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.     

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

Polycyclic aromatic hydrocarbons in Australian coals II. Novel tetracyclic components from Victorian brown coal

Gas chromatographic-mass spectrometric (GC-MS) analysis of a polycyclic aromatic hydrocarbon (PAH) fraction of a Victoria brown coal sample has revealed the presence of a novel series of tetracyclic triterpenoid derived components. The base peak of their mass spectra, at m/z 169, suggests an 8, 14-seco (C-ring cleaved) structural configuration with the triterpenoid derived A- and B-rings fully aromatized. Photochemically induced or acid-catalyzed processes are seen as two possibilities to account for the diagenetic formation of these compounds.     

Petrological and organic geochemical investigation of recent peats with known environments of deposition

A series of recent peat samples from tropical, sub-tropical and temperate locations were investigated using coal petrographical and organic geochemical techniques. Maceral and biomarker compositions were examined to see if they correlated or diverged from the known environment of deposition of the peats.The proportion of humotelinite was related to the water depth and the frequency of dry periods. The pH and trophic level have a modifying influence on the preservation of tissues. Furthermore, the proportions of sclerotinite in the peats seem to reflected the oxygen status in the mire, which was also mirrored in the abundance of humic and fulvic acids.A facies diagram was calculated for the peat samples to see how maceral indices would fare in interpreting their known environments of deposition. The results proved to be generally unsuccessful as the herbaceous and woody peats did not always give the predicted high humodetrinite and humotelinite compositions, respectively.The aliphatic hydrocarbon fraction from the extracts of the peat samples show that mainly odd-numbered n-alkanes are present. Diterpenoids, triterpenoids and hopanoids were found in most samples and were mainly unsaturated in nature. The relative proportion of hopanoids in pears appears to be related to bacterial activity in acidic environments. De-A-triterpenoids were also detected in the peat stage of diagenesis.In an angiosperm dominated peat type (Mariscus), polycyclic aromatic triterpenoids were present in the aromatic fraction of the extract. Their occurrence and proportion appears to be related to the degree of humification. In a Taxodium peat, mono-, di-and triaromatic diterpenoids were detected. The presence of these aromatic biomarkers indicate the rapid formation of these compounds in the peat stage, mainly mediated by microbial activity.     

含铀物质对有机质生烃的实验研究

采用密闭容器水热模拟实验方法,考察含铀物质对有机质热解生烃过程的影响。对热模拟实验产物分析发现,在暗色泥岩和煤岩样品中加入含铀物质后,气态烃和液态烃的生烃量都有比较明显的增加。其中煤岩的气态烃产量平均增加值为34%,而泥岩样品平均增加值也达到了30%以上。液态烃产率分析表明,含铀矿物也促进了泥岩和煤岩的液态烃产率。从泥岩氯仿沥青‘A’族组成分析表明,加入催化剂后泥岩的饱和烃和芳烃在高温阶段具有规律性的明显增大的趋势,反映出非烃和沥青质,甚至不溶有机质向相对稳定的饱和烃转化以及芳烃随演化程度增加的高聚合作用。综合以上分析,认为放射性铀对油气生成具有氧化催化作用。     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

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.     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource…     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin,NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5(E,K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YHI (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series.The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.     

济阳拗陷特殊生物降解油的初步研究

济阳拗陷草古100平19井奥陶系储层原油,饱和烃馏分均已损失殆尽,仅残余藿烷系列化合物;同时,芳烃馏分化合物也已损失殆尽,仅残余三芳甾烷系列化合物。上述芳烃化合物俱已损失殆尽的蚀变特征,在相关文献中的报道较为少见。原油中不受水洗作用影响的正构烷烃和不受生物降解作用影响的有机硫化合物(苯并噻吩和二苯并噻吩)均已损失殆尽,显然暗示了原油蚀变是遭受水洗作用和生物降解作用共同作用的结果。原油芳烃馏分的“UCM”鼓包幅度明显大于饱和烃馏分的“UCM”鼓包,暗示了芳烃化合物的降解速率平行甚至超过饱和烃的降解速率。原油中低分子量芳烃化合物的快速降解,暗示了油藏可能是在氧化条件下而非在还原条件下发生蚀变的。     

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.     

