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1.
Within a variety of sedimentary rocks of differing maturity, the configurations of a suite of acyclic isoprenoid acids have been examined by gas Chromatographic (in a few cases also by combined gas chromatography-mass spectrometry) analysis of their diastereoisomeric methyl and (?)-menthyl esters. The samples include the Eocene Messel (Germany) and Green River (U.S.) shales, the Permian Irati shale (Brazil) and a number of Lower Toarcian shales from the Paris Basin. The isomer distributions show that isomerisation occurs at the chiral centres with increasing maturation (to increase the number of isomers) and that the rate of isomerisation increases for centres (C-2,C-3) closest to the carboxyl group. These results suggest that adsorption of the carboxyl group to a catalyst surface may control the isomerisation rates by way of access to the catalyst.  相似文献   

2.
The exchange of aromatic hydrogen in the presence of clay catalysts has been studied by measuring the rates of detritiation of some tritiated naphthalene derivatives on homoionic bentonites. The rate of reaction is influenced by the position of tritium on the ring, the presence of a methoxysubstituent on the ring and the acidity of the clay catalyst. It is inferred that the mechanism of exchange involves an adsorbed species similar to the arenium ion intermediate of electrophilic aromatic substitutions in homogeneous systems. In some cases exchange of hydrogen between acidic clay surfaces and naphthalene derivatives could be detected at temperatures as low as 23°C, and in aqueous slurries at 70°C. This observed reactivity suggests that these reactions could occur in sedimentary environments where organic matter, such as petroleum hydrocarbons, is in contact with clay surfaces. The hydrogen isotopic composition of aromatic hydrogen in petroleum may therefore be related to that of the acidic water adsorbed on clay surfaces with which the petroleum has been in contact.  相似文献   

3.
The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.  相似文献   

4.
The changes in configuration at a number of chiral centres in certain acyclic isoprenoid alkanes, steranes, rearranged steranes and triterpanes of the hopane type in a suite of fourteen Toarcian shales (Paris Basin) have been determined by gas chromatography and combined gas chromatography-mass spectrometry. A sequence of changes in the ratios of various stereoisomers occurs both with increasing maximum depth of burial and in a North-South direction for shallow samples (maximum burial depth < 1000m). These changes cover the full range of maturity shown by the samples. The presence of 5α(H), 14β(H), 17β(H)-steranes in immature samples indicates the presence of a reworked component. The extent of epimerisation at a number of the chiral centres suggests that it relates to the extent of steric hindrance at the centres.  相似文献   

5.
Suspended particulate materials and bottom sediments from the Cariaco Trench were analysed for lipid content to investigate the diagenesis of organic matter in an anoxic water column and sediment. Distributions of fatty acids, sterols, and the acyclic isoprenoid hydrocarbons, lycopane and 2,6,10,15,19-pentamethyleicosane, support the hypothesis that alteration of organic matter usually attributed to sedimentary diagenesis occurs in the water column. Typical indicators of diagenetic processes, including preferential loss of unsaturated fatty acids, increased abundances of branched fatty acids, stenol-to-stanol conversion, and abundant acyclic isoprenoids, were observed in the water column across the oxic/anoxic interface in the Cariaco Trench. Lipid distributions in the sediment were remarkably uniform with depth. We conclude that organic material delivered to the sediment has been extensively altered in the water column, but that which is buried is preserved without much additional alteration.  相似文献   

6.
The D/H ratios of separated size fractions of clay minerals in two deep sea sediments taken from depths of 30 and 1100cm in a North Pacific Ocean core were measured to investigate the extent of hydrogen isotope exchange between detrital clay minerals and sea water. The D/H ratio of each size fraction of the shallower sample was compared with that of the corresponding size fraction of the deeper sample. No differences were detected between D/H ratios of corresponding size fractions from the two levels in the core except for the <0.1μm size fraction, which makes up only 5% of the sample. Even in this size fraction only about 8–28% D/H exchange is apparent. This is interpreted as indicating that no significant hydrogen isotope exchange between clay minerals and sea water has occurred during the past 2–3 Myr. Therefore information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the D/H ratios of deep sea sediments younger than 2–3 Myr.  相似文献   

