Conversion of sedimentary fatty acids from extractable (unbound + bound) to tightly bound form during mild heating     

Kimitaka Kawamura  Ryoshi Ishiwatari 《Organic Geochemistry》1985,8(3):197-201

Prolonged heating (1–248 days) of a recent sediment was conducted under mild conditions (65 and 83°C) to understand the thermal behavior of extractable (unbound and bound) fatty acids (C_12C32). In the course of the heating, the concentrations of saturated and monounsaturated fatty acids first decreased, and then increased. This indicates that extractable fatty acids can be converted to a tightly bound form upon heating, before fatty acids are extensively released from sediment matrices. Changes in molecular distributions of extractable fatty acids upon heating were also observed. The higher molecular weight fatty acids (?C₂₀) are more likely to become tightly bound than are lower molecular weight (<C₂₀). Monounsaturated fatty acids (C_16:1 and C_18:1) are more easily converted to the tightly bound form than polyunsaturated fatty acids (C_18:2 and C_18:3). These differences probably reflect their mode of occurrence in sediments, which are closely related to their origin.  相似文献   

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis     

R Ishiwatari  M Ishiwatari  B.G Rohrback  I.R Kaplan 《Geochimica et cosmochimica acta》1977,41(6):815-828

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.  相似文献   

Evaluation of alkaline permanganate oxidation method for the characterization of young kerogen     

Tsumoto Machihara  Ryoshi Ishiwatari 《Organic Geochemistry》1983,5(3):111-119

Alkaline potassium permanganate oxidation of a young kerogen (lacustrine) and 34 model compounds (saturated and unsaturated fatty acids, hydroxy acid, aliphatic dicarboxylic acids, aliphatic alcohols, normal hydrocarbon, β-carotene, phenolic acids, benzenecarboxylic acids, carbohydrates, amino acids and proteins) were conducted, followed by GC and GC-MS analysis of the degradation products. The stability of the degradation products of kerogen in permanganate solution and the relationship between degradation products and kerogen building blocks were determined.The results showed that aliphatic acids C₁₂–C₁₆ monocarboxylic acids and C₆–C₁₀ α,ω-dicarboxylic acids) were rather susceptible to oxidation compared with benzenecarboxylic acids and the former were degraded into lower molecular weight decarboxylic acids. It was concluded that oxidation at milder conditions (60° C, 1 hr) is appropriate for qualitative and quantitative characterization of the aliphatic structure of young kerogen. It was noteworthy that benzoic acid was produced in a significant amount by oxidation of amino acids (phenylalanine) and proteins, C₁₈-isoprenoidal ketone from phytol, and C₈ and C₉ α,ω-dicarboxylic acids from unsaturated fatty acids, respectively; furthermore, 2,2-dimethyl succinic and 2,2-dimethyl glutaric acids were produced from β-carotene.  相似文献   

脂肪酸在古土壤层和黄土层中的分布差异及其环境指示意义     

颜备战  贾蓉芬 《江苏地质》1996,20(4):237-241

陕西洛川黄土剖面中的黄土层及古土壤层中脂肪酸存在显著差异：黄土层中的正构脂肪酸以不对称的双峰分布，前峰高于后峰，Ｃ１６：０为主峰；古土壤层中，脂肪酸以三组峰分布，Ｃ９，Ｃ１６，Ｃ２８近乎相等；古土壤层中的异构脂肪酸有ｉＣ１７，ｉＣ１９，反异构脂肪酸有ａｉＣ１４，ａｉＣ１５，ａＩＣ１７，ａｉＣ２０等，黄土层中几乎不见它们的，均含有Ｃ１６；１，Ｃ１８：１不饱和脂肪酸，其中Ｃ１８；１含量高。Ｌ２，Ｓ２的  相似文献   

The stereochemistry of bound and extractable pentacyclic triterpenoids during closed system pyrolysis     

Mark A Sugden  Geoffrey D Abbott   《Organic Geochemistry》2002,33(12):2

The distributions of hopanoic acids, ranging from C₃₀ to C₃₄, in the Messel oil shale were characterized in both the free and bound states. The bound acids were released by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). These were compared with the distributions of the hopanoic acids and hopanes released or generated from Messel oil shale kerogen following closed system microscale pyrolysis. This comparison revealed that epimerization had occurred at C-17, C-21 and C-22 during heating. It was also clear that the residual bound hopanoic acids had undergone configurational isomerization. During the pyrolysis there is a large loss of hopanoic acids following their rapid release from the kerogen into the free fraction even at 250 °C. In these particular experiments this loss does not appear to result in exclusive formation of hopanes, by way of decarboxylation or reduction reactions, unless the resulting hopanes are either themselves rapidly transformed into other compounds or the reaction rates are a function of the total number of carbon atoms in each hopanoic acid precursor.  相似文献   

