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)

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 (δ¹²³Sb), however, show similar values and trends of gradual simultaneous increase with δ³⁴S 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 HSb₂S₄^– 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 δ¹²³Sb values are accompanied by a decrease in the δ³⁴S 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 CO₂-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.