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Cobalt, Nickel and Selenium in Tasmanian Ore Minerals

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Cobalt, Nickel and Selenium in Tasmanian Ore Minerals COBALT, NICKEL ANU SELENIUM IN TASMANIAN ORE MINERALS by G. D. LOFTUS-HILLS, B.Sc. (lions.) Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy. UNIVERSITY OF TASMANIA HOBART 1968 This thesis contains no material which has been accepted for the award of any other degree or diploma in any University and, to the best of my knowledge and belief, contains no copy or paraphrase of material previously published or written by another person, except where due reference is made in the text of the thesis. G. D. LOFTUS-HILLS. University of Tasmania, November, 1968, ABSTRACT Analyses of Co, Ni and Se in pyrites and other minerals from a wide variety of Tasmanian ore deposits support a genetic relationship between the Mt. Lyell (pyritic - Cu) and Rosebery (banded In-Pb-Cu) deposits, and the Cambrian eugeosynclinal volcanic rocks in which they occur. The concentration trends for all the ores due to fundamental availability contain smaller-scale components due to depositional processes, which, except in one case, do not interfere with these trends. The components include impoverishment of Co (and Ni) during remobilization of sulphides, increase in Ni and decrease in Co away from the centre of zoned deposits, impoverishment of Ni (and Co) in replacement as compared with vein lodes, and regular and irregular partitioning of respectively Co-Ni and Se between coexisting minerals. The trends of Co-Ni in pyrite due to availability include the following: (a) The sedimentary-diagenetic pyrites generally contain Co/Ni < 0.5, but show no correlation of Co-Ni values with rock type, age, or degree of recrystallization. (b) Pyrites in the Cambrian acid-intermediate igneous rocks have Co/Ni ratios ranging 1-150, and contain up to 0.8% Co. (c) Pyrites from Devonian hypogene replacement and vein deposits show two main trends - 0-1500 ppm Ni, with Co/Ni < 1; and 0100 ppm Co, with Ni ranging 10-100 ppm. The Se contents of sulphides associated with Cambrian and Devonian acid-intermediate igneous activity are indistinguishable, but the Savage River magnetite ore, the Cuni Cu-Ni ore, and particularly the Mt. Lyell ore are all enriched in Se, whereas the Rosebery ore is impoverished. The Co-Ni values in the Mt. Lyell and Rosebery ores follow the trend for pyrites in the Cambrian acid-intermediate igneous rocks. The dispersion of Se at Mt. Lyell is consistent with the postulated open-cast origin for the massive ores, and within the Rosebery lode, the stratification of the Co-Ni values, and their gradation between . lode and normal sedimentary types, strongly suggest a sedimentary origin. These and other collated data suggest that ores associated with geo- synclinal vulcanism may be characterized by (i) high to very high Co/Ni ratios, and often marked impoverishment in Ni, (ii) greater Co and Ni concentrations associated with Cu than with Pb-Zn ores, both within and between deposits, and (iii) a tendency for Co to correlate with Cu within deposits. In Tasmania, Se and 5S 34 values are more closely controlled than Co-Ni in their fundamental availability by other than genetic factors, and within deposits they show less variation due to depositional processes. Selenium was analyzed by X-ray fluorescence spectrography, and Co and Ni by atomic absorption spectrophotometry. In the latter technique, because Fe caused both non-atomic absorption and chemical interferences in the flame, it was extracted with di-isopropyl ether. CONTENTS Page 1. INTRODUCTION 1 SCOPE OF THESIS 1 ACKNOWLEDGEMENTS 2 2. THE STUDY OF TRACE ELEMENTS IN ORE MINERALS 4 DISPERSION OF TRACE ELEMENTS 4 APPLIED STUDIES 5 Metallogenic Provinces 5 Environments and Conditions of Deposition 7 PROBLEMS OF INVESTIGATION 10 THE STUDY OF TASMANIAN ORES 12 3. DISPERSION OF COBALT, NICKEL, SELENIUM AND CADMIUM 15 COBALT AND NICKEL 15 Crystal Chemistry 15 Primary Dispersion 18 - Availability 18 - Depositional processes 24 Secondary Dispersion 24 - Sedimentation 24 - Metamorphism 28 Discussion 29 SELENIUM • 31 Crystal Chemistry 31 Primary Dispersion 32 - Availability 32 - Depositional processes 33 Secondary Dispersion 34 - Sedimentation 34 - Metamorphism 35 Discussion 35 CADMIUM IN SPHALERITE 36 SUMMARY 38 4. SAMPLING AND ANALYSIS 40 SAMPLING 40 SAMPLE PREPARATION 41 ANALYSIS 42 Cobalt and Nickel 43 Selenium 59 Copper, Iron and Zinc 62 5. METALLOGENESIS OF TASMANIA 65 GEOLOGICAL HISTORY 65 METALLOGENIC HISTORY 69 6. COBALT, NICKEL, SELENIUM AND CADMIUM IN ORE MINERALS 80 COBALT AND NICKEL ANALYSES 84 Sedimentary-Diagenetic 84 Precambrian (?) Intramagmatic 91 Cambrian Intramagmatic 91 - Acid-intermediate Rocks 91 - Mafic-ultramafic Rocks 91 Devonian Intramagmatic and Hydrothermal 92 Mt. Lyell 93 Rosebery-Hercules District 93 Mt. Farrell