THE GEOCHEMISTRY of SEDIMENTS and MINE TAILINGS in the ALICE ARM AREA. by ALBERT JUSTIN LOSHER Diplom. Technische Universitat Mu
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THE GEOCHEMISTRY OF SEDIMENTS AND MINE TAILINGS IN THE ALICE ARM AREA. by ALBERT JUSTIN LOSHER Diplom. Technische Universitat Munchen, 1981 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES Oceanography We accept this thesis as conforming ta the required standard THE UNIVERSITY OF BRITISH COLUMBIA OCTOBER 1985 © ALBERT JUSTIN LOSHER, 1985 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia 1956 Main Mall Vancouver, Canada V6T 1Y3 •6 (3/81) ABSTRACT A geochemical study of the composition of natural sediments and contaminating mine tailings in Hastings and Alice Arms has been carried out. Apart from the geochemical investigation on the solid fraction, pore waters from six sediment cores have been analyzed to evaluate the diagenetic processes in the sediments of these two inlets. Differences in the mineralogy as well as in the chemical composition of the sediments were used to distinguish the natural sediments from contaminated sediments and pure tailings. In Alice Arm, two types of tailings could be differentiated with these methods. The first tailings type originated from the Kitsault Mo-deposit, which was mined in the past two decades by the B.C. Molybdenum Corporation and AMAX/Canada. These tailings are characterized by a number of features which make them distinguishable from natural sediments. The K-feldspar content of the tailings is significantly increased, mainly at the expense of plagioclase, which is the main characteristic for the mineralogical identification of this tailings type. The enhanced K-feldspar content is the cause for increased K and Rb values in the Mo-mine tailings. Another indicator specific to these recent tailings is an increased Mo content. The second tailings type is derived from an older mining operation in the Kitsault Valley, most likely the Dolly Varden Silver Mine. A specific indicator for these tailings is their high Ba content which is due to large amounts of barite. This mineral phase could be identified by X-ray diffraction methods in a heavy mineral fraction of the relevant sediment layers. Both tailings types show enrichment in their Pb, Zn and S concentrations, caused by an increased amount of metal-sulphides in the ore materials. In this area, these elements can therefore serve as a general indicator for the contamination of natural sediment with either tailings type. The interstitial water analyses indicated that the sediments in both inlets become reducing at a fairly shallow depth (10-15 cm), resulting in the mobilization of Mn, Fe and Mo from the solid phase. In the deeper parts of the cores, consumption of these metals could usually be observed which is likely due to precipitation of authigenic components. The dissolved Mo concentrations in the sediments contaminated with the modern tailings were much higher than in the natural sediments. In the pore water of the pure tailings the concentration reaches some 300 times that of the overlying water, which is the highest value ever reported for saline pore waters. These high Mo concentrations must support a flux of Mo from the sediment into the overlying water, and it is shown that such a flux could increase the inventory of naturally occuring dissolved Mo in the deep waters of Alice Arm by up to 4%. ii Table of Contents ABSTRACT i 1. INTRODUCTION 1 1. STUDY AREA 3 1. Physiography 3 2. GEOLOGICAL SETTING 6 1. Regional geology 6 2. Geology of the Kitsault intrusives 9 3. Sediment supply 10 3. MINING HISTORY OF THE ALICE ARM AREA 10 1. History of the Lime Creek Molybdenum Deposit 13 2. PHYSICAL OCEANOGRAPHY OF ALICE AND HASTINGS ARMS 14 1. Temperature and Salinity Distribution 14 2. Currents 17 3. Interna] Waves 18 4. Recent Sedimentation . 19 5. Previous Work on Alice Arm and Hastings Arm Sediments 21 3. MINERALOGY 22 1. INTRODUCTION 22 2. MINERAL IDENTIFICATION 23 1. QUARTZ 23 2. FELDSPAR 23 1. Plagioclase 23 2. K-Feldspar 25 3. CLAY MINERALS 25 1. Chlorite 25 2. Mica 26 3. Kaolinite 26 4. HALITE 26 5. BARITE 26 6. HORNBLENDE 27 7. SPHALERITE 27 8. PYRITE 27 9. MOLYBDENITE 27 3. MineraiogicaJ Composition of Natural and Contaminated Sediments .... 