title: Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs.
abstract: BACKGROUND
  The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling.
  
  
  RESULTS
  Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L(-1)) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ(34)S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed.
  
  
  CONCLUSIONS
  The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.
authors: Department of Geology and Earth Systems Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA ; Max-Planck Institute for Marine Microbiology, Department of Biogeochemistry, Celsiusstrasse 1, D-28359 Bremen, Germany ; Department of Geological and Environmental Sciences, The Faculty of Natural Sciences, Ben-Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105, Israel.
authors: Alexey
authors: A
authors: Kamyshny
authors: Department of Earth Sciences, Indiana University Purdue University Indianapolis, Indianapolis, IN 46202, USA.
authors: Gregory
authors: G
authors: Druschel
authors: Department of Geology and Earth Systems Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA.
authors: Zahra F
authors: ZF
authors: Mansaray
authors: Department of Geology and Earth Systems Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA.
authors: James
authors: J
authors: Farquhar
keywords: Hydrothermal springs; Isotope geochemistry; Multiple sulfur isotopes; Sulfide oxidation; Sulfur cycle; Sulfur disproportionation; Yellowstone national park