HRTEM Study of Desulfurization of Pt- and Pd-Rich Sulfides from New Caledonia Ophiolite

Abstract

Oxygen-bearing platinum group minerals (O-bearing PGMs) are intergrown with base metal sulfides (BMS, e.g., pentlandite–[NiFe]9S8) within fractures in chromite grains from chromitite bodies on Ouen Island, New Caledonia. These PGMs are hosted in chlorite and serpentine, which formed during serpentinization of olivine and pyroxene. The Obearing PGM grains are polygonal, show microfracturing (indicating volume loss), and contain Pt-Pd-rich sulfide remnants, suggesting pseudomorphic replacement of primary (magmatic) sulfides. They display chemical zonation, with Pt(-Pd-Ni-Fe) relict sulfide cores replaced by Pt-Fe-Ni oxidized alloy mantles and Pt-Cu-Fe(-Pd) alloy rims (tulameenite), indicating desulfurization. The core and mantle show a nanoporous structure, interpreted as the result of coupled dissolution–reprecipitation reactions between magmatic sulfides and low fO2–f S2 serpentinite-related fluids, probably formed during olivine transformation to serpentine + magnetite (early stages of serpentinization). This fluid infiltrated magmatic sulfides (PGE-rich and BMS), degrading them to secondary products and releasing S and metals that were accommodated in the mantle and rim of O-bearing PGMs. Upon olivine exhaustion, an increase in fO2 might have stabilized Pt-Fe-O compounds (likely Pt0/PtFe + Fe oxyhydroxides) alongside Ni-Fe alloys. Our results show that post-magmatic desulfurization of primary sulfides produces complex nano-scale intergrowths, mainly driven by changes in the fluid’s physicochemical properties during serpentinization.