Laboratory simulation of natural sulphurization: I. Formation of monomeric and oligomeric isoprenoid polysulphides by low-temperature reactions of inorganic polysulphides with phytol and phytadienes

Graaf, Wim de; Damsté, Jaap S. Sinninghe; Leeuw, J.W. de

doi:10.1016/0016-7037(92)90275-n

Cited by 104 publications

(38 citation statements)

References 14 publications

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“…Porewater S 2-concentration increases from a water column-like concentration of < 0.1 mM near the surface to 9.0 mM at 215 cm and then decreases below. Both SO 4 2-and S 2-become progressively 34 S-enriched in deeper sediments, a common pattern associated with distillation of the porewater sulfate reservoir by dissimilatory microbial SO 4 2-reduction ( LaLonde et al, 1987;de Graaf et al, 1992;Rowland et al, 1993;Schouten et al, 1994;Kok et al, 2000;Werne et al, 2003;Amrani and Aizenshtat, 2004a,b . Pyrite sulfur is present at ca. 1.3 wt% in surface sediments.…”

Section: Site Backgroundmentioning

confidence: 99%

“…C 20 isoprenoid thiophenes have been widely observed in non-polar fractions of extracts from sediments (e.g. Sinninghe Damsté et al, 1987;Wakeham et al, 1995) and experimental studies (de Graaf et al, 1992;Rowland et al, 1993;Krein and Aizenshtat, 1994;Gelin et al, 1998) . Here, two identical C 20 isoprenoid thiophenes were observed in multiple polarity fractions and could not be isolated in a single fraction using column chromatography.…”

Section: Osc Identification and Abundancementioning

confidence: 99%

“…Schmid et al, 1987;Sinninghe Damsté et al, 1987;Sinninghe Damsté and De Leeuw, 1990). Although some of the organic sulfur compounds (OSCs) in marine sediments have been reproduced under laboratory conditions (LaLonde et al, 1987;de Graaf et al, 1992;Rowland et al, 1993;Schouten et al, 1994;Kok et al, 2000;Amrani and Aizenshtat, 2004a,b), the relationship between sulfurization reactions in natural systems and the sulfur isotopic composition of sedimentary OM has not been determined.…”

Section: Introductionmentioning

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: Site Backgroundmentioning

confidence: 99%

Section: Osc Identification and Abundancementioning

confidence: 99%

Section: Introductionmentioning

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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“…Sulfur can thereby be incorporated into different types of organic compounds, including alkenes, aldehydes (de Graaf et al, 1992;Krein and Aizenshtat, 1994;Schouten et al, 1994), carbohydrates and complex algal material (Kok et al, 2000;van Dongen et al, 2003). The incorporation of sulfur likely protects labile organic matter from microbial alterations (Anderson and Pratt, 1995).…”

Section: Introductionmentioning

confidence: 99%

Experimental Evidence for Abiotic Sulfurization of Marine Dissolved Organic Matter

et al. 2017

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Dissolved organic sulfur (DOS) is the largest pool of organic sulfur in the oceans, and as such it is an important component of the global sulfur cycle. DOS in the ocean is resistant against microbial degradation and turns over on a millennium time scale. However, sources and mechanisms behind its stability are largely unknown. Here, we hypothesize that in sulfate-reducing sediments sulfur is abiotically incorporated into dissolved organic matter (DOM) and released to the ocean. We exposed natural seawater and the filtrate of a plankton culture to sulfidic conditions. Already after 1-h at 20 • C, DOS concentrations had increased 4-fold in these experiments, and 14-fold after 4 weeks at 50 • C, indicating that organic matter does not need long residence times in natural sulfidic environments to be affected by sulfurization. Molecular analysis via ultrahigh-resolution mass spectrometry showed that sulfur was covalently and unselectively bound to DOM. Experimentally produced and natural DOS from sediments were highly similar on a molecular and structural level. By combining our data with published benthic DOC fluxes we estimate that 30-200 Tg DOS are annually transported from anaerobic and sulfate reducing sediments to the oceans. Uncertainties in this first speculative assessment are large. However, this first attempt illustrates that benthic DOS flux is potentially one order of magnitude larger than that via rivers indicating that this could balance the estimated global net removal of refractory DOS.

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“…The nine conjugated double bonds of isorenieratene make it highly susceptible to reaction with reduced inorganic sulphur species (e.g., de Graaf et al, 1992;Schouten et al, 1994) that are present in abundance in the anoxic water column and the top layers of the sediment. Incorporation of sulphur into isorenieratene results in the formation of multiple S-linked isorenieratane moieties in HMW fractions such as the polar and asphaltene fractions and the kerogen during early diagenesis (Sinninghe Damst6 et al, 1989;Kohnen et al, 1990).…”

Section: Introductionmentioning

confidence: 99%

Diagenetic and catagenetic products of isorenieratene: Molecular indicators for photic zone anoxia

Koopmans

Köster

Kaam-Peters

et al. 1996

Geochimica et Cosmochimica Acta

365

152

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Abstract--A wide range of novel diagenetic and catagenetic products of the diaromatic carotenoid isorenieratene, a pigment of the photosynthetic green sulphur bacteria Chlorobiaceae, has been identified in a number of sedimentary rocks ranging from Ordovician to Miocene. Compound identification is based on NMR, mass spectrometry, the presence of atropisomers, and stable carbon isotopes. Atropisomers contain an axially chiral centre which, in combination with other chiral centres, results in two or more diastereomers that can be separated on a normal GC column. Chlorobiaceae use the reverse TCA cycle to fix carbon, so that their biomass is enriched in 13C. High ~3C contents of isorenieratene derivatives therefore support their inferred origins.Isorenieratene derivatives include C4o, C33, and C32, diaryl isoprenoids and short-chain aryl isoprenoids with additional aromatic and/or S-containing rings. C33 and C32 compounds are diagenetic products of C33 and C32 "carotenoids" formed from isorenieratene during early diagenesis through expulsion of toluene and m-xylene, respectively. Cyclisation of the polyene acyclic isoprenoid chain can proceed via an intramolecular Diels-Alder reaction, followed by aromatisation of the newly formed ring. Sulphurisation is also an important process during early diagenesis, competing with expulsion and cyclisation. Sulphur-bound isorenieratane is released during progressive diagenesis, due to cleavage of relatively weak S-S and C-S bonds. Cleavage of C-C bonds during aromatisation of newly formed rings and during catagenesis yields short-chain compounds. The inherent presence of a conjugated double bond system in carotenoids implies that similar diagenetic and catagenetic reactions can occur with all carotenoids.Chlorobiaceae live at or below the oxic/anoxic boundary layer and require both light and H2S. The presence of isorenieratene or its diagenetic and catagenetic products in ancient sedimentary rocks and crude oils is therefore an excellent indication for photic zone anoxia in the depositional environment. Diagenetic and catagenetic products of isorenieratene are expected to find applications in reconstruction of palaeoenvironments and in oil-oil and oil-source rock correlation studies. Their presence in several petroleum source rocks suggests that anoxia is an important environmental parameter for the preservation of organic matter.

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Laboratory simulation of natural sulphurization: I. Formation of monomeric and oligomeric isoprenoid polysulphides by low-temperature reactions of inorganic polysulphides with phytol and phytadienes

Cited by 104 publications

References 14 publications

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Experimental Evidence for Abiotic Sulfurization of Marine Dissolved Organic Matter

Diagenetic and catagenetic products of isorenieratene: Molecular indicators for photic zone anoxia

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