Saturated and aromatic diterpenoids and triterpenoids in Eocene coals and mudstones from China

Several series of saturated, diaromatic, triaromatic C-ring cleaved and triaromatic diterpenoids and triterpenoids have been detected in 4 immature coal and mudstone samples. A number of these compounds appear to represent intermediates in a series of postulated pathways for progressive aromatization of biogenic diterpenoids and triterpenoids. Diagenetic pathways for the formation of tricyclic aromatic hydrocarbons from abietane and pimarane type diterpenoid precursors and for the formation of diaromatic, triaromatic C-cleaved and triaromatic hydrocarbons from β-amyrin and other triterpenoid precursors are proposed. Saturated and aromatized abietanes, pimaranes and phyllocladanes, which are the most abundant compounds in all 4 samples, indicate a predominant higher plant input which can be related to the Coniferales group but not to individual plant families. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. The relative concentrations of the triaromatic and triaromatic C-ring cleaved hydrocarbons are higher in samples 9602 (mudstone) and 9603 (coal) than samples 9601 (coal) and 9604 (mudstone) indicating samples 9602 (mudstone) and 9603 (coal) contain relatively more angiosperm derived organic matter than samples 9601 (coal) and 9604 (mudstone). The distribution patterns and the relative concentrations of saturated and aromatic diterpenoids and triterpenoids thus are valuable markers for the determination of the relative contents of biological sources of organic material in geological samples.     

Identification of steranes and tritepanes in geolipid extracts by high-resolution gas chromatography and mass spectrometry

One method for the analysis of complex organic mixtures from geological sources is the use of high-resolution gas chromatographic data together with mass spectra obtained by combined gas chromatography-mass spectrometry (gc-ms). The present study involved examination of a variety of authentic triterpenoid alkanes (triterpanes) and steroid alkanes (steranes) for reference purposes, by measurement of their Kovats indices on OV-101 and Dexsil 300 liquid phases, and by the recording of their low-resolution mass spectra by gc-ms. These measurements provide reference data for analysis of the triterpenoid alkanes in geological samples and show that mass spectrometry is a valuable technique for triterpane analysis, permitting in many cases gross structural assignments which may be refined by a comparison of Kovats indices with those of authentic standards.     

A comparison of terpenoid and leaf fossil vegetation proxies in Paleocene and Eocene Bighorn Basin sediments

Plant-derived terpenoids, long recognized as biomarkers, can help reveal the major taxonomic groups of land plants present in ancient environments, even if rocks and sediments do not preserve plant macro- or microfossils. Previous studies have used simple di- to triterpenoid ratios to reconstruct floral changes in the geologic past, but few have compared terpenoid ratios with estimates of floral composition from fossils. Further, reconstructions have not taken into account differences in biomarker production (i.e. concentration relative to leaf biomass) between different types of plants. Here, we have examined terpenoids from early Cenozoic fluvial rocks from the Bighorn Basin (Wyoming, USA), where fossil flora has been studied in detail. We analyzed the distributions of diterpenoids, triterpenoids and n-alkanes from leaf wax in a total of 43 samples from 15 stratigraphic horizons of late Paleocene (63 Ma) to early Eocene (53 Ma) in age. In nearly all samples, triterpenoids, derived from angiosperms, were significantly lower in abundance than conifer-specific diterpenoids, a finding that contrasted with plant fossil evidence for the same rocks. This suggests that di- to triterpenoid ratios severely underestimate the abundance of angiosperms in paleovegetation. Angiosperms dominated n-alkane production among modern plants, and we propose a new paleovegetation proxy based on the ratio of diterpenoids (conifers) to n-alkanes (angiosperms), corrected for lipid production estimated from extant vegetation. Using diterpenoids and alkanes, we infer the composition of paleovegetation to be similar to that inferred from plant fossils. Although the approach works well for the Bighorn Basin, we stress the new paleovegetation proxy will need to be evaluated for other time periods, communities, paleogeography and depositional environments with pollen or megafossil data available.     

加拿大阿萨巴斯卡地区Mildred泥炭柱脂类化合物的组成特征

利用气相色谱-质谱联用仪(GC-MS)系统地分析了阿萨巴斯卡地区Mildred泥炭柱37个样品的脂类化合物,研究了它们的组成特征及可能来源。结果表明,样品中检出的正构烷烃、正烷酮、正烷醛、正烷醇、脂肪酸和脂肪酸甲酯均由高碳数化合物构成,并具明显的奇碳或偶碳优势,GC-MS质量色谱图中甾类和萜类极性化合物呈现显著的高峰。根据泥炭分子地球化学分析,Mildred泥炭柱沉积有机质主要来源于原地堆积的高等植物,苔藓类、水生植物对泥炭有机质也有一定程度的贡献,其中松柏、杜鹃花科等木本植物、莎草科草本植物以及泥炭藓类是主要的成炭植物。萜类和甾类极性化合物的分布存在明显差异,萜类化合物主要集中于剖面的上部,其形成与泥炭藓类植物存在联系;甾类化合物来源不具专属性,多与高等植物的输入有关,也可能是受微生物的改造作用而形成。     

