S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides
Shanks, Wayne C.
Rouxel, Olivier J.
MetadataShow full item record
KeywordSulfur isotope; Multiple-isotope; Mass-dependent; S-33; S-36; Sulfur cycle; Hydrothermal; Vent; Mass-independent; Isotope fractionation
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ33S (≡ δ33S – 0.515 δ34S) values of up to 0.04 ‰ even if δ34S values are identical. Detection of such small Δ33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006 ‰ (2σ). Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10° N, 13° N, and 21° S and Mid-Atlantic Ridge (MAR) 37° N yield Δ33S values ranging from –0.002 to 0.033 and δ34S from –0.5 to 5.3 ‰. The combined δ34S and Δ33S systematics reveal that 73 to 89 % of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27 % from seawater-derived sulfate. Pyrite from EPR 13° N and marcasite from MAR 37° N are in isotope disequilibrium not only in δ34S but also in Δ33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.
Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 71 (2007): 1170-1182, doi:10.1016/j.gca.2006.11.017.
Showing items related by title, author, creator and subject.
Friedman, Carrie T. (Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1998-02)Stable sulfur isotopes (δ34S) and trace Co are analyzed in sulfide and sulfate minerals from six sample types collected from the TAG active mound, 26°N Mid-Atlantic Ridge. δ34S values range from 2.7 to 2O.9%, with sulfate ...
Tostevin, Rosalie; Turchyn, Alexandra V.; Farquhar, James; Johnston, David T.; Eldridge, Daniel L.; Bishop, James K. B.; McIlvin, Matthew R. (Elsevier, 2014-04-16)We present 28 multiple sulfur isotope measurements of seawater sulfate (δ34SSO4δ34SSO4 and Δ33SSO4Δ33SSO4) from the modern ocean over a range of water depths and sites along the eastern margin of the Pacific Ocean. The ...
Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems : highlighting the role of isomers in the sulfite and sulfoxylate systems Eldridge, Daniel L.; Guo, Weifu; Farquhar, James (2016-09)We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30–40H2O clusters spanning the range ...