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1.
Abundant aryl isoprenoids have been detected in source rock extracts from the 25-65 Ma saline lacustrine formations in the western Qaidam Basin, NW China. Identification was based mainly on comparison of mass spectra and gas chromatographic behaviour with literature data. Two pseudohomologous series in the range C13-C40 were assigned as 2,3,6- and 2,3,4-trimethyl monoaryl isoprenoids. The C40 2,3,4-trimethylaryl isoprenoid, okenane, was the most abundant component of the series, while its C40 2,3,6-trimethylaryl isomer, chlorobactane, was present in low abundance. Two C40 monoaromatic isoprenoids with a cyclohexyl ring were tentatively assigned as β-isorenieratane and β-renierapurpurane. One C40 diaryl isoprenoid was identified as isorenieratane. Identification of okenane, chlorobactane and isorenieratane was confirmed by co-elution experiments using synthetic standards. In addition, two novel series of aryl isoprenoids in the C12-C39 range were tentatively assigned as 2,6- and 2,3-dimethylaryl isoprenoids. The C39 2,3-dimethylaryl isoprenoid homologue was the most abundant component of the series, while the C39 2,6-dimethylaryl isomer was only present in low abundance. Two C39 monoaromatic bicyclic compounds were tentatively assigned as 2,6- and 2,3-dimethylaryl isoprenoids with a terminal cyclohexyl ring. Furthermore, a minor C38 component was tentatively assigned as a diaryl isoprenoid with a 2,3-/2,3-dimethyl substitution pattern. These dimethylaryl isoprenoids seem to be formed by demethylation of their parent trimethylaryl isoprenoid counterparts, the location of the demethylated position being exclusively at C-3, C-4 or C-6 of the aromatic ring. This specificity points to a biologically-mediated process (as opposed to an abiotic, maturity-related transformation) that needs to be further investigated.  相似文献   

2.
四川南桐地区二叠系龙潭煤层具有良好的生油潜力。其生物标记物包括正构和异构烷烃,类异戊二烯烷烃,倍半萜烷,二萜烷,三环萜烷,藿烷,一种未知结构的五环三萜烷(C30),甾烷,4-甲基甾烷等。煤层生物标记物特征表明在其形成过程中有藻类和细菌等微生物物质的加入。  相似文献   

3.
A sample of the sediment-water column interface which lies on the continental shelf under the Peru upwelling regime, has been examined for fatty acids, fatty alcohols, ketones and hydrocarbons. Fatty acids were the most abundant compound class, ranging from C12-C24, with 16:0 as the major component (765.5 μg/g dry sediment). The alcohols were dominated by 3,7,11,15-tetramethylhexadeca-2-en-ol (phytol), with even-chain n-alcohols in the range C14-C20. The ketones consisted of C37-C39 di- and tri-unsaturated alken-2-ones and alken-3-ones. Both alkanes and alkenes were present in the hydrocarbon fraction; the alkanes ranging from C13 — C20 and comprising both straight chain and isoprenoid compounds; the alkenes consisting of isomeric pairs of C25 branched trienes and tetraenes. The data indicate that the organic content has been contributed very largely from marine sources (probably mainly from phytoplankton and bacteria), showing little terrigenous influence. The presence of labile compounds such as polyunsaturated fatty acids (with two to six double bonds), implies that the sediment has undergone very little diagenetic alteration, and the lipids are probably largely unchanged from the state in which they actually reached the sediment. They may therefore serve as a useful baseline in assessing diagenesis in older sediments, where diagenetic transformations are more advanced.  相似文献   

4.
Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C15, n-C17, n-C19 alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C21, n-C23, n-C25 homologues from aquatic plants, and the n-C29, n-C31 homologues from vascular plants. In contrast, the n-C27 alkane is not categorized in the n-C29 and n-C31 group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ13Corg), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ13Corg, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ13Corg, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.  相似文献   

5.
Novel side chain methylated and hexacyclic hopanes have been identified in coals and oils from around the world. Extended hopanes (>C32) with an additional methyl in the side chain (“isohopanes”) were identified by comparison with synthetic standards. The major C33-C35 isohopanes are 31-methylbishomohopanes, 32-methyltrishomohopanes and 33-methyltetrakishomohopanes. Extended hopanes methylated at C-29 were not detected. The 17α(H),21β(H)-31-methyltrishomohopanes show four peaks on gas chromatography because of the extra asymmetric carbon at C-31. Like regular hopanes, the isohopanes extend beyond C35. Low concentrations of novel hexacyclic hopanes having 35 or more carbons were also detected in oils and coal extracts. The C35 hexacyclic hopanes were identified as 29-cyclopentylhopanes. Isohopanes are released from the kerogen by hydrous pyrolysis and hydropyrolysis. The 22S/(22S + 22R) ratio for 31-methylbishomohopanes and other isohopanes is around 0.60 at equilibrium in geological samples. They isomerize slightly more slowly than regular C33 hopanes. Isohop-17(21)-enes, 2α-methylisohopanes and two series of rearranged isohopanes were tentatively identified. Isohopanes can be biodegraded to form the corresponding 25-norhopanes. When 25-norhopanes are not formed, the isohopanes are much more resistant to biodegradation than regular hopanes. In biodegraded oil seeps from Greece, 30-norisohopanes were tentatively assigned. The composition and relative abundance of C33 and C34 isohopanes in a worldwide set of coals and crude oils was determined. Isohopanes are abundant in coal and coal-generated oils, where they can account for more than 5% of all extended hopanes, and low in abundance in oils from source rocks deposited under anoxic conditions.  相似文献   

