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1.
Organic matter (OM) associated with the Dongsheng sedimentary U ore hosting sandstone/siltstone was characterized by Rock-Eval, gas chromatography–mass spectrometry and stable C isotope analysis and compared to other OM in the sandstone/siltstone interbedded organic matter-rich strata. The OM in all of the analyzed samples is Type III with Ro less than 0.6%, indicating that the OM associated with these U ore deposits can be classified as a poor hydrocarbon source potential for oil and gas. n-Alkanes in the organic-rich strata are characterized by a higher relative abundance of high-molecular-weight (HMW) homologues and are dominated by C25, C27 or C29 with distinct odd-to-even C number predominances from C23 to C29. In contrast, in the sandstone/siltstone samples, the n-alkanes have a higher relative abundance of medium-molecular-weight homologues and are dominated by C22 with no or only slight odd-to-even C number predominances from C23 to C29. Methyl alkanoates in the sandstone/siltstone extracts range from C14 to C30, maximizing at C16, with a strong even C number predominance, but in the organic-rich layers the HMW homologues are higher, maximizing at C24, C26 or C28, also with an even predominance above C22. n-Alkanes in the sandstone/siltstone sequence are significantly depleted in 13C relative to n-alkanes in most of the organic-rich strata. Diasterenes, ββ-hopanes and hopenes are present in nearly all the organic-rich sediments but in the sandstone/siltstone samples they occur as the geologically mature isomers. All the results indicate that the OM in the Dongsheng U ore body is derived from different kinds of source materials. The organic compounds in the organic-rich strata are mainly terrestrial, whereas, in the sand/siltstones, they are derived mainly from aquatic biota. Similar distribution patterns and consistent δ13C variations between n-alkanes and methyl alkanoates in corresponding samples suggest they are derived from the same precursors. The OM in the organic-rich strata does not appear to have a direct role in the precipitation of the U ore in the sandstone, but an indirect role cannot be excluded. The OM in the U hosting sandstone shows a relatively low hydrogen index, presumably due to oxidation or radiolytic damage.  相似文献   

2.
A molecular study of linear, branched and isoprenyl alkylbenzene skeletons and alkenylbenzenes in the soluble fraction extracted from a sulfur-rich Utrillas coal was carried out using gas chromatography–mass spectrometry (GC–MS). The presence of C24–C28 diaromatic compounds, not previously reported in coals, suggests that photosynthetic green sulfur bacteria may have made an input of organic matter to these coals. The unsaturated linear alkenylbenzenes and isoprenyl (C15 and C20) alkylbenzene skeletons are also described for the first time in the soluble fraction of geological samples.  相似文献   

3.
The molecular composition of Carboniferous–Permian coals in the maturity range from 0.66 to 1.63% vitrinite reflectance has been analysed using organic geochemistry to investigate the factors influencing the biomarker compositions of humic coals. The Carboniferous–Permian coal has a variable organofacies and is mainly humic-prone. There is a significant difference in the distribution of saturated and aromatic hydrocarbons in these coals, which can be divided into three types. The Group A coals have biomarker compositions typical of humic coal, characterised by high Pr/Ph ratios, a lower abundance of tricyclic terpanes with a decreasing distribution from C19 tricyclic terpane to C24 tricyclic terpane and a high number of terrigenous-related biomarkers, such as C24 tetracyclic terpane and C29 steranes. The biomarker composition of Group B coals, which were deposited in a suboxic environment, have a higher abundance of rearranged hopanes than observed in Group A coals. In contrast, in Group C coals, the Pr/Ph ratio is less than 1.0, and the sterane and terpane distributions are very different from those in groups A and B. Group C coals generally have abnormally abundant tricyclic terpanes with a normal distribution maximising at the C23 peak; C27 steranes predominates in the m/z 217 mass fragmentograms. The relationships between biomarker compositions, thermal maturity, Pr/Ph ratios and depositional environments, indicate that the biomarker compositions of Carboniferous–Permian coals in Ordos Basin are mainly related to their depositional environment. This leads to the conclusion that the biomarker compositions of groups A and B coals collected from Shanxi and Taiyuan formations in the northern Ordos Basin are mainly related to their marine–terrigenous transitional environment, whereas the biomarker compositions for the Group C coals from Carboniferous strata and Shanxi Formation in the eastern Ordos Basin are associated with marine incursions.  相似文献   

4.
The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on the basis of theoretical considerations and empirical observations. The PAC maturity parameters, unlike those derived from saturated biomarker stereoisomers, are typically effective across the entire oil generation window. To compensate for the effects of OM type on the maturity parameters, they were combined using principal components analysis. The resulting first principal component was in good agreement with independent indicators of maturity. The relative distributions of C0–C3 alkylphenanthrenes, dibenzothiophene, methyldibenzothiophenes and methyldibenzofurans were evaluated by a separate principal components analysis. The results permitted an independent grouping of the samples by OM type and suggested additional, simple molecular ratios that allow graphical recognition of OM type, including the ratio of dibenzothiophenes to dibenzofurans and a ratio using C2-alkylphenanthrene isomers.  相似文献   

