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1.
The distribution patterns of Organic Sulphur Compounds (OSC), occurring in certain sediments and immature crude oils, were compared with those of the corresponding hydrocarbons. Because of the complexity of the OSC mixtures, they were desulphurized to hydrocarbons (n-alkanes, isoprenoid alkanes, steranes, triterpanes and branched alkanes). The hydrocarbons produced by desulphurization of the OSC exhibited distribution patterns different from those of the hydrocarbons originally present. Therefore reaction of elemental sulphur with these hydrocarbons at elevated temperatures must be considered as an unlikely origin for these OSC. Sulphur incorporation reactions on an intramolecular basis with suitable functionalized precursors at the early stages of diagenesis are probably the major origin for these OSc. Desulphurization of high molecular weight fractions also produced hydrocarbons, dominated by n-alkanes up to C40. Therefore it is assumed that these substances contain n-alkanes, 2,5-dialkyl-thiophenes and -thiolanes linked to each other by sulphur briddges. These findings stronly suggest that sulphur-containing high molecular weight substances are formed by the same sulphur incorporation reactions as OSC, but in an intermolecular fashion.  相似文献   

2.
Three sulphur-rich commercial crude oils have been studied, which contain sulphur as high as up to 4–12%. These samples were collected from Tertiary hypersaline lake sediments of the Jianghan Basin, Hubei Province at different depths, but above the oil generation threshold (2200m). FPD-GC and GC-MS data show that aromatic fractions of the crude oils are composed of different homologues of sulphur-containing compounds, including long-chain normal alkyl-thiophenes and-thiolanes, long-chain isoprenoid-thiophenes and -thiolanes, and benzothiophenes. It is worth noting that the distribution patterns of long-chain alkyl-thiophenes and -thiolanes from two shallow-seated crude oils are quite similar to those of normal alkanes showing marked even-odd predominance. It seems that the even-odd predominance of sulphur-containing compounds decreases with increasing burial depth of the crude oils. The major component of aliphatic fraction is phytane, and similarly the major peaks of aromatic fractions also represent C20 isoprenoid thiophenes. Some preliminary conclusions have been drawn from the above discussion: (1) Abundant sulphur-containing compounds may be used as an indicator of low mature or immature crude oils produced from hypersaline lake sediments; (2) Sulphur-containing compounds are considered to be early diagenetic products of reactions between elemental sulphur or sulfides and alkanes or their precursors (phytols, fatty acids, alcohols, etc.), or of bacterial activities, but not direct inputs of organisms.  相似文献   

3.
The lipid fraction extracted from uninfected shoots of a fossil conifer, Frenelopsis alata, was analysed by gas-chromatography–mass-spectrometry, and compared with shoots of the same conifer infected by extinct epiphyllous fungi, so as to study the effects of fungal infection on the chemical composition of extracts from higher plant remains. The extracts from the uninfected shoots appeared to be composed of (i) common constituents of higher plant lipids such as n-alkanes and fatty acids, (ii) elemental sulphur, and (iii) substantial amounts of terpenoids characteristic of conifers, such as cadalene, beyerane, dehydroabietane and related compounds. Comparison of this extract with that of fungal-infected shoots revealed, in addition to the aforementioned compounds, the presence of substantial amounts of hydroxysuccinic acid and functionalised benzoic compounds that were interpreted as degradation products of lignin by fungi. This study afforded preliminary indications of the composition of extracts from higher plant remains infected by fungi.  相似文献   

4.
Monocyclic alkanes in Ordovician organic matter   总被引：1，自引：0，他引：1  
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   

5.
A series of novel long-chain 3,4-dialkylthiophenes (C36–C54) was identified in a number of sediments ranging from Pleistocene to Cretaceous. The identifications were based on mass spectral characterisation, desulphurisation and mass spectral data of synthesised model compounds. These organic sulphur compounds are probably formed by sulphur incorporation into mid-chain dimethylalkadienes with two methylenic double bonds. These putative precursor lipids are unprecedented and may be considered rather unusual. The distribution of 3,4-dialkylthiophenes in sediments varies considerably with the depositional palaeoenvironment, indicating that these compounds have a potential as molecular markers reflecting changes in palaeoenvironment.  相似文献   

6.
Samples of the Mt Isa formation (Australia, c, 1.5 Ga), and the Shungit formation (U.S.S.R., c. 2.3 Ga) were studied by organic geochemical means. All samples were freed of any low-molecular-weight solvent soluble organic material in order to insure the authenticity of the analysed material. The isolation of biochemical compounds entrapped in sulfides was the major goal of this work.Organic compounds that were entrapped during the early stages of sulfide formation may obviously survive extended periods of time and can be released by a mild hydrogenation of the sulfides. Preliminary investigations of the hydrocarbon fraction indicate n-alkanes, monomethylalkanes, cycloalkanes, and an unknown series of branched alkanes as major constituents. Their distribution patterns show great selectivity with respect to structures and chain lengths of individual compounds. Differences between the hydrogenation reaction product and the sample extract may arise from the release of a different kind of lipid material through dissolution of the sulfides.  相似文献   