6.
Several isoprenoid compounds were isolated from a heat-treated marine sediment in the southern California continental shelf (from Tanner Basin) which were not present in the original sediment. Among the compounds identified were: phytol, dihydrophytol, C18-isoprenoid ketone, phytanic and pristanic acids, C19- and C20-monoolefins, and the alkanes 2,6,10-trimethylpentadecane, pristane and phytane. The significance and possible routes leading to these compounds is discussed.  相似文献   

7.
A selection of Precambrian kerogens has been characterized by Curie-point pyrolysis combined with gas chromatography and gas chromatography-mass spectrometry. The resulting pyrograms can be classified into two groups. The first group of pyrograms is derived from kerogens whose pyrolysis products are dominated by alkanes, alkenes and alkadienes, whereas the second group contains pyrograms from kerogens that produce complex mixtures of branched hydrocarbons dominated by components at every third carbon number (C9, C12, C15, C18, C21, and up to C33). It is suggested that these branched hydrocarbons may remotely represent remains of isoprenoid hydrocarbons, or other branched hydrocarbons, of the original organisms.  相似文献   

8.
In this study, the molecular composition and biomarker distribution of lacustrine sediments from Val-1 drillhole in the central zone of the western part of the Valjevo-Mionica basin were investigated at depth interval of 0–400 m. Former investigations have shown that the core material can be separated into six depth intervals based on bulk geochemical, mineralogical and sedimentological characteristics. Concerning the quality of organic matter, presence of specific minerals, and high salinity and anoxicity, or alkalinity, three zones are of highest interest, defined at depth intervals of 15–75 m (A), 75–200 m (B) and 360–400 m (F). The first aim of the study was to identify which biomarkers characterize these specific intervals. The second aim, addressing the transitions zones of these intervals, was to extend the changes in the characteristics of the organic substance, to reflect the changes of conditions in the depositional environment as well as to define biomarker parameters which are the most sensitive sedimentological indicators.The sediments from the hypersaline anoxic and alkaline environment show high contribution of algal precursor biomass, what is in accordance with the good quality of organic substances in the sediments from these zones. High squalane content and low content of regular isoprenoid C25 are typical for hypersaline anoxic environment, whereas sediments from alkaline environment have high regular isoprenoid C25 content.Transition to specific sedimentation zones is characterized by change in total organic matter content, and of both free and pyrolysis-derived, and change in hydrogen index value. In the biomarker distributions, more significant changes were detected in distributions of n-alkanes and isoprenoids, compared to polycyclic alkanes. The most intensive changes in alkane distribution are reflected in changes in n-C17 content compared to n-C27, and phytane compared to n-C18. In addition, significant sensitivity was seen in ratios between squalane and n-alkane C26 (hypersaline depositional environment), or isoprenoid C25 and n-alkane C22 for high alkalinity environment.This study showed that Sq/n-C26 ratio can be used to assess the quality of organic substance in immature lacustrine sediments.  相似文献   

9.
Recent sediments from Tanner Basin (off southern California) and Bandaras Bay (in Gulf of California) have been analyzed for normal, isoprenoid and steroidal alcohols using chromatographic (column, GLC, TLC), and spectroscopic (u.v., i.r., MS) methods, prior to and after heat-treatment (from 65 to 150°C). Normal saturated alcohols (C14-C24) and monounsaturated alcohols (C22-C24) were identified, as well as the isoprenoid alcohols, phytol and dihydrophytol.Two series of sterols (Δ5 and Δ7) were found in Tanner Basin, and Δ5-sterols and triterpenes, in Bandaras Bay sediment. Sterols from both sediments contained the corresponding stanols.  相似文献   

10.
A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter.The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C15 to n-C32, with an odd carbon number that predominate in almost all the samples. The contents of n-C27 and n-C29 alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C27 to C31, but without C28, is typical for the Soko Banja coals.The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.  相似文献   

11.
We determined the distribution of lipids (n-alkanes and n-alkan-2-ones) in present-day peat-forming plants in the Roñanzas Bog in northern Spain. Consistent with the observation of others, most Sphagnum (moss) species alkanes maximized at C23, whereas the other plants maximized at higher molecular weight (C27 to C31). We show for the first time that plants other than seagrass and Sphagnum moss contain n-alkan-2-ones. Almost all the species analysed showed an n-alkan-2-one distribution between C21 and C31 with an odd/even predominance, maximizing at C27 or C29, except ferns, which maximized at lower molecular weight (C21-C23). We also observed that microbial degradation can be a major contributor to the n-alkan-2-one distribution in sediments as opposed to a direct input of ketones from plants.  相似文献   

