首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 62 毫秒
1.
The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C29 5α(H), 14α(H), 17α(H) normal-steranes and the C29 iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.  相似文献   

2.
A series of tricyclic terpenoid carboxylic acids (C20–C40) was found in the acidic fraction of Tasmanian tasmanite bitumen, occurring as a mixture of stereoisomers with mainly the 13β(H), 14α(H)-and 13α(H),14α(H)-configurations. These dominant acidic tricyclic constituents have the same carbon skeleton as the ubiquitous tricyclic terpane biomarkers. A novel series of ring-C monoaromatic tricyclic terpenoid carboxylic acids was also characterized. The series ranges from C19 to C39 and is the acidic counterpart of the recently described series of monoaromatic tricyclic terpanes.  相似文献   

3.
A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C29 steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (Ro). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.  相似文献   

4.
A tetradeuteriated cholestane was heated with kerogen isolated from the Messel oil shale at 350 °C for 25 different time periods (ranging from 0.5 to 80 h) in borosilicate vessels. Three isomers of tetradeuteriated dimethylperhydrophenanthrene were formed and one of these was the major saturated hydrocarbon product under most conditions. The stereochemistry for these isomers was unknown but if the stable 5α,8β,9α(H),10β(CH3) sterane configuration is inherited from the cholestane then there are four possible isomers namely: I and II [13β(H) and 13α(H) diastereomers, respectively, of 10,13-dimethylperhydrophenanthrene] as well as III and IV [14β(H) and 14α(H) diastereomers, respectively, of 10,14-dimethylperhydrophenanthrene]. Molecular mechanics revealed that I is the most stable form and therefore is the component that dominated the saturated hydrocarbon degradation products. The identification of only three isomers of deuteriated dimethylperhydrophenanthrene in the pyrolysis experiments is supported by the calculated stabilities (ΔΔG) as isomer IV is considerably more unstable (by 1.7 kcal/mol) than II which is the least stable of I, II and III. If these compounds can be detected in crude oils their distributions may be useful maturity indicators in oils that have been generated at high thermal maturity.  相似文献   

5.
Molecular markers have considerable promise as thermal maturation indicators in source rocks having a well-defined depositional environment. This occurs in the Kishenehn Formation (northwest Montana and southeast British Columbia), an Oligocene unit comprised of fluvial and lacustrine shales. Up to 3 km of these non-marine sediments were deposited in a 900 sq.km elongated half graben atop the Precambrian rocks of the Lewis Thrust sheet. Specific outcrops of the Coal Creek Member of the Kishenehn Formation are known to contain excellent potential source rocks, including extensive oil shales. The source rock potential and molecular marker geochemistry of most of the major Kishenehn outcrops have now been investigated, and regional results are presented in this paper.source rock analysis of a regional suite of Kishenehn samples indicates excellent petroleum potential (immature Type I kerogen) throughout the basin. Several classes of distinctive diagenetic molecular markers occur within the Coal Creek Member of the Kishenehn Formation, including diasterenes, spirosterenes, methylspirosterenes, B-ring monoaromatic anthrasteroids, ββ-hopanes and moretanes. Molecular markers indicative of non-marine deposition include dehydroabietane (conifer input) and an onocerane recently identified in leaf fossils of Miocene lacustrine beds in adjacent Idaho. Triterpane ratios are significantly more sensitive than vitrinite reflectance methods in assessing thermal maturation in the Kishenehn, and are successfully used in this study to order outcrop locations according to thermal maturity level. The systematic variation of specific markers with increasing thermal maturation suggests that molecular correlation is feasible, and could provide a method of assessing stratigraphic continuity in the basin.  相似文献   

6.
Mixtures of hopane diastereomers obtained by fractionation of the organic extract from an immature oil shale have been heated in the presence of clay-containing substrates. In experiments conducted at 250°C with an extracted source rock as the substrate, the relative amounts of 17β(H),21β (H)-hopanes were found to decrease with respect to the moretanes and 17α(H),21β(H)-hopanes in a manner parallelling that observed with increasing maturity in sediments. In this case however, the change was shown to be due to the selective removal of the 17β(H),21β(H)-hopanes, rather than conversion of these compounds into the other diastereomers. In order to assess whether the use of elevated temperatures was enhancing processes other than those which operate in natural systems, a second experiment was conducted in which the sample of immature hopanes was heated at 75°C with the very catalytically active substrate aluminum montmorillonite. In this experiment also, the changes in hopane composition was shown to be due to selective removal of 17β(H),21β(H)-hopanes rather than conversion into the corresponding compounds in the other two series of diastereomers. These results suggest that the observed relative depletion of 17β(H),21β(H)-hopanes in sedimentary rocks of increasing maturity may similarly be due to removal by selective catalytic processes, and not to interconversion processes associated with isomerisation at C-17 and C-21 as had previously been believed.  相似文献   