7.
Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6.  相似文献   

8.
Finely divided samples of the Messel shale that had first been extracted with organic solvents were subjected to pyrolysis at 330°C for 3 days in the presence of excess water or heavy water and also with added pure organic substances. About 8% of the organic carbon was converted into an assemblage of saturated hydrocarbons that closely resembled petroleum hydrocarbons. No olefins were observed in the products. When the reaction was performed in heavy water, extensive deuteration occurred. The extent of substitution and the position of heavy hydrogen in a variety of hydrocarbon structural types were measured by mass spectrometry. A control experiment in which a saturated hydrocarbon was added showed that this deuterium substitution was not due to simple homogeneous exchange.A mechanism for the production of polydeuterated hydrocarbons is advanced, based on a model wherein the molecular fossils that are chemically bonded into kerogen matrix are released as free radicals. During the subsequent chain reactions, migration of olefinic bonds in intermediates and attack by deuterium free radicals result in multiple deuteration with retention of the carbon skeleton of the molecular fossil.  相似文献   

9.
The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity.Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes.  相似文献   

10.
Deuterium-enriched amino acids occur in the Murchison carbonaceous chrondrite. This meteorite underwent a period of aqueous alteration with isotopically light water. With the objective of setting limits on the conditions of aqueous alteration, the exchange of the carbon-bonded hydrogen atoms of amino acids with D2O has been studied from 295 to 380 K as a function of time and meteorite/heavy water ratio. The amount of Murchison or Allende dust present has a significant effect on the rate and amount of hydrogen-deuterium exchange observed. At elevated temperatures, the alpha-hydrogens of all the amino acids studied were found to exchange with deuterium. In glycine and aspartic acid, this process resulted in total exchange of the carbon-bonded hydrogen. A completely deuterated isotopomer of alanine was produced in significant quantities only when the rock/water ratio was greater than 0.5. No exchange of carbon-bonded hydrogens was observed in the case of amino acids which do not possess an alpha-hydrogen atom. The rates of H/D exchange for amino acids observed here did not correspond to deuterium enrichment of the amino acids in the Murchison meteorite. These results suggest that H/D exchange with water had a negligible effect on the observed deuterium enrichment of amino acids found in Murchison and that the temperature at which the amino acids were exposed to liquid water was close to 273 K.  相似文献   

11.
浅析北方红粘土对碳酸盐岩溶蚀作用的影响   总被引：1，自引：0，他引：1  
北方碳酸盐岩发育的红色风化壳大都是第Ⅰ、Ⅱ间冰期湿热气候条件下溶蚀与风化作用的结果,形成硅铝—铁型风化壳。风化壳中红粘土化学成分R_2O_3(Al_2O_3+Fe_2O_3)含量达20—30％。当降水或地表水的垂直下渗、红粘土的氢离子浓度加大,溶蚀性增强,沿红粘土和碳酸盐岩接触面产生溶蚀作用,形成石芽、溶沟、溶槽、溶痕等岩溶地形,并在它们的表面保留有红粘土痕迹。  相似文献   

12.
All ten of the possible five-carbon acyclic primary β-, γ-, and δ-amino alkanoic acids (amino position isomers of the valines) have been positively identified in hot-water extracts of the Murchison meteorite using combined gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography. With the exception of δ-aminovaleric acid, none of these amino acids has been previously reported to occur in meteorites or in any other natural material. The γ-amino acids (4-aminopentanoic acid, 4-aminc-2-meth-ylbutanoic acid, and 4-amino-3-methylbutanoic acid) are present at higher concentrations (about 5 nmol g?1) than are the β-amino isomers (3-aminopentanoic acid, 3-amino-2-methylbutanoic acid, allo-3-amino-2-methylbutanoic acid, 3-amino-3-methylbutanoic acid, 3-amino-2-ethylpropanoic acid, and 3-amino-2,2-dimethylpropanoic acid) which are present at concentrations of 1–2 nmol g?1. These amino acids are less abundant in the meteorite than either the corresponding α-amino acids or the four-carbon homologues. Thirty-six amino acids have now been positively identified in the Murchison meteorite, 17 of which are apparently unique to carbonaceous chondrites. The fact that the meteorite contains all possible five-carbon acyclic primary α-, β-, γ-, and δ-amino alkanoic acids is consistent with a synthetic process involving random combination of single-carbon precursors.  相似文献   

