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Volumn 324, Issue 5925, 2009, Pages 370-373

Anomalous fractionations of sulfur isotopes during thermochemical sulfate reduction

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ACID; ISOTOPE; ORGANIC MATTER; SULFATE; SULFUR; SULFUR DIOXIDE;

EID: 65249165379     PISSN: 00368075     EISSN: 10959203     Source Type: Journal    
DOI: 10.1126/science.1169289     Document Type: Article
Times cited : (135)

References (37)
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    • The abundance ratios of the stable isotopes of S (32, 33, 34, and 36) in a material (i) are typically reported as d values relative to the Vienna-Canyon Diablo troilite (V-CDT, such as δ33i, o, 33/32/(33/32)V-cDT, 1J × 1000. δ33i, δ34 i, and δ36i values of most Earth materials, especially those younger than ∼2.4 billion years, are typically related by δ33i ≈ 0.51 × δ34i and δ36i ≈ 1.9 × δ34i, which are termed mass-dependent fractionation (MDF, Deviations from the MDF lines (or reference arrays) are commonly expressed with Δ33i and Δ36i. In this study, we
    • i values fall outside of 0.51 ± 0.01 and 1.9 ± 0.1, respectively, the material is deemed to contain either mass-independently fractionated (MIF), non-mass dependently fractionated, or anomalously fractionated S isotopes. We used anomalously fractionated S isotopes in this report, rather than MIF-S, because MDF relationships vary substantially depending on the types of reactions (for example, equilibrium, kinetic, chemisorption, or radical) and species involved.
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    • A. Vairavamurthy, M. A. A. Schoonen, Eds, American Chemical Society, Washington, DC
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    • Materials and methods are available as supporting material on Science Online.
    • Materials and methods are available as supporting material on Science Online.
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    • We prepared the Cr-solution by the reducing the acidified chromic (III) chloride solution to chromous (II, This solution does not reduce organic S or S from SO42- to H2S but does reduce S from FeS2, elemental S, and acid-volatile monosulfide S (such as FeS and ZnS) to H2S. We used this solution after removing acid-volatile monosulfide S with a 6-N HCl solution
    • 2S. We used this solution after removing acid-volatile monosulfide S with a 6-N HCl solution.
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    • 2S.
    • 2S.
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    • Suppose the initial Δ33 and Δ36 values of H2S were +2.1 and -l.l%o, respectively, with respect to the initial SO42, Δ33 and Δ36 of H2S generated with TSR after a 90% SO 42- reduction would be -2.6%o and +1.4% o, respectively, and those of residual SO42- would be -4.6%o and +2.4%o, respectively. In systems in which the product H2S is removed from its parental SO 42- and then reoxidized to SO42- by some oxidants such as ferric iron oxides, Δ33 and Δ36 of the second generation of H2S may be +4.2%o and -2.2%o, respectively
    • o, respectively.
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    • 2- reduction and for discussions. We thank D. Walizer, H. Hamasaki, A. Klarke, B. Wing, A. L. Masterson, and S.-T. Kim for technical assistance; A. C. Lasaga, T. Otake, S. R. Poulson, and I. Johnson for discussions and review of an earlier manuscript; and three anonymous reviewers for useful comments. This study was supported by grants to H.O. from the NASA Astrobiology Institute (CA#NNA04CC06A), NASA Exobiology Program (CA#NNG04GK00G), and NSF (EAR-0229556).
    • 2- reduction and for discussions. We thank D. Walizer, H. Hamasaki, A. Klarke, B. Wing, A. L. Masterson, and S.-T. Kim for technical assistance; A. C. Lasaga, T. Otake, S. R. Poulson, and I. Johnson for discussions and review of an earlier manuscript; and three anonymous reviewers for useful comments. This study was supported by grants to H.O. from the NASA Astrobiology Institute (CA#NNA04CC06A), NASA Exobiology Program (CA#NNG04GK00G), and NSF (EAR-0229556).


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