7.
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   

8.
The kinetics of the aromatisation of both rearranged and non-rearranged monoaromatics have been investigated in the laboratory under free radical conditions. These studies have indicated that the aromatisation rate constant for the non-rearranged is greater than that for the rearranged isomers at any one particular temperature. Since the members of the rearranged series coelute with their non-rearranged counterparts when both series are present in geological extracts, these results suggest that care needs to be exercised when assessing extents of maturation using monoaromatic and triaromatic steroid hydrocarbons.  相似文献   

9.
Since many immature oils have been found in a number of Tertiary basins of China, a series of cores (Oligocene) and several immature rocks after thermal simulation have been investigated for their biomarker distributions by GC and GC-MS. The presence of biomarkers in the cores seem to follow a rule of less to greater stability of hopenes, ββ-hopanes, diasterenes with increasing the depth of cores, and subsequently the 22R, 22S configuration of hopanes reaches equilibrium. The thermal simulation experiments with immature rocks demonstrated that it is possible to generate some immature oils from immature rocks during the diagenesis stage. The tricyclic terpanes generated from source rocks during diagenesis stage tended to be enriched in the oils compared to their source rocks and the relative abundance of lower molecular weight tricyclic terpanes to their higher molecular weight homologues may be useful for the subdivision of diagenesis.  相似文献   

10.
A novel series of 3-alkyl and 3-carboxyalkyl-5β(H)-steranes 7–10 along with a full homologous series of carboxyalkyl-sterane (C1 to C6) 4–6 with 3α(H)5α(H) configuration have been identified in marine-evaporitic oils from Fazenda Belém, Potiguar Basin (Brazil) on the basis of mass spectral interpretation. The synthesis of enantiomerically pure 3α-alkyl-5β(H)-cholestane and 3β-alkyl-5α(H)-cholestane standards and their coinjection with petroleum fractions confirmed the structural assignments.  相似文献   

11.
Core samples were collected in Lagoa Vermelha, a hypersaline lagoon located about 100 km east of Rio de Janeiro (Brazil). The sediment composition is predominantly carbonate in amounts up to 93%. Analysis of δ13C of the total organic matter in the sediments showed that marine organic matter predominates throughout the core (δ13C ranges from −15.84 to −22.64‰ vs. PDB). Organic carbon contents (TOC) ranged from 0.81 to 13.28%. A series of cadinane-type sesquiterpenoids can be recognized in the gas chromatography-mass spectrometry data. Essentially the same components are present in all the samples, with variations only in their relative abundances. The most abundant compounds are α- and β-cubebene, α- and β-cedrene, cadinenes (different isomers), α-curcumene and calamenene, with minor amounts of calarene, humulene, calacorene and cadalene. Since this lagoon is surrounded by dunes with only minor vegetation typical of this environment (grasses, small non-resinous shrubs and no forest) with no potential source for sesquiterpenoids, a terrestrial origin for these compounds is excluded and an algal origin is more consistent with the locale and the recognition of sesquiterpenoids (including cadinol) in microbial mats from the lagoon. Only the natural product precursor sesquiterpenoids are present in the microbial mats with no detectable diagenetic derivatives (e.g. calamenene and cadalene). This indicates that the compounds in the mats are from recent input and those found in the sediments are most likely derived from former algal biomass in this lagoon, a fact confirmed by the recognition of a series of diagenetic aromatic components in the sediments. Surface sediments contain n-alkanes with no even-to-odd predominance indicating that microbial activity is higher in shallower sediments. Moreover, mass fragmentograms (m/z 191) of biomarkers revealed the presence of 17α(H),21β(H)-hopanes, the mature isomers, together with their ββ precursors and low amounts of the intermediates with the βα configuration (moretanes). This indicates a contribution of mature organic matter to these immature sediments.  相似文献   

12.
Acid-catalysed alkyl hydrogen exchange and configurational isomerisation has been studied in a series of acyclic isoprenoid acids when they were heated at 160°C in the presence of a montmorillonite. Hydrogen exchange occurred between the adsorbed water of the clay surface and the a position of the isoprenoid acids. In cases where this position was chiral, exchange was accompanied by configurational isomerisation. Configurational isomerisation occurred more slowly in experiments conducted without a clay matrix in the presence of water. These results have been rationalized in terms of a reaction mechanism involving protonation of the carbonyl oxygen causing enolization and consequent hydrogen exchange at the a position of the acids. This mechanism was used to account for the relatively fast rate of isomerisation of C-2 chiral centres in sedimentary acyclic isoprenoid acids during maturation.  相似文献   

13.
The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c27-c29 diasteranes [