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1.
Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17α(H), 18α(H), 21β(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.  相似文献   

2.
Two C28H48-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring DEcis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
This paper describes the occurrence and significance of hydrocarbons present in two bituminous marl layers and one distinct gypsum layer from a Messinian sedimentary basin, where hypersaline conditions prevailed. Several new compounds were detected and tentatively identified: of these 20R and 20S 4α, 24-dimethyl-5α(H),14β(H),17β(H) and 20R and 20S 4β,24-dimethyI-5α(H),14β(H),17β(H) cholestanes; 4-methylspirosterenes; 4,4-dimethyl-5α(H),14β(H),17β(H) pregnanes and homopregnanes are discussed in this paper. Several of these compounds might be considered as biological markers for a (hyper)saline environment. The short side chain 4-desmethylsteranes, 5α(H),14β(H),17β(H), 5α(H),14β(H),17α(H) and 5α(H),14α(H), 17α(H) pregnanes and homopregnanes, are the most abundant compounds in the extract from the gypsum sample. It is suggested that in this case these compounds do not reflect the stage of diagenesis but are related to certain organisms exclusively occurring in hypersaline environments. In addition the very low pristane/phytane ratio, often considered as an indicator for anoxicity, could also be interpreted as a useful indicator for hypersalinity.  相似文献   

6.
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   

7.
对南海东沙海域九龙甲烷礁冷泉碳酸盐岩的藿烷酸系列化合物进行了研究, 结果显示冷泉碳酸盐岩中含有17β(H), 21β(H)-30-藿烷酸至17β(H), 21β(H)-33-藿烷酸系列化合物. 其中site1样品TVG3-C2(ANME-2古菌种群为主)中的17β(H), 21β(H)-32-藿烷酸化合物亏损13C(-69.8‰), 且其同位素值较接近iso-/aiso-C15:0脂肪酸(-75.2‰~-90.0‰), 说明其母质摄入了甲烷来源的碳.尽管site2(TVG13-C3和TVG14-C2)和site3(TVG8-C5)自生碳酸盐岩中藿烷酸化合物都表现出了非渗漏特征(-30.7‰~-40.3‰, ANME-1古菌种群为主), 但这些样品中藿烷酸的δ13C值同样较接近硫酸盐还原菌来源的iso-/anteiso-C15:0的δ13C值(-32.5‰~-49.8‰).由此说明大多数存在于以ANME-1种群为主的渗漏环境中的硫酸盐还原菌并没有参与到甲烷厌氧氧化作用中, 而导致藿烷酸化合物和硫酸盐还原菌来源的生物标志物并不明显亏损13C, 并且δ13C值相近.   相似文献   

8.
The presence of elevated As in ground waters exploited for drinking water and irrigation in South-East Asia is causing serious impacts on human health. A key mechanism that causes the mobilization of As in these waters is microbially mediated reductive transformation of As-bearing Fe(III) hydrated oxides and the role of degradable organic matter (OM) in this process is widely recognized. A number of different types of OM that drive As release in these aquifers have been suggested, including petroleum derived hydrocarbons naturally seeping into shallow sediments from deeper thermally mature source rocks. However, the amount of information on the characteristics of the OM in South-East Asian aquifers is limited. Here the organic geochemical analyses of the saturated hydrocarbon fractions and radiocarbon analysis, of two additional sites in SE Asia are reported. The results show that the OM in a given sedimentary horizon likely derives from multiple sources including naturally occurring petroleum. The importance of naturally occurring petroleum as one of the sources was clearly indicated by the n-alkane CPI of approximately 1, the presence of an unresolved complex mixture, and hopane (dominated by 17α(H),21β(H) hopanes) and sterane distribution patterns. The results also indicate that the OM in these aquifers varies tremendously in content, character and potential bioavailability. Furthermore, the presence of petroleum derived OM in sediments at both sites doubles the number of locations where their presence has been observed in association with As-rich, shallow aquifers, suggesting that the role of petroleum derived OM in microbially mediated As release might occur over a wider range of geographical locations than previously thought.  相似文献   

