{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T14:03:06Z","timestamp":1791295386925,"version":"4.1.0"},"reference-count":37,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"5925","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Science"],"published-print":{"date-parts":[[2009,4,17]]},"abstract":"<jats:p>\n                    Anomalously fractionated sulfur isotopes in many sedimentary rocks older than 2.4 billion years have been widely believed to be the products of ultraviolet photolysis of volcanic sulfur dioxide in an anoxic atmosphere. Our laboratory experiments have revealed that reduced-sulfur species produced by reactions between powders of amino acids and sulfate at 150\u00b0 to 200\u00b0C possess anomalously fractionated sulfur isotopes: \u0394\n                    <jats:sup>33<\/jats:sup>\n                    S = +0.1 to +2.1 per mil and \u0394\n                    <jats:sup>36<\/jats:sup>\n                    S = \u20131.1 to +1.1 per mil. These results suggest that reactions between organic matter in sediments and sulfate-rich hydrothermal solutions may have produced anomalous sulfur isotope signatures in some sedimentary rocks. If so, the sulfur isotope record of sedimentary rocks may be linked to the biological and thermal evolution of Earth in ways different than previously thought.\n                  <\/jats:p>","DOI":"10.1126\/science.1169289","type":"journal-article","created":{"date-parts":[[2009,4,16]],"date-time":"2009-04-16T16:53:12Z","timestamp":1239900792000},"page":"370-373","source":"Crossref","is-referenced-by-count":148,"title":["Anomalous Fractionations of Sulfur Isotopes During Thermochemical Sulfate Reduction"],"prefix":"10.1126","volume":"324","author":[{"given":"Yumiko","family":"Watanabe","sequence":"first","affiliation":[{"name":"The NASA Astrobiology Institute and Department of Geosciences, Pennsylvania State University, University Park, PA 16802, USA."},{"name":"Department of Geology and Earth System Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"James","family":"Farquhar","sequence":"additional","affiliation":[{"name":"The NASA Astrobiology Institute and Department of Geosciences, Pennsylvania State University, University Park, PA 16802, USA."},{"name":"Department of Geology and Earth System Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hiroshi","family":"Ohmoto","sequence":"additional","affiliation":[{"name":"The NASA Astrobiology Institute and Department of Geosciences, Pennsylvania State University, University Park, PA 16802, USA."},{"name":"Department of Geology and Earth System Science Interdisciplinary Center, University of Maryland, College Park, MD 20742, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_1_2_2","unstructured":"The abundance ratios of the stable isotopes of S ( 32 S 33 S 34 S and 36 S) in a material ( i ) are typically reported as d values relative to the Vienna-Canyon Diablo troilite (V-CDT) such as \u03b4 33 S i (\u2030) = [( 33 S\/ 32 S) i \/( 33 S\/ 32 S) V-CDT \u2013 1] \u00d7 1000. \u03b4 33 S i \u03b4 34 S i and \u03b4 36 S i values of most Earth materials especially those younger than \u223c2.4 billion years are typically related by \u03b4 33 S i \u2248 0.51 \u00d7 \u03b4 34 S i and \u03b4 36 S i \u2248 1.9 \u00d7 \u03b4 34 S i which are termed mass-dependent fractionation (MDF). Deviations from the MDF lines (or reference arrays) are commonly expressed with \u0394 33 S i and \u0394 36 S i . In this study we define \u0394 33 S i = \u03b4 33 S i \u2013 0.515 \u00d7 \u03b4 34 S i and \u0394 36 S i = \u03b4 36 S i \u2013 1.89 \u00d7 \u03b4 34 S i . When \u0394 33 S i and\/or \u0394 36 S i values deviate from the MDF lines by at least \u00b10.2\u2030 and \u00b10.4\u2030 respectively and \u03b4 33 S i \/\u03b4 34 S i and\/or \u03b4 36 S i \/\u03b4 34 S i values fall outside of 0.51 \u00b1 0.01 and 1.9 \u00b1 0.1 respectively the material is deemed to contain either mass-independently fractionated (MIF) non\u2013mass 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."},{"key":"e_1_3_1_3_2","doi-asserted-by":"publisher","DOI":"10.1029\/JZ070i014p03475"},{"key":"e_1_3_1_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemgeo.2008.01.020"},{"key":"e_1_3_1_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0012-821X(03)00296-6"},{"key":"e_1_3_1_6_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac200072122243"},{"key":"e_1_3_1_7_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.289.5480.756"},{"key":"e_1_3_1_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.epsl.2006.12.015"},{"key":"e_1_3_1_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0012-821X(03)00295-4"},{"key":"e_1_3_1_10_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1138700"},{"key":"e_1_3_1_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0016-7037(03)00059-0"},{"key":"e_1_3_1_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature02260"},{"key":"e_1_3_1_13_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1063811"},{"key":"e_1_3_1_14_2","doi-asserted-by":"publisher","DOI":"10.1029\/2000JE001437"},{"key":"e_1_3_1_15_2","doi-asserted-by":"publisher","DOI":"10.1089\/153110702753621321"},{"key":"e_1_3_1_16_2","first-page":"517","year":"1997","unstructured":"H. Ohmoto, M. B. Goldhaber, in