Mineralogical Characterization of Uranium Ores, Blends and Resulting Leach Residues from Key Lake Pilot Plant, Saskatchewan, Canada
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MINERALOGICAL CHARACTERIZATION OF URANIUM ORES, BLENDS AND RESULTING LEACH RESIDUES FROM KEY LAKE PILOT PLANT, SASKATCHEWAN, CANADA A Thesis Submitted to the College of Graduate Studies and Research in Partial Fulfillment of the Requirements for the Degree of Master of Science in the Department of Geological Sciences University of Saskatchewan, Saskatoon, SK, Canada By MD. ALAUDDIN HOSSAIN Copyright Md. Alauddin Hossain, October 2014. All rights reserved. PERMISSION TO USE In presenting this thesis in partial fulfilment of the requirements for a Postgraduate degree from the University of Saskatchewan, I agree that the Libraries of this University may make it freely available for inspection. I further agree that permission for copying of this thesis in any manner, in whole or in part, for scholarly purposes may be granted by the professor or professors who supervised my thesis work or, in their absence, by the Head of the Department or the Dean of the College in which my thesis work was done. It is understood that any copying or publication or use of this thesis or parts thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of Saskatchewan in any scholarly use which may be made of any material in my thesis. Requests for permission to copy or to make other use of material in this thesis in whole or part should be addressed to: Head of the Department of Geological Sciences University of Saskatchewan 114 Science Place Saskatoon, Saskatchewan Canada S7N 5E2 i ABSTRACT The production and storage of uranium mine mill tailings have the potential to contaminate local groundwater and surface waters with metals and metalloids. As such, an understanding of the solids reservoirs for potential contaminants in uranium ore blends and leach residues (solid wastes generated by the milling of ore) is required to predict long-term controls on these contaminants in tailings porewaters. This study characterized the distribution of the elements of concern (EOCs; As, Mo, Ni, and Se) in uranium ores and waste rock used to blend the mill feeds in the milling process and leach residues from the Key Lake mining operation, Saskatchewan. This study also evaluated the alteration of the clay minerals in these uranium ores, waste rocks and leach residues. X-ray diffraction, electron micro-probe, and mineral liberation analyses showed that the reservoirs for As, Mo, Ni, and Se (in ores and ore blends) were dominated by sulphides including cobaltite, gersdorffite, molybdenite, pyrite, galena and chalcopyrite, secondary Ni-arsenates (annabergite?), Fe-arsenate (scorodite?) and Ni-Co/Ni- sulfates. The secondary arsenates and sulfates present in special waste were identified as major As, Mo, Ni, and Se bearing minerals and most likely the product of oxidation of arsenide-bearing sulphide minerals within the special waste rock. Analyses also showed that sulphides and arsenates occurred in trace amounts in the ores and special waste rock (0.5 to 1.0 wt %). Data showed that 55 to 90% pyrite, 36 to 51% chalcopyrite, 23 to 37% molybdenite, and 52 to 70% galena remained unleached in the leach residues after milling of the ore blends. The percentages of unleached minerals varied between mill feeds and were dependent on the grain-size distribution and the degree of mineral liberation. Cation exchange capacity (CEC) analysis indicated an increase of the CEC values in the leach residues suggesting possible evolution of 2:1 layers into high-charge layers during the milling. ii ACKNOWLEDGEMENTS I would like to express my special appreciation and gratefulness to my supervisors Prof. Dr. Jim Hendry and Prof. Dr. Yuanming Pan, for their guidance, advices and valuable suggestions throughout my M.Sc. study and research. I would like to thank them for encouraging me and for allowing me to grow as a graduate student. Sincere thanks to my committee member Dr. Tom Kotzer for his insightful comments and research questions about my research that improved my thesis. I also want to thank my defense external Dr. Derek Peak for an enjoyable defense, and for your brilliant comments and suggestions. Sincere thanks to Dr. Joseph Essilfie-Dughan. His valuable suggestions, ideas and recommendations have encouraged me along the way. I am indebted to Dr. Mario Gomez for teaching me XRD and Raman spectroscopy. Special thanks to Dr. Ali Hooshiar, for his cordial inspiration and guidance with clay minerals analysis. I would also like to thank Mr. Tom Bonli for helping me with the EPMA and SEM, and Dr. Jianzhong Fan for collecting ICP-MS data for me. Thanks to Mr. Michael Shaffer for teaching me Mineral