7.
A Pliocene oil shale (Pula, Hungary), a C3 plant Triticum aestivum and a C4 plant Zea mays were compared using isotopic composition of bulk organic matter, along with distributions and individual carbon isotope ratios of n-alkanes from organic extracts. The microalga Botryococcus braunii (A race) was thus shown to be the main source of the predominant 27, 29 and 31 n-alkanes of Pula sediment Therefore, the dominance of odd carbon-numbered n-alkanes in the range C25–35 in extracts from immature sediments shall not be systematically assigned to higher plant contribution but algal input is also possible. In fact, the long chain n-alkanes with an odd predominance previously observed in extracts of various immature sediments are likely to be derived at least partially, from algae.  相似文献   

8.
Isotopic analysis by compound specific gas chromatography–isotope ratio mass spectrometry (GC–IRMS) is used to detect and characterize petroleum pollution in surficial sediments along the St Lawrence River, near Quebec City. Unusually mature n-alkane distributions have been found in some recent intertidal sediments in the region. GC–IRMS results suggest that the n-alkanes are not derived from indigenous organic sources because they carry δ13C values between −30.0 and −27.0‰, as well as very small isotopic differences between odd and even numbered n-alkanes, which are both typically associated with petroleum products. Comparison of these sediments with bunker fuel, an oil used in the shipping industry, has shown a close isotopic correlation in some sites, which is further supported by biomarkers. Overall, the contamination has been dispersed along the river but is generally localized around the industrial region where hydrocarbon transfer from shore storage to ships takes place. This study illustrates how GC–IRMS can be used effectively in the detection and characterization of petroleum pollutants in sediments.  相似文献   

9.
The geochemical composition of lake bed sediments of a tropical reservoir in Brazil have been investigated. The C, N, P composition showed almost no variation between the different sampling points. All samples contained inorganic phosphorus (IP) ranging from 52 to 70%. The Redfield ratios show that the lake is without significant anthropogenic inputs. Most of the organic matter is composed by higher plants decomposition revealed in the total organic carbon (TOC):nitrogen (N) ratio ranging from 15.4 to 57.2. Also, TOC:organic phosphorus (OP) ranged from 265.3 to 933.6, suggesting that most of the organic matter has terrestrial origin from wood plants. The ratios suggest that most organic matter is influenced by the terrestrial characteristics of the watershed. Furthermore, the relative abundance of n-alkane homologues in the sediments was investigated. All samples have been analyzed for the n-alkanes C8 to C40. The sediments were dominated by n-alkanes C25–C38. It is concluded that n-alkane in sediments mainly come from terrestrial plants, however there is a contribution of submerged aquatic plants, especially in those sites in deeper areas of the lake. On the basis of Paq index the n-alkanes in sediments comes from terrestrial plants, however there is a contribution from emerged/floating plants.The investigated lake seems to be considered as meso to eutrophic. Because of the relatively high primary productivity in the lakes, there is a substantial organic-matter flux to the sediments, which rapidly becomes anoxic. According to the pristine/phytane ratio the sediments represent an anoxic environment with values found between 0.38 and 1.72.  相似文献   

10.
Carbon Preference Index (CPI values) of higher plant-derived long-chain n-alkanes extracted from 62 surface soil samples in eastern China exhibited a specific pattern of variations, namely gradual increase with the increasing latitudes. Such regular variations existed in both forest soil and grassland soil. Our data implied that CPI values of higher plant-derived long-chain n-alkanes had a certain connection with climatic conditions, and such a connection was not influenced by vegetation types. Together with previous data from marine sediments, loess/paleosol sequences, tertiary red clay and modern plants, our observation made us conclude that CPI values of higher plant-derived long-chain n-alkanes may be used as an excellent proxy for paleoclimatic studies.  相似文献   

11.
Biomarker distributions based on GC and GC-MS data supplemented by stable carbon isotopic compositions based on irm (isotope ratio monitoring) GC-MS data have been used to investigate changes in depositional conditions in a number of samples from a 2 m core (Rheinberger Heide) covering the entire deposition of the Permian Kupferschiefer (Lower Rhine Basin, northwest Germany). Compound classes investigated are aliphatic and aromatic hydrocarbons and maleimides (1H-pyrrole-2,5-diones). The core has been previously divided into four sections: TI, TIIA, TIIB and TIII based on lithology. The biomarker distributions and the δ13C values of components indicate contributions from cyanobacteria, algae, green sulphur bacteria and higher plants (minor) throughout Kupferschiefer deposition. All of the phytoplanktonic components show 13C enrichment in the lowest section, suggesting a greater productivity. The occurrence of components derived from green sulphur bacteria (Chlorobiaceae) indicates that the entire deposition was characterised by periods of photic zone anoxia. Such conditions were rapidly established after the initial transgression of the Zechstein Sea and may have been productivity-driven, but were less prevalent during deposition of the upper core sections.  相似文献   

12.
2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)-pentadeca-2,5E,9E,13-tetraene I possessing a C25 highly branched isoprenoid skeleton has been isolated from the marine diatom Rhizosolenia setigera and identified by 1H and 13C NMR spectroscopy.  相似文献   