Carbon catalysed hydrogen exchange in petroleum source rocks

Exchange of carbon bound hydrogen has been observed when alkenes, saturated and aromatic hydrocarbons are heated at moderate temperatures on carbonaceous surfaces (activated carbon and coal). Isomerisation of alkenes and the formation of hydrogenated/dehydrogenated products from the saturated and aromatic reactants resulted. A suite of crude oils from the Carnarvon Basin (Western Australia) have been analysed with a view to comparing their relative abundances of structurally similar hydrocarbons. The consistent relationships between hydrocarbons in crude oils that are chemically related via hydrogenation/dehydrogenation reactions suggest that a hydrogen exchange process similar to that demonstrated in laboratory experiments occurs during crude oil formation in sedimentary rocks.     

Characterization and quantification of biomarkers from biomass burning at a recent wildfire site in Northern Alberta,Canada

The composition of organic matter (OM) in pine vegetation and soil samples from a pine forest which was charred by a wildfire was analyzed using solid-state nuclear magnetic resonance (¹³C NMR) and gas chromatography–mass spectrometry (GC–MS) of solvent extracts to study the effects of thermal alteration on soil organic matter (SOM). The NMR data revealed the presence of unaltered biomolecules (cellulose, proteins) and low contents of aromatic C (15%) in the charred pine wood and cones while the charred soil samples exhibited higher contents of aromatic C (39–56%). The solvent extraction of charred and uncharred plant and soil samples yielded diterpenoids, triterpenoids, steroids, a series of aliphatic lipids, phenols and carbohydrates indicating the predominant input of higher plant OM and minor contributions from microorganisms and/or fauna. The lower yield of solvent extractable aliphatic lipids in the charred samples versus the uncharred samples suggests that these compounds are thermally degraded during a wildfire. Molecular markers for the burning of cellulose (levoglucosan, mannosan, galactosan) were detected in all charred samples. The comparison of charred and uncharred samples allowed the identification of unaltered pine derived biomolecules and their thermal alteration products in the charred samples. Terpenoid and steroid biomolecules were in part altered during incomplete combustion to aromatic, unsaturated and polar derivatives (“pyromolecules”) that still retained the characteristic skeleton of their precursors. Since some of the polar degradation products found in the charred soils can be generated either from thermal or microbial degradation, the aromatic and unsaturated hydrocarbon products are preferred as molecular markers for SOM burning. Ratios of biological precursors to aromatic (diterpenoids) or unsaturated products (steroids) indicate that the cyclic lipids in the pine wood and the soil surface horizon were highly altered. In conclusion, the solvent extractable lipids and carbohydrates in charred SOM are valuable, source-specific molecular markers for the burning of plant biomass and for tracing the biogeochemistry of charred residues in soils.     

Molecular parameters of maturation in the Toarcian shales,Paris Basin,France—III. Changes in aromatic steroid hydrocarbons

Three series of monoaromatic steroid hydrocarbons (basepeak = m/z 239, 253 and 267) and four series of triaromatic steroid hydrocarbons (basepeak = m/z 217, 231, 245 and 259) have been recognised by computerised gas chromatography-mass spectrometry in a variety of samples of Lower Toarcian shales from the Paris Basin. An increase in the extent of aromatisation of the monoaromatic steroid hydrocarbons in the m/z 253 series (measured by the abundance of monoaromatic components relative to triaromatic components in the m/z 231 series) is observed with increasing maturity. Variations between reported maximum burial depth and extent of aromatisation are explicable partly in terms of new maximum burial depth information for some of the shales. The extent of carbon-carbon bond cracking in the side chains of the aromatic steroid hydrocarbons has only begun to be significant in certain of the deepest samples.     

