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Magmatic volatile phase
Pyrite
coupled SIMS δ34S and LA-ICP-MS trace element data
Submarine hydrothermal systems
Black smokers
Magmatic fluids
In-situ sulfide chemistry
Abstract:
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.
