Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere: State of the art and future research

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

doi:10.1016/0146-6380(90)90145-p

Cited by 425 publications

(168 citation statements)

References 60 publications

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“…Part of the organic sulfide/thiol may be the result of sulfurization processes occurring at high sulfide concentrations, when reactive sites of degraded organic particles are "quenched" by inorganic sulfide under the formation of thiol functional groups [31,32]. Thiol groups in turn react to form mono-and disulfidic (-S-and -S-S-) bridges in organic compounds [33]. Despite daily supplementation of Fe to the reactors, the concentration of Fe in the liquid fraction was below the detection limit (precipitated as FeS).…”

Section: Sulfur K-edge Xanes Data Collection and Analysismentioning

confidence: 99%

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors

Yekta

Gustavsson

Svensson

et al. 2012

Talanta

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The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (~60% of total S) and reduced organic S (~30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction 2 that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed.

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Section: Sulfur K-edge Xanes Data Collection and Analysismentioning

confidence: 99%

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors

Yekta

Gustavsson

Svensson

et al. 2012

Talanta

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“…This reactive organic material can subsequently undergo abiotic condensation and polymerization reactions to generate stable, macromolecular, amorphous material called kerogen (Vandenbrouke and Largeau, 2007). Special condensation reactions can occur in the presence of sulfide (e.g., Sinninghe Damsté et al, 1988;Kohnen et al, 1991) in which sulfur is added to OM by reaction with functionalized organic compounds, generating 'abiogenic organic S.' The resulting sulfur-rich OM is relatively resistant to biodegradation (Boussafir et al, 1995;Sinninghe Damsté and De Leeuw, 1990), making OM sulfurization a potential mechanism for enhancing OM preservation. Still, the timescale of this process -i.e., whether it occurs within sinking particles, versus solely in sediments -remains unclear.…”

Section: Introductionmentioning

confidence: 99%

Rapid organic matter sulfurization in sinking particles from the Cariaco Basin water column

Raven

Sessions

Adkins

et al. 2016

Geochimica et Cosmochimica Acta

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Organic matter (OM) burial in marine sediments is a potentially important control on global climate and the long-term redox state of the earth's surface. Still, we have only a limited understanding of the processes that stabilize OM and facilitate its preservation in the geologic record. Abiotic reactions with (poly)sulfides can enhance the preservation potential of OM, but for this process to be significant it needs to compete with OM remineralization, the majority of which occurs before sinking particles reach the sea floor. Here we investigate whether OM sulfurization occurs within sinking particles in the Cariaco Basin, a modern sulfidic marine environment with high rates of OM burial.Proto-kerogen in sinking particles is frequently more sulfur-rich and 34 S-depleted than expectations for biomass, with a composition that is difficult to explain by mixing with resuspended or terrigenous material. Instead, it appears that sulfur is being incorporated into OM on a timescale of days in sinking particles. The flux of this abiogenic organic S from particles is equivalent to approximately two-thirds of the total amount of protokerogen S at 10 cm depth in underlying sediments (ODP Core 1002B); after 6000 years of more gradual sulfurization reactions, potential water column sources are still equivalent to nearly half of the total proto-kerogen S in Cariaco sediments. Water column sulfurization is most extensive during periods of upwelling and high primary productivity 2 and appears to involve elemental S, possibly via polysulfides. This process has the potential to deliver large amounts of OM to the sediments by making it less available for remineralization, generating OM-rich deposits. It represents a potentially dynamic sink in the global carbon cycle that can respond to changes in environmental conditions, including the size and intensity of O 2 -depleted environments. Water column OM sulfurization could also have played a more significant role in the carbon cycle during ocean anoxic events, for example during the Cretaceous.

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“…Consequently, the organic matter in the Tarfaya kerogen is thought, in line with petrographic analyses, to be derived from one biogenic source, i.e., resistant algal biopolymers, which has become enriched in organo-sulphur moieties by reaction with reduced sulphur species (Sinninghe Damst6 and de Leeuw, 1990;Sinninghe Damst6 et al, 1993). A reconsideration of previous results brings to light other DGC studies of kerogens in which large variations in density also were not reflected by significant variations in the chemical compositions of their pyrolysates.…”

Section: Curie-point Pyrolysis-gas Chromatography (Py-gc) and Curie-pmentioning

confidence: 99%

96/04671 The influence of mineral matter on the separation of amorphous marine kerogens using density gradient centrifugation

1996

Fuel and Energy Abstracts

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Abstract--Three relatively immature amorphous marine kerogens were subjected to density gradient centrifugation (DGC). The density fractions obtained were analyzed by Curie-point pyrolysis in combination with gas chromatography (Py~C) and with gas chromatography-mass spectrometry (Py~C-MS). Despite the variations in density, no significant variations were observed in chemical compositions of the flash pyrolysates of the density fractions of each kerogen. The variations in density were due to varying amounts of inorganic matter, in particular pyrite, which remained after chemical demineralization procedures and was insufficiently removed during the sample processing. This was substantiated by the ash content of individual density fractions, which is linearly correlated to the densities of the kerogen density fractions. Further micronization and cryogenic treatment followed by a sink-float procedure of the Posidonia kerogen prior to DGC resulted in only a partial removal of the inorganic phase, as indicated by a shift of the average density towards lower densities. These results demonstrate the substantial effect of mineral matter, in particular pyrite, on the separation of amorphous marine kerogens into chemically distinct entities due to an intimate association of the organic and inorganic phase.

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Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere: State of the art and future research

Cited by 425 publications

References 60 publications

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors

Rapid organic matter sulfurization in sinking particles from the Cariaco Basin water column

96/04671 The influence of mineral matter on the separation of amorphous marine kerogens using density gradient centrifugation

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