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1.
The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c27-c29 diasteranes [13β(H),17α(H); 20R + S] and C28-C29 regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C27-C29 regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.  相似文献   

2.
The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C27, C28, C29, C30 and C31 families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C27 compounds, Ts/Tm.  相似文献   

3.
Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.  相似文献   

4.
A novel series of 3-alkyl and 3-carboxyalkyl-5β(H)-steranes 7–10 along with a full homologous series of carboxyalkyl-sterane (C1 to C6) 4–6 with 3α(H)5α(H) configuration have been identified in marine-evaporitic oils from Fazenda Belém, Potiguar Basin (Brazil) on the basis of mass spectral interpretation. The synthesis of enantiomerically pure 3α-alkyl-5β(H)-cholestane and 3β-alkyl-5α(H)-cholestane standards and their coinjection with petroleum fractions confirmed the structural assignments.  相似文献   

5.
A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C29 steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (Ro). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.  相似文献   

6.
The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C29 5α(H), 14α(H), 17α(H) normal-steranes and the C29 iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.  相似文献   

7.
Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in 13C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in 13C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C16:1 ω7 and C16:0 fatty acids with a lesser amount of the C18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C14 to C18 range, and iso-C15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ13C=−37.8‰) were considerably depleted in 13C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.  相似文献   

8.
The relationship between the lipid composition of organisms in the water column of an eutrophic lake and the lipid composition of underlying sediments, previously examined for n-alkanols and steroids, is now reported for hydrocarbons, ketones and carboxylic acids.The n-C7 alkane and alkenoic acids from two primary sources are rapidly metabolized in the water column and surficial sediment. Bacterial biomarkers, including hopenes and fatty acids, were detected in the photosynthetic bacterial layer occurring just above the sediment-water interface.Within the sediment the apparent conversion of free n-alkanes, alkan-2-ones and ω-hydroxy acids to the corresponding bound form is noted; microbiological oxidation of n-alkanes to alkan-2-ones is supported by the detection of the intermediate alkan-2-ols with a distribution similar to that of the ketones. The geochemistry of sediment deposited c. 1900, prior to biological study of the site, was interpreted from stable biomarkers and the diagenetic changes recognised in the study of contemporary deposition. A qualitative difference in algal input to the older sediment is inferred from the low Δ7-sterol content and presence of 2,6,10-trimethyl-7-(3-methylbutyl)-dodecane. However, there was still significant dinoflagellate input, as indicated by the presence of 4α-methylsterols. A difference in higher-plant input to the older sediment, indicated from the n-alkane, alkene and triterpenoid ketone distributions, is consistent with the recent development of tree cover.  相似文献   

9.
A tetradeuteriated cholestane was heated with kerogen isolated from the Messel oil shale at 350 °C for 25 different time periods (ranging from 0.5 to 80 h) in borosilicate vessels. Three isomers of tetradeuteriated dimethylperhydrophenanthrene were formed and one of these was the major saturated hydrocarbon product under most conditions. The stereochemistry for these isomers was unknown but if the stable 5α,8β,9α(H),10β(CH3) sterane configuration is inherited from the cholestane then there are four possible isomers namely: I and II [13β(H) and 13α(H) diastereomers, respectively, of 10,13-dimethylperhydrophenanthrene] as well as III and IV [14β(H) and 14α(H) diastereomers, respectively, of 10,14-dimethylperhydrophenanthrene]. Molecular mechanics revealed that I is the most stable form and therefore is the component that dominated the saturated hydrocarbon degradation products. The identification of only three isomers of deuteriated dimethylperhydrophenanthrene in the pyrolysis experiments is supported by the calculated stabilities (ΔΔG) as isomer IV is considerably more unstable (by 1.7 kcal/mol) than II which is the least stable of I, II and III. If these compounds can be detected in crude oils their distributions may be useful maturity indicators in oils that have been generated at high thermal maturity.  相似文献   