甘南沼泽沉积脂类生物标志化合物的组成特征

较为系统地分析了寒冷潮湿高原气候条件下形成的沼泽泥炭中脂类化合物，研究了它们的组成，来源和成岩过程，结果表明，正构烷烃，正构烯烃，正构脂肪酸，直链烷基酮和直链烷基醇都由长链组分所构成，这些长链组分来自草本植物，并且得到它们单体碳同位素证据的支持，丰富的奥利烯醇和羽扇烷醇均起源于陆源高等植物，存在很少报道过的一系列藿醇化合物，它们起源于细菌，甾酮和甾醇都以C29组分为主，C28和C29组分主要来自高等植物，而27组分则具有一个细菌源。无奇偶优势的短链正构烷烃，细菌起源的脂肪酸（C14，C15，异构和不饱和脂肪酸），直链烷基－2－酮，藿类和一些甾酮的存在，都说明在这种沉积环境中沉积有机质已经历了强烈改造作用。甾烯酮和甾烯醇分别向它们烷烃的化学和生物化学转化也十分明显。     

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep,Red Sea

Hydrocarbons and bulk organic matter of two sediment cores (No. 84 and 126, CHAIN 61 cruise) located within the Atlantis II Deep have been analyzed. Although the brines overlying the coring areas were reported to be sterile, microbial inputs and minor terrestrial sources represent the major sedimentary organic material. This input is derived from the upper water column above the brines.Both steroid and triterpenoid hydrocarbons show that extensive acid-catalyzed reactions are occurring in the sediments. In comparison with other hydrothermal (Guaymas Basin) or intrusive systems (Cape Verde Rise), the Atlantis II Deep exhibits a lower degree of thermal maturation. This is easily deduced from the elemental composition of the kerogens and the absence of polynuclear aromatic hydrocarbons of a pyrolytic origin in the bitumen.The lack of carbon number preference among the n-alkanes suggests, especially in the case of the long chain homologs, that the organic matter of Atlantis II Deep sediments has undergone some degree of catagenesis. However, the yields of hydrocarbons are much lower than those observed in other hydrothermal areas. The effect of lower temperature and poor source-rock characteristics appear to be responsible for the differences.     

Esters of acyclic and polycyclic isoprenoid alcohols: Biochemical markers in lacustrine sediments

Esters of phytol or related isoprenoid acids and fatty acid esters of pentacyclic triterpenoid alcohols and sterols have been isolated from lacustrine sediments varying in age from contemporary to c. 50,000 years old. The esters were analysed by C-GC-MS and identified by GC retention data and mass spectral interpretation based on comparison with authentic compounds.In surface sediment of a productive lake, phytyl and steryl esters are biochemical markers of input from algal and Zooplankton sources. Esters of pentacyclic triterpenols detected in an older, peat-derived sediment may reflect constituents of peat-forming plant species. In sediments derived mainly from terrestrial organic matter, steryl esters containing the same acyl group showed a lower stanol/Δ⁵-stenol ratio than did the corresponding free sterols.     

Biogeochemical aromatic markers in the sediments from mahakam delta (Indonesia)

Analysis of the tri-, tetraand pentaaromatic hydrocarbon fractions of several sediments (0–600 m) from the Mahakam Delta (Indonesia), indicate the predominance of polycyclic aromatic hydrocarbons (PAH) diagenetically related to triterpenoid natural precursors. High resolution Shpol'skii spectrofluorometry (HRS) proved to be a valuable analytical tool, in conjunction with high performance liquid chromatography (HPLC) and capillary gas chromatography coupled with mass spectrometry (CGC/MS), for the identification of individual components in Chromatographic fractions obtained after a high resolution reverse phase liquid chromatography.     

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C₂₇–C₂₉ steranes], hopanoid [17α(H) C₂₇ trisnorhopane, 17α(H), 21β(H) C₂₉–C₃₂ hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.     

Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: synthesis of a dithiane triterpenoid

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.     

Organic geochemical characteristics of sediments from the anoxic brine-filled Tyro basin (eastern Mediterranean)

Soxhlet-extractable organic compounds of sediments from the anoxic brine-filled Tyro basin (eastern Mediterranean) were analyzed by gas chromatography and gas chromatography-mass spectrometry. Cholesterol and 22,29,30-trisnorhopan-21-one are the major compounds identified. The occurrence of this triterpenoid ketone, as well as 22,29,30-trisnorhop-6-en-21-one and diplopterol (both tentatively identified), is ascribed to an input of microbiota living at the brine-seawater interface.     

