Aspects of the supergene geochemistry of copper, nickel and bismuth

  • Meagan E. Clissold

Western Sydney University thesis: Doctoral thesis

Abstract

The solution geochemical conditions associated with the development of supergene copper mineralisation in the E22, E26 and E27 deposits at Northparkes, New South Wales, have been explored. Determination of a stability constant for sampleite [NaCaCu5(PO4)4Cl5H2O], a conspicuous species in the upper oxidised zone of E26, has led to an understanding of the differences between the three deposits in terms of the influence of groundwater geochemistry on their mineralogical diversity. Modelling of copper dispersion from the three deposits using current ground water compositions as proxies for past solution conditions has shown that the elevated chloride concentrations associated with E26 have negligible influence on total dissolved copper concentrations over a wide pH range. The results are discussed with respect to applications in exploration geochemistry for the discovery of new ore deposits in the region. Determination of a stability constant for lavendulan [NaCaCu5(AsO4)4Cl5H2O], the arsenate isomorph of sampleite, suggests that solid solution between lavendulan and sampleite is likely to be extensive and this has been established by reference to mineral compositions from a number of deposits. Activity-activity phase diagrams have been developed to explain the common mineral associates of lavendulan and differences between the analogous phosphate and arsenate systems. With respect to the occurrence of lavendulan in the oxidised zone of the Widgiemooltha 132 N ore body, Western Australia, its crystal chemistry explains why Ni does not substitute for Cu in the lattice. This is despite Ni being abundantly available in the deposit and substituting freely into other copper-based minerals. The substitution of Ni for Cu was explored in a study of supposedly Ni-rich paratacamite, Cu2Cl(OH)3, from the deposit. It transpires that much of this is a new mineral, gillardite, Cu3NiCl(OH)6, the isomorph of herbertsmithite, Cu3ZnCl(OH)6. The nature of gillardite was thoroughly investigated and the mineral was approved as a new species by the International Mineralogical Association. A high resolution single-crystal X-ray structure of gillardite has been completed. In addition, the substitution of Ni in simple carbonate lattices has been explored as gasp-ite, NiCO3, Ni-rich magnesite, MgCO3, and calcite, CaCO3, are all common species in the oxidised zone of the Widgiemooltha 132 N deposit. Attention was subsequently focussed on the geochemistry of the element Bi, with special reference to deposits of the Kingsgate region, New South Wales. This study has led to a modern assessment of the Mo-Bi deposits in the area and new Bi sulfosalts from the Wolfram pipe at Kingsgate are described. A survey of secondary Bi minerals from a host of deposits has led to the development of a model for the dispersion of Bi in the supergene environment, which will have widespread applications in exploration geochemistry where Bi is used as a pathfinder element. Calculations of aqueous Bi species in equilibrium with bismite, Bi2O3, bismoclite, BiOCl, and bismutite, Bi2O2CO3, over a wide pH range show that the element is very insoluble under ambient oxidising conditions. It is noted that the results of previous geochemical exploration campaigns in the region will have to be reassessed.
Date of Award2007
Original languageEnglish

Keywords

  • copper ores
  • nickel ores
  • bismuth ores
  • geochemistry
  • Australia

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