Timothy D. Murphy Bsc (Hons), UWS

BISMUTH IN THE SUPERGENE ENVIRONMENT Timothy D. Murphy BSc (Hons), UWS This thesis is submitted for the degree of Doctor of Philosophy in the University of Western Sydney Supervisors: Professor Peter A. Williams and Professor Peter Leverett March 2015 ACKNOWLEDGEMENTS I sincerely thank my supervisor Professor Peter Williams, for sharing his extensive knowledge in chemistry and mineralogy which made the project possible. His guidance, support and encouragement throughout has been greatly appreciated. I would also like to thank my co-supervisor Professor Peter Leverett for his invaluable assistance and perspectives on my thesis which have been greatly appreciated. Dr Ric Wuhrer and the Advanced Materials Characterisation Facility provided assistance with X-ray diffraction as well as support, guidance and equipment training. Jim Sharp is thanked for his assistance with fieldwork and sharing his experience in mineralogy and X-ray diffraction. John Rankin is acknowledged for sharing his knowledge on the mineralogy of the New England Oregon. I would like to thank my fellow PhD students Matthew Sciberras, Adam Roper, Mitchel Nancarrow and Simon Hager for their invaluable help, support and friendship throughout the project. Finally I would like to thank the people who have helped and encouraged me outside of the academic environment throughout this endeavour, especially my Mother, Father and Sister whose help, support, encouragement and love have helped me become the person I am today, as well as my friends. STATEMENT OF AUTHENTICATION This thesis contains work that, to the best of my knowledge and belief, is original except where due acknowledgment appears in the text. I declare that material in this thesis has not been submitted in any form for a degree or diploma at any other university or institution of tertiary education. ..........………………… Timothy David Murphy March 2015 TABLE OF CONTENTS Chapter 1 Introduction 1 1.1 Abstract 2 1.2 Geochemical Exploration 3 1.3 Bismuth as a path finder element 6 1.4 Project Outline 13 1.5 References 13 Chapter 2 Bismoclite, Bismtutite, Cannonite and Riomarinaite 22 2.1 Abstract 23 2.2 Introduction 23 2.2.1 Bismite, bismoclite, bismutite, cannonite and riomarinaite 23 2.2.2 Rare and other bismuth oxide, carbonates, chloride, and sulfate minerals 26 2.3 Experimental 28 2.3.1 Syntheses of cannonite and riomarinaite 28 2.3.2 Solubility Studies 29 2.4 Results 30 2.4.1 Synthesis of cannonite and riomarinaite 30 2.4.2 Solubility Studies 30 2.5 References 40 Chapter 3 Rooseveltite, Preisingerite and Atelestite 45 3.1 Abstract 46 3.2 Introduction 46 3.3 Experimental 50 3.3.1 Syntheses of rooseveltite, tetrarooseveltite, atelestite and preisingerite 50 3.3.2 Solubility Studies 51 3.4 Results 51 3.4.1 Syntheses of rooseveltite, tetrarooseveltite, atelestite and preisingerite 51 3.4.2 Solubility Studies 55 3.5 References 60 Chapter 4 Russellite, Koechlinite and Sardignaite 66 4.1 Abstract 67 4.2 Introduction 67 4.3 Experimental 73 4.3.1 Syntheses of russellite, koechlinite and sardignaite 73 4.3.2 Solubility Studies 74 4.4 Results 75 4.4.1 Syntheses of russellite, koechlinite and sardignaite 75 4.4.2 Solubility Studies 79 4.5 References 84 Chapter 5 Smirnite and Chekhovichite 90 5.1 Abstract 91 5.2.1 Introduction 91 5.3 Experimental 94 5.3.1 Syntheses of smirnite and chekhovichite 94 5.3.2 Solubility Studies 95 5.4 Results 95 5.4.1 Syntheses of smirnite and chekhovichite 95 5.4.2 Solubility Studies 98 5.5 References 102 Chapter 6 Conclusion 105 6.1 Abstract 106 6.2 Introduction 106 6.3 Discussion of Data 108 6.3.1 Chapter 2 Discussion 108 6.3.2 Chapter 3 Discussion 110 6.3.3 Chapter 4 Discussion 112 6.3.4 Chapter 5 Discussion 114 6.4 Reverse Ground Water Modelling 116 6.5 Bismuth Model for the Cobar Region 117 6.6 Bismuth Model for the New England Region 125 6.7 Conclusion 130 6.8 References 131 Appendix A 137 CHAPTER 1 INTRODUCTION 1 | P a g e 1.1 ABSTRACT Bismuth minerals associated with Mo, W, and Sn, are often found amongst the highly acidic deposits of the eastern ranges of Australia (Plimer, 1975; Weber et al., 1978). It is important to gain an understanding of the mobility and dispersion of Bi in the supergene zone and make an assessment of these areas, as they have been the focus for geochemical exploration to develop prospects and mining operations. A review of the literature on bismuth as a pathfinder element, with respect to its ground water and regolith concentrations, uncovered significant documentation including scientific, industrial and government reports, the use of various sampling methods, and the use of assumptions in previous studies due to the information and techniques available at the time (MacDuff, 1971; 1971a; 1971b; 1972; Siegal, 1974; Roes et al., 1979; Levinson, 1980; Plant et al., 1989; Plant et al., 1991; Fiella; 2010). Furthermore, information on the Gibbs free energy of formation values