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The mechanism of charge compensation in Cu-Fe-PGE thiospinels from the Penikat layered intrusion, Finland

¹ Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal, Quebec H3A 2A7, Canada
² Regional Office for Mid-Finland, Geological Survey of Finland, P.O. Box 1237, FIN-70211, Kuopio, Finland

Correspondence: ^* E-mail: barkov{at}eps.mcgill.ca

Thiospinels of Cu-(Fe) and platinum-group elements (PGE) are relatively abundant in the Kirakkajuppura PGE deposit of the Penikat layered complex, Finland. In actinolite-clinochlore rock that is nearly base-metal sulfide-free and relatively poor in chromite, the thiospinels occur as subhedral or anhedral grains (up to 0.4 mm). They are members of the cuprorhodsite-ferrorhodsite and cuprorhodsite-malanite series, relatively poor in cuproiridsite, and display considerable grain-to-grain variations in Cu, Fe, Pt, and Rh. Strong negative Fe-Cu, Pt(+Ir)-Fe, Rh-Cu, and Rh-Pt and strong positive Pt(+Ir)-Cu and Rh-Fe correlations in these thiospinels are indicative of a coupled substitution: Fe-for-Cu substitution in the tetrahedral (A) sites causes an excess in formal positive charge, which is compensated by Rh-for-(Pt+Ir) substitution in the octahedral (B) sites. Probable valence states in the Fe-free and Fe-rich end-members of the solid-solution series at Penikat are Cu⁺[Rh³⁺(Pt,Ir)⁴⁺]S^2–₄ and (Fe³⁺_0.5Cu⁺_0.5)Rh³⁺₂ S^2–₄, and these suggest the heterovalent substitution scheme ^AFe³⁺ + 2 ^BRh^{3+ A}Cu⁺ + 2 ^BPt⁴⁺(+2 Ir⁴⁺) to incorporate Fe in the ferrorhodsite-rich end member.

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