Low temperature alteration of magmatic Ni-Cu-PGE sulfides as a source for hydrothermal Ni and PGE ores: A quantitative approach using automated mineralogy

Magmatic Ni-Cu-PGE sulfide assemblages are almost ubiquitously comprised of pyrrhotite-pentlandite-chalcopyrite(-pyrite). Sulfide alteration is common during syn- or post-magmatic fluid interaction, usually replacing sulfides with amphiboles or serpentine. However, some are altered to a low temperature (<200 °C) hydrothermal assemblage of pyrite-millerite-chalcopyrite (PMC). An example is the Ni-Cu-PGE mineralisation in the Grasvally-Norite-Pyroxenite-Anorthosite (GNPA) Member, northern Bushveld Complex, which displays a continuum of mineralogical styles formed through progressive alteration: Style 1 primary pyrrhotite-pentlandite-chalcopyrite; which is altered to Style 2 pyrrhotite-pyrite-pentlandite-chalcopyrite; Style 3 pyrite-pentlandite-chalcopyrite; Style 4 pyrite-pentlandite-millerite-chalcopyrite; and Style 5 pyrite-millerite-chalcopyrite-cubanite. Modelling using CHILLER confirms this mineralogical sequence is thermodynamically possible at ∼200 °C. Quantitative characterisation using automated Energy-Dispersive X-ray spectroscopy mapping alongside in situ laser ablation analyses determined mineral proportions, major and trace element concentrations and deportments in each style. The early loss of pyrrhotite removes over half of the bulk Fe and S during the initial stages of PMC alteration, increasing Cu, Ni and PGE tenors of the remaining sulfides significantly. As water–rock interaction progresses, pyrrhotite is replaced by pyrite and pentlandite by millerite, with concurrent losses in Fe, S and Ni. Copper is lost throughout the alteration, and is most pronounced in the more advanced stages. The fluids responsible were most likely acidic and oxidised, with metals mobilised as chloride complexes. Using Rh as an immobile normalising element, the overall mass loss in the most altered samples is calculated to be up to 90%, consistent with textural relationships that indicate 40–90% volume loss from Styles 2–5, with sulfides replaced by secondary silicates, including phlogopite, quartz, chlorite, pyroxenes and minor amphiboles. Magnetite is not a significant alteration product and thus Fe is mobilised, or incorporated into silicates. Most trace elements present in the magmatic sulfide (the IPGE, Rh and Bi) remain in the sulfide phases, and are effectively transferred to pyrite during PMC alteration, except Pd, which remains in pentlandite, and is liberated from the sulfide assemblage when pentlandite disappears. Selenium tenors increase slightly with alteration, demonstrating that alteration decreases S/Se ratios. The significant mobilisation of Ni, Cu and Pd during PMC alteration produces fluids enriched in these elements that may represent a metal source for a number of enigmatic hydrothermal Ni deposits such as Avebury, Enterprise and Talvivaara, whose metal sources remain speculative. The PMC alteration of the GNPA Member may be specifically a source for the nearby Waterberg hydrothermal Pt deposit. Furthermore, this study has implications not only for magmatic ore deposits, but also for the general implications of sulfide transformation and metal transfer in ore systems in general.