Sulfur Isotopes

Sulfur isotopes
These isotopes are useful in determining water sources in sulphate-rich sediments and in determining degrees/and types of diagenesis. Volcanogenic S, not included, except as a reference list.

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"Sulfur Isotopes" Introduction to use of oxygen isotopes
Sulfur (S) has 25 known isotopes with mass numbers ranging from 26 to 49, four of which are stable: 32S (95.02%), 33S (0.75%), 34S (4.21%), and 36S (0.02%). The preponderance of sulfur-32 is explained by its production from carbon-12 plus successive fusion capture of five helium nuclei, in the so-called alpha process of exploding type II supernovae (see silicon burning).
Other than 35S, the radioactive isotopes of sulfur are all comparatively short-lived. 35S is formed from cosmic ray spallation of 40Ar in the atmosphere. It has a half-life of 87 days. The next longest-lived radioisotope is sulfur-38, with a half-life of 170 minutes. The shortest-lived is 49S, with a half-life shorter than 200 nanoseconds.
When sulfide minerals are precipitated, isotopic equilibration among solids and liquid may cause small differences in the δS-34 values of co-genetic minerals. The differences between minerals can be used to estimate the temperature of equilibration. The δC-13 and δS-34 of coexisting carbonates and sulfides can be used to determine the pH and oxygen fugacity of the ore-bearing fluid during ore formation.
In most forest ecosystems, sulfate is derived mostly from the atmosphere; weathering of ore minerals and evaporites also contribute some sulfur. Sulfur with a distinctive isotopic composition has been used to identify pollution sources, and enriched sulfur has been added as a tracer in hydrologic studies. Differences in the natural abundances can also be used in systems where there is sufficient variation in the 34S of ecosystem components. Rocky Mountain lakes thought to be dominated by atmospheric sources of sulfate have been found to have different δS-34 values from lakes believed to be dominated by watershed sources of sulfate.

Sulfur isotopes Bibliography

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Sulfur isotopes and Volcanics Bibliography

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Capasso G., Favara R., and Inguaggiato S. (2000) Interaction between fumarolic gases and thermal groundwaters at Vulcano Island (Italy): evidences from chemical composition of dissolved gases in waters. J. Volcanol. Geoth. Res. 102, 309-318.

Carapezza M. L., Inguaggiato S., Brusca L., and Longo M. (2004) Geochemical precursors of the activity of an open-conduit volcano: The Stromboli 2002-2003 eruptive events. Geoph. Res. Letters 31, L07620.

Faure and Mensing, 2005

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Favara R., Grassa F., Inguaggiato S., Pecoraino G., and Capasso G. (2002) A simple method to determine the ? 13C content of total dissolved inorganic carbon. Geofisica Internacional 41, 313-320

Giammanco S., Inguaggiato S., and Valenza M. (1998) Soil and fumarole gases of Mount Etna: geochemistry and relations with volcanic activity. J. Volcanol. Geoth. Res. 81 , 297-310.

Grassa F., Capasso G., Favara R., Inguaggiato S., Faber E., and Valenza M. (2004) Molecular and isotopic composition of free hydrocarbon gases from Sicily, Italy. Geoph. Res. Letters 31, L06607.

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Inguaggiato S., Martin-Del Pozzo A. L., Aguayo A., Capasso G., and Favara R. (2005) Isotopic, chemical and dissolved gas constraints on spring water from Popocatepetl (Mexico): evidence of gas-water interaction magmatic component and shallow fluids. J. Volcanol. Geoth. Res. 141, 91-108.

Inguaggiato S., Pecoraino G., and D'Amore F. (2000) Chemical and isotopical characterization of fluid manifestations of Ischia Island (Italy). J. Volcanol. Geoth. Res. 99, 151-178.

Inguaggiato S., Taran Y. A., Grassa F., Capasso G., Favara R., Varley N., and Faber E. (2004) Nitrogen isotopes in thermal fluids of a forearc region (Jalisco Block, Mexico): evidence for heavy nitrogen from continental crust. Geochemistry, Geophysics, Geosystems 5, Q12003.

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Sortino F., Inguaggiato S., and Francofonte S. (1991) Determination of HF, HCI and total sulphur in fumarolic condensates by ionic cromotography. Acta Vulcanologica 1, 89-91.

Taran Y. A., Inguaggiato S., Marin M., and Yurova L. M. (2002) Geochemistry of fluids from submarine hot springs at Punta de Mita, Nayarit, Mexico. J. Volcanol. Geoth. Res. 115, 329-338.

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Useful Thermogenic References
Aharon, P. and Fu, B., 2000, microbial sulfate reduction rates and sulfur and oxygen isotope fractionations at oil and gas seeps in deepwater Gulf of Mexico. Geochimica et Cosmochimica Acta, 64(2), 233–246.

Amrani, A. , Lewan, M.D., And Aizenshtat, Z., 2005,  Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb limestone, Israel. Geochimica et Cosmochimica Acta,  69 (22), 5317–5331.

Bailey, N.J.L., Jobson, A.M., and Rogers, M.A., 1973, Bacterial Degradation Of Crude Oil: Comparison Of Field And Experimental Data. Chemical Geology, 11, 203–221.

