Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

Hartgers, Walter A.; López, Jordi F.; Damsté, Jaap S. Sinninghe; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

doi:10.1016/s0016-7037(97)00279-2

Cited by 96 publications

(31 citation statements)

References 68 publications

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“…The high amounts of reactive iron are the cause for the lack or low concentrations of dissolved hydrogen sulfide over most of the sediment column (for a detailed discussion on iron cycling in these sediments see Riedinger et al, 2014). Produced sulfide is immediately scavenged, either via oxidation coupled to the reduction of the iron oxides or by precipitation with dissolved ferrous iron produced by the reduction of ferric iron (Berner and Westrich, 1985;Hartgers et al, 1997;Riedinger et al, 2014). Sulfide can only build up in the pore water when the rates of sulfide formation exceed those of iron-phase alteration, leading to the establishment of a sulfidic zone (Figure 3).…”

Section: Discussionmentioning

confidence: 99%

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Riedinger

Brunner

Krastel³

et al. 2017

Front. Earth Sci.

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The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope-a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory-conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS).Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper Riedinger et al.Non-steady State Subsurface Sulfur Cycling sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

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Section: Discussionmentioning

confidence: 99%

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Riedinger

Brunner

Krastel³

et al. 2017

Front. Earth Sci.

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“…Therefore, sulfur atoms in OSCs in Jinxian oil should be closely combined with those steroids with a continuous carbon number distribution; as a result, it explained the occurrence of high abundant OSCs with wide carbon number ranges. In factor, it is absolutely realistic and true for the wide sulfurization of steroids in many compounds in sediments because only sterols have much more double bond, hydroxyl group, and carbonyl group, which are prone to combine with inorganic sulfur leading to natural sulfurization (Schouten et al, 1993;Schaeffer et al, 1995;Hartgers et al, 1997).…”

Section: Explanation For the Different Distribution Of Oscsmentioning

confidence: 99%

Molecular characterization of sulfur compounds in some specieal sulfur-rich Chinese crude oils by FT-ICR MS

Shi

et al. 2013

Sci. China Earth Sci.

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“…), which result in the generation of low molecular weight organic sulfur compounds (LMW-OSC) and sulfur-bonded macromolecular (ten Haven et al, 1985;Sinninghe Damsté et al, 1988Adam et al, 1991;Kohnen et al, 1991Kohnen et al, , 1993Schouten et al, 1998). Thus, owing to the existence of the double bond, hydroxide radical and carbonyl group, sterol compounds can be easily combined with inorganic sulfur and occurred with natural sulfurization (de Graaf et al, 1992;Schouten et al, 1993;Hartgers et al, 1997), which result in the extensive sulfurization that occurred in steroids within numerous compounds (Schouten et al, 1993(Schouten et al, , 1995Hartgers et al, 1997). As a consequence, the concentration of sulfur-containing steroids can even substantially exceed the free steranes in the saturated hydrocarbon fractions (Schouten et al, 1993;Schaeffer et al, 1995;Hartgers et al, 1997).…”

Section: Formation Pathway Of Sulfur-containing Steroids and The Hydrmentioning

confidence: 99%

Identification and formation of sulfur-containing steroids in sulfur-rich heavy oils in the Jinxian Sag, Bohai Bay Basin, North China

Wang

Jiang

et al. 2013

Sci. China Earth Sci.

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High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag, Bohai Bay Basin, North China. These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain. Based on the previous reports of sulfur-containing steroids with methylthio-steroids and intra-molecular form, four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds. Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids: abiogenic chemical hydrogenation of H 2 S and HS -leads to the formation of regular steranes; a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes. This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes (higher than the common regular steroids, phytane and n-alkanes) in S-rich heavy oils and source rocks in the Jinxian Sag, Bohai Bay Basin, North China. sulfur-containing steroids, short-chain steranes, sulfurization, hydrogenation, C-S bond, H 2 S, Jinxian Sag Citation:Lu H, Wang Q T, Jiang L X, et al. Identification and formation of sulfur-containing steroids in sulfur-rich heavy oils in the Jinxian Sag, Bohai Bay

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Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

Cited by 96 publications

References 68 publications

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Molecular characterization of sulfur compounds in some specieal sulfur-rich Chinese crude oils by FT-ICR MS

Identification and formation of sulfur-containing steroids in sulfur-rich heavy oils in the Jinxian Sag, Bohai Bay Basin, North China

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