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Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

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Abstract

The sulfide (H2S/HS−) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [\( {\text{S}}_{\text{x}}^{2 - } \)] and thiosulfate [\( {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } \)], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H2S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10−3 μM/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.

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Acknowledgments

This paper is submitted in the memory and honor of John W. Morse who made significant contributions to geochemistry and oceanography including the founding of Aquatic Geochemistry (Mackenzie et al. 2010). This work was supported by grants from the US National Science Foundation (OCE-0732439 to GWL, OCE-0732369 to PRG, OCE-0732333 to Charles R. Fisher), via the Ridge 2000 program. None of this work would have been possible without the expertise and patience of the ROV JASON II and the R/V Melville crews in 2006, and the ROV JASON II, and the R/V Thomas G. Thompson crews in 2009. We thank Arunima Sen for her assistance with the substrate data. Special thanks to Dr. Charles R. Fisher for his skills as chief scientist and for facilitating data collection.

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Author notes

  1. Shufen Ma

    Present address: Department of Earth and Planetary Science, University of California, Berkeley, CA, 94720, USA

  2. Mustafa Yücel

    Present address: Laboratory of Benthic Ecogeochemistry (LECOB), Observatoire Oceanologique de Banyuls, Université Pierre et Marie Curie—Paris 6, 66651, Banyuls-sur-mer, France

Authors and Affiliations

  1. School of Marine Science and Policy, College of Earth, Ocean and Environment, University of Delaware, Lewes, DE, 19958, USA

    Amy Gartman, Mustafa Yücel, Andrew S. Madison, Shufen Ma & George W. Luther III

  2. Department of Chemistry and Biochemistry, School of Marine Science and Policy, College of Earth, Ocean and Environment, University of Delaware, Lewes, DE, 19958, USA

    David W. Chu

  3. Department of Chemistry, Susquehanna University, Selinsgrove, PA, 17870, USA

    Christopher P. Janzen

  4. Biology Department, Penn State University, University Park, PA, 16801, USA

    Erin L. Becker

  5. Department of Organismic & Evolutionary Biology, Harvard University, Cambridge, MA, 02138, USA

    Roxanne A. Beinart & Peter R. Girguis

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  1. Amy Gartman
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Correspondence to Amy Gartman.

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Gartman, A., Yücel, M., Madison, A.S. et al. Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents. Aquat Geochem 17, 583–601 (2011). https://doi.org/10.1007/s10498-011-9136-1

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