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Platinum-Group Elements Within the Merensky Reef, Western Limb, Bushveld Complex: Results of a High Resolution Mineralogical and Geochemical Study

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Platinum-Group Elements Within the Merensky Reef, Western Limb, Bushveld Complex: Results of a High Resolution Mineralogical and Geochemical Study Platinum-group elements within the Merensky reef, Western Limb, Bushveld complex: results of a high resolution mineralogical and geochemical study by Justine Magson For submission in accordance with the requirements for the degree Magister Scientiae in the Faculty of Natural and Agricultural Sciences, Department of Geology at the University of the Free State; 2016 PART 1 (Main Text) Supervisor: Prof. M. Tredoux, Department of Geology, UFS Co-supervisor: Dr. F. Roelofse, Department of Geology, UFS 1 DECLARATION I, Justine Magson, declare that this document is my own work, that it has not been submitted for any degree or examination in any other university, and that all the sources I have used or quoted have been indicated and acknowledged by complete references. Justine Magson …………………….. ……………………… Signed Date i ACKNOWLEDGEMENTS I would like to thank my supervisor Prof M. Tredoux and my co-supervisor Dr F. Roelofse, both from the department of Geology at the University of the Free State, for assisting me with everything from lab work, travel arrangements, financial problems and for their expertise and guidance. Thanks to: The Department of Geology, University of the Free State, for the use of the facility, laboratories and for sample preparation. The Inkaba YeAfrica Project for providing funding for the project. Mr B. Cilliers and Mr C. Vermaak from Impala Platinum Mine for the samples, financial support and assistance. Without you this project wouldn’t be possible. Dr. I. McDonald, School of Earth and Ocean Sciences, Cardiff University, Wales, for the use of the inductively coupled plasma mass spectrometer, his assistance, patience and hospitality during my stay in Cardiff. Mrs C. Cloete from the Council for Geoscience, South Africa, for her assistance and willingness to always help in sample preparations and for her advice. Dr. G. Costin and the Geology Department of Rhodes University for the use of the Jeol JXA 8230 Superprobe, instrument sponsored by NRF/NEP grant 40113 (UID 74464) is kindly acknowledged. Special thanks to Mrs R. Immelman for helping me with travel arrangements, administration and accountancy work. ii ABSTRACT The formation of the Merensky reef still remains controversial despite of its economic importance and decades of research. Remaining questions like, the variability of the Merensky reef and how this effects the platinum distribution (e.g. whether the grade or distribution of platinum is influenced by the presence or not of pegmatoidal Merensky reef, whether PGE distribution are more associated with sulphides or with chromites) are still unanswered. Data were generated in order to address some of these questions. This study was undertaken in the south-western portion of the Western lobe of the Bushveld Complex on intersections of pegmatoidal and non-pegmatoidal Merensky reef from Impala Platinum Mine. The two non-pegmatoidal reefs correspond to the normal Merensky ‘A’ type reef and the pegmatoidal reef corresponds to the Merensky ‘B’ type reef according to the classification by Leeb-du Toit (1986). The core was analysed in 2 cm intervals. Samples were analysed by optical microscopy. Quantitative analysis was done using scanning electron microproscopy and electron microprobe analysis. Major elements and trace elements were determined by using ICP-MS (inductively coupled plasma mass spectrometry). Platinum-group elements (PGE) were determined by Ni-S fire assay with an ICP-MS finish and sulphur by an Eltra Infrared Analyser. Macroscopic investigation of the drillcores identified an anorthositic footwall with an overlying basal chromitite stringer and a pyroxenite hangingwall for the two non-pegmatoidal reefs. The pegmatoidal reef consists of an anorthositic footwall, a bottom chromitite stringer, a pegmatoidal layer with an overlying top chromitite stringer and a pyroxenite hangingwall. Microscope analysis showed one sulphide inclusion visible in a chromitite grain which displayed a negative crystal shape imposed by the crystal structure of the host chromite. This could indicate the presence of sulphide liquid in the system at a very early stage. This might be an indication of PGE accumulation in a deeper staging chamber. There is a correlation between the bottom chromitite stringer from the pegmatoidal Merensky reef and the single basal chromitite stringer from the non-pegmatoidal reef. There is also a Cr2O3 correlation between the single basal chromitite stringer from the non-pegmatoidal reef and the top chromitite stringer from the pegmatoidal reef. iii Whole rock geochemistry is strongly governed by the mutual influence and proportion of co- precipitating minerals competing for the same major cations like chromium, iron, aluminium and