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Telluride mineralogy at the Deer Horn Au-Ag-Te-(Bi-Pb-W) deposit, Lindquist Peak, west-central British… Roberts, Jordan 2017

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  TELLURIDE MINERALOGY AT THE DEER HORN Au-Ag-Te-(Bi-Pb-W) DEPOSIT, LINDQUIST PEAK, WEST-CENTRAL BRITISH COLUMBIA: IMPLICATIONS FOR THE GENERATION OF TELLURIDES   by  Jordan Roberts  H. B.Sc., University of Western Ontario, 2013   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)  October 2017  © Jordan Roberts, 2017   ii  Abstract The Deer Horn property is located 150 km south of Smithers in west-central British Columbia and covers 51 km2.  The deposit is an intrusion-related polymetallic system enriched in Au-Ag-Te-W-Cu with lesser amounts of Bi-Pb-Zn-Mo; the Au and Ag are hosted in telluride minerals.  The quartz-sulfide vein system containing the main zones of Au-Ag-Te mineralization and sericite alteration is found in the hanging wall of a local, spatially related thrust fault.  The age of the sericite alteration is 56 ± 2 Ma.  Biotite K-Ar ages of 57–48 Ma for the nearby Nanika granodiorite intrusive suite indicates that it is likely genetically responsible for the Au-Ag-Te mineralizing event. The telluride minerals are 0.1–525 μm and commonly form whole euhedral to subhedral grains or composite grains of Ag-, Bi-, Pb-, and Au-rich telluride minerals (e.g., hessite, tellurobismuthite, volynskite, altaite, and petzite).  Panchromatic cathodoluminescence imaging revealed four generations of quartz.  Locally, oscillatory zoning observed in quartz II suggests the participation of hydrothermal fluids.  Fine-grained veinlets of quartz III and IV intersect quartz I and II, which is evidence of at least two shearing events; veinlets of calcite intersect all generations of quartz. Three types of fluid inclusions were observed: (1) aqueous liquid and vapour inclusions (L-V); (2) aqueous carbonic inclusions (L-L-V); and (3) carbonic inclusions (V-rich). Fluid inclusions that are thought to be primary or pseudosecondary and related to the telluride mineralization were tested with microthermometry.  Homogenization temperatures are 130.0–240.5 °C for L-V inclusions and 268.0–336.4 °C for L-L-V inclusions.  Four of eight aqueous carbonic inclusions had solid CO2 melting temperatures from –56.8 to –62.1 °C, indicating the presence of 0.5–13.2% dissolved methane in these inclusions. Sulfur isotope analysis of 34S/32S using 20 samples of pyrite was conducted. δ34S readings are close to 0 (from –1.6 to 1.6 per mil) and confirm that the sulfur is very likely magmatic/igneous in origin.  iii  Lay Summary Although the Deer Horn occurrence has been explored since the 1940s, very little is known about its extent and metallogenesis. Deer Horn is a gold, silver, tellurium, copper, bismuth, lead, and tungsten deposit located in west-central British Columbia.  In 2012 the United States Department of Energy gave tellurium a rank of 3 out of 4 for "importance to clean energy" and 2 out of 4 for "supply risk" in both short (2010–2015) and medium (2015–2025) terms, for an overall rating of "near critical" (only the heavy rare earth elements ranked higher). The objective of the proposed study is to fully characterize and describe the tellurium-bearing minerals that occur in association with gold and silver and to attempt to determine a deposit model that explains how the occurrence formed. This information will be used to guide future exploration and development of the property.               iv  Preface This thesis is an independent work with original content by the author, Jordan Roberts, who plans to publish a more condensed version of the manuscript in 2018.  Data collection was conducted mostly by the author, with the exception of electron microprobe data being collected with the help of Dr. Radek Skoda and Dr. Jan Cempírek and sulfur isotope data being collected by the Queen’s University Facility for Isotope Research (QFIR).  Data interpretation in Chapters 5 and 6 was aided by Dr. Jan Cempírek, Dr. Paul Spry, and Dr. Thomas Chudy. Chapter edits of the thesis were conducted by the author’s supervisor, Dr. Lee Groat, as well as Mackenzie Parker, Dr. Jan Cempírek, Dr. Mati Raudseep, Dr. Jim Mortensen, and Dr. Paul Spry.               v  Table of Contents  Abstract.........................................................................................................................................ii Lay Summary...............................................................................................................................iii Preface...........................................................................................................................................iv Table of Contents.......................................................................................................................viii List of Tables................................................................................................................................ix List of Figures............................................................................................................................xvii Acknowledgements...................................................................................................................xviii 1. Introduction...............................................................................................................................1  1.1 Importance of Studying Telluride Deposits....…..........................................................1 1.2 Au-(Ag) Telluride Transport and Deposition...............................................................2 1.3 Tellurium Extraction and Recovery..............................................................................4  1.4 Scientific Significance and Scope of the Thesis………….……..................................5   2. Background...............................................................................................................................7  2.1 Location of the Deer Horn Deposit..............................................................................7 2.2 Regional Geology.......................................................................................................11  2.3 Local Geology............................................................................................................20  2.3.1 Sedimentary Rocks......................................................................................23 2.3.2 Metamorphic Rocks.....................................................................................24 2.3.3 Plutonic and Intrusive Rocks.......................................................................24  2.4 Structural Relationships..............................................................................................26 2.5 Mineralization and Alteration.....................................................................................28 2.5.1 Au-Ag-Te Vein Mineralization....................................................................28 vi  2.5.2 Tungsten Mineralization..............................................................................32 2.5.3 Molybdenum Mineralization.......................................................................33 2.5.4 Alteration.....................................................................................................34  2.6 Previous Analytical Work..........................................................................................35 3. Methodology...........................................................................................................................37 3.1 Recent Field Work and Sample Selection.................................................................37 3.2 Polished Thin Section Examination..........................................................................39 3.3 SEM Methodology....................................................................................................39 3.4 EPMA Methodology.................................................................................................40 3.5 μXRD Methodology..................................................................................................41 3.6 Panchromatic Cathodoluminescence Methodology..................................................42 3.7 Fluid Inclusion Methodology....................................................................................42 3.8 Stable Sulfur Isotope Methodology...........................................................................43 4. Results.....................................................................................................................................45 4.1 Panchromatic Cathodoluminescence of Quartz.........................................................45 4.2 Petrography and SEM Observations..........................................................................48  4.2.1. Quartz.........................................................................................................48  4.2.2 Scheelite......................................................................................................51  4.2.3 Sulfide Minerals..........................................................................................52  4.2.4 Oxide Minerals............................................................................................56  4.2.5 Telluride Minerals.......................................................................................57  4.2.6 Alteration Phases.........................................................................................64  4.2.7 Hydroxylbastnäsite-(Nd).............................................................................66 vii  4.3 EPMA Results............................................................................................................68 4.4 μXRD Analysis..........................................................................................................70 4.5 Fluid Inclusion Analysis.............................................................................................71  4.5.1 Aqueous Fluid Inclusions............................................................................71 4.5.2 Aqueous Carbonic Fluid Inclusions............................................................73  4.5.3 Carbonic Fluid Inclusions............................................................................75 4.6 Sulfur Isotope Analysis...............................................................................................77 4.7 Deposit Metal Zonation..............................................................................................78 5. Interpretation of Results........................................................................................................79 5.1 Panchromatic Cathodoluminescence of Quartz..........................................................79 5.2 Petrography and SEM Observations...........................................................................81  5.2.1. Quartz..........................................................................................................81  5.2.2 Scheelite.......................................................................................................82  5.2.3 Sulfide Minerals...........................................................................................83  5.2.4 Oxide Minerals.............................................................................................84  5.2.5 Telluride Minerals........................................................................................85  5.2.6 Alteration Phases..........................................................................................91  5.2.7 Hydroxylbastnäsite-(Nd)..............................................................................91  5.2.8 Summary of Petrography and SEM-CL Interpretation................................93 5.3 EPMA..........................................................................................................................95 5.4 Fluid Inclusion Analysis..............................................................................................96  5.4.1 Aqueous Fluid Inclusions.............................................................................96  5.4.2 Aqueous Carbonic Fluid Inclusions.............................................................96 viii   5.4.3 Carbonic Fluid Inclusions............................................................................97 5.4.4 Summary of fluid inclusion interpretation...................................................97 5.5 Sulfur Isotope Analysis...............................................................................................99 6. Comparisons and Conclusions.............................................................................................100 6.1 Bi-(Te) melts as Au scavengers................................................................................100 6.2 Comparisons with Deposits Worldwide...................................................................102   6.2.1 Is Deer Horn an IRGS?..............................................................................102 6.2.2 Intrusion-related Telluride Deposits..........................................................106 6.3 Metallurgy of Au-(Ag) Extraction & Recovery Potential at Deer Horn…..............109 6.4 Summary of Conclusions….....................................................................................109 6.5 Future Work & Recommendations..........................................................................111 References.................................................................................................................................113 Appendices................................................................................................................................122 Appendix A: Data and Results.......................................................................................122 A.1 Selected Core Sample Photographs.............................................................122   A.2 Selected Digital Scans of Polished Thin Sections.......................................128   A.3 Selected SEM-BSE Images.........................................................................133   A.4 EPMA Data Tables......................................................................................141   A.5 μXRD Targets, GADDS Images, and Diffraction Patterns.........................164   A.6. Selected Panchromatic Cathodoluminescence Images of Quartz...............182 Appendix B: Tellurium & Au-(Ag) Tellurides...............................................................187 B.1 Access to Property........................................................................................187 B.2 History of the Deer Horn Property...............................................................187 ix  List of Tables Table 1.1       World Refinery Production and Reserves of Tellurium...................................4 Table 3.1       Deer Horn Deposit samples investigated with corresponding drill core depth, zone, and assay grade of Au and Ag, and ICP data for Te............................38 Table 4.2       Telluride Minerals in the Deer Horn Samples confirmed with EPMA...........62 Table 4.3       Preliminary Fluid Inclusion Study: Microthermometry Data for L-V, L-L-V, and V-rich inclusions at the Deer Horn occurrence........................................76 Table 4.4       Sulfur isotope data from pyrite at the Deer Horn occurrence..........................77 Table 5.1       Paragenetic Sequence for the Deer Horn occurrence.......................................92 Table 6.1       Comparative table with other intrusion-related Au-Te deposits worldwide..108               x  List of Figures Figure 1.1 A simplified map of British Columbia with a yellow star indicating the location of the Deer Horn property (Deer Horn Metals Inc., 2014).……………………………………………...7 Figure 1.2 An overview of the locations of the major mineral occurrences on the property from the Deer Horn Metals Inc. (2014).  These occurrences include the Au-Ag-Te vein system, area of tungsten mineralization, and new copper showings to the northwest. The Deer Horn mine adit is located at the red tri-point symbol…………………………………………………………….….9 Figure 1.3 Map of the MINFILE occurrences in British Columbia and the distribution of Cretaceous and Tertiary volcanic-arc rocks. The red circle is the approximate location of the Deer Horn property showing a part of the Nanika Plutonic Suite (dark pink) directly to the right of the circle.  (Figure modified from MacIntyre 2006)……..…………………………………..10 Figure 2.1 (top) A birdseye view map and (bottom) a cross section of the five major tectonic belts in British Columbia. From oldest to youngest (east to west) these are the Foreland, Omineca, Intermontane, Coast, and Insular belts (Monger & Price 2002).  Deer Horn is located in the Intermontane tectonic belt, where it contacts the eastern edge of the Coast Plutonic Complex………………………………………………………………………………………...12 Figure 2.2 Regional map of the Canadian and Alaskan Cordillera showing the most prominent terranes of British Columbia (Nelson & Colpron 2007).  Deer Horn is located in the Stikine terrane (light forest green)…………………………………………………………………..…..13 Figure 2.3 Schematic of the stratigraphy of the Stikine terrane and its corresponding overlaps (modified from Alldrick 1993)……………………………………………………………….…15 Figure 2.4 Intrusive activity in the Stikine terrane of the Canadian Cordillera showing the  timing of the emplacement of the Nanika Suite (Alldrick 1993)……………………………….17 xi  Figure 2.5 Geologic time scale showing intrusive and extrusive activity in the study area.  Data is positioned based on U-Pb and40Ar/39Ar dating (Grainger et al. 2000) ……………………...…..18 Figure 2.6 Stratigraphic and magmatic relationships between the Stikine Terrane and  the Skeena Arch (MacIntyre 2006)…. …………………………………………………………..19 Figure 2.7 A regional geological map of the area surrounding the Deer Horn occurrence (red rectangle), in which the extent of the Eocene (Tertiary) intrusive granites (pink) can be observed.  Geological rock type found in legend to the left.  The Deer Horn property is indicated with a red box (map and legend modified from the British Columbia Geological Survey)…...........………19 Figure 2.8 A recent local geological map of the Lindquist Lake area showing the relationship between various rock types and the claim boundary of the property in pink (modified from Lane & Giroux 2012).  Yellow stars represent each of the four BCGS MINfile inventory occurrences within the study area.  The red four-pronged star represents the top of Lindquist Peak and the black line through the property represents the major thrust fault…………………….……...….21 Figure 2.9 Digitally recreated geological map of surface outcrops around the Deer Horn occurrence, showing the silicified zone (yellow), where the Au-Ag-Te vein system mineralization occurs, is mostly near the contact between foliated quartz diorite (purple) and sedimentary/greenstone rock packages (Skeena Group). The red granite is the Eocene granodiorite/granite from the Nanika intrusive suite (map modified from Duffell 1959)…........22 Figure 2.10 Schematic cross-section showing the geometry of the thrust fault and vein system containing the Main Vein and Contact Zone at the Deer Horn Property (by Roberts & Chudy 2017)……………………………………………………………………………………………..27 Figure 2.11 The distribution of Au-Ag-Te mineralization throughout the MV (red) appears to be structurally controlled by the northwest-striking faults (black lines) because mineralization xii  grades highest in the zones with quartz veins and significant alteration (purple) increases at the intersection point between the northwest-striking faults and the MV (modified from Renning et al. 2007).  Drill hole sample numbers are in yellow, blue, and black……………………….….31 Figure 2.12 Scheelite-bearing talus showing the WO3 weighted averages from samples collected by Duffell (1959)… ………………………………………………………………………….....33 Figure 4.1 (a) and (b) SEM-CL backscattered-electron and (c) cross-polarized transmitted-light images of the relationships between quartz generations I (bright core), II (darker rim around quartz I), and III (in fractures and along grain boundaries of quartz I + II)……………………45 Figure 4.2 (a) Cross-polarized transmitted-light image with a green box indicating the area shown in the SEM backscattered-electron image of (b).  The SEM-CL back-scattered electron image (b) shows the relationships between quartz generations I–IV (Sample DH11-114)..…..47  Figure 4.3 (a) Cross-polarized transmitted-light image and (b) plane-polarized image of quartz generations I to IV from sample DH11-111b..  Quartz I + II are coarser grained and have strong undulose extinction while the quartz III + IV are finer grained, found around quartz I + II grain boundaries and fractures. These images give examples of how opaque minerals (solid black) are mostly associated with/enclosed in quartz III and IV……………………………….…….…....49 Figure 4.4 (a) Cross-polarized transmitted-light image and (b) plane-polarized image of quartz generations I to IV from sample DH11-130. Quartz I + II are coarser grained and have strong undulose extinction while the quartz III + IV are finer grained, found around quartz I + II grain boundaries and fractures. These images give examples of how opaque minerals (solid black) are mostly associated with/enclosed in quartz III and IV….………………………………......…...50 Figure 4.5 Image of a core sample under short-wave UV with light blueish-white fluorescent scheelite grains….………..……………………………………………………………….…….51 xiii  Figure 4.6 SEM backscattered-electron image of primary scheelite in a sulfide-poor quartz vein being replaced stolzite………………………………………………………………………….52 Figure 4.7 Reflected-light image of sample DH09-092 with pyrrhotite being locally altered to collomorph aggregates of pyrite II that has a spongy “melnikovite” texture (concentric growth texture) showing in-situ replacement (po = pyrrhotite, py = pyrite)………………………...….53 Figure 4.8 Reflected-light image from sample DH09-090 of euhedral pyrite being overgrown by marcasite (top right) with its classic spearhead shape; sphalerite with chalcopyrite disease crystallized later as it is found surrounding a crystal of marcasite (top left)…………...……….54   Figure 4.9 Reflected-light images of (a) sphalerite (light brownish-grey) with a large number of chalcopyrite inclusions (yellow-orange) forming along crystallographic planes in sample DH09-090. (b) Chalcopyrite disease in sphalerite filling cracks and cross-cutting sections in euhedral to subhedral pyrite I from sample DH09-079…………………………………………………..….55 Figure 4.10 Reflected-light image of galena from sample DH11-120 exhibiting triangular holes from being polished off along its three cleavage planes………………………………………..56 Figure 4.11 SEM backscattered-electron images (a) to (c) are examples of composite grains with complex exsolution textures…………………………………………………………………….58 Figure 4.12 (a) SEM backscattered-electron (sample DH11-104bi) and (b) reflected-light (sample DH11-103) images showing telluride minerals as clusters or disseminations within fractures, interstices, or veinlets of quartz III & IV, typically very near sulfide grains and following distinct planes…………………………………………………………..………….…59 Figure 4.13 SEM backscattered-electron images (a) and (b) showing tellurides as inclusions in sulfides, within fractures of sulfides, and along grain boundary contacts between sulfides and quartz………………………………………………………………………………..………..…60 xiv  Figure 4.14 SEM backscattered-electron images of (a) and (b) showing tellurides near grain boundary contacts between sulfides (in this case (a) sphalerite + chalcopyrite in sample DH11-146a and (b) sphalerite + pyrite in sample DH11-110e1.………………………………………..61 Figure 4.15 SEM backscattered-electron image of hessite forming trails along fractures and crystallographic planes in pyrite…………………………….……………...………….…….......62 Figure 4.16 SEM backscattered-electron images (a) and (b) showing clusters of telluride minerals associated with K-Al-Si-rich sericitic alteration…………………………...…………..63 Figure 4.17 (a) cross-polarized and (b) SEM backscattered-electron images of alteration minerals at the Deer Horn deposit [chlorite and sericite (muscovite)] that is fine-grained, sometimes with an acicular crystal habit.  These display typical replacement textures…………………………..64 Figure 4.18 (a) plane-polarized transmitted-light image of biotite altering to chlorite and (b) carbonate (calcite with rhombohedral cleavage) filling fractures in quartz near sulfides……….65 Figure 4.19 SEM back-scattered electron image of calcite cross-cutting sericitic alteration…....66 Figure 4.20 (a) Zoomed-out SEM backscattered-electron image of hydroxylbastnäsite-(Nd) in quartz near sulfides and (b) zoomed-in SEM backscattered-electron image of the red square box from (a) showing the interesting intergrowth texture of hydroxylbastnäsite-(Nd)………………67 Figure 4.21 (a), (b), and (c) are ternary diagrams from EPMA analysis showing how the compositions of tellurides vary throughout the samples……………………………………...