Formation of C20 isoprenoid thiophenes in modern sediments

Fukushima, Kazuo; Yasukawa, Masako; Muto, Naoko; Uemura, Hitoshi; Ishiwatari, Ryoshi

doi:10.1016/0146-6380(92)90146-o

Cited by 53 publications

(18 citation statements)

References 20 publications

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“…Those in the non-polar fraction (F1), which are comparable to previous observations (e.g. Brassell et al, 1986;Fukushima et al, 1992), are interpreted to represent C 20 isoprenoid thiophenes present in the original sample. Because thiophenes can form at elevated temperature, we interpret the more abundant C 20 isoprenoid thiophenes in F3 as forming in the GC injector, for example by ring closure or aromatization of a more polar precursor with a similar phytol-derived skeleton.…”

Section: Osc Identification and Abundancesupporting

confidence: 75%

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: Osc Identification and Abundancesupporting

confidence: 75%

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Raven

Adkins

Werne

et al. 2015

Organic Geochemistry

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“…3, indicated the presence of a thiophene ring with two, one and zero methyl groups, respectively. These compounds were identified as isoprenoid thiophenes with 20 carbons (C 20 H 36 S) by comparing their relative retention times and the mass spectra with those reported by Brassell et al (1986) and Fukushima et al (1992), and are listed in Table 1. Furthermore, three C 25 alkyl thiophenes were detected on the mass fragmentogram of m/z 378 ( Fig.…”

Section: Analysesmentioning

confidence: 99%

“…Thiophenes have been widely found in sedimentary rocks and crude oils (Brassell et al, 1986;Sinninghe Damsté et al, 1987, 1989aFukushima et al, 1992). Among these thiophenes alkyl thiophenes provide information for palaeobiota and depositional environment Sinninghe Damsté et al, 1990;Fukushima et al, 1992;de las Heras et al, 1997).…”

Section: Introductionmentioning

confidence: 99%

“…Among these thiophenes alkyl thiophenes provide information for palaeobiota and depositional environment Sinninghe Damsté et al, 1990;Fukushima et al, 1992;de las Heras et al, 1997). C 20 Isoprenoid and C 25 highly branched isoprenoid (HBI) thiophenes were possibly produced by the reaction of H 2 S to phytol or phytadiene derived from chlorophyll (Brassell et al, 1986) and C 25 HBI alkenes derived from the phytoplankton such as diatoms (Sinninghe Damsté et al, 1989c), respectively, during early turity parameter for both marine and terrestrial organic matter (Radke et al, 1986).…”

Section: Introductionmentioning

confidence: 99%

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Alkyl and polynuclear aromatic thiophenes in Neogene sediments of the Shinjo basin, Japan.

Katsumata

Shimoyama

2001

Geochem. J.

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Alkyl and polynuclear aromatic thiophenes were detected in sedimentary rocks of a stratigraphic sequence from Miocene to Pliocene in Shinjo basin, Japan. C 25 Highly branched isoprenoid (HBI) thiophenes, dibenzothiophene, C 1 -and C 2 -alkyldibenzothiophenes, and benzo [b]naphto[1,2-d]thiophene were rather predominantly present. The C 25 HBI thiophenes consist of three isomers including a pair of diastereomers. They were present in sediments from the Nakawatari to the upper part of the Kusanagi Formations and absent at the middle and lower parts of the Formation. The depth profiles of their concentrations do not coincide with those of the C 25 HBI alkane concentration and bulk sulfur content in the same sediment samples. It is postulated that the C 25 HBI thiophenes and the C 25 HBI alkane were produced by the reaction of C 25 HBI alkadiene and C 25 HBI polyene, respectively, with reduced sulfur during early diagenesis. The variation in composition of the C 25 HBI thiophene isomers was observed in the sediments, suggesting that they were derived from different kinds of C 25 HBI alkadienes. The concentrations of the polynuclear aromatic thiophenes showed an increasing trend downwards the upper to middle Kusanagi Formation. Among these thiophenes dibenzothiophene and benzo [b]naphto[1,2-d]thiophene concentrations varied from 10 to 730 and 14 to 210 pmol g -1 , respectively. The depth profiles of their concentrations were different from that of the C 25 HBI thiophenes. It is likely that the polynuclear aromatic thiophene formation started from different precursors followed by different processes from those of the C 25 HBI thiophenes. diagenesis. Recently, several studies of C 25 HBI thiophenes pointed out that incorporation of reduced sulfur species depends on double bond positions in C 25 HBI alkadienes and C 25 HBI polyenes (Sinninghe Damsté et al., 1989a;Kohnen et al., 1992;de las Heras et al., 1997).Polynuclear aromatic thiophenes are a useful indicator for the evaluation of source rocks and diagenetic maturation (Chakhmakhchev and Suzuki, 1995a, b). Dibenzothiophenes were more abundant in marine crude oils than in non-marine ones (Fan et al., 1990). Radke et al. (1982a, b) reported that dibenzothiophene and 4-methyldibenzothiophene were the most abundant di-nuclear aromatic thiophenes found in the type III kerogen. Furthermore, the ratio of 4-/1-methyldibenzothiophene was proposed as a ma-

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“…In the laboratory, the interaction of polysulphide or H2S with various organic mat ter has been investigated to show an abiotic for *Present Address: Department of Earth and Planetary Sciences , Sapporo 060, Japan Graduate School of Science, Hokkaido University, Kita-ku, mation of OSC Mango, 1983;Lalonde et al, 1987;Moers et al, 1988;Suzuki and Philp, 1990;Fukushima et al, 1992). The addition of H2S (or polysulfides) to double bonds or reaction with other functionalities can initiate the formation of OSC (Brassell et al, 1986;Vairavamurthy and Mopper, 1987;Fukushima et al, 1992;Rowland et al, 1993). Some possible incorpora tion mechanisms of inorganic sulphur into organic matter in recent and ancient sediments have been reviewed by Sinninghe Damste and de .…”

Section: Introductionmentioning

confidence: 99%

Pyrolysis-GC analyses of the recent cyanobacterial mats reacted with H2S under mild condition.

Suzuki¹,

Philp²

1995

Geochem. J.

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JapanIn order to investigate the formation of organosulphur compounds during the very early stage of diagenesis, experiments were designed to simulate sulphur incorporation from H2S, or elemental sulphur, into recently deposited natural sedimentary organic matter (cyanobacterial mats from salt ponds in Baja California) and performed under relatively mild reaction conditions (40°C, 2 to 30 days, hydrous and anhydrous). The sulphur-containing moieties in the reaction products were examined by pyrolysis-gas chromatography (GC) using a GC equipped with a flame photometric detector (FPD) and a flame ionization detector (FID), and pyrolysis-gas chromatography/mass spectrometry (GC/MS).Sulphur incorporation from H2S into recently deposited cyanobacterial mats occurred fairly readily, but elemental sulphur does not react as readily with the cyanobacterial mats. Sulphur incorporation into humic acids occurred more rapidly than into proto-kerogens. Sulphur incorporation into lipid fractions was not observed. Two major sulphur incorporation stages are proposed, with the formation of thiols by reac tion between H2S and active carbonyl groups considered to be the most likely mechanism of sulphur incorporation in the first stage. The second stage of sulphur incorporation is proposed to be related to the reaction between H2S and proteinaceous organic matter.

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Formation of C20 isoprenoid thiophenes in modern sediments

Cited by 53 publications

References 20 publications

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Alkyl and polynuclear aromatic thiophenes in Neogene sediments of the Shinjo basin, Japan.

Pyrolysis-GC analyses of the recent cyanobacterial mats reacted with H2S under mild condition.

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