In this work, we investigated in situ isotopic compositions of antimony (Sb) minerals from two substages of the ore deposits near Pezinok (Slovakia). The δ¹²³Sb values of the primary Sb minerals range from −0.4 and +0.8‰ and increase progressively along the precipitation sequence. In the substage II, the early-formed gudmundite (FeSbS) shows in all sections the lowest δ¹²³Sb values, followed by berthierite (FeSb₂S₄), stibnite (Sb₂S₃), and valentinite (Sb₂O₃) with the heaviest δ¹²³Sb values. A similar trend was observed for the substage III, from the initially-formed stibnite, followed by kermesite (Sb₂S₂O), valentinite, senarmontite (both Sb₂O₃), and schafarzikite (FeSb₂O₄). The evolution can be rationalized by a Rayleigh fractionation model with a starting δ¹²³Sb value in the fluid of +0.3‰, applying the same mineral-fluid fractionation factor to all minerals. Thus, the texturally observed order of mineralization is confirmed by diminishing trace element contents and heavier δ¹²³Sb values in successively crystallized Sb minerals. Antimony in substage III was likely supplied from the oxidative dissolution of stibnite that formed earlier during substage II. The data interpretation, although limited by the lack of reliable mineral-fluid fractionation factors, implies that Sb precipitation within each substage occurred from an episodic metal precipitation, likely associated with a similar Sb isotope fractionation between fluid and all investigated Sb minerals. Large isotopic variations, induced by precipitation from a fluid as a response to temperature decrease, may be an obstacle in deciphering the metal source in hydrothermal ore deposits. However, Sb isotopes appear to be an excellent instrument to enhance our understanding on how hydrothermal systems operate.

在这项工作中，我们现场研究了佩济诺克（斯洛伐克）附近矿床两个亚阶段的锑 (Sb) 矿物的同位素组成。原生锑矿物的δ ¹²³ Sb 值范围为-0.4 至+0.8‰，并沿降水序列逐渐增加。在子阶段 II 中，早期形成的硅锰矿 (FeSbS) 在所有部分中都显示出最低的 δ ¹²³ Sb 值，其次是贝铁矿 (FeSb ₂ S ₄ )、辉锑矿 (Sb ₂ S ₃ ) 和七价铬矿 (Sb ₂ O ₃ )具有最重的 δ ¹²³ Sb 值。对于亚阶段 III 观察到类似的趋势，从最初形成的辉锑矿开始，然后是硅镁石 (Sb ₂ S ₂ O)、七价铬矿、钠锰矿（均为 Sb ₂ O ₃）和白铁矿 (FeSb ₂ O ₄ )。该演变可以通过瑞利分馏模型合理化，流体中的起始δ ^{123 Sb 值为+0.3‰，对所有矿物应用相同的矿物流体分馏因子。}因此，通过连续结晶的锑矿物中微量元素含量的减少和较重的δ ¹²³ Sb 值证实了从结构上观察到的矿化顺序。第三阶段中的锑可能是由第二阶段早期形成的辉锑矿的氧化溶解提供的。数据解释虽然受到缺乏可靠的矿物流体分馏因素的限制，但意味着每个亚阶段内的锑沉淀是由偶发性金属沉淀发生的，可能与流体和所有研究的锑矿物之间类似的锑同位素分馏有关。由于温度下降而从流体中沉淀而引起的大同位素变化可能是破译热液矿床中金属来源的障碍。然而，锑同位素似乎是增强我们对热液系统如何运行的理解的绝佳工具。