Coupled substitutions in PGE-enriched cobaltite: new evidence from the Rio Jacaré layered complex, Bahia state, Brazil

Microcrystals of platinum-group element (PGE)-bearing cobaltite occur in the Gulcari A deposit of vanadiferous titanomagnetite in the lower zone of the Rio Jacare mafic-ultramafic layered intrusion, Brazil. Aggregates of cobaltite and sperrylite are cluster-like and developed generally along the boundary of Fe-Ti oxide grains with deuteric silicates. Our observations of cryptic zoning, compositional variability and interelement correlations are based on 37 analytical points (wavelength-dispersion spectrometry mode) of cobaltite, and indicate that Ir and Rh behave uniformly with Ni and antipathetically with Co which, in turn, correlates directly with S content. Iridium, Rh and Ni apparently substitute for Co in the As-enriched grain core, and the substitution mechanism invokes solid solution with a cattierite-type molecule: (Ni + Ir + Rh) + (AsS) = Co + (S2). The PGE-bearing cobaltite probably crystallized as a primary phase at 500 to 300°C, from microvolumes of a late fluid phase. The observed enrichment in S and decrease in the As:S ratio at the cobaltite grain margins is a reflection of the increase in sulfur fugacity ( f S2) with decrease in temperature of crystallization.