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1.
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
2.
The saturated and unsaturated hydrocarbons of two samples (HD-19 and HD-21) from the same section of the Middle Eocene lacustrine Huadian oil shale in NE China were identified and shown to be mainly from algal and bacterial sources. Comparison of the two samples provided an opportunity to explore the contribution from telalginite to the hydrocarbon profiles. Cells identified from microscopy as Botryococcus in the telalginite of HD-21 were confirmed as belonging to the L race of B. braunii from the presence of monoaromatic lycopane derivatives and small amounts of several lycopadienes. Lycopane was abundant and was probably derived from biohydrogenation of lycopadienes and related lipids on the basis of δ13C values. Hopane distributions showed a dominance of those with the biological 17β,21β-stereochemistry, as expected for an immature shale, with low amounts of 17β,21α-hopanes (moretanes) and 17α,21β-hopanes. Two hopenes were also abundant and assigned as C29 and C30 neohop-13(18)-enes, which occurred together with the C29 and C30 hop-17(21)-enes. These had depleted carbon isotope values (−43.7‰ to −50.8‰), indicative of production by methane oxidizing bacteria (methanotrophs). The high proportion of hopanoids with carbon numbers < C32 indicates extensive post-depositional diagenetic alteration of bacteriohopanepolyols as well as a direct input of C30 hopanoids. The data clearly indicate that there was active utilization of methane in this lacustrine depositional setting, but isoprenoid hydrocarbon biomarkers for methanogens, such as pentamethylicosane (PMI) and squalane, were in surprisingly low abundance. It is possible that these bacterial contributions were present as polar lipids. The origins of an unusual C38 isoprenoid alkane assigned as bipristane are uncertain, but may be from methanogens. Steranes and sterenes were relatively minor components, but abundant diasterenes and 4-methyldiasterenes were present, reflecting significant conversion of the original lipid composition by way of clay-catalysed diagenesis. The biomarker data suggest that the bottom waters in the original depositional environment had low O2 content, but the sediments were probably neither sulfidic nor strongly reducing. The high content of organic matter in the shale likely reflects both high (but fluctuating) productivity due to eutrophic conditions in the overlying water and good preservation in the sediments. 相似文献
3.
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
4.
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
5.
The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of 13C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, 13C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ13C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ13C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ13C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs. 相似文献
6.
Paul Farrimond Andrew N Bishop Helen E Innes Colin E Snape 《Geochimica et cosmochimica acta》2003,67(7):1383-1394
Hopanoids bound into the insoluble organic matter (kerogen) of Recent sediments from a freshwater lake (Priest Pot) and an anoxic sulphidic fjord (Framvaren) were released by hydropyrolysis and examined by gas chromatography-mass spectrometry. Bound hopanoids are present in high concentration (190-1400 μg/g TOC) and represent 22 to 86% of the total analysable hopanoids (i.e., bound and solvent-soluble), this proportion increasing with depth in Framvaren Fjord. The hopanes generated by hydropyrolysis contain higher amounts of the C35, C32, and C30 homologues, reflecting the carbon number distribution of the bound hopanoids and indicating that both biohopanoids (C30 and C35) and their diagenetic products (dominated by C32) are incorporated into the kerogen on a timescale of only 0 to 350 years. Sequential (multiple temperature) hydropyrolysis experiments gave an indication of the relative strengths of bonds being cleaved in association with hopane generation: The hopanoids of a sediment from Priest Pot are almost entirely bound by strong covalent bonds, interpreted to be mainly ether linkages, whilst a Framvaren sediment contains hopanoids that are bound by a mixture of weak di-/polysulphide linkages and stronger ether bonds. Labelling with deuterium indicated that the strong covalent linkages dominate, even for the Framvaren sediment. 相似文献
7.
Hans Peter Nytoft 《Organic Geochemistry》2011,42(5):520-539
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
8.
J.Michael Moldowan Wolfgang K. Seifert Edward Arnold Jon Clardy 《Geochimica et cosmochimica acta》1984,48(8):1651-1661
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 cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils. 相似文献
9.
《China Geology》2020,3(4):602-610
Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC12-nC33) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ13C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin. 相似文献
10.
Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel 总被引：1，自引：0，他引：1
The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ18OSMOW=+24.4 to +26.5‰δ13CPDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ18OSMOW=+18.4 to +25.8‰; δ13CPDB=?2.1 to +0.2‰), and calcite (δ18OSMOW=+21.3 to +32.6‰; δ13CPDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ18O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ18O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite. 相似文献
11.