Simulated diagenesis and catagenesis of marine kerogen precursors: Melanoidins as model systems for light hydrocarbon generation     

M.H. Engel  J. Rafalska-Bloch  C.F. Schiefelbein  J.E. Zumberge  A. Serban 《Organic Geochemistry》1986,10(4-6)

Amino acids and sugars are principal constituents of marine organisms. The condensation of amino acids and sugars is one possible nonenzymatic, early diagenetic pathway for the incorporation of these compounds into more complex geopolymers. In this study, aqueous solutions consisting of l-lysine, l-histidine, l-arginine and d-(+)-glucose were heated (100°C) for up to 288 h. Portions of the melanoidin polymer isolated after heating were reheated in the presence of water (hydrous pyrolysis) for 72 h at 325°C. Reaction products were identified by GC and GC/MS. Stable isotopic (δ¹³C) and elemental analyses were used to follow thermal evolution.While the initial melanoidin was synthesized from a simple, four component system, the products generated during hydrous pyrolysis are of considerable complexity, and include straightchain and branched alkanes, alkadienes, alkynes, indole, dimethyl indane, ethyl phenol, quinoline, and xylenes, in addition to a multitude of as yet, unidentified components. Stable carbon isotopic values for the reactants and products correspond to trends observed for naturally generated geopolymers and light gases. Elemental analyses of the melanoidin prior and subsequent to hydrous pyrolysis indicate a kerogen evolution pathway similar to that observed for natural samples. Considering the intractable nature of kerogen, laboratory simulation studies of simple systems can provide an alternative approach for elucidating the origins of geopolymers and their potential for hydrocarbon generation.  相似文献   

Monocyclic alkanes in Ordovician organic matter   总被引：1，自引：0，他引：1  

M.G. Fowler  P. Abolins  A.G. Douglas 《Organic Geochemistry》1986,10(4-6)

The major compounds in the C₁₅₊ branched/cyclic alkane fractions of two Ordovician oils (Pine Unit and Midland Farms oils) and an immature Ordovician rock (Guttenberg Oil Rock) are monocyclics. One series of these compounds was identified as n-alkylcyclohexanes and another tentatively identified as methyl-n-alkylcyclohexanes. The carbon number distribution of these compounds resembled those of the n-alkanes found in these samples with an odd carbon number predominance. It is suggested that the monocyclic alkanes, in these Ordovician samples, may be principally derived from the cyclisation of straight-chain algal fatty acids, by mechanisms that involve decarboxylation. However, there is evidence from the m/z 97 fragmentograms of these samples, to indicate that methyl-n-alkylcyclohexanes can also be derived from fatty acids by a less preferred mechanism that does not involve decarboxylation or from other precursors.In addition, a sample of kerogen from the Guttenberg Oil Rock was hydrously pyrolysed. The saturated hydrocarbon products of this experiment showed very similar distributions (including monocyclics) to those observed in the Ordovician oils. This suggests that although the oils and the Guttenberg Oil Rock come from widely differing geographical locations, their precursor (algal derived) organic matter was very similar.  相似文献   

Lipid Distribution in Marine Sediments from the Northern South China Sea and Association with Gas Hydrate     

OU Wenji  LEI Huaiyan  LU Wanjun  ZHANG Jie  SHI Chunxiao  GONG Chujun  HAN Chao 《《地质学报》英文版》2014,88(1):226-237

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   

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks     

Noriyuki Suzuki 《Geochimica et cosmochimica acta》1984,48(2):243-249

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic$\text{H}\text{C}$ ratio and the lowest atomic $\text{N}\text{C}$ ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C₁₆ and C₁₈ acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic $\text{H}\text{C}$ ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.  相似文献   

Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis     

M.D. Lewan  T.E. Ruble 《Organic Geochemistry》2002,33(12)

This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 °C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-IIS kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.  相似文献   