9.
The yield of alkanes released from three coals by liquefaction in tetralin at 400°C is 6–8 times greater than the yield obtained by Soxhlet extraction with the azeotropic micture of benzene and ethanol. The alkanes are dominated by a series of n alkanes, in most cases in the range C14-C34, together with major amounts of pristane and phytane. Homologous series of pentacyclic triterpanes are also present, according to GC/MS analyses. These consist almost entirely of hydrocarbons of the hopane and moretane series (17αH, 21βH and 17βH, 21αH), in the range C27-C34 (C28 being absent). Several members of the series are found in S and R epimeric pairs. Differences in several aspects of alkane distribution between extract and liquefaction products were carefully examined. taking an overall view, the distributions in extract and product oil from any one coal were quite closely similar. It is concluded that the additional alkanes yielded by liquefaction had most probably been physically trapped inside the macromolecular network of the coals, and releasable only on disruption of that network.  相似文献   

10.
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   

11.
The changes in configuration at a number of chiral centres in certain acyclic isoprenoid alkanes, steranes, rearranged steranes and triterpanes of the hopane type in a suite of fourteen Toarcian shales (Paris Basin) have been determined by gas chromatography and combined gas chromatography-mass spectrometry. A sequence of changes in the ratios of various stereoisomers occurs both with increasing maximum depth of burial and in a North-South direction for shallow samples (maximum burial depth < 1000m). These changes cover the full range of maturity shown by the samples. The presence of 5α(H), 14β(H), 17β(H)-steranes in immature samples indicates the presence of a reworked component. The extent of epimerisation at a number of the chiral centres suggests that it relates to the extent of steric hindrance at the centres.  相似文献   

12.
Earlier studies have shown that an unusual C27 triterpane is abundant in sediments from the Norwegian Continental Shelf and the North Sea. This compound was assigned the tentative structures 24,28,30-trisnormoretane or 25,28,30-trisnormoretane, but we have now shown from detailed retention time measurements and a reinterpretation of the mass spectral data that its correct structure is 17α(H),18α (H),21β(H)-25,28,30-trisnorhopane. Two other triterpanes, 25,28,30-trisnormoretane and 28,30-bisnormoretane, have also been identified as minor constituents of extracts of sediments from the North Sea. Possible origins for these compounds are discussed.  相似文献   

13.
The high molecular weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high resolution gas chromatography and combined gas chromatography-mass spectrometry. The following compounds are present: perhydrolycopene (1; lycopane), together with one or more unsaturated analogues with the same skeleton; a series of 4-methylsteranes (2c) in higher abundance than their 4-desmethyl analogues; two series of pentacyclic triterpanes, one series (C27-C32) based on the hopane structure (3a-e), and the other (C27-C31) based on the 17α-H hopane structure (3a-d, 17αH); and an intact triterpene hop-17 (21)-ene [3c, Δ 17(21)]. Only two additional triterpanes were detected in minor concentrations, viz. 30-normoretane (3b, 21αH) and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment. Comparison of the tri- and tetraterpenoid hydrocarbons with those of the Green River Shale indicates differences in the organisms contributing to the two sediments.  相似文献   

14.
Comparison of biological marker alkanes in the kerogen pyrolyzate and bitumen from a sediment is a useful test for the indigenous nature of sediment extracts. For the pyrolysis conditions used, the bulk of the hydrocarbons is released from the kerogen matrix between 375° and 550°C; and its steriochemistry is almost the same as that observed in the extractable bitumen in a genuine source rock. Examples are given to demonstrate that, during pyrolysis, the sterane/terpane ratio decreases and secondary terpanes are generated at the expense of primary ones.The mechanism of artificial petroleum generation by pyrolysis differs from ‘natural’ diagenesis during geological time and is reflected in the composition of certain C27-C29 steranes, as demonstrated by simulation experiments and C29-C30 moretanes and hopanes. The 5α5β-sterane ratios, jointly with 17α(H)-hopane17β(H)-moretane ratios, tricyclic terpane concentrations and 17α(H)17β(H)-trisnorhopane ratios, allow the differentiation of kerogens from adjacent stratigraphies.  相似文献   