5.
The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state 13C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C19), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C1–C6 alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.  相似文献   

6.
The current geochemical study of n-alkanes, steranes, and triterpanes in bitumen from the Late Maastrichtian–Paleocene El Haria organic-rich facies in West of Gafsa, southern Tunisia, was performed in order to characterize with accuracy their geochemical pattern. The type of organic matter as deduced from n-alkanes, steranes, and triterpanes distributions is type II/III mixed oil/gas prone organic matter. Isoprenoids and biomarkers maturity parameters (i.e., T s/T m, 22S/(22S?+?22R) of the C31 αβ-hopanes ratios, 20S/(20R?+?20S) and ββ/(ββ?+?αα) of C29 steranes), revel that the organic-rich facies were deposited during enhanced anoxic conditions in southern Tunisa. The organic matter is placed prior to the peak stage of the conventional oil window (end of diagenesis–beginning of catagenesis). All these result are suggested by total organic carbon analysis, bitumen extraction and liquid chromatography data. Thus, the n-alkanes, triterpane, and steranes study remains valuable and practical for geochemical characterization of sedimentary organic matter.  相似文献   

7.
The Utrillas coal facies are located in the Maestrazgo basin in NE Spain. This mining district of Teruel contains sub-bituminous deposits from the Middle Albian (Lower Cretaceous 105 Ma) in areas near a delta estuary with abundant sulphur. The high sulphur content is due to an influx of sulphate caused by the geological recycling of Triassic gypsum from the catchment area into the delta estuary. In some outcrops, the weathered coal reveals leonardite deposits. The depositional environment of the basin originated coals, some of which are currently mined. The organic matter of the coals has been the object of scattered reports. Studies have focused on bulk pyrolysis parameters and microscopic observation in Utrillas samples, as well as the inorganic and insoluble organic fraction.We analysed the organic soluble extract of the Utrillas coals using GC–MS in order to characterize their aliphatic, aromatic and organosulphur compounds. The biomarker distribution allowed us to recognize different inputs, assess their depositional palaeoenvironment and finally determine their degree of maturity. In particular, homologous series of hopanes related to eubacteria were present. Biomarkers characteristic of higher plant inputs were also widely distributed (e.g. phyllocladane or C29 steranes). The presence of linear alkylbenzenes allowed us to recognize the palaeodepositional reducing environments where they were deposited. Specifically, thienylhopanes were associated with sulphur-reducing environments. Finally, the abundance of unsaturated biomarkers such as diacholestenes indicated low-maturity coals. Various aromatic ratios such as the methylphenanthrene index also suggested diagenesis in the initial stage.  相似文献   

8.
The formation or generation of hopanes are important processes during both the natural heating of organic-rich sediments and laboratory pyrolysis experiments. Molecular maturity parameters as well as the amounts (ng/g rock) of the C31 hopanes and C30–C32 hopanoic acids were quantified in a Jurassic silty shale horizon (Isle of Skye, Scotland) as a function of distance from an igneous intrusion. The maturity profiles of the homohopanes and the hopanoic acids are comparable. There is also a correlation between the decreasing amounts of C30–C32 hopanoic acids and concomitant increases in C29–C31 hopanes suggesting that free hopanoic acids could be one potential source of hopanes in this particular horizon. Other possible sources could include hopanoic acids that are bound into the macromolecular fraction.  相似文献   

9.
The Murchison meteorite contains aliphatic and aromatic hydrocarbons similar to those made in static Fischer-Tropsch-type syntheses. Principal compound classes above C8 are n-alkanes, mono- and dimethylalkanes, alkenes, alkylbenzenes and -naphthalenes. Below C8, n-alkanes are virtually absent; instead, benzene, toluene, branched alkanes dominate. The CH4/C2H6 ratio is greater than 30, possibly greater than 700. Isoprenoids from C17 to C20 occur in a surface rinse but not in subsequent extracts and appear to be terrestrial contaminants. Thiophenes, porphyrin-like pigments and chlorobenzenes were also found; the latter appear to be contaminants. In the Allende meteorite, only methane, benzene, toluene and an aromatic polymer seem to be indigenous.  相似文献   

10.
Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ13Corg, δDorg and δ15Norg values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C1/(C2 + C3) and by comparing their stable isotope compositions, especially δ13CCH4 and δDCH4. The δ13CC2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires  相似文献   

