Occurrence of two novel benzothiophene hopanoid families in sediments

doi:10.1016/0146-6380(95)00051-F

Organic Geochemistry

Volume 23, Issue 7, July 1995, Pages 607-616

https://doi.org/10.1016/0146-6380(95)00051-F Get rights and content

Abstract

Two novel families of C₃₄–C₃₅ benzothiophene hopanoids have been identified in laminated marlstones and limestones of Hauptdolomit (Germany, Upper Triassic), Calcaires en Plaquettes (France, Upper Jurassic) and Ghareb (Jordan, Upper Cretaceous) Formations. Structures were assigned on the basis of Raney nickel desulphurization, deuteriated nickel boride desulphurization, mass spectral data and GC behaviour. Based on quantitative analysis, a precursor-product relationship between thiophene hopanoids and benzothiophene hopanoids seems likely. This means that the novel hopanoids are not formed by sulphur incorporation into benzohopanes, but instead cyclization and aromatization of the hopanoid side chain occur after sulphur incorporation.

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δ<sup>13</sup>C of aromatic compounds in sediments, oils and atmospheric emissions: A review
2018, Organic Geochemistry
Citation Excerpt :
In such cases additional separation steps are required to achieve baseline separation. Techniques to isolate specific sections of the chromatogram include thin-layer chromatography (van Kaam-Peters et al., 1995; Grice et al., 1998a, 2005a), preparative high-performance liquid chromatography (Killops and Readman, 1985) and preparative GC (Summons and Powell, 1987). In addition, alumina column chromatography has been employed to separate aromatic fractions by number of aromatic rings (Summons and Powell, 1987; Jiang et al., 2013).
This review discusses major applications of stable carbon isotopic measurements of aromatic compounds, along with some specific technical aspects including purification of aromatic fractions for baseline separation. δ¹³C measurements of organic matter (OM) in sediments and oils are routine in all fields of organic geochemistry, but they are predominantly done on saturated compounds. Aromatic compounds are important contributors to sedimentary organic matter, and provide indication of diagenetic processes, OM source, and thermal maturity. Studies have found evidence for a small ¹³C-enrichment during diagenetic aromatisation of approximately 1–2‰, but the formation of polycyclic aromatic hydrocarbons (PAHs) from combustion and hydrothermal processes seems to produce no effect. Likewise, maturation and biodegradation also produce only small isotopic effects. An early application of δ¹³C of aromatic compounds was in the classification of oil families by source. Bulk measurements have had some success in differentiating marine and terrigenous oils, but were not accurate in all settings.
Compound-specific analyses measure certain aromatics with strong links to source, therefore allowing more accurate source identification. δ¹³C measurements of individual aromatic compounds also allow identification of higher plant input in ancient sediments, even after severe diagenetic alteration or combustion to PAHs. Perylene, a PAH with a historically contentious origin, was assigned a source from wood-degrading fungi on the basis of its isotopic composition. Stable carbon isotopic measurements are also important in the analysis of organic matter from Chlorobiaceae, which is an important indicator of photic zone euxinic conditions in ancient sediments. A large range of aromatic products are formed from the carotenoid pigments of Chlorobiaceae, with an enriched carbon isotopic composition characteristic of the reverse tricarboxylic acid photosynthetic pathway employed by this family of organisms. In future, site-specific isotope analysis using techniques such as nuclear magnetic resonance spectrometry and high-resolution isotope ratio mass spectrometry may reveal more information about isotopic effects associated with aromatisation processes and maturation.
Recent advances in hopanoids analysis: Quantification protocols overview, main research targets and selected problems of complex data exploration
2015, Journal of Steroid Biochemistry and Molecular Biology
Citation Excerpt :
Organic fractions obtained from different extracting solvents are often combined to receive the total organic extract [33,35]. Pre-treatment may include precipitation of asphaltenes by non-polar liquids (e.g. n-hexane) and target analytes saponification in alkaline conditions [36]. Additional fractionation is performed by sequence extraction with organic liquids characterized by different polarity.
