Precious metals in magmatic Fe-Ni-Cu sulfides from the Potosí chromitite deposit, eastern Cuba
Abstract
We report new results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of platinum-group elements (PGE)-rich base-metal sulfides. The Ni-Fe-Cu base-metal sulfides (BMS) studied are millerite (NiS), pentlandite [(Ni,Fe)9S8], pyrite (FeS2), and chalcopyrite (CuFeS2). These BMS were found forming composite inclusions (<60 μm across) within larger unaltered chromite from the Caridad chromite deposit, which is hosted in the mantle section of the Mayarí-Baracoa Ophiolite in eastern Cuba. Electron probe microanalysis of BMS revealed PGE values of up to 1.3 wt%, except for pentlandite grains where PGE concentrations can reach up to 12.8 wt%. Based on the amount of Ru, two types of pentlandite are defined: (1) Ru-rich pentlandite with up to 8.7 wt% of Ru and <3.5 wt% of Os, and (2) Ru-poor pentlandite with Ru <0.4 wt% and Os <0.2 wt%. Ru-rich pentlandite contains Ir-Pt nanoparticles, whereas the other sulfides do not host nanometer-sized platinum-group minerals (PGM). The Ir-Pt inclusions are found as: (1) idiomorphic, needle-shape (acicular) nanoparticles up to 500 nm occurring along the grain boundaries between Ru-rich pentlandite and millerite, and (2) nanospherical inclusions (<250 nm) dispersed through the matrix of Ru-rich pentlandite. HRTEM observations and analysis of the selected-area electron diffraction patterns revealed that nanoparticles of Ir-Pt form domains within Ru-rich pentlandite. Fast Fourier transform analyses of the HRTEM images showed epitaxy between Ir-Pt domain and PGE-poor millerite, which argues for oriented growth of the latter phase. These observations point to sub-solidus exsolution of the Ir-Pt alloy, although the presence of nanospherical Ir-Pt inclusions in some other grains suggest the possibility that Ir-Pt nanoparticles formed in the silicate melt before sulfide liquid immiscibility. These Ir-Pt nanocrystals were later collected by the sulfide melt, preceding the formation of Ru-rich pentlandite. Early crystallization of the Ru-rich pentlandite and Ir-Pt nanoparticles led to the efficient scavenging of PGE from the melt, leaving a PGE-poor sulfide residue composed of millerite, pyrite, chalcopyrite, and a second generation of PGE-poor pentlandite. The Moa-Baracoa ophiolite in eastern Cuba is one of the few known ophiolites that display sulfide mineralization attributable to a magmatic origin in association with podiform-chromite ores hosted in the mantle-crust transition. These sulfide ores chiefly consist of Fe-Ni-Cu sulfides, namely pyrrhotite, pentlandite, chalcopyrite and cubanite partly altered to valleriite. The sulfide mineralization is located along the contact between the podiform-like chromite ores and intruding pegmatitic gabroic dykes. The detailed mineralogical study of the sulfide mineralization coupled with the first ever laser ablation ICP-MS analysis reveals that this sulfide mineralization show contents of the precious metals (Os, Ir, Ru, Pt, Re, Au, Ag) and other (semi)-metals (Co, Ni, Cu, Se, Te, Bi, Pb, As Sb) comparable to those sulfides from the magmatic sulfide deposits associated with mafic complexes hosted in the continental crust. The results obtained from this study confirm that Fe-Ni-Cu sulfides at Potosí are magmatic in origin, and very likely derived from the solidification of droplets of sulfide melt segregated by immiscibility from the intruding mafic melts once they interacted with the pre-existing chromitite at the mantle-crust transition zone of the ophiolite. The immiscibility of sulfide melt was achieved as a result of a progressive increase of fS2, very likely triggered by a set of circumstances, including the progressive fractionation of the intruding mafic melt leading to increase of aSiO2 and accumulation of volatiles as well as the crystallization of oxides. Two main generations of pentlandite were observed. One generation is primary in origin and it was locally exsolved along with pyrrhotite from monosulfide solid solution (MSS) during low-temperature cooling. The second type of pentlandite resulted from the reaction of MSS with coexisting droplets of Cu-and Ni-rich sulfide melt. LA-ICP-MS analysis reveals that most precious metals (Ru, Os, Ir, Re, Au, Ag) were concentrated along with the base-metal sulfides (BMS), although their distribution among the different BMS (pyrrhotite, pentlandite, chalcopyrite and cubanite) does not strictly follow the expected distribution according to the known melt-solid and solid-solid partition coefficients. Unlike the other analyzed PGEs, Pt was not preferentially concentrated in BMS but as discrete micrometer-sized sperrylite grains. The crystallization of sperrylite took place before and contemporaneous to sulfide segregation, and Pt-As nanoparticles probably played an important role in the Pt uptake as nucleation seeds for the formation of micron-sized sperrylite grains. These observations highlight the open-system nature of the ore forming system as well as the important role of arsenic in concentrating PGE in high-temperature silicate and sulfide melts. We report new results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of platinum-group elements (PGE)-rich base-metal sulfides. The Ni-Fe-Cu base-metal sulfides (BMS) studied are millerite (NiS), pentlandite [(Ni,Fe)9S8], pyrite (FeS2), and chalcopyrite (CuFeS2). These BMS were found forming composite inclusions (<60 μm across) within larger unaltered chromite from the Caridad chromite deposit, which is hosted in the mantle section of the Mayarí-Baracoa Ophiolite in eastern Cuba. Electron probe microanalysis of BMS revealed PGE values of up to 1.3 wt%, except for pentlandite grains where PGE concentrations can reach up to 12.8 wt%. Based on the amount of Ru, two types of pentlandite are defined: (1) Ru-rich pentlandite with up to 8.7 wt% of Ru and <3.5 wt% of Os, and (2) Ru-poor pentlandite with Ru <0.4 wt% and Os <0.2 wt%. Ru-rich pentlandite contains Ir-Pt nanoparticles, whereas the other sulfides do not host nanometer-sized platinum-group minerals (PGM). The Ir-Pt inclusions are found as: (1) idiomorphic, needle-shape (acicular) nanoparticles up to 500 nm occurring along the grain boundaries between Ru-rich pentlandite and millerite, and (2) nanospherical inclusions (<250 nm) dispersed through the matrix of Ru-rich pentlandite. HRTEM observations and analysis of the selected-area electron diffraction patterns revealed that nanoparticles of Ir-Pt form domains within Ru-rich pentlandite. Fast Fourier transform analyses of the HRTEM images showed epitaxy between Ir-Pt domain and PGE-poor millerite, which argues for oriented growth of the latter phase. These observations point to sub-solidus exsolution of the Ir-Pt alloy, although the presence of nanospherical Ir-Pt inclusions in some other grains suggest the possibility that Ir-Pt nanoparticles formed in the silicate melt before sulfide liquid immiscibility. These Ir-Pt nanocrystals were later collected by the sulfide melt, preceding the formation of Ru-rich pentlandite. Early crystallization of the Ru-rich pentlandite and Ir-Pt nanoparticles led to the efficient scavenging of PGE from the melt, leaving a PGE-poor sulfide residue composed of millerite, pyrite, chalcopyrite, and a second generation of PGE-poor pentlandite.
Keywords: Sulfide mineralization; platinum-group elements; mantle-crust transition; chromitite; LA-ICP-MS
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To Cite this article: González-Jiménez, J.M.; Proenza, J.A.; Pastor-Oliete, M.; Saunders, E.; Aiglsperger, T.; Pujol-Solà, N.; Melgarejo, J.C.; Gervilla, F.; & Garcia-Casco, A. (2020). Precious metals in magmatic Fe-Ni-Cu sulfides from the Potosí chromitite deposit, eastern Cuba. Ore Geology Reviews, 103339.
DOI: 10.1016/j.oregeorev.2020.103339
