The speciation of Au in gold-bearing arsenopyrite (FeAsS) from four gold deposits (Olympiada, Sentachan, São Bento and Sheba) was determined by micro-X-ray absorption near-edge structure (XANES) on grains well characterized microscopically and by electron-microprobe and secondary-ion mass spectrometry analyses and images. "Invisible" gold in arsenopyrite occurs in two apparently mutually exclusive chemical forms: chemically bound and elemental. Arsenopyrite from the Sentachan, São Bento and Sheba deposits contains chemically bound gold. With comparable constituent electronegativities and a white-line feature in the XANES indicating unoccupied Au 5d-states, but absorption-edge positions comparable to Au 1+ species, the bonding is interpreted as being covalent rather than ionic. The invisible gold in arsenopyrite from the Olympiada deposit, on the other hand, occurs as very small particles of Au 0 , probably less than a few nanometers in diameter. Micro-XANES data for the Olympiada and Sentachan arsenopyrite support earlier results obtained by 197 Au Mössbauer spectroscopy on arsenopyrite concentrates. In some arsenopyrite crystals, the gold concentration is closely related to growth zoning. This feature represents conditions during crystallization and does not correlate with the chemical form of the gold. Similarly, selenium, where present, correlates with gold in some deposits and not in others, irrespective of the gold speciation. The finding of two types of invisible gold in arsenopyrite from different deposits has beneficial implications for extractive metallurgy.
Abstract-We have performed six experiments in which we equilibrated monosulfide solid solution (mss) with sulfide melt in evacuated silica capsules containing solid buffers to fix oxygen and sulfur fugacity, at temperatures of 950°C, 1000°C and 1050°C at bulk concentrations of ϳ50 ppm for each of the PGE and Au, 5% Ni, and 7% Cu. Concentrations of O, S, Fe, Ni and Cu were determined by electron microprobe, whereas precious metal concentrations were determined by laser-ablation inductively-coupled mass spectrometry. Partition coefficients of all elements studied show minimal dependences on oxygen fugacity from the IW to the QFM buffers when sulfur fugacity is fixed at the Pt-PtS buffer. Cu, Pt, Pd and Au are strongly incompatible and Ru remains moderately to strongly compatible under all conditions studied. At all oxygen fugacities, at the Pt-PtS sulfur buffer, Ir and Rh remain highly compatible in mss. In the single run at both low oxygen and low sulfur fugacity Ir and Rh were found to be strongly incompatible in mss. At QFM and Pt-PtS the partition coefficient for Ni shows weak temperature dependence, ranging from 0.66 at 1050°C to 0.94 at 950°C. At lower oxygen and sulfur fugacity Ni showed much more incompatible behavior. Comparison with the compositions of sulfide ores from the Lindsley deposit of Sudbury suggests that the sulfide magma evolved under conditions close to the QFM and Pt-PtS buffers. The compatible behavior observed for Ni, Ir and Rh at Lindsley and most other magmatic sulfide deposits hosted by mafic rocks requires equilibration of mss and sulfide liquid at moderately high sulfur fugacity and low temperatures near to the solidus of the sulfide magma. We argue that this constraint requires that the sulfide magma must have evolved by equilibrium crystallization, rather than fractional segregation of mss as is commonly supposed.
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