Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) $δ$34S values range from −5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of $δ$34S for cubic cubanite and H2S range from −1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero $Δ$33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. $Δ$33S values indicate that SO2 disproportionation is an additional process that contributes sulfur to a different back-arc system and to acid spring-type hydrothermal fluid circulation. At the sedimented Guaymus Basin, near-zero $Δ$33S values are also observed, despite negative $δ$34S values that indicate inputs of biogenic pyrite for some samples. In contrast with previous studies reporting isotope disequilibrium between H2S and chalcopyrite, the $δ$34S values of chalcopyrite sampled from the inner 1–2 mm of a chimney wall are within ±1‰ of $δ$34S values for H2S in the paired vent fluid, suggesting equilibrium fluid-mineral sulfur isotope exchange at 300–400 °C. Isotopic equilibrium between hydrothermal fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in the chalcopyrite lining across a chimney wall may accurately record past hydrothermal activity.