The sulfur-isotopic compositions of benzothiophenes and dibenzothiophenes as a proxy for thermochemical sulfate reduction

Amrani, Alon; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Hill, Ronald J.; Moldowan, J. Michael; Wei, Zhibin

doi:10.1016/j.gca.2012.01.023

Cited by 90 publications

(49 citation statements)

References 41 publications

(69 reference statements)

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“…Unlike for other light isotopes (H, C, N), we have not observed chromatographic separation of sulfur isotopologues, meaning that 34 S/ 32 S ratio values are invariant across even large chromatographic peaks. This is consistent with previous observations (Amrani et al, 2012;. Poor chromatographic peak shapes and/or coelution were the dominant source of measurement uncertainty, particularly during early analyses.…”

Section: Compound-specific δ 34 S Analysis Using Gc-icpmssupporting

confidence: 92%

“…The sulfur isotopic composition of individual GC-amenable organic compounds from all fractions was measured with a multicollector inductively-coupled plasma mass spectrometry (MC-ICPMS; Thermo Neptune + ) using an Agilent 6890 GC instrument for gas-phase sample introduction and separation following the approach described by Amrani (2009 Amrani et al (2009Amrani et al ( , 2012 for complex environmental samples.…”

Section: Compound-specific δ 34 S Analysis Using Gc-icpmsmentioning

confidence: 99%

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Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Raven

Adkins

Werne

et al. 2015

Organic Geochemistry

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Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are 34 Senriched relative to coexisting sulfide, and experiments have produced 34 S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography -inductively coupled plasma mass spectrometry, to measure the compoundspecific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in 34 S relative to coexisting kerogen and 2 porewater sulfide. We hypothesize that this 34 S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon-sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary pore water. The 34 Sdepleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization.3

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Section: Compound-specific δ 34 S Analysis Using Gc-icpmssupporting

confidence: 92%

Section: Compound-specific δ 34 S Analysis Using Gc-icpmsmentioning

confidence: 99%

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Raven

Adkins

Werne

et al. 2015

Organic Geochemistry

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“…Ion currents were integrated by the Neptune software (v. 3.1.0.27) in 189 ms increments and exported to Excel in ASCII format. Further details about the peak integration, calibration and processing can be found in Amrani et al (2009) and Amrani et al (2012). However, in the present study, because of the challenging background and peak density, we used a relatively small number of integration points, down to 5-10 points in the extreme cases.…”

Section: Instrumental Set-upmentioning

confidence: 99%

“…These reactions can form organic sulfur compounds (OSCs) such as thiols, sulfides, thiophenes, and condensed thiophenes such as benzo-and dibenzothiophenes (BTs and DBTs, Cai et al, 2003;Amrani et al, 2008Amrani et al, , 2012Zhang et al, 2008a,b). In a compound-specific sulfur isotope analysis (CSSIA) study, benzothiophenes (BTs) in oils of the Smackover Formation were significantly enriched in 34 S compared with dibenzothiophenes (DBTs), and had d 34 S values close to that of the sulfate minerals in the reservoirs .…”

Section: Introductionmentioning

confidence: 99%

Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

Gvirtzman

Said–Ahmad

Ellis

et al. 2015

Geochimica et Cosmochimica Acta

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“…These results indicate that the origin and fate of organic compounds are far more complicated than was previously assumed. Individual organosulfur compounds may reveal 34 S-variations of up to 50 ‰ in oils from the same source rock (Amrani et al 2012;Amrani 2014).…”

Section: Oilmentioning

confidence: 99%

Variations of Stable Isotope Ratios in Nature

Hoefs¹

2015

Stable Isotope Geochemistry

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The sulfur-isotopic compositions of benzothiophenes and dibenzothiophenes as a proxy for thermochemical sulfate reduction

Cited by 90 publications

References 41 publications

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

Variations of Stable Isotope Ratios in Nature

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