15.
Total organic carbon (TOC) determination, Rock‐Eval pyrolysis, extractable organic matter content (EOM) fractionation, gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS) analyses, were carried out on 79 samples from eleven outcrop cross sections of the Bahloul Formation in central and northern Tunisia. The TOC content varied between 0.23 to 35.6%, the highest average values (18.73%, 8.46% and 4.02%) being at the east of the study area (at Ain Zakkar, Oued Bahloul and Dyr Ouled Yahia localities, respectively). The Rock‐Eval maximum pyrolysis temperature (Tmax) values in the 424–453°C range delineated a general east‐west trend increase in the organic matter (OM) maturity. The disparity in hydrogen index (HI) values, in the range 114–824 mg hydrocarbons (HC) g?1 TOC, is relevant for the discrepancy in the level of OM preservation and maturity among localities and samples. The n‐alkane distributions, maximizing in the C17 to C20 range, are typical for a marine planktonic origin, whereas pristine/phytane (Pr/Ph) average values in the 1–2 range indicate an oxic to suboxic depositional environment. Pr/n‐C17 and Ph/n‐C18 ratios in the 0.38–6.2 and 0.68–3.25 range, respectively, are consistent with other maturity indicators and the contribution of specific bacteria to phytol as a precursor of isoprenoids. The thermal maturity varies between late diagenesis to main‐stage of petroleum generation based on the optic and the cis‐trans isomerisation of the C29 sterane [20S/(20S+20R) and 14β(H),17β(H)/(14β(H),17β(H)+14α(H),17α(H)), respectively] and the terpane [18α(H)22,29,30‐Trisnorneohopane/(18α(H)22,29,30‐Trisnorneohopane+17α(H)22,29,30‐Trisnorhopane): Ts/(Ts+Tm)] ratios. The Bahloul OM is represented by an open marine to estuarine algal facies with a specific bacterial contribution as revealed by the relative abundance of the ααα‐20R C27 (33–44%), C28 (22–28%) and C29 (34–41%) steranes and by the total terpanes/total steranes ratio (1.2–5.33). These results attested that the Bahloul OM richness was controlled both by an oxygen minimum zone induced by high productivity and restricted circulation in narrow half graben structures and around diapirs of the Triassic salt.  相似文献   

16.
Relatively abundant 17α（H）-diahopanes have been detected in the lower cretaceous lacustrine source rocks from the Lishu Fault Depression in the Songliao Basin Northeast China. Rich long chain tricyclic terpanes （carbon number up to C35） and gammacerane have been observed in those source rocks with relatively abundant 17α（H）-diahopanes, which is rarely seen in previous reports. In this paper, the formation of 17α（H）-diahopanes has been discussed from three aspects including maturity, oxidation-reduction nature of depositional environment and parent material composition by the GC/MS analyses. The results reveal that maturity and oxidation-reduction nature of depositional environment have little effect on the formation of 1 7α（H）-diahopanes in the investigated area. How- ever, the positive correlation between long-chain tricyclic terpanes and 17α（H）-diahopanes argues strongly for a common origin, and the origin is related to the algaes in saline water environment. The algaes in saline water envi- ronment may be a kind of origin of 1 7α（H）-diahopanes.  相似文献   

17.
Novel biological marker parameters are applied to problems of geochemical correlation of crude oils in the McKittrick Field, California. An attempt is described to distinguish four diagenetic parameters; namely, source input, source maturation, migration and ‘in reservoir’ maturation. The tools include the absolute concentration of steranes, terpanes and paraffins (n + iso) in combination with internal ratios of individual biomarkers such as primary/secondary terpanes, 17α(H)-trisnorhopane/18α(H)-trisnorhopane II (both maturation specific), 5β/5α-steranes, 5β-steranes/17α(H)-hopanes and rearranged steranes/5α-steranes (all migration oriented), 5α/5α-steranes and a number of terpane ratios of partially unknown chemical structure (source input specific).Among other new correlation parameters are: two series of mass chromatograms (m/e 253 and 239), signaling monoaromatized steranes, a series of presumably rearranged steranes (m/e 259), and a series of methylhopanes (m/e 205).The results obtained on the molecular level exceed the degree of information obtainable from organic geochemical ‘bulk’ parameters such as yields of saturates, aromatics, sulfur compounds and C13/C12 ratios by far; however, both types of parameters are mutually supporting. All conclusions are consistent with subtle stratigraphie and overall geologic prerequisites.  相似文献   

18.
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19.
The Yangtze River receives 37.5% of the municipal sewage of China, whose fate constitutes a major environmental and health concern. This study applied phytosterols, 5β(H)-stanols, tetrahymanol and 17α,21β(H)-C30-hopane to examine sewage and petroleum-derived organic pollutants, and assess their impact on the biogeochemistry of the lower river benthic environment. The results showed that significant contributions from sewage and petroleum pollutants were preserved in the riverbed. These potentially contributed to O2 depletion and apparently an anoxic environment in the riverbed, either directly or via an impact on primary productivity.  相似文献   

20.
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   

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