Tetra- and pentacyclic,naturally-occurring,aromatic hydrocarbons in recent sediments

Several polycyclic aromatic hydrocarbons (PAH) have been identified in recent Amazon River and Cariaco Trench sediments. The skeletal structures of these compounds suggest triterpenoid precursors. The tetracyclic compounds seem to result from A-ring cleavage and the pentacyclic compounds from aromatization which begins with ring A and proceeds through ring D. These compounds are another example of the environmental occurrence of natural PAH.     

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part II: synthesis of a S-spiro-like dithiolane triterpenoid

A sulfide with a bicyclic squalene hydrocarbon skeleton present in sediments from various depositional settings and of different geological age has been identified by synthesis of a reference compound. In contrast to previous expectations [cf. 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; Gug, S., Schaeffer, P., Adam, P., Klein, S., Motsch, E., Albrecht, P., 2009. Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: Synthesis of a dithiane triterpenoid. Organic Geochemistry 40, 876–884.], this sulfide bears two “S-spiro type“ thiolane moities, but not the two thiochromane moieties originally envisaged. The synthesis resulted in the formation of a complex isomeric mixture of compounds, all co-eluting in gas chromatography (GC) in the form of one broad peak, as is the case with the geochemical compound. The spiro-type sulfide was formed by intramolecular sulfurization of a polyunsaturated bicyclic squalene derivative of unknown biological origin. The presence of this sulfide in a number of Triassic to Miocene marine sediments from various and contrasting depositional settings (upwelling environments, shallow continental platforms, lagoonal sub-basins, hypersaline environments), all characterized by strongly anoxic conditions, but with or without photic zone anoxia, indicates that the microorganisms biosynthesizing the precursor bicyclic squalene occupy diverse ecological niches.     

Distribution Patterns of Pentacyclic TriterpenoidHydrocarbons in Low-Mature Source Rocksfrom Eastern China

Four typical distribution patterns of pentacyclic triterpenoid hydrocarbons (types A-D) are distinguished in the low-mature source rocks from eastern China. Type A has a relatively high content of pentacyclic triterpenes. It exists in immature sediments and the distribution and abundance of triterpenes vary with the maturity of the sediments. An unknown C30 triterpene (UCT2) has also been detected in very shallow sediments. This compound is very unstable and disappears rapidly with the increase of depth. Type B is characterized by a relatively high amount of 17α(H), 21β(H)-30-homohopane. This kind of distribution pattern is common in coals and terrestrial sediments of low maturity. Type C has a relatively high content of diahopane and neohopane series. The analysis shows that this distribution pattern may have an indirect relationship with the input of higher plants despite its microbial source. There are C30-unconfirmed triterpane (UCT2) and a relatively high content of C35 hopane in type D. The dist     

The occurrence of bisnorhopane,trisnorhopane and 25-norhopanes as free hydrocarbons in some Australian shales

The triterpenoid hydrocarbons of some West Australian shales have been examined by GC-MS. In addition to the common 17α(H),21β(H)-hopanes, 17β(H),21β(H)-hopanes and 17β(H),21α(H)-moretanes, 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes were identified in the organic extracts. In contrast, pyrolysates of the solvent-extracted sediments contained only the common hopane and moretane series, indicating that 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes are not bonded to kerogen, but rather are present in the sediments as free hydrocarbons.     

Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Geochemical characteristics of sphagnum brown coal — A possible oil-generating precursor

A preliminary study of newly discovered sphagnum brown coal from the Jingsuo Basin, Yunnan Province, China, which is quite rich in montan wax, indicates the predominance of highern-alkane homologues and aromatized triterpenoid components. Aromatic hydrocarbons are composed mainly of pentacyclic and tetracyclic di-, tri- and tetra-aromatic components, which are obviously diagenetically related to higher plant-derived triterpenoids naturally occurring in the biosphere. Because the sphagnum brown coal still remains in the highly immature stage, it seems that the progressive diagenetic aromatization of the higher plant-derived triterpenoids may start at a very early stage.     

Baccharane (18,19-secolupane): A rare triterpenoid skeleton widespread in Triassic sediments and petroleum from the Adriatic Basin

Baccharane (18,19-secolupane) 1, a triterpenoid skeleton seldom encountered in living organisms, has been characterized together with 17βH-des-E-lupane 2, one of its minor degradation products, in Italian Triassic sediment and crude oil samples from the Adriatic Basin by synthesis of standards.Reports of baccharane-derived triterpenoids in the field of natural products are scant and up to now restricted to terrestrial plants (angiosperms and ferns). In this regard, sedimentary baccharane derivatives may indicate a continental contribution (ferns?) to fossil organic matter; but they may also represent a contribution of as yet undetermined marine microorganisms, as has been proposed for dammarenes and dammaranes. Alternatively, they could be the bio/geochemical transformation products of biosynthetically closely related precursors such as lupane- or dammarane-type triterpenoids.The apparently restricted occurrence of baccharane derivatives in geological samples (up to now detected only in Triassic sediments of the Adriatic Basin) confers upon these compounds great value as correlation parameters and possibly as source indicators.     

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.