13.
The abundances and distribution patterns of mono-, di- and trimethylated 2-methyl-2-(4,8,12-trimethyltridecyl) chromans (MTTCs) and long-chain alkylbenzenes in extracts of marl (66 samples), anhydrite (15) and halite (1) strata of the Salt IV Formation of the Oligocene Mulhouse Basin are reported. The distributions of the methylated MTTCs indicate salinity changes of the upper part of a density stratified water column of the basin. These variations are explained by a tectonically or climatically induced change in the supply of water of relative lower salinity to form a layer overlying the deeper water brine. Hence, it is suggested that mesohaline (3.5–15%) conditions in the surface waters were established as a result of periodic incursions of marine water and subsequent evaporation. Conversely, during periods when the surface water was derived mainly from fresh water from the hinterland, lower average salinity in the surface layer resulted. The distributions of long-chain alkylbenzenes also appear to record these changes.  相似文献   

14.
深入研究了与朱家庄自然硫矿共生之硫磺沥青的生物标志物组成,检出了两个新化合物--GX与C33含硫藿烷。分子有机地化特征表明,硫的再聚集与成岩早期阶段膏盐相生油岩相中有机质的还原作用和细菌活动有关,自然硫矿可能属成岩之层控矿床。  相似文献   

15.
The diagnosis of Estherites corrugatus from the basal part of the Coniacian Second Member of the Nenjiang Formation in Nenjiang County, north-east China is revised following the application of a new preparation technique to some of the carapaces and an examination of specimens under a scanning electron microscope, both of which revealed morphological features on the carapace that had not been recognized previously. Restudy of the type species of the two subgenera Estherites (Euestherites) and Estherites (Parestherites) also revealed details of carapace features not seen hitherto. These indicate that they should be separated from Estherites. As a result, Euestherites is upgraded to genus level and Parestherites is placed in synonymy. The importance of Estherites and Euestherites is considered in the context of Late Cretaceous assemblages of these crustaceans and the three conchostracan provinces (South-West, South-East and North China) that are recognized to have been present in China during the Turonian–Santonian period.  相似文献   

16.
Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C16–C29 range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.  相似文献   

17.
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18.
The elastic properties of coexisting natural 3T and 2M 1 phengite samples (Cima Pal, Sesia Zone; Val Savenca; Western Alps, Italy) with similar chemical compositions have been studied by room temperature–high pressure powder diffraction, using synchrotron radiation on the ID9A beam-line at ESRF (Grenoble, France). The P–V curves have been modelled by the Birch–Murnaghan model; a third-order expansion fitted to the experimental data yields for 3T and 2M 1 K 0=60.4(±0.7) GPa, K′=5.79(±0.11) at V 0=703.8851 Å3, and K 0=57.3(±1.0) GPa, K′=6.97(±0.24) at V 0=938.8815 Å3, respectively. The relative stability of 3T vs. 2M 1 has been explored as a function of pressure and temperature in terms of configuration and deformation contributions to the Gibbs energy, using the elastic properties determined here and other thermodynamic parameters from earlier investigations. The results presented agree with the hypothesis of stability of the 3T polytype in the high pressure regime.  相似文献   

19.
Summary. Hydromechanical experiments have been carried out since 1997 within a small fractured calcareous rock mass in southeastern France, at a site called Coaraze. Simultaneous measurements of fluid pressure and joint displacement were performed during these experiments. The interpretation generated has led to characterizing various types of hydromechanical behavior of the jointed rock mass and has provided several lessons. An original analytical interpretation, coupled with a modeling approach, has allowed one to derive the in situ normal joint stiffness, which proves to be highly non-linear. It has been shown that a coefficient able to take into account stiffness contribution from the surrounding rock mass must be included in order to fully interpret the pressure-displacement curves. This analytical interpretation also yields an estimate of the normal stress across the fracture. A comparison between in situ data and laboratory tests is also presented.  相似文献   

20.
A part of the IUGS-UNESCO research project "Landslide Hazard Assessment and Cultural Heritage" (IGCP-Project No. 425) includes testing the application of geophysical methods for assessing hazard risks to people and cultural assets. In this work, Austria contributed with a study on the assessment of rock-fall hazards. As the Old Town of Salzburg is a prime example of such hazards, systematic GPR-measurements were made on major rock surfaces. The aim of the exploration with GPR was to assess the potential of the method for monitoring rock walls. That is, whether structures in the rock mass which could become important when considering the risk of a rock fall, can be imaged. To manage this problem successfully, moving the antenna over the rough rock surface was made as regular as possible. The effects of vegetation lifting the antenna from the rock surface and of overhanging regions could not be avoided. Due to the loss of coupling of the antenna and the change of radiation pattern, some interference of the records occurred. Thus, only after processing could it become clear which reflections came from within the rock. A three-dimensional survey of discontinuities in the rock requires accurate mapping of the rock surface by photogrammetric methods, to get a digital terrain model for the analysis of the GPR records. The results of repeated measurements have proved to be of essential relevance. They have shown that it is possible to reveal changes with time. For the interpretation of such observations, modeling is a very useful tool.  相似文献   

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