The State of Platinum in Pyrite Studied by X-Ray Absorption Spectroscopy of Synthetic Crystals

Pyrite (FeS2) is a typical container of Pt in ores of magmatic and hydrothermal origin and in some carbonrich ores of sedimentary-diagenetic origin. Knowledge of the state of Pt disseminated in the matrix of pyrite, including local atomic environment (type of atoms in the nearest and distant coordination shells, coordination numbers, interatomic distances) and oxidation state, is necessary for physical-chemical modeling of platinum group element mineralization and for the improvement of Pt ore extraction and processing technologies. Here we report results of an investigation of local atomic structure of synthetic Pt-bearing pyrites by means of X-ray absorption spectroscopy (XAS). Synthesis experiments, performed at 580° and 590°C in a Pt-saturated system by means of salt-flux method, yielded crystals of pyrite with concentrations of Pt up to 4 wt %. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) showed that the distribution of Pt within the pyrite grains is of zonal character, but within the distinct zones Pt is distributed homogeneously. Negative correlation between the concentrations of Pt and Fe was observed in the synthesized pyrite grains. The slope of the correlation line corresponds to the formation of the solid solution in the Pt-Fe-S system and/or to the formation of PtS2. The XAS experiments revealed the existence of two forms of Pt in pyrite. The main form is the solid solution Pt(IV), which isomorphically substitutes for Fe. The Pt-S distance in pyrite is ~0.1 Å longer than that of Fe-S in pure pyrite. The distortion of the pyrite crystal structure disappears at R >2.5 Å. The second Pt-rich form was identified by means of high-resolution transmission electron microscopy (HRTEM) as nanosized inclusions of PtS2. Heating experiments with in situ registration of X-ray absorption spectra resulted in partial decomposition (dissolution) of PtS2 nanosized inclusions with the formation of the solid solution (Fe1–xPtx)S2. Therefore, the PtS2 nanosized particles can be considered as a quench product. Our data demonstrate that both Pt solid solution and PtS2 nanosized inclusions (at high Pt content) can exist in natural Pt-bearing pyrites.