The Wombat Hole Prospect is a small copper–bismuth–(tellurium) exoskarn cropping out in the Morass Creek gorge, near Benambra, in eastern Victoria, Australia. Its main primary sulfide constituent is bornite in a grossular‒vesuvianite matrix. The skarn formed in a megaclast of Lower Silurian limestone from metal-bearing fluids accompanying the high-level emplacement of the Late Silurian–Lower Devonian Silver Flat Porphyry. Though the primary bornite mineralisation has been nearly obliterated by weathering, there are small relict patches containing exsolved grains of wittichenite (Cu3BiS3) and chalcopyrite, as well as inclusions of bismuth tellurides in the tetradymite group, namely sulphotsumoite (Bi3Te2S) and hedleyite (Bi7Te3). Joséite-A (Bi4TeS2), a mineral with a formula Bi3(Te,S)4, several unnamed Cu–Bi‒Te phases and minute grains of native bismuth have also been detected. Pervasive veining by chrysocolla throughout the garnet‒vesuvianite host contains a range of unusual secondary bismuth minerals that have crystallised at various times. These include mrázekite, namibite, pucherite, schumacherite and eulytine. Other secondary minerals present include wulfenite, bismutite, azurite, malachite and a poorly-crystalline bismuth oxide containing several weight percent tellurium. Rare grains of gold (electrum) containing up to 23 wt.% Ag are also present. The assemblage of grossular–vesuvianite with minor diopside is indicative of formation in a low-${\rm X}_{{\rm C}{\rm O}_ 2}$ environment under fluid-buffered conditions. A temperature range between ~650°C and as low as ~150°C can be estimated from the exsolution of wittichenite and chalcopyrite from the bornite. The tetradymite-group inclusions formed first under low values of $f_{{\rm S}_ 2}$ /$f_{{\rm T}{\rm e}_ 2}$, with bornite crystallising as values increased. The primary Cu‒Bi‒Te mineralogy and the unusual secondary mineral assemblage makes the Wombat Hole skarn unique in southeastern Australia. The deposit provides scope for studying the mobility of elements such as Bi and Te over short distances during weathering of hypogene ore minerals.

A thermodynamic prediction of the Gibbs free energy of formation (ΔGfo) of nukundamite (empirical composition Cu5.5FeS6.5) was made in order to specify whether the nukundamite + chalcopyrite or the bornite + pyrite assemblage is stable in the Cu-Fe-S system. The results of calculations using previously reported data of ΔGfo values of some Cu-Fe-sulphide minerals in equilibrium with nukundamite indicate that the total free energy of the nukundamite + chalcopyrite assemblage is appreciably higher than that of the bornite + pyrite assemblage in the temperature range 250–400°C. This means that nukundamite + chalcopyrite is a metastable assemblage under common ore-forming conditions.

The occurrence of nukundamite is not uncommon in the Fijian kuroko deposits in contrast to the Japanese kuroko deposits. A thermochemical treatment for this phenomenon leads to the interpretation that the black ore containing nukundamite in the Fijian deposit was formed under relatively highsulphidation and low-pH conditions. This suggestion is in good agreement with the present experimental result that the bornite + pyrite assemblage was produced in the temperature range 350–250°C by using near-neutral hydrothermal solutions.

Intermediate compositions along the bornite–digenite join exsolve during quenching from above-solvus temperatures. This involves vacancy clustering and cation ordering processes, and is facilitated by fast cation diffusion rates in the presence of a large (10–25%) metal vacancy population. Samples of six different compositions across the bornite–Cu9S5 join, synthesised from component elements in sealed quartz capsules, were water-quenched from 600°C and analysed using high-resolution neutron powder diffraction (HRPD). Time-of-flight spectra measured at room temperature showed all intermediate compositions had exsolved into mixtures of bornite and low digenite with a 5.0a superstructure. No evidence for the presence of any other phase was found. Variations in the lattice parameters of the exsolved bornite phase were observed for different bulk compositions across the join, and ascribed to variations in the degree of order. Bornite exsolved from digenite-rich compositions may not be fully ordered due to the much lower solvus temperatures at the Cu-rich end of the solid solution. As only slight differences were observed between the diffraction patterns of a visibly exsolved and a rapidly quenched sample of the same bulk composition, the formation of optically-visible exsolution lamellae on {100} is ascribed to a process of coalescence of sub-microscopic domains initially formed during the quenching process. The rapid kinetics of exsolution at geologically low temperatures, explains the lack of authenticated natural occurrences of intermediate compositions in the solid solution in nature, and the limited degree of stoichiometric variation observed in end-members.

