 34.39 0.37 0.89 13JZBH003 VOL Illite 2197.05 0.18 32.14 0.23 0.78 13JZBH004 VOL Illite 2196.73 0.20 33.18 0.27 0.72 13JZBH005 VOL Montmo-rillonite Illite 2218.58 0.05 30.85 0.17 0.31 13JZBH006 S2 Dickite Kaolinite Illite 2207.40 0.11 29.73 0.04 2.70 13JZBH007 S2 Illite 2198.78 0.06 32.59 0.07 0.79 13JZBH008 S2 Illite 2195.47 0.09 32.04 0.11 0.74 13JZBH009 S2 Illite 2197.97 0.11 33.69 0.12 0.91 13JZBH010 S2 Illite Kaolinite 2205.36 0.14 33.08 0.11 1.21 13JZBH010a S2 Illite Kaolinite 2207.69 0.20 31.01 0.12 1.75 13JZBH011 S2 Kaolinite Illite Muscovite 2208.20 0.14 28.10 0.07 2.01 13JZBH011a S2 Kaolinite Illite 2207.77 0.09 29.52 0.08 1.20 13JZBH012 S1 Kaolinite 13JZBH013 S1 Illite 2203.77 0.04 28.42 0.05 0.86 13JZBH014 S1 Illite 2198.33 0.05 31.38 0.06 0.86 13JZBH015 IB Illite Muscovite 2202.74 0.08 28.94 0.06 1.34 13JZBH017 VOL Illite 2194.13 0.22 32.20 0.28 0.78 13JZBH018 VOL Illite 2197.44 0.08 32.31 0.14 0.62 13JZBH020 S2 Illite Kaolinite 2203.01 0.07 32.80 0.12 0.63 13JZBH021 S2 Illite 2194.42 0.24 33.07 0.26 0.93 13JZBH021a S2 Illite Kaolinite 2206.88 0.17 31.70 0.25 0.67 13JZBH023 S2 Illite 2204.10 0.14 33.79 0.12 1.12 13JZBH024 S1 Illite Muscovite 2206.19 0.20 30.60 0.13 1.50 13JZBH024a S1 Illite 2203.25 0.12 31.43 0.15 0.79 13JZBH025 S1 Illite 2201.35 0.13 31.12 0.09 1.42 13JZBH025a S1 Illite Kaolinite 2200.07 0.13 28.99 0.11 1.15 13JZBH027 S1 Illite 2205.89 0.15 30.77 0.10 1.58 13JZBH028 BBX Illite 2202.49 0.11 33.01 0.14 0.80 13JZBH029 SMR Illite 2210.75 0.07 34.10 0.11 0.68 13JZBH030 SMR Illite 2207.28 0.11 31.00 0.08 1.42 13JZBH031 S2 Illite 2202.71 0.10 29.78 0.09 1.14 13JZBH032 S2 Illite 2208.51 0.10 25.20 0.19 0.55 13JZBH033 S2 Illite Kaolinite 2207.29 0.28 33.56 0.23 1.18 13JZBH034 S2 Illite 2197.40 0.11 32.16 0.12 0.98 13JZBH035 S1 Kaolinite 13JZBH036 S1 Kaolinite * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 155 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 Mineral 3 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 13JZBH037 S1 Illite 2202.53 0.08 32.40 0.08 0.94 13JZBH039 IB Illite 2210.46 0.06 31.35 0.07 0.89 13JZBH040 BBX Illite Kaolinite 2208.35 0.13 25.38 0.20 0.66 13JZBH041 VOL Montmo-rillonite 2210.62 0.04 25.30 0.23 0.16 13JZBH042 VOL Nacrite Kaolinite 13JZBH043 VOL Kaolinite Nacrite 13JZBH044 VOL Illite Kaolinite 2208.14 0.31 26.71 0.43 0.71 13JZBH045 VOL Kaolinite 13JZBH046 VOL Illite Montmo-rillonite Kaolinite 2208.52 0.09 27.96 0.23 0.36 13JZBH047 S2 Illite 2208.65 0.06 24.64 0.06 1.05 13JZBH049 S2 Illite Kaolinite 2208.22 0.28 28.45 0.26 1.11 13JZBH050 S2 Kaolinite Illite 2208.38 0.16 31.01 0.18 0.92 13JZBH051 S2 Illite 2185.70 0.11 28.17 0.19 0.57 13JZBH052 S2 Illite 2207.76 0.09 30.06 0.08 1.07 13JZBH053 S2 Illite 2207.82 0.07 33.06 0.09 0.78 13JZBH054 S2 Muscovite Dickite Illite 2206.53 0.09 29.43 0.07 1.37 13JZBH054a S2 Illite Muscovite 2207.89 0.07 27.33 0.04 1.72 13JZBH055 S2 Illite Nacrite 2209.04 0.05 25.70 0.04 1.34 13JZBH059 S1 Illite 2200.62 0.04 28.84 0.09 0.51 13JZBH061 S2 Illite 2206.75 0.14 31.93 0.27 0.51 13JZBH062 S2 Kaolinite Illite 2207.58 0.16 33.07 0.26 0.64 13JZBH063 S2 Kaolinite Illite 2190.62 0.22 35.74 0.41 0.54 13JZBH064 S2 Kaolinite Illite 2208.43 0.12 28.01 0.12 1.00 13JZBH066 S1 Kaolinite 13JZBH072 S2 Kaolinite Illite 2208.56 0.20 26.72 0.13 1.55 13JZBH073 S2 Kaolinite 13JZBH074 S2 Kaolinite 13JZBH075 S2 Kaolinite 13JZBH076 S2 Kaolinite 13JZBH077 S2 Kaolinite 13JZBH078 S2 Kaolinite 13JZBH079 S2 Kaolinite 13JZBH083 S1 Illite 2205.51 0.06 29.15 0.06 1.07 13JZBH084 S1 Illite 2208.36 0.08 27.97 0.11 0.69 13JZBH085 BBX Illite 2192.15 0.15 33.76 0.27 0.54 13JZBH086 BBX Illite 2194.90 0.15 35.18 0.25 0.60 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 156 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 13JZBH087 BBX Kaolinite 13JZBH088 S2 Montmorillonite 2208.25 0.06 25.63 0.25 0.23 13JZBH089 S2 Illite 2206.18 0.15 32.15 0.37 0.42 13JZBH090 S2 Illite 2195.95 0.09 32.65 0.13 0.74 13JZBH092 S1 Kaolinite 13JZBH093 S1 Kaolinite 13JZBH094 S1 Kaolinite Dickite 13JZBH095 S1 Illite 2204.66 0.09 30.22 0.12 0.74 13JZBH097 IB Illite 2192.30 0.18 33.57 0.24 0.74 13JZBH099 BBX Illite 2186.33 0.04 26.28 0.09 0.42 13JZBH100 BBX Illite 2188.00 0.07 30.43 0.14 0.52 13JZBH103 VOL Montmorillonite Nacrite 2204.15 0.31 31.17 0.34 0.91 13JZBH104 SMR Montmorillonite 2227.90 0.01 26.43 0.24 0.04 13JZBH105 S2 Illite Montmorillonite 2208.23 0.09 27.02 0.24 0.38 13JZBH106 S2 Montmorillonite Halloysite 2208.66 0.12 23.77 0.25 0.52 13JZBH107 S2 Kaolinite 13JZBH108 S1 Illite 2205.62 0.06 29.97 0.08 0.71 13JZBH109 S1 Illite 2205.20 0.06 29.63 0.08 0.83 13JZBH110 S1 Illite 2203.41 0.10 30.77 0.13 0.82 13JZBH112 IB Kaolinite 13JZBH113 BBX Illite Kaolinite 2207.70 0.07 28.79 0.06 1.16 13JZBH113a BBX Illite Kaolinite 2208.57 0.06 27.76 0.04 1.55 13JZBH114 BBX Illite 2208.69 0.20 27.40 0.32 0.62 13JZBH115 S2 Illite 2200.51 0.22 34.63 0.27 0.84 13JZBH116 S1 Illite Montmorillonite 2208.32 0.05 32.21 0.12 0.42 13JZBH117 S1 Montmorillonite 2208.87 0.03 25.73 0.20 0.14 13JZBH124 S2 Illite 2209.31 0.06 29.55 0.15 0.41 13JZBH125 S2 Illite 2207.80 0.09 29.00 0.17 0.57 13JZBH126 S2 Illite 2192.21 0.07 30.45 0.10 0.73 13JZBH127 S2 Illite 2195.70 0.18 32.27 0.26 0.69 13JZBH132 VOL Illite 2196.57 0.29 33.98 0.39 0.75 13JZBH133 VOL Illite 2197.23 0.25 32.74 0.29 0.86 13JZBH134 VOL Illite 2194.08 0.18 32.71 0.26 0.72 13JZBH135 SMR Illite 2199.80 0.11 29.82 0.13 0.81 13JZBH136 SMR Illite 2199.19 0.12 31.90 0.12 1.04 13JZBH138 S2 Illite 2196.81 0.27 33.94 0.36 0.75 13JZBH139 S2 Illite 2200.15 0.19 33.19 0.23 0.83 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 157 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 13JZBH140 S2 Illite 2200.74 0.21 34.41 0.25 0.85 13JZBH141 S2 Montmorillonite 2208.87 0.03 25.73 0.12 0.26 13JZBH144 SMR Illite 2199.32 0.22 33.23 0.27 0.82 13JZBH145 SMR Illite 2198.88 0.15 27.90 0.22 0.69 13JZBH146 VOL Illite 2196.49 0.19 34.66 0.20 0.95 13JZBH147 VOL Illite 2204.71 0.13 32.19 0.15 0.89 13JZBH148 VOL Montmorillonite 2207.35 0.03 23.17 0.18 0.16 13JZBH149 SMR Illite 2208.85 0.17 31.83 0.23 0.71 13JZBH151 S2 Montmorillonite 2209.30 0.11 23.93 0.26 0.43 13JZBH152 S2 Kaolinite 13JZBH153 S2 Illite 2204.69 0.06 28.81 0.11 0.56 13JZBH154 S1 Muscovite Illite 2205.75 0.10 30.66 0.12 0.83 13JZBH159 S1 Illite 2204.39 0.04 27.62 0.06 0.74 13JZBH160 IB Illite 2203.59 0.10 26.77 0.11 0.93 13JZBH161 S2 Illite 2206.84 0.14 31.63 0.31 0.43 13JZBH163 S2 Montmorillonite Palygorskite 2214.28 0.05 28.32 0.24 0.20 13JZBH167 VOL Illite Montmorillonite 2208.78 0.09 21.67 0.19 0.48 13JZBH168 S2 Illite 2201.73 0.11 32.02 0.08 1.41 13JZBH170 S2 Illite 2202.43 0.07 30.73 0.10 0.71 13JZBH170a S2 Illite 2203.25 0.14 31.11 0.10 1.39 13JZBH171 S2 Illite 2194.16 0.25 32.59 0.28 0.89 13JZBH172 S1 Illite 2199.64 0.12 32.58 0.09 1.35 13JZBH173 BBX Illite 2210.24 0.06 30.82 0.05 1.19 13JZBH174 BBX Illite Montmorillonite 2208.29 0.04 27.41 0.06 0.69 13JZBH175 VOL Illite 2206.12 0.22 32.52 0.29 0.76 13JZBH176 S2 Illite 2207.71 0.13 28.83 0.16 0.79 13JZBH177 S2 Illite 2197.34 0.11 33.04 0.12 0.93 13JZBH178 S2 Kaolinite 13JZBH179 S1 Illite 2203.25 0.09 30.85 0.13 0.71 13JZBH182 S1 Illite Muscovite 2199.66 0.07 29.39 0.13 0.58 13JZBH184 SMR Illite 2208.00 0.09 29.27 0.15 0.61 13JZBH185 SMR Illite 2206.63 0.18 30.74 0.23 0.80 13JZBH186 VOL Illite 2195.66 0.11 33.32 0.17 0.69 13JZBH187 VOL Illite 2194.48 0.31 33.49 0.43 0.72 13JZBH188 VOL Illite 2202.58 0.09 34.82 0.19 0.50 13JZBH188a VOL Illite 2202.14 0.25 35.23 0.32 0.79 13JZBH189 VOL Montmorillonite 2207.17 0.06 26.45 0.30 0.19 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 158 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 Mineral 3 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 13JZBH190 S2 Illite 2197.62 0.11 33.07 0.14 0.74 13JZBH191 S2 Illite 2199.85 0.14 33.24 0.16 0.85 13JZBH192 S2 Illite Montmo-rillonite Halloysite 2206.37 0.08 26.05 0.15 0.52 13JZBH193 S2 Montmo-rillonite Illite 2208.08 0.10 27.14 