….69 Figure 4.22 L-V fluid inclusion examples: (a) analysis # 15 (AN15, sample DH11-110C), (b) analysis #16 (AN16, sample DH11-110c), (c) analysis #11, 12, and 13 (AN11, AN12, AN13, sample DH11-147D). (L = liquid, V = vapour)………………………………………………….72 xv  Figure 4.23 L-L-V inclusion from sample DH11-110B (analysis #5) at (a) room temperature (19 °C), (b) water frozen at –26.7 °C (note the appearance of ice crystals around the vapour bubble), and (c) CO2 frozen at –81.0 °C)……………………………………………………………..….73 Figure 4.24 L-L-V inclusion from sample DH11-110B (analysis #5) at (a) room temperature (19 °C), (b) at about 230.0 °C during heating, and (c) at 275.0 °C (the point of homogenization)…74 Figure 4.25 A histogram showing the range of homogenization temperatures for L-V and L-L-V inclusions………………………………………………………………………………..…...….74 Figure 4.26 An example of a CO2 vapour-rich inclusion (a) at room temperature (19 °C) and (b) frozen at –56.8 °C…………………………………………………………….….……..…...…..75 Figure 5.1 SEM-CL image of quartz I and II filled with healed micro-cracks and oscillatory zoning………………………………………………………………………………………...….79 Figure 5.2 SEM backscattered-electron image showing tellurides forming throughout fractures and as small inclusions in pyrite. Secondary scheelite was likely remobilized by hydrothermal fluids and deposited in fractures of pyrite………………………………………………….…....83 Figure 5.3 SEM backscattered-electron image showing birds-eye texture of pyrrhotite being replaced by pyrite II, creating a concentric growth texture towards Fe-rich sphalerite….……...84 Figure 5.4 SEM backscattered-electron images of a composite grain with tellurobismuthite forming a complex, bladed intergrowth texture formed by exsolution………………….…...….86 Figure 5.5 SEM backscattered-electron images (a) and (b) of euhedral tellurobismuthite crystals forming whole grains with a distinct blocky, tabular habit……………………………………...86 Figure 5.6 SEM backscattered-electron image with earlier grains of galena rimmed by altaite...87 Figure 5.7 Backscattered-electron images (a) and (b) of hessite with a porous, Swiss-cheese texture…..………………………………………………………………………………………..88 xvi  Figure 5.8 SEM backscattered-electron images (a), (b), and (c) display how hessite commonly makes up the largest volume of any telluride in each composite grain………………………….89 Figure 5.9 SEM backscattered-electron images of (a) inclusions of gold in hessite, (b) inclusion of gold surrounded by multiple tellurides in a composite grain, and (c) a composite grain with a tiny inclusion of gold in petzite………………………………………………………………….90 Figure 5.10 (a) A reflected-light and (b) cross-polarized transmitted-light image of the same area from sample DH11-143. These images show the general style of Te-mineralization found near sulfides and alteration minerals (sericite + chlorite) within fractures/along grain boundaries in quartz. Abbreviations: cpy = chalcopyrite, gal = galena, sph = sphalerite, ser = sericite, chl = chlorite..……………………………………………………………………………….……..….94 Figure 5.11 The green rectangle shows the average distribution of salinities vs. homogenization temperatures found at Deer Horn, categorizing the inclusions in the epithermal to mesothermal range (figure modified from data by Large 1988 and Wilkinson 2001)……………….………..98 Figure 6.1 Phase diagram by Tooth et al. (2008) of the Au-Bi system at 1 bar showing the eutectic temperature of 241 °C…………………………………………………………………101 Figure 6.2 Deposits worldwide that are considered to be proposed to be RIRGS. The location of the Deer Horn deposit is marked with a yellow star. Figure modified from Hart (2007)…...…104 Figure 6.3 Common metal associations and mineralization types in a cooling RIRGS (Hart 2007) which is very similar to the paragenesis at Deer Horn…………………………………..…..…104 Figure 6.4 Magnetic survey over the Deer Horn property from 2011 (conducted by Precision GeoSurveys Inc.) showing that areas which correlate geologically to the Eocene intrusion are mostly green to slightly yellowish-red in some areas indicating it is neither very strongly reduced or oxidized.………………………………………………………………………….……….…105 xvii  Figure 6.5 Metal associations with various primary oxidation states and degrees of fractionation.  It is likely the Deer Horn deposit falls close to the ilmenite-magnetite boundary within the yellow RIRGS area.……………………………………………………………………………105                     xviii  Acknowledgements  First and foremost the author wishes to thank her supervisor, Dr. Lee Groat, for welcoming her into his Mineralogy Research Group (MRG) initially as a lab assistant and later as a Master’s student.  I would not have come this far and acquired the new skills and knowledge I have learned over the last three years without his faith that I could accomplish this goal and his willingness to teach me.  I have grown immensely both as a student and person from being a part of this mineralogical family and look forward to future projects with him and the MRG.  The National Science and Engineering Research Council (NSERC) is gratefully acknowledged for a 6 month Research Engage Grant that was received in September 2014.  Without this financial support, the field work for this project would not have been possible.  Deer Horn Capital is also thanked for their financial support and for permitting us to visit the property and retrieve the samples for this project.  Tony Fogarassy and Bob Lane of Deer Horn Capital are also thanked for their openness to questions about the property and geology, and for always taking the time to respond to my messages.   The author is immensely grateful to Dr. Jan Cempírek and Dr. Thomas Chudy for always being there to answer any question, help with data interpretation, and encourage me to think outside the box when trying to understand the complexity of an ore deposit.  The members of my committee, Prof. Mati Raudsepp and Prof. Jim Mortensen, are thanked for providing guidance and advice on this project.  I am also very appreciative of Dr. Paul Spry’s direction and expertise in the techniques behind the study of telluride minerals and how to analyze the data accurately.   Prof. Robert Linnen and Prof. Roberta Flemming at the University of Western Ontario are thanked for guiding me through the fluid inclusion and μXRD analysis, respectively.  They were also instrumental in supporting me during the completion of my undergraduate degree and xix  thesis.  They both played an enormous role in inspiring me to study mineralogy and ore deposits and are the reason I was able to find my way to the MRG at UBC.  Last but not least, I am eternally appreciative of the support of my family and friends.  I am particularly grateful to Mackenzie Parker for always allowing me to pick her brain about nearly everything, guiding me through my writing, and sharing “editor nerd moments” with me.             1  1. Introduction  1.1 Importance of Studying Telluride Deposits  In 2012 the United States Department of Energy gave Te a rank of three out of four for "importance to clean energy" and two out of four for "supply risk" in both short (2010–2015) and medium (2015–2025) terms, for an overall rating of "near critical" (with only the heavy rare-earth elements ranking higher). Tellurium is important to the clean-energy industry, as it is used in the production of cadmium-tellurium photovoltaic cells for solar panels. Other uses for tellurium include improving the machining properties of steel and as a vulcanizing agent for the chemicals industry, among many other things (Hoffmann et al. 2011). Global estimates from a 2017 USGS report (prepared by Anderson 2017) suggest consumption percentages for Te are as follows: 40% solar, 30% thermoelectric production, 15% metallurgy, 5% rubber applications, and 10% other. As of the 2017 USGS report Canada remains the leading source of Te imports to the United States, almost double the amount of China, the next-largest supplier (USGS 2017). Of the wide variety of Au-(Ag)-Te-(Se) deposits found worldwide the most common are intrusion-related (e.g., intrusion related gold systems, IRGS), epithermal, and orogenic deposits. Telluride enrichment also occurs in Au-rich VMS deposits, porphyry-Au(Cu) deposits, and Au skarns (Ciobanu et al. 2006, Cook et al. 2009). In order to determine the character of a deposit, one must evaluate the telluride ± selenide mineralogy and phase relationships before assessing the ore genesis processes (Cook et al. 2009) because knowing the mineralogy is critical for determining the conditions of ore formation (Ciobanu et al. 2006). Investigating the relationship between the mineralogy and physiochemical characteristics of a deposit can help determine the 2  conditions under which Te-bearing ore formed.  This relationship has been the focus of many recent telluride studies (e.g., Pals & Spry 2003, Fadda et al. 2005a, b, Ciobanu et al. 2006c, Scherbarth & Spry 2006, Vikentyev 2006, Voudrais et al. 2011), and will be the main focus for this research paper as well.  1.2 Au-(Ag) Telluride Transport and Deposition  In a particular deposit, the mechanisms involved in Te transport and local setting can determine whether Te-rich ore will precipitate separately from native Au or at the same place as native Au (Cook et al. 2009).  Studies such as Cooke & McPhail (2001) state that magmatically derived Te can be transported as aqueous/vapour species in a hydrothermal fluid.  Precipitation can occur due to either multi-stage boiling, pressure-variation, or fluid-rock interaction. The process of Te transport (via hydrothermal fluids) and precipitation (due to multi-stage boiling) can be observed, for example, in certain epithermal porphyry systems at <5 km depth (e.g., Jensen & Barton 2000), but it is not applicable to all epithermal deposits (Cook et al 2009). Phase separation and precipitation of Te-bearing Au±Ag deposits formed in deeper settings (>5 km), such as in orogenic systems, is commonly attributed to a large drop in fluid pressure (Cook et al. 2009 and references therein), but not in every type of Te-bearing orogenic deposit. Finally, an association between alkaline magmatism and Te-bearing epithermal mineralization is observed worldwide (e.g., Emperor, Cripple Creek, Montana Au-Ag belt). This association between the presence of tellurides and alkaline magmatism is thought by Jensen & Barton (2000) to be highly dependent on the melting of Te-rich ocean floor sediments (an important source for mantle-derived alkaline-rich magmas) that form in subduction settings, but some authors 3  question this association and think it is exaggerated in the literature (Cook & Ciobanu 2005, Ciobanu et al. 2006).  Therefore, no matter which deposit type is considered, the mechanisms behind Te-transport and precipitation need further investigation so that more coherent arguments can be made on how tellurides form. Grundler et al. (2013) has also stated that the chemistry behind the hydrothermal processes involved in the formation of Te-bearing phases is still not well understood, despite the relationship seen between Au and Te in many orogenic, epithermal, and magmatic-hydrothermal ore deposits (Ciobanu et al. 2006, Grundler et al. 2013). In one scenario, we know that slightly basic and mildly reduced aqueous fluids can transport Au and Te species, as shown by the thermodynamic calculations of Grundler et al. (2013). Gold is transported efficiently as Au(HS)2– and can also incorporate significant amounts of Te, depending on the temperature and pH of the fluid; for example, at about 300 °C somewhat basic, reduced fluids can transport substantial amounts of Au as Au(HS)2– and approximately 100 ppb of Te. Another scenario suggests that, under magmatic-hydrothermal conditions, oxidized fluids (accompanied by gaseous SO2) can transport large quantities of Te as Te(IV) complexes. The precipitation of telluride minerals can occur when reduction of Te(IV) from fluid occurs (either via  fluid–rock interaction or fluid mixing interaction), causing the solubilities of Au and Te to decrease, which allows for the precipitation of Te-mineralization (Grundler et al. 2013).        4  1.3 Tellurium Extraction and Recovery  The extraction and recovery of tellurium is done mainly by cyanide heap leaching. It is important to note that although the occurrence of telluride minerals is relatively widespread, they generally do not form large ore bodies, meaning a deposit will not be mined solely for Te. It is common that as a result of mining base-metal sulfide deposits (rich in Cu, Ni, Au, Ag, and Pb) the recovery of Te is inevitable if it is present (Hoffmann et al. 2011). Although some of the data are estimated or withheld, Table 1.1 (modified from USGS 2017) shows an estimate of the world production and reserves of Te from refineries from 2015 and 2016. This estimate only includes Te contained in Cu reserves and assumes that about half of the Te in unrefined Cu-anode slimes is recoverable (USGS 2017). It has been calculated that after treating 500 t of copper ore, about 1 lb of tellurium is produced (Hoffmann et al. 2011).  TABLE 1.1 WORLD REFINERY PRODUCTION AND RESERVES OF TELLURIUM  Refinery production Reserves  Country 2015 2016e   United States W W 3,500 Canada 9 10 800 Japan 37   Peru - - 3,600 Russia 35 35 n.a. Sweden 33 33 670 Other countries  n.a. n.a. 16,000 World total (rounded) n.a. n.a. 25,000 Notes: Table modified from Anderson (2017).  n.a. – not available; W – withheld; e – estimated.    5  1.4 Scientific Significance and Scope of the Thesis   The presence of Bi-rich tellurides at Deer Horn are of particular interest, as there is research showing that Bi can play an important role in the scavenging of Au (Ciobanu et al. 2005, 2006, Tomkins et al. 2007, Tooth et al. 2008, 2011). Past research suggests that the Au-scavenging mechanism of Bi-Te melts can form the basis of a model for the distribution of telluride minerals in Au deposits worldwide (Ciobanu et al. 2005). This thesis will offer another Au-(Ag) telluride deposit as an example for observation and comparison of potential correlations between Bi and the location and style of telluride mineralization. Examining the processes behind the transport and precipitation of Te-bearing Au-Ag phases at Deer Horn (as well as determining what type of deposit Deer Horn is) can provide another example to assess what type of mechanisms are at work during the formation of tellurides in certain environments, and potentially shed light on the discrepancies discussed in Section 1.2. On a macroscopic scale, this study is significant because it contributes more information about the mineral endowment of western British Columbia, especially since it is located in the Stikine terrane, one of the most significant areas for metal resources (especially Au and Cu) in the province (MacIntyre et al. 1994). Research on the Deer Horn deepens our understanding of the conditions of formation of Au-Ag-Te deposits, and encourages further mineral exploration in surrounding areas. Deer Horn is particularly interesting from a genetic standpoint, as there are very few Au-telluride occurrences in British Columbia, and other Au-Te systems along the western coast of the United States are typically associated with alkaline systems, unlike the calc-alkaline system at Deer Horn. 6  The goal of this research was to determine temporal and spatial geologic relationships and mineralogical and geochemical properties underlying the Au-Ag-Te- and W-rich mineralization found at the Deer Horn property by: (1) carrying out a thorough qualitative analysis of the mineralogy of the multiphase quartz ± sulfide vein system that hosts the mineralization using optical microscopy, scanning electron microscopy (SEM), and panchromatic cathodoluminescence (CL) spectroscopy; (2) carrying out quantitative analyses of all types of mineralization found at the deposit using X-ray diffraction for crystal structures, electron probe micro-analysis (EPMA) for chemical compositions, and sulfur isotopes to determine the origin of sulfur; (3) resolving possible genetic and spatial associations between the veins, surrounding host rocks, granitic intrusions, and dikes; (4) examining the physiochemical properties of the fluids involved in telluride formation using fluid inclusion microthermometry and comparing the results with other telluride occurrences worldwide; (5) conducting sulfur isotope analysis to determine the source of S in the rocks; and (6) attempting to determine a deposit classification type. Specific methods including petrography, SEM, EPMA, microthermometry, and sulfur isotope analysis were chosen to mirror other telluride deposit studies in the literature (e.g., Spry et al. 1996, Spry et al. 1997, Pals & Spry 2003, Scherbarth & Spry 2006, Tombros et al. 2007, Fornadel et al. 2011) so that similarities and differences can be drawn between Deer Horn and other Au-Ag-Te deposits worldwide.  This study also provides the sponsor company with mineralogical and geochemical information which can be used to create a more detailed deposit model that will hopefully aid in further exploration and drilling decisions.      7  2. Background   2.1 Location of the Deer Horn Deposit  The Deer Horn Au-Ag-Te occurrence is located on the southern slope of Lindquist Peak, which lies on the eastern edge of the Coast Range in the North American Cordillera in west-central British Columbia (53°21’43” N, 127°17’19” W) (Fig. 1.1) (Lane 2009, Lane & Giroux 2012, Lane et al. 2013). It is situated in the Skeena-Nass region, which the British Columbia Geological Survey (BCGS) deemed one of the most richly endowed mineral resource areas in the province, with over 1950 mineral occurrences (mostly base and precious metal deposits) recorded in the MINFILE data base (MacIntyre et al. 1994).             Figure 1.1 A simplified map of British Columbia with a yellow star indicating the location of the Deer Horn property (Deer Horn Metals Inc., 2014). 8  Prior to this study, a distinct deposit classification type had not been determined for the Deer Horn occurrence as a whole, as the deposit contains a variety of intrusion-related, skarn-, orogenic-, and/or porphyry-like characteristics and has experienced multiple deformation, shearing, and recrystallization events. Four separate mineral occurrences have been identified on the Deer Horn property and are filed in the MINFILE inventory of the BCGS: (1) the principal deposit type of the property, which has received the most exploration and  is the primary focus of this thesis, is the Au-Ag-Te-base metal vein system (Deerhorn, Minfile 093E 019); (2) two narrow polymetallic veins (Old Timer, Minfile 093E 021) composed mostly of pyrite, galena, sphalerite, and pyrrhotite with up to 44.6 g/t Ag and lesser amounts of gold; (3) a tungsten-rich area comprised of quartz diorite and altered volcanic and sedimentary rocks that host a narrow network of scheelite-bearing quartz veins (Harrison Scheelite, Minfile 093E 020), which was described by Sinclair (1995a) as a potential porphyry tungsten system; and (4) a molybdenum occurrence (Cob, Minfile 093E 045) composed of molybdenite-bearing quartz veins which cross-cut andesitic volcanic rocks. This Mo mineralization was described by Sinclair (1995b) as a porphyry molybdenum system (low F-type) that occurs along the margins of an Eocene granodiorite intrusion. More recently, copper-rich staining was found slightly northwest of the W occurrence, but this has not yet been formalized as a separate Minfile occurrence (Lane, pers. commun.). Figure 1.2 gives a general overview of the locations of the major mineral occurrences on the property, although the exact relationships between the Au-Ag-Te quartz ± sulfide vein system, the W mineralization 1 km to the west, and the copper showings to the northwest are unclear. Presently it is thought that the polymetallic Au-Ag-Te vein system is genetically related to the Eocene-aged Nanika granodiorite intrusion complex (Fig. 1.3) (Diakow & Koyanagi 1988a, Childe & Kaip 2000, Renning et al. 2007, Lane et al. 2013). 9                         Figure 1.2 An overview of the locations of the major mineral occurrences on the property from the Deer Horn Metals Inc. (2014). These occurrences include the Au-Ag-Te vein system, area of tungsten mineralization, and new copper showings to the northwest. The Deer Horn mine adit is located at the red tri-point symbol. 10                         Deer Horn (Lindquist Lake at center of circle for a point of reference) Figure 1.3 Map of the MINFILE occurrences in British Columbia and the distribution of Cretaceous and Tertiary volcanic-arc rocks. The red circle is the approximate location of the Deer Horn property showing a part of the Nanika Plutonic Suite (dark pink) directly to the right of the circle.  (Figure modified from MacIntyre 2006). 11  2.2 Regional Geology  The northern Cordillera formed over a period of 1.8 Ga and has a complex tectonic history, from the cratonization of the continental core of Laurentia to its current state of subduction and transform motion along the westernmost margin (Nelson & Colpron 2007). The wide variety of metallogenetic styles that comprise the mineral wealth of the Cordillera can be attributed to many tectonic settings evolving over time, from the Proterozoic intacratonic basins forming via Paleozoic rifting to the assemblage of Mesozoic to Early Cenozoic intraoceanic and continental margin arcs (Nelson & Colpron 2007). The northern part of the Cordillera of British Columbia, Yukon, and Alaska is divided into five major tectonic belts (sometimes referred to as superterranes) that were accreted onto the westernmost margin of North America throughout the Mesozoic and Early Cenozoic periods (Price 1994, Monger & Price 2002, Nelson & Colpron 2007). From oldest to youngest (east to west) these are the Foreland, Omineca, Intermontane, Coast, and Insular belts (Fig. 2.1) (Monger & Price 2002). The Deer Horn occurrence is located in the Intermontane tectonic belt, where it contacts the eastern edge of the Coast tectonic belt (Lane et al. 2013). The physiographic units found in the Intermontane belt are the Interior, Skeena, and Yukon plateaus, as well as the Skeena Mountains (Monger & Price 2002). Common rock types of the Intermontane belt include sedimentary, ultramafic, mafic, and arc volcanic rocks, as well as plutonic rocks, all of which have undergone less metamorphism than rock units in the Omineca belt to the east and the Coast tectonic belt to the west (Price 1994). More specifically, the relative ages, compositions, and tectonic characters of the most common rock types in the Intermontane belt include: (1) Devonian to Early Jurassic rocks which are sedimentary to volcanic in composition and formed in island arcs and accretionary complexes 12  that were chert-rich; (2) Middle Jurassic to Early Cenozoic volcanic rocks formed most commonly in continental arcs; (3) Middle Jurassic to Early Cenozoic marine and non-marine clastic rocks which formed via erosion of the uplifting Omineca Belt; and (4) Devonian to Cenozoic granitic rocks that were deformed primarily by Mesozoic compression and Early Cenozoic extension-transtension (Monger & Price 2002). Some of the major terranes found in the Intermontane belt include the Cache Creek, Stikine, Quesnel, and Slide Mountain terranes. Deer Horn is located in the Stikine terrane (Fig. 2.2).   Figure 2.1 (top) A birdseye view map and (bottom) a cross section of the five major tectonic belts in British Columbia. From oldest to youngest (east to west) these are the Foreland, Omineca, Intermontane, Coast, and Insular belts (Monger & Price 2002).  Deer Horn is located in the Intermontane tectonic belt, where it contacts the eastern edge of the Coast Plutonic Complex.  13          Figure 2.2 Regional map of the Canadian and Alaskan Cordillera showing the most prominent terranes of British Columbia (Nelson & Colpron 2007).  Deer Horn is located in the Stikine terrane (light forest green).  