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1.
Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C16–C29 range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.  相似文献   

2.
《China Geology》2020,3(4):602-610
Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC12-nC33) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ13C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.  相似文献   

3.
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   

4.
The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography–mass spectrometer (GC–MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd–even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17β(H), 21β(H)-hopanoid acids were detected with C32 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17β(H), 21β(H)-hopanoic acid among samples (−30.7‰ to −69.8‰). The δ13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.  相似文献   

5.
Two Greek Pleistocene tufa stromatolites were examined petrographically and with stable isotope geochemistry to determine whether calcite spar is of primary or diagenetic origin. The younger (ca 100 ka) tufa from Zemeno primarily is micritic, with primary columnar calcite spar restricted to areas immediately above chironomid larval tubes. This relationship suggests that chironomid larval feeding behaviour is responsible for the development of Zemeno tufa columnar calcite, probably involving biological substances smeared onto the tufa surface. Most micritic crystals are not suitably oriented to allow later post‐depositional growth resulting in columnar fabrics. The older (ca 1 Ma) predominantly sparry tufa from Nemea contains some chironomid tubes and organic cyanobacterial filaments preserved in crystal fans but also contains many fabrics found in primary speleothem spar. Columnar spar here is unlikely to be the result of post‐depositional crystal growth. A comparison of stable isotopic trends between the two tufa deposits suggests that both contain interpretable seasonal trends and implies little or minor post‐depositional alteration of either tufa. Consequently, there is no basis for the common assumption that sparry tufa fabrics must be of diagenetic origin.  相似文献   

6.
Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.  相似文献   

7.
The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18(or C19) and n-C27 –n-C31 as well as at C29(or C31). The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters(n-FAMEs) that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2(400–420 cm depth) and ZS5-2(241–291 cm depth).  相似文献   

8.
In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ13CPC and δ18OPC) showed more variation compared with non‐pedogenic pond calcretes (δ13CSPC and δ18OSPC) in profile‐B. The δ13CPC and δ13CSPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ18OPC and δ18OSPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ13COM) and n‐alkanes (δ13Cn‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ13COM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ13COM values is a result of the difference in the sources and preservation of organic matter. However, the δ13Cn‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ13Cn‐alk values are unaffected by the pedogenic modifications.  相似文献   

9.
We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ13C values of odd carbon numbered C23-C33n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C25-C31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.  相似文献   

10.
Agricultural soils are regarded as one potential sink for atmospheric CO2 via photosynthetic fixation in plant biomass and subsequent transformation into soil organic matter upon soil diagenesis. The difference in C-isotope signatures of C3- vs. C4-plants allows for a natural isotopic labelling of soil organic matter after changes from C3- to C4-cropping. In this study, we demonstrate that isotopic shifts are paralleled by molecular signatures of C3- vs. C4-crop alkyl lipids. Turnover times vary significantly, based on cropping techniques. For grain-maize cropped soils at steady state average turnover times of 40 years for bulk SOC, 35 years for n-alkanes and 21 years for n-carboxylic acids were determined. Turnover times for silage-maize cropped soil at steady state were on average 250 years for bulk SOC, 60 years for n-alkanes and 49 years for n-carboxylic acids. Turnover times reported here for silage-maize cropped soils may be taken as maximum values only, because they derive from a single trial, which was affected by addition of anthropogenic refractory carbon. Discrimination of input from various plant parts (roots, stems and leaves) based on bulk C-isotopes is not feasible but can easily be achieved using compositions of carboxylic acids, especially the ratio of n-C24 vs. n-C22+26 and their respective C-isotope values. This enables delineation of the influence of different cropping techniques, e.g., silage- or grain-maize, on carbon storage in soils. Admixture of external sources of organic matter to the soil organic carbon pool of an urban site in Halle, Germany was identified based on alkyl lipid distributions. Nearby lignite mining was identified as a source for non-crop-derived alkyl lipids, primarily based on the elevated n-C26-carboxylic acid content and heavier carbon isotopic signatures.  相似文献   