27 4. GEOCHEMISTRY OF THE MAJOR ELEMENTS 33 1. INTRODUCTION 33 2. DISTRIBUTION OF THE ELEMENTS 34 1. Silicon and aluminium 34 2. Titanium 41 3. Potassium and sodium 45 4. Calcium 45 5. Magnesium and lithogenous iron 50 6. Manganese and oxide iron 55 7. Phosphorus 58 8. Sulphur 60 9. Carbon 63 5. MINOR ELEMENT DISTRIBUTION 66 iii 1. Introduction 66 2. DISTRIBUTION OF THE MINOR ELEMENTS 66 1. Distribution of Cobalt, Chromium, Nickel and Vanadium 67 2. Distribution of Molybdenum, Copper, Lead and Zinc 72 3. Distribution of Rubidium 81 4. Distribution of Barium and Strontium 84 5. Distribution of Zirconium 87 6. SEDIMENTS INFLUENCED BY THE ANYOX OPERATION .... 90 1. MAJOR ELEMENTS 90 2. MINOR ELEMENTS 92 7. INTERSTITIAL WATER CHEMISTRY 95 1. INTRODUCTION 95 2. NUTRIENT DISTRIBUTION IN THE INTERSTITIAL WATER 97 1. Distribution of interstitial silica 97 - 2. Distribution of¥0\~, NOJ, NHj, SO* , H2S and titration alkalinity ... 99 3. METAL DISTRIBUTION IN THE INTERSTITIAL WATER 113 1. Distribution of Mn2+ . 115 2. Distribution of Fe2+ in interstitial water 118 3. Distribution of Mo in interstitial water 119 4. DISCUSSION 120 8. SUMMARY 130 Appendix I: Sample collection and initial sample preparation 135 Appendix II: Analytical methods 136 1. Pore water sampling and analysis 136 2. Titration alkalinity 137 3. Sulphate 137 4. Nutrient analysis 138 5. H2S determination 138 6. Dissolved Fe, Mn and Mo 139 7. X-ray diffraction analysis 139 1. Sample preparation 141 2. Operating conditions 142 8. X-ray fluorescence spectrometry 142 1. Major element sample preparation 142 2. Minor element sample preparation 143 3. XRF-analytical procedure 143 4. Accuracy of the measuring program 145 9. Correction for sea salt effects 146 10. Carbon analysis 146 1. Total carbon 146 2. Carbonate carbon 147 Appendix IH: Chemical data 149 Bibliography 182 iv List of Figures 1. Study area and core locations 4 2. Longitudinal sections of the inlets 5 3. Geological map of the Alice Arm area 8 4. Mineral claims in the Alice Arm area 12 5. Monthly runoff for Alice Arm drainage area 15 6. Temperature and Salinity profiles in Alice Arm 16 7. Generalized grainsize distribution of Alice Arm sediments 20 8. Slow speed high resolution XRD-scan 24 9. XRD-scan from contaminated sediments 31 10. Vertical distribution of Si 35 11. Vertical distribution of Al 36 12. Si versus Al for core AA-8 39 13. Si versus Al for cores HA-2, AA-5 and AA-8 40 14. Vertical distribution of Ti 42 15. Ti versus Al for cores HA-2, AA-5 and AA-8 44 16. Vertical distribution of Na and K 46 17. Na versus K for cores HA-2, AA-5 and AA-8 47 18. Distribution of total and cabonate free Ca 49 19. Vertical distribution of Mg 51 20. Vertical distribution of Fe 52 21. Mg versus Fe for cores HA-2, AA-5 and AA-8 54 22. Vertical distribution of Mn 56 23. Vertical distribution of solid phase phosphorus 59 24. Total sulphur distribution in the solid sediment 62 25. Vertical distribution of C 64 26. Correlation of Cr and Ni with V 69 27. Correlation of Ni, Cr, V and Co with Fe 70 28. Correlation of Ni, Cr, V and Co with Mg . 71 29. Vertical distribution of Co, Cr, Ni and V 73 30. Vertical distribution of Mo, Cu, Pb and Zn 76 31. Correlations of K, Si, Fe and Al with Mo 77 32. Relationships of Mo with Cu, Pb and Zn 79 33. Relationship of Cu, Pb and Zn 80 34. Correlation of Rb and K 82 35. Vertical distribution of Rb 83 36. Correlation of Ba and Sr 85 37. Vertical distribution of Ba and Sr 86 38. Vertical distribution of Zr 88 39. Minor and major element distribution at station HA-6 93 40. Dissolved silica profiles 98 41. Biologically mediated redox processes 100 42. Distribution of dissolved constituents in core HA-2 102 43. Distribution of dissolved constituents in core HA-6 103 44. Distribution of dissolved NH4 , PO4- and Mo in core AA-4 104 45. Distribution of dissolved constituents in core AA-4 105 46. Distribution of dissolved constituents in core AA-5' 106 47. Distribution of dissolved constituents in core AA-1 107 v 48. Distribution of dissolved constituents in core AA-8 108 49. Theoretical profiles of interstitial constituents 114 50. Pore water Mo and solid phase Mo 121 51. Pore water Mo vs. solid Mo from core AA-4 126 52. Eh/pH diagram for aqueous Mo species 128 vi List of Tables 1. Stratigraphy of the Alice Arm area 7 2. Feldspar peak-height ratios from Hasting and Alice Arm sediments 30 3. Si/Al ratios of Hastings and Alice Arm sediments 37 4. Mg/Al ratios of Hastings and Alice Arm sediments 53 5. C/N ratio of cores HA-2 and AA-8 65 6.