Geochemistry of Hydrothermal Ore Deposits, H. L. Barnes, Ed. (Wiley, New York, 1997), pp. 517\u2013611.","journal-title":"Geochemistry of Hydrothermal Ore Deposits"},{"key":"e_1_3_1_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0037-0738(00)00176-7"},{"key":"e_1_3_1_18_2","doi-asserted-by":"publisher","DOI":"10.2475\/ajs.305.6-8.645"},{"key":"e_1_3_1_19_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature05044"},{"key":"e_1_3_1_20_2","first-page":"291","volume":"198","year":"2006","unstructured":"H. Ohmotoet al., in Evolution of Early Earth's Atmosphere, Hydrosphere, and Biosphere: Constraints from Ore Deposits, S. E. Kesler, H. Ohmoto, Eds. (Geological Society of America, Boulder, CO, 2006), vol. 198, pp. 291\u2013331.","journal-title":"Evolution of Early Earth's Atmosphere, Hydrosphere, and Biosphere: Constraints from Ore Deposits"},{"key":"e_1_3_1_21_2","first-page":"412","year":"1995","unstructured":"M. B. Goldhaber, W. L. Orr, in Geochemical Transformations of Sedimentary Sulfur, A. Vairavamurthy, M. A. A. Schoonen, Eds. (American Chemical Society, Washington, DC, 1995), pp. 412\u2013425.","journal-title":"Geochemical Transformations of Sedimentary Sulfur"},{"key":"e_1_3_1_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.epsl.2008.01.016"},{"key":"e_1_3_1_23_2","first-page":"29","year":"2000","unstructured":"M. T. Madigan, J. M. Martinko, J. Parker, in BROCK Biology of Microorganisms. (Prentice-Hall, Upper Saddle River, NJ, 2000), pp. 29\u201347.","journal-title":"BROCK Biology of Microorganisms"},{"key":"e_1_3_1_24_2","unstructured":"S. M. S. Libes An Introduction to Marine Biogeochemistry (Wiley New York 1992)."},{"key":"e_1_3_1_25_2","doi-asserted-by":"publisher","DOI":"10.1046\/j.1472-4669.2003.00002.x"},{"key":"e_1_3_1_26_2","unstructured":"J. M. J. Hunt Petroleum Geochemistry and Geology (Freeman New York ed. 2 1996)."},{"key":"e_1_3_1_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0016-7037(97)00164-6"},{"key":"e_1_3_1_28_2","first-page":"709","year":"1992","unstructured":"H. Strauss, T. B. Moore, in The Proterozoic Biosphere, J. W. Schopf, C. Klein, Eds. (Cambridge University Press, New York, 1992), pp. 709\u2013798.","journal-title":"The Proterozoic Biosphere"},{"key":"e_1_3_1_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-9268(82)90153-X"},{"key":"e_1_3_1_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/0016-7037(68)90088-4"},{"key":"e_1_3_1_31_2","unstructured":"Materials and methods are available as supporting material on Science Online."},{"key":"e_1_3_1_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2541(86)90078-1"},{"key":"e_1_3_1_33_2","unstructured":"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 SO 4 2\u2013 to H 2 S but does reduce S from FeS 2 elemental S and acid-volatile monosulfide S (such as FeS and ZnS) to H 2 S. We used this solution after removing acid-volatile monosulfide S with a 6-N HCl solution."},{"key":"e_1_3_1_34_2","first-page":"241","volume":"30","year":"1979","unstructured":"A. Sasaki, Y. Arikawa, R. E. Folinsbee, Bull. Geol. Surv. Japan30, 241 (1979).","journal-title":"Bull. Geol. Surv. Japan"},{"key":"e_1_3_1_35_2","unstructured":"We prepared the Kiba-solution [Stannous (II)\u2013strong phosphoric acid] by adding tin (II)\u2013chloride dehydrate to dehydrated ortho-phosphoric acid. In contrast to the Cr-solution the Kiba solution reduces S from SO 4 2\u2013 and organic S as well as S from FeS 2 to H 2 S."},{"key":"e_1_3_1_36_2","unstructured":"Suppose the initial \u0394 33 S and \u0394 36 S values of H 2 S were +2.1 and \u20131.1\u2030 respectively with respect to the initial SO 4 2\u2013 . \u0394 33 S and \u0394 36 S of H 2 S generated with TSR after a 90% SO 4 2\u2013 reduction would be \u20132.6\u2030 and +1.4\u2030 respectively and those of residual SO 4 2\u2013 would be \u20134.6\u2030 and +2.4\u2030 respectively. In systems in which the product H 2 S is removed from its parental SO 4 2\u2013 and then reoxidized to SO 4 2\u2013 by some oxidants (such as ferric iron oxides) \u0394 33 S and \u0394 36 S of the second generation of H 2 S may be +4.2\u2030 and \u20132.2\u2030 respectively."},{"key":"e_1_3_1_37_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature06202"},{"key":"e_1_3_1_38_2","unstructured":"We are grateful to H. Naraoka for the suggestion to use amino acids in SO 4 2\u2013 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)."}],"container-title":["Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.science.org\/doi\/pdf\/10.1126\/science.1169289","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,1,10]],"date-time":"2024-01-10T04:58:51Z","timestamp":1704862731000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.science.org\/doi\/10.1126\/science.1169289"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,4,17]]},"references-count":37,"journal-issue":{"issue":"5925","published-print":{"date-parts":[[2009,4,17]]}},"alternative-id":["10.1126\/science.1169289"],"URL":"https:\/\/doi.org\/10.1126\/science.1169289","relation":{},"ISSN":["0036-8075","1095-9203"],"issn-type":[{"value":"0036-8075","type":"print"},{"value":"1095-9203","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,4,17]]}}}