11.
POULTON  BOTTRELL  UNDERWOOD 《Sedimentology》1998,45(5):875-887
Lower Cretaceous mudstones exposed at Speeton in North Yorkshire, UK, contain lobsters and burrows preserved in diagenetic phosphate concretions. Isotopic compositions of sulphur in both diagenetic sulphide and structural sulphate in diagenetic phosphate have been measured in an attempt to constrain diagenetic porewater chemistry. The occurrence of phosphatized and pyritized lobsters and similarly preserved burrows, allows a detailed comparison of these microenvironments with the host sediments. Host sediments are extensively bioturbated and characterized by very light sulphide isotopic compositions (mean sulphide δ34S = –48·3 ± 3‰ (1σ, n = 19)) and sulphate isotopic compositions that are lighter than Lower Cretaceous seawater sulphate (mean sulphate δ34S = +8·7 ± 3·2‰ (1σ, n = 19)). These isotopic values can be explained by the action of bioturbating macrofauna; the introduction of oxygen in ventilating seawater results in the oxidation of early formed isotopically light pyrite, resulting in porewater sulphate that is enriched in 32S. Subsequent pyrite formation via bacteriogenic reduction of isotopically light porewater sulphate leads to the formation of isotopically light pyrite, whilst residual porewater sulphate apparently remains relatively enriched in the 32S isotope. Sulphur isotopic values for the burrows are very different; sulphide isotopic compositions average –34·4 ± 0·4‰ (1σ, n = 3) and sulphate isotopic compositions average –14·4 ± 6·6‰ (1σ, n = 4). These isotopic compositions are the result of rapid development of closed system conditions in burrows, resulting in the build-up of acidity necessary for phosphate precipitation and coprecipitation of isotopically light sulphate (formed by oxidation of isotopically light sulphide surrounding the burrows). Lobster shell isotopic compositions fall between these two groups. On the basis of their isotopic compositions, some lobsters appear to have died close to the sediment–water interface, whilst others appear to have been buried (in burrows) prior to death.  相似文献   

12.
Atmospheric dust samples collected along a transect off the West African coast have been investigated for their lipid content and compound-specific stable carbon isotope compositions. The saturated hydrocarbon fractions of the organic solvent extracts consist mainly of long-chain n-alkanes derived from epicuticular wax coatings of terrestrial plants. Backward trajectories for each sampling day and location were calculated using a global atmospheric circulation model. The main atmospheric transport took place in the low-level trade-wind layer, except in the southern region, where long-range transport in the mid-troposphere occurred. Changes in the chain length distributions of the n-alkane homologous series are probably related to aridity, rather than temperature or vegetation type. The carbon preference of the leaf-wax n-alkanes shows significant variation, attributed to a variable contribution of fossil fuel- or marine-derived lipids. The effect of this nonwax contribution on the δ13C values of the two dominant n-alkanes in the aerosols, n-C29 and n-C31 alkane, is, however, insignificant. Their δ13C values were translated into a percentage of C4 vs. C3 plant type contribution, using a two-component mixing equation with isotopic end-member values from the literature. The data indicate that only regions with a predominant C4 type vegetation, i.e. the Sahara, the Sahel, and Gabon, supply C4 plant-derived lipids to dust organic matter. The stable carbon isotopic compositions of leaf-wax lipids in aerosols mainly reflect the modern vegetation type along their transport pathway. Wind abrasion of wax particles from leaf surfaces, enhanced by a sandblasting effect, is most probably the dominant process of terrigenous lipid contribution to aerosols.  相似文献   

13.
Biomarker ratios, together with stable carbon (δ13C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C17 and Ph/n-Cl8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ13C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ13C values of n-alkanes in their respective oils.  相似文献   

14.
Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ13C values are found in the Tarim and Qaidam basins (δ13C1: − 19.0 to − 29.9‰; δ13C2: − 18.8 to − 27.1‰), and those with lowest δ13C values occur in the Turpan-Harmi and Junggar basins (δ13C1: − 40.1 to − 44.0‰; δ13C2: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ13C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.  相似文献   

15.
Variations in the carbon isotopic composition (δ13C) of pristane, phytane, n-heptadecane (n-C17), C29 ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ13C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C17 (−32‰) and C29 ααα 20R sterane (−31‰) are enriched in 13C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of 13C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ13C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.  相似文献   