Polar constituents of organic matter rich marls from evaporitic series of the Mulhouse basin

A suite of marl samples from the evaporitic series of the Mulhouse basin (France; Lower Oligocene) was studied for its biomarker content, in particular its polar constituents. Novel series of 3-carboxyalkyl steranes and 15-oxo triaromatic ketones were identified by synthesis. The 3-carboxyalkyl steranes probably originate from highly polar precursors yet unreported in living organisms. Our data suggest that micro-algae could be the major source of these compounds which seem to be indicators of high algal input rather than characteristic of evaporitic environments. The 15-oxo triaromatic ketones could be oxidation products of triaromatic steroid hydrocarbons formed during diagenesis, although their formation during work-up procedure could not be excluded.     

海拉尔盆地贝尔凹陷原油芳烃化合物组成和分布特征

通过色谱-质谱分析,对海拉尔盆地贝尔凹陷35个原油样品进行聚类分析,将之分成4类.Ⅰ类原油是贝尔凹陷原油主体,占分析样品的77%,特点足菲系列含量高,平均值为64.7%,三芳甾类化合物和三芴类化合物含量次之,分别为11.42%和11.81%.Ⅱ类原油为高三芳甾类原油,三芳甾类化合物占芳烃化合物的53.9%,是该类原油的主要成份,非系列化合物含量较低,为32.5%,萘系列含量和三芴化合物含量最低,分别为0.6%和3.54%.Ⅲ类原油为高菲系列和高萤蒽含量原油,菲系列为64%,萤蒽含量高达11%,是其它原油的16倍以上.Ⅳ类原油具有高萘、高三芴化合物和低菲系列化合物的特点,分别占原油芳烃馏分的30%、32%和26%,三芳甾类化合物含量低,占3.6%.这充分说明海拉尔箍地烃源岩沉积期间有不同的沉积环境,原油有不同的牛烃母质.Ⅱ类原油以藻类为主要生烃母质,Ⅲ类原油以高等植物为主,Ⅰ类原油介于Ⅱ类和Ⅲ类原油之间,为混合型生烃母质.Ⅳ原油沉积环境和前三类原油明显不同,为咸水强还原湖相沉积环境.     

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.     

A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids

Pyrolysates of high-molecular-weight sedimentary fractions of the Duvernay Formation (Western Canada Basin) are dominated by 1,2,3,4- and 1,2,3,5-tetramethylbenzene, which, generated via beta-cleavage, indicate the presence of diaromatic carotenoids in the macromolecular aggregates. This was substantiated by desulphurization of sulphur-rich aggregates of the polar fraction, which released (partly) hydrogenated carotenoids. Furthermore, these components were important constituents of the aromatic hydrocarbon fractions and related oils. Apart from renieratane and isorenieratane, 1H NMR analysis established the aromatic substitution pattern of the most abundant component present, which was identified as a diaromatic compound with an unprecedented 2,3,6-/3,4,5-trimethyl aromatic substitution pattern. Molecular and isotopic analyses of both soluble and insoluble fractions of organic matter revealed relationships between diagenetically-derived carotenoids found in bitumen and related oils and their precursors incorporated into high-molecular-weight fractions. Aryl isoprenoids, important components in extracts and oils, were apparently derived from thermal cracking of bound diaromatic carotenoids rather than cleavage of free carotenoids as previously suggested. Furthermore, products derived from diaromatic carotenoids were substantially enriched in 13C relative to n-alkanes of algal origin. Together with the characteristic carotenoids, this isotopic enrichment provides evidence of significant contributions from photosynthetic green sulphur bacteria (Chlorobiaceae), which fix carbon via the reversed tricarboxylic acid (TCA) cycle. In spite of the prominence of these molecular signals, the overall isotopic composition of the organic matter indicated that only a very small portion of the preserved organic carbon was derived from the biomass of photosynthetic green sulphur bacteria.     

伊通地堑下第三系原油和生油岩中芳构化五环三萜及其地球化学意义

详细研究了吉林伊通地堑下第三系生油岩和原油中的芳烃生物标志物，包括常规的多环芳烃，以及丰富的来源于高等植物的芳香二萜和芳构化的五环三萜。目前，原油中芳构化五环三萜类生物类生物标志物国内外均尚报道极少。还详细讨论了利用原油中最新发现的芳构化五环三萜在解决本区生物输入，油源对比以及石油成因等方面的重要意义。     

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.