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite     

C. Largeau  S. Derenne  E. Casadevall  A. Kadouri  N. Sellier 《Organic Geochemistry》1986,10(4-6)

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.  相似文献   

Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry     

Elodie Salmon  Françoise BeharPatrick G. Hatcher 《Organic Geochemistry》2011,42(4):301-315

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.  相似文献   

Hydroxy acids in Antarctic lake sediments and their geochemical significance     

Genki I. Matsumoto  Kunihiko Watanuki  Tetsuya Torii 《Organic Geochemistry》1988,13(4-6)

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

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions   总被引：1，自引：0，他引：1  

Mark A. Teece  Marilyn L. Fogel  Michael E. Dollhopf  Kenneth H. Nealson   《Organic Geochemistry》1999,30(12):1285

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.  相似文献   

Distributions of phospholipid and glycolipid fatty acids in two strains of different functional Erythrobacter sp. isolated from South China Sea     

Huan Yang  Xiangru Ma  Qiang Li  Nianzhi Jiao  Shucheng Xie 《Frontiers of Earth Science》2009,3(1):91-99

The comparison of the fatty acids between aerobic anoxygenic phototrophic bacteria (AAPB) and their phylogenetic relatives has been a fascinating but yet enigmatic topic, enhancing our understanding of physiological variations between these evolutionarily related microorganisms. Two strains of marine bacteria, both phylogenetically falling into Erythrobacter sp., were isolated from the South China Sea, and demonstrated, respectively, to be an aerobic anoxygenic phototrophic bacteria (AAPB) (JL475) which is capable of anoxygenic photosynthesis via BChl a, and an obligate heterotroph (JL316) with a lack of BChl a, on the basis of phylogenetic analysis and pure culture cultivation. Phospholipid fatty acids (PLFA) and glycolipid fatty acids (GLFA) of the two strains were extracted and analyzed by gas chromatographymass spectrometry. The PLFA in JL475 AAPB are characterized by C_18:1 C_18:2ω7,13 and C_18:1, with the C_18:2ω7,13 being a specific compound for AAPB and in particular for Erythrobacter longus and some of its phylogenetically closely related relatives. The JL316 strain is characterized in PLFA by the presence of C_18:1, C_16:1 and C_16:0, and in particular C_17:1. GLFA do not show any discrimination between the two strains. Four α,ω-dicarboxylic acids, including 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid and 1,11-undecanedioic acid, are present only in JL316 GLFA, presumably derived from metabolic products. C₁₄-C₁₆ 2-hydroxy fatty acids were found in the two strains, probably assuming a similar function of their LPS in outer membranes.  相似文献   

The nature of straight-chain aliphatic structures in green river kerogen     

D.K. Young  T.F. Yen 《Geochimica et cosmochimica acta》1977,41(10):1411-1417

Previous studies of the Green River kerogen only provide apparently contradictory conclusions about the size of the straight-chain aliphatic structures as well as the manner in which these structures form part of the kerogen matrix.The present investigation is an attempt to resolve this contradiction. A mild stepwise oxidation procedure was followed so that extensive degradation of kerogen-derived intermediates could be prevented. Products isolated from each oxidation step were analyzed by conventional GLC techniques, GC-MS, and proton-NMR measurements in order to ascertain the significance of the straight-chain aliphatic structures present in the Green River kerogen.The following results were obtained: (a) Green River kerogen contains a substantial portion (ca 2–4 carbons out of every 10) of straight-chain aliphatic structures which are longer than C₄, (b) the kerogen matrix forms a three-dimensional network of non-straight-chain clusters interconnected by long polymethylene cross-links, (c) the ‘core’, in comparison with the ‘periphery’ of the kerogen matrix, contains a greater proportion of straight-chain and branched aliphatic structures which are attached to the kerogen matrix at one terminus, (d) some of the straight-chain structures may exist as physically entrapped components in the kerogen matrix.  相似文献   

The occurrence and geochemistry of Di - and trimethyl - 2- (4,8,12 trimethyltridecyl) chromans and benzohopanes in Fushun cannel coal,Northeast China     

Fan Shanfa  Fu Jiamo  Geoffery Eglinton  Simon C. Brassell 《中国地球化学学报》1989,8(4):317-321

