Pyrite trace element proxies for magmatic volatile influx in submarine subduction-related hydrothermal systems

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 δ34S composition of pyrite and native S, as reported by high-resolution coupled SIMS δ34S 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 δ34S 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 δ34S composition. This suggests that Te/As and Te/Sb ratios are more sensitive to a magmatic volatile influx into seawater-dominated hydrothermal systems than δ34S 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.