0.20 0.53 13JZBH194 S2 Kaolinite 13JZBH195 S2 Illite Muscovite 2202.07 0.10 30.70 0.12 0.87 13JZBH195a S2 Illite 2200.81 0.07 31.35 0.13 0.61 13JZBH199 IB Muscovite Illite 2204.19 0.10 28.03 0.12 0.83 13JZBH200 IB Illite 2208.31 0.05 29.00 0.02 2.03 13JZBH206 S2 Illite 2199.20 0.08 32.28 0.13 0.65 13JZBH207 S2 Illite 2198.71 0.15 34.49 0.16 0.92 13JZBH208 S2 Illite 2202.35 0.05 32.83 0.07 0.71 13JZBH208a S2 Illite 2203.40 0.16 33.46 0.14 1.10 13JZBH210 SMR Illite 2202.55 0.06 30.78 0.04 1.35 13JZBH211 S2 Illite 2200.92 0.10 32.82 0.11 0.85 13JZBH212 S2 Illite Montmo-rillonite 2208.16 0.08 27.01 0.18 0.42 13JZBH213 S2 Illite 2209.14 0.06 24.77 0.09 0.60 13JZBH214 S2 Illite 2193.80 0.08 33.01 0.13 0.57 13JZBH215 S2 Illite 2200.92 0.25 33.95 0.39 0.64 13JZBH218 S2 Illite Montmo-rillonite 2206.66 0.12 26.71 0.20 0.59 13JZBH221 S2 Montmo-rillonite 2208.51 0.03 26.66 0.10 0.32 13JZBH222 S2 Illite 2195.92 0.20 33.39 0.29 0.69 13JZBH225 S1 Illite 2201.66 0.06 31.36 0.03 2.14 13JZBH225a S1 Illite 2204.01 0.06 29.79 0.07 0.80 13JZBH226 S1 Illite Kaolinite Dickite 2209.30 0.05 31.27 0.05 1.15 13JZBH227 S2 Illite Halloysite 2205.33 0.16 30.99 0.18 0.91 13JZBH228 S2 Kaolinite Montmo-rillonite Illite 2208.90 0.10 24.14 0.15 0.64 13JZBH228a S2 Kaolinite Montmo-rillonite Illite 2208.71 0.19 25.16 0.41 0.46 13JZBH230 S2 Illite 2207.05 0.13 29.92 0.28 0.49 13JZBH232 S1 Illite 2209.79 0.04 28.56 0.06 0.60 13JZBH233 S1 Illite 2205.29 0.06 29.69 0.10 0.61 13JZBH234 S1 Illite 2200.27 0.06 30.14 0.13 0.46 14JZBH235 SMR Illite 2203.06 0.08 31.30 0.14 0.54 14JZBH236 SMR Illite 2202.48 0.06 30.06 0.11 0.53 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 159 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 Mineral 3 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 14JZBH237 SMR Illite 2203.90 0.04 29.68 0.11 0.35 14JZBH237a SMR Illite 2204.00 0.06 29.41 0.10 0.62 14JZBH238 S2 Montmo-rillonite Palygorskite 2212.46 0.07 31.19 0.27 0.24 14JZBH239 S2 Montmo-rillonite 2217.86 0.04 31.53 0.10 0.37 14JZBH240 S2 Montmo-rillonite Palygorskite 2215.42 0.04 28.60 0.25 0.17 14JZBH241 S2 Montmo-rillonite 2208.73 0.05 26.23 0.16 0.30 14JZBH242 S1 Illite Montmo-rillonite 2208.59 0.06 29.53 0.17 0.35 14JZBH243 S1 Montmo-rillonite 2208.30 0.03 26.76 0.07 0.40 14JZBH244 S1 Montmo-rillonite 2208.85 0.04 23.91 0.18 0.20 14JZBH245 S1 Illite 2208.73 0.05 25.93 0.09 0.48 14JZBH248 S2 Montmo-rillonite 2209.81 0.07 25.40 0.34 0.21 14JZBH249 S2 Montmo-rillonite 2208.88 0.06 24.61 0.21 0.28 14JZBH250 S1 Montmo-rillonite 2208.81 0.05 23.19 0.19 0.27 14JZBH251 S1 Montmo-rillonite 2210.53 0.06 28.55 0.30 0.18 14JZBH252 S1 Montmo-rillonite Illite 2208.44 0.09 26.45 0.30 0.30 14JZBH253 IB Illite Montmo-rillonite 2203.05 0.04 28.80 0.09 0.39 14JZBH254 S1 Kaolinite Illite 2208.28 0.04 21.75 0.06 0.66 14JZBH259 SMR Muscovite Illite 2206.41 0.07 32.47 0.07 1.02 14JZBH260 S2 Illite 2214.37 0.06 27.99 0.15 0.36 14JZBH261 S2 Illite Montmo-rillonite 2209.43 0.05 32.68 0.11 0.46 14JZBH262 S1 Illite 2208.10 0.04 32.82 0.08 0.52 14JZBH264 IB Illite 2201.71 0.04 32.37 0.02 1.54 14JZBH267 S2 Illite 2205.14 0.10 30.16 0.16 0.64 14JZBH268 S2 Illite 2192.04 0.07 31.79 0.11 0.65 14JZBH268a S2 Illite 2196.89 0.11 32.45 0.13 0.78 14JZBH269 S2 Illite 2201.96 0.07 32.41 0.11 0.64 14JZBH269a S2 Illite 2203.67 0.13 32.75 0.09 1.36 14JZBH270 IB Illite Muscovite 2206.14 0.05 27.48 0.03 1.63 14JZBH270a S2 Illite Kaolinite 2205.81 0.06 29.26 0.03 2.11 14JZBH271 S1 Illite Kaolinite Muscovite 2206.21 0.06 30.46 0.07 0.88 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 160 Appendix C: SWIR data, identified phyllosilicate minerals, and their spectral features Sample ID Litho. Unit Mineral 1 Mineral 2 Mineral 3 w2200 (nm)* Hqd 2200* Width 2200* Hqd 1900* Sericite Crysta-llinity 14JZBH273 KLS Illite 2208.12 0.04 31.65 0.06 0.71 14JZBH277 SMR Illite Muscovite 2208.46 0.09 27.23 0.06 1.51 14JZBH278 S2 Kaolinite 14JZBH279 S2 Kaolinite 14JZBH283 BBX Illite 2198.01 0.05 32.26 0.09 0.57 14JZBH284 BBX Illite Kaolinite 2208.34 0.20 29.05 0.16 1.29 14JZBH285 VOL Illite 2207.35 0.08 27.99 0.15 0.53 14JZBH286 GDI Illite 2200.87 0.02 26.68 0.16 0.14 14JZBH287 S1 Kaolinite 14JZBH288 VOL Illite Montmo-rillonite 2195.86 0.23 32.54 0.27 0.88 14JZBH290 BBX Illite Dickite 2207.83 0.07 26.96 0.04 1.45 14JZBH291 KLS Illite 2208.89 0.07 25.73 0.07 0.96 14JZBH292 VOL Illite 2197.67 0.31 34.38 0.36 0.85 14JZBH293 S2 Kaolinite Illite 2208.66 0.29 27.74 0.13 2.22 14JZBH294 VOL Illite 2195.91 0.20 33.39 0.24 0.84 14JZBH295 S2 Illite Kaolinite 2204.28 0.14 33.34 0.13 1.08 14JZBH295a S2 Illite Kaolinite 2207.71 0.14 30.47 0.09 1.46 14JZBH296 VOL Illite 2197.63 0.28 34.30 0.35 0.82 14JZBH297 S2 Illite 2197.76 0.25 33.79 0.30 0.85 14JZBH298 S2 Illite 2197.96 0.18 33.57 0.20 0.88 14JZBH299 S2 Illite Muscovite Kaolinite 2203.01 0.13 31.25 0.12 1.07 14JZBH299a S2 Illite Kaolinite 2204.61 0.11 30.50 0.07 1.47 14JZBH300 S2 Kaolinite 14JZBH301 S2 Illite 2208.02 0.06 27.28 0.12 0.47 14JZBH302 S2 Illite 2198.41 0.06 30.72 0.12 0.55 * w2200 - wavelength at the minimum point of 2200 absorption feature; hqd – relative depth at the minimum point of the appropriate absorption feature; width2200 – width of the 2200 absorption feature; data obtained by The Spectral Geologist© software 161 Appendix D: Isocon diagrams for limestone, S1, S2 and andesite units representing the mass transfer during the rock alteration TiHfNbZrAuSiAl FeCaMgNaKMnPCSBaBeCoCsGaRbSnSrTaThUWMoCuPbZnNiAsCdSbBiAgHgTlSey = 7.3464x1.0506R² = 0.99910.010.11101001000100001000001000000100000000.001 0.1 10 1000 100000Mineralized rocks (ppm)Non-mineralized rocks (ppm)Limestone 162 Appendix D: Isocon diagrams for limestone, S1, S2 and andesite units representing the mass transfer during the rock alteration ZrTiHfNbAu SiAlFeCaMgNaKMnPCSBaGaRbSnSrTaThUWMoCuPbZnNiAsCdSbBiAgHg TlSey = 1.612x0.99R² = 0.99480.010.111010010001000010000010000000.001 0.01 0.1 1 10 100 1000 10000 100000 1000000Mineralized rocks (ppm)Non-mineralized rocks (ppm)S1 163 Appendix D: Isocon diagrams for limestone, S1, S2 and andesite units representing the mass transfer during the rock alteration ZrTiHfNbAuSiAlFeCaMgNaKMnPCSBaBeCoCsGaRbSnSrTaThUWMoCuPbZnNiAsCdSbBiAgHgTlSey = 1.3325x0.9846R² = 0.99990.010.111010010001000010000010000000.001 0.01 0.1 1 10 100 1000 10000 100000 1000000Mineralized rocks (ppm)Non-mineralized rocks (ppm)S2 164 Appendix D: Isocon diagrams for limestone, S1, S2 and andesite units representing the mass transfer during the rock alteration ZrTiHfNbAuAlFeCaMgNaKMnPCSBaBeCoCsGaRbSnSrTaThUWMoCuPbZnNiAsCdSbBiAgHgTl Sey = 0.9352x1.013R² = 0.99970.010.111010010001000010000010000000.001 0.1 10 1000 100000Mineralized rocks (ppm)Non-mineralized rocks (ppm)Andesite 165 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Hole ID* Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD053 01-53 460 461 SMR Marl 3.69 20.35 0.006 6.8 0.44 0.08 0.13 0.02 BHDD053 02-53 465 466 SMR Marl 1.70 19.75 0.018 17.5 1.89 0.12 0.025 0.04 BHDD053 03-53 470 471 SMR Marl 2.55 21.64 0.009 22.2 3.22 0.12 0.07 0.03 BHDD053 04-53 475 476 SMR Marl 1.84 22.14 0.005 4.2 0.51 0.08 0.025 0.02 BHDD053 05-53 480 481 SMR Marl 1.15 18.95 0.005 2.7 0.32 0.1 0.06 0.005 BHDD053 06-53 485 486 S2 Sandstone 1.67 19.22 0.005 0.5 0.47 0.05 0.07 0.005 BHDD053 07-53 490 491 S2 Sandstone -0.88 17.31 0.005 0.5 1.32 0.05 0.025 0.02 BHDD053 08-53 495 496 S2 Fault -0.46 17.09 0.047 16.8 1.06 0.09 0.15 0.02 BHDD053 09-53 500 501 S2 Breccia 0.13 17.16 0.051 72.5 4.97 0.1 0.1 0.04 BHDD053 10-53 505 506 S2 Sandstone 1.39 19.08 0.163 162 4.17 0.08 0.39 0.03 BHDD053 11-53 510 511 S2 Sandstone 2.58 21.31 0.008 0.5 0.55 0.02 0.025 0.03 BHDD053 12-53 515 516 S2 Sandstone 2.02 20.41 0.006 2 0.5 0.01 0.025 0.005 BHDD053 13-53 520 521 S2 Sandstone 2.27 22.42 0.005 56.7 1.62 0.03 0.025 0.04 BHDD053 14-53 525 526 S2 Sandstone 2.53 23.12 0.005 5.9 0.61 0.01 0.025 0.005 BHDD053 15-53 530 531 S2 Sandstone 2.39 24.89 0.01 24.8 0.86 0.05 0.025 