Liberation Analysis (MLA) and helping me to collect MLA data. Finally, I would also like to acknowledge Cameco Corp., NSERC, Department of Geological Sciences and the University of Saskatchewan for financial support. iii TABLE OF CONTENTS PERMISSION TO USE i ABSTRACT ii ACKNOWLEDGEMENTS iii Chapter 1 Introduction 1 1.1 Overview 1 1.2 Tailings management 7 1.3 Objectives of the study 8 Chapter 2 Literature review 10 2.1 Location of the mill and milling process 10 2.2 Geology of the McArthur River deposit 12 2.3 Geology of the Millennium deposit 15 2.4 Key Lake special wastes 16 2.5 Mineralogy of uranium deposits 18 2.6 Clay minerals: structures and properties 21 2.6.1 The 1:1 clay minerals 22 2.6.2 The 2:1 clay minerals 23 2.6.3 The 2:1:1 clay minerals 24 2.6.4 Mixed-layer clay minerals 24 2.6.5 Layer charge and variable charge 25 2.6.6 Cation exchange capacity 26 Chapter 3 Geochemical and mineralogical analysis 27 3.1 Inductively coupled plasma spectrometry (ICP-MS) 27 3.2 X-Ray diffraction 27 3.3 Electron probe micro-analyzer (EPMA) 29 3.4 Automated mineralogy 30 3.4.1 Mineral liberation analysis 32 3.4.2 Instrumentation and performance 34 Chapter 4 Material and methods 40 4.1 Mini-mill design and sample collection 40 4.2 Whole-rock geochemistry 41 4.3 X-ray diffraction analysis 41 4.4 Electron micro-probe analysis 42 4.5 Mineral liberation analysis 42 4.6 Cation Exchange Capacity 43 Chapter 5 Results and discussion 44 5.1 Elemental analysis 44 iv 5.2 Primary minerals 49 5.2.1 XRD analysis 49 5.2.2 Electron microscopy analysis 51 5.2.3 Mineral composition 59 5.2.4 Distribution of the Elements of Concern (EOCs) 69 5.2.5 Mineral liberation analysis 79 5.2.5.1 Quantitative modal mineralogy 82 5.2.5.2 Grain size distribution 84 5.2.5.3 Liberation and leaching 86 5.3 Clay minerals 91 5.3.1 XRD analysis 91 5.3.2 Cation exchange capacity (CEC) 97 Chapter 6 Summary and conclusion 101 Chapter 7 Suggestions for future research 104 References 105 Appendix A Elemental assay of the studied samples using ICP-MS 122 Appendix B Calculated elemental assay using MLA 124 v CHAPTER 1 INTRODUCTION 1.1 Overview Increase in global energy demand coupled with global warming associated with fossil fuel has made nuclear energy a viable alternative option for both developed and developing economies. This has resulted in a demand for uranium (U) globally. U ore deposits spread out all over the world and are found in large quantities in Australia, Kazakhstan, and Canada. The Athabasca Basin, located in northern Saskatchewan, Canada, hosts the largest and richest reserves of U ore in the world (Jamieson and Frost, 1997). Presently 19% of the world’s U is produced from this Basin (IAEA, 2012). The mining and milling of U ores result in the generation of large masses of tailings, estimated to be about one billion tons from 4000 U mines world-wide (IAEA, 2004; Abdelouas, 2006). Globally, U ore with low carbonate content is extracted by acid leaching. In case of U ore with high carbonate contents, alkaline leaching is employed. After ore extraction, the residues are dominated by solid residues that contain unleached primary minerals and secondary minerals formed during raffinate neutralization. Raffinate is the remaining solution after U extraction. Both the solids and liquid raffinate are neutralized by the addition of CaCO 3 and/or Ca(OH) 2 (Abdelouas, 2006). Then these materials are discharged into the tailings management facility (TMF) which can be a large waste retention pit or lake. The highest amount of tailings has been generated so far in Kazakhstan (IAEA, 2004). Canada has produced 3% of the global U tailings which is equal to around 30 million tonnes of tailings (Scissons, 1997; IAEA, 2004). In 1953, Beverlodge mill first started U production and associated tailings (Donahue, 2000). Before 1996, the U mill tailings were discharged in above ground TMFs at Rabbit Lake, Cluff Lake and Key lake sites (Scissons, 1997; Donahue, 2000). The tailings consist of the processed waste materials from the mill. These materials usually contain naturally occurring radionuclides (e.g. U 238 , Ra 226 , Rn 222 , Th 230 ), and toxic metals (e.g. As, Se, Pb, Hg) found in U ores (Nilsson and Forssberg, 1988; Landa et al., 1991; Lottermoser and Ashley 2005; Abdelouas, 2006). These elements are frequently referred to as elements of concern (EOCs). Tailings located in this region are generally characterized by 15 elevated concentrations of Ra 226 , As, Ni, Mo and Se (Essilfie-Dughan et al., 2013, 2012, 2011; Gomez et al., 2013; Liu and Hendry, 2011; Moldovan and Hendry, 2005; Moldovan et al., 2008, 2003; Shaw et al., 2011). Some of these elements can have adverse effects on human health and aquatic life/biota (Lener and Bibr, 1984, USEPA, 1998 and Goldhaber, 2003).