16.
Hydrocarbon distributions and stable isotope ratios of carbonates (δ13Ccar, δ18Ocar), kerogen (δ13Cker), extractable organic matter (δ13CEOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C12 and C13n-alkanes, C14, C16 and C18n-alkylcyclopentanes and to a lesser extend C15, C17 and C21n-alkylcyclohexanes. The progressive 13C-enrichment (up to 3.9‰) with metamorphism of the C>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C1 and C2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C29 to C31 range and 5α(H),14α(H),17α(H)-20R C27, C29 steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C29Ts) vs. 17α(H),21β(H)-30-norhopane [C29Ts/(C29Ts + C29)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.  相似文献   

17.
The sedimentary record of carbonate carbon isotopes (δ13Ccarb) provides one of the best methods for correlating marine strata and understanding the long‐term evolution of the global carbon cycle. This work focuses on the Late Ordovician Guttenberg isotopic carbon excursion, a ca 2·5‰ positive δ13Ccarb excursion that is found in strata globally. Substantial variability in the apparent magnitude and stratigraphic morphology of the Guttenberg excursion at different localities has hampered high‐resolution correlations and led to divergent reconstructions of ocean chemistry and the biogeochemical carbon cycle. This work investigates the magnitude, spatial scale and sources of isotopic variability of the Guttenberg excursion in two sections from Missouri, USA. Centimetre‐scale isotope transects revealed variations in δ13Ccarb and δ18Ocarb greater than 2‰ across individual beds. Linear δ13Ccarb to δ18Ocarb mixing lines, together with petrographic and elemental abundance data, demonstrate that much of the isotopic scatter in single beds is due to mixing of isotopically distinct components. These patterns facilitated objective sample screening to determine the ‘least‐altered’ data. A δ18Ocarb filter based on empirical δ18Ocarb values of well‐preserved carbonate mudstones allowed further sample discrimination. The resulting ‘least‐altered’ δ13Ccarb profile improves the understanding of regional as well as continental‐scale stratigraphic relations in this interval. Correlations with other Laurentian sections strongly suggest that: (i) small‐scale variability in Guttenberg excursion δ13Ccarb values may result in part from local diagenetic overprinting; (ii) peak‐Guttenberg excursion δ13Ccarb values of the Midcontinent are not distinct from their Taconic equivalents; and (iii) no primary continental‐scale spatial gradient in δ13Ccarb (for example, arising from chemically distinct ‘aquafacies’) is required during Guttenberg excursion‐time. This study demonstrates the importance of detailed petrographic and geochemical screening of samples to be used for δ13Ccarb chemostratigraphy and for enhancing understanding of epeiric ocean chemistry.  相似文献   

18.
This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ 13Ccarb − δ 13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb-n-C19 = δ 13Ccarb − δ 13C n-C19) during the Permian–Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23–25 and 26–29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ13Ccarb-kero and Δ13Ccarb-n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian–Triassic transition. Both the variations of Δ13Ccarb-n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ13Ccarb-n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb-n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian–Triassic crisis.  相似文献   

19.
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.  相似文献   

20.
Stable carbon (δ13C) and hydrogen (δD) isotopic compositions of n-alkanes, anteiso-alkanes, n-alkanoic acids, n-alkanols, phytol and sterols in raw leaves of Acer argutum and Acer carpinifolium, their fallen leaves, mold and soils from a natural Acer forest were measured in order to: (1) understand isotopic variation of the plant biomarkers in a plant-soil system and (2) evaluate which biomarker is the most effective recorder of soil vegetation. Long-chain (> C24) n-alkanes, n-alkanoic acids and n-alkanols are gradually enriched in 13C up to 12.9‰ (average of 4.3‰) and depleted in D up to 94‰ (average of 55‰) from raw leaves to soils. However, anteiso-alkanes, phytol and sterols show little variation in both δ13C (< ± 1‰) and δD (< ± 2‰) from raw leaves to soils. These isotope signatures in a plant-soil system indicate that isoprenoid plant biomarkers such as sterols in soils faithfully preserve the isotopic compositions of dominant higher plants growing on the soils without a diagenetic effect upon the isotopic compositions. In contrast, long-chain n-alkyl molecules in soils undergo specific isotopic modification during biodegradation associated with early diagenesis and/or a significant contribution from heterotrophic reworking.  相似文献   

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