0.005 BHDD053 16-53 535 536 S1 Sandstone 1.99 25.31 0.01 22.1 1 0.03 0.025 0.03 BHDD053 17-53 540 541 S1 Sandstone 0.69 24.61 0.005 8 0.71 0.03 0.025 0.01 BHDD053 18-53 545 546 S1 Sandstone 2.32 27.66 0.005 5.9 0.62 0.02 0.025 0.005 BHDD053 19-53 550 551 S1 Sandstone 2.73 29.17 0.005 5.3 0.4 0.01 0.025 0.005 BHDD053 20-53 555 556 S1 Sandstone 2.49 27.36 0.005 4.3 0.42 0.01 0.06 0.005 BHDD053 21-53 560 561 S1 Sandstone 1.13 25.25 0.01 17.7 0.87 0.04 0.025 0.03 BHDD053 22-53 565 566 S1 Sandstone 0.81 17.39 0.032 15.8 0.9 0.03 0.025 0.03 BHDD053 23-53 570.1 570.9 S1 Sandstone 1.71 21.10 0.005 15.8 0.9 0.03 0.025 0.03 BHDD056 24-56 132 133 SMR Marl -1.03 15.00 0.06 27.6 0.79 0.08 0.3 0.03 BHDD056 25-56 137 138 S2 Sandstone -0.48 15.04 0.005 1.4 0.56 0.08 0.025 0.005 BHDD056 26-56 142 143 S2 Sandstone -0.92 15.38 0.008 61.5 5.14 0.34 0.07 0.06 BHDD056 27-56 147 148 S2 Sandstone 0.31 18.68 0.008 25.4 1.66 0.13 0.11 0.005 BHDD056 28-56 152 153 S2 Conglomerate 2.25 18.74 0.008 3.7 0.75 0.1 0.13 0.005 BHDD056 29-56 157 158 S2 Conglomerate 1.92 18.06 0.012 5.8 1.46 0.17 0.09 0.005 BHDD056 30-56 162 163 S2 Sandstone 2.52 18.32 0.04 147 7.1 0.43 1.19 0.03 BHDD056 31-56 167 168 S2 Sandstone -1.04 13.88 0.032 82.4 5.94 0.34 0.36 0.06 BHDD056 31-56a 167 168 S2 Vein -0.99 19.58 BHDD056 32-56 172 173 S2 Sandstone 2.17 16.88 0.074 129 5.42 0.61 0.68 0.19 BHDD056 33-56 177 178 S2 Sandstone 1.07 15.76 0.252 173 16.3 1.59 1.32 1.01 BHDD056 34-56 182 183 S2 Sandstone -0.25 14.93 0.306 249 25.4 3.48 1.8 0.61 BHDD056 35-56 187 188 S2 Sandstone 1.17 17.16 0.474 240 73.4 4.8 2.4 2.24 BHDD056 36-56 192 193 S1 Sandstone -0.81 15.44 0.464 69 18 2.16 1.35 1.16 * Drill hole collar coordinates and orientation are in Appendix G 166 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD056 37-56 197 198 S1 Sandstone 2.35 21.74 0.796 137 16.9 2.52 1.8 1.34 BHDD056 38-56 202 203 S1 Mudstone 0.20 16.99 0.432 310 25.3 2.66 2.26 1.18 BHDD056 39-56 207 208 BBX Mudstone -1.59 12.77 0.028 349 21.6 1.38 0.58 0.19 BHDD056 40-56 212 213 IB Mudstone -0.78 15.10 3.62 240 99.2 5.6 3.94 9.43 BHDD056 41-56 217 218 KLS Vein 0.86 14.03 BHDD056 42-56 222 223 KLS Limestone 1.72 17.76 0.006 16 1.6 0.17 0.13 0.21 BHDD056 43-56 227 228 KLS Limestone 2.02 18.27 0.044 47.8 4.67 0.67 0.42 0.18 BHDD056 44-56 232 233 KLS Limestone 2.35 18.88 0.015 28.4 3.15 0.48 0.29 0.19 BHDD056 45-56 237 238 KLS Limestone 0.26 16.93 0.124 57.1 11.9 1.61 0.68 1.01 BHDD056 46-56 242 243 KLS Limestone 0.39 17.68 0.198 53.4 12.3 1.81 0.41 1.47 BHDD056 47-56 247 248 KLS Limestone 0.45 15.89 0.104 77.5 33.2 0.9 0.62 0.69 BHDD056 48-56 252 253 KLS Limestone 0.26 12.11 0.096 42.5 7.37 0.76 0.59 0.58 BHDD056 49-56 257 258 KLS Limestone 1.23 18.01 0.416 78.7 21.2 2.79 0.76 1.95 BHDD056 50-56 262 263 KLS Limestone 1.66 21.15 0.486 102 26 2.68 0.81 1.76 BHDD056 51-56 267 268 KLS Limestone 1.75 14.71 0.306 88.9 17.5 2.22 0.65 1.25 BHDD056 52-56 272 273 KLS Limestone 1.36 13.87 0.2 67.4 15.5 1 0.75 1.17 BHDD056 53-56 277 278 KLS Limestone 0.53 14.52 0.154 64 26.7 1.44 0.99 0.97 BHDD056 54-56 282 283 KLS Limestone 1.04 16.64 0.144 147 36.4 2.78 1.81 0.93 BHDD056 55-56 287 288 KLS Limestone 1.85 26.21 0.036 72.5 8.77 1.04 0.58 0.43 BHDD056 56-56 292 293 JLS Limestone 2.43 23.91 0.011 18.8 2.32 0.32 0.14 0.37 BHDD056 57-56 297 298 JLS Limestone 2.19 25.38 0.011 18.7 4.79 0.25 0.06 0.45 BHDD056 58-56 302 303 JLS Limestone 1.00 25.75 0.007 6.5 3.22 0.05 0.025 0.21 BHDD056 59-56 307 308 JLS Limestone 2.41 24.35 0.023 14.5 2.27 0.15 0.025 0.11 BHDD056 60-56 312 313 JLS Limestone 2.33 15.59 0.088 17.2 2.68 0.35 0.11 0.53 BHDD056 61-56 317 318 JLS Limestone 1.52 15.51 0.074 27.3 4.49 0.48 0.2 1.04 BHDD056 62-56 322 323 JLS Limestone 1.31 14.74 0.04 22.1 2.55 0.35 0.23 0.38 BHDD057 63-57 244 245 S1 Sandstone 2.92 22.04 0.26 94.1 2.81 0.35 0.44 0.26 BHDD057 64-57 249 250 S1 Sandstone 2.87 21.57 0.12 77 2.06 0.24 0.23 0.15 BHDD057 65-57 254 255 S1 Sandstone 1.52 22.08 0.093 70.8 2.38 0.23 0.18 0.11 BHDD057 66-57 259 260 IB Sandstone 0.78 16.60 0.005 6.1 0.84 0.07 0.025 0.06 BHDD057 67-57 264 265 IB Mudstone 1.85 16.31 0.047 59.9 4.82 0.13 0.5 0.09 BHDD057 68-57 269 270 IB Mudstone 1.19 16.19 0.122 219 6.01 0.34 0.51 0.19 BHDD057 69-57 274 275 KLS Fault 1.28 19.39 0.504 362 10.6 0.9 1.18 1.12 BHDD057 70-57 279 280 KLS Limestone 1.61 23.98 0.404 21.8 3.61 0.28 0.15 0.44 BHDD057 71-57 284 285 KLS Limestone 1.01 17.80 0.13 5.2 0.91 0.08 0.025 0.07 BHDD057 72-57 289 290 KLS Limestone 1.57 16.77 0.04 2.8 1.1 0.02 0.025 0.08 * Drill hole collar coordinates and orientation are in Appendix G 167 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD057 73-57 294 295 KLS Limestone 1.00 15.31 0.022 3.3 1.98 0.03 0.025 0.07 BHDD057 74-57 299 300 KLS Limestone 0.87 21.60 0.205 6.4 1.3 0.05 0.025 0.11 BHDD057 75-57 304 305 KLS Limestone 2.43 25.21 0.278 6.5 1.23 0.1 0.025 0.09 BHDD057 76-57 309 310 KLS Limestone 2.81 26.71 0.336 15.1 1.13 0.09 0.025 0.09 BHDD057 77-57 314 315 KLS Limestone 2.33 24.09 0.212 12.6 1.21 0.08 0.06 0.05 BHDD057 78-57 319 320 KLS Limestone 2.35 24.93 0.038 31.5 2.48 0.29 0.08 0.2 BHDD058 79-58 280 281 SMR Marl 4.33 20.00 0.02 1.9 0.28 0.1 0.13 0.04 BHDD058 80-58 285 286 SMR Marl 2.37 19.73 0.01 1.2 0.21 0.07 0.11 0.02 BHDD058 81-58 290 291 SMR Marl 2.25 21.67 0.011 1.6 0.98 0.08 0.17 0.005 BHDD058 82-58 295.2 296.2 SMR Marl 1.91 22.61 0.008 5.4 0.32 0.09 0.19 0.01 BHDD058 83-58 300 301 SMR Marl 1.75 23.15 0.006 3.1 0.25 0.08 0.11 0.005 BHDD058 84-58 305 306 SMR Marl 3.26 24.21 0.007 3.9 0.25 0.07 0.06 0.005 BHDD058 85-58 310 311 SMR Marl 1.72 23.46 0.008 19.8 0.67 0.07 0.06 0.05 BHDD058 86-58 315 316 SMR Marl 3.26 24.61 0.007 3.6 0.18 0.06 0.13 0.02 BHDD058 87-58 320 321 SMR Marl 2.60 24.11 0.007 5.5 0.33 0.05 0.15 0.08 BHDD058 88-58 325 326 SMR Marl 4.34 25.70 0.007 0.5 0.1 0.07 0.025 0.005 BHDD058 89-58 330 331 SMR Marl 3.32 25.18 0.007 8 0.28 0.1 0.18 0.02 BHDD058 90-58 335 336 SMR Marl 4.10 25.98 0.008 4.2 0.2 0.06 0.025 0.005 BHDD058 91-58 340 341 SMR Fault 2.78 24.21 0.007 4.5 0.28 0.05 0.06 0.04 BHDD058 92-58 345 346 SMR Sandstone 3.14 26.00 0.006 3 0.18 0.03 0.025 0.005 BHDD058 93-58 350 351 SMR Sandstone 1.82 21.98 0.008 7 0.22 0.05 0.05 0.03 BHDD058 94-58 355 356 SMR Marl 1.62 22.37 0.007 8.6 0.17 0.09 0.025 0.02 BHDD058 95-58 360 361 SMR Marl 1.72 22.80 0.006 8.3 0.12 0.1 0.09 0.02 BHDD058 96-58 365 366 SMR Marl 2.72 22.68 0.005 10.3 0.12 0.1 0.11 0.05 BHDD058 97-58 370 371 SMR Sandstone 3.28 22.57 0.009 10.6 0.35 0.1 0.21 0.02 BHDD058 98-58 375 376 S2 Sandstone 1.06 24.04 0.005 4.5 0.21 0.01 0.09 0.005 BHDD058 99-58 380 381 S2 Conglomerate 1.42 23.04 0.006 6 0.32 0.05 0.025 0.01 BHDD058 100-58 385 386 S2 Conglomerate 2.74 21.86 0.005 2.6 0.17 0.04 0.025 0.04 BHDD058 101-58 390 391 S2 Sandstone 1.78 20.17 0.009 6.5 0.21 0.03 0.09 0.02 BHDD058 102-58 395 396 S2 Sandstone 0.32 17.71 0.008 3.3 0.23 0.05 0.025 0.03 BHDD058 103-58 400 401 S2 Sandstone 1.11 18.93 0.008 1.9 0.1 0.05 0.06 0.005 BHDD058 104-58 405 406 S2 Sandstone 1.59 20.47 0.008 1.2 0.06 0.02 0.09 0.005 BHDD058 105-58 410 411 S2 Sandstone 1.23 18.03 0.006 1.4 0.1 0.01 0.05 0.005 BHDD058 106-58 415 416 S2 Sandstone 2.80 23.21 0.005 2 0.11 0.01 0.025 0.005 BHDD058 107-58 420 421 S2 Sandstone 1.97 22.71 0.005 2.4 0.24 0.01 0.09 0.005 BHDD058 108-58 425 426 S2 Sandstone 3.09 25.38 0.007 1.3 0.19 0.01 0.025 0.01 * Drill hole collar coordinates and orientation are in Appendix G 168 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD058 109-58 430 431 S2 Sandstone 3.57 24.60 0.008 3.7 0.1 0.04 0.025 0.005 BHDD058 110-58 435 436 S1 Sandstone 1.72 25.95 0.008 6.8 0.21 0.04 0.025 0.005 BHDD058 111-58 440 441 S1 Sandstone 1.52 23.46 0.01 4.6 0.18 0.04 0.05 0.005 BHDD058 112-58 445 446 S1 Sandstone 2.82 26.71 0.008 3.4 0.22 0.04 0.025 0.005 BHDD058 113-58 450 451 S1 Sandstone 1.43 26.58 0.009 3.4 0.3 0.03 0.025 0.005 BHDD058 114-58 455 456 S1 Sandstone 1.58 27.24 0.008 13.7 0.69 0.1 0.025 0.005 BHDD058 115-58 460 461 S1 Sandstone 1.85 