group, Mt. Remus 94 Lake George Mine, Captain's Flat, N.S.W. 94 SELENIUM ANALYSES 95 ANALYSES OF CADMIUM IN SPHALERITE 96 DEPOSITIONAL AND POST-DEPOSITIONAL VARIATIONS 97 Distribution Functions 97 Variation within Single Minerals 98 Correlations with Mode of Emplacement 100 - Massive-disseminated 100 - Vein-replacement 100 - Vein-sedimentary 102 Remobilization 104 Partition between Minerals 107 Dilution 109 Zoning 110 Discussion 113 METALLOGENIC SUBPROVINCES 114 ORES OF UNCERTAIN ORIGIN 115 Savage River 115 Mt. Lyell 117 Rosebery-Hercules District 120 Mt. Farrell 123 Magnet 124 Mt. Remus 124 Lake George Mine, Captain's Flat, N.S.W. 124 Discussion 125 CONCLUSIONS 126 Processes 126 Mineralization of Known Origin 129 Mineralization of Uncertain Origin 130 Investigational Procedures 132 Generalizations 132 REFERENCES 134 APPENDIX 1 : CADMIUM AND IRON IN SPHALERITES - SAMPLE PREPARATION AND ANALYSES. APPENDIX 2 : ANALYSES OF CADMIUM AND IRON IN TASMANIAN SPHALERITES. APPENDIX 3 : SPECTROPHOTOMETRIC DETERMINATION OF COBALT - 2-NITROS0-1-NAPHTHOL METHOD. APPENDIX 4 : ATOMIC AbSORPTION SPECTROPHOTOMETRIC DETERMINATION OF COBALT AND NICKEL. APPENDIX b INDEPENDENT SELENIUM ANALYSES. REFERENCES : APPENDICES. APPENDED REPRINTS : (i) Loftus-Hills and Solomon (1967). (ii) Loftus-Hills, Solomon and Hall (1967). LIST OF FIGURES Following page 3.1 Suggested partition of Co and Ni between ore minerals. 15 4.1 CompariSOn of Ni analyses by atomic absorption and )01F. 44 4.2 Comparison of Co analyses by atomic absorption and spectrophotometry. 44 4.3 Interferences in the atomic absorption analysis of Co and Ni in Fe-rich solutions. 48 4.4 Atomic absorption analysis: erratic dilution behaviour of Fe-rich solutions of Zn and Co. 51 4.5 Comparison of Se analyses by three laboratories. 61 4.6 XRF analysis: standard graphs for CU, Fe and Zn. 64 5.1 GeOlogical map of Tasmania. 65 5.2 summary of geological history and mineralization of the mineralized areas of Tasmania. 66 - 5.3 Locality map for the sets of samples other than from the west coast of Tasmania. 66 5.4 Geological and locality map of the west coast of Tasmania. 66 5.5 Geological and locality map of the Mt. Lyell area. 72 5.6 Distribution of S -isotope ratios from some ores and sedimentary pyrites within the Mt. Read Volcanics. 73 5.7 Geology of the Rosebery and Hercules deposits. 74 5.8 Geological and locality map of the Tullah area. 76 6.1 Co and Ni in sedimentary -diagenetic pyrites ' with definition of Trend I. 84 Following • page 6.2 Textures of some sedimentary pyrite nodules. 89 6.3 Co and Ni in pyrites and magnetites from Savage River. 91 6.4 Co and Ni in pyrites, magnetites, and Cu-Ni ore, from mineralization in Cambrian igneous rocks, with definition of Trend II. 91 6.5 Co and Ni in pyrites and pyrrhotites from Devonian ores: west coast area. 92 6.6 Co and Ni in pyrites from Devonian ores: Moina and north-east areas. Definition of Trends III, IV, and V. 92 6.7 Co and Ni in pyrites and chalcopyrites from the West Lyell area. 93 6.8 Co and Ni in pyrites from Mt. Lyell lodes other than in the West Lyell area. 93 6.9 Co and Ni in pyrite and pyritic ore from the main lode, Rosebery Mine. 93 6.10 Co and Ni in pyrites and pyritic ore, Rosebery-Hercules area. 93 6.11 Co and Ni in pyrite (and arsenopyrite) from the mines in the Tullah area (Mt. Farrell group), and in pyrite from Mt. Remus, and Captain's Flat. 94 6.12 Histogram of all Se analyses. 95 6.13 Histogram of all analyses of Cd in sphalerite. 96 6.14 Co and Ni distribution histograms. 97 6.15 Variation in Co and Ni concentrations in. one mineral within single specimens. 98 Fig. Following page 6.16 Variation of Se concentration in one mineral within single specimens. 99 6.17 Distribution of Se concentrations in the different ore-types at Mt. Lyell. 99 6.18 Locality and geological maps of the Mt. Bischoff area. 100 6.19 North-south cross-section through Mt. Bischoff. 100 6.20 Cross-sections through the Renison Bell Mine. 100 6.21 Co and Ni in pyrite, pyrrhotite and arsenopyrite from vein and replacement deposits at Mt. Bischoff and Renison Bell. 101 6.22 Averaged Co and Ni concentrations for Mt. Bischoff and Renison Bell, and within-specimen concentration variations. 101 6.23 Co and Ni in pyrites and pyrrhotites from the Nairne Deposit, South Australia. 103 6,24 The effect of remobilization on the Co and Ni contents of pyrite and chalcopyrite, West Lyell. 105 6.25 Partition of Co and Ni between associated minerals - individual specimens. 107 6,26 Averaged results of the partitioning of Co and Ni between pyrite and other associated minerals. 107 6.27 Variation of parameters of possible thermometric significance with spatial position at Mt. Bischoff. 110 Fig. Following page 6.28 Spatial distribution of Co and Ni in pyrite, pyrrhotite, and arsenopyrite at Mt. Bischoff. 110 6.29 Zoning of Co and Ni at Zeehan and Story's Creek.
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