Cai, C., Li, K., Li, H., and Zhang, B., 2008, Evidence for cross formational hot brine flow from integrated 87Sr/86Sr, REE and fluid inclusions of the Ordovician veins in Central Tarim, China. Applied Geochemistry, Volume 23 (8), 2226–2235.

Cai, C., Zhang, C., Cai, Wu, G., Lei, J., Xi, Z. Li, Ma, A., and Chen, L., 2009, Origins of Palaeozoic oils in the Tarim Basin: Evidence from sulfur isotopes and biomarkers. Chemical Geology, 268 (3-4), 197–210.

Cai, C., Hu, W., and Worden, R.H., 2001, Thermochemical sulphate reduction in Cambro–Ordovician carbonates in Central Tarim. Marine and Petroleum Geology,  18 (6), 729–741.

Farquhar, J. and Wing, B.A., 2003, Multiple Sulfur isotope analyses: Applications in geochemistry and cosmochemistry. Earth and Planetary Science Letters, 213(1-2), 1–13.

Farquhar, J. and Wing, B.A. 2005, The terrestrial record of stable sulphur isotopes: a review of the implications for evolution of Earth’s sulphur cycle, in McDonald, I., Boyce,A. J., Butler, I. B.,Herrington, R. J. & Polya,D.A. (eds), Mineral Deposits and Earth Evolution. Geological Society, London, Special Publications, 248, 167–177.

Farquhar J., Wu, N.P., Canfield D.E., Oduro, H.,  2010, Connections between sulfur cycle evolution, sulfur isotopes, sediments, and base metal VMS, SEDEX, and MVT deposits, Economic Geology 105: 509–533.

Krouse, H.R., 1977. Sulfur isotope studies and their role in petroleum
exploration. J. Geochem. Explor. 7, 189–211.

Machel, H.G., Krouse, H. R., Riciputi, L.R., and Cole, D.R., 1995, Devonian Nisku Sour Gas Play, A Unique Natural Laboratory for Study of Thermochemical Sulfate Reduction. Ch. 25, In: ACS Symposium Series 612, eds. Murthy A Vairavamurthy & Martin A A Schoonen, “Geochemical Transformations of Sedimentary Sulfur”, pp 439–454.

Machel, H.G., Krouse, H.R., and Sassen, R., 1995, Products and distinguishing criteria of bacterial and thermochemical sulfate reduction. Applied Geochemistry, 10, 373–389.

Machel, H.G., 2001, Bacterial and thermochemical sulfate reduction in diagenetic settings - old and new insights. Sedimentary Geology 140 (1-2), 143 -175.

Oduro, H., Kamyshny, A. Jr, Guo, W., Farquhar,J., 2011, Multiple sulfur isotope analysis of volatile organic sulfur compounds and their sulfonium precursors in coastal marine environments. Mar. Chem 124 (1–4), 78–89.

Ono, S., Eigenbrode, JL, Pavlov, AA, and Kharecha,P., 2003, New insights into Archean sulfur cycle from mass-independent sulfur isotope records from the Hamersley Basin, Australia.  Earth and Planetary Sciences, Earth and Planetary Science Letters 213 (2003) 15–30.

Peters, M., Strauss, H., Farquhar, J., Ockert, C., Eickmann, B., Jost, C.L., 2010 Sulfur cycling at the Mid-Atlantic Ridge: a multiple sulfur isotope approach Chemical Geology, 269, 180–196.

Rooney, M.A., claypool, G.E., and Chung, H.M., 1995, Modeling thermogenic gas generation using carbon isotope ratios of natural gas hydrocarbons. Chemical Geology, 126 (3–4), 219–232.

Van Stempvoort, D. R. and Krouse, H. R.  1994, Environmental Geochemistry of Sulfide Oxidation, Chapter DOI: 10.1021/bk-1994-0550. ACI Series, Vol. 550. Ch. 29 , 446–480.
Controls of δ18O in Sulfate. IN: Review of Experimental Data and Application to Specific Environments; Editors: C. N Alpers and D. W Blowes.

Wang, Q., 2008, Generation mechanism and control measures for H2S in oil wells, Liaohe Oilfield. Petroleum Exploration and Development, 35 (6), 349–354.

Watanabe, Y., Farquhar, J., and Ohmoto, H., 2009, Anomalous Fractionations of Sulfur isotopes During Thermochemical Sulfate Reduction. Science, 324, 370-73.

Other Important References
Jassim, S.Z., Raiswell, R.  and Bottrell, S.H.,1999, Genesis of the Middle Miocene stratabound sulphur deposits of northern Iraq.  Journal of the Geological Society, 156 (2), 25-39.

Kajiwara, Y. and Krouse,  H. R, 1971, Sulfur isotope Partitioning in Metallic Sulfide Systems.  Canadian Journal of Earth Sciences, 8(11), 1397-1408.

Ruckmick, J.C. ,  Wimberly, B.H. and Edwards, A.F., 1979, Classification and genesis of biogenic sulfur deposits. Economic Geology, 74 (2) 469-474.
Thomazo, C., Pinti, D.L., Busigny, V., Ader, M., Hashizume, K., and Philippot, P, 2009, Biological activity and the Earth’s surface evolution: Insights from carbon, sulfur, nitrogen and iron stable isotopes in the rock record. C.R. Paleo  l8, 665–678.  General palaeontology (Palaeobiochemistry)
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