27.57 0.006 3.8 0.24 0.03 0.025 0.005 BHDD058 116-58 465 466 S1 Sandstone 0.74 21.30 0.01 7.6 0.23 0.03 0.025 0.005 BHDD058 117-58 470 471 S1 Sandstone 2.03 26.65 0.008 74.8 0.86 0.04 0.65 0.005 BHDD058 118-58 475 476 S1 Sandstone 0.77 24.10 0.006 3.8 0.19 0.02 0.025 0.005 BHDD058 119-58 480 481 S1 Sandstone 0.65 23.21 0.009 3.3 0.15 0.02 0.025 0.02 BHDD058 120-58 485 486 S1 Sandstone 2.34 24.00 0.007 4.6 0.25 0.03 0.025 0.005 BHDD058 121-58 490 491 S1 Sandstone 2.29 23.87 0.009 2.6 0.27 0.03 0.025 0.005 BHDD058 122-58 495 496 S1 Sandstone 1.53 27.23 0.009 1.1 0.23 0.02 0.025 0.005 BHDD058 123-58 500 500.7 S1 Sandstone 1.22 23.96 0.006 1.1 0.23 0.02 BHDD058 124-58 505 506 S1 Sandstone 2.62 22.71 0.007 6.5 0.26 0.03 0.025 0.005 BHDD058 125-58 510 511 S1 Sandstone 1.55 21.35 0.006 18.7 0.71 0.04 0.13 0.005 BHDD058 126-58 515 516 S1 Sandstone 2.10 22.37 0.006 3.6 0.15 0.02 0.025 0.005 BHDD058 127-58 520 521 S1 Sandstone 1.32 21.40 0.006 5.1 0.66 0.04 0.025 0.005 BHDD058 128-58 525 526 S1 Sandstone 1.65 21.00 0.007 6.5 0.91 0.04 0.05 0.06 BHDD058 129-58 530 531 S1 Sandstone 0.90 19.82 0.01 6.6 0.83 0.05 0.025 0.03 BHDD058 130-58 535 536 S1 Sandstone 2.63 19.83 0.005 5.4 0.44 0.05 0.08 0.02 BHDD058 131-58 540 541 S1 Sandstone 2.30 21.28 0.005 5.5 0.3 0.04 0.05 0.005 BHDD058 132-58 545 546 IB Sandstone 0.79 19.76 0.013 31 2.51 0.08 0.025 0.005 BHDD058 133-58 550 551 BBX Breccia 1.04 18.05 0.448 282 3.99 0.07 0.66 0.005 BHDD058 134-58 555 556 BBX Breccia 2.52 24.01 0.011 18.7 0.93 0.07 0.025 0.005 BHDD058 135-58 560 561 BBX Breccia 2.75 23.92 0.006 3.1 0.32 0.03 0.025 0.005 BHDD058 136-58 565 566 KLS Limestone 1.72 24.60 0.022 5.2 1.21 0.05 0.025 0.07 BHDD058 137-58 570 571 KLS Limestone 1.41 17.29 0.02 3 1.17 0.02 0.06 0.06 BHDD058 138-58 575 576 KLS Limestone 1.66 22.92 0.024 1.9 1.48 0.01 0.025 0.005 BHDD068 139-68 160 161 S2 Sandstone 0.36 17.42 0.483 335 20.6 0.22 1.85 0.06 BHDD068 140-68 165 166 S2 Conglomerate 3.06 19.75 0.783 3134 38.9 0.86 5.37 0.18 BHDD068 141-68 170 170.9 S2 Sandstone 2.22 21.63 3.613 27.1 16.6 0.21 0.07 0.03 BHDD068 142-68 175 176 S2 Sandstone 1.82 19.59 0.022 5.4 2.97 0.06 0.025 0.005 BHDD068 143-68 180 181 S2 Sandstone 0.83 19.29 0.005 413 26.7 19.9 4.28 2.54 BHDD068 144-68 185 186 S2 Sandstone 1.77 18.48 2.192 626 59.4 39.8 13.7 6.05 * Drill hole collar coordinates and orientation are in Appendix G 169 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD068 145-68 190 191 S2 Sandstone 1.23 19.33 3.458 142 24.4 6.69 1.45 1.07 BHDD068 146-68 195 196 S1 Sandstone -1.04 13.30 3.202 144 25.3 6.8 1.63 1.18 BHDD068 147-68 200 201 S1 Sandstone 2.72 23.62 1.29 16.6 2.77 0.68 0.09 0.02 BHDD068 148-68 205 206 S1 Sandstone 2.12 24.76 0.492 16.1 1.58 0.41 0.07 0.03 BHDD068 149-68 210 211 S1 Sandstone 1.74 24.13 0.862 20.2 2.2 0.47 0.09 0.05 BHDD068 150-68 215 216 S1 Sandstone 2.05 22.38 0.354 16.6 1.94 0.3 0.025 0.03 BHDD068 151-68 220 221 S1 Sandstone 1.55 22.91 0.42 22.3 1.69 0.29 0.025 0.08 BHDD068 152-68 225 226 S1 Sandstone 1.98 22.74 0.126 21.8 1.56 0.28 0.025 0.005 BHDD068 153-68 230 231 S1 Sandstone 1.48 23.32 0.172 17.8 1.83 0.22 0.08 0.02 BHDD068 154-68 235 236 S1 Sandstone 2.01 23.08 0.132 32.1 2.5 0.4 0.025 0.12 BHDD068 155-68 240 241 S1 Sandstone 1.44 20.32 0.166 47.4 2.4 0.36 0.24 0.15 BHDD068 156-68 245 246 S1 Sandstone 1.52 18.74 0.276 64.3 2.7 0.35 0.11 0.13 BHDD068 157-68 250 251 S1 Sandstone 0.72 25.26 0.009 29.8 0.88 0.1 0.025 0.005 BHDD068 158-68 255 256 IB Breccia 0.09 16.63 0.011 66.1 1.18 0.13 0.22 0.05 BHDD068 159-68 260 261 IB Breccia 2.81 23.58 0.038 52 1.5 0.07 0.09 0.02 BHDD068 160-68 265 266 IB Mudstone -1.50 15.62 0.019 94.1 3.06 0.14 0.24 0.02 BHDD068 162-68 275 276 IB Mudstone -2.34 14.54 0.42 221 28.5 1.57 0.53 0.66 BHDD068 163-68 280 281 KLS Limestone 0.15 17.06 0.558 58.8 107 0.72 0.13 5.41 BHDD068 164-68 285 286 KLS Limestone 0.29 16.07 0.086 12.4 3.35 0.13 0.025 0.03 BHDD068 165-68 290 291 KLS Limestone 1.36 17.49 0.232 18 32.6 0.52 0.12 1.05 BHDD068 166-68 295 296 KLS Limestone 0.91 22.33 0.572 13.8 3.34 0.2 0.025 0.36 BHDD068 167-68 300 301 KLS Limestone -0.05 17.29 0.256 16.4 2.64 0.16 0.08 0.18 BHDD068 168-68 305 306 KLS Limestone 1.64 22.56 1.062 15.3 4.23 0.3 0.24 0.41 BHDD068 169-68 310 311 KLS Limestone 0.85 23.26 1.4 18.4 3.93 0.4 0.18 0.43 BHDD068 170-68 315 316 KLS Limestone 1.49 25.77 0.164 24.2 2.46 0.32 0.14 0.24 BHDD068 171-68 320 321 KLS Limestone 1.92 18.10 0.234 107 8.49 1.16 0.53 0.67 BHDD068 172-68 325 326 JLS Limestone 0.67 18.24 0.226 5.8 0.69 0.08 0.06 0.01 BHDD068 173-68 330 331 JLS Limestone -0.97 15.45 0.308 11.6 1.96 0.09 0.11 0.06 BHDD068 174-68 335 336 JLS Limestone -0.01 15.22 0.476 21.7 3.59 0.15 0.07 0.68 BHDD068 175-68 340 341 JLS Limestone 0.39 15.52 0.436 5.8 1.5 0.06 0.08 0.12 BHDD068 176-68 345 346 JLS Limestone 0.85 20.96 0.088 7.3 1.53 0.05 0.025 0.11 BHDD068 177-68 350 351 JLS Limestone 0.42 22.06 0.012 26.6 2.2 0.14 0.025 0.1 BHDD068 178-68 355 356 JLS Limestone 0.48 21.51 0.01 7.6 0.78 0.04 0.025 0.06 BHDD068 179-68 360 361 JLS Limestone 0.86 24.12 0.016 5.9 0.59 0.05 0.025 0.04 BHDD068 180-68 365 366 JLS Limestone 1.22 22.24 0.012 9.8 1.64 0.09 0.025 0.15 BHDD068 181-68 370 371 JLS Limestone 0.90 19.67 0.018 9.4 0.94 0.09 0.08 0.13 * Drill hole collar coordinates and orientation are in Appendix G 170 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD068 182-68 375 376 JLS Limestone 0.92 20.14 0.064 16.8 2.41 0.1 0.06 0.12 BHDD068 183-68 380 381 JLS Limestone 0.53 23.82 0.028 3.3 0.69 0.09 0.06 0.06 BHDD068 184-68 385 386 JLS Limestone 0.49 24.05 0.054 6 0.59 0.06 0.025 0.01 BHDD068 185-68 390 391 JLS Limestone 0.44 20.40 0.013 8.2 0.97 0.07 0.025 0.005 BHDD068 186-68 395 396 JLS Limestone 0.18 15.90 0.008 2.1 0.84 0.04 0.025 0.11 BHDD068 187-68 400 401 JLS Limestone 0.36 20.06 0.041 5.1 0.92 0.09 0.06 0.14 BHDD076 188-76 195 196 SMR Marl 0.77 14.84 0.005 1.7 0.22 0.03 0.025 0.005 BHDD076 189-76 200 201 S2 Sandstone 1.17 20.89 0.005 1.3 0.24 0.04 0.05 0.04 BHDD076 190-76 205 206 S2 Sandstone 2.38 20.14 0.006 0.5 0.14 0.04 0.025 0.01 BHDD076 191-76 210 211 S2 Sandstone 1.11 15.28 0.006 0.5 0.14 0.03 0.025 0.02 BHDD076 192-76 215 216 S2 Sandstone -2.70 15.24 0.006 3.9 0.16 0.04 0.05 0.005 BHDD076 193-76 220 221 S2 Sandstone 2.16 20.41 0.005 1.1 0.14 0.01 0.06 0.03 BHDD076 194-76 225 226 S2 Sandstone 1.66 20.75 0.005 0.5 0.1 0.01 0.06 0.03 BHDD076 195-76 230 231 S2 Sandstone 1.24 19.51 0.006 1.1 0.09 0.01 0.025 0.005 BHDD076 196-76 235 236 S2 Sandstone 2.97 20.17 0.006 1.8 0.09 0.01 0.07 0.02 BHDD076 197-76 240 241 S1 Sandstone 2.12 21.31 0.079 52.8 2.02 0.22 0.13 0.09 BHDD076 198-76 245 246 S1 Sandstone 1.52 22.19 0.006 10.5 0.5 0.07 0.08 0.03 BHDD076 199-76 250 251 S1 Sandstone 2.21 26.58 0.005 8.3 0.45 0.06 0.025 0.02 BHDD076 200-76 255 256 S1 Sandstone 2.51 26.10 0.005 5.1 0.43 0.05 0.025 0.01 BHDD076 201-76 260 261 S1 Sandstone 2.46 27.63 0.006 7 0.59 0.09 0.025 0.01 BHDD076 202-76 265 266 S1 Sandstone 2.45 27.87 0.01 9.1 0.79 0.16 0.05 0.08 BHDD076 203-76 270 271 S1 Sandstone 2.04 26.31 0.011 7.5 0.69 0.09 0.025 0.02 BHDD076 204-76 275 276 S1 Sandstone 1.90 22.00 0.005 6 0.77 0.08 0.025 0.02 BHDD076 205-76 280 281 S1 Sandstone 2.32 22.62 0.235 64.9 1.86 0.42 0.17 0.03 BHDD076 206-76 285 286 S1 Sandstone 2.00 22.78 0.006 4.7 0.59 0.05 0.06 0.01 BHDD076 207-76 290 291 S1 Sandstone 1.51 22.42 0.009 7.1 0.77 0.09 0.21 0.04 BHDD076 208-76 295 296 S1 Sandstone 1.85 22.32 0.006 6.9 0.49 0.1 0.025 0.03 BHDD076 209-76 300 301 S1 Sandstone 2.12 20.80 0.012 7.2 0.49 0.03 0.025 0.02 BHDD076 210-76 305 306 S1 Sandstone 0.88 18.27 0.008 4.5 0.21 0.08 0.025 0.05 BHDD076 211-76 310 311 IB Mudstone -1.50 18.47 0.006 9.9 0.38 0.12 0.025 0.09 BHDD076 212-76 315 316 BBX Breccia 1.97 22.34 0.005 13 0.36 0.12 0.025 0.01 BHDD076 213-76 320 321 BBX Conglomerate 0.18 18.14 0.005 27.6 0.96 0.16 0.025 0.03 BHDD076 214-76 325 326 BBX Breccia 3.20 22.91 0.019 28 1.5 0.16 0.025 0.02 BHDD076 215-76 330 331 KLS Limestone 2.21 22.70 0.042 12.6 1.91 0.15 0.025 0.08 BHDD076 216-76 335 336 KLS Limestone 1.90 22.42 0.066 3.5 1.2 0.05 0.025 0.05 BHDD076 218-76 345 346 KLS Limestone 1.37 23.14 0.076 4.8 2.02 0.07 0.025 0.09 * Drill hole collar coordinates and orientation are in Appendix G 171 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD076 219-76 350 351 KLS Limestone 2.55 24.86 0.02 12.2 1.05 0.29 0.025 0.05 BHDD076 219-76a 350 351 KLS Vein 2.37 17.72 BHDD076 220-76 355 356 KLS Limestone 2.74 23.01 0.19 19.6 2.75 0.24 0.025 0.07 BHDD076 221-76 360 361 JLS Limestone 0.79 20.36 0.015 1 0.6 0.03 0.025 0.02 BHDD076 222-76 365 366 JLS Limestone 1.10 20.28 0.021 10.8 0.99 0.05 0.025 0.07 BHDD076 223-76 370 371 JLS Limestone 1.75 18.70 0.015 1.7 0.74 0.01 0.025 0.05 BHDD076 224-76 375 376 JLS Limestone 1.68 18.03 0.015 2.1 1.13 0.03 0.025 0.04 BHDD076 225-76 380 381 JLS Limestone 0.70 19.62 0.011 0.5 0.78 0.02 0.025 0.04 BHDD076 226-76 385 386 JLS Limestone 0.15 20.03 0.017 2.6 1.19 0.05 0.025 0.04 BHDD076 227-76 390 391 JLS Limestone 0.73 19.43 0.024 2.2 0.89 0.02 0.025 0.06 BHDD076 228-76 395 396 JLS Limestone 1.39 19.90 0.01 2.4 0.95 0.03 0.025 0.03 BHDD076 229-76 400 401 JLS Limestone 2.34 24.89 0.006 2.4 0.64 0.03 0.025 0.02 BHDD076 230-76 405 406 JLS Limestone 1.24 22.19 0.007 1.9 0.67 0.02 0.025 0.03 BHDD076 231-76 410 411 JLS Limestone -1.73 21.56 0.007 7.9 3.13 0.03 0.025 0.04 BHDD076 232-76 415 416 JLS Limestone -1.11 22.32 0.006 13.9 6.15 0.05 0.07 0.1 BHDD076 233-76 420 421 JLS Limestone 0.92 21.29 0.006 4 1.9 0.03 0.025 0.03 BHDD076 234-76 425 426 JLS Limestone 1.24 20.51 0.007 1 0.93 0.01 0.025 0.01 BHDD076 235-76 430 431 JLS Limestone 1.33 20.96 0.006 1.8 0.86 0.02 0.025 0.02 BHDD084 236-84 120 121 SMR Marl -0.20 14.84 0.006 4.5 1.25 0.08 0.025 0.005 BHDD084 237-84 125 126 SMR Marl 0.73 16.37 0.005 BHDD084 238-84 130 131 SMR Marl 0.15 15.83 0.012 4.2 0.94 0.07 0.025 0.01 BHDD084 239-84 135 136 S2 Sandstone 0.58 19.35 0.005 1.3 1.88 0.07 0.07 0.02 BHDD084 240-84 140 141 S2 Sandstone 1.84 19.24 0.005 0.5 1.97 0.08 0.025 0.02 BHDD084 241-84 145 146 S2 Sandstone 1.02 17.88 0.005 3.2 3.22 0.07 0.05 0.02 BHDD084 242-84 150 151 S2 Sandstone -0.39 15.88 0.005 3.7 1.48 0.05 0.1 0.02 BHDD084 243-84 155 156 S2 Sandstone 0.79 17.53 0.008 6 1.88 0.05 0.12 0.03 BHDD084 244-84 160 161 S2 Conglomerate 2.24 18.85 0.012 8.5 1.31 0.05 0.025 0.01 BHDD084 245-84 165 166 S2 Conglomerate 0.94 18.90 0.017 39.1 2.89 0.09 0.1 0.1 BHDD084 246-84 170 171 S2 Sandstone 1.21 17.32 0.598 289 7.17 0.39 1.02 0.42 BHDD084 247-84 175 176 S2 Sandstone -2.96 15.85 0.237 118 3.79 0.17 0.37 0.2 BHDD084 248-84 180 181 S2 Sandstone 0.58 19.03 0.005 6.3 0.62 0.1 0.025 0.01 BHDD084 249-84 185 186 S2 Sandstone 0.39 16.40 0.005 27.3 3.26 0.21 0.025 0.03 BHDD084 250-84 190 191 S2 Sandstone -0.80 16.37 0.528 318 10.2 0.7 0.84 0.07 BHDD084 251-84 195 196 S2 Sandstone 0.14 15.03 1.656 262 13.1 1.58 1.55 0.3 BHDD084 252-84 200 201 S2 Sandstone -2.86 14.20 1.926 112 16 3.95 1.52 4.42 BHDD084 253-84 205 206 S1 Sandstone 1.53 20.79 0.144 22.9 2.57 0.59 0.15 0.12 * Drill hole collar coordinates and orientation are in Appendix G 172 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHDD084 254-84 210 211 S1 Sandstone 1.38 20.05 0.376 17.4 2.36 0.24 0.2 0.13 BHDD084 255-84 215 216 S1 Sandstone 0.48 16.83 0.202 62.3 4.43 0.49 1.08 0.32 BHDD084 256-84 220 221 S1 Sandstone -1.31 15.55 0.044 155 4.93 0.24 0.31 0.14 BHDD084 257-84 225 226 S1 Sandstone 1.83 19.08 0.072 68.6 4.31 0.2 0.62 0.61 BHDD084 258-84 230 231 S1 Sandstone -0.23 16.82 0.082 504 5.35 0.18 0.87 0.04 BHDD084 259-84 235 236 IB Mudstone -1.61 17.43 0.019 82.4 2.02 0.16 0.06 0.02 BHDD084 260-84 240 241 IB Mudstone -3.12 16.06 0.008 37.1 2.79 0.25 0.07 0.04 BHDD084 261-84 245 246 IB Breccia -1.58 15.52 0.448 293 65.9 0.81 2.53 3.1 BHDD084 262-84 250 251 BBX Breccia -0.83 17.08 0.674 167 256 1.51 1.42 4.45 BHDD084 263-84 255 256 KLS Limestone -0.66 12.88 0.016 15.3 3.2 0.25 0.09 0.11 BHDD084 264-84 260 261 KLS Limestone 1.76 20.52 0.016 27.6 5.07 0.77 0.2 0.3 BHDD084 265-84 265 266 KLS Limestone -0.48 18.16 0.006 20.9 2.81 0.3 0.12 0.14 BHDD084 266-84 270 271 KLS Limestone 1.04 14.14 0.009 7.9 1.04 0.11 0.06 0.08 BHDD084 267-84 275 276 KLS Limestone 0.49 13.96 0.026 9.5 1.02 0.12 0.025 0.06 BHDD084 268-84 280 281 KLS Limestone 0.82 16.88 0.016 9.7 0.94 0.36 0.025 0.04 BHDD084 269-84 285 286 KLS Limestone 1.10 13.97 0.012 6 0.72 0.1 0.11 0.08 BHDD084 270-84 290 291 KLS Limestone 1.96 15.39 0.042 3.3 0.53 0.09 0.025 0.07 BHDD084 271-84 295 296 KLS Limestone -0.21 10.57 0.016 3.8 0.71 0.04 0.025 0.04 BHDD084 272-84 300 301 KLS Limestone 0.87 10.96 0.044 12.2 7.45 0.17 0.17 0.33 BHDD084 273-84 305 306 KLS Limestone -0.75 12.13 0.162 12.1 2.81 0.23 0.64 0.17 BHDD084 273-84a 305 306 KLS Vein 0.72 17.00 BHDD084 274-84 310 311 KLS Limestone -1.76 12.10 0.406 12.4 5.49 0.54 0.75 0.45 BHDD084 275-84 315 316 KLS Limestone 0.32 16.42 0.312 33.4 16.3 3.07 0.55 1.28 BHDD084 276-84 320 321 KLS Limestone 1.83 14.38 0.146 17.3 6.81 1.21 0.25 0.84 BHDD084 277-84 325 326 KST Limestone 1.37 14.03 0.122 63.6 6.17 1.5 0.59 0.73 BHDD084 278-84 330 331 JLS Limestone 3.25 27.77 0.035 9.5 2.19 0.11 0.025 0.32 BHDD084 279-84 335 336 JLS Limestone 2.57 20.44 0.006 5.2 0.69 0.13 0.025 0.09 BHDD084 280-84 340 341 JLS Limestone 2.83 25.14 0.005 1.3 0.29 0.06 0.025 0.04 BHRC046 281-46R 139 140 S2 Sandstone 2.07 20.07 0.006 2.3 1.31 0.05 0.025 0.005 BHRC046 282-46R 144 145 S2 Sandstone 1.72 17.96 0.006 1.2 0.97 0.03 0.025 0.005 BHRC046 283-46R 149 150 S2 Sandstone 1.21 15.85 0.006 1.6 2.04 0.07 0.025 0.03 BHRC046 284-46R 154 155 S2 Sandstone 0.64 16.26 0.006 1.6 2.72 0.05 0.025 0.005 BHRC046 285-46R 159 160 S2 Sandstone 1.68 16.08 0.14 196 4.25 0.14 0.59 0.12 BHRC046 286-46R 164 165 S2 Sandstone 1.71 16.77 0.008 14.8 4.36 0.09 0.13 0.05 BHRC046 287-46R 169 170 S2 Sandstone 2.09 18.20 0.367 107 7.77 0.44 0.44 0.26 BHRC046 288-46R 174 175 S2 Sandstone 0.61 15.15 0.968 213 12.6 1.47 0.61 0.55 * Drill hole collar coordinates and orientation are in Appendix G 173 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC046 289-46R 179 180 S2 Sandstone 0.39 17.42 0.216 137 9.31 0.67 0.34 0.13 BHRC046 290-46R 184 185 S2 Sandstone 1.10 17.78 0.212 173 8.95 2.56 0.4 0.11 BHRC046 291-46R 189 190 S2 Sandstone 1.15 16.67 0.076 101 10.4 2.42 0.39 0.09 BHRC046 292-46R 194 195 S2 Sandstone -0.21 16.20 0.088 149 12.2 4.15 0.41 0.2 BHRC046 293-46R 199 200 S1 Sandstone -0.51 13.61 0.292 151 69.4 0.53 1.02 0.14 BHRC046 294-46R 204 205 S1 Sandstone -1.60 12.89 0.061 41.5 9.25 0.12 0.32 0.06 BHRC046 295-46R 209 210 S1 Sandstone -0.53 13.60 0.106 41.1 17.9 0.38 1.8 1.01 BHRC046 296-46R 214 215 S1 Sandstone 0.14 13.13 0.013 14.9 1.79 0.1 0.11 0.03 BHRC046 297-46R 219 220 S1 Sandstone -0.07 15.31 0.007 17.6 1.18 0.09 0.3 0.08 BHRC046 298-46R 224 225 S1 Sandstone 1.11 15.89 0.012 53.9 1.53 0.14 0.39 0.16 BHRC046 299-46R 229 230 S1 Sandstone 0.22 16.55 0.152 41.7 2.15 0.22 0.2 0.17 BHRC046 300-46R 234 235 S1 Sandstone -1.03 16.71 0.444 42.5 3.06 0.19 0.35 0.14 BHRC046 301-46R 239 240 S1 Sandstone 0.79 19.54 0.308 43.8 2.56 0.23 0.12 0.03 BHRC046 302-46R 244 245 IB Sandstone -2.01 13.78 0.086 134 17.7 0.65 0.13 0.24 BHRC046 303-46R 249 250 IB Sandstone -0.63 14.32 0.124 491 96.7 0.88 0.48 0.13 BHRC046 304-46R 254 255 IB Sandstone -0.31 16.42 0.89 349 46 1.21 1.28 0.39 BHRC046 305-46R 259 260 BBX Sandstone -2.09 12.57 0.242 588 27.6 0.61 0.09 0.04 BHRC046 306-46R 264 265 BBX Limestone -1.42 13.82 0.104 272 29.9 1.57 1.12 0.83 BHRC046 307-46R 269 270 KLS Limestone -0.47 13.20 0.194 113 11.7 0.61 0.57 1.16 BHRC046 308-46R 274 275 KLS Limestone 2.28 14.53 0.064 18.5 2.84 0.2 0.025 0.58 BHRC046 309-46R 279 280 KLS Limestone 0.60 14.10 0.026 15.5 1.71 0.12 0.2 0.11 BHRC046 310-46R 284 285 KLS Limestone 1.38 14.84 0.034 10.9 0.91 0.12 0.025 0.15 BHRC046 311-46R 289 290 KLS Limestone 1.63 16.58 0.056 27.4 2.68 0.2 0.12 0.2 BHRC105 312-105R 71 72 SMR Marl 0.32 14.54 0.031 8.4 0.32 0.14 0.08 0.06 BHRC105 313-105R 76 77 SMR Marl 1.04 18.32 0.052 13.1 0.48 0.16 0.28 0.07 BHRC105 314-105R 81 82 SMR Marl 1.36 20.57 0.01 13.5 0.24 0.08 0.09 0.03 BHRC105 315-105R 86 87 SMR Marl 1.00 19.22 0.007 11.6 0.16 0.05 0.1 0.04 BHRC105 316-105R 91 92 SMR Marl 0.14 17.52 0.005 6.9 0.19 0.07 0.11 0.02 BHRC105 317-105R 96 97 SMR Marl 1.03 18.67 0.005 5.5 0.14 0.09 0.06 0.04 BHRC105 318-105R 101 102 S2 Sandstone 2.24 21.33 0.007 50.6 0.49 0.11 0.11 0.12 BHRC105 319-105R 106 107 S2 Sandstone 1.39 19.42 0.006 23.4 0.22 0.09 0.1 0.08 BHRC105 320-105R 111 112 S2 Sandstone 1.39 18.78 0.012 19.1 0.17 0.1 0.08 0.09 BHRC105 321-105R 116 117 S2 Sandstone 1.12 18.38 0.012 4.2 0.08 0.05 0.06 0.03 BHRC105 322-105R 121 122 S2 Sandstone -1.94 16.33 0.009 4.1 0.1 0.04 0.025 0.03 BHRC105 323-105R 126 127 S2 Sandstone -0.90 18.21 0.025 9.8 0.1 0.06 0.06 0.15 BHRC105 324-105R 131 132 S2 Sandstone -1.52 16.45 0.019 47.7 0.23 0.17 0.09 0.34 * Drill hole collar coordinates and orientation are in Appendix G 174 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC105 325-105R 136 137 S2 Sandstone -2.19 17.06 0.01 4.5 0.11 0.06 0.025 0.02 BHRC105 326-105R 141 142 S2 Sandstone -1.73 18.38 0.008 35.3 0.47 0.16 0.07 0.14 BHRC105 327-105R 146 147 S2 Sandstone 0.98 17.26 0.01 49.5 1.47 0.16 0.16 0.24 BHRC105 328-105R 151 152 S2 Sandstone 2.30 19.56 0.171 312 10.1 0.66 2.77 1.21 BHRC105 329-105R 156 157 S1 Sandstone -0.40 17.39 0.49 182 9.14 1.02 5.79 2.1 BHRC105 330-105R 161 162 S1 Sandstone 3.31 21.58 0.226 83.3 6.47 0.53 1.88 0.7 BHRC105 331-105R 166 167 S1 Sandstone 1.81 21.32 0.302 120 4.91 0.58 2.25 0.74 BHRC105 332-105R 171 172 IB Sandstone 0.54 16.96 0.688 243 8.68 1.46 5.67 1.67 BHRC105 333-105R 176 177 S1 Sandstone 1.93 19.83 0.71 180 6.89 1.29 3.99 1.05 BHRC105 334-105R 181 182 S1 Sandstone 2.40 20.03 1.116 178 10.2 1.79 4.09 1.59 BHRC105 335-105R 186 187 S1 Sandstone 3.04 22.69 1.214 141 8.38 1.54 3.93 1.55 BHRC105 336-105R 191 192 S1 Sandstone 2.94 22.01 1.546 193 10.6 2.18 7.06 2.14 BHRC105 337-105R 196 197 S1 Sandstone 1.38 16.93 6.56 537 11.3 1.82 10.8 3.13 BHRC105 338-105R 201 202 IB Sandstone 1.05 16.58 0.75 847 8.5 0.35 5.32 2.02 BHRC105 339-105R 206 207 IB Sandstone 1.30 15.38 0.386 576 2.76 0.25 0.94 1.34 BHRC105 340-105R 211 212 BBX Breccia -0.56 15.50 0.076 383 1.06 0.26 1.11 0.74 BHRC105 341-105R 216 217 BBX Breccia 0.78 14.86 0.063 488 0.8 0.5 0.87 0.46 BHRC130 342-130R 136 137 S2 Sandstone 0.31 15.96 0.005 BHRC130 343-130R 141 142 S2 Sandstone 1.41 15.37 0.005 BHRC130 344-130R 146 147 S2 Sandstone 0.69 19.12 0.005 BHRC130 345-130R 151 152 S2 Sandstone 1.57 17.47 0.005 BHRC130 346-130R 156 157 S2 Sandstone -0.08 15.49 0.067 BHRC130 347-130R 161 162 S2 Sandstone 0.89 17.88 0.005 BHRC130 348-130R 166 167 S2 Sandstone -0.53 15.63 0.031 BHRC130 349-130R 171 172 S2 Sandstone 1.43 17.49 0.008 BHRC130 350-130R 176 177 S1 Sandstone 2.26 20.92 0.005 BHRC130 351-130R 181 182 S1 Sandstone 1.74 23.48 0.028 BHRC130 352-130R 186 187 S1 Sandstone 2.68 24.33 0.062 BHRC130 353-130R 191 192 S1 Sandstone 1.82 19.96 0.005 BHRC130 354-130R 196 197 S1 Sandstone 2.25 19.61 0.008 BHRC130 355-130R 201 202 S1 Sandstone 0.69 17.50 0.048 BHRC130 356-130R 206 207 S1 Sandstone 0.82 19.69 0.248 BHRC130 357-130R 211 212 IB Mudstone -1.80 15.05 0.046 BHRC130 358-130R 216 217 IB Mudstone -3.86 14.22 0.024 * Drill hole collar coordinates and orientation are in Appendix G 175 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC130 359-130R 221 222 IB Mudstone -2.79 15.37 0.048 BHRC130 360-130R 226 227 BBX Breccia 1.34 16.79 0.072 BHRC130 361-130R 231 232 BBX Breccia -5.91 19.12 1.18 BHRC130 362-130R 236 237 KLS Limestone -2.31 14.53 1.274 BHRC130 363-130R 241 242 KLS Limestone -0.84 14.93 0.382 BHRC130 364-130R 246 247 KLS Limestone 0.54 15.05 0.152 BHRC130 365-130R 251 252 KLS Limestone -2.38 15.30 0.264 BHRC130 366-130R 256 257 KLS Limestone -1.35 14.42 0.126 BHRC130 367-130R 261 262 KLS Limestone -0.84 14.66 0.058 BHRC130 368-130R 266 267 KLS Limestone -2.08 12.80 0.082 BHRC130 369-130R 271 272 KLS Limestone -0.60 14.34 0.03 BHRC130 370-130R 276 277 KLS Limestone 0.91 12.60 0.022 BHRC130 371-130R 281 282 KLS Limestone -4.62 17.23 0.033 BHRC130 372-130R 286 287 KLS Limestone -0.63 15.39 0.046 BHRC130 373-130R 291 292 KLS Limestone -0.82 12.87 0.066 BHRC130 374-130R 296 297 KLS Limestone 1.20 10.66 0.164 BHRC130 375-130R 301 302 KLS Limestone -0.89 12.45 0.294 BHRC143 376-143R 8 9 S2 Sandstone 0.57 20.17 0.011 BHRC143 377-143R 13 14 S2 Sandstone 0.13 18.89 0.007 BHRC143 378-143R 18 19 S2 Sandstone 0.13 18.51 0.015 BHRC143 379-143R 23 24 S2 Sandstone -0.73 19.05 0.009 BHRC143 380-143R 28 29 S2 Sandstone -0.74 19.71 0.009 BHRC143 381-143R 33 34 S2 Sandstone 0.44 19.70 0.007 BHRC143 382-143R 38 39 S2 Sandstone 1.33 21.19 0.014 BHRC143 383-143R 43 44 S2 Sandstone 1.01 21.81 0.007 BHRC143 384-143R 48 49 S2 Sandstone 0.47 21.62 0.018 BHRC143 385-143R 53 54 S2 Sandstone 1.09 22.01 0.012 BHRC143 386-143R 58 59 S2 Sandstone 1.87 23.52 0.008 BHRC143 387-143R 63 64 S1 Sandstone 1.97 25.34 0.015 BHRC143 388-143R 68 69 S1 Sandstone 1.94 26.28 0.024 BHRC144 388-143a 68 69 S1 Vein 1.75 23.33 BHRC143 389-143R 73 74 S1 Sandstone 2.82 27.04 0.005 BHRC143 390-143R 78 79 S1 Sandstone 2.80 27.57 0.006 BHRC147 391-147R 3 4 S2 Sandstone 1.85 23.64 0.018 * Drill hole collar coordinates and orientation are in Appendix G 176 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC147 392-147R 8 9 S2 Sandstone 1.57 24.67 0.031 BHRC147 393-147R 13 14 S2 Sandstone 1.53 23.66 0.02 BHRC147 394-147R 18 19 S2 Sandstone 1.89 20.94 0.01 BHRC147 395-147R 23 24 S2 Sandstone 1.47 19.25 0.026 BHRC147 396-147R 28 29 S2 Sandstone 0.76 21.68 0.007 BHRC147 397-147R 33 34 S2 Sandstone -0.83 19.01 0.037 BHRC147 398-147R 38 39 S2 Sandstone -1.07 18.80 0.009 BHRC147 399-147R 43 44 S2 Sandstone 0.92 20.76 0.012 BHRC147 400-147R 48 49 S2 Sandstone -0.27 18.33 0.016 BHRC147 401-147R 53 54 S2 Sandstone 0.79 19.35 0.007 BHRC147 402-147R 58 59 S2 Sandstone 1.18 20.76 0.008 BHRC147 403-147R 63 64 S2 Sandstone 3.07 21.05 0.01 BHRC147 403-147Ra 63 64 S2 Vein -0.86 16.29 BHRC147 404-147R 68 69 S2 Sandstone 2.43 22.17 0.011 BHRC147 405-147R 73 74 S2 Sandstone 1.74 22.15 0.013 BHRC147 406-147R 78 79 S2 Sandstone 1.71 22.63 0.009 BHRC147 407-147R 83 84 S2 Sandstone 0.63 21.15 0.009 BHRC147 408-147R 88 89 S1 Sandstone 2.84 27.35 0.064 BHRC147 409-147R 93 94 S1 Sandstone 2.75 26.76 0.061 BHRC147 410-147R 98 99 S1 Sandstone 2.81 26.46 0.021 BHRC147 411-147R 103 104 S1 Sandstone 3.06 26.42 0.006 BHRC147 412-147R 108 109 S1 Sandstone 2.41 26.63 0.014 BHRC159 413-159R 8 9 S2 Sandstone 1.94 22.42 0.005 BHRC159 414-159R 13 14 S2 Sandstone 1.86 22.31 0.006 BHRC159 415-159R 18 19 S2 Sandstone 1.55 23.74 0.017 BHRC159 416-159R 23 24 S2 Sandstone 1.46 22.16 0.006 BHRC159 417-159R 28 29 S2 Sandstone 1.40 23.13 0.005 BHRC159 418-159R 33 34 S2 Sandstone 1.14 23.47 0.005 BHRC159 419-159R 38 39 S2 Sandstone 0.93 21.83 0.011 BHRC159 420-159R 43 44 S2 Sandstone 1.28 23.40 0.005 BHRC159 421-159R 48 49 S1 Sandstone 2.51 27.35 0.005 BHRC159 422-159R 53 54 S1 Sandstone 1.88 27.30 0.016 BHRC159 423-159R 58 59 S1 Sandstone 2.01 26.76 0.015 BHRC159 424-159R 63 64 S1 Sandstone 1.25 26.48 0.006 * Drill hole collar coordinates and orientation are in Appendix G 177 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC159 425-159R 68 69 S1 Sandstone 2.16 26.30 0.032 BHRC159 426-159R 73 74 S1 Sandstone 1.48 24.49 0.008 BHRC159 427-159R 78 79 S1 Sandstone 1.45 24.20 0.015 BHRC159 428-159R 83 84 BBX Sandstone 1.06 25.22 0.007 BHRC159 429-159R 88 89 IB Sandstone 1.69 23.11 0.005 BHRC159 430-159R 93 94 IB Mudstone -2.70 18.48 0.005 BHRC159 431-159R 98 99 IB Mudstone -2.28 17.77 0.005 BHRC159 432-159R 103 104 JLS Limestone 1.88 25.92 0.005 BHRC159 433-159R 108 109 JLS Limestone 1.53 21.34 0.071 BHRC172 434-172R 148 149 S2 Sandstone 1.43 14.26 0.005 BHRC172 435-172R 153 154 S2 Sandstone 1.88 15.12 0.006 BHRC172 436-172R 158 159 S2 Sandstone 1.89 18.64 0.005 BHRC172 437-172R 163 164 S2 Sandstone 1.93 20.43 0.006 BHRC172 438-172R 168 169 S2 Sandstone 1.27 19.19 0.005 BHRC172 439-172R 173 174 S2 Sandstone 2.39 20.72 0.005 BHRC172 440-172R 178 179 S2 Sandstone 1.69 20.02 0.005 BHRC172 441-172R 183 184 S2 Sandstone 0.44 19.44 0.006 BHRC172 442-172R 188 189 S1 Sandstone 1.51 20.05 1.673 BHRC172 443-172R 193 194 S1 Sandstone 0.21 21.05 1.556 BHRC172 444-172R 198 199 S1 Sandstone 2.44 24.73 0.502 BHRC172 445-172R 203 204 S1 Sandstone 1.17 22.12 0.064 BHRC172 446-172R 208 209 S1 Sandstone 2.27 24.80 0.006 BHRC172 447-172R 213 214 S1 Sandstone -2.30 19.59 0.16 BHRC172 448-172R 218 219 S1 Sandstone 1.52 24.46 0.024 BHRC221 449-221R 3 4 SMR Marl 0.80 18.95 0.005 BHRC221 450-221R 8 9 SMR Marl 1.28 19.28 0.005 BHRC221 451-221R 13 14 SMR Marl 0.39 18.60 0.005 BHRC221 452-221R 18 19 SMR Marl 1.77 19.81 0.005 BHRC221 453-221R 23 24 SMR Marl 0.87 20.07 0.005 BHRC221 454-221R 28 29 SMR Marl 2.08 19.95 0.005 BHRC221 455-221R 33 34 SMR Marl 1.57 20.22 0.005 BHRC221 456-221R 38 39 SMR Marl 1.32 19.87 0.005 BHRC221 457-221R 43 44 SMR Marl 1.05 19.32 0.005 BHRC221 458-221R 48 49 S2 Sandstone 2.26 24.48 0.005 * Drill hole collar coordinates and orientation are in Appendix G 178 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC221 459-221R 53 54 S2 Sandstone 1.32 22.07 0.005 BHRC221 460-221R 58 59 S2 Sandstone 0.86 21.10 0.005 BHRC221 461-221R 63 64 S2 Sandstone 2.32 22.60 0.005 BHRC221 462-221R 68 69 S2 Sandstone 0.71 19.68 0.005 BHRC221 463-221R 73 74 S2 Sandstone -0.17 20.22 0.005 BHRC221 464-221R 78 79 S2 Sandstone -0.13 19.81 0.016 BHRC221 465-221R 83 84 S2 Sandstone 0.51 18.33 0.005 BHRC221 466-221R 88 89 S2 Sandstone 0.79 20.34 0.005 BHRC221 467-221R 93 94 S2 Sandstone 1.52 19.83 0.005 BHRC221 468-221R 98 99 S2 Sandstone 2.07 19.25 0.005 BHRC221 469-221R 103 104 S2 Sandstone 2.21 22.92 0.005 BHRC221 470-221R 108 109 S2 Sandstone 2.62 21.01 0.005 BHRC221 471-221R 113 114 S2 Sandstone 2.26 25.57 0.005 BHRC221 472-221R 118 119 S2 Sandstone 1.23 21.95 0.005 BHRC221 473-221R 123 124 S2 Sandstone 1.96 21.77 0.005 BHRC221 474-221R 128 129 S2 Sandstone 0.02 21.10 0.005 BHRC221 475-221R 133 134 S1 Sandstone 2.45 25.18 0.005 BHRC221 476-221R 138 139 S1 Sandstone 2.56 24.39 0.021 BHRC221 477-221R 143 144 S1 Sandstone 1.78 26.85 0.006 BHRC221 478-221R 148 149 S1 Sandstone 2.36 27.50 0.005 BHRC221 479-221R 153 154 S1 Sandstone 2.57 26.72 0.005 BHRC221 480-221R 158 159 S1 Sandstone 3.56 25.97 0.005 BHRC222 481-222R 5 6 SMR Marl 0.61 16.31 0.005 BHRC222 482-222R 10 11 SMR Marl 1.26 17.21 0.005 BHRC222 483-222R 15 16 SMR Marl 1.52 17.17 0.005 BHRC222 484-222R 20 21 SMR Marl 2.06 18.84 0.005 BHRC222 485-222R 25 26 SMR Marl 2.31 19.75 0.005 BHRC222 486-222R 30 31 SMR Marl 1.12 19.16 0.005 BHRC222 487-222R 35 36 SMR Marl 1.07 18.86 0.005 BHRC222 488-222R 40 41 SMR Marl 0.58 18.48 0.016 BHRC222 489-222R 45 46 SMR Marl 1.28 19.45 0.005 BHRC222 490-222R 50 51 SMR Marl 1.07 19.60 0.005 BHRC222 491-222R 55 56 SMR Marl 1.59 20.01 0.005 BHRC222 492-222R 60 61 SMR Marl 1.42 18.80 0.005 * Drill hole collar coordinates and orientation are in Appendix G 179 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC222 493-222R 65 66 S2 Sandstone 1.30 20.32 0.005 BHRC222 494-222R 70 71 S2 Sandstone 1.84 23.42 0.005 BHRC222 495-222R 75 76 S2 Sandstone 1.90 21.26 0.005 BHRC222 496-222R 80 81 S2 Sandstone 1.37 20.03 0.005 BHRC222 497-222R 85 86 S2 Sandstone 2.22 19.37 0.026 BHRC222 498-222R 90 91 S2 Sandstone -0.68 18.16 0.005 BHRC222 499-222R 95 96 S2 Sandstone 1.18 19.56 0.005 BHRC222 500-222R 100 101 S2 Sandstone -1.22 18.19 0.02 BHRC222 501-222R 105 106 S2 Sandstone 0.40 17.44 0.005 BHRC222 502-222R 110 111 S2 Sandstone 1.97 16.98 0.005 BHRC222 503-222R 115 116 S2 Sandstone 1.51 21.15 0.005 BHRC222 504-222R 120 121 S2 Sandstone 1.10 18.60 0.005 BHRC222 505-222R 125 126 S2 Sandstone 1.15 21.43 0.005 BHRC222 506-222R 130 131 S2 Sandstone 0.50 17.44 0.006 BHRC222 507-222R 135 136 S2 Sandstone 1.85 21.78 0.04 BHRC222 508-222R 140 141 S1 Sandstone 2.15 21.17 0.074 BHRC222 509-222R 145 146 S1 Sandstone 2.15 22.12 0.044 BHRC222 510-222R 150 151 S1 Sandstone 1.55 23.55 0.102 BHRC222 511-222R 155 156 S1 Sandstone 2.18 23.63 0.324 BHRC222 512-222R 160 161 S1 Sandstone 1.65 21.53 0.16 BHRC222 513-222R 165 166 S1 Sandstone 1.18 18.75 0.318 BHRC222 514-222R 170 171 S1 Sandstone 1.50 20.38 0.167 BHRC222 515-222R 175 176 S1 Sandstone 1.04 16.98 0.182 BHRC222 516-222R 180 181 S1 Sandstone 0.71 15.42 0.03 BHRC222 517-222R 185 186 S1 Sandstone 0.83 14.80 0.009 BHRC222 518-222R 190 191 S1 Sandstone 0.45 16.52 0.075 BHRC222 519-222R 195 196 IB Mudstone -0.37 14.88 0.041 BHRC222 520-222R 200 201 BBX Breccia -0.41 13.45 0.458 BHRC222 521-222R 205 206 KLS Limestone 2.53 16.99 0.04 BHRC222 522-222R 210 211 KLS Limestone 1.21 12.15 0.214 BHRC222 523-222R 215 216 KLS Limestone 0.66 15.14 0.194 BHRC222 524-222R 220 221 KLS Limestone 0.60 12.09 0.51 BHRC222 525-222R 225 226 KLS Limestone 0.68 17.28 0.4 BHRC222 526-222R 230 231 KLS Limestone 2.55 14.49 1.278 * Drill hole collar coordinates and orientation are in Appendix G 180 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC222 527-222R 235 236 KLS Limestone 1.26 14.64 1.574 BHRC222 528-222R 240 241 KLS Limestone 1.33 17.41 0.078 BHRC222 529-222R 245 246 JLS Limestone -0.84 21.64 0.109 BHRC222 530-222R 250 251 JLS Limestone -1.59 20.41 0.006 BHRC229 531-229R 110 111 S2 Sandstone -2.02 15.00 0.005 BHRC229 532-229R 115 116 S2 Sandstone 2.52 18.13 0.005 BHRC229 533-229R 120 121 S2 Sandstone 0.24 17.56 0.022 BHRC229 534-229R 125 126 S2 Sandstone -1.43 16.07 0.005 BHRC229 535-229R 130 131 S2 Sandstone 1.70 13.80 0.009 BHRC229 536-229R 135 136 S2 Sandstone 2.09 17.11 0.005 BHRC229 537-229R 140 141 S2 Sandstone 1.16 18.27 0.005 BHRC229 538-229R 145 146 S2 Sandstone 0.43 18.52 0.005 BHRC229 539-229R 150 151 S2 Sandstone 1.94 18.65 0.005 BHRC229 540-229R 155 156 S2 Sandstone -1.12 16.02 0.009 BHRC229 541-229R 160 161 S2 Sandstone -2.57 14.84 0.069 BHRC229 542-229R 165 166 S2 Sandstone -3.29 15.74 0.109 BHRC229 543-229R 170 171 S2 Sandstone -2.82 15.23 0.03 BHRC229 544-229R 175 176 S1 Sandstone -0.18 16.19 0.37 BHRC229 545-229R 180 181 S1 Breccia -0.82 14.38 0.012 BHRC229 546-229R 185 186 BBX Breccia 0.62 17.25 0.013 BHRC229 547-229R 190 191 BBX Breccia 0.35 15.44 0.338 BHRC229 548-229R 195 196 BBX Breccia 0.84 14.58 0.49 BHRC229 549-229R 200 201 KLS Limestone 2.49 18.62 0.029 BHRC229 550-229R 205 206 KLS Limestone 3.75 16.47 0.074 BHRC229 551-229R 210 211 KLS Limestone 2.64 14.51 0.022 BHRC229 552-229R 215 216 KLS Limestone -0.66 15.80 0.039 BHRC229 553-229R 220 221 KLS Limestone 0.21 14.46 0.048 BHRC229 554-229R 225 226 KLS Limestone 1.98 18.02 0.032 BHRC229 555-229R 230 231 KLS Limestone 2.37 18.16 0.174 BHRC229 556-229R 235 236 KLS Limestone 2.27 23.93 0.142 BHRC229 557-229R 240 241 KLS Limestone 1.03 18.23 0.016 BHRC229 558-229R 245 246 KLS Limestone 2.64 11.93 0.051 BHRC229 558-229Ra 245 246 KLS Vein -4.48 18.65 BHRC229 559-229R 250 251 KLS Limestone 1.44 15.24 0.058 * Drill hole collar coordinates and orientation are in Appendix G 181 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC229 560-229R 255 256 KLS Limestone 0.92 24.40 0.015 BHRC229 561-229R 260 261 KLS Limestone 2.23 28.43 0.006 BHRC229 562-229R 265 266 KLS Limestone 2.03 27.85 0.005 BHRC283 563-283R 5 6 SMR Marl 2.83 17.82 0.006 BHRC283 564-283R 10 11 SMR Marl 1.49 15.84 0.005 BHRC283 565-283R 15 16 SMR Marl -0.88 14.83 0.006 BHRC283 566-283R 20 21 SMR Marl -0.17 14.58 0.014 BHRC283 567-283R 146 147 S2 Sandstone -0.53 14.64 0.023 BHRC283 568-283R 151 152 S2 Sandstone 0.57 15.36 0.027 BHRC283 569-283R 156 157 S2 Sandstone -1.79 13.85 0.005 BHRC283 570-283R 161 162 S2 Sandstone 2.21 16.46 0.005 BHRC283 571-283R 166 167 S2 Sandstone 2.69 18.92 0.005 BHRC283 572-283R 171 172 S2 Sandstone 2.79 18.38 0.005 BHRC283 573-283R 176 177 S2 Sandstone 2.24 19.45 0.038 BHRC283 574-283R 181 182 S2 Sandstone 0.71 17.12 0.036 BHRC283 575-283R 186 187 S2 Sandstone 3.31 19.82 4.618 BHRC283 576-283R 191 192 S1 Sandstone 2.87 24.00 3.518 BHRC283 577-283R 196 197 S1 Sandstone 2.27 22.51 0.104 BHRC283 578-283R 201 202 S1 Sandstone 3.39 24.28 2.318 BHRC283 579-283R 206 207 S1 Sandstone 3.14 22.69 0.126 BHRC297 581-297R 140 141 S2 Sandstone -3.50 15.28 0.544 BHRC297 582-297R 145 146 S2 Sandstone 0.13 18.43 0.61 BHRC297 583-297R 150 151 S2 Sandstone -1.80 17.39 1.482 BHRC297 584-297R 155 156 S2 Conglomerate -0.48 16.07 0.474 BHRC297 585-297R 160 161 S2 Sandstone -0.67 15.69 0.408 BHRC297 586-297R 165 166 S2 Conglomerate -1.13 17.86 2.064 BHRC297 587-297R 170 171 S1 Sandstone 2.10 18.45 3.016 BHRC297 588-297R 175 176 S1 Sandstone -0.05 16.04 3.056 BHRC297 589-297R 180 181 S1 Sandstone 1.20 14.42 1.352 BHRC297 590-297R 185 186 S1 Sandstone -0.03 13.30 0.368 BHRC297 591-297R 190 191 S1 Sandstone 0.67 14.27 0.134 BHRC297 592-297R 195 196 IB Mudstone -0.98 12.60 0.076 BHRC297 593-297R 200 201 IB Mudstone -2.72 11.76 1.516 BHRC297 594-297R 205 206 IB Mudstone 2.15 17.24 3.536 BHRC297 596-297R 215 216 BBX Breccia -0.30 13.52 4.254 * Drill hole collar coordinates and orientation are in Appendix G 182 Appendix E.1: Carbon and oxygen isotope data from Bigar Hill, Korkan West, and Korkan South rocks Drill Hole Sample ID From To Stratigraphic Unit Lithology δ13C (VPDB) δ18O (VPDB) Au (ppm) As (ppm) Sb (ppm) Tl (ppm) Te (ppm) Hg (ppm) BHRC297 597-297R 220 221 KLS Breccia 1.30 11.46 0.44 BHRC297 598-297R 225 226 KLS Limestone 0.13 13.37 0.042 BHRC297 599-297R 230 231 KLS Limestone 1.78 13.95 0.114 BHRC297 600-297R 235 236 KLS Limestone 2.01 19.25 0.68 BHRC297 601-297R 240 241 KLS Limestone -2.20 12.55 0.07 BHRC297 602-297R 245 246 KLS Limestone 1.03 15.71 0.072 BHRC297 602-297Ra 245 246 KLS Vein -0.71 13.92 BHRC297 603-297R 250 251 KLS Limestone 1.61 14.73 0.114 BHRC297 604-297R 255 256 KLS Limestone 2.10 16.21 0.066 BHRC297 605-297R 260 261 KLS Limestone 1.44 13.06 0.088 BHRC297 606-297R 265 266 KLS Limestone -1.53 8.93 1.792 BHRC297 607-297R 270 271 KLS Limestone -0.13 14.33 2.544 BHRC297 608-297R 275 276 JLS Limestone 0.51 20.70 0.24 BHRC297 609-297R 280 281 JLS Limestone 1.23 18.68 0.1 KWDD005 KW5-235 5 6 SMR Marl 1.21 26.55 0.005 KWDD005 KW5-236 15 16 SMR Marl 3.69 27.19 0.005 KWDD005 KW5-238 21 21.5 S2 Sandstone 2.66 29.01 0.005 KWDD005 KW5-241 99 100 S2 Sandstone 2.27 27.07 0.005 KWDD005 KW5-242 107 108 S1 Sandstone 4.23 28.71 0.005 KWDD005 KW5-243 113 114 S1 Sandstone 2.63 28.17 0.005 KWDD005 KW5-245 273 274 S1 Sandstone 2.95 25.91 0.005 KWDD005 KW5-246 290 291 JLS Limestone 1.87 28.74 0.005 KWDD005 KW5-247 305 306 JLS Limestone 2.39 29.60 0.005 KWDD008 KW8-249 59 59.9 S2 Sandstone 1.59 27.67 0.005 KWDD008 KW8-252 81 81.8 S1 Sandstone 2.11 29.60 0.005 KWDD008 KW8-253 200 200.4 IB Siltstone 1.51 25.26 0.005 KWDD008 KW8-254 241 241.5 S1 Sandstone 0.99 24.23 0.005 KWDD008 KW8-255 245 245.5 JLS Limestone 1.65 31.07 0.005 KODD028 KO28-259 202 203 SMR Marl 2.61 25.15 0.005 KODD028 KO28-260 238 239 S2 Sandstone 2.41 24.49 0.005 KODD028 KO28-261 282 283 S2 Sandstone 2.58 26.16 0.005 KODD028 KO28-262 293 294 S1 Sandstone 2.02 28.52 0.005 KODD028 KO28-265 473 473.7 KLS Limestone 2.23 25.37 0.005 KODD028 KO28-266 592 592.7 JLS Limestone 1.26 21.35 0.005 * Drill hole collar coordinates and orientation are in Appendix G 183 Appendix E.2: The spatial variability of O isotope in each stratigraphic unit in drill holes along the A-B cross section 184 Appendix F: K-Ar Radiometric Age Dating X-Ray Powder Diffraction Analysis 14JZBH292 andesite Illite is the dominant mineral phase in this sample. Illite/smectite and chlorite occur in a small amount. Quartz is present in the separate in a minor amount. 14JZBH294 andesite Discrete illite and illite/smectite are present in the sample in almost equal proportion. Chlorite, discrete smectite, quartz, and gypsum are also present in the separated <2 μm fraction. 185 14JZBH296 andesite Three different size fractions (<2 µm; <5 µm; and the <10 µm) were separated and analyzed with XRPD method. There are only minor differences between the three samples. The clay minerals are illite and illite/smectite. The latter one contains approximately 10-15% smectite interstratification. The relative proportion of the pure illite in the <10 µm fraction is a bit higher compared to the smaller size fractions. Dolomite, calcite, quartz, and chlorite occur in the <10 µm fraction, but their amount decreases in the smaller fractions. In the <2 µm fraction their proportion is almost negligible. 14JZBH295 sandstone Clay minerals in this sample are discrete smectite and discrete illite. Chlorite and kaolinite are also present. Quartz and calcite occur in a minor amount. 186 14JZBH299 sandstone Discrete, well-crystallized illite is dominant in the sample. Kaolinite, quartz, and calcite occur in low amount. 187 Appendix G: Bigar Hill, Korkan, Korkan West, Rakita, and Crna Reka drill hole collar locations and orientation data Hole ID Easting Northing UTM Zone Elevation (m) Azimuth (Degrees) Dip (Degrees) BHDD004 570364.5 4898443.9 UTM(WGS84)34N 700.7 270 -60 BHDD005 570533.1 4898412.4 UTM(WGS84)34N 747.4 270 -60 BHDD007 570534.4 4898247.9 UTM(WGS84)34N 775.9 270 -60 BHDD009 570540.3 4898087.1 UTM(WGS84)34N 779.8 270 -60 BHDD010 570700.4 4898243.2 UTM(WGS84)34N 771.2 270 -60 BHDD017 570854.2 4898097.4 UTM(WGS84)34N 742.1 270 -60 BHDD020 570372.5 4898558.9 UTM(WGS84)34N 691.3 270 -60 BHDD021 570394.3 4898250.5 UTM(WGS84)34N 748.6 270 -60 BHDD026 570219.6 4898565.5 UTM(WGS84)34N 685.2 270 -60 BHDD032 570781.4 4897931.3 UTM(WGS84)34N 771.4 45 -60 BHDD041 570220.8 4898488.4 UTM(WGS84)34N 686.3 270 -60 BHDD047 570598.6 4898502.3 UTM(WGS84)34N 722.6 270 -60 BHDD049 570454.7 4898400.3 UTM(WGS84)34N 729.8 270 -60 BHDD053 571503.6 4898163.3 UTM(WGS84)34N 708.8 270 -60 BHDD056 570468.3 4898171.4 UTM(WGS84)34N 774.6 270 -60 BHDD057 570863.8 4898153.9 UTM(WGS84)34N 734.0 270 -60 BHDD058 571342.3 4898160.6 UTM(WGS84)34N 702.7 270 -60 BHDD063 570925.0 4898075.2 UTM(WGS84)34N 717.9 270 -60 BHDD065 570700.4 4898012.4 UTM(WGS84)34N 787.3 270 -60 BHDD067 570926.8 4898011.0 UTM(WGS84)34N 724.5 270 -60 BHDD068 570761.0 4898165.7 UTM(WGS84)34N 769.0 270 -60 BHDD076 571003.9 4898167.4 UTM(WGS84)34N 691.1 270 -60 BHDD080 571521.3 4898384.2 UTM(WGS84)34N 660.8 270 -60 BHDD081 571331.1 4898418.7 UTM(WGS84)34N 676.8 270 -60 BHDD083 570704.0 4898132.1 UTM(WGS84)34N 784.7 80 -60 BHDD084 570652.4 4898169.4 UTM(WGS84)34N 785.3 270 -60 BHDD085 570697.5 4898213.3 UTM(WGS84)34N 774.7 270 -60 BHDD086 570430.6 4898381.7 UTM(WGS84)34N 723.5 260 -60 BHDD087 570521.1 4898327.1 UTM(WGS84)34N 761.1 270 -60 BHRC046 570691.7 4898161.1 UTM(WGS84)34N 782.1 270 -60 BHRC105 570376.4 4898172.8 UTM(WGS84)34N 751.7 270 -60 BHRC130 570579.5 4898170.9 UTM(WGS84)34N 787.4 270 -60 BHRC143 570182.0 4898172.1 UTM(WGS84)34N 684.7 275 -60 BHRC147 570225.0 4898169.1 UTM(WGS84)34N 701.7 275 -60 BHRC159 570142.7 4898168.3 UTM(WGS84)34N 666.5 275 -60 BHRC172 570815.3 4898170.8 UTM(WGS84)34N 747.8 270 -60 BHRC221 570307.1 4898171.5 UTM(WGS84)34N 732.8 273 -60 BHRC222 570339.3 4898177.0 UTM(WGS84)34N 741.3 272 -60 BHRC229 570423.8 4898170.0 UTM(WGS84)34N 765.7 270 -60 BHRC283 570895.9 4898171.0 UTM(WGS84)34N 722.9 270 -60 BHRC297 570498.7 4898168.6 UTM(WGS84)34N 779.7 270 -60 CRDD002 574478.9 4888710.6 UTM(WGS84)34N 812.1 120 -50 CRDD005 574327.4 4888083.6 UTM(WGS84)34N 743.5 135 -50 KODD028 570881.6 4899187.7 UTM(WGS84)34N 708.5 270 -60 KWDD005 569494.3 4899762.7 UTM(WGS84)34N 739.4 0 -60 KWDD008 568862.4 4900428.4 UTM(WGS84)34N 737.2 0 -60 RADD001 572784.5 4896009.7 UTM(WGS84)34N 889.4 130 -60
Thesis/Dissertation
eng
Geological Sciences
Vancouver : University of British Columbia Library
Attribution-NonCommercial-NoDerivatives 4.0 International
Graduate
Structural, stratigraphic and temporal constraints of gold mineralization in the Bigar Hill deposit, Timok region, Serbia
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