10.
Agricultural grasses cover a major part of the land surface in temperate agro-ecosystems and contribute significantly to the formation of soil organic matter. Crop-derived lipids are assumed to be responsible for fast carbon turnover in soils. Differences in lipid distribution patterns between crops following C3 and C4 photosynthesis pathways have rarely been described, but could be useful for source apportionment of crop-derived input into soils or sediments. The distribution of long chain n-carboxylic acids (C22, C24, C26) reveals significant differences between crop plants following either the C3 or the C4 photosynthetic carbon fixation pathway. The plant compartments leaves, stems and roots of C4 plants contain relatively large proportions (> 40%) of n-C24 carboxylic acid when compared to C3 plants. These reveal larger relative proportions of n-C22 and n-C26 acids, whose relative abundance is subject to change between different plant compartments and during the growing season. The carboxylic acid ratio [CAR = n-C24/(n-C22 + n-C26) carboxylic acids] provides distinct ratios for C4 (> 0.67) and C3 crops (< 0.67) and can thus be used as a molecular marker for the differentiation of crop plant biomass. In combination with the bulk stable carbon isotopic composition (δ13C) the CAR can be used as a tool for the estimation of the C4 derived carbon proportion in soils or sediments.  相似文献   

11.
Equilibrium 2H/1H fractionation factors (αeq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for Hα in ketones (Wang et al., 2009). The total uncertainty in reported αeq values is estimated at 10–20‰. The effects of functional groups were found to increase the value of αeq for H next to electron-donating groups, e.g. OR, OH or O(CO)R, and to decrease the value of αeq for H next to electron-withdrawing groups, e.g. (CO)R or (CO)OR. Smaller but significant functional group effects are also observed for Hβ and sometimes Hγ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be −90‰ to −70‰ for n-alkanes and around −100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of αeq agree well with field data for thermally mature hydrocarbons (δ2H values between −80‰ and −110‰ relative to water). Therefore the observed δ2H increase of individual hydrocarbons and the disappearance of the biosynthetic δ2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ2H values that are close to equilibrium with water. In these cases, constant down-core δ2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.  相似文献   

12.
Series of α, β, ω and (ω-1) hydroxy fatty acids (FAOHs) were determined in several freshwater and brackish water lacustrine sediments in Japan. Analytical procedure used was digestion of the solvent-extracted sediment with HF/HCl followed by solvent and saponification extraction of the residue. Abundances of α/β and ω-FAOH determined by this procedure were 2–3 times higher than those obtained by single alkaline saponification and of the same order with those provided by HCl hydrolysis. Major portion of α/β-FAOH was obtained by solvent extraction of the acid-treated sediments, while subsequent alkaline saponification was needed for the majority of ω-FAOH to be recovered. Thus determined FAOHs comprised 33–61% (Av. = 42%) of the “bound” acid constituents in the lacustrine surface sediments. The α/β and ω-FAOH composition was principally the same among the samples examined, except for relative proportions of the iso to anteiso C15 and C17 ß(α)-FAOH, which showed significant variations in the ranges of 0.30–1.1 and 0.46–1.5, respectively. In the holomictic lakes, the ratios together with the same ratios of the “bound” branched monocarboxylic acids tended to decrease with increasing water depth of the lakes, suggesting that the ratios may indicate an extent of the early diagenetic alteration of the bacteria-derived lipids either in water column or in surface sediment.  相似文献   

13.
The Alberta oil sands contain 1–2% organic solvent insoluble organic matter chemisorbed to the inorganic matrix. Analysis of the monocarboxylic fraction (1–14%) of the chemisorbed material has revealed the presence of C12–C32 normal, iso, anteiso alkenoic acids, mono and diunsaturated acids, cyclopropylalkanoic and cyclic terpenoid carboxylic acids. Some of the main components of the acyclic acids were similar to those which have been identified in various petroleums and Alberta oil sand bitumens (in small concentrations) by Mackenzie et al. (Advances in Organic Geochemistry 1981, pp 637–649, Wiley/Heyden, 1983), and attributed to bacterial degradation of the oils via the aerobic pathway of biosynthesis.The presence of these acids in the chemisorbed fraction and virtual absence in the bitumen lends additional support to earlier proposals that the Alberta oil sand bitumens have undergone severe microbial degradation.  相似文献   

14.
Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO2, with δ13CCO2 and δ13C1 values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO2 and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO2 pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ13C1 values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ13C1 < δ 13C2 < δ13C3 < δ 13C4. In contrast, the δ13C1 values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ13C1 > δ13C2 > δ 13C3 > δ13C4). Inorganic gases also tend to show less negative δ13CCO2 values (−10‰) than biogenic gases (<−10‰).  相似文献   