14  The stratigraphy of the Stikine terrane is quite complex, with the oldest rocks being the Stikine and Asitka assemblages, which comprise Devonian to Permian sedimentary rocks with volcanic strata interbedded between successions (Grainger et al. 2000, MacIntyre et al. 2001, Nelson & Colpron 2007). Stratigraphic and faunal resemblances between the Stikine and Quesnel terranes suggest that the former could be a fragment of the Late Paleozoic to Early Mesozoic age island arc that originated from the Quesnel terrane (Monger & Price 2002). The formation of the Stikine terrane was followed by the Stuhini and Takla groups of Late Triassic age, which are composed mainly of porphyritic pyroxene basalts and basaltic andesites and pyroxene-feldspar-porphyritic flows, and lesser amounts of siltstones and conglomerates. Hazelton Group strata overlie the Late Triassic rocks; these are Early to Middle Jurassic, mostly volcaniclastic sedimentary rocks and calc-alkaline basalt to rhyolite. A terrane collision occurred after the formation of the Hazelton Group, causing the Bowser Basin sedimentary rocks to align with the Skeena Arch, beginning the formation of the overlap assemblage (i.e., a set of lithostratigraphy which overlies a particular terrane) that overlies the Stikine terrane (Alldrick 1993, MacIntyre 2006). A detailed schematic of the stratigraphy of the Stikine terrane and its overlap assemblage is shown in Figure 2.3 (modified from Alldrick 1993).        15                   Intrusive rocks in the Stikine terrane and Skeena Arch exhibit the commonly observed magmatic evolution of the Canadian Cordillera: episodic pulses which had different extents, locations, intensities, and durations depending on which type of motion the plate was experiencing at the time (Grainger et al. 2000, MacIntyre 2006, Nelson & Colpron 2007). In the Stikine terrane, the major intrusive rocks include the Late Triassic to Early Jurassic Topley and Early to Middle Jurassic Spike Peak suites, both of which are composed of granodiorite and Figure 2.3 Schematic of the stratigraphy of the Stikine terrane and its corresponding overlaps (modified from Alldrick 1993). 16  quartz diorite. In the Skeena Arch, the Buckley intrusions formed circa 78 Ma, followed by another pulse in the Early to Middle Eocene (approximately 55–45 Ma) (MacIntyre 2006). A widespread group of small, high-level Eocene dikes forms the core of the Skeena Arch and includes three major intrusive suites: (1) the Goosly Lake gabbroic suite, (2) the Babine granodiorite suite (associated with Cu porphyry deposits in the area, Nelson & Colpron 2007), and (3) the Nanika granitic suite (thought to be related to the main mineralizing event at the Deer Horn occurrence; Renning et al. 2007). Figure 2.4 summarizes the extent of intrusive activity across the Stikine terrane and Skeena Arch from 240 Ma to the present (Alldrick 1993). Figure 2.5 outlines similar information as Figure 2.4 but shows more specific ages (using U-Pb and 40Ar/39Ar data) of various intrusive and extrusive events that occurred in the area, most importantly, the Nanika intrusives (Grainger et al. 2000). Figure 2.6 is a simplified schematic cross-section showing a summary of the major stratigraphy and magmatism throughout the Stikine terrane and Skeena Arch (MacIntyre 2006). Finally, Figure 2.7 is a regional geologic map (modified from the British Columbia Geological Survey) of the rock types surrounding the Deer Horn occurrence (study area found in the red rectangle).  17   Figure 2.4 Intrusive activity in the Stikine terrane of the Canadian Cordillera showing the  timing of the emplacement of the Nanika Suite (Alldrick 1993).         18   Figure 2.5 Geologic time scale showing intrusive and extrusive activity in the study area.  Data is positioned based on U-Pb and40Ar/39Ar dating (Grainger et al. 2000).           19  Figure 2.6 Stratigraphic and magmatic relationships between the Stikine Terrane and  the Skeena Arch (MacIntyre 2006).                        Figure 2.7 A regional geological map of the area surrounding the Deer Horn occurrence (red rectangle), in which the extent of the Eocene (Tertiary) intrusive granites (pink) can be observed.  Geological rock type found in legend to the left.  The Deer Horn property is indicated with a red box (map and legend modified from the British Columbia Geological Survey). 20  2.3 Local Geology  The Deer Horn occurrence is located close to the contact between the Coast Range batholith and a group of pre-Jurassic to Early Cretaceous siliceous to shaly sediments. This contact occurs along a thrust fault that strikes E–W and dips approximately 50° to the south (Papezik 1957). The oldest rocks exposed in outcrop near the occurrence are a pre-Jurassic quartz diorite on the southwest side of Lindquist Peak and pre-Early Jurassic mafic volcanic and volcaniclastic strata; the youngest rock type exposed in the area is Eocene granodiorite which is thought to form part of the Nanika intrusive complex (Renning et al. 2007). The Deer Horn occurrence is primarily underlain by meta-volcanic rocks of the Gamsby Group and foliated quartz diorite, both of pre-Jurassic age, which were thrust on top of layered volcanic strata of the Early to Middle-Jurassic Telkwa Formation (Hazelton Group) and the Skeena Group, a sedimentary package of Late Cretaceous rocks (Duffell 1959, Childe & Kaip 2000, Lane et al. 2013). All of the aforementioned rock types are intruded by (1) the Coast Plutonic Complex, comprising Late Cretaceous to Tertiary granodiorite and quartz diorite, along the southeastern flanks of Lindquist Peak (Childe & Kaip 2000); and (2) Eocene granodiorite and associated dikes (Diakow & Koyanagi 1988a, Lane et al. 2013). Figure 2.8 is a recent local geological map of the Lindquist Lake area showing the relationship between various rock types and the claim boundary of the property (modified from Lane & Giroux 2012). This Figure also shows (with yellow stars) the locations of each of the four BCGS MINfile inventory occurrences in the study area. A more detailed surface map of the immediate geology around the Au-Ag-Te vein system (Fig. 2.9, modified from Duffell 1959) gives an outline of the geology surrounding 21  the main mineralized area on the property. All of the drill-hole samples for the present study were obtained from this area.                     Figure 2.8 A recent local geological map of the Lindquist Lake area showing the relationship between various rock types and the claim boundary of the property in pink (modified from Lane & Giroux 2012).  Yellow stars represent each of the four BCGS MINfile inventory occurrences within the study area.  The red four-pronged star represents the top of Lindquist Peak and the black line through the property represents the major thrust fault. 22                  Figure 2.9 Digitally recreated geological map of surface outcrops around the Deer Horn occurrence, showing the silicified zone (yellow), where the Au-Ag-Te vein system mineralization occurs, is mostly near the contact between foliated quartz diorite (purple) and sedimentary/greenstone rock packages (Skeena Group). The red granite is the Eocene granodiorite/granite from the Nanika intrusive suite (map modified from Duffell 1959).    23  2.3.1 Sedimentary Rocks  Cretaceous Skeena Group. Folk (1990a) separated strata in the Skeena Group into four distinct units based on lithology, even though they appear to grade into each other (Lane & Giroux 2012). They are listed from highest to lowest based on their structural sequence: (1) quartzite with a blocky form in outcrop is a very fine-grained rock with a pale grey to yellow-grey colour. Locally fine-grained disseminated pyrite is found in fractures in the quartzite; (2) greywacke of multiple lithologies from quartzite to argillite with varying amounts of metamorphic foliation has colors ranging from greenish-grey to greyish-brown to greenish-brown, depending on the amount of weathering that has occurred; (3) argillite is brownish-black and has a phyllitic sheen to the naked eye, with highly indurated, thin layers which, in some areas, are metamorphosed to andalusite schist. Andalusite megacrysts are up to 3 mm in size with varying amounts of sericitic alteration; (4) feldspathic greywacke is fine-grained, breaks with a conchoidal fracture, ranges from medium to dark grey in color, and weathers to a pitted and grainy surface. This rock type was not encountered during drilling and was only observed in outcrops on Lindquist Peak (Folk 1990a, Lane & Giroux 2012, Lane et al. 2013).        24  2.3.2 Metamorphic Rocks  Pre-Jurassic Gamsby Group. The meta-volcanic rocks of the pre-Jurassic Gamsby Group occur west and south of Lindquist Lake and consist of greenish-grey tuffs, flows, and schists that are metamorphosed to greenschist facies and are composed of epidote, albite, and chlorite. The Gamsby Group is spatially associated with a quartz diorite of similar age which intrudes the lower level of the Gamsby succession (Diakow & Koyanagi 1988a, Lane et al. 2013). An east-striking, south-dipping thrust fault places them both structurally above the Early Cretaceous strata of the Skeena Group (Childe & Kaip 2000). The major deformation of the Gamsby Group is defined by a penetrative foliation and locally sheared texture (Diakow & Koyanagi 1988a, Lane et al. 2013). Early Jurassic Telkwa Formation. Volcanic rocks of the Early Jurassic Telkwa Formation (Hazelton Group) underlie a substantial part of the north to northwest portion of Lindquist Peak and consist mostly of pyroclastic flows of alternating crystal-lapilli tuff and ash tuff lava flows (Lane & Giroux 2012, Lane et al. 2013). Diakow & Koyanagi (1988a) described the characteristic maroon to red and locally green color of these well-bedded rock units, which are mainly in fault contact with the younger strata of the Skeena Group.  2.3.3 Plutonic and Intrusive Rocks  Pre-Jurassic Quartz Diorite. The bulk of the central area of interest at the occurrence is composed of a faintly to intensely foliated, commonly highly altered, pale to dark green quartz diorite which is spatially associated with metavolanic rocks of similar age. It is the primary host 25  rock for the Au-Ag-Te vein system (Lane et al. 2013). This unit is exposed from the Deer Horn mine adit (location shown in Fig. 1.2; red tri-point symbol) in the north to approximately 100 m south, along the shores of Lindquist Lake (Childe & Kaip 2000). This rock unit consists of fine- to medium-grained quartz, plagioclase, and 10–35% hornblende, which is typically altered entirely to chlorite (Lane et al. 2013). The intensity of deformation increases close to the Main Zone (MZ) and Contact Zone (CZ) (these zones are described in more detail in Chapters 3 and 4) of quartz veins, where the thrust fault emplaced the quartz diorite over the younger volcanic and sedimentary strata and where a strong foliated fabric is observed (Childe & Kaip 2000, Renning et al. 2007, Lane & Giroux 2012, Lane et al. 2013).  Cretaceous/Tertiary (Paleogene/Eocene) Granodiorite. The Eocene granodiorite is thought to belong to the Nanika plutonic suite, which has a high quartz and K-feldspar content and has been classified as a calc-alkaline intrusion (Wojdak & Febbo 2008). The Eocene granodiorite is typically pale grey in color and is medium- to coarse-grained with a porphyritic to equigranular texture. Minerals consist of quartz, plagioclase, K-feldspar, and up to 10% accessory biotite, which ranges from fresh vitreous crystals to highly altered patches of chlorite (Childe & Kaip 2000, Renning et al. 2007, Lane et al. 2013). The granodiorite unit is in intrusive contact with the Gamsby and Skeena group strata, all of which are cut by felsic dikes associated with the main body of granodiorite (Renning et al. 2007, Lane et al. 2013).  Dikes. Mafic dikes were observed both on the surface and in drill core and occur in many different orientations. They are about 1 m in width with a dark-grey to dark-greenish color and contain <1 mm diameter phenocrysts of feldspar and disseminated magnetite. Felsic dikes are 26  light greenish-grey and moderately siliceous with fine-grained plagioclase, quartz, and K-feldspar (Papezik 1957, Lane et al. 2013). They commonly have calcite filling cavities or pockets and weather to a light beige to medium brown color, locally with minor spots of Fe oxidation (Folk 1990a, Lane et al. 2013).  2.4 Structural Relationships  The Deer Horn occurrence is positioned on an east to west-striking thrust fault that dips moderately to the south, which places volcanic rocks of the pre-Jurassic Gamsby Group and the foliated quartz diorite structurally on top of the sedimentary strata of the Early Cretaceous Skeena Group (Duffell 1959, Folk 1990a, Childe & Kaip 2000). The penetrative fabric of both the quartz diorite and sedimentary strata exhibit an east to west trend, with planar bedding features striking from 076 to 081° and foliation in the quartz diorite trending 077 to 122°; both dip about 50° to the south (Fig. 2.10). Further indications that thrusting motion may have affected the rocks in the area include the presence of pervasive crenulation cleavage and minor folds and fault splays on the western edge of the occurrence. It is difficult to discern the thrust fault when in the mine adit because successive alteration and mineralization events have completely obscured it (Renning et al. 2007). The main thrust fault is cut and offset by a series of smaller, younger NW–SE and NE–SW striking faults. The NW–SE faults tend to bound the main zones of mineralization (Childe & Kaip 2000, Renning et al. 2007, Lane et al. 2013). When examined in outcrop, these smaller faults have numerous mineralized quartz veins (some with a sigmoidal morphology), suggesting that one or more shearing events occurred during the mineralizing event (Folk 1990a). Therefore, 27  Figure 2.10 Schematic cross-section showing the geometry of the thrust fault and vein system containing the Main Vein and Contact Zone at the Deer Horn Property (by Roberts & Chudy 2017). it is possible that metal-rich hydrothermal fluids from the granodiorite intrusion invaded a pre-existing local thrust fault and followed smaller right- and left-lateral fault structures, creating a conduit along which Au-Ag-Te mineralization could precipitate. Some of the younger previously mentioned faults also correlate with linear magnetic lows, which could potentially be due to hydrothermal fluids altering magnetite along fractures and conduits in the rock (Renning et al. 2007, Lane et al. 2013); hematite, a common oxidation product of magnetite, is found in and near fault zones. Dikes. A set of mafic dikes, less than 1 m wide on average, trend marginally north of east and dip steeply towards the south. They locally occur in argillite, close to the sedimentary strata-quartz diorite contact, and also intrude the quartz diorite in multiple locations (Renning et al. 2007, Lane et al. 2013). The felsic dikes in the area are much larger and more commonly identifiable across the property. Individual dikes been traced for about 800 m along strike and cut both sedimentary strata and the quartz diorite. In outcrop the dikes form irregular shaped bodies with amygdaloidal characteristics (Lane et al. 2013). Minor folding, crenulation cleavage, and vein offsets near these dikes indicate that the thrust fault was reactivated after dike emplacement and may have caused the aforementioned products of deformation (Renning et al. 2007).  28  2.5 Mineralization and Alteration  2.5.1 Au-Ag-Te Vein Mineralization  The near-surface Au-Ag-Te base-metal quartz vein system extends for approximately 2.4 km (Fig. 1.2). Only a third of the eastern part of the 2.4 km strike length vein system has been delineated by diamond drilling. The drilled section contains the two main geological structures that host the bulk of the mineralization. These structures are: (1) the MV (Main Vein – a series of somewhat flat, echelon-shaped veins, up to 4.5 m thick, which cross-cut foliation) (blue area in Fig. 2.10); and (2) the CZ (Contact Zone – an area directly above and parallel to the thrust fault) (brownish-yellow area in Fig. 2.10); both are located in the Main Resource Area (MRA), are thought to conjoin at depth, and are associated with narrower quartz veins and stringers. The investigated vein and stockwork system is located in an area that is 875 m long, with 450 m of it being particularly Au-Ag-Te-rich (Lane 2013). The mineralization is hosted within this vein system and was developed in the intermediate hanging wall of the thrust fault described above (a birdseye view of the thrust fault can be seen in Fig. 2.8) (Childe & Kaip 2000, Renning et al. 2007, Lane & Giroux 2012, Lane et al. 2013). The MV and CZ occur within 250 m of the contact between the quartz diorite and Skeena Group and are characterized by many stringer zones and other narrow veins (Lane & Giroux 2012, Lane et al. 2013). The white to translucent-grey quartz veins of both the MV and CZ crosscut quartz diorite, greywacke, quartzite, and granodiorite and most exhibit similar mineralogy, including pyrite, pyrrhotite, galena, sphalerite, chalcopyrite, and magnetite. Precious metals (Au-Ag) are hosted in telluride minerals that appear to display a positive correlation with 29  sulfide content. Telluride minerals (e.g., hessite, altaite, tellurobismuthite) are typically found as disseminations or in small patches throughout micro-fractures in quartz veins. Folk (1990a) observed that quartz veinlets and stringer zones occur in areas where the CZ and MV meet and concluded that it is possible that the vein systems developed simultaneously; however, because of their differing geometries in certain areas, Lane et al. (2013) characterized the CZ as a “fault-filled” vein system and the MV as an associated “extensional vein” system. Assays obtained for a 450 m stretch of the 2.4 km vein system show an indicated resource of 429,000 tonnes at 4.97 g/t Au (68,000 contained ounces or 1928 kg), 153.42 g/t Ag (2,120,000 contained ounces or 61,100 kg), and 158 ppm Te (67,782 contained kg) (Lane et al. 2013). Some other notable assay results from drill cores from the MZ include 16.76g/t Au and 605.2g/t Ag (Childe & Kaip 2000). The MV mineralization in the hanging-wall quartz diorite occurs as a series of en echelon quartz veins that strike west and dip 20–45° to the north and are several meters in width and up to 100 m along strike (Folk 1990a, Childe & Kaip 2000). Papezik (1957) observed from underground mapping that the dip of the MV changes to a more shallow (>20°) southerly dip as it impinges on the CZ, which Papezik (1957) suggested could be the result of drag folding related to reactivation of normal movement along the thrust fault. Figure 2.11 shows drill holes (black, yellow, and blue numbers with red pointers indicating the direction and approximate length of the hole) as well as how the distribution of Au-Ag-Te mineralization throughout the MV (red-filled areas) appears to be controlled by the northwest-striking faults (black lines), because mineralization grades highest in the zones with quartz veins and significant alteration (purple-filled area) increases at the intersection point between the northwest-striking faults and the MV (Renning et al. 2007). The CZ strikes west and dips 55–60° south and occurs in the area directly above and sub-parallel to the thrust fault (Joubin 1950, Lane et al. 2013). The 30  mineralization in the CZ commonly occurs in 1.8 m-wide quartz veins and in a series of multiple stringer zones up to 4.6 m across, typically near patches of sericite-rich alteration within quartz diorite. Both wide, potentially bulk-tonnage Au-Ag mineralization and narrow, high-grade Au-Ag veins occur on the property. An interval from a narrow high-grade vein (from drill hole 90-57) 11.2 m in length, from about 44.1–55 m depth and 210 m west of the adit portal, showed noteworthy grades averaging 14.36 g/t Au, 781.5 g/t Ag, 1.02% Zn, 0.40% Cu, 0.34% W, and 0.24% Pb (Renning et al. 2007, Lane & Giroux 2012, Lane et al. 2013). Diakow & Koyanagi (1988a) tested a section of sericite alteration from the CZ and interpreted the age of the sericite, 56 ± 2 Ma, to be synchronous with the Au-Ag-Te vein mineralization. This is similar to the age of the neighboring Nanika granodiorite pluton, for which K-Ar dates from biotite range from 57–48 Ma (Grainger et al. 2000 and references therein). This indicates that the vein-mineralizing event and intrusive granodiorite body both occurred in the Early Eocene and are likely genetically related. This is supported by the field observations that quartz veins cut all lithologies, including the granodiorite (except for dikes), and both the granodiorite and vein system cut the thrust fault, indicating that the thrust fault is significantly older than the mineralization, but did provide a structural channel for the movement of hydrothermal fluids along the planes of weakness (Folk 1990a, Lane & Giroux 2012, Lane et al. 2013).     31   Figure 2.11 The distribution of Au-Ag-Te mineralization throughout the MV (red) appears to be structurally controlled by the northwest-striking faults (black lines) because mineralization grades highest in the zones with quartz veins and significant alteration (purple) increases at the intersection point between the northwest-striking faults and the MV (modified from Renning et al. 2007).  The position of drill-hole sample numbers are in yellow, blue, and black. 32  2.5.2 Tungsten Mineralization  The Harrison scheelite deposit (the area shaded in cross-hatched squares in Fig. 2.9) on the Deer Horn property is located in an area of extensive talus about 1 km SW of Lindquist Peak and directly west of the Au-Ag-Te vein system, roughly 250–300 m from the west end of the MV. There are two distinct areas of talus which trend sinuously NW and are situated near the contact between Hazelton Group sedimentary-volcanic rocks and rocks of the Coast Range Batholith (diorite, quartz diorite, and granite) (Diakow & Mihalynuk 1987b, Lane et al. 2013). The bulk of the tungsten mineralization occurs as scheelite in narrow quartz veins and stringers hosted in the diorite and altered volcanics and sedimentary rocks. The mineralization occurs over an area of about 485 m by 50 m. Duffell (1959) reported on a detailed sampling study of the talus which yielded a total weighted average of 0.35% WO3, with various bedrock samples collected from a 40 m trench that averaged up to 1.55% WO3 over 22 m. A schematic diagram of each sampled area of talus and the corresponding WO3 average is presented in Figure 2.12 (from Duffell 1959).  33   Figure 2.12 Scheelite-bearing talus showing the WO3 weighted averages from samples collected by Duffell (1959).  2.5.3 Molybdenum Mineralization  The molybdenum occurrence at Deer Horn, labelled Cob in the Minfile data base, is located in the easternmost part of the property (Fig. 2.8). Although only a small amount of prospecting and geochemical sampling has been done on this showing, chemical analyses of 11 rock samples and four soil samples collected by Renning et al. (2007) yielded up to 1350 ppm Mo. Additional sampling of stream sediments also showed unusually high levels of Mo, but no follow-up studies have been attempted thus far.   34  2.5.4 Alteration  Quartz-sericite alteration. The most common type of alteration found at Deer Horn is quartz-sericite, which occurs in both the quartz diorite and sedimentary strata near the thrust fault contact of the CZ (Folk 1990a, Childe & Kaip 2000, Lane & Giroux 2012, Lane et al. 2013). The highly altered rocks are a distinct pale-green to off-white color, are very sericitized and silicified, and are cut by quartz stringer veins. The foliation in the rocks is locally masked by intense silicification (Folk 1990a). With increasing distance from the CZ thrust contact, within the hanging wall of quartz diorite, nearly all of the mafic minerals have been destroyed and altered to chlorite ± actinolite (Folk 1990a, Childe & Kaip 2000), and sericite is still present but is not as frequent. The localized nature of the quartz-sericite alteration indicates it is likely related to fluids moving along fractures and faults, because the amount of alteration significantly decreases away from these structures (Folk 1990a).  Quartz-epidote alteration. Within the footwall of the thrust fault, the quartz-sericite alteration begins to grade into quartz-epidote alteration, called “epidote skarn alteration” by Folk (1990a). This quartz-epidote alteration most commonly affects the sedimentary strata located close to the thrust fault contact, especially in the greenish-brown greywacke unit where patchy, skarn-like bands occur. These bands range from 2–4 m in width and contain 10–50% epidote with moderate to intense silicification. The greywacke is also cut by tiny quartz-carbonate-epidote veinlets (Folk 1990a, Childe & Kaip 2000, Lane et al. 2013). Folk (1990a) remarked that these skarn-like minerals likely formed as a result of metasomatism during intrusion of the Eocene granodiorite pluton. 35  Silicification. Folk (1990a) observed intense silica alteration in drill hole DDH 89-04, where extensive replacement of cataclastic breccia occurs and causes the rock to be light grey in color with a very fine-grained texture, making it nearly impossible to see any remnants of the previously existing rock. The extreme intensity of this alteration and the fact that no one has observed this amount of silicification anywhere on the surface or near the adit indicates that there is likely a deep-seated fluid source nearby (Folk 1990a).   