13.
Hydrogen isotopic compositions of individual lipids from Methylococcus capsulatus, an aerobic, methane-oxidizing bacterium, were analyzed by hydrogen isotope-ratio-monitoring gas chromatography-mass spectrometry (GC-MS). The purposes of the study were to measure isotopic fractionation factors between methane, water, and lipids and to examine the biochemical processes that determine the hydrogen isotopic composition of lipids. M. capsulatus was grown in six replicate cultures in which the δD values of methane and water were varied independently. Measurement of concomitant changes in δD values of lipids allowed estimation of the proportion of hydrogen derived from each source and the isotopic fractionation associated with the utilization of each source.All lipids examined, including fatty acids, sterols, and hopanols, derived 31.4 ± 1.7% of their hydrogen from methane. This was apparently true whether the cultures were harvested during exponential or stationary phase. Examination of the relevant biochemical pathways indicates that no hydrogen is transferred directly (with C-H bonds intact) from methane to lipids. Accordingly, we hypothesize that all methane H is oxidized to H2O, which then serves as the H source for all biosynthesis, and that a balance between diffusion of oxygen and water across cell membranes controls the concentration of methane-derived H2O at 31%. Values for αl/w, the isotopic fractionation between lipids and water, were 0.95 for fatty acids and 0.85 for isoprenoid lipids. These fractionations are significantly smaller than those measured in higher plants and algae. Values for αl/m, the isotopic fractionation between lipids and methane, were 0.94 for fatty acids and 0.79 for isoprenoid lipids. Based on these results, we predict that methanotrophs living in seawater and consuming methane with typical δD values will produce fatty acids with δD between −50 and −170‰, and sterols and hopanols with δD between −150 and −270‰.  相似文献   

14.
We investigated the distribution of lipids in Lower Triassic sedimentary rocks (252–247 myr) from South China, including a shallow water microbialite in the uppermost section of the outcrop. Archaeal derived hydrocarbons were the major constituents of the microbialite from the latest Early Triassic. Among these, we detected (i) abundant C40 acyclic and monocyclic biphytanes (possibly derived from glycerol dialkyl glycerol tetraether lipids) and their degradation products, C30–39 pseudohomologues and (ii) a C25 head-to-tail linked (regular) isoprenoid hydrocarbon [possibly derived from dialkyl glycerol diether lipids (DGDs)] and its degradation products, C21–24 pseudohomologues and abundant pristane and phytane. Through combination of compound-specific stable carbon isotope analysis of isoprenoid hydrocarbons, which had average δ13C values of −35‰ to −30‰, and their molecular distribution, it was not possible to unambiguously define the archaeal source for the biphytanes in the microbialite. The δ13C values for pristane and phytane were similar to those for head-to-tail linked C21–25 isoprenoids; potential source organisms for these compounds were halophilic archaea. Except for methane seep microbialites, no other ancient or recent phototrophic microbialites have been reported to contain predominantly archaeal isoprenoid hydrocarbons. Our findings suggest the presence of a new type of microbialite.  相似文献   

15.
潮白河受水区再生水入渗盐污染模拟柱试验   总被引：1，自引：0，他引：1  
根据工程地质勘察及采样测试分析,选取北京市顺义潮白河再生水受水区3种典型代表性土壤介质(砾石含砂、细砂、粉质粘土)装柱,并采用受水区再生水进行淋溶模拟土柱试验。测试结果分析表明,在3种典型土壤介质中,阳离子交换吸附作用主要体现为K+与Ca2+之间的交换,且粉质粘土柱中阳离子的离子交换作用较砾石含砂柱和细砂柱更为显著。另外,试验结果还表明,随着土壤介质中粘粒含量、总有机碳含量、阳离子交换容量和粘土矿物总量的增加,典型介质淋溶模拟土柱试验中阳离子交换作用达到平衡时所需要的时间也就越长,分别为砾石含砂72 d、细砂80 d和粉质粘土86 d。定量结果计算也证明：粉质粘土介质的各阴、阳离子本底含量最高,单位质量粉质粘土介质硬度及溶解性总固体(TDS)的贡献量最大,分别为5 767 mg/g和6 952 mg/g。  相似文献   