12.
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   

13.
Currently, the presence of free n-alkanes and isoprenoid alkanes in carbonaceous meteorites is usually explained either by microbial contamination during the period between the meteorite fall and collection or by contamination from the environment of analytical laboratories and museums. The goal of this research was to repeat analysis of hydrocarbon components in meteorites and to investigate possible meteorite contamination routes discussed in the literature. Experimental analysis of free organic constituents in five carbonaceous meteorites by infrared spectroscopy (IR) and gas chromatographic (GC) methods confirmed the presence of extractable aliphatic components, n-alkanes in the C15H32-C27H56 range and isoprenoid alkanes (phytane, pristane, and norpristane), in some of these meteorites. The contents of these compounds vary depending on the source. Insoluble organic components of two meteorites (meteorite kerogens) were isolated, and their composition was analyzed by IR and cracking/GC methods. Comparison with the data on several terrestrial contamination sources proposed in the literature shows that the presence of free saturated hydrocarbons in meteorites and the composition of the meteorite kerogen could not be explained either by microbial contamination or by contamination from the laboratory environment. The types of the hydrocarbons in meteorites resemble those typical of ancient terrestrial deposits of organic-rich sediments, except for the absence of lighter hydrocarbons, which apparently slowly evaporated in space, and multi-ring naphthenic compounds of the biologic origin, steranes, terpanes, etc. The prevailing current explanation for the presence of free linear saturated hydrocarbons in carbonaceous meteorites, apart from contamination, is the abiotic route from hydrogen and carbon monoxide. However, the data on the structure of meteorite kerogens require a search for different routes that initially produce complex polymeric structures containing n-alkyl and isoprenoid chains which are attached, via polar links (esters, salts, etc.), to a cross-linked polymer matrix. Later, the polymer slowly decomposes with the liberation of free aliphatic hydrocarbons.  相似文献   

14.
We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C24 to C30 alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C27 to C33 alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C24 to C30 alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C24 to C30 alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ13C values of n-C27 to C33 alkanes (e.g. ?29‰ to ?33‰ for C31) indicate the presence of C3-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C24 to C30 alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C27 to C33 alkane parameter are generally higher than those using lignin phenol or n-C24 to C30 alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.  相似文献   

15.
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   

16.
Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C4 and C3 plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C11 to C31, and the C4-derived n-alkenes/alkanes were approx. 8‰ more enriched in 13C than the C3-derived compounds. Both the C4 and C3-derived n-alkenes/alkanes (C20-C30) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in 13C than the lower mol. wt (C1111-C19) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C4 and C3-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.  相似文献   

17.
A mechanistic model consisting of 13,206 lumped free radical reactions has been developed to describe the thermal evolution of a mixture of 78 alkanes: all n-alkanes from C1 to C32 and 46 branched alkane model compounds from C4 to C32. The mixture was meant to represent the major part of the saturated fraction of petroleum. The rate constants used are available from the literature. The lumping together procedure is described and the model validated on the basis of several experimental results from the literature and relating to pure alkanes. The model is also compared to the saturated fraction obtained from pyrolysis of Elgin oil at 372 °C for up to 1000 h. The cracking global activation energy of n-C15 as well as iso-C15 is close to 69 kcal/mol in the range 200-350 °C. The implications of the model for geological reservoirs will be discussed in a following paper.  相似文献   

18.
Organic matter from the Lower Paleozoic strata on the northern margin of the Tarim Basin of China contains abundant alkylcyclohexanes.The n-alkylcyclohexanes show the even(C16-C20) and odd (C17-C21) carbon number predominance and smooth distribution,and the methyl-n-alkylcycolhexanes the odd carbon number predominance(C17-C21) and smooth distribution,which may be related to their depositional environments and organic precursors.There are some differences in carbon number distribution between the two series of monocyclic alkanes and the n-alkanes marked by smooth distribution.The genetic relationship between the three series of compounds needs to be further studied.  相似文献   

19.
A lightly biodegraded crude oil from the Tolkinsk field (Upper Jurassic), situated in north-west Siberia, was found to contain a series of C28–C39 isoprenoid alkanes. Most of these components contain a pristane unit linked head-to-head with other isoprenoid units. The structures of these components were elucidated by mass spectral interpretations, comparisons with a synthesised standard and by reference to data published previously in the literature. These results extend the carbon number range, the variety of structural types, and the number of reported occurrences of these compounds in geological samples. These results provide further evidence for a contribution of bacterial cell-wall lipids to crude oils.  相似文献   

20.
A regular C25 isoprenoid alkane (2,6,10,14,18-pentamethyleicosane) has been isolated from highly saline Tertiary sediments. The isolation utilized elution chromatography, urea adduction and gas chromatography; identification was based on the mass spectrum. This C25 isoprenoid may represent a biological marker, possibly typical for a lagoonal-type, saline environment.  相似文献   

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