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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 (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_Sbof 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. 

Published Sn isotope data along with 150 new analyses of cassiterite and four granite analyses constrain two major tin isotope fractionation steps associated with (1) separation of tin from the magma/orthomagmatic transitional environment and (2) hydrothermal activity. A distinct Sn isotope difference across deposit type, geological host rocks, and time of ore deposit formation demonstrates that the difference in the mean δ124Sn value represents the operation of a unified process. The lower Sn isotope values present in both residual igneous rocks and pegmatite suggest that heavier Sn isotopes were extracted from the system during orthomagmatic fluid separation, likely by F ligands with Sn. Rayleigh distillation models this first F ligand-induced fractionation. The subsequent development of the hydrothermal system is characterized by heavier Sn isotope composition proximal to the intrusion, which persists in spite of Sn isotope fractionating towards isotopically lighter Sn during hydrothermal evolution.