magnesium. Whole rock Mg# is the lowest in the chromitite layer, which is in contrast with what is seen in the mineral chemistry where Mg# is more primitive in the chromitite layer. This could be due to the subsolidus effect where the orthopyroxene within the chromitite layer is more enriched in Mg, due to the exchange with the chromite The general evolution from bottom to top of the pegmatoidal reef is not so clear, with considerable irregularity. Whole rock PGE content indicated that there is a close relationship between chromium and PGE enrichment, with the highest PGE content associated with the basal chromitite stringer in the case of the non-pegmatoidal reef and with the top chromitite stringer in the case of the pegmatoidal reef. Extremely high Pt/Pd ratios of up to 8.2 and Pt up to 40 ppm in the non- pegmatoidal chromitite stringer is noted but could be an artefact of the small sample sizes used. Whether some of the results found are a local or a general characteristic, can only be determined by analysing more sections. The results of this study indicate that a combination of geochemical processes and multiple replenishments of magma with subsequent processes such as: crystallization of PGE as PGM, (Tredoux et al., 1995), collection of PGE by an immiscible sulphide liquid (Campbell et al., 1983 and Barnes and Maier, 2002b) and perhaps redistribution of PGE by late magmatic/hydrothermal fluids (Boudreau & Meurer, 1999). Trends of a deeper staging chamber as suggested by Hutchinson et al (2015) is supported by several of the observations made in this study and these processes could be responsible for the formation of the pegmatoidal and non-pegmatoidal Merensky reefs. iv TABLE OF CONTENTS Declaration i Acknowledgements ii Abstract iii Table of contents v List of tables viii List of figures x List of abbreviations xv List of mineral abbreviations xvi Part 1 (Main text) Chapter 1: Introduction 1.1 General geology 1 1.2 The Merensky unit 1.2.1 General features of the Merensky Cyclic Unit 5 1.2.2 General features of the Merensky reef 6 1.2.3 The Merensky reef at Impala Platinum Mine 8 1.3 Models for PGE mineralisation and chromitite formation 9 1.3.1 Models for chromitite formation 9 1.3.2 Models for PGE mineralisation 9 1.3.3 Models for the formation of metalliferous (PGE) reefs 9 1.4 Previous studies on the Merensky reef and aim of the project 10 Chapter 2: Material and methods 2.1 Sample description 12 2.2 Sample preparation 17 2.2.1 Preparation of thin sections 17 2.2.2 Preparation of fusion discs 17 2.2.3 Preparation for PGE analysis 18 2.2.4 Preparation for REE, traces and majors 18 v 2.2.5 Preparation for sulphur analysis 18 2.3 Analytical procedures 2.3.1 Optical Microscopy 19 2.3.2 Scanning electron microscope (SEM) 19 2.3.3 Electron microprobe analysis (EMPA) 20 2.3.4 X-ray fluorescence spectrometry (XRF) 21 2.3.5 Inductively coupled plasma mass spectrometry (ICP-MS) 22 2.3.6 Sulphur analysis: Eltra Infrared analyser 23 Chapter 3: Results 3.1 Petrography 24 3.2 Mineral chemistry 37 3.2.1 Plagioclase 37 3.2.2 Orthopyroxene 41 3.2.3 Clinopyroxene 43 3.2.4 Chromite 44 3.2.5 Mica (phlogopite) 44 3.2.6 Base metal sulphides 45 3.3 Major element geochemistry 48 3.4 Trace element geochemistry 53 3.5 PGE geochemistry 55 Chapter 4: Discussion 59 4.1 Petrography 59 4.2 Whole rock major element data 67 4.3 Whole rock trace element data 73 4.4 PGE data 75 4.5 Comparison between mineral chemistry and whole rock major element data 80 Chapter 5: Conclusions 85 References 89 vi Part 2 (Appendices) Table of contents i Appendix A: Description of core sets, standards and crystals used during analysis A1 – A3 Appendix B: Petrography (modal mineral proportions) B1 – B2 Appendix C: EMPA data sheets C1 – C13 Appendix D: ICP-MS (whole rock: major element) data sheets D1 – D14 Appendix E: ICP-MS (whole rock: trace element) data sheets E1 – E12 Appendix F: PGE analysis data sheets F1 – F2 Appendix G: Sulphur analysis G1 Appendix H: Conference proceedings H1 – H4 vii LIST OF TABLES Table 2.1: Specifications of the microscope used in the study at the University of the Free State. Reflected and transmitted light was used to identify different mineral phases and to identify the best areas of interest for further quantitative analytical methods. (19) Table 2.2: Characteristics of the scanning electron microscope (SEM). Energy dispersive X- ray spectrometry (EDS-SEM) was used to identify areas of interest and mineral phases for further quantitative analysis with the electron microprobe (EMPA). (20) Table 2.3: Outline and characteristics of the electron microprobe (EMPA). Quantitative wavelength dispersive X-ray spectrometry was used to quantify phases and determine concentrations of elements in the different phases. (20) Table 2.4: Outline and characteristics of X-ray fluorescent spectrometry done at the University of the Free State. X-ray fluorescence was used to determine concentrations of major elements in whole rock samples. (21) Table 2.5: Instrumental parameters for inductively coupled plasma mass spectrometry (ICP- MS).
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