《Applied Geochemistry》2004,19(1):55-72
Bulk and molecular stable C isotopic compositions and biomarker distributions provide evidence for a diverse community of algal and bacterial organisms in the sedimentary organic matter of a carbonate section throughout the Permian–Triassic (P/Tr) transition at the Idrijca Valley, Western Slovenia. The input of algae and bacteria in all the Upper Permian and Lower Scythian samples is represented by the predominance of C15–C22 n-alkanes, odd C-number alkylcyclohexanes, C27 steranes and substantial contents of C21–C30 acyclic isoprenoids. The occurrence of odd long-chain n-alkanes (C22–C30) and C29 steranes in all the samples indicate a contribution of continental material. The decrease of Corg and Ccarb contents, increase of Rock-Eval oxygen indices, and 13C-enrichment of the kerogen suggest a decrease in anoxia of the uppermost Permian bottom water. The predominance of odd C-number alkylcycloalkanes, C27 steranes, and C17 n-alkanes with δ13C values ∼−30‰, and 13C-enrichment of the kerogens in the lowermost Scythian samples are evidence of greater algal productivity. This increased productivity was probably sustained by a high nutrient availability and changes of dissolved CO2 speciation associated to the earliest Triassic transgression. A decrease of Corg content in the uppermost Scythian samples, associated to a 13C-depletetion in the carbonates (up to 4‰) and individual n-alkanes (up to 3.4‰) compared to the Upper Permian samples, indicate lowering of the primary productivity (algae, cyanobacteria) and/or higher degradation of the organic matter. 相似文献
12.
In addition to the previously reported 25-norhopanes and 25-norhopanoic acids, for the first time we report the identification of 25-norbenzohopanes. The hydrocarbon composition of the bitumen from Palaeozoic carbonates in northern Alberta displays molecular evidence for severe levels of biodegradation characterised by the removal of C30–C35 hopanes. Biodegradation is also indicated by the removal of C32 and C33 benzohopanes. The appearance of C31 and C32 25-norbenzohopanes corresponds to the decrease in C32 and C33 benzohopanes, suggesting that 25-norbenzohopanes originate by demethylation of benzohopane counterparts. Demethylation at C-10 in the hopanoids affects a broader class of compounds that so far includes the hopanes and hopanoic acids, as well as the benzylated hopanoid species. 相似文献
13.
《Organic Geochemistry》2012,42(12):1277-1284
Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C21–C25 n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ18O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C23 n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ13C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C23 n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores. 相似文献
14.
Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls 总被引：2，自引：0，他引：2
Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ18O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ18O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO2 and aqueous HCO?3. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ18O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate. 相似文献
15.
Ze Zhang Canfa Wang Xuan Qiu Xianyu Huang Shucheng Xie 《Frontiers of Earth Science》2009,3(3):320-326
Based on gas chromatography and gas chromatography-mass spectrometry analyses, an amazing amount of hopanoids was detected
in the peat deposits in the Dajiuhu National Wetland Park in central China. The hopanoids identified included hopanes (C27-C31 αβ, C27-C32 ββ, C29 βα), hopenes (hop-22(29)-ene, 22,29,30-trinorhop-17(21)-ene, hop-17(21)-ene, hop-13(18)-ene, etc.), hopanoic acids (C31-C34 ββ, C32-C33 βα, C32 αβ), hopanols (C32 ββ and αβ) and hopanone (22,29,30-trinorhop-21-one). C31 αβ-22R hopane was found to be the dominant hopanoid, more abundant than individual nalkanes derived from higher plants. These
hopanoids, exclusive of some hopenes, are proposed to be primarily from bacteria. The dominant C31 αβ-22R hopane in young sediments, without any thermal maturation, might be formed through microbial epimerization under acidic
conditions in the peatland as suggested before, or directly from aerobic bacteria. This finding highlights the importance
of microbes in the formation of peatland as well as in the reconstruction of paleoenvironments. 相似文献
16.
The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ13C values from–6.6 to 1.3‰ and δ18O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ13C from–5.2 to–2.9 and δ18O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ13C from–16.4 to–13.1 and δ18O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ13C from–13.0 to–10.4‰ and δ18O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ18O from 18.7 to 17.6‰ and δ13C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO2. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions. 相似文献
17.