16.
Diamondoids are hydrocarbons with a carbon skeleton that is superimposable on the diamond lattice. Adamantane is the cage-shaped primary unit of diamondoids and occurs widely in sediments and petroleum. The first report of adamantane isolated from petroleum extends back seven decades, but the precursors and reaction mechanisms for the formation of adamantane and related diamondoids in sediments has remained unclear. We report the formation of alkyl adamantanes by heating β-ionone with activated carbon in closed system pyrolysis experiments in the range 170-320 °C. In addition, hydrogen exchange, demethylation, methyl transfer and isomerisation reactions were observed when the model compounds adamantane and 1,3-dimethyladamantane were heated at moderate temperature with activated carbon. A reaction pathway for the formation and reactions of alkyl adamantanes is proposed on the basis of ring isomerisation of adamantane to protoadamantane on the activated carbon surface. The carbonaceous surface reactions described help account for the occurrence and distribution of alkyl adamantanes in petroleum basins, as evidenced by the strong linear relationships between compound pairs related by isomerisation and demethylation for a set of crude oils from the Carnarvon Basin, Western Australia.  相似文献   

17.
基于全耦合的地表径流与土壤水分运动数值模拟   总被引：2，自引：0，他引：2       下载免费PDF全文
针对降雨径流从坡面流下的过程中会发生下渗,导致土壤水非饱和带含水率增大这一动力学过程,从物理机制上对土壤水和地表水进行耦合,将二维平面地表水模型叠置在土壤水模型的顶部,对土壤水、地表水模型进行相同的空间和时间离散,在模型的计算过程中通过达西流关系对两者之间的水量交换进行计算(双层结点法耦合)或整合离散方程的整体法进行耦合。通过对两种耦合方法的比较以及与前人的实验结果对比,该模型与耦合方法能够准确地模拟和预测地表径流与土壤水分运动过程。研究结果可为分析地表水流与饱和-非饱和带水分与溶质耦合机理提供理论支持。  相似文献   

18.
In the geochemical study of sedimentation, hydrogen and oxygen isotope data are useful for a discussionon formation conditions and material sources of sediments. Hydrogen and oxygen isotope analyses were madeon clays separated from the sea-floor surface sediments at 9 stations in the western sea region of the AntarcticPeninsula. On the basis of these isotopic data and the clay mineral components and by use of statistical dia-grams, it may be concluded that the clay fraction in this sea region is composed mainly of terrigenous detritus:i.e. it was formed by surface weathering or supergene alteration of the rocks from the terrigenous region in thepeninsular in the presence of meteoric water. However, at least a part of montmorillonite is a marine authigenicmineral formed by alteration of submarine eruptive materials or terrigenous pyroclasts in the presence of seawater. The above result is consistent with the idea derived from the study of clay mineralogy.  相似文献   

19.
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   

20.
钱雅倩  郭吉保 《地学前缘》1998,5(2):251-260
矿物水体系氢同位素平衡分馏系数和动力分馏系数是同位素地球化学研究中的重要参数。这些参数大多由实验测定。氢同位素分馏的实验研究主要包括矿物水体系氢同位素交换实验,交换实验前后矿物、水的氢同位素分析及分馏机理、平衡分馏、动力分馏理论研究。为确保氢同位素分馏系数和一系列动力学参数的准确可靠,实验中防止氢透过容器壁扩散,避免空气中水汽污染样品,正确控制实验温度等都很重要。本研究以石英管代替前人常用的金（银、铂）管作反应容器,建立了一套实验研究羟基矿物水体系氢同位素平衡分馏和动力分馏的新方法,并开展了电气石水、黑柱石水体系氢同位素分馏的实验研究。所得一系列参数的精度明显好于国外报道的资料。此研究方法可广泛应用于羟基矿物水体系的氢同位素分馏的实验研究。  相似文献   

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