Pentacyclic triterpenoids, particularly hopanoids, are organism-specific compounds and are generally considered as useful biomarkers that allow fingerprinting and classification of biological, environmental and geological samples. Simultaneous quantification of various hopanoids together with battery of related non-polar and low-molecular mass compounds may provide principal information for geochemical and environmental research focusing on both modern and ancient investigations. Target compounds can be derived from microbial biomass, water columns, sediments, coals, crude fossils or rocks. This create number of analytical problems due to different composition of the analytical matrix and interfering compounds and therefore, proper optimization of quantification protocols for such biomarkers is still the challenge. In this work we summarizing typical analytical protocols that were recently applied for quantification of hopanoids like compounds from different samples. Main steps including components of interest extraction, pre-purification, fractionation, derivatization and quantification involving gas (1D and 2D) as well as liquid separation techniques (liquid–liquid extraction, solid-phase extraction, planar and low resolution column chromatography, high-performance liquid chromatography) are described and discussed from practical point of view, mainly based on the experimental papers that were published within last two years, where significant increase in hopanoids research was noticed. The second aim of this review is to describe the latest research trends concerning determination of hopanoids and related low-molecular mass lipids analyzed in various samples including sediments, rocks, coals, crude oils and plant fossils as well as stromatolites and microbial biomass cultivated under different conditions. It has been found that majority of the most recent papers are based on uni- or bivariate approach for complex data analysis. Data interpretation involves number of physicochemical parameters and hopanoids quantities or given biomarkers mass ratios derived from high-throughput separation and detection systems, typically GC–MS and HPLC–MS. Based on quantitative data reported in recently published experimental works it has been demonstrated that multivariate data analysis using e.g. principal components computations may significantly extend our knowledge concerning proper biomarkers selection and samples classification by means of hopanoids and related non-polar compounds.
Enrichment and identification of cyclized hopanoids from Shengli lignite
2015, Fuel Processing Technology
Citation Excerpt :
Along with the identification of benzo[16,17,20]hopanes (B16Hs) and phenylhopanes, two other cyclization reactions of bacteriohopanetetrol cyclized at the C16 [12] or C30 [7] position were proposed. Furthermore, some other cyclized hopanoids, such as A-ring methyl B20Hs [13], benzo[20,21]-25-norhopanes [14], hexahydro-B20Hs [10,15], and heteroatom-containing cyclized hopanoids [7,16–19], were also identified. However, to our knowledge, no report was issued on the enrichment and identification of rearranged B16Hs (7, 10, and 11), C32-tetrahydro[20,21]hopane (2), and C32-benzo[20,21]neohopane (3) from any coals.
Fourteen cyclized hopanoids, including hydrobenzohopanes, benzohopanes, and rearranged benzohopanes, were enriched from Shengli lignite via fractional extraction and preparative medium-pressure liquid chromatography. Their structures were tentatively identified by gas chromatography/mass spectrometry. Rearranged benzohopanes, which were unreported before, are probably produced from the corresponding benzohopanes via methyl rearrangement reaction.
Biomarker evidence for intermittent photic zone euxinia in the Aptian-Albian organic sedimentary record from the Ionian Zone (Epirus, Greece)
2013, Organic Geochemistry
Citation Excerpt :
Sulfurization of isorenieratene during diagenesis results in numerous sulfur-containing isorenieratene derivatives which can be, and have been, subsequently recognized in sediments (Koopmans et al., 1996a,b; Kok et al., 2000). Diagenetic and catagenetic isorenieratene derivatives have been found in organic carbon rich sedimentary rocks from many different palaeoenvironmental settings, ranging from Precambrian to Cenozoic age (van Kaam-Peters et al., 1995; Koopmans et al., 1996a; Bosch et al., 1998; Sinninghe Damsté and Köster, 1998; Passier et al., 1999; Schouten et al., 2000; Pedentchouk et al., 2004; Wagner et al., 2004; Bowden et al., 2006; Brocks and Schaeffer, 2008; Heimhofer et al., 2008). Stable carbon isotopes and molecular distribution patterns have also been used to document the source of PSB biomarkers (Ostroukhov et al., 1982; Summons and Powell, 1986, 1987; Schwark and Püttmann, 1990; Requejo et al., 1992; Hartgers et al., 1994).
