Coupled antimony and sulfur isotopic composition of stibnite as a window to the origin of Sb mineralization in epithermal systems (examples from the Kremnica and Zlatá Baňa deposits, Slovakia)

Abstract

Stibnite is a relatively common mineral in epithermal deposits, with little known about Sb transport and efficient stibnite precipitation. The famous Kremnica Au-Ag low-sulfidation deposit and Zlatá Baňa intermediate-sulfidation Pb-Zn-Cu-Au-Ag-Sb deposit are hosted in two different Neogene volcanic fields in Western Carpathians, Slovakia. In both deposits, stibnite-rich veins occur outside of major vein structures, accompanied by illite, illite/smectite, and kaolinite alteration, and affiliated to late-stage fluids (< 2 wt% NaCl eq., < 150 °C). Sulfur isotopic composition of stibnite and sulfides is different at both deposits, likely due to a different magmatic-hydrothermal evolution of the parental magmatic chambers in the Central and Eastern Slovak Volcanic Fields. The Sb isotopes (δ 123 Sb), however, show similar values and trends of gradual simultaneous increase with δ 34 S values, explained by a progressive precipitation of stibnite and its fractionation with the fluid. The data were modeled by two coupled Rayleigh fractionation models, (for Sb and for S), assuming a predominant Sb transport in HSb 2 S 4 – with a variable amount of S species. Higher molality ratio m S /m Sb of fluids was found in Kremnica (~ 3–4) than in Zlatá Baňa (~ 2). At both deposits, the heaviest δ 123 Sb values are accompanied by a decrease in the δ 34 S values probably due to the commencement of pyrite/marcasite precipitation. According to thermodynamic models of solubility of Sb(III) complexes and observations from active geothermal fields, stibnite precipitation was triggered by temperature decrease accompanied by mixing with a mildly acidic fluid (pH 4–5) of a steam-heated CO 2 -rich condensate on margins and in the final stages of epithermal systems. The proposed model for the origin of stibnite-bearing veins in epithermal systems can be used for their better targeting and efficient mineral exploration.

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