15.
Hydroxy acids in sediments of Lakes Bonney, Fryxell, Joyce and Vanda, and unnamed ponds (B2, NF1, NF2 and L4) as well as in cyanobacterial mats from the McMurdo Sound region of southern Victoria Land in Antarctica have been studied to clarify their features and elucidate their source organisms. Normal and branched (iso and anteiso) 2-hydroxy acids were found in all the samples studied with the predominance of even- and odd-carbon numbers, respectively. The most dominant 2-hydroxy acids in the sediments were mainly short-chain components (<C20). Normal and branched 3-hydroxy acids were detectewith the predominance of even- and odd-carbon numbers, respectively, in total concentrations between 0.48 and 53 μg/g of dry sediment. (ω-1)-Hydroxy acids were all long-chains (C22, C24, C26, C28 and C30). 9,10-Dihydroxyhexadecanoic and/or 9,10-dihydroxyoctadecanoic acids were identified in all the sediments and a cyanobacterial mat. The composition of hydroxy acids differ considerably among the lakes and ponds, suggesting the difference of source organisms. These 2-, 3- and (ω-1)-hydroxy, and 9,10-dihydroxy acids may be derived from cyanobacteria and microalgae, in addition to non-photosynthetic microorganisms. Cyanobacteria and microalgae which are widely distributed in the world, may be important sources of hydroxy acids in the natural environments.  相似文献   

16.
Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C21–C35) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C31, C27, C22 or C24, C23 or C25 and C22, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C29 homologues. C28 and C29 steroids are derived mainly from higher plants, whereas the C27 component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C14, C15, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C20 components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.  相似文献   

17.
Carbon isotope and molecular compositions of Mississippian to Upper Cretaceous mud gases have been examined from four depth profiles across the Western Canada Sedimentary Basin (WCSB). The profiles range from the shallow oil sands in the east (R0 = 0.25) to the very mature sediments in the overthrust zone to the west (R0 = 2.5). In the undisturbed WCSB, δ13C1–δ13C2 and δ13C2–δ13C3 cross-plots show three maturity and alteration trends: (1) pre-Cretaceous gas sourced from type II kerogen; (2) Cretaceous Colorado Group gas; and (3) Lower Cretaceous Mannville Group biodegraded gas. A fourth set of distinctly different maturity trends is recognized for Lower Cretaceous gas sourced from type III kerogen in the disturbed belt of the WCSB. Displacement of these latter maturity trends to high δ13C2 values suggests that the sampled gas was trapped after earlier formed gas escaped, probably as a result of overthrusting. Unusually 13C-enriched gas (δ13C1 = −34‰, δ13C2 = −13‰, and δ13C3 = 0‰), from the Gething Formation in the disturbed belt, is the result of late stage gas cracking in a closed system. In general, gas maturity is consistent with the maturity of the host sediments in the WCSB, suggesting that migration and mixing of gases was not pervasive on a broad regional and stratigraphic scale. The ‘Deep Basin’ portion of the WCSB is an exception. Here extensive cross-formational homogenization of gases has occurred, in addition to updip migration along the most permeable stratigraphic units.  相似文献   

18.
Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.  相似文献   

19.
Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ13C values of C1–C4 gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ13CiC4 value is higher than that of the δ13CnC4, the dominant ranges for the δ13C1, δ13C2, and δ13C3 values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ13C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ13C1, δ13C2 and δ13C3 values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.  相似文献   

20.
19-Norisopimarane and isopimarane have been synthesized from isopimara-9(11), 15-diene-3β, 19-diol. Analysis of the alkane fractions of an Australian crude oil by GC-MS showed the presence of nine diterpenoid hydrocarbons (diterpanes), of which one was bicyclic two were tricyclic and six were tetracyclic.19-Norisopimarane and isopimarane were identified by comparison of their mass spectra and GC retention times with those of the synthetic standards. ent-Beyerane, 16a(H)-phyllocladane, 16)β(H)-phyllocladane, ent-16α(H)-kaurane and labdane were also identified by comparison with authentic reference compounds. The remaining two compounds were tentatively identified as rimuane and as a 17-nortetracyclic diterpane on the basis of mass spectral evidence. The diterpanes are probably derived from conifer resins.  相似文献   

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