New biomarker evidence is presented that constrains the conditions of deposition and preservation of sediments rich in extractable organic matter from the Aptian–Albian sedimentary record of the Ionian Zone in NW Greece. Analyses were specifically carried out on total lipid extracts from 12 organic rich samples from the Vigla Shale Member, two of which represent the regional record for the early Albian Paquier Event of OAE1b. In the aliphatic fractions, compound groups such as n-alkanes, isoprenoid alkanes, steroids, hopanoids and terpenoids were recognized, pointing to a mixed origin from algae and prokaryotes with an additional measurable contribution from terrigenous plant matter. These compounds suggest deposition of the primary organic sediments under conditions of decreased bottom water oxygen concentrations. Mass spectral evidence from the aromatic fractions of most samples reveal the variable presence of diagenetic and catagenetic derivatives of carotenoid pigments (including some with bound sulfur) that are characteristic of photoautotrophic sulfur bacteria. The presence of specific biomarkers originating from photosynthetic anaerobic microorganisms, similar to those in ancient and contemporary euxinic basins such as the Black Sea, suggest that photic zone euxinic conditions were intermittently operative in the Aptian–Albian stages of the Ionian Basin, but were not exclusively characteristic of the black shale representing the Paquier Event itself.
Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: synthesis of a dithiane triterpenoid
2009, Organic Geochemistry
In order to confirm the tentative structure of a dithiane sulfide with a bicyclic squalene hydrocarbon skeleton representing the predominant alkyl sulfide in Shell Beach samples from the Monterey Formation (Miocene, CA) and also occurring in various immature sulphur-rich sediments [Schouten, S., Sinninghe Damsté, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958], synthesis of a reference compound bearing two thiochromane moieties has been carried out. The product was obtained as a diastereomeric mixture appearing in the form of five peaks (partly) resolved in gas chromatography (GC). This is in sharp contrast with the geochemical compound, which appears as a single broad peak in GC. Co-elution experiments showed that none of the peaks from the synthetic mixture coelute in GC with that of the geochemical sulfide. Furthermore, the different synthetic isomers have identical mass spectra, which are clearly distinct from that of the naturally-occurring compound. The results unambiguously indicate that the natural compound is not the dithiane triterpenoid originally envisaged. Instead, we propose that the compound has a structure of a bicyclic squalene derivative bearing two “S-spiro”-type moieties as is the case for other sulfides related to regular polycyclic polyprenoids and hopanoids in Monterey sediments.
The wide diversity of hopanoid sulfides evidenced by the structural identification of several novel hopanoid series
2006, Organic Geochemistry
We describe the structural elucidation of four novel series of hopanoid sulfides bearing a thiane or a thiolane ring fused to the pentacyclic hopanoid skeleton and the partial identification of an additional spiro-type hopanoid sulfide series which occurs in various immature sulfur-rich sediments and crude oils. These novel diagenetic hopanoid derivatives have been identified either by isolation of one member of the series, followed either by nuclear magnetic resonance (NMR) structural characterization, by synthesis of a reference compound or by deuterium labelling experiments. Location of the C–S bonds between the C-30 or C-31 positions from the side chain and the C-16, C-17, C-20 or C-21 positions in rings D or E of the polycyclic hopanoid skeleton likely indicates that intramolecular sulfurization occurred on precursor molecules functionalized at C-17 and C-21, such as hop-17(21)-ene derivatives, but also, for some of them, at C-16 or C-20. The predominance of one series over the others is variable within the different samples. Their occurrence in a wide variety of sediments and crude oils of different maturity and ranging in age from Triassic to Upper Miocene suggests that the precursor molecules which underwent sulfurization are relatively widespread and that the sulfurization processes involved in their formation are operative during early diagenesis.

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Occurrence of two novel benzothiophene hopanoid families in sediments

Abstract

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Geochim. Cosmochim. Acta

Palaeogeogr., Palaeoclimatol., Palaeoecol.