We report the hydrogen isotope ratio 2H/1H (expressed as δ2H values) of 8 selected hopanes, tricyclic and tetracyclic terpanes from oils and source rocks in the Potiguar Basin, and of associated formation water. Hopanes ranged in δ2H value from −79‰ to −142‰, whereas tri- and tetracyclic terpanes (TTTs) ranged from −137‰ to −225‰. Formation water δ2H values ranged from −23‰ to −32‰. The most significant pattern in the data is the systematic 2H enrichment of hopanes relative to TTTs, by an average of 45‰ in oils and 78‰ in source rock extracts. The hopanes appear close to hydrogen isotopic equilibrium with coeval formation water, whereas TTTs are significantly more 2H depleted. Given the similarities in structure between the two compound classes, it is unlikely that hopanes would be exchanged completely while the others would not. More likely, both classes have undergone a limited extent of exchange, but with the hopanes being biosynthesized with δ2H values closer to equilibrium. Our data suggest that at least some primary environmental and/or biotic information can be retained in the δ2H values of biomarkers in oils and extracts, and is not completely obscured by hydrogen exchange. 相似文献
18.
GUAN Hongxiang XU Lanfang WANG Qinxian CHEN Duofu WU Nengyou MAO Shengyi 《《地质学报》英文版》2019,93(1):167-174
Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidization of methane(AOM). Considering that the environmental conditions of the carbonates precipitation and the sources of carbon and organic matter need to be further declared, molecular fossils and compound-specific carbon isotopic investigations of the carbonates were conducted in this study. According to lipid biomarkers of 2,6,10,15,19-pentamethyleicosane(PMI) and squalane diagnostic to methanotrophic archaea, as well as the extremely low δ13C values(as low as -113.4‰) detected in samples JA-4, JA-5 and JX-8, these carbonates were revealed to be a result of AOM. Based on the varied δ13C values of characteristic archaea biomarkers in specific samples, biogenic methane was proposed to be responsible for the formation of samples JA-4 and JA-5, whereas a mixed carbon source of 13C-depleted methane and 13C-enriched residual CO_2 from methanogenesis was suggested for the carbonate of JX-8 due to the co-occurrence of a highly positive δ13 Ccarb value(+8‰) and a moderate 13C depletion of PMI. The low content of AOM-related biomarkers and the absence of indicators for ANME-2 suggested that these carbonates were formed in weak seep settings. By comparison, no typical lipid biomarkers for methanotrophic archaea was detected in carbonate BG-12. The short-chain and long-chain n-alkanes accounted for 30% and 45% of all hydrocarbons, respectively, with a CPI value of 1.2, suggesting that the n-alkanes were derived from both marine organisms and terrestrial inputs. A low thermal maturity could be revealed by the incomplete equilibrium value of the C31αβ 22S/(22S+22R) ratio(0.5), and the carbonate BG-12 was probably deposited in a suboxic condition indicated by a value of Pr/Ph ratio(2.5). 相似文献
19.
The Coalport (Shropshire, U.K.) Tar Tunnel bitumen has been known since 1787 and the first geochemical data are reported here. The bitumen was analyzed for molecular markers useful for correlational studies. Gas chromatographic analysis of aliphatic and aromatic hydrocarbons failed to detect any specific major components normally used for genetic correlational and maturational studies. A search for minor and trace components by gas chromatographic-mass fragmentographic analysis showed the presence of triterpenoid hydrocarbons primarily of the 17α (H)-hopane series (C27 to C35, ex. C28) and a C26 to C31 series of ring A/B demethylated hopanes. Two homologous sterane series (C27 to C29) of the 5α, 14β, 17β (H)-sterane and 13β, 17α (H)-diasterane type were also detected. Pophyrins of the DPEP and etio series (C27 to C41, DPEP/etio > 1) were also found. Characterization of their alkyl substitution pattern demonstrated C1, C2 and C3 substituents on the pyrole moieties of the parent petroporphyrins.The molecular markers detected in this bitumen indicate its biogenic origin and show evidence of diagenetic and geothermal maturation processes. The overall geochemical characteristics of the Coalport Tar Tunnel bitumen suggest that it corresponds to a well matured crude oil, which was heavily altered by in-reservoir biodegradation or close to surface exposure. 相似文献
20.
Ewa Kolaczkowska Nacer-Eddine Slougui David S. Watt Robert E. Maruca J. Michael Moldowan 《Organic Geochemistry》1990,16(4-6)
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