The sulphur-poor portions of the dry condensed Cu-Fe-Pd-S system were studied at 1000°C, 900°C and 725°C by synthesis in evacuated silicate glass tubes, along with textural observations and electron microprobe analyses of equilibrated reaction products. Sulphide melt coexists with Cu-Fe-Pd alloys, bornite, Fe1-xS and iss (intermediate solid solution, Cabri, 1973) and Pd4S. Compositional data were obtained for the associations bornite-alloy-melt, pyrrhotite-alloy-melt and for immiscible Cu-rich sulphide melts. Partition coefficients for all three metals were derived for the association alloy-melt. Formation of the two new Cu-Pd alloy minerals, skaergaardite and nielsenite, is discussed in terms of the present findings.

The surfaces of fresh and tarnished (through exposure to the atmosphere) bornite have been studied by measurement of reflectance and quantitative colour parameters in the visible region, X-ray photoelectron and Auger electron spectroscopy, and conversion electron Mössbauer spectroscopy. The results of these studies, in combination with those of previous workers, indicate that a surface coating of an iron hydroxy-oxide forms on bornite, leaving beneath it a layer with a copper sulphide composition. A model to explain this alteration process is proposed based on a suggested surface reconstruction in bornite, leading to metals in essentially trigonal planar coordination. Resulting destabilization of iron relative to copper in this crystal chemical environment is suggested to account for its preferential oxidation.

Trace mineral assemblages in the bornite- and chalcopyrite-rich Cu-Fe zone of the Ocna de Fier-Dognecea skarn deposits, Banat, SW Romania provide additional constraints on the genesis of this classic zoned skarn system. Observed assemblages substantiate a model, in which the Cu-Fe zone forms the proximal fluid-plume root of the system. Observed trace mineral assemblages in the magnesian forsterite-bearing skarns crystallized at ~650°C in a volatile-rich environment, evidenced by widespread phlogopite, ludwigite, valleriite and apatite. The entire assemblage thus belongs to the initial stage of skarn formation. Prolonged cooling led to sequential exsolution of trace mineral phases from bornite and chalcopyrite during the retrograde stage, although still at temperatures in excess of 500°C. Bornite is typified by the abundance of exsolved phases along cleavage planes and along crystal margins, notably chalcopyrite and pyrrhotite, but also cobalt pentlandite, carrollite, wittichenite, galena, mawsonite, silver and electrum. Chalcopyrite hosts cobalt pentlandite, carrollite, wittichenite, galena and a sequence of Se- and Te-bearing minerals (kawazulite, bohdanowiczite, hessite, volynskite), along, although not restricted to, grain margins. The assemblage bornite-chalcopyrite-magnetite, with the trace phases, cobalt pentlandite, carrollite, wittichenite and various Se- and Te-bearing minerals represents a characteristic assemblage common to a disparate range of deposits formed at temperatures in excess of 500°C in the presence of volatiles and typified by relatively low fS2 fluids.

Phase relations along the join bornite (Cu5FeS4)-digenite (Cu8.52Fe0.12S4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite-digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.

The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu5FeS4-Cu9S5. The thermal anomalies are correlated with structural phase transitions in componen phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu5FeS4 and T = 265°C. This temperature corresponds to that of the tricritical intermediate-high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.