Chalcophile-siderophile element systematics of hydrothermal pyrite from martian regolith breccia NWA 7533

Unlike other martian meteorites studied so far, Martian regolith breccia NWA 7533 and paired meteorites that have sampled 4.4 Ga-old impact lithologies show only sulfides of hydrothermal origin (mostly pyrite (<1 vol.%) and scarce pyrrhotite). NWA 7533 pyrite has been analyzed for 25 chalcophile-siderophile trace elements with laser ablation-inductively coupled plasma mass spectrometer (LA-ICPMS). Micronuggets of highly siderophile elements-HSE (Os, Ir, Pt, Ru, Rh) along with occasional detection of Mo and Re were observed in half of the 52 analyzed crystals as random concentration spikes in time-resolved LA-ICPMS data. These nuggets are interpreted as variably altered remnants from repeated meteorite bombardment of the early martian crust, as are chondritic Ni/Co ratios of pyrite (10-20). Pyrite displays superchondritic S/Se (54,000-3300) and Te/Se (0.3 to >1). The reasonably good positive correlation (R2 = 0.72) between Se and Ni reflects a temperature control on the solubility of both elements. Apart from the chalcogens S, Se and Te, pyrite appears to be a minor contributor (<20%) to the whole-rock budget for both HSE (including Ni and Co) and chalcophile metals Ag, As, Au, Cu, Hg, Pb, Sb, Tl and Zn. This deficit can result from (i) high (>400 °C) temperature crystallization for NWA 7533 pyrite, as deduced from its Se and Ni contents, (ii) magmatic sulfide-depletion of brecciated early martian crust, (iii) precipitation from near neutral H2S-HS-H2O-rich hydrothermal fluids that did not provide halogen ligands for extensive transport of chalcophile-siderophile metals. It is suggested that the 1.4 Ga lithification event that precipitated hydrothermal pyrite left the chalcophile-siderophile element budget of the early martian crust nearly unmodified, except for S, Se and Te.