11.
Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.  相似文献   

12.
A suite of 18 oils from the Barrow Island oilfield, Australia, and a non-biodegraded reference oil have been analysed compositionally in order to detail the effect of minor to moderate biodegradation on C5 to C9 hydrocarbons. Carbon isotopic data for individual low molecular weight hydrocarbons were also obtained for six of the oils. The Barrow Island oils came from different production wells, reservoir horizons, and compartments, but have a common source (the Upper Jurassic Dingo Claystone Formation), with some organo-facies differences. Hydrocarbon ratios based on hopanes, steranes, alkylnaphthalenes and alkylphenanthrenes indicate thermal maturities of about 0.8% Rc for most of the oils. The co-occurrence in all the oils of relatively high amounts of 25-norhopanes with C5 to C9 hydrocarbons, aromatic hydrocarbons and cyclic alkanes implies that the oils are the result of multiple charging, with a heavily biodegraded charge being overprinted by fresher and more pristine oil. The later oil charge was itself variably biodegraded, leading to significant compositional variations across the oilfield, which help delineate compartmentalisation. Biodegradation resulted in strong depletion of n-alkanes (>95%) from most of the oils. Benzene and toluene were partially or completely removed from the Barrow Island oils by water washing. However, hydrocarbons with lower water solubility were either not affected by water washing, or water washing had only a minor effect. There are three main controls on the susceptibility to biodegradation of cyclic, branched and aromatic low molecular weight hydrocarbons: carbon skeleton, degree of alkylation, and position of alkylation. Firstly, ring preference ratios at C6 and C7 show that isoalkanes are retained preferentially relative to alkylcyclohexanes, and to some extent alkylcyclopentanes. Dimethylpentanes are substantially more resistant to biodegradation than most dimethylcyclopentanes, but methylhexanes are depleted faster than methylpentanes and dimethylcyclopentanes. For C8 and C9 hydrocarbons, alkylcyclohexanes are more resistant to biodegradation than linear alkanes. Secondly, there is a trend of lower susceptibility to biodegradation with greater alkyl substitution for isoalkanes, alkylcyclohexanes, alkylcyclopentanes and alkylbenzenes. Thirdly, the position of alkylation has a strong control, with adjacent methyl groups reducing the susceptibility of an isomer to biodegradation. 1,2,3-Trimethylbenzene is the most resistant of the C3 alkylbenzene isomers during moderate biodegradation. 2-Methylalkanes are the most susceptible branched alkanes to biodegradation, 3-methylalkanes are the most resistant and 4-methylalkanes have intermediate resistance. Therefore, terminal methyl groups are more prone to bacterial attack compared to mid-chain isomers, and C3 carbon chains are more readily utilised than C2 carbon chains. 1,1-Dimethylcyclopentane and 1,1-dimethylcyclohexane are the most resistant of the alkylcyclohexanes and alkylcyclopentanes to biodegradation. The straight-chained and branched C5–C9 alkanes are isotopically light (depleted in 13C) relative to cycloalkanes and aromatic hydrocarbons. The effects of biodegradation consistently lead to enrichment in 13C for each remaining hydrocarbon, due to preferential removal of 12C. Differences in the rates of biodegradation of low molecular weight hydrocarbons shown by compositional data are also reflected in the level of enrichment in 13C. The carbon isotopic effects of biodegradation show a decreasing level of isotopic enrichments in 13C with increasing molecular weight. This suggests that the kinetic isotope effect associated with biodegradation is site-specific and often related to a terminal carbon, where its impact on the isotopic composition becomes progressively ‘diluted’ with increasing carbon number.  相似文献   

13.
Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% Rr and for Posidonia Shale at >0.88% Rr). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C1- and C2-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C2-carbazoles, are not easy to interpret.  相似文献   

14.
For the first time a biological source for the long-chain alkyl 1,14-diols and 12-hydroxy methyl alkanoates, lipids widely occurring in the marine water column and sediments, has been identified. Cultures of Proboscia indica and Proboscia alata, rhizosolenoid diatoms belonging to the widespread diatom genus Proboscia, contain C28, C28:1, C30, and C30:1 alkyl 1,14-diols, and C27 and C29 12-hydroxy methyl alkanoates as major neutral lipids. These components form a substantial fraction of lipid fractions from sediment traps or sediments, especially in areas with an elevated primary production such as upwelling regions. Examination of literature data reveals that as much as 20 to 35% of the total lipid flux in the Arabian Sea is derived from Proboscia diatoms during the start of the upwelling season. Their rapid transfer to the water-sediment interface may explain why corresponding 1,14-keto-ols, inferred oxidation products of diols, are hardly formed. These interpretations are supported by compound-specific carbon isotopic analysis of long-chain keto-ols and diols in surface sediments of the Arabian Sea. The data indicate that long-chain alkyl 1,14-diols and 12-hydroxy methyl alkanoates can be applied as indicators for high-nutrient conditions in the photic zone.  相似文献   