was limited to 3 out of the 65 known bismuth secondary minerals (Clissold, 2007). A study on a range of secondary bismuth minerals in the supergene zone, (Rankin et al., 2001, 2002; Sharpe and Williams, 2004) showed that even though bismuth minerals are considered to be rare, localised areas of Bi concentration are in fact quite common. Examples of this can be found in certain deposits in eastern Australia such as the New England Orogen. Therefore, the geochemical modelling carried out in this thesis has focused on eastern Australia and examines potential impacts on geochemical exploration where Bi has been used as a pathfinder element. Furthermore this work can be been applied to exploration sites around the world where 2 | P a g e Bi is employed as a pathfinder element. To do this, a rigorous investigation including Bi mineral synthesis, solubility and stabilities was undertaken thus yielding an assessment of the suitability of bismuth as a pathfinder for future geochemical surveys. 1.2 GEOCHEMICAL EXPLORATION Due to the nature and growth of manufacturing and consumption worldwide and the need for mineral resources to meet these demands, the discovery of large-scale near-surface deposits are in decline and thus the push to find deeper deposits has inevitably increased (Aspandiar et al., 2008). Therefore, it is necessary to constantly review and scrutinise new, current and historic exploration techniques to discover hidden ore bodies that are commercially significant. Exploration geochemistry is used in virtually every exploration program whereby geochemical prospecting for minerals include any method of mineral exploration based on systematic measurement of one or more chemical properties of a natural occurring material e.g. Hawkes and Webb, 1962. The earliest reports of geochemical research date back to the 1930’s which were carried-out in the former Soviet Union, and were known as metallometric surveying, which we know today as geochemical surveys (Hawkes and Webb, 1962). It was not until the late 1930’s to 1940’s that there was a rise in geochemical research by Western countries, largely due to the increased resource requirements of World War II. Since then, geochemical exploration methods have become increasingly sophisticated due to advances in analytical instrumentation, yet much is still to be discovered and a greater understanding to be obtained 3 | P a g e Geochemical exploration strategies include a number of key phases such as planning, sampling, chemical analysis, interpretation and follow-up. Each stage is critical and exploration geologists have to be cautious at each phase to ensure the integrity of the data that is to be applied to the succeeding stages. Although for a variety of commodities, or for a specifically targeted commodity, most deposits in a given geological setting have, on average, the same profile or type deposit settings with respect to elemental dispersion characteristics over regional landscapes. However, specific environments within this may contain deposits with a degree of uniqueness (i.e. geochemical signature) due to the differences in the geological, geomorphological and environmental setting. Furthermore, many localities have well documented information from which geochemical exploration studies can be undertaken while others do not. One of the greatest challenges in geochemical surveys is the confidence to distinguish between anomalous and background concentration in soils and ground waters. A review of mining reports and reported data created by Siegal (1974), Rose et al. (1979), Roes et al. (1979), Levinson (1980), Plant et al. (1989) and Plant et al. (1991) provide a solid in site. However, due to the targeted nature of these reports extraction of additional data requires the application of newer analytical methods which were/may not have been available (or un-needed for the specific task) at the time. For example, for the elements Bi and W, in some cases (MacDuff, 1971; 1971a; 1971b; 1972 and Fiella, 2010) reports have honestly stated that because of a lack of references in the literature to similar sampling programs, the results of their survey and previous data have to be arbitrarily interpreted. 4 | P a g e Exploration across depositional landforms, both simple and complex, and with shallow to deep transported regolith cover by using various geochemical techniques has reaffirmed the important need to conduct and understand surface geochemistry and to make it effective for new green field locations. Australia exhibits a unique landscape with many of the landforms having their origins 300 Ma ago at the beginning of the break-up of Gondwana (Aspandiar, 2008). Since that time the Australian land mass has been exposed to wide ranging climatic conditions, from tropical to glacial periods as well as undergoing various tectonic events which have been well documented (Anand, 2005).

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