The distribution of methyl-2-methyl-2-(4,8,12-trimethyltridecyl)chromans (M - MTTC) is related to sedimentary environments. 5,7,8 - tri-Me-MTTC, 5,8 -di - Me-MTTC and 7,8 - di - Me - MTTC have been found in coal for the first time, implying that M-MTTC is widely spread in sediments.The distribution of M - MTTC. the presence of C₃₂—C₃₅ benzohopanes, high Pr/Ph ratio, obvious even - odd predominance in C₂₄—C₃₄ alkanes and odd-even predominance in normal alkanes provide strong evidence of a near - shore lacustrine environment.  相似文献   

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation     

Michael D. Lewan  Stéphanie Roy 《Organic Geochemistry》2011,42(1):31-41

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C₁₅₊ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen.  相似文献   

Stepwise pyrolysis-gas chromatography of kerogen in sedimentary rocks     

Joel S. Leventhal 《Chemical Geology》1976,18(1):5-20

Stepwise pyrolysis-gas chromatography is used to examine and characterize the carbonaceous matter in sedimentary rocks. Low-temperature steps remove material normally volatile or extracted by benzene-methanol. Successively-higher temperature steps degrade the insoluble carbonaceous matter (kerogen) into smaller molecular pieces. The sequential pyrolysis steps have the advantage of breaking the kerogen at several temperatures which may be related to bond type or strength. The pyrolysis product chromatograms from each step can be compared. The molecular sizes (chain length) of kerogens fragments can be determined. The results presented here show the molecules in the range C₁₁ to C₂₃ because: (1) they can be compared to normal petroleum source rock extractables; and (2) these large molecules give a feeling for the molecular construction of the kerogen.Green River and Antrim shales show low-temperature material which is indigenous and not modified compared to the pyrolyzed kerogen fragments in the range C₁₁C₂₃. Kupferletten shows low-temperature material of a narrow molecular weight range of C₁₅C₁₉ which is probably derived from the kerogen. Monterey shale low-temperature material appears to be unrelated to the kerogen as represented by its pyrolysis products. The Pierre shale kerogen shows molecules over the range C₁₁C₂₃. Kerogen from the Romney shale has no molecules large than C₈ in its pyrolysis products and no petroleum potential due to thermal and tectonic diagenesis.  相似文献   

Hydrocarbon source potential and depositional environment of the Surma Group shales of Bengal basin,Bangladesh     

Md. Farhaduzzaman  Wan Hasiah Abdullah  Md. Aminul Islam 《Journal of the Geological Society of India》2014,83(4):433-446

Surma Group is the most important geological unit of Bengal basin, Bangladesh, because petroleum resources occur within this group. It is mainly composed of alternation of shale and sandstone and the shale fraction has long been considered as source rocks and the sandstone fraction as reservoir. These source and reservoir rocks have been studied by different authors by different approach but none of them adopted organic geochemistry and organic petrology as a means of study of source rock and their possible depositional environment. A total of thirty shale core samples have been collected from eight different gas fields to fulfill the short coming. The collected samples have been subjected to Source Rock Analysis (SRA) and/or Rock-Eval (RE) followed by pyrolysis gas chromatography (PyGC), gas chromatography mass spectrometry (GCMS), elemental analysis (EA) and organic petrological study such as vitrinite reflectance measurement and maceral analysis. The analyzed organic matter extracted from the shales of Surma Group consists mainly of Type III along with some Type II kerogen. The studied shales are mostly organically lean (TOC ±1%) and the extracted organic matter is fair to moderate. Based on these results, the analyzed shales have been ranked as poor (mostly) to fair quality source rock. The organic matter of the analyzed shale samples is thermally immature to early mature for hydrocarbon generation considering their T_max and measured mean vitrinite reflectance values. The hopane 22S/(22S + 22R), moretane/hopane ratio and sterane parameters are also in good agreement with these thermal maturity assessments. The predominance of odd carbons over even carbons (most common) and/or even carbons over odd carbon numbered n-alkanes, moderate Pr/Ph ratio, low to high Tm/Ts ratio, comparative abundance of sterane C₂₉ (i.e., C₂₉ >C₂₇>C₂₈), Pr/nC₁₇ — Ph/nC₁₈ values, C/S ratio and dominance of vitrinite macerals group with the presence of liptinite macerals demonstrate that the organic matter has derived mainly from terrestrial inputs with an insignificant contribution from the marine sources. The condition of deposition alternates from oxic to anoxic.  相似文献