15.
Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C27, C28, and C29 sterane isomers. The useful maturity indicators include the C29 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C27, C28, and C29 steranes, and the rearranged to normal sterane ratio. In addition, C27 rearranged steran es appear to form at a faster rate than C28 or C29 rearranged steranes. However, the isomerization of the C27 biological component appears to occur at a slower rate than the C29 counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C27 trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C31+ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C31–C34).  相似文献   

16.
Petroleum geologists have debated whether the hydrocarbons from Jurassic coal measures are derived from the coals, carbonaceous mudstones or coal-measure mudstones in the Turpan Basin. Based on the geochemistry analysis of the 20 crude oils and 40 source rocks from the Turpan Basin, some data have been obtained as follows: carbon preference index and methylphenanthrene index of the Jurassic oils are 1.16–1.45 and 0.28–0.80, and the ααα C29 sterane 20S/(20S+20R) and C29 sterane ββ/(ββ+αα) are 0.44–0.51 and 0.4–0.54 respectively, which show the normal maturity of oils; the vitrinite reflectance of the source rocks from the Xishanyao to Badaowan Formations range from 0.47% to 0.97%, which indicate immature to mature thermal evolutionary stage and sufficient conditions for generating mass mature oil. The effect of hydrocarbon expulsion should be considered when studying the source of coal-derived oil by using Biomarkers. Biomarkers in the Jurassic oils from the basin are similar to those in the coals and carbonaceous mudstones, with a strong predominant content of pristane, relatively high ratio of C15/C16 sesquiterpenoids (>1), a relatively high content of low carbon number tricyclic terpanes and C24 tetracyclic terpane, little gammacerane and C29 Ts detected, an absolute predominant content of C29 sterane and a relatively high content of diasterane. However, the opposite characteristics are shown in mudstones, with an approximately equal content of pristane and phytane, relatively low ratio of C15/C16 sesquiterpenoids (<1), a relatively high content of high carbon number tricyclic terpanes and a low content of C24 tetracyclic terpane, peaks of gammacerane and C29 Ts detected obviously and an increasing C27 sterane content. All of these characteristics identify the coals and carbonaceous mudstones as the possible major oil source rocks in this area, and they were formed in the stronger oxidizing environment with shallower water than mudstones.  相似文献   

17.
Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.  相似文献   

18.
Even-carbon number C22-C28n-alkanes, are present in higher concentrations than their C21-C29 odd-carbon number homologs in an organic-rich rock of Mississippian (ca. 310 × 106-yr-old) age, which contains algae-like remnants. Environmental indicators associated with this organic-rich rock permitted environmental comparison with ancient and modern environments that contain n-alkanes which exhibit similar distributions. The results of these comparisons suggest that even-carbon number n-alkanes are preferentially produced in highly saline, carbonate environments where aerobic and anaerobic bacteria have subsisted on the remains of blue-green algae.  相似文献   

19.
In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH4 (0.01–50.55 mol%) with low δ13C–CH4 values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ13C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH4 to ethane and propane ratios (3–35 mol%; C1/C2 + C3) and high δ13C and δD values of CH4 (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH4 was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ13C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO4 values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ13C–DIC values (<−22‰) and relatively high SO4 concentrations (up to 12.31 mmole/L) in many brine samples point to SO4 reduction, which likely limits microbial CH4 generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH4 in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH4 are present at shallow depths along Lake Erie and in western NY.  相似文献   

20.
Six North American bituminous coals (four Carboniferous and two Cretaceous) and eight maceral concentrates from Carboniferous British seams have been heated with tetralin and hydrogen to 400°C. The hexane-soluble parts of the products were separated by column chromatography and the fractions were then analyzed by gas chromatography/mass spectrometry. In all cases the aromatic hydrocarbon fraction was a very complex mixture containing a number of alkylated biphenyls, diphenylmethanes and -ethanes, and polycyclic compounds. However single ioncchromatography (m/z = 142) showed that, in addition to these, the products from five of the six American coals contained homologous series of long chain n-alkylnapththalenes with alkyl groups extending to C16. In other fractions from the American coals, homologous series of n-alkylfurans and alkylphenols were found to be major components, as also were many alkylcyclohexenones related to isophorone. Extensive homologous series of n-alkyl aromatics were not detected in products from any of six vitrinites from British seams, though series of n- and iso-alkylphenols were found in the products from two sporinite concentrates. A number of polycyclic ketones apparently related to sterols were found in the products from the British vitrinites but not from any American coals. Reasons for what appear to be systematic structural differences between the American and British coals are discussed. Differences in stratigraphy are noted and it seems not impossible that differences in source vegetation are significant.  相似文献   

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