2.6 Previous Analytical Work  In 1987, L.J. Diakow and V. Koyanagi collected a bulk sample of sericite-altered diorite from the Deer Horn occurrence for K-Ar dating in order to determine a possible age for the Au-Ag-Te vein mineralization. Their study (Diakow & Koyanagi 1988a) reported that the age of the sericite alteration which envelopes the Contact Zone is approximately 56 ± 2 Ma. Biotite sampled from a nearby granodiorite intrusion gave a very similar Early Eocene age (57–48 Ma), which suggests that the Au-Ag-Te mineralizing event may be genetically related to the granodiorite (Lane et al. 2013). From 1989–1990, Golden Knight Resources Inc. conducted prospecting, geological mapping, and soil sampling of 2,090 samples across a 1 × 3 km area at the property (Childe & Kaip 2000). A magnetometer survey and underground chip sampling were also conducted for preliminary metallurgical analysis (Folk 1990a, b). These data were reviewed and taken into account by Childe & Kaip (2000) and Renning et al. (2007) in their examinations of the Au-Ag-Te bearing quartz-sulfide veins and molybdenum anomalies, respectively. Renning et al. (2007) 36  reported that the extent of mineralization and high-grade float and grab samples suggest that there is a strong possibility of a sizable bulk-tonnage target at the Deer Horn property. Nine years later, thin sections of six core samples from the 2009 drilling season were studied by Dr. P.C. Le Couteur. The thin sections were selected based on assay content and were examined petrographically to determine the ore minerals for Au, Ag, and Te. Le Couteur concluded that five of the six samples were mostly 40–98% deformed quartz with 3–60% sulfides (pyrite, pyrrhotite, galena, chalcopyrite, and sphalerite) (Le Couteur 2010). The remaining sample contained mostly magnetite. Eight species of telluride minerals were observed (hessite, empressite, stützite, volynskite, hedleyite, tellurobismuthite, tsumoite, and altaite) with grain sizes ranging from 2–200 microns. Most importantly, no native Au or Au-rich telluride minerals were observed (Le Couteur 2010). Further prospecting towards the northwestern part of the property in 2012 led to the discovery of a significant Cu anomaly (up to 4240 ppm Cu and 6.6 g/t Ag in rock samples; Deer Horn Metals Inc. 2014), which may indicate a Cu porphyry in the area; however, no additional research has been done to confirm its presence or relationship to other mineralized areas on the property (Lane, pers. commun.).        37  3. Methodology  3.1 Recent Field Work and Sample Selection  Exploration and drilling done by Deer Horn Metals Inc. from 2009–2011 showed significant quantities of Au-Ag-Cu-W-Te and lesser amounts of Pb-Zn-Mo on the 51 km2 property. Assay results indicate that Au and Ag are present within telluride minerals and prompted additional field work to collect samples for the current study. In September 2014, the author, her supervisor (Prof. Lee A. Groat), and a post-doctoral fellow (Dr. Jan Cempírek) travelled to the Deer Horn property and retrieved 46 samples of drill core. All of the samples were taken from the 2011 drilling season and strategically selected based on their assay grades, zone, and azimuth at the Deer Horn mine site.  This was done to ensure a substantial variety of high-grade Au-Ag-Te samples were chosen for the mineralogical and geochemical investigations outlined in this paper. Each core sample was then photographed with a Nikon digital SLR camera in both regular and short-wave UV light (relevant photographs of core can be found Appendix A.1).  Selected samples were then sent to Vancouver GeoTech Labs to be made into polished thin sections. Table 3.1 provides details of the samples studied, including depth, length of sample interval, assay results for Au and Ag, ICP (inductively-coupled plasma) data for Te, and zone.     38   TABLE 3.1 THE DEER HORN DEPOSIT SAMPLES INVESTIGATED WITH CORRESPONDING DRILL CORE DEPTH, ZONE, AND ASSAY GRADE OF Au AND Ag, AND ICP DATA FOR Te Drill Hole  Specific Field Sample Intervals (m)  Length of field sample interval (m) Entire Sample Interval (m) Assay Grade: Au (g/T) Assay Grade: Ag (g/T) ICP Result:  Te (ppm) Zone  DH09-064A   33.35 33.43  0.08 33.00–35.00 6 90 138 CZ DH09-064B   50.92 50.98  0.06 n/a - - - CZ DH09-073  28.40 28.46  0.06 28.38–29.38 10.3 720.3 495 CZ DH09-079  14.39 14.41  0.02 12.88–14.88 7.29 427.6 266 MV DH09-090  30.36 30.45  0.09 30.00–31.50 2.74 102 - MV DH09-092  19.11 19.20  0.09 18.82–19.52 29.9 1014.1 737 MV DH11-098  18.20 18.30  0.1 16.92–19.00 8.4 84 341.7 EMRA DH11-102  32.40 32.50  0.1 31.00–33.30 3.8 34.5 100.9 EMRA DH11-103  33.00 33.30  0.3 33.05–33.35 20.7 212 543.9 EMRA DH11-104a  10.30 10.40  0.1 7.60–10.60 3.95 107 133 EMRA DH11-104b (i)  9.00 9.10  0.1 7.60–9.10 6.5 166 220.8 EMRA DH11-104b (ii)  35.50 35.60  0.1 34.50–35.70 5.6 99 201.9 EMRA DH11-104c  40.10 40.20  0.1 40.00–40.50 4.4 108 165.1 FV2 DH11-105  18.20 18.30  0.1 18.00–18.80 49.9 1042 1281 HV4 DH11-108  45.95 46.10  0.15 46.00–46.10 369.9 3353 >6000 SGR DH11-110a  30.80 30.90  0.1 30.00–31.60 29.5 896 963.8 MVN DH11-110b  31.10 31.20  0.1 30.00–31.60 29.5 896 963.8 MVN DH11-110c  32.40 32.60  0.2 31.60–33.10 27.8 711 755.1 MVN DH11-110d1  63.00 63.20  0.2 62.70–63.30 25.6 385 691.2 FV1 DH11-110d2  63.00 63.20  0.2 62.70–63.30 25.6 385 691.2 FV1 DH11-110e1  120.80 120.90  0.1 120.20–121.20 11.8 270 379.7 FV7 DH11-110e2  120.80 120.90  0.1 120.20–121.20 11.8 270 379.7 FV7 DH11-110f  72.90 73.00  0.1 71.80–73.60 12.6 510 471.8 FV2 DH11-111a  6.60 6.70  0.1 6.12–7.08 4.9 133 147.6 MVN DH11-111b  7.90 8.00  0.1 7.92–8.80 7.8 274 279.1 MVN DH11-111c  7.80 7.90  0.1 7.08–7.92 20 578 721.7 MVN DH11-111d  8.20 8.30  0.1 7.92–8.80 7.8 274 279.1 MVN DH11-114  20.90 21.10  0.2 19.90–21.30 2.2 155 176.1 FV2 DH11-116a  29.70 30.20  0.5 29.70–30.20 43.8 1136 1562 VN DH11-116b  30.20 30.50  0.3 30.20–31.70 3.5 116 153 VN DH11-120  19.30 19.40  0.1 18.85–19.77 13 572 472.7 MVN DH11-122a  33.00 33.20  0.2 32.50–33.20 14.9 342 430.3 MVN DH11-122b  33.40 33.60  0.2 33.20–34.00 - - 8.7 MVN DH11-127  55.80 56.00  0.2 55.85–56.40 17.2 1282 836.4 MVN DH11-130  10.50 10.60  0.1 9.60–11.28 2.4 114 93.8 COZ DH11-131  50.45 50.54  0.09 50.45–50.54 14.6 748 732.2 STK DH11-135a  103.00 103.10  0.1 102.84–103.1 - - <0.2 n/a DH11-137  44.60 44.70  0.1 44.40–45.00 - - 0.3 n/a DH11-140  54.80 54.90  0.1 54.55–55.25 17.9 1181 744.8 COZ DH11-141  36.80 37.00  0.2 36.10–37.33 13.8 422 381.2 VN DH11-143  40.50 40.60  0.1 45.50–41.00 14.8 588 494.2 COZ DH11-145  33.10 33.20  0.1 32.50–33.30 6.5 117 169 VN DH11-146a  20.80 20.90  0.1 19.5–21.00 - - 9 COZ DH11-146b  41.60 41.76  0.16 41.60–41.76 20 533 468.7 COZ DH11-147a1  67.60 67.80  0.2 67.45–67.85 11.6 71 336.6 FV2 DH11-147a2  67.60 67.80  0.2 67.45–67.85 11.6 71 336.6 FV2 DH11-147b  42.90 43.05  0.15 42.80–43.45 51.8 655 1156 MVN DH11-147c  40.80 42.90  2.1 41.65–42.80 2.1 <50 44.1 SGR DH11-147d  43.05 43.20  0.15 42.80–43.45 51.8 655 1156 MVN DH11-149  21.00 22.00  1 21.00–22.00 7.8 330 303.2 VN DH11-150  37.80 37.90  0.1 37.50–39.00 4.3 87 98.3 COZ CZ – Contact Zone; MVN and VN – Main Vein; EMRA – Resource extension east of main resource area; STR – Stringer mineralization; FV1, FV2, FV7 - Footwall Vein to Main Vein (1 denotes closest FW vein to Main vein, 7 denotes farthest FW vein to Main Vein);  HV4 – Hangingwall vein to main vein (1 denotes closest HW vein to Main Vein, 5 denotes farthest HW vein to Main Vein);  STK – Stockwork mineralization marginal to discrete veins; n/a = not available.  (Intervals, assays, ICP data, and zone location from Lane et al. 2013).  39  3.2 Polished Thin Section Examination  In August 2014, six polished thin sections from the 2009 drilling season were provided by Deer Horn Capital for examination and comparison with the 46 samples from the 2011 drilling season collected in September 2014 by the author and her supervisor. The set of 52 polished thin sections was then examined with optical microscopy using transmitted (plane-polarized and cross-polarized) light to observe non-opaque minerals and reflected light to observe the opaque minerals (sulfides and tellurides). Textures, grain sizes, habits, and the relative order of mineral formation were observed. Special attention was paid to tellurium-bearing minerals because past studies indicated valuable elements such as Au, Ag, Bi, and Pb likely coexisted in the form of tellurides (Childe & Kaip 2000, Lane & Giroux 2012, Lane et al. 2013). Selected digital scans of the polished thin sections in both plane-polarized and cross-polarized transmitted-light are provided in Appendix A (section A.2) as a petrographic reference to show the relative modal estimates and textures of opaque, silicate, and alteration minerals.   3.3 SEM Methodology  After inspecting the samples with optical microscopy, the thin sections were examined with a Philips XL30 scanning electron microscope, equipped with a Bruker Quantax 200 energy-dispersion microanalytical system, at 15.0 kV, to study characteristics of the telluride minerals and environments they commonly occur in. A select few of the SEM backscattered-electron images are provided in the thesis and the full set of labelled images can be found in Appendix A 40  (section A.3) as a reference to document the relationships between various telluride assemblages, sulfides, silicates, and alteration minerals.  3.4 EPMA Methodology  Electron-probe micro-analysis (EPMA) data were collected at Masaryk University in Brno, Czech Republic, with Drs. Jan Cempírek and Radek Skoda, to confirm the identification of the minerals using chemical composition (especially Te/metals ratios in tellurides) and to assess the role of minor elements (e.g., Fe in sphalerite thermometer, Ag in galena, minor elements in chalcopyrite and in tellurides, composition of alteration minerals, etc.). The tellurides were analyzed with a beam current of 25 keV and 20 nA, a beam diameter of 2 μm, and the following standards and lines: Au for AuLα, Cu for CuKα, pyrite for FeKα and SKα, synthetic PbSe for SeLb and PbMα, pararammelsbergite for AsLβ, HgTe for TeLβ, synthetic Bi2Te3 for BiMβ, Ag for AgLα, Sb for SbLβ, and coloradoite (HgTe) for HgMβ. Sulfide minerals were examined with a beam current of 25 keV and 20 nA, a beam diameter of 2 μm, and the following standards and lines: sphalerite for ZnKα, pyrite for FeKα and SKα, Mn for MnKα, Cu for CuKα, pararammelsbergite for NiKα and AsLβ, PbSe for SeLβ and PbMα, indium arsenide for (InAs) InLα, Cd for CdLβ, Ag for AgLα, gallium arsenide (GaAs) for GaKα, Ge for GeLα, TlBr0.5I0.5 for TlMα, and coloradoite (HgTe) for TeLβ. Micas and feldspars were both analyzed at 15 keV and 10 nA, with a beam diameter of 5 μm, and the standards and lines used were: albite for NaKα, sanidine for SiKα, AlKα, and KKα, pyrope for MgKα, vanadinite for ClKα, titanite for TiKα, baryte for BaLα, chromite for CrKα, wollastonite for CaKα, almandine for FeKα, spessartine for MnKα, ScVO4 for VKα, gahnite for ZnKα, topaz for FKα, celestine for SrLα, synthetic Ni2SiO4 41  for NiKα, albite for NaKα, sanidine for SiKα, AlKα, and KKα, wollastonite for CaKα, baryte for BaLα, andradite for FeKα, celestine for SrLα, and fluorapatite for PKα, respectively. Calcite was analyzed at 15 keV and 10 nA, a beam diameter of 8 μm, and the following standards and lines: forsterite for MgKα, albite for NaKα, celestine for SrLα and SKα, sanidine for SiKα, fluorapatite for CaKα and PKα, almandine for FeKα, spessartine for MnKα, gahnite for ZnKα, baryte for BaLα, and vanadinite for ClKα and PbMα.  All EPMA data are found in Appendix A.4.  3.5 μXRD Methodology  In situ micro X-ray diffraction (μXRD) analysis was conducted at the University of Western Ontario with Dr. Roberta Flemming to confirm selected mineral identities based on their crystal structures. The diffractometer used was a Bruker D8 Discover with a 60 mm Co Gobel mirror and a 300 μm collimator. The samples were positioned with a birds eye-view microscope and the correct height for the sample was ensured using a red laser, placed at 45°. The laser appears on the crosshairs of the microscope when the sample is at the centre of the diffraction circle. Diffracted rays from the target sample are detected by the general area detector diffraction system (GADDS), and 2D images are constructed representing a diffraction pattern for the crystal structure of the mineral under investigation. The omega-scan parameters of the μXRD for spots 1 and 2 were set to θ1 (°) = 14.5, θ2 (°) = 31, ω = 20, and t = 20 for frame 1, and θ1 (°) = 43.5, θ2 (°) = 40, ω = 10, and t = 20 for frame 2. For spots 3–10 the omega-scan parameters were set to θ1 (°) = 14.5, θ2 (°) = 26, ω = 15, and t = 15 for frame 1, and θ1 (°) = 38.5, θ2 (°) = 40, ω = 15, and t = 20 for frame 2. Phases were identified using EVA diffraction software, which deciphers diffraction patterns of minerals from the 2D GADDS images. Selected target spots, 42  GADDS images, and resulting diffraction patterns with the identified phases are found in Appendix A (A.5).  3.6 Panchromatic Cathodoluminescence Methodology  Cathodoluminescence (SEM-CL) of quartz was completed with a Philips XL30 scanning electron microscope (Bruker Quantax 200 energy-dispersion X-ray microanalysis system, XFlash 6010 SDD detector, Robinson panchromatic cathodoluminescence detector) at the University of British Columbia. This procedure involved collecting images of varying quartz textures to observe the relationship between the multiple generations of quartz present and to determine if any zoning is present. A selection of noteworthy SEM-CL images which were collected but not included within the thesis are provided in Appendix A (A.6).  3.7 Fluid Inclusion Methodology  A preliminary fluid inclusion study was conducted in the Department of Earth Sciences at the University of Western Ontario with Prof. Robert Linnen. After examining the 52 thin sections with optical microscopy, a total of 11 samples with the highest concentrations of fluid inclusions were selected to be made into doubly polished wafers for data collection. The goal of this analysis was to try and provide constraints on the physiochemical environment of the ore-forming fluids that caused the precipitation of the minerals of interest. The fluid inclusions were analyzed with a Linkham THMSG600 heating-freezing stage which was calibrated before measuring took place to ensure the thermometer was working properly. Calibration was done 43  with a standard synthetic one-component fluid inclusion of pure water to check the ice-melting temperature (at 0.0 °C) and critical point of water (observing the disappearing meniscus of the inclusion as it is heated and homogenizes into a “critical fluid” at 374.0 °C). The experiments for both the ice melting and homogenization experiments were conducted three times each to ensure the readings were consistent. For the ice-melting test, the temperatures of the experiments were +0.1, 0.0, and +0.1 °C, all within the accepted range of deviation. For the homogenization experiments, the temperatures were 374.6, 374.8, and 374.5 °C, which are also within the accepted range of deviation, confirming that the apparatus was giving accurate readings. After calibration was complete, 21 fluid inclusions were each tested with three rounds of freezing (to approximately –150 °C) and three rounds of heating (to 340 °C) to record different temperature variables (e.g., first ice-melting temperature, water freezing and melting temperature, carbon dioxide freezing and melting temperature, homogenization temperature, etc.) in order to give insight to the composition of the liquid and vapour phases trapped in the inclusion, and characteristics of the hydrothermal fluids that may have deposited the mineralization.  3.8 Stable Sulfur Isotope Methodology  Cut slabs with the coarsest sulfide minerals were selected from drill core for isotope analysis. Pyrite was the best mineral found for this analysis, as it appeared the most pure in hand sample and under the microscope. Each pyrite crystal was hand-ground with a mortar and pestle into a powder. In between samples, the mortar and pestle was cleaned with two rounds of quartz sand grinding followed by an ethanol wash in order to try and eliminate sample contamination. Twenty plastic vials were filled with 0.2–0.6 mg of the powdered pyrite. The analysis was 44  conducted at Queen’s University in the Queen’s Facility for Isotope Research (QFIR) stable isotope lab using a MAT 253 Stable Isotope Ratio Mass Spectrometer coupled to a Costech ECS 4010 Elemental Analyzer for 34S/32S analysis. At the QFIR, the samples were weighed into tin capsules and the S-isotopic composition was measured. The δ34S values were calculated by normalizing the 34S/32S ratios in the sample to that in the Vienna Canyon Diablo Troilite (VCDT) international standard; values are reported using the delta (δ) notation in units of permil (‰), and are reproducible to 0.2‰. The goal of this analysis was to try and determine the source of sulfur in the sulfide minerals.                45  4. Results  4.1 Panchromatic Cathodoluminescence of Quartz  The observations from the SEM-CL of quartz are presented before petrography and SEM results in order to layout the different quartz generations which is important to understanding the rest of the mineralogy.   The SEM-CL of the largest quartz grains revealed bright cores (quartz I) with remnant zoning, rimmed by younger homogeneous darker zones (quartz II) (Fig. 4.1a). Locally, oscillatory zoning was observed in large quartz II grains from sample DH11-122a (Fig. 4.1b). The larger grains of quartz (I and II) are intersected by younger veinlets of fine-grained quartz (quartz III) (dark grey in SEM-CL) (Fig. 4.1c). Quartz III is more fine-grained and has irregular grain boundaries, with brighter cores than its younger rims (quartz IV), which are darker grey in SEM-CL (Fig. 4.2a, b). All quartz types are intersected by late veinlets of calcite, which appear as thin, bright veinlets in SEM-CL (Fig. 4.1a).            (a) 46                         (C) Qtz III Qtz I+II Qtz I+II Qtz III Figure 4.1 (a) and (b) SEM-CL backscattered-electron and (c) cross-polarized transmitted-light images of the relationships between quartz generations I (bright core), II (darker rim around quartz I), and III (in fractures and along grain boundaries of quartz I + II). 1 mm (b) 47  Figure 4.2 (a) Cross-polarized transmitted-light image with a green box indicating the area shown in the SEM backscattered-electron image of (b).  The SEM-CL back-scattered electron image (b) shows the relationships between quartz generations I–IV (Sample DH11-114).                        (a) (a) 1 mm (b) 48  4.2 Petrography and SEM Observations  4.2.1 Quartz  When examining each thin section in this study, quartz (in quartz veins mostly hosted in hanging-wall quartz diorite and a few from quartz veins in the Skeena Group footwall) makes up 50 to 95% of the total volume, with the remainder of the sample being composed of opaque minerals (sulfides, tellurides), silicates, oxides, and alteration minerals. There are only a few samples where the modal percentage of quartz is <50%. Four types of quartz were observed using panchromatic cathodoluminescence as stated in section 4.1.  The first two are distinguishable from each other mainly in CL, whereas quartz III and IV are readily observable with a petrographic microscope.  A variety of grain sizes and textures were observed in the quartz from the mineralized veins and are described in more detail below.   Quartz I is coarse-grained, anhedral, and typically exhibits undulose extinction and straight grain boundaries between the quartz grains; in mineralized vein sections it is typically partially replaced by quartz II along grain boundaries (visible with CL only; Fig. 4.1a). Both quartz I and II are crosscut by quartz III (Fig. 4.1c), which is fine-grained, anhedral, and has irregular and interpenetrated grain boundaries. Quartz III also has very little to no internal deformation, as there is no apparent undulose extinction. Some samples (Figs. 4.3a, b and 4.4a, b) contain very fine-grained quartz IV associated with quartz III and sometimes sulfides minerals (e.g., sphalerite, chalcopyrite, and pyrrhotite); its border with quartz III is sometimes sharp. Quartz 49  generations III and IV more frequently host the opaque minerals (sulfides) and the bulk of the Te-bearing mineralization.                      (a) Qtz I + II Qtz III Qtz IV 2 mm (b) sulfides quartz Figure 4.3 (a) Cross-polarized transmitted-light image and (b) plane-polarized image of quartz generations I to IV from sample DH11-111b..  Quartz I + II are coarser grained and have strong undulose extinction while the quartz III + IV are finer grained, found around quartz I + II grain boundaries and fractures. These images give examples of how opaque minerals (solid black) are mostly associated with/enclosed in quartz III and IV.  2 mm 50                         (a) Qtz I + II Qtz I + II Qtz III Qtz IV 2 mm (b) 2 mm sulfides quartz Figure 4.4 (a) Cross-polarized transmitted-light image and (b) plane-polarized image of quartz generations I to IV from sample DH11-130. Quartz I + II are coarser grained and have strong undulose extinction while the quartz III + IV are finer grained, found around quartz I + II grain boundaries and fractures. These images give examples of how opaque minerals (solid black) are mostly associated with/enclosed in quartz III and IV.  51  4.2.2 Scheelite  Very little scheelite was found in the polished thin sections. This was expected, as only four W-rich drill-hole intervals were selected for sampling. Additionally, seven of 46 core samples that were viewed with short-wave UV light contained <10% scheelite (Fig. 4.5). The fluorescence color of the few occurrences of scheelite (CaWO4) observed in the drill core and thin sections ranged from blue to bright bluish-white. In one thin section scheelite was found being replaced by stolzite along its grain boundary (Fig. 4.6).                 Figure 4.5 Image of a core sample under short-wave UV with light blueish-white fluorescent scheelite grains. 52                4.2.3 Sulfide Minerals  The sulfide minerals are enclosed almost exclusively in quartz III + IV, or they form veinlets on quartz I grain boundaries and in fractures. Sulfide minerals are also found around the edges of many grains of quartz II. The earliest sulfide is pyrite I, which forms either anhedral grains and grain aggregates, or less frequently, euhedral crystals. In some cases, pyrrhotite is locally altered to collomorph aggregates of pyrite II that have a spongy “melnikovite” texture (Fig. 4.7). Pyrite and pyrrhotite are sometimes associated with minor hematite. Fresh pyrite is also associated with marcasite Figure 4.6 SEM backscattered-electron image of primary scheelite in a sulfide-poor quartz vein being replaced stolzite. 53  crystals with a characteristic spearhead shape (Fig. 4.8). Euhedral and corroded pyrite is found rimmed or crosscut by younger chalcopyrite I and/or sphalerite (Fig. 4.9). Both chalcopyrite I and sphalerite frequently form grain aggregates several cm in size (or locally millimeter-sized subhedral crystals). Galena overgrows and crosscuts both chalcopyrite and sphalerite, and forms inclusions in pyrite. Galena can be easily distinguished in reflected-light by characteristic trails of microscopic triangular holes where galena was plucked along three cleavage planes (Fig 4.10).                 Figure 4.7 Reflected-light image of sample DH09-092 with pyrrhotite being locally altered to collomorph aggregates of pyrite II that has a spongy “melnikovite” texture (concentric growth texture) showing in-situ replacement (po = pyrrhotite, py = pyrite).  quartz galena po py chalcopyrite Fe-Si rich phase 54                         quartz pyrite marcasite sphalerite with chalcopyrite disease   chalcopyrite 1 mm Figure 4.8 Reflected-light image from sample DH09-090 of euhedral pyrite being overgrown by marcasite (top right) with its classic spearhead shape; sphalerite with chalcopyrite disease crystallized later as it is found surrounding a crystal of marcasite (top left). 55                         (a) sphalerite with chalcopyrite disease   1 mm (b) sphalerite  chalcopyrite  pyrite 2 mm Figure 4.9 Reflected-light images of (a) sphalerite (light brownish-grey) with a large number of chalcopyrite inclusions (yellow-orange) forming along crystallographic planes in sample DH09-090. (b) Chalcopyrite disease in sphalerite filling cracks and cross-cutting sections in euhedral to subhedral pyrite I from sample DH09-079. 56                4.2.4 Oxide Minerals   Magnetite and hematite appear to be limited to samples from the MV (Main Vein) zone. In several samples the pyrite-pyrrhotite-magnetite relationship is ambiguous. There are a few samples where pyrrhotite and pyrite are altered to magnetite. In most cases, hematite is secondary after pyrite and magnetite.    1 mm galena Figure 4.10 Reflected-light image of galena from sample DH11-120 exhibiting triangular holes from being polished off along its three cleavage planes. 57  4.2.5 Telluride Minerals  The telluride minerals are in general from <1 to 525 m in size and form veinlets, whole euhedral to anhedral grains, or more commonly, composite grains (multiple minerals exsolved within one larger grain which exhibit complex intergrowth textures; i.e., tellurides are fully enclosed, forming laths in, or as blebs along the rims of other minerals; Figs. 4.11a–c) of Ag-, Bi-, Pb-, and Au-rich telluride minerals including hessite, stützite, tellurobismuthite, volynskite, altaite, rucklidgeite, kochkarite, petzite, and frohbergite. These minerals tend to form in the following environments: (1) as clusters or disseminations within fractures, interstices, or veinlets of quartz III and IV, typically very near sulfide grains and following distinct planes of weakness (Figs. 4.12a, b); (2) within sulfide minerals (most commonly pyrite or sphalerite, less commonly in chalcopyrite or pyrrhotite, and very rarely in galena or magnetite), as inclusions, filling fractures, or at grain boundary contacts with quartz III and IV (Figs. 4.13a, b); (3) at grain boundary contacts between sulfide minerals (commonly between pyrite + chalcopyrite or sphalerite + chalcopyrite) (Figs. 4.14a, b); (4) as very fine-grained inclusions in sulfide minerals (e.g., galena), or forming trails along fractures or crystallographic planes (e.g., pyrite, chalcopyrite) (Fig. 4.15); and (5) less frequently, within and near alteration phases (sericite and chlorite) (Figs. 4.16a, b). Deposit-wide, telluride minerals in very shallow intervals (i.e., shallow depth, <30 m deep) are very sparse and fine-grained (1–225 μm). The coarsest telluride minerals (from 250–535 μm) are generally found in the middle of the vein system and at depths >30 m, although a few outliers do occur. Telluride minerals found in the Deer Horn samples and their chemical formulae confirmed by EPMA are listed in Table 4.2.   58                         (a) (b)   (c)   Figure 4.11 SEM backscattered-electron images (a) to (c) are examples of composite grains with complex exsolution textures. 59                         (b) 1 mm (a) Figure 4.12 (a) SEM backscattered-electron (sample DH11-104bi) and (b) reflected-light (sample DH11-103) images showing telluride minerals as clusters or disseminations within fractures, interstices, or veinlets of quartz III & IV, typically very near sulfide grains and following distinct planes.  60                         (a) (b) Figure 4.13 SEM backscattered-electron images (a) and (b) showing tellurides as inclusions in sulfides, within fractures of sulfides, and along grain boundary contacts between sulfides and quartz. 61                         (a) (b) Figure 4.14 SEM backscattered-electron images of (a) and (b) showing tellurides near grain boundary contacts between sulfides (in this case (a) sphalerite + chalcopyrite in sample DH11-146a and (b) sphalerite + pyrite in sample DH11-110e1. 62                TABLE 4.2 TELLURIDE MINERALS IN THE DEER HORN SAMPLES CONFIRMED WITH EPMA Mineral Chemical Formula hessite Ag2Te tellurobismuthite Bi2Te3 altaite PbTe volynskite AgBiTe2 stützite Ag5–xTe3 petzite Ag3AuTe2 rucklidgeite PbBi2Te4 kochkarite PbBi4Te7 frohbergite FeTe2 Note: listed in approximate order from the most abundant to the least abundant telluride minerals found in 51 polished thin sections.  Figure 4.15 SEM backscattered-electron image of hessite forming trails along fractures and crystallographic planes in pyrite.  63                         Figure 4.16 SEM backscattered-electron images (a) and (b) showing clusters of telluride minerals associated with K-Al-Si-rich sericitic alteration. (a) (b) 64  4.2.6 Alteration Phases  The alteration minerals chlorite and sericite (muscovite) commonly have similar fine-grained, acicular morphologies and show typical replacement textures (Fig. 4.17a, b). Very fine-grained sericite followed by chlorite (rimming the edges) was observed in altered feldspar grains in quartz near sulfide minerals. Biotite is partially altered to chlorite (Fig. 4.18a), and carbonate is observed filling cracks in quartz (Fig. 4.18b). Calcite is the latest alteration mineral, and is observed cross cutting sericitic minerals and quartz (Fig. 4.19).                (a) (b) 2 mm Figure 4.17 (a) cross-polarized and (b) SEM backscattered-electron images of alteration minerals at the Deer Horn deposit [chlorite and sericite (muscovite)] that is fine-grained, sometimes with an acicular crystal habit.  These display typical replacement textures. 65                         (a) (b) Figure 4.18 (a) plane-polarized transmitted-light image of biotite altering to chlorite and (b) carbonate (calcite with rhombohedral cleavage) filling fractures in quartz near sulfides. biotite chlorite sphalerite quartz calcite 1 mm 1 mm 66       4.2.7 Hydroxylbastnäsite-(Nd)  Hydroxylbastnäsite-(Nd) [Nd(CO3)(OH)] was found in one sample. This mineral has a cross-hatched intergrowth texture and was found in quartz near magnetite, Fe-rich sphalerite, and chloritic alteration minerals (Figs. 4.20a, b).    Figure 4.19 SEM back-scattered electron image of calcite cross-cutting sericitic alteration. 67                         (a) (b) Figure 4.20 (a) Zoomed-out SEM backscattered-electron image of hydroxylbastnäsite-(Nd) in quartz near sulfides and (b) zoomed-in SEM backscattered-electron image of the red square box from (a) showing the interesting intergrowth texture of hydroxylbastnäsite-(Nd). 68  4.3 EPMA Results  The purpose of the EPMA study was to identify mineral compositions quantitatively, especially telluride minerals, as many whole and composite grains can be difficult to recognize with an optical microscope, and to detect the roles of minor elements, if any. There were two sets of analyses conducted, one focused on identifying telluride and sulfide minerals, and a set targeting silicates and oxides. The ternary diagrams for tellurides (Figs. 4.21a–c) show how their compositions vary between samples. Table 4.2 lists all of the telluride minerals confirmed by EPMA (hessite, tellurobismuthite, altaite, volynskite, stützite, petzite, rucklidgeite, kochkarite, and frohbergite) and their corresponding chemical formulae. The silicate minerals characterized via EPMA include chlorite, biotite, muscovite, feldspar, and titanite. The oxide minerals confirmed include magnetite, hematite, rutile, and spinel. The carbonates identified were mostly calcite, with a few occurrences of hydroxylbastnäsite-(Nd). The tungstates found include scheelite and stolzite. Very low concentrations of Mo in the scheelite confirm they are definitely scheelite, and not the Mo-rich solid solution end member (powellite), which is what was expected, as no yellowish fluorescence was seen with short-wave UV light when observed in hand sample or thin section.       69                         (a) (b) 70                4.4 μXRD Analysis  The purpose of the μXRD study was to identify grains that could not be identified by composition alone, generally because there were two or more possibilities with similar compositions. Four samples were studied: DH11-104bi, DH11-127, DH11-147b, and DH11-150. The minerals identified using the in situ micro X-ray diffractometer (μXRD) include: stolzite, altaite, tsumoite, hessite, petzite, volynskite, tellurobismuthite, and gold. The full set of photomicrographs, 2D GADDS images, and diffraction patterns can be found in Appendix A.5.  (c) Figure 4.21 (a), (b), and (c) are ternary diagrams from EPMA analysis showing how the compositions of tellurides vary throughout the samples. 71  4.5 Fluid Inclusion Analysis  Preliminary fluid inclusion analysis of the 11 doubly polished wafers of quartz-sulfide-Te-bearing veins was conducted by first inspecting them with an optical microscope to choose useful areas with abundant inclusions that appeared to be related to Te-mineralization (i.e., inclusions in fine-grained quartz III ± IV where tellurides minerals were most frequently observed). During the examination three different types of inclusions were found: (1) aqueous liquid and vapour inclusions which have two phases with one component (liquid-vapour or L-V); (2) aqueous carbonic inclusions which have three phases with two components (liquid-liquid-vapour or L-L-V); and (3) carbonic inclusions which are one phase with one component (vapour-rich or V-rich). All microthermometry data collected for each type of fluid inclusion can be found in Table 4.3.  4.5.1 Aqueous Fluid Inclusions  Ten aqueous fluid inclusions (L-V) ranging in size from 4 to 18 μm enclosed in quartz III and IV were tested. The eutectic temperatures for ice [Te(ice)] ranged from –28.1 to –39.6 °C and the ice melting temperatures [Tm(ice)] from –3.0 to 0 °C. Homogenization temperatures were not obtained for three of the 10 inclusions as they decrepitated at 143, 183, and 205 °C, preventing data collection. The remaining seven gave homogenization temperatures of 130.0–240.2 °C. The ratio of liquid to vapour in all of the L-V inclusions tested (n = 10) is higher (L>V), with the vapour bubble taking up approximately 10–40% of the inclusion (Figs. 4.22a–c).  72                         V L L V L (a) L V (b) (c) Figure 4.22 L-V fluid inclusion examples: (a) analysis # 15 (AN15, sample DH11-110C), (b) analysis #16 (AN16, sample DH11-110c), (c) analysis #11, 12, and 13 (AN11, AN12, AN13, sample DH11-147D). (L = liquid, V = vapour). 73  4.5.2 Aqueous Carbonic Fluid Inclusions  Eight aqueous carbonic inclusions 5 to 25 μm in size enclosed in quartz III and IV were tested. The Te(ice) data range –25.8 (Figs. 4.23a, b) to –32.7 °C. The eutectic temperatures for CO2 have a relatively wide range, from –78.9 to –103.0 °C (Fig. 4.23c). Four of eight inclusions gave solid CO2 melting [T(m)CO2] temperatures above –56.6 °C, from –56.8 to –62.1 °C.  The remaining four inclusions returned CO2 melting temperatures close to –56.6 °C (from –55.0 to –56.7 °C). In most cases the clathrate eutectic temperatures were too difficult to observe because of their small size, but two of eight inclusions gave a Te(cl) of  –25.8 to –27.0 °C. The melting temperatures of the clathrates [T(m)cl)] in seven of eight inclusions were somewhat easier to observe, ranging from 9.4 to 11.5 °C. Although two of the eight inclusions decrepitated (at 281.2 and 288.0 °C), the homogenization temperatures for the carbonic phase of the others were 268.0–336.4 °C (Figs. 4.24a–c). Figure 4.25 is a histogram displaying the range of homogenization temperatures for the all of the L-V and L-L-V inclusions analyzed in this study.          L V CO2 (a) Figure 4.23 L-L-V inclusion from sample DH11-110B (analysis #5) at (a) room temperature (19 °C), (b) water frozen at –26.7 °C (note the appearance of ice crystals around the vapour bubble), and (c) CO2 frozen at –81.0 °C). (b) (c) 74  Figure 4.25 A histogram showing the range of homogenization temperatures for L-V and L-L-V inclusions.                        (c) L V CO2 (a) (b) Figure 4.24 L-L-V inclusion from sample DH11-110B (analysis #5) at (a) room temperature (19 °C), (b) at about 230.0 °C during heating, and (c) at 275.0 °C (the point of homogenization).  75  4.5.3 Carbonic Fluid Inclusions  This preliminary fluid inclusion study only allowed for three carbonic inclusions to be tested, although they are widespread throughout the samples. These inclusions appear very dark, as they are nearly 100% vapour (Fig. 4.26). The tested inclusions were from 10–20 μm in size, although throughout the samples they range in size from 0.5–30 μm. The eutectic temperatures for CO2 range from –93.9 to –94.8 °C and the CO2 melting temperatures from –55.9 to –56.8 °C, which are very close to the triple point for pure CO2, at –56.6 °C. The homogenization temperatures for each of the carbonic inclusions are 23.8, 24.3, and 26.1 °C.  Figure 4.26 An example of a CO2 vapour-rich inclusion (a) at room temperature (19 °C) and (b) frozen at –56.8 °C. (a) (b) 76   TABLE 4.3  PRELIMINARY FLUID INCLUSION STUDY: MICROTHERMOMETRY DATA FOR L-V, L-L-V, AND V-RICH INCLUSIONS AT THE DEER HORN OCCURRENCE Sample Sample Area  Analysis # Type and phases present Size Te(ice) (°C) Te(CO2) (°C) Tm(CO2) (°C) Tm(ice) (°C) Te(cl) (°C) Tm(cl) (°C) Th (°C) 110B FL24 AN1 aqueous (L>V) 8 μm –28.9 to –29.3 - - n.a. - - 130.0 to 131.6 110B FL24 AN2 aqueous (L>V) 6 μm –30.7 to –31.1 - - –0.3 to –0.4 - - 165.4 to 165.6  110B FL24 AN3 aqueous carbonic (L-L-V) 10 μm - –101.3 to –103.0 –60.9 to –62.1 n.a. n.a. n.a. 298.8 to 302.4 110B  FL24 AN4 aqueous carbonic (L-L-V) 15 μm –26.5 to –27.0 –80.2 to –82.3 –56.3 to –57.1 n.a. n.a. 10.0 to 10.5 300.8 to 301.6  110B FL24 AN5 aqueous carbonic (L-L-V) 12 μm –26.7 to –27.4 –78.9 to –81.0 –57.0 to –58.5 n.a. n.a. 9.7 to 9.9 271.3 to 275.0  147D FL16 AN6 aqueous carbonic (L-L-V) 25 μm –32.3 to –32.5 –92.3 to –93.4 –56.8 to –56.9 n.a. –26.3 to –27.0 9.6 to 9.9 288.0 (decrep.) 147D FL16 AN7 aqueous carbonic (L-L-V) 20 μm –32.5 to –32.7 –95.6 to –95.9 –56.7 to –57.2 n.a. –25.8 to –26.1 9.4 to 9.7 281.2 (decrep.) 147D FL16 AN8 aqueous (L>V) 4 μm –35.5 to –35.8 - - –2.9 to –3.1 - - n.a. 147D FL16 AN9 aqueous (L>V) 6 μm –39.3 to –39.6 - - –2.7 to –3.0 - - 223.5 to 224.5 147D FL16 AN10 aqueous carbonic (L-L-V) 15 μm –26.1 to –26.4 –93.8 to –95.0 –56.0 to –56.3 n.a. - 9.9 to 10.3 336.0 to 336.4 147D FL13 AN11 aqueous (L>V) 18 μm –28.3 to –28.5 - - –0.4 to –0.6 - - 143 (decrep.) 147D FL13 AN12 aqueous (L>V) 7 μm –29.1 to –29.4 - - –0.4 to –0.5 - - 183 (decrep.) 147D FL13 AN13 aqueous (L>V) 5 μm –29.5 to –29.9 - - –0.2 to –0.1 - - 210 to 213 147D FL13 AN14 aqueous carbonic (L-L-V) 15 μm –25.8 to –26.1 –99.2 to –99.7 –59.1 to –59.6 n.a. - 11.0 to 11.5 318 to 323 110C FL19 AN15 aqueous (L>V) 12 μm –29.1 to –30.0 - - –1.9 to –2.0 - - 239.1 to 240.2 110C FL19 AN16 aqueous (L>V) 10 μm –36.8 to –38.0 - - n.a. - - 205 (decrep.) 150 FL4 AN17 aqueous (L>V) 4 μm –28.1 to –28.9 - - n.a. - - 193 to 199 150 FL4 AN18 aqueous carbonic (L-L-V) 5 μm –26.7 to –27.0 –96.5 to –98.0 –55.0 to –56.0 n.a. - 10.2 to 10.5 268 to 272 147D FL16 AN19 carbonic (V-rich) 20 μm - –94.1 to –94.8 –56.1 to –56.2 - - - 24.3 147D FL16 AN20 carbonic (V-rich) 15 μm - –93.9 to –94.6 –56.6 to –56.8 - - - 23.8 147D FL17 AN21 carbonic (V-rich) 10 μm - –94.3 to –94.8  –55.9 to –56.2 - - - 26.1 77  4.6 Sulfur Isotope Analysis  Sulfur isotope analysis (34S/32S) of 20 samples of pyrite from various zones (Table 4.4) of the deposit was done to determine the source of sulfur in the sulfide minerals, in order to define the conditions of ore formation and the origin and evolution of the hydrothermal fluids (Spry et al. 1996 and references therein). Goldfarb & Groves (2015) state that understanding the sulfur source is critical in defining a source region for gold because sulfur is a complexing agent for gold. All of the δ34S readings are close to 0 and form in a very narrow range (from 1.6 to –1.6 per mil).  The fact that the zones have slightly varying compositions (e.g., the EMRA from 1.2 to 1.4 and the MVN –1.6 to –1.1) demonstrates there was no contamination during sample preparation. TABLE 4.4 SULFUR ISOTOPE DATA FROM PYRITE AT THE DEER HORN OCCURRENCE Sample ID Drill Hole # Mineral  Zone δ34S ‰ vs. VCDT (per mil) DH_1 DH11-098 Pyrite EMRA 1.4 DH_2 DH11-098 Pyrite EMRA 1.3 DH_3 DH11-098 Pyrite EMRA 1.3 DH_4 DH11-098 Pyrite EMRA 1.4 DH_5 DH11-098 Pyrite EMRA 1.2 DH_6 DH11-104c Pyrite FV2 1.6 DH_7 DH11-104c Pyrite FV2 1.1 DH_8 DH11-104c Pyrite FV2 1.2 DH_9 DH11-104c Pyrite FV2 1.3 DH_10 DH11-104c Pyrite FV2 1.2 DH_11 DH11-105 Pyrite HV4 1.3 DH_12 DH11-105 Pyrite HV4 1.3 DH_13 DH11-105 Pyrite HV4 1.1 DH_14 DH11-105 Pyrite HV4 1.0 DH_15 DH11-111c Pyrite MVN –1.2 DH_16 DH11-111c Pyrite MVN –1.1 DH_17 DH11-111c Pyrite MVN –1.2 DH_18 DH11-111c Pyrite MVN –1.3 DH_19 DH11-122a Pyrite MVN –1.6 DH_20 DH11-131 Pyrite STK –0.1 Zone abbreviations:  MVN – Main Vein; EMRA – resource extension East of Main Resource Area; FV2 - Footwall Vein to Main Vein (1 denotes closest FW Vein to Main Vein, 7 denotes farthest FW Vein to Main Vein); HV4 – Hanging wall Vein to Main Vein (1 denotes closest HW Vein to Main Vein, 5 denotes farthest HW Vein to Main Vein); STK – Stockwork mineralization marginal to discrete veins. 78   4.7 Deposit Metal Zonation  Based on the mineralogy found in the investigated samples, the Deer Horn deposit appears to display moderate metal zoning (Fig. 2.10). From west to east, it ranges from a W-rich area rich in scheelite (e.g., core, EPMA, and optical microscope images of samples DH11-135 and DH11-137) followed by a zone of galena (Pb-rich) with little to no telluride mineralization (e.g., see EPMA images from samples DH11-131 and DH11-122 in Appendix A.4), followed by a sphalerite (Zn-rich) area where telluride mineralization becomes more common. Slightly farther east, Bi- and Ag-(Au)-rich telluride mineralization is most prominent, with abundant occurrences of telluride minerals in the Main Vein, Contact Zone, and EMRA areas (e.g., EPMA and optical microscope images from samples DH11-103, DH11-110a to f, and DH11-147a to d). Bismuth tellurides tend to occur closer to the Main Vein, and Ag-tellurides tend to occur slightly father away from the Main Vein. In the easternmost drill core sample investigated (sample DH11-098), telluride minerals are less abundant and are still relatively coarse-grained (up to 310 μm), suggesting the vein system may continue farther to the east where drilling has not been done. Please refer to the topographic map (Fig. 2.11) for exact locations of drill holes.        79  Figure 5.1 SEM-CL image of quartz I and II filled with healed micro-cracks and oscillatory zoning. 5. Interpretation of Results  5.1 Panchromatic Cathodoluminescence of Quartz  The coarsest grains of quartz with bright cores surrounded by remnant zoning (homogeneous darker zones around the rims, Fig. 4.1a) represent primary hydrothermal quartz I (bright cores), partially overprinted due to dynamic recrystallization and infiltrating fluids (quartz II; dark rims). This remnant zoning is not observable with an optical microscope. Characteristics of quartz that indicate dynamic recrystallization include strong undulatory extinction and subgrain formation observed with the optical microscope (Figs. 4.3 & 4.4), whereas characteristics of quartz which indicate the participation of infiltrating fluids include healed micro-cracks and oscillatory zoning observed with SEM-CL (Fig. 5.1) (Müller et al. 2012 and references therein).           80  The fact that quartz I is partially resorbed and fragmented indicates that quartz II is likely related to a tectonic event (which fragmented quartz I and formed micro-cracks) which allowed the introduction of new fluids that partly recrystallized quartz I, forming quartz II (and healing micro-cracks); therefore, these generations of quartz formed by a combination of both dynamic recrystallization and infiltrating fluids (fluid-driven overprint) (Müller et al. 2012). The same type of zoning is observed in the Nesodden quartz veins from Norway (see Figs. 4.14 d and e in Müller et al. 2012). Local oscillatory zoning found in quartz II also suggests participation of hydrothermal fluids with slightly varying fluid compositions pulsing episodically during formation (Fig. 4.1b). Quartz I and II are intersected by veinlets of fine-grained quartz III (Fig. 4.1c) (and very fine-grained quartz IV, which is very dark gray in SEM-CL). The fact that quartz III shows grain boundary migration along grain boundaries and in fractures of quartz I and II suggests it formed dominantly by dynamic recrystallization, otherwise the grain size would be coarser and there would have been a reduction in grain boundary length (Müller et al. 2012 and references therein). Quartz IV heals micro-cracks in quartz III and is even finer-grained, suggesting it formed dominantly from infiltrating fluids. In some cases, quartz IV has replaced quartz III around the grain boundaries (Fig. 4.2b). The fracturing and fragmenting found within the quartz generations as well as their differing zoning, grain sizes, and textures is evidence of at least two, possibly three, shearing events (see Appendix A.6 for selected panchromatic CL images). All quartz types are intersected by late veinlets of calcite which appear as thin, bright veinlets in SEM-CL. SEM-CL imaging also helped confirm that sulfide and telluride minerals are most commonly enveloped in quartz generations III and IV.  81  5.2 Petrography and SEM  5.2.1 Quartz  The variety of grain sizes and textures seen in quartz from the mineralized veins supports the occurrence of at least two, and in some cases three, recrystallization and shearing/deformation events. The earliest quartz I is coarse-grained, anhedral, and typically exhibits strong undulose extinction and straight grain boundaries between the quartz grains; in mineralized vein sections it is typically partially replaced by quartz II along grain boundaries. Quartz II represents a product of deformation and hydrothermal recrystallization of older quartz I; this is indicated by common partial dissolution of quartz I, presence of minor fracturing in quartz I, and locally visible oscillatory zoning in the Qtz II in CL. Both quartz I and II are crosscut by quartz III, which is fine-grained, anhedral, and commonly shows irregular and interpenetrated grain boundaries which are easily visible with an optical microscope; this texture is usually attributed to pressure-driven recrystallization by the grain boundary migration mechanism (Müller et al. 2012). Quartz III also has very little to no internal deformation as it does not exhibit undulose extinction. Some samples contain very fine-grained quartz IV associated with quartz III, sulfide minerals (e.g., sphalerite, chalcopyrite, and pyrrhotite), and alteration minerals; its border with quartz III is sometimes sharp. Finally, quartz generations III and IV tend to host the opaque minerals (sulfides) and the bulk of the Te-bearing mineralization, indicating they came later than quartz generations I and II.   82  5.2.2 Scheelite  The small amount (<10%) of scheelite found in seven of 46 drill core samples makes it hard to determine the exact relationship between the W and Te mineralization. What can be said is that the W came before the sulfide minerals, because primary scheelite is associated with quartz I and II and is found separately in quartz veins with few sulfides. A small amount of late, fracture-filling scheelite was found in drill core from the EMRA (resource extension east of the main resource area), which is unusual because the W skarn is farthest from these samples. However, the fact that the scheelite in the EMRA sample does not appear to be primary indicates that it could have been remobilized by hydrothermal fluids and re-precipitated later (Fig. 5.2). This is likely, because W can be easily remobilized in slightly reduced CO2-rich (see fluid inclusion section 4.5.3 for images of CO2 vapor-rich inclusions) hydrothermal systems like the Deer Horn deposit (Hart 2007). Additionally, if this late scheelite (found with no distinct crystal habit, as well as filling fractures in pyrite) was not a product of remobilization, one would expect this type of occurrence to be more common throughout the samples, which it is not. The fact that the UV-fluorescence color found throughout the samples ranges from blue to bright bluish-white indicates that the scheelite has a very high W content with very little to no Mo, as even the slightest amount of Mo (6 mol.% CaMoO4 and higher) begins to give scheelite a yellowish fluorescence under short-wave UV light (Tyson et al. 1988). It is also apparent a Pb-rich stage occurred after the W event because scheelite was found being replaced by stolzite along its grain boundaries (Fig. 4.6).   83                5.2.3 Sulfide Minerals  The fact the pyrrhotite was found locally altered to collomorph aggregates of pyrite II with a spongy “melnikovite” texture (Fig. 4.7) suggests that the pyrrhotite was pseudomorphosed as it underwent in situ replacement by pyrite, creating “birds-eye” textures (Fig. 5.3). Petrographic images of pyrite being rimmed and crosscut by both chalcopyrite I and sphalerite indicates that a Fe-rich phase came before a Cu,Zn-rich phase. The irregular intergrowths between chalcopyrite I and sphalerite suggest partial simultaneous crystallization followed by crystallization of sphalerite alone. The sphalerite crystallized from a Cu- and Zn-rich Figure 5.2 SEM backscattered-electron image showing tellurides forming throughout fractures and as small inclusions in pyrite. Secondary scheelite was likely remobilized by hydrothermal fluids and deposited in fractures of pyrite. 84  fluid, as indicated by the common presence of numerous microscopic inclusions (also known as “chalcopyrite disease”) of chalcopyrite II in sphalerite formed by exsolution from an earlier Cu,Fe-enriched sphalerite (Figs. 4.9a). The observation that galena overgrows and crosscuts both chalcopyrite and sphalerite, and forms inclusions in pyrite, indicates it is the last sulfide mineral to form.            5.2.4 Oxide Minerals  In a few samples pyrrhotite and pyrite are altered to magnetite, which previous studies have shown can be a low-temperature oxidization product of earlier-formed sulfide minerals (Graham et al. 1987) that forms as a hydrothermal fluid system cools. In most cases, hematite is secondary after pyrite and magnetite, which indicates that the system is oxidizing, because hematite is a common dissolution product of magnetite (Lagoeiro 1998). Figure 5.3 SEM backscattered-electron image showing birds-eye texture of pyrrhotite being replaced by pyrite II, creating a concentric growth texture towards Fe-rich sphalerite. 85  5.2.5 Tellurides  Fe-telluride. Although relatively uncommon throughout the samples, the Fe-telluride frohbergite (FeTe2) was potentially one of the earlier telluride minerals to form as it appears the least stable (very rough, porous surface) and is found being rimmed by hessite and tellurobismuthite. Nearly all of the frohbergite crystals are subhedral to anhedral in shape. The fact that solitary frohbergite grains are always found very near to Fe-bearing sulfide minerals suggest that they could have precipitated from fluids carrying Te and interacting with pyrite and/or pyrrhotite, which provided the source of Fe. The remaining frobergite that forms a part of a composite grain likely formed by exsolution and is therefore coeval (formed at the same time) with the other minerals it is found in contact with (hessite, tellurobismuthite, and petzite).  Bi-telluride. The only solely-Bi telluride mineral confirmed in this study is tellurobismuthite (Bi2Te3). Tellurobismuthite is commonly found in composite telluride grains and has a complex, bladed intergrowth texture formed by exsolution (Fig. 5.4). It is found in contact (and therefore is coeval) with five of the other telluride minerals (hessite, petzite, volynskite, frohbergite, and altaite). It is important to note, however, that tellurobismuthite is also the telluride most frequently found to occur as a whole grain (i.e., not as a composite grain). Whether found as a whole grain or as a part of a composite grain, tellurobismuthite regularly forms distinctive long, rectangular, and blocky euhedral crystals, unlike any of the other telluride minerals observed (Figs. 5.5a, b).   86                        Figure 5.4 SEM backscattered-electron images of a composite grain with tellurobismuthite forming a complex, bladed intergrowth texture formed by exsolution. Figure 5.5 SEM backscattered-electron images (a) and (b) of euhedral tellurobismuthite crystals forming whole grains with a distinct blocky, tabular habit. (a) (b) 87  Bi±Pb±Ag-tellurides. Kochkarite (PbBi4Te7) and rucklidgeite (PbBi2Te4) are not very common in the samples. These minerals were always observed intergrown with other telluride minerals (exsolution) as small sections within a composite grain. Volynskite (AgBiTe2) is much more common throughout the samples and was found in composite grains as a part of an exsolution texture and rarely on its own. It is was found in contact with kochkarite, rucklidgeite, petzite, hessite, altaite, and tellurobismuthite, indicating that they are coeval.  Pb-telluride. Galena is thought to be the source of Pb for the formation of altaite (PbTe) when it is observed as a whole grain. When altaite is found on its own as a whole grain, it typically occurs in fractures in quartz near hessite and galena and is usually <20 μm in size. There are several examples where altaite occurs forming a rim around an existing grain of galena (Fig. 5.6). When altaite is part of a composite grain with exsolution textures, it is always found as a much smaller inclusion, on the edge or tip of a composite grain. It occurs in contact with hessite, petzite, volynskite, and tellurobismuthite.          Figure 5.6 SEM backscattered-electron image with earlier grains of galena  rimmed by altaite. 88  Ag+Au Tellurides and Ag-rich Gold. Hessite (Ag2Te) is by far the most common telluride mineral found in the samples. It is almost always found in contact with or very near petzite (Ag3AuTe2), which makes sense because a solid solution exists between these two minerals (Cabri 1964). Hessite usually has a porous, Swiss-cheese texture (Figs. 5.7a, b) and is present in almost all (about 90%) of the composite grains. It also tends to take up the most volume in a grain (Figs. 5.8a–c) compared to all the other telluride minerals, which form noticeably smaller sections of composite grains. Hessite is found in contact with volynskite, petzite, altaite, frohbergite, tellurobismuthite, and Ag-rich gold (“electrum”). Hessite is also the second most common telluride mineral to form whole grains, next to tellurobismuthite. Petzite is always found as a part of a composite grain and was observed in contact with hessite, altaite, volynskite, tellurobismuthite, frohbergite, and Ag-rich gold. Very-fine grained (usually <15 μm) occurrences of Ag-rich gold (“electrum”) are very rare and are always found as inclusions in composite telluride grains (Figs. 5.9a–c). Silver-rich gold is always the smallest part of a composite grain and is only ever found in contact with hessite and petzite. Given that Ag-rich gold is only ever in contact with petzite and hessite (therefore after Bi-rich tellurides) indicates it is possible that Bi was acting as a gold “scavenger” (discussed in more detail in section 6.1).       Figure 5.7 Backscattered-electron images (a) and (b) of hessite with a porous, Swiss-cheese texture. (a) (b) 89                         (a) (b) (c) Figure 5.8 SEM backscattered-electron images (a), (b), and (c) display how hessite commonly makes up the largest volume of any telluride in each composite grain. 90                         gold (a) gold (b) gold (c) Figure 5.9 SEM backscattered-electron images of (a) inclusions of gold in hessite, (b) inclusion of gold surrounded by multiple tellurides in a composite grain, and (c) a composite grain with a tiny inclusion of gold in petzite. 91  5.2.6 Alteration Phases  Chlorite + sericite + carbonate alteration post-dates the main sulfide mineralization events because the mineral assemblage forms late veinlets which crosscut quartz and all sulfide minerals. In some cases the sericite is associated with telluride minerals, indicating they are likely related to the same event (Fig. 4.16).  5.2.7 Hydroxylbastnäsite-(Nd)  The rare occurrence of the carbonate mineral hydroxylbastnäsite-(Nd) [Nd(CO3)(OH)] suggests that the hydrothermal fluids were low in F during stages III and IV in the paragenetic sequence (Table 5.1), as it does not form in high-F environments (Hsu 1992).            92    TABLE 5.1 PARAGENETIC SEQUENCE FOR THE DEER HORN OCCURRENCE Mineral  Stage I Stage II Stage III Stage IV Quartz ---------------- ---------------- -------------- ------------ K-feldspar -----    Scheelite ---  - - - -  Stolzite                --(?)  Biotite   --------   Muscovite  --------   Magnetite     ----- - -(?)  Hematite                       ---- ---- (?) Pyrite        ---------       --------   Marcasite             ---------    Pyrrhotite                    --------    Chalcopyrite                ---------- - - - -  Sphalerite                                  --------- --------  Galena                    ------- --------  Frohbergite    ---------  Tellurobismuthite                  ------------  Volynskite    ------------  Altaite    ------------  Petzite   ------------  Hessite                         ------------  Ag-rich gold (“electrum”)              -------  Sericite            ---------- ------- Chlorite                           ------- Calcite                                         ------- Hydroxylbastnäsite-(Nd)                      - - - - - - (?)          93  5.2.8 Summary of Petrography and SEM-CL Interpretation  Optical microscope and SEM-CL observations revealed four generations of quartz  associated with sulfide minerals (pyrite, pyrrhotite, marcasite, sphalerite, chalcopyrite, galena), tellurides, Ag-rich gold (“electrum”), oxides (magnetite, hematite), and alteration mineral veinlets with minor amounts of chlorite, sericite, and carbonate (calcite). The telluride minerals typically occur as inclusions in sulfides phases (most commonly pyrite or sphalerite), or as separate grains and veinlets in the vicinity of sulfide minerals within quartz III and IV and/or alteration phases (Figs. 5.10a, b). Although it is common to find sulfosalt and sulfotelluride minerals along with tellurides in many other telluride deposits, neither mineral type was observed in this study. The observation made by Childe & Kaip (2000) that the Au-Ag mineralization displays a positive correlation with sulfide content was confirmed in this study, as clusters of telluride minerals do tend to concentrate within, bordering, or very close to sulfide minerals. Additionally, although the initial bulk rock assay data obtained by Deer Horn Capital exhibit erratic Au and Ag grades throughout the CZ and MV zones, the highest Au-Ag grades are associated with a high Te content. This correlation of high Te content with high Au-Ag grade is confirmed in this study, as Au and Ag are always associated with telluride minerals.      94                         sph gal cpy tellurides ser + chl quartz (a) (b) sph gal cpy tellurides ser + chl quartz Figure 5.10 (a) A reflected-light and (b) cross-polarized transmitted-light image of the same area from sample DH11-143. These images show the general style of Te-mineralization found near sulfides and alteration minerals (sericite + chlorite) within fractures/along grain boundaries in quartz. Abbreviations: cpy = chalcopyrite, gal = galena, sph = sphalerite, ser = sericite, chl = chlorite. 2 mm 2 mm 95  5.3 EPMA  Throughout the samples, it is clear from the ternary diagrams that the composition of petzite varied most drastically from its end-member (with Au:Ag contents varying up to about 20 wt.%), while the other telluride minerals were relatively consistent and close to their ideal compositions. The large deviation of petzite from its endmember composition makes sense because it forms a solid solution with hessite. When relating the compositional data plotted on the ternary diagrams to the images of the complex intergrowth textures of telluride minerals (including noting which tellurides are in contact with each other), it becomes apparent that the tellurides likely crystallized via exsolution. Four patterns were observed in the EMPA analyses: (1) biotite from DH11-111d (main vein, 8.2–8.3 m depth) is Al-rich; (2) muscovite from DH11-104bi (resource area east of the main vein, 9.0–9.1 m depth) is more Mg-rich than Fe-bearing; (3) muscovite from DH11-137 (from the western, tungsten-rich end of the occurrence) is more Fe- than Mg-rich; and (4) almost all of the sphalerite from the Main Vein and Contact Zone is slightly Fe-rich. The EPMA data tables with compositions for selected sulfide, telluride, silicate, oxide, carbonate, and tungstate minerals can be found in the appendices (B.4).        96  5.4 Fluid inclusions  5.4.1 Aqueous fluid inclusions  The Te(ice) data (–28.1 to –39.6 °C) indicate that these inclusions likely contain NaCl with minor amounts of KCl and CaCl2. This inference is drawn because of the varying eutectic temperatures of water depending on the salts present. The corresponding effects on the eutectic temperature of water are: (1) with pure NaCl, water freezes at around –21.0 °C; (2) with KCl at –30.0 °C; and (3) with CaCl2 at –55.0 °C (Roedder 1984). Therefore, some combination of the three aforementioned salts are likely present in these inclusions. The ratio of liquid to vapour in all of the L-V inclusions tested is higher (L>V), with the vapour bubble taking up approximately 10–40% of the inclusion (Figs. 4.22a–c), implying that the fluid has a moderate to high density (Kim et al. 2016).  5.4.2 Aqueous carbonic fluid inclusions   The Te(ice) data (–25.8 to –32.7 °C) in these types of inclusions indicates the presence of NaCl and KCl salts. The solid CO2 melting temperatures [T(m)CO2]for four out of eight inclusions was above –56.6 °C, from –56.8 to –62.1 °C, indicating the presence of approximately 0.5–13.2% dissolved methane (CH4) (based on calculations from Thiéry et al. 1994 and Fornadel et al. 2011). The other four inclusions had T(m)CO2 temperatures closer to –56.6 °C (from –55.0 to –56.7 °C), indicating they are mostly pure CO2. The melting temperatures of clathrates (T(m)cl = 9.4 to 11.5 °C) indicates that the salinity of these inclusions is quite low, about 1.2 to 5.1 wt.%. 97  5.4.3 Carbonic fluid inclusions  The eutectic temperatures for CO2 range from –93.9 to –94.8 °C and the CO2 melting temperatures are from –55.9 to –56.8 °C, very close to the triple point for pure CO2 at –56.6 °C, indicating that these inclusions are almost 100% pure CO2 with little to no other volatiles.  5.4.4 Summary of fluid inclusion interpretation  The bulk of the inclusions resemble epithermal to mesothermal and intrusion-related inclusions, rather than those of orogenic origin (Roedder 1984, Wilkinson 2001, Spry, Linnen, Allan, pers. commun.). In some cases, inclusions may be considered mesothermal because of the amount of CO2 present, which commonly is not produced in shallow epithermal deposits because it takes slightly higher pressure-temperature gradients to dissolve larger amounts of CO2 into an inclusion (Roedder 1984, Diamond 2003, Spry, Linnen, Allan, pers. commun.). This is not always the case, however, as it is possible to have carbonic-rich inclusions in some epithermal deposits (Wilkinson 2001, Spry, pers. commun.). Figure 4.25 is a histogram displaying the range of homogenization temperatures for the all of the L-V and L-L-V inclusions analyzed in this study. The homogenization temperature peaks are used to reconstruct the temperature evolution of geologic events and represent the minimum trapping conditions of the fluids (Roedder 1984). The green rectangle in Figure 5.11 shows the average distribution of salinities vs. homogenization temperatures found at Deer Horn, therefore categorizing most of the inclusions in the epithermal to mesothermal range (Figure modified from data by Large 1988 and Wilkinson 2001). 98  The fact that quartz, the mineral in which the inclusions are enclosed, underwent multiple shearing and recrystallization events hampered determination of timing relationships and verification of the inclusions as primary and/or related to the Te mineralization. They are tentatively interpreted to be primary instead of secondary, because the latter type would contain multiple planar arrays of inclusions that formed later as fractures healed over time. Although secondary inclusions are also present in the samples, all of the tested inclusions were not aligned along crystallographic planes or fractures and appear to be stand-alone, primary inclusions. They were also chosen mostly from quartz III, the quartz generation thought to be most closely related to the Te mineralization, and in contact with or in close vicinity to a telluride mineral. Therefore, the preliminary microthermometry data collected (Table 4.3) are likely representative of the physiochemical characteristics of the mineralizing hydrothermal fluids (Wilkinson 2001, Spry, pers. commun.).            Figure 5.11 The green rectangle shows the average distribution of salinities vs. homogenization temperatures found at Deer Horn, categorizing the inclusions in the epithermal to mesothermal range (figure modified from data by Large 1988 and Wilkinson 2001). 99  5.5 Sulfur Isotopes  The δ34S values for pyrite samples from Deer Horn (from 1.6 to –1.6 per mil) confirm that the sulfur is very likely magmatic/igneous in origin (Zheng 1990, Spry, pers. commun.). This conclusion was drawn because if it were an orogenic system, the S-isotope signatures would likely have a much wider and more variable range of δ34S values (as low as –20 and as high as +25‰), as there are no unique signatures for S-isotopes found in Au-bearing fluids in orogenic systems (Goldfarb & Groves 2015). The fact that the data indicate a magmatic source for S was expected as many other characteristics of the deposit appear to be intrusion-related (e.g., moderate metal zoning, mineralization style, type of fluid inclusions, and close proximity to an igneous intrusion). The very narrow range of S-isotope values can also be the result of fluid-present metamorphism which allows for pervasive fluid-rock interaction (Zheng 1990). This is another piece of evidence that both dynamic recrystallization via tectonic activity as well as the infiltration of magmatic fluids were responsible for the formation of the quartz generations (i.e., quartz was not solely a product of “dry” dynamic recrystallization).         100  6. Comparisons and Conclusions  6.1 Bi-(Te) melts as Au scavengers  Using petrographic evidence, the general sequence of mineral formation at the Deer Horn occurrence was: Fe  Cu  Zn  Pb-sulfide precipitation, followed by Te+Fe±Bi±Pb±Ag±Au tellurides ± alteration minerals. The fact that petzite (Ag3AuTe2) and hessite (Ag2Te) are found in contact with tellurobismuthite (Bi2Te) and volynskite (AgBiTe2), and Ag-rich gold (“electrum”) is found only in contact with hessite and petzite (not tellurobismuthite or volynskite), suggests that the Bi-rich telluride minerals (which were coeval with the formation of petzite and hessite) may have acted as a scavenger for Au. The Bi could have attracted Au into a melt and as exsolution within a certain composite grain occurred, Au partitioned into the petzite–hessite solid solution until the grain cooled further, allowing Ag-rich gold to exsolve. There are certain “melt-(precipitation) windows” in which the process of Au scavenging by Bi-(Te) melts plays an important role in the association, precipitation, and distribution of Au in different types of Au-(Ag) deposits (Ciobanu et al. 2005). When Bi-rich melts act as scavengers the process usually occurs in one of two ways. The first is via partial melting of pre-existing ores, known as the melt-assisted mobilization mechanism (Tomkins et al. 2007, Tooth et al. 2011). This process can only take place when a reasonably large percentage of melt composed of low-melting chalcophile elements (LMCE) is formed by partial melting of pre-existing ore, and can therefore redistribute the components in certain chemical microenvironments, as long as they form an interconnected network (Tomkins et al. 2007, Tooth et al. 2011). Secondly, Bi-melt scavenging can occur with a hydrothermally assisted melt-collector model (Tooth et al. 2011), 101  which occurs when polymetallic melts scavenge elements from hydrothermal fluids by “melt–fluid” interaction (which would likely be the method most suited to the Deer Horn deposit if Bi was acting as a scavenger). In this scenario, relatively small amounts of melt are able to influence metal distribution on a deposit scale via “chemical communication” (defined by Tomkins et al. 2007) without migrating around the deposit. For example, if a fluid is undersaturated in Au by two orders of magnitude, even a small amount of Bi melt can scavenge up to several wt.% Au from the fluid and promote the precipitation of Au (Tooth et al. 2008, 2011). The question is, were the fluids carrying the mineralization at the Deer Horn deposit hot enough for Bi melts to act as a scavenger in the first place? The phase diagram from Tooth et al. (2008) shows the Au-Bi system at 1 bar (Fig. 6.1) with a eutectic temperature of 241 °C. Homogenization temperature peaks in this study (225 °C for L-V inclusions and 310 °C for L-L-V inclusions) indicate that the system was hot enough (>241 °C) for Bi to potentially have acted as a scavenger at some times during mineralization, but not the entire time. Additionally, it should be noted that the homogenization temperatures for L>V inclusions never rose to 241 °C, therefore the only fluids which would have been able to carry Bi±Au-Ag-Te-mineralization (and had Bi acting as scavenger for Au) would be fluids found in L-L-V inclusions which all had homogenization temperatures >241 °C.        Figure 6.1 Phase diagram by Tooth et al. (2008) of the Au-Bi system at 1 bar showing the eutectic temperature of 241 °C. 102  6.2 Comparisons with Deposits Worldwide  6.2.1 Is Deer Horn an IRGS?  The topic and classification of intrusion-related gold systems (IRGS) began to be explored in the 1980s after the gold price increased considerably (Pertzel 2008). Over the last 20+ years, some controversial and problematic associations have been made in the literature because authors defined too many characteristics to be considered for a single model. Many papers on IRGS report too wide a range of tectonic settings, granitoid associations, metal chemistries, etc. to be considered diagnostic features and can lead to misclassification, especially because some authors indicate there may be features that overlap with orogenic deposits (Hart 2005, Hart & Goldfarb 2005). Although this deposit type suffers from nomenclature and knowledge gap issues there are some IRGS deposits that are not as controversial as others and allow us to define their potential characteristics. Initially, a distinction must be made between oxidized and reduced IRGS (RIRGS), which are two different types of intrusion-related Au-mineralizing systems. Oxidized systems are thought to be associated with mafic, magnetite-series intrusions and with a Cu porphyry; whereas reduced systems (Fig. 6.2, modified from Hart 2007) are associated with felsic, ilmenite-series intrusions and are linked to nearby W occurrences, quartz veins with low sulfide content, and inclusions in quartz that are methane-rich and aqueous-carbonic with low salinity (Hart 2005, 2007). The Deer Horn deposit shares many of the aforementioned characteristics of a reduced system. It also shares many similarities with the typical paragenesis of evolving metal associations found in cooling RIRGS worldwide (Fig. 6.3, Hart 2007). A TMI (total magnetic intensity) survey done over the Deer Horn property in 2011 (conducted by 103  Precision GeoSurveys Inc.) shows that areas which correspond geologically to the Eocene intrusion are neither magnetically very high nor low (green to yellow with small areas of red; Fig. 6.4). This indicates that the signature is neither strongly oxidized nor reduced in either direction, which would place the intrusion close to the ilmenite-magnetite boundary (Fig. 6.5, Hart 2007) where some RIRGS deposits are found (Thompson et al. 1999, Hart 2007). Lane et al. (2013) stated that some faults which host local mineralization correlate with linear magnetic lows, signifying a slightly more reduced than oxidized character near important mineralized structures. Other “critically distinguishing” features at the Deer Horn deposit that are associated with potential RIRGS deposits from Hart’s (2007) empirical model (based on “type” occurrences from Alaska and Yukon) include: (1) a broad mineralizing system extending outside of the intrusion’s boundaries; (2) concentric metal zoning; (3) parallel sheeted veins; (4) deposit-type zonation outward from the pluton (skarn- and replacement-style proximal to the pluton with structurally controlled stockworks and veins more distal to the pluton); (5) Au and W forming ore but do not directly correlate with each other; and (6) co-eval (±2 Ma) timing of pluton emplacement with Au-mineralization (Hart 2005, 2007). The major difference between “type” deposits in Yukon, Alaska, and British Columbia and the Deer Horn deposit is that “type” deposits are commonly associated with plutons with a peraluminous to alkalic character (Hart 2007), whereas the Deer Horn deposit appears to be related to a more calc-alkaline intrusion.    104                   Figure 6.3 Common metal associations and mineralization types in a cooling RIRGS (Hart 2007) which is very similar to the paragenesis at Deer Horn. Figure 6.2 Deposits worldwide that are considered to be proposed to be RIRGS. The location of the Deer Horn deposit is marked with a yellow star. Figure modified from Hart (2007). 105                         Figure 6.4 Magnetic survey over the Deer Horn property from 2011 (conducted by Precision GeoSurveys Inc.) showing that areas which correlate geologically to the Eocene intrusion are mostly green to slightly yellowish-red in some areas indicating it is neither very strongly reduced or oxidized. Figure 6.5 Metal associations with various primary oxidation states and degrees of fractionation.  It is likely the Deer Horn deposit falls close to the ilmenite-magnetite boundary within the yellow RIRGS area. 106  6.2.2 Intrusion-related Telluride Deposits  Table 6.1 displays a summary of data collected from multiple intrusion-related Au-telluride deposits for which similar analytical techniques were used (fluid inclusion study, salinity, and S-isotope data) to determine the physiochemical characteristics of the system. For example, the range of homogenization temperatures for L-V inclusions at the Deer Horn deposit is 130.0–240.5 °C and that is comparable to L-V inclusions from (1) the Panormos Bay deposit in Greece: 198–253 °C (Tombros et al. 2007); (2) Palea Kavala in Greece: 216.0–420.0 °C (Fornadel et al. 2011); (3) the Golden Sunlight deposit in Montana: 131.8–398.2 °C (Spry et al. 1996); and (4) Tuvatu in Fiji: 85–400 °C (Scherbarth & Spry 2006). Of the four deposits listed in Table 6.1, the Deer Horn deposit is most similar to Palea Kavala, but it also shares some characteristics with Golden Sunlight. Like the Deer Horn deposit, Palea Kavala is related to a granodioritic intrusion, forms a sheeted quartz-vein system, has similar metal occurrences (e.g., Bi, Te, Pb, Au), has comparable Te(CO2) and Th (°C) values for L-L-V inclusions, as well as similar δ34S values (–1.9 to 1.0 ‰ for Palea Kavala and –1.6 to 1.6 ‰ for the Deer Horn deposit). The Golden Sunlight deposit also has similar metal occurrences (e.g., Au-Ag-Te-Bi-Mo), salinity for L-L-V inclusions (1.2 to 4.7 wt.% for Golden Sunlight and 1.2 to 5.1 wt.% for the Deer Horn deposit), and comparable Te(CO2), Tm(ice), Tm(cl), and Th (°C) temperatures for L-L-V inclusions (see Table 6.1). δ34S values for worldwide deposits suggested to be intrusion-related gold ± telluride systems is compared to the Deer Horn deposit in Figure 6.6 (modified from Fornadel et al. 2011). The deposits with the most controversial classifications are underlined in red, as debate still exists for some areas. 107  The major difference between the Deer Horn deposit and other intrusion-related Au±(Ag) telluride deposits worldwide is size. Many of the recognized deposits are many magnitudes larger (e.g., reserves at Golden Sunlight are 64.2 million tonnes at 1.69 g/t Au) than the Deer Horn deposit’s indicated (429,000 tonnes at 4.97 g/t Au, 153.42 g/t Ag indicated) or inferred size (estimated pit delineation resource of 951,000 tonnes at 2.45 g/t Au and 77 g/t Ag). However it is certainly possible that there is more Te mineralization in the Deer Horn area yet to be discovered. Despite the relatively small size of the Deer Horn deposit compared to other well-known Au-telluride deposits worldwide, its presence is interesting from a genetic standpoint because very few Au-Te systems have been found in British Columbia and this opens an opportunity for further exploration. Au-Te deposits are much more common in the western United States (e.g., Golden Sunlight), but those are typically related to alkaline rather than calc-alkaline systems as found at the Deer Horn deposit.    Figure 6.6 δ34S values from suggested intrusion-related Au ± Te deposits worldwide.  The most controversially classified deposits are underlined in red and Deer Horn is in the blue rectangle. Figure modified from Fornadel et al. 2011.  108  TABLE 6.1 COMPARATIVE TABLE WITH OTHER INTRUSION-RELATED Au-Te DEPOSITS WORLDWIDE  109  6.3 Metallurgy of Au-(Ag) Extraction & Recovery Potential at the Deer Horn Deposit  The extraction of Au and Ag from telluride minerals involves cyanidation, although gravity concentration and floatation can also be used to separate the gold from the gold ore (Spry et al. 2004). Fortunately, most of the Au-Ag-telluride minerals (about 70%) at the Deer Horn deposit are found in micro-fractures and veinlets in variable quartz and alteration phases and will be easily recoverable with cyanidation. The remaining telluride minerals occurring as inclusions in cyanide-insoluble sulfide minerals, such as pyrite, chalcopyrite, and pyrrhotite, are not recoverable and will end up in the tailings. This same problem was studied by Spry & Thieben (2000) at the Golden Sunlight deposit in Montana, where tiny inclusions of native gold, petzite, calaverite, buckhornite, and krennerite encapsulated in pyrite, chalcopyrite, and tennantite were not recoverable. It is thought that this input into the tailings accounts for approximately 3–25% of the unrecoverable gold processed during the mine’s lifetime (Spry & Thieben 2000).  6.4 Summary of Conclusions  The Deer Horn deposit is a relatively low-temperature, intrusion-related, polymetallic system enriched with Au-Ag-Te-Bi-Pb-W-Mo. A local, spatially related thrust fault likely served as a conduit for metal-bearing hydrothermal fluids, sourced from the genetically related Nanika granodiorite intrusion, to deposit the Au-Ag-Te mineralization in the early Eocene. During this time, at least two recrystallization and shearing events occurred, as recorded by a variety of foliated and strained textures in multiple generations of quartz. The Au-Ag-Bi-Pb-telluride mineralization formed later than the Fe-, Pb-, and Zn-sulphide minerals, is mostly restricted to 110  quartz III and IV, and is sometimes associated with chlorite and sericite alteration. Telluride mineral species formed via interactions between hydrothermal fluids and pre-existing mineralization (e.g., Fe in frohbergite from pyrite and/or pyrrhotite and Pb in altaite from galena). Average homogenization temperatures for L-L-V inclusions (310 °C) indicate that the Au-(Ag) mineralization was possibly a consequence of Bi acting as a scavenger via the hydrothermally-assisted melt-collector model (Tooth et al. 2011) which occurs when polymetallic melts scavenge elements from hydrothermal fluids by melt–fluid interaction. However, if this was the case, the mechanism was only active when the system was >241 °C (the eutectic temperature for the Au-Bi system at 1 bar), below which it would not be hot enough to continue. An orogenic origin is largely ruled out, as orogenic deposits are typically considered to form during compressive deformation and regional metamorphism of fluids that are not connected to an intrusive body (Sillitoe & Thompson 1998 and references therein). Additionally, δ34S analysis from this study confirmed with readings close to 0 (–1.6 to 1.6 per mil) that the source of sulfur is related to an intrusive body (probably the Nanika granodiorite) and is therefore likely magmatic in origin (orogenic δ34S values would not have such a narrow range and would not be so close to 0 per mil). The Deer Horn deposit also has many characteristics typically comparable to or diagnostic of reduced IRGS [e.g., concentric metal zoning, parallel sheeted quartz veins with low sulfide content, multiple mineralization styles (skarn, stockworks, and veins), and co-eval (±2 Ma) timing of pluton emplacement with Au-mineralization] and intrusion-related Au-telluride deposits (see Table 6.1) worldwide, supporting a magmatic/igneous association. 111  The recovery of Au-(Ag) from the Deer Horn deposit would likely be about 70%. This estimate is based on the fact that, for the most part, the telluride minerals are enclosed in quartz and would be easily recoverable via cyanide leaching. The remaining telluride minerals (approximately 30%) occur within cyanide-insoluble sulfides (e.g., pyrite, pyrrhotite, and chalcopyrite) and would be left behind in the tailings.  6.5 Future Work & Recommendations  Future work on this deposit could include a more in-depth fluid inclusion study and/or further petrography with new drill core. The author recommends that more thin sections be made from a wider area across the property to draw links between each of the four mineralization types (W, Mo, Au-Ag-Te-Bi-Pb, and Cu). The Cu showing to the northwest is particularly interesting, especially considering the large metal endowment of the immediate area; hence, further exploration for Cu-bearing rocks could prove promising. This study assumes that the Au-Ag-Te vein system is not superimposed on a larger, Cu-Mo deposit of unknown type which has yet to be discovered. Further study of the Cu showing is necessary to confirm this assumption. A more detailed look at the Nanika intrusion, which is thought to be related to the Au-Ag-Te mineralization, is warranted. Geochemical analysis would help determine whether the magma is of slightly more reduced or oxidized character. Although past studies classify it as a calc-alkaline intrusion, no direct geochemistry data has been collected from the intrusion on the Deer Horn property. It is possible, if the system is superimposed, that the age data for the Nanika intrusions are incorrect. Theoretically, if there was an overprint, the K-Ar ages for the extracted biotite (57–48 Ma, Diakow & Koyanagi 1988a) could have been reset. Conducting U-Pb dating 112  on zircon from the granodiorite to reaffirm its age would be valuable and would help to confirm the author’s classification of the Deer Horn deposit as intrusion-related, and that the system was not overprinted and is not orogenic. Similarly, 40Ar/39Ar dating of sericite alteration is needed to reaffirm the Eocene K-Ar age. Raman spectroscopy of the three phases in the L-L-V inclusions would give more precise data on the compositions (e.g., presence of CH4, N2, salts) of the mineralizing hydrothermal fluids.                 113  References ALLDRICK, D.J. (1993) Geology and metallogeny of the Stewart mining camp, northwestern B.C. British Columbia Ministry of Energy, Mines and Petroleum Resources, British Columbia Geological Survey Bulletin 85, 105 pp. CHILDE, F. & KAIP, A. (2000) Assessment Report for Surface Work on the Deer Horn Mine Property. British Columbia Ministry of Energy, Mines and Petroleum Resources.  CIOBANU, C.L., COOK, N.J., & PRING, A. 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Mineralogy & Petrology 103, 79–100.  WILKINSON, J.J. (2001) Fluid inclusions in hydrothermal ore deposits. Lithos 55, 229–272 WOJDAK, P. & FEBBO, G. (2008) Northwest Region. Exploration and Mining in British Columbia, Ministry of Energy, Mines and Petroleum Recourses, 34 pp.  ZHENG, Y.-F. (1990) Sulfur isotopes in metamorphic rocks. Neues Jahrbuch für Mineralogie – Abhandlungen 161(3), 303–325.           122  Appendices  Appendix A: Data and Results A.1 Selected Core Sample Photographs                     123                         124                         125                         126                         127                         128  A.2 Selected Digital Scans of Polished Thin Sections  Note: Plane-polarized transmitted-light images are on the left and cross-polarized transmitted-light images are on the right.   Sample: DH11-098           Sample: DH11-110a           129  Sample: DH11-111b             Sample: DH11-120           130   Sample: DH11-122             Sample: DH11-147b           131   Sample: DH11-130            Sample: DH11-137             132  Sample: DH11-141                       133  A.3 Selected SEM-BSE Images                       134                         135                         136                         137  `                       138                         139                         140                         141  A.4 EPMA Data Tables Note for all tables: a.p.f.u. = atoms per formula unit  Magnetite: All Fe was measured as FeO, and was recalculated for Fe2+/Fe3+  Mineral Magnetite Magnetite Magnetite Magnetite Analysis 6 / 1 .  7 / 1 .  13 / 1 .  14 / 1 .  Comment DH11_111d DH11_111d DH11_111d DH11_111d SiO2 0.13 0.00 0.37 0.23 TiO2 0.18 0.17 0.26 0.19 Al2O3 0.38 0.17 0.28 0.25 V2O3 0.13 0.13 0.14 0.13 MgO 0.08 0.00 0.00 0.00 CaO 0.00 0.00 0.00 0.00 MnO 0.13 0.00 0.11 0.16 FeO tot. 91.72 92.65 92.00 92.36 Fe2O3 cal. 67.44 68.28 67.05 67.72 FeO cal. 31.03 31.21 31.66 31.42 Total 99.50 99.96 99.87 100.11 Formula (a.p.f.u.)     Si 0.005 0.000 0.014 0.009 Ti 0.005 0.005 0.007 0.005 Al 0.017 0.008 0.013 0.011 V 0.004 0.004 0.004 0.004 Mg 0.005 0.000 0.000 0.000 Ca 0.000 0.000 0.000 0.000 Mn 0.004 0.000 0.003 0.005 Fe3+ 1.958 1.978 1.940 1.956 Fe2+ 1.001 1.005 1.018 1.009  Si/Al 0.02 0.01 0.03 0.02 Fe/Mg 2.98 2.99 2.97 2.98            142  Micas & alteration minerals:  Formula calculation based on 12 anions, OH calculated as OH=(2-F-Cl). (Norm. 12 anions) Detection limits: Na – 609 ppm, Si – 438 ppm, Al – 368 ppm, Mg – 439 ppm, Cl – 212 ppm, Ti – 282 ppm, Ba – 586 ppm, Cr – 411 ppm, K – 343 ppm, Ca – 335 ppm, Fe – 1039 ppm, Mn – 604 ppm, V – 589 ppm, Zn – 1115 ppm, F – 548 ppm, Sr – 885 ppm, Ni – 928 ppm.   Mineral chlorite chlorite chlorite   Al-rich biotite Al-rich biotite Al-rich biotite Al-rich biotite Al-rich biotite Analysis 25 / 1 .  26 / 1 .  6 / 1 .    4 / 1 .  5 / 1 .  8 / 1 .  10 / 1 .  11 / 1 .  SiO2 30.41 30.18 37.71   36.32 36.63 37.58 36.74 36.73 TiO2 0.01 0.00 0.04   1.90 1.85 1.89 1.78 1.80 Al2O3 20.56 19.89 15.29   15.61 15.36 16.19 16.83 16.28 V2O3 0.17 0.21 0.04   0.02 0.05 0.01 0.02 0.04 Cr2O3 0.12 0.10 0.11   0.00 0.00 0.01 0.03 0.00 MgO 21.11 21.68 7.90   9.16 9.21 9.33 9.30 9.30 MnO 1.39 1.57 0.22   0.48 0.44 0.50 0.42 0.49 FeO 14.89 13.39 26.68   22.38 21.66 21.57 20.67 21.20 NiO 0.01 0.00 0.02   0.03 0.01 0.00 0.03 0.03 ZnO 0.00 0.00 0.07   0.08 0.11 0.15 0.15 0.11 CaO 0.13 0.09 0.15   0.08 0.01 0.02 0.01 0.05 SrO 0.00 0.00 0.01   0.01 0.00 0.00 0.00 0.00 BaO 0.01 0.00 0.00   0.03 0.08 0.05 0.05 0.04 Na2O 0.03 0.04 0.04   0.01 0.03 0.03 0.05 0.05 K2O 0.01 0.00 0.04   9.51 9.75 9.49 9.64 9.49 F 0.21 0.26 0.04   1.36 1.36 1.32 1.06 1.09 Cl 0.01 0.00 0.03   0.00 0.01 0.01 0.02 0.00 Total 89.07 87.41 88.39   96.98 96.56 98.15 96.80 96.70 Formula (a.p.f.u.) Si 0.506 0.502 0.628   0.604 0.610 0.625 0.611 0.611 Ti 0.000 0.000 0.001   0.024 0.023 0.024 0.022 0.023 Al 0.403 0.390 0.300   0.306 0.301 0.318 0.330 0.319 V 0.002 0.003 0.001   0.000 0.001 0.000 0.000 0.001 Cr 0.002 0.001 0.001   0.000 0.000 0.000 0.000 0.000 Mg 0.524 0.538 0.196   0.227 0.228 0.232 0.231 0.231 Mn 0.020 0.022 0.003   0.007 0.006 0.007 0.006 0.007 Fe2+ 0.207 0.186 0.371   0.311 0.302 0.300 0.288 0.295 Ni 0.000 0.000 0.000   0.000 0.000 0.000 0.000 0.000 Zn 0.000 0.000 0.001   0.001 0.001 0.002 0.002 0.001 Ca 0.002 0.002 0.003   0.001 0.000 0.000 0.000 0.001 Sr 0.000 0.000 0.000   0.000 0.000 0.000 0.000 0.000 Ba 0.000 0.000 0.000   0.000 0.001 0.000 0.000 0.000 Na 0.001 0.001 0.001   0.000 0.001 0.001 0.002 0.002 K 0.000 0.000 0.001   0.202 0.207 0.201 0.205 0.201 Fe2+ 0.011 0.014 0.002   0.071 0.071 0.069 0.056 0.057 Cl 0.000 0.000 0.001   0.000 0.000 0.000 0.000 0.000 143  Micas & alteration minerals (continued): Formula calculation based on 12 anions, OH calculated as OH=(2-F-Cl). (Norm. 12 anions) Mineral muscovite (Mg-rich) muscovite (Mg-rich) muscovite (Mg-rich) muscovite (Mg-rich) muscovite (Mg-rich) muscovite (Mg-rich) muscovite (Mg-rich) Analysis 4 / 1 .  7 / 1 .  8 / 1 .  9 / 1 .  10 / 1 .  11 / 1 .  12 / 1 .  SiO2 45.21 47.10 46.07 47.47 46.77 46.98 46.91 TiO2 0.63 0.78 0.92 0.85 1.11 1.04 0.91 Al2O3 28.50 32.33 32.70 31.63 32.26 32.31 32.09 V2O3 0.05 0.02 0.05 0.07 0.06 0.02 0.11 Cr2O3 0.08 0.04 0.04 0.03 0.00 0.00 0.00 MgO 1.51 1.35 1.27 1.50 1.40 1.38 1.34 MnO 0.06 0.02 0.02 0.07 0.06 0.05 0.09 FeO 2.70 1.98 1.94 2.28 2.21 2.11 1.90 NiO 0.01 0.01 0.00 0.01 0.00 0.01 0.01 ZnO 0.12 0.03 0.00 0.03 0.05 0.04 0.07 CaO 0.05 0.03 0.05 0.03 0.02 0.02 0.00 SrO 0.04 0.00 0.00 0.00 0.00 0.00 0.00 BaO 0.13 0.14 0.18 0.16 0.17 0.25 0.19 Na2O 0.19 0.23 0.25 0.17 0.25 0.20 0.20 K2O 9.56 11.04 10.78 10.94 10.96 11.18 11.17 F 0.35 0.27 0.27 0.33 0.31 0.32 0.29 Cl 0.04 0.01 0.00 0.02 0.01 0.01 0.00 Total 89.23 95.38 94.54 95.59 95.64 95.92 95.28 Formula (a.p.f.u.) Si 0.752 0.784 0.767 0.790 0.778 0.782 0.781 Ti 0.008 0.010 0.011 0.011 0.014 0.013 0.011 Al 0.559 0.634 0.641 0.620 0.633 0.634 0.629 V 0.001 0.000 0.001 0.001 0.001 0.000 0.001 Cr 0.001 0.001 0.001 0.000 0.000 0.000 0.000 Mg 0.037 0.033 0.032 0.037 0.035 0.034 0.033 Mn 0.001 0.000 0.000 0.001 0.001 0.001 0.001 Fe2+ 0.038 0.028 0.027 0.032 0.031 0.029 0.026 Ni 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Zn 0.001 0.000 0.000 0.000 0.001 0.000 0.001 Ca 0.001 0.001 0.001 0.001 0.000 0.000 0.000 Sr 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Ba 0.001 0.001 0.001 0.001 0.001 0.002 0.001 Na 0.006 0.007 0.008 0.005 0.008 0.006 0.007 K 0.203 0.234 0.229 0.232 0.233 0.237 0.237 Fe2+ 0.018 0.014 0.014 0.018 0.016 0.017 0.015 Cl 0.001 0.000 0.000 0.001 0.000 0.000 0.000    144  Micas & alteration minerals (continued): Formula calculation based on 12 anions, OH calculated as OH=(2-F-Cl). (Norm. 12 anions) Mineral muscovite (Fe-rich) muscovite (Fe-rich) muscovite (Fe-rich) muscovite (Fe-rich) muscovite (Fe-rich) muscovite (Fe-rich) muscovite (Fe-rich) Analysis 13 / 1 .  14 / 1 .  15 / 1 .  16 / 1 .  17 / 1 .  18 / 1 .  19 / 1 .  SiO2 48.35 48.85 49.56 48.61 48.86 48.95 49.24 TiO2 0.13 0.12 0.40 0.46 0.11 0.04 0.06 Al2O3 31.29 30.84 29.41 29.82 31.92 30.05 32.82 V2O3 0.04 0.12 0.10 0.07 0.03 0.07 0.04 Cr2O3 0.00 0.01 0.01 0.01 0.05 0.00 0.00 MgO 0.48 0.64 0.71 0.63 0.53 0.60 0.65 MnO 0.02 0.01 0.02 0.00 0.01 0.01 0.05 FeO 4.45 4.38 4.54 4.15 3.16 4.81 3.07 NiO 0.00 0.02 0.03 0.00 0.00 0.03 0.05 ZnO 0.00 0.06 0.00 0.03 0.02 0.02 0.00 CaO 0.11 0.21 0.12 0.35 0.14 0.11 0.20 SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 BaO 0.04 0.04 0.01 0.05 0.02 0.02 0.04 Na2O 0.18 0.15 0.17 0.19 0.30 0.17 0.25 K2O 10.54 10.35 9.72 9.68 9.61 10.41 10.33 F 0.18 0.18 0.20 0.16 0.15 0.18 0.19 Cl 0.01 0.02 0.02 0.02 0.05 0.04 0.03 Total 95.82 96.00 95.02 94.23 94.96 95.51 97.02 Formula (a.p.f.u.) Si 0.805 0.813 0.825 0.809 0.813 0.815 0.820 Ti 0.002 0.001 0.005 0.006 0.001 0.001 0.001 Al 0.614 0.605 0.577 0.585 0.626 0.589 0.644 V 0.001 0.002 0.001 0.001 0.000 0.001 0.001 Cr 0.000 0.000 0.000 0.000 0.001 0.000 0.000 Mg 0.012 0.016 0.018 0.016 0.013 0.015 0.016 Mn 0.000 0.000 0.000 0.000 0.000 0.000 0.001 Fe2+ 0.062 0.061 0.063 0.058 0.044 0.067 0.043 Ni 0.000 0.000 0.000 0.000 0.000 0.000 0.001 Zn 0.000 0.001 0.000 0.000 0.000 0.000 0.000 Ca 0.002 0.004 0.002 0.006 0.003 0.002 0.004 Sr 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Ba 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Na 0.006 0.005 0.005 0.006 0.010 0.005 0.008 K 0.224 0.220 0.206 0.205 0.204 0.221 0.219 Fe2+ 0.009 0.010 0.011 0.008 0.008 0.009 0.010 Cl 0.000 0.000 0.001 0.001 0.001 0.001 0.001    145  Tungstates:  Detection limits: Al – 270 ppm, Pb – 2481 ppm, Nb – 657 ppm, Si – 222 ppm, Ca – 588 ppm, W – 2037 ppm, Mn – 531 ppm, Sn – 1664 ppm, F – 645 ppm, Mo – 991 ppm.   Mineral stolzite scheelite Analysis 1 / 1 .  2 / 1 .  Ta2O5 bdl bdl Al2O3 0.01 bdl MgO bdl bdl PbO 48.46 bdl Nb2O5 bdl 0.00 Sc2O3 bdl bdl SiO2 bdl 0.02 CaO 0.09 19.62 WO3 49.60 79.76 FeO bdl bdl MnO 0.03 0.06 ZnO bdl bdl SnO2 bdl 0.07 F 0.05 0.01 TiO2 bdl bdl MoO3 1.44 bdl Total 99.673 99.541 (a.p.f.u.)   Ta 0.00 0.00 Al 0.01 0.00 Mg 0.00 0.00 Pb 16.24 0.00 Nb 0.00 0.00 Sc 0.00 0.00 Si 0.00 0.02 Ca 0.12 17.38 W 16.01 16.26 Fe 0.00 0.00 Mn 0.03 0.04 Zn 0.00 0.00 Sn 0.00 0.02 F 0.18 0.03 Ti 0.00 0.00 Mo 0.75 0.00 O 66.67 66.26 Total 100.00 100.00  146  Sulfides: As, Se, Ag, Ga, Tl, Te we sought but were b.d.l. (below detection limit) Detection limits: Zn – 478 ppm, Fe – 342 ppm, Mn – 192 ppm, Te – 1428 ppm, Cu – 222 pm, Tl – 859 ppm, Ni – 198 ppm, Ge – 724 ppm, As – 1244 ppm, Ga – 323 ppm, Ag – 847 ppm, S – 166 ppm, In – 197 ppm, Pb – 941 ppm, Cd – 1016 ppm.  Mineral pyrrhotite pyrrhotite pyrrhotite pyrrhotite chalcopyrite chalcopyrite chalcopyrite  Analysis 11 / 1 .  57 / 1 .  67 / 1 .  38 / 1 .  13 / 1 .  30 / 1 .  55 / 1 .  Zn 0.00 0.00 0.00 0.00 0.17 0.00 0.05 Fe 46.86 47.14 46.91 46.98 30.29 30.19 30.07 Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Cu 0.00 0.00 0.00 0.00 35.02 35.02 35.00 Ni 0.00 0.00 0.00 0.00 0.00 0.00 0.00 S 52.79 53.53 53.37 53.42 35.30 35.33 35.70 In 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Pb 0.19 0.15 0.13 0.15 0.12 0.13 0.13 Cd 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 99.85 100.81 100.41 100.55 100.90 100.67 100.95 Formula (a.p.f.u.)       Zn 0.000 0.000 0.000 0.000 0.005 0.000 0.001 Fe 1.012 1.007 1.006 1.006 0.987 0.986 0.977 Mn 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Cu 0.000 0.000 0.000 0.000 1.003 1.004 1.000 Ni 0.000 0.000 0.000 0.000 0.000 0.000 0.000 S 1.986 1.992 1.993 1.993 2.004 2.009 2.021 In 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Pb 0.001 0.001 0.001 0.001 0.001 0.001 0.001 Cd 0.000 0.000 0.000 0.000 0.000 0.000 0.000          147  Sulfides (continued):  As, Se, Ag, Ga, Tl, Te we sought but were b.d.l. (below detection limit). Mineral sphalerite sphalerite Fe-rich sphalerite Fe-rich sphalerite Fe-rich sphalerite Fe-rich sphalerite Analysis 10 / 1 .  12 / 1 .  29 / 1 .  37 / 1 .  41 / 1 .  68 / 1 .  Zn 60.68 59.81 56.47 53.58 53.74 57.30 Fe 1.41 2.29 5.31 7.78 8.61 5.16 Mn 0.03 0.10 0.09 0.18 0.12 0.03 Cu 0.02 0.06 0.02 0.00 0.00 0.00 Ni 0.00 0.00 0.00 0.00 0.00 0.00 S 32.97 33.37 33.50 33.28 33.32 33.35 In 0.02 0.00 0.02 0.00 0.03 0.03 Pb 0.00 0.00 0.00 0.00 0.10 0.00 Cd 5.76 5.53 5.37 4.83 4.69 4.78 Total 100.90 101.17 100.78 99.64 100.60 100.65 Formula (a.p.f.u.)      Zn 0.913 0.893 0.841 0.802 0.798 0.854 Fe 0.025 0.040 0.093 0.136 0.150 0.090 Mn 0.001 0.002 0.002 0.003 0.002 0.001 Cu 0.000 0.001 0.000 0.000 0.000 0.000 Ni 0.000 0.000 0.000 0.000 0.000 0.000 S 1.011 1.016 1.018 1.016 1.009 1.014 In 0.000 0.000 0.000 0.000 0.000 0.000 Pb 0.000 0.000 0.000 0.000 0.000 0.000 Cd 0.050 0.048 0.047 0.042 0.041 0.041           148  Sulfides (continued): As, Se, Ag, Ga, Tl, Te we sought but were b.d.l. (below detection limit). Mineral galena galena galena galena galena galena Analysis 17 / 1 .  19 / 1 .  20 / 1 .  21 / 1 .  31 / 1 .  32 / 1 .  Sample # DH11-143 DH11-143 DH11-143 DH11-143 DH11-116A DH11-116A Fe 0.01 0.04 0.03 0.01 0.00 0.02 Cu 0.00 0.11 0.04 0.01 0.01 0.00 Ag 0.13 0.05 0.04 0.15 0.10 0.13 Au 0.00 0.01 0.00 0.00 0.00 0.02 Hg 0.03 0.02 0.05 0.01 0.00 0.00 Pb 85.72 86.48 87.68 86.47 85.88 87.15 Bi 0.93 0.58 0.49 0.66 0.73 0.48 As 0.09 0.02 0.05 0.06 0.10 0.10 Sb 0.00 0.10 0.10 0.01 0.03 0.00 S 13.56 13.49 13.82 13.63 13.46 13.52 Se 0.11 0.05 0.07 0.05 0.16 0.17 Te 0.36 0.10 0.06 0.15 0.08 0.12 Total 100.93 101.06 102.42 101.19 100.56 101.70        cat. norm. 1 1 1 1 1 1 (a.p.f.u.)       Fe 0.000 0.002 0.001 0.000 0.000 0.001 Cu 0.000 0.004 0.001 0.001 0.001 0.000 Ag 0.003 0.001 0.001 0.003 0.002 0.003 Au 0.000 0.000 0.000 0.000 0.000 0.000 Hg 0.000 0.000 0.001 0.000 0.000 0.000 Pb 0.983 0.984 0.987 0.987 0.985 0.988 Bi 0.011 0.007 0.005 0.007 0.008 0.005 As 0.003 0.001 0.001 0.002 0.003 0.003 Sb 0.000 0.002 0.002 0.000 0.001 0.000 S 1.004 0.991 1.006 1.005 0.998 0.990 Se 0.003 0.001 0.002 0.001 0.005 0.005 Te 0.007 0.002 0.001 0.003 0.001 0.002      149  Gold (Au-Ag alloy/“electrum”): Mineral Ag-rich gold  Ag-rich gold  Ag-rich gold  Ag-rich gold  Analysis 115 / 1 .  116 / 1 .  117 / 1 .  118 / 1 .  Sample # DH11-127 DH11-127 DH11-127 DH11-127 Fe 0.63 0.04 0.05 0.04 Cu 0.01 0.06 0.00 0.00 Ag 24.89 23.01 25.11 20.82 Au 75.92 77.92 76.74 81.25 Hg 0.92 0.68 0.79 0.44 Pb 0.00 0.00 0.00 0.00 Bi 0.00 0.00 0.00 0.00 As 0.00 0.00 0.06 0.07 Sb 0.00 0.04 0.13 0.00 S 0.05 0.00 0.00 0.01 Se 0.00 0.00 0.00 0.00 Te 0.00 0.01 0.01 0.00 Total 102.42 101.76 102.88 102.63      cat. norm. 10 10 10 10 (a.p.f.u.)     Fe 0.178 0.010 0.013 0.012 Cu 0.002 0.016 0.000 0.000 Ag 3.649 3.472 3.701 3.168 Au 6.098 6.440 6.194 6.769 Hg 0.073 0.055 0.063 0.036 Pb 0.000 0.000 0.000 0.000 Bi 0.000 0.000 0.000 0.000 As 0.000 0.000 0.012 0.015 Sb 0.000 0.005 0.017 0.000 S 0.026 0.000 0.001 0.007 Se 0.000 0.001 0.000 0.000 Te 0.000 0.001 0.002 0.000      150  Tellurides: Detection limits: Au – 1157 ppm, Cu – 220 ppm, Fe – 262 ppm, Se – 1489 ppm, As – 1274 ppm, Te – 1052 ppm, S – 251 ppm, Pb – 1259 ppm, Bi – 3864 ppm, Ag – 1394 ppm, Sb – 1775 ppm, Hg – 2048 ppm.  Mineral altaite    altaite    altaite    altaite    altaite    altaite    altaite    altaite    Analysis 52 / 1 .  61 / 1 .  85 / 1 .  2 / 1 .  104 / 1 .  18 / 1 .  22 / 1 .  25 / 1 .  Sample # DH11-116A DH11-127 DH11-147c DH11-143 DH11-147c DH11-143 DH11-143 DH11-143 Fe 0.36 0.00 0.06 0.00 0.03 0.11 0.00 0.00 Cu 0.01 0.01 0.00 0.00 0.00 0.18 0.00 0.01 Ag 1.03 0.68 1.34 0.48 0.61 0.56 0.72 0.77 Au 0.04 0.00 0.03 0.05 0.04 0.01 0.00 0.18 Hg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Pb 61.46 60.48 59.89 58.53 58.63 59.83 58.58 59.22 Bi 0.66 1.22 0.39 1.05 1.26 1.80 2.16 1.11 As 0.00 0.02 0.03 0.07 0.04 0.00 0.00 0.01 Sb 0.11 0.22 0.13 0.18 0.20 0.05 0.19 0.21 S 0.06 0.04 0.00 0.00 0.00 0.04 0.05 0.02 Se 0.03 0.05 0.00 0.00 0.02 0.00 0.04 0.00 Te 39.15 38.46 38.18 38.11 38.22 38.79 38.82 38.47 Total 102.90 101.17 100.06 98.48 99.05 101.36 100.55 100.01          cat. norm. 1 1 1 1 1 1 1 1 (a.p.f.u.)         Fe 0.021 0.000 0.004 0.000 0.002 0.006 0.000 0.000 Cu 0.000 0.000 0.000 0.000 0.000 0.009 0.000 0.001 Ag 0.030 0.020 0.041 0.015 0.019 0.017 0.022 0.024 Au 0.001 0.000 0.001 0.001 0.001 0.000 0.000 0.003 Hg 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Pb 0.936 0.954 0.945 0.959 0.951 0.938 0.938 0.949 Bi 0.010 0.019 0.006 0.017 0.020 0.028 0.034 0.018 As 0.000 0.001 0.001 0.003 0.002 0.000 0.000 0.000 Sb 0.003 0.006 0.003 0.005 0.005 0.001 0.005 0.006 S 0.006 0.004 0.000 0.000 0.000 0.004 0.005 0.002 Se 0.001 0.002 0.000 0.000 0.001 0.000 0.002 0.000 Te 0.968 0.985 0.978 1.014 1.006 0.988 1.010 1.001    151   Tellurides (continued): Mineral altaite    altaite    altaite    altaite    altaite    altaite    altaite    Analysis 33 / 1 .  35 / 1 .  39 / 1 .  40 / 1 .  43 / 1 .  96 / 1 .  112 / 1 .  Sample # DH11-116A DH11-116A DH11-116A DH11-116A DH11-116A DH11-147c DH11-147c Fe 0.00 0.00 0.00 0.00 0.22 0.00 0.02 Cu 0.01 0.00 0.01 0.01 0.00 0.00 0.00 Ag 0.59 0.57 0.70 0.63 0.35 0.38 0.47 Au 0.04 0.03 0.03 0.00 0.00 0.04 0.02 Hg 0.00 0.00 0.00 0.00 0.06 0.00 0.00 Pb 59.36 59.92 59.08 59.32 59.97 60.02 60.06 Bi 1.31 1.10 1.46 1.63 1.39 0.75 1.00 As 0.00 0.08 0.02 0.05 0.05 0.04 0.05 Sb 0.19 0.13 0.13 0.14 0.22 0.11 0.00 S 0.05 0.06 0.05 0.04 0.04 0.00 0.01 Se 0.02 0.00 0.05 0.02 0.05 0.00 0.06 Te 38.67 38.45 38.11 38.50 38.47 37.98 38.76 Total 100.23 100.34 99.63 100.32 100.84 99.32 100.46         cat. norm. 1 1 1 1 1 1 1 (a.p.f.u.)        Fe 0.000 0.000 0.000 0.000 0.013 0.000 0.001 Cu 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Ag 0.018 0.017 0.022 0.019 0.011 0.012 0.015 Au 0.001 0.001 0.000 0.000 0.000 0.001 0.000 Hg 0.000 0.000 0.000 0.000 0.001 0.000 0.000 Pb 0.955 0.958 0.950 0.949 0.945 0.971 0.965 Bi 0.021 0.017 0.023 0.026 0.022 0.012 0.016 As 0.000 0.004 0.001 0.002 0.002 0.002 0.002 Sb 0.005 0.003 0.004 0.004 0.006 0.003 0.000 S 0.005 0.006 0.005 0.004 0.004 0.000 0.001 Se 0.001 0.000 0.002 0.001 0.002 0.000 0.003 Te 1.010 0.998 0.995 1.000 0.985 0.997 1.012    152   Tellurides (continued): Mineral frobergite frobergite frobergite frobergite Analysis 78 / 1 .  79 / 1 .  90 / 1 .  91 / 1 .  Sample # DH11-147c DH11-147c DH11-147c DH11-147c Fe 18.10 18.22 18.16 18.27 Cu 0.00 0.02 0.02 0.01 Ag 0.01 0.03 0.00 0.00 Au 0.01 0.04 0.04 0.04 Hg 0.21 0.23 0.25 0.19 Pb 0.01 0.03 0.04 0.00 Bi 0.17 0.02 0.00 0.08 As 0.00 0.00 0.00 0.00 Sb 0.28 0.26 0.30 0.30 S 0.01 0.01 0.01 0.01 Se 0.05 0.02 0.02 0.04 Te 80.22 80.40 80.11 80.17 Total 99.07 99.28 98.95 99.11      cat. norm. 1 1 1 1 (a.p.f.u.)     Fe 0.987 0.987 0.987 0.988 Cu 0.000 0.001 0.001 0.000 Ag 0.000 0.001 0.000 0.000 Au 0.000 0.001 0.001 0.001 Hg 0.003 0.003 0.004 0.003 Pb 0.000 0.000 0.001 0.000 Bi 0.003 0.000 0.000 0.001 As 0.000 0.000 0.000 0.000 Sb 0.007 0.006 0.008 0.007 S 0.001 0.001 0.001 0.001 Se 0.002 0.001 0.001 0.001 Te 1.914 1.906 1.905 1.897     153   Tellurides (continued): Mineral hessite hessite hessite hessite hessite hessite hessite hessite hessite Analysis 51 / 1 .  53 / 1 .  54 / 1 .  56 / 1 .  58 / 1 .  59 / 1 .  60 / 1 .  62 / 1 .  63 / 1 .  Sample # DH11-116A DH11-116A DH11-116A DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 Fe 0.06 0.03 0.07 0.00 0.06 0.13 0.00 0.10 0.21 Cu 0.00 0.01 0.01 0.02 0.00 0.00 0.00 0.00 0.00 Ag 62.91 63.29 62.96 63.33 62.95 63.09 63.47 63.35 62.66 Au 0.25 0.02 0.10 0.00 0.08 0.00 0.05 0.00 0.09 Hg 0.00 0.06 0.09 0.07 0.04 0.00 0.07 0.06 0.04 Pb 0.00 0.00 0.00 0.00 0.02 0.00 0.02 0.00 0.00 Bi 0.10 0.00 0.07 0.00 0.00 0.00 0.00 0.00 0.00 As 0.04 0.05 0.01 0.00 0.03 0.03 0.02 0.03 0.00 Sb 0.02 0.06 0.10 0.20 0.08 0.21 0.10 0.06 0.12 S 0.09 0.09 0.09 0.07 0.06 0.09 0.05 0.06 0.08 Se 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Te 37.14 37.11 37.14 37.07 37.19 37.13 37.06 37.12 37.19 Total 100.62 100.71 100.63 100.76 100.50 100.68 100.83 100.78 100.40           cat. norm. 2 2 2 2 2 2 2 2 2 (a.p.f.u.)          Fe 0.004 0.002 0.004 0.000 0.004 0.008 0.000 0.006 0.013 Cu 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 Ag 1.988 1.992 1.988 1.992 1.990 1.985 1.994 1.990 1.981 Au 0.004 0.000 0.002 0.000 0.001 0.000 0.001 0.000 0.002 Hg 0.000 0.001 0.001 0.001 0.001 0.000 0.001 0.001 0.001 Pb 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Bi 0.002 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 As 0.002 0.002 0.000 0.000 0.001 0.002 0.001 0.001 0.000 Sb 0.000 0.002 0.003 0.005 0.002 0.006 0.003 0.002 0.003 S 0.009 0.009 0.010 0.008 0.007 0.010 0.005 0.007 0.009 Se 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Te 0.992 0.988 0.991 0.986 0.994 0.987 0.984 0.986 0.994     154   Tellurides (continued): Mineral hessite hessite hessite hessite hessite hessite hessite hessite hessite Analysis 64 / 1 .  65 / 1 .  66 / 1 .  69 / 1 .  70 / 1 .  71 / 1 .  72 / 1 .  73 / 1 .  84 / 1 .  Sample # DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 DH11-127 DH11-147c Fe 0.03 0.04 0.03 0.00 0.02 0.02 0.00 0.00 0.01 Cu 0.01 0.00 0.00 0.00 0.02 0.01 0.01 0.00 0.01 Ag 63.28 63.26 63.77 63.08 62.71 63.13 63.15 63.29 62.89 Au 0.15 0.06 0.04 0.05 0.18 0.21 0.03 0.13 0.16 Hg 0.00 0.01 0.09 0.04 0.00 0.07 0.05 0.04 0.12 Pb 0.02 0.01 0.02 0.00 0.01 0.02 0.01 0.01 0.00 Bi 0.00 0.00 0.01 0.02 0.00 0.00 0.02 0.04 0.04 As 0.05 0.03 0.04 0.09 0.04 0.03 0.05 0.00 0.02 Sb 0.02 0.06 0.07 0.17 0.16 0.10 0.07 0.19 0.12 S 0.07 0.05 0.05 0.05 0.06 0.06 0.08 0.07 0.11 Se 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.08 0.00 Te 37.31 37.17 36.78 36.78 36.41 36.73 36.00 36.17 36.49 Total 100.92 100.68 100.89 100.31 99.60 100.38 99.45 100.02 99.96           cat. norm. 2 2 2 2 2 2 2 2 2 (a.p.f.u.)          Fe 0.002 0.002 0.002 0.000 0.001 0.001 0.000 0.000 0.001 Cu 0.000 0.000 0.000 0.000 0.001 0.000 0.001 0.000 0.000 Ag 1.992 1.993 1.992 1.989 1.988 1.989 1.994 1.991 1.989 Au 0.003 0.001 0.001 0.001 0.003 0.004 0.001 0.002 0.003 Hg 0.000 0.000 0.001 0.001 0.000 0.001 0.001 0.001 0.002 Pb 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Bi 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 As 0.002 0.001 0.002 0.004 0.002 0.001 0.002 0.000 0.001 Sb 0.001 0.002 0.002 0.005 0.005 0.003 0.002 0.005 0.003 S 0.007 0.006 0.005 0.006 0.007 0.006 0.008 0.008 0.012 Se 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.003 0.000 Te 0.993 0.990 0.971 0.980 0.976 0.978 0.961 0.962 0.976      155   Tellurides (continued): Mineral hessite hessite hessite hessite hessite hessite hessite Analysis 6 / 1 .  7 / 1 .  14 / 1 .  15 / 1 .  16 / 1 .  24 / 1 .  102 / 1 .  Sample # DH11-143 DH11-143 DH11-143 DH11-143 DH11-143 DH11-143 DH11-147c Fe 0.14 0.02 0.01 0.01 0.06 0.00 0.01 Cu 0.00 0.02 0.02 0.01 0.01 0.01 0.00 Ag 61.82 62.70 62.84 62.85 62.64 60.07 62.80 Au 0.56 0.04 0.03 0.12 0.07 0.21 0.08 Hg 0.20 0.10 0.00 0.04 0.04 0.18 0.11 Pb 0.00 0.00 0.00 0.04 0.00 0.01 0.01 Bi 0.00 0.00 0.01 0.00 0.00 0.00 0.00 As 0.00 0.06 0.00 0.04 0.05 0.02 0.04 Sb 0.11 0.11 0.13 0.08 0.10 0.13 0.08 S 0.07 0.05 0.06 0.07 0.10 0.05 0.04 Se 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Te 38.41 36.63 36.61 36.36 36.72 36.87 36.67 Total 101.31 99.72 99.70 99.62 99.80 97.55 99.85         cat. norm. 2 2 2 2 2 2 2 (a.p.f.u.)        Fe 0.009 0.001 0.001 0.001 0.004 0.000 0.001 Cu 0.000 0.001 0.001 0.000 0.001 0.001 0.000 Ag 1.975 1.990 1.994 1.991 1.988 1.987 1.991 Au 0.010 0.001 0.001 0.002 0.001 0.004 0.001 Hg 0.003 0.002 0.000 0.001 0.001 0.003 0.002 Pb 0.000 0.000 0.000 0.001 0.000 0.000 0.000 Bi 0.000 0.000 0.000 0.000 0.000 0.000 0.000 As 0.000 0.003 0.000 0.002 0.002 0.001 0.002 Sb 0.003 0.003 0.004 0.002 0.003 0.004 0.002 S 0.008 0.005 0.006 0.008 0.010 0.006 0.004 Se 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Te 1.037 0.983 0.982 0.974 0.985 1.031 0.983    156  Tellurides (continued): Mineral stützite stützite stützite Analysis 36 / 1 .  47 / 1 .  26 / 1 .  Sample # DH11-116A DH11-116A DH11-143 Fe 0.02 0.20 0.00 Cu 0.00 0.00 0.00 Ag 59.88 57.83 59.64 Au 0.08 0.02 0.52 Hg 0.10 0.09 0.20 Pb 0.00 1.63 0.00 Bi 0.11 0.00 0.00 As 0.00 0.02 0.05 Sb 0.25 0.14 0.12 S 0.07 0.21 0.05 Se 0.00 0.01 0.00 Te 39.17 38.05 39.26 Total 99.66 98.19 99.83     cat. norm. 5 5 5 (a.p.f.u.)    Fe 0.003 0.033 0.000 Cu 0.000 0.001 0.000 Ag 4.967 4.878 4.953 Au 0.003 0.001 0.024 Hg 0.004 0.004 0.009 Pb 0.000 0.071 0.000 Bi 0.005 0.000 0.000 As 0.000 0.002 0.005 Sb 0.018 0.010 0.008 S 0.020 0.061 0.014 Se 0.000 0.001 0.000 Te 2.746 2.714 2.756     157  Tellurides (continued): Mineral petzite petzite petzite petzite petzite Analysis 114 / 1 .  23 / 1 .  28 / 1 .  98 / 1 .  50 / 1 .  Sample # DH11-147c DH11-143 DH11-143 DH11-147c DH11-116A Fe 0.54 0.00 0.00 0.04 0.07 Cu 0.00 0.00 0.00 0.00 0.01 Ag 44.90 42.72 45.57 48.67 46.16 Au 23.47 30.06 27.55 22.90 31.37 Hg 0.02 0.00 0.00 0.00 0.00 Pb 0.00 0.00 0.00 0.00 0.00 Bi 0.00 0.00 0.00 0.00 0.00 As 0.00 0.00 0.00 0.00 0.00 Sb 0.15 0.10 0.13 0.13 0.09 S 0.04 0.04 0.04 0.03 0.18 Se 0.00 0.00 0.00 0.00 0.00 Te 32.05 24.62 26.86 30.63 25.21 Total 101.15 97.54 100.14 102.39 103.09       cat. norm. 4 4 4 4 4 (a.p.f.u.)      Fe 0.070 0.000 0.000 0.005 0.008 Cu 0.000 0.000 0.000 0.000 0.001 Ag 3.048 2.887 3.000 3.171 2.904 Au 0.873 1.113 0.993 0.817 1.081 Hg 0.001 0.000 0.000 0.000 0.000 Pb 0.000 0.000 0.000 0.000 0.000 Bi 0.000 0.000 0.000 0.000 0.000 As 0.000 0.000 0.000 0.000 0.000 Sb 0.009 0.006 0.007 0.007 0.005 S 0.009 0.009 0.008 0.005 0.038 Se 0.000 0.000 0.000 0.000 0.000 Te 1.839 1.407 1.494 1.687 1.341     158  Tellurides (continued): Mineral kochkarite kochkarite kochkarite kochkarite kochkarite Analysis 74 / 1 .  75 / 1 .  80 / 1 .  82 / 1 .  83 / 1 .  Sample # DH11-147c DH11-147c DH11-147c DH11-147c DH11-147c Fe 0.00 0.02 0.11 0.00 0.00 Cu 0.01 0.01 0.01 0.00 0.00 Ag 0.84 0.82 0.95 1.05 1.10 Au 0.01 0.00 0.13 0.00 0.03 Hg 0.00 0.03 0.08 0.00 0.09 Pb 6.87 7.62 7.25 6.54 6.60 Bi 43.85 44.81 42.79 43.44 43.81 As 0.00 0.00 0.00 0.00 0.00 Sb 0.50 0.63 0.43 0.62 0.54 S 0.01 0.00 0.01 0.00 0.00 Se 0.00 0.00 0.02 0.07 0.05 Te 46.66 47.51 46.53 45.89 46.24 Total 98.74 101.45 98.31 97.63 98.45       cat. norm. 5 5 5 5 5 (a.p.f.u.)      Fe 0.000 0.006 0.038 0.000 0.000 Cu 0.003 0.001 0.003 0.000 0.000 Ag 0.155 0.143 0.173 0.192 0.198 Au 0.001 0.000 0.013 0.000 0.003 Hg 0.000 0.003 0.008 0.000 0.008 Pb 0.661 0.695 0.685 0.621 0.621 Bi 4.181 4.053 4.011 4.087 4.084 As 0.000 0.000 0.000 0.000 0.000 Sb 0.081 0.098 0.070 0.100 0.086 S 0.009 0.000 0.005 0.002 0.000 Se 0.000 0.000 0.006 0.017 0.013 Te 7.287 7.037 7.142 7.070 7.060     159  Tellurides (continued): Mineral rucklidgeite  rucklidgeite  rucklidgeite  rucklidgeite  rucklidgeite  Analysis 88 / 1 .  89 / 1 .  1 / 1 .  3 / 1 .  45 / 1 .  Sample # DH11-147c DH11-147c DH11-143 DH11-143 DH11-116A Fe 0.00 0.00 0.00 0.00 0.03 Cu 0.00 0.00 0.00 0.00 0.00 Ag 1.47 1.40 1.40 1.28 0.96 Au 0.01 0.00 0.00 0.07 0.01 Hg 0.02 0.04 0.00 0.00 0.00 Pb 12.81 12.37 13.67 13.19 12.80 Bi 38.94 37.45 38.38 38.53 41.06 As 0.00 0.00 0.00 0.00 0.00 Sb 0.36 0.28 1.15 0.77 0.06 S 0.00 0.05 0.03 0.00 0.04 Se 0.01 0.10 0.02 0.10 0.03 Te 45.30 44.05 46.29 45.11 44.64 Total 98.92 95.74 100.93 99.04 99.62       cat. norm. 3 3 3 3 3 (a.p.f.u.)      Fe 0.000 0.000 0.000 0.000 0.005 Cu 0.000 0.000 0.000 0.000 0.000 Ag 0.154 0.153 0.143 0.133 0.099 Au 0.001 0.000 0.000 0.004 0.001 Hg 0.001 0.003 0.000 0.000 0.000 Pb 0.700 0.704 0.727 0.717 0.691 Bi 2.110 2.113 2.026 2.076 2.198 As 0.000 0.000 0.000 0.000 0.000 Sb 0.034 0.028 0.104 0.071 0.006 S 0.000 0.018 0.011 0.001 0.013 Se 0.001 0.014 0.002 0.014 0.005 Te 4.019 4.071 4.002 3.979 3.914      160  Tellurides (continued): Mineral rucklidgeite  rucklidgeite  rucklidgeite  rucklidgeite  Analysis 93 / 1 .  95 / 1 .  101 / 1 .  109 / 1 .  Sample # DH11-147c DH11-147c DH11-147c DH11-147c Fe 0.04 0.00 0.09 0.05 Cu 0.00 0.00 0.00 0.00 Ag 1.42 1.45 1.45 0.37 Au 0.01 0.01 0.00 0.00 Hg 0.02 0.07 0.09 0.02 Pb 12.75 12.73 12.61 20.91 Bi 39.22 39.23 39.19 36.03 As 0.00 0.00 0.00 0.00 Sb 0.41 0.47 0.47 0.44 S 0.01 0.01 0.01 0.01 Se 0.04 0.00 0.07 0.00 Te 45.38 45.59 45.53 45.03 Total 99.30 99.55 99.50 102.86      cat. norm. 3 3 3 3 (a.p.f.u.)     Fe 0.008 0.000 0.017 0.009 Cu 0.000 0.000 0.001 0.000 Ag 0.148 0.151 0.150 0.036 Au 0.000 0.000 0.000 0.000 Hg 0.001 0.004 0.005 0.001 Pb 0.693 0.691 0.682 1.076 Bi 2.112 2.111 2.102 1.839 As 0.000 0.000 0.000 0.000 Sb 0.038 0.043 0.043 0.038 S 0.004 0.002 0.002 0.005 Se 0.005 0.000 0.010 0.000 Te 4.003 4.017 4.000 3.765      161  Tellurides (continued): Mineral tellurobismuthite tellurobismuthite tellurobismuthite tellurobismuthite Analysis 8 / 1 .  108 / 1 .  110 / 1 .  107 / 1 .  Sample # DH11-143 DH11-147c DH11-147c DH11-147c Fe 0.00 0.16 0.02 0.05 Cu 0.03 0.00 0.00 0.02 Ag 0.93 0.26 0.36 0.35 Au 0.05 0.03 0.00 0.02 Hg 0.17 0.05 0.07 0.04 Pb 0.07 0.40 0.46 2.27 Bi 36.91 49.85 49.54 48.12 As 0.00 0.00 0.00 0.00 Sb 9.54 0.72 0.62 0.70 S 0.08 0.00 0.03 0.00 Se 0.03 0.07 0.02 0.06 Te 50.12 47.55 48.57 47.64 Total 97.91 99.10 99.69 99.27      cat. norm. 2 2 2 2 (a.p.f.u.)     Fe 0.000 0.023 0.003 0.007 Cu 0.003 0.000 0.000 0.002 Ag 0.065 0.019 0.027 0.026 Au 0.002 0.001 0.000 0.001 Hg 0.006 0.002 0.003 0.002 Pb 0.002 0.015 0.018 0.087 Bi 1.331 1.892 1.908 1.830 As 0.000 0.000 0.000 0.000 Sb 0.590 0.047 0.041 0.046 S 0.019 0.000 0.007 0.000 Se 0.002 0.007 0.002 0.006 Te 2.961 2.956 3.064 2.967      162  Tellurides (continued): Mineral volynskite   volynskite   volynskite   volynskite   volynskite   volynskite   volynskite   Analysis 76 / 1 .  77 / 1 .  5 / 1 .  27 / 1 .  46 / 1 .  94 / 1 .  97 / 1 .  Sample # DH11-147c DH11-147c DH11-143 DH11-143 DH11-116A DH11-147c DH11-147c Fe 0.01 0.01 0.00 0.00 0.38 0.03 0.00 Cu 0.00 0.01 0.00 0.01 0.00 0.00 0.01 Ag 18.54 18.57 19.21 19.82 18.56 19.50 19.57 Au 0.05 0.00 0.06 0.34 0.01 0.01 0.10 Hg 0.10 0.11 0.15 0.13 0.00 0.06 0.04 Pb 0.00 0.00 0.00 0.14 0.04 0.00 0.00 Bi 34.65 34.97 35.10 34.23 34.67 35.55 34.76 As 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sb 0.33 0.25 0.60 0.92 0.01 0.36 0.36 S 0.03 0.02 0.08 0.03 0.07 0.06 0.10 Se 0.03 0.00 0.00 0.00 0.03 0.07 0.00 Te 45.45 44.46 44.85 45.14 43.76 44.14 43.73 Total 99.19 98.39 100.04 100.76 97.54 99.77 98.68         cat. norm. 2 2 2 2 2 2 2 (a.p.f.u.)        Fe 0.001 0.001 0.000 0.000 0.039 0.003 0.000 Cu 0.000 0.001 0.000 0.000 0.000 0.000 0.001 Ag 1.007 1.005 1.012 1.026 0.997 1.019 1.032 Au 0.002 0.000 0.002 0.010 0.000 0.000 0.003 Hg 0.003 0.003 0.004 0.004 0.000 0.002 0.001 Pb 0.000 0.000 0.000 0.004 0.001 0.000 0.000 Bi 0.971 0.977 0.954 0.915 0.961 0.959 0.946 As 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Sb 0.016 0.012 0.028 0.042 0.000 0.017 0.017 S 0.005 0.004 0.015 0.006 0.013 0.011 0.018 Se 0.002 0.000 0.000 0.000 0.002 0.005 0.000 Te 2.087 2.035 1.997 1.975 1.987 1.950 1.949      163  Tellurides (continued):  Mineral volynskite   volynskite   volynskite   volynskite   volynskite   volynskite   Analysis 99 / 1 .  100 / 1 .  103 / 1 .  105 / 1 .  106 / 1 .  113 / 1 .  Sample # DH11-147c DH11-147c DH11-147c DH11-147c DH11-147c DH11-147c Fe 0.00 0.02 0.01 0.12 0.15 0.00 Cu 0.00 0.00 0.00 0.00 0.00 0.00 Ag 19.27 19.40 19.21 19.12 19.31 19.55 Au 0.06 0.01 0.06 0.01 0.02 0.03 Hg 0.08 0.18 0.05 0.00 0.10 0.12 Pb 0.00 0.00 0.00 0.00 0.01 0.00 Bi 35.21 34.50 34.97 34.57 34.92 35.78 As 0.00 0.00 0.00 0.00 0.00 0.00 Sb 0.37 0.37 0.37 0.49 0.45 0.27 S 0.04 0.16 0.04 0.04 0.03 0.02 Se 0.00 0.00 0.00 0.02 0.00 0.01 Te 44.11 44.15 43.91 44.17 44.75 44.61 Total 99.13 98.78 98.62 98.54 99.73 100.38        cat. norm. 2 2 2 2 2 2 (a.p.f.u.)       Fe 0.000 0.002 0.001 0.012 0.015 0.000 Cu 0.000 0.000 0.000 0.000 0.000 0.000 Ag 1.018 1.030 1.020 1.016 1.014 1.020 Au 0.002 0.000 0.002 0.000 0.000 0.001 Hg 0.002 0.005 0.001 0.000 0.003 0.003 Pb 0.000 0.000 0.000 0.000 0.000 0.000 Bi 0.961 0.945 0.958 0.948 0.946 0.963 As 0.000 0.000 0.000 0.000 0.000 0.000 Sb 0.017 0.018 0.018 0.023 0.021 0.012 S 0.007 0.028 0.006 0.007 0.006 0.003 Se 0.000 0.000 0.000 0.002 0.000 0.000 Te 1.971 1.981 1.971 1.985 1.986 1.967      164  A.5 μXRD Targets, GADDS Images, and Diffraction Patterns  Bruker D8 Discover 60 mm Co Gobel mirror, 300 um snout April 22, 2016   Sample DH11-104bi – targets 1 & 2   01   001    -12.552  -6.002  15.089      02   001    -12.757  -6.002  15.089      01   002    -12.552  -6.002  15.089      02   002    -12.757  -6.002  15.089   Sample 104bi –target 1                                165    Sample 104bi – target 2               01-072-1624 (C) - Scheelite - CaWO4 - Tetragonal - I41/a (88)01-087-2096 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)00-044-1486 (*) - Wulfenite, syn - PbMoO4 - Tetragonal - I41/a (88)00-019-0708 (*) - Stolzite, syn - PbWO4 - Tetragonal - I41/a (88)Y + 18.0 mm - File: 104bi_02 [001].rawY + 8.0 mm - File: 104bi_01 [001].rawLin (Counts)01020304050607080901001101201301401501601701801902-Theta - Scale24 30 40 50 60 70 80 90 100166  01-072-1624 (C) - Scheelite - CaWO4 - Tetragonal - I41/a (88)01-087-2096 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)00-044-1486 (*) - Wulfenite, syn - PbMoO4 - Tetragonal - I41/a (88)00-019-0708 (*) - Stolzite, syn - PbWO4 - Tetragonal - I41/a (88)Y + 18.0 mm - File: 104bi_02 [001].rawY + 8.0 mm - File: 104bi_01 [001].rawLin (Counts)01020304050607080901001101201301401501601701801902-Theta - Scale24 30 40 50 60 70 80 90 100                       sto sto 167  Sample 150 - Targets 3 & 4  03   001    -14.280  -6.437  15.101      04   001    -14.084  -6.437  15.111      03   002    -14.280  -6.437  15.101      04   002    -14.084  -6.437  15.111       Sample 150 – target 3                   168  150                             150. DeerHorn               150. DeerHorn [00101-085-0439 (C) - Bismuth Telluride - Bi2Te3 - Rhombo.R.axes - R-3m (166)00-022-0117 (N) - Tsumoite - (Bi,Te)Te - Hexagonal - P-3m1 (164)01-078-1905 (C) - Altaite - PbTe - Cubic - Fm-3m (225)01-088-2302 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)Operations: Background 0.174,0.010 | Range Op. Merge | Import [001]Y + 2.0 mm - File: 150_03 [001].rawLin (Counts)01020304050607080902-Theta - Scale20 30 40 50 60 70 80 90          Sample 150 – target 4         169             00-015-0041 (N) - Antimony Telluride - beta-(Sb,Te) - 01-085-0439 (C) - Bismuth Telluride - Bi2Te3 - Rhombo.R.axes - R-3m (166)00-022-0117 (N) - Tsumoite - (Bi,Te)Te - Hexagonal - P-3m1 (164)01-078-1905 (C) - Altaite - PbTe - Cubic - Fm-3m (225)01-088-2302 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)Y + 18.5 mm - File: 150_04 [001].rawY + 8.2 mm - File: 150_03 [001].rawLin (Counts)01020304050607080901001102-Theta - Scale23 30 40 50 60 70 80 90 100170  Sample 127 - Targets 5, 6, & 7   06   001    -18.610  -6.037  15.104      05   001    -18.404  -6.037  15.104      07   001    -18.976  -6.037  15.104      06   002    -18.610  -6.037  15.104      05   002    -18.404  -6.037  15.104      07   002    -18.976  -6.037  15.104       Sample 127 – target 5                  py hes Au 171    Sample 127 – target 5 chi 1        01-071-1680 (C) - Pyrite - FeS2 - a 5.41700 - b 5.41700 - c 5.41700 - P00-022-0731 (N) - Sphalerite, Hg-rich - (Zn,Hg)S - a 5.45500 - b 5.455000-004-0784 (*) - Gold, syn - Au - a 4.07860 - b 4.07860 - c 4.07860 - F00-034-0142 (*) - Hessite, syn - Ag2Te - a 8.16980 - b 8.94000 - c 8.065Operations: Background 0.174,0.010 | Range Op. Merge | Import [001]Y + 2.0 mm - File: 127_05 [001].rawLin (Counts)01002003004005002-Theta - Scale20 30 40 50 60 70 80172             Sample 127 – target 5 chi 2            173              Sample 127 – target 5 chi 3           174             Sample 127 – target 6            175  01-075-0940 (C) - Chalcopyrite - CuFeS2 - Tetragonal - I-42d (122)00-022-0731 (N) - Sphalerite, Hg-rich - (Zn,Hg)S - Cubic - F-43m (216)00-004-0784 (*) - Gold, syn - Au - Cubic - Fm-3m (225)00-042-1340 (*) - Pyrite - FeS2 - Cubic - Pa-3 (205)01-081-1985 (C) - Hessite - Ag2Te - Monoclinic - P21/c (14)Y + 3.0 mm - File: 127_06 [001].rawLin (Counts)01020304050607080901001101201301401501601701801902002102202302402502602702-Theta - Scale20 30 40 50 60 70 80 90                   176   Sample 127 – target 7                      177  01-071-2219 (C) - Pyrite - FeS2 - Cubic - Pa-3 (205)Y + 1.0 mm - File: 127_07 [001].rawLin (Count s)01002003004005006007008009001000110012001300140015001600170018001900200021002-Theta - Scale20 30 40 50 60 70 80 90 100           Sample 147b -  targets 8, 9, & 10  08   001    -18.983  -4.542  14.970      09   001    -19.471  -4.542  14.970      08   002    -18.983  -4.542  14.970      09   002    -19.471  -4.542  14.970      10   001    -18.876  -4.294  14.953      10   002    -18.876  -4.294  14.953       Sample 147b – target 8      178             01-073-2376 (C) - Chlorite - Mg6Si4O10(OH)8 - Triclinic - C1 (0)01-088-2302 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)00-015-0863 (*) - Tellurobismuthite, syn - Bi2Te3 - Rhombo.H.axes - R-3m (166)Y + 2.0 mm - File: 147b_10 [001].rawLin (Counts)01002003004005006007002-Theta - Scale20 30 40 50 60 70 80 90 100179  Sample 147b – target 9                      180   Sample 147b – target 10   00-018-1173 (N) - Volynskite - AgBiTe2 - Hexagonal - P-3m1 (164)00-034-0142 (*) - Hessite, syn - Ag2Te - Monoclinic - P2/n (13)00-044-1420 (I) - Petzite - Ag3AuTe2 - Cubic - I4132 (214)01-087-2096 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)Y + 1.0 mm - File: 147b_09 [001].rawLin (Count s)01020304050607080901001101201301401502-Theta - Scale23 30 40 50 60 70 80 90 100181  01-073-2376 (C) - Chlorite - Mg6Si4O10(OH)8 - Triclinic - C1 (0)01-088-2302 (C) - Quartz - SiO2 - Hexagonal - P3221 (154)00-008-0027 (N) - Tellurobismuthite - Bi2Te3 - Rhombo.H.axes - R-3m (166)00-015-0863 (*) - Tellurobismuthite, syn - Bi2Te3 - Rhombo.H.axes - R-3m (166)Y + 2.0 mm - File: 147b_10 [001].rawLin (Counts)01002003004005006007002-Theta - Scale20 30 40 50 60 70 80 90 100                 182  A.6 Selected Panchromatic Cathodoluminescence Images of Quartz                       183                         184                         185                         186                         187  Appendix B: Access and History of the Deer Horn Property B.1 Access to Property  The Deer Horn property is directly north of Lindquist Lake and 36 km south of the Huckleberry open-pit copper mine.  Burns Lake is the closest major town, located approximately 135 km northeast of Deer Horn, and serves as a hub for nearby mining operations (Papezik 1957, Lane et al. 2013).  The current claim configuration of the Deer Horn property extends over an area of approximately 5133 hectares, and comprises a total of 18 cell claims [or Mineral Titles Online (MTO’s)].  The elevation of the claims range from 875–1788 m, with mine workings occurring mainly above the treeline (Lane & Giroux 2012, Lane et al. 2013). The property is accessible by helicopter or float plane from neighbouring towns such as Smithers, Burns Lake, or Houston, with flight times of about one hour from each.  It is also accessible by barge from Andrews Bay or Ootsa Lake; upon reaching the landing dock at Lindquist Lake, an overgrown 7.8 km-long road extends up to the claim, where the main adit is located at an elevation of approximately 1290 m (Lane 2009, Lane & Giroux 2012, Lane et al. 2013). B.2 History of the Deer Horn Property The first claim was staked in the area in 1943, approximately 1 km south of Lindquist Peak, where evident scheelite mineralization was found.  This claim was later named the Harrison property (Papezik 1957, Lane & Giroux 2012).  In 1944 Franc Joubin discovered gold-bearing quartz veins about 300 m east of the scheelite occurrence (Joubin 1950, Papezik 1957, Lane et al. 2013).  The Harrison property was optioned by Pioneer Gold Mines Ltd. a short time after Joubin’s discovery.  The property was then trenched and drilled for three consecutive years, completing a total of nearly 4,000 m of drilling, until the group was bought by Deer Horn Mines 188  Ltd. in 1950 (Papezik 1957).  Between 1951 and 1955 Deer Horn Mines Ltd. conducted exploration, underground and surface diamond drilling, and built a road from Whitesail Lake to the property (Lane et al. 2013).  Additional road works and trenching were completed by Granby Consolidated Mining, Smelting, and Power in 1967, but no more drilling or exploration was conducted.  In 1975 the land was returned to the Crown because it was in a “No Staking Reserve” and could potentially become a part of Tweedsmuir Provincial Park.  The “No Staking Reserve” was lifted in 1989 and the property was granted to Golden Knight Resources Inc., who carried out extensive geological mapping, ground sampling, geochemical soil sampling, magnetometer surveying, and road restoration until Repadre Capital Inc. acquired the assets of Golden Knight Resources Inc. in 1990 (Lane 2009, Lane & Giroux 2012, Lane et al. 2013).  Nothing was done on the claim from 1990 to 2000, when Repadre Capital sold it to Guardsmen Resources Inc., who changed all of their legacy claims to MTO (mineral titles online) claims in 2005.  In 2009, Guardsmen Resources Inc. optioned the property to Golden Odyssey Mining Inc., who drilled 35 diamond drill holes totaling 1706 m in length.  Golden Odyssey Mining Inc. became Deer Horn Metals Inc., who continued to conduct exploration, mapping, and drilling from 2009–2011 (Lane 2009, Lane & Giroux 2012, Lane et al. 2013).  No drilling has been done on the Deer Horn property since 2011.  Deer Horn Metals Inc. changed their name to Deer Horn Capital on October 7th, 2014.     

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