Seafloor massive sulfides are modern analogues to ancient volcanogenic massive sulfide deposits, which are particularly enriched in volatile and precious metals (e.g., Te, Au, Ag, Cu, Bi, Se) in subduction-related settings. However, the sources of metals are still poorly constrained, and it remains elusive, whether magmatic volatile influx controls their distribution in submarine hydrothermal systems on the plate tectonic-scale. Here, we demonstrate, for the first time, that Te, As, and Sb contents as well as related Te/As and Te/Sb ratios vary systematically with the δS composition of pyrite and native S, as reported by high-resolution coupled SIMS δS and trace element LA-ICP-MS micro-analysis. The better correlation of element ratios (Te/As, Te/Sb) opposed to trace element contents (e.g., Te) with δS in pyrite demonstrates that element ratios provide a more robust record of magmatic volatile influx than their absolute contents. On this basis, we define a quantitative threshold of high Te/As (>0.004) and Te/Sb (>0.6) ratios in pyrite that are indicative of magmatic volatile influx to submarine subduction-related hydrothermal systems. Two-component fluid mixing simulations further revealed that <5 % of magmatic volatile influx drastically changes the Te/As (and Te/Sb) ratio of the modelled fluid, but only slightly changes its δS composition. This suggests that Te/As and Te/Sb ratios are more sensitive to a magmatic volatile influx into seawater-dominated hydrothermal systems than δS signatures if the magmatic volatile influx was low. Beyond this, our results demonstrate that magma-derived fluid mixing with seawater only has a negligible effect on the magmatic volatile record of Te/As and Te/Sb, while the S isotope system is prone for seawater overprinting leading to commonly ambiguous source signatures. Thus, Te/As and Te/Sb systematics in pyrite provide a robust proxy to evaluate the contribution of magmatic volatiles to submarine hydrothermal systems from the grain- to plate tectonic-scale.

中文翻译：

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海底俯冲相关热液系统中岩浆挥发物流入的黄铁矿微量元素代理

海底块状硫化物是古代火山块状硫化物矿床的现代类似物，在俯冲相关环境中特别富含挥发性金属和贵金属（例如碲、金、银、铜、铋、硒）。然而，金属的来源仍然缺乏约束，并且岩浆挥发性流入是否控制了它们在板块构造尺度上的海底热液系统中的分布，仍然难以捉摸。在这里，我们首次证明，如高分辨率耦合 SIMS 所报告的，Te、As 和 Sb 含量以及相关的 Te/As 和 Te/Sb 比率随黄铁矿和天然硫的 δS 组成而系统变化δS 和痕量元素 LA-ICP-MS 微量分析。元素比（Te/As、Te/Sb）相对于痕量元素含量（例如 Te）与黄铁矿中 δS 的更好相关性表明，元素比比其绝对含量提供了更可靠的岩浆挥发分流入记录。在此基础上，我们定义了黄铁矿中高 Te/As (>0.004) 和 Te/Sb (>0.6) 比率的定量阈值，该阈值表明岩浆挥发物流入海底俯冲相关热液系统。双组分流体混合模拟进一步表明，<5% 的岩浆挥发分流入会极大地改变模拟流体的 Te/As（和 Te/Sb）比率，但仅轻微改变其 δS 成分。这表明，如果岩浆挥发物流入量较低，Te/As 和 Te/Sb 比值对岩浆挥发物流入以海水为主的热液系统的影响比 δS 特征更敏感。除此之外，我们的结果表明，岩浆衍生流体与海水混合对 Te/As 和 Te/Sb 岩浆挥发记录的影响可以忽略不计，而 S 同位素系统很容易出现海水叠印，导致通常不明确的来源特征。因此，黄铁矿中的 Te/As 和 Te/Sb 系统学为从颗粒到板块构造尺度评估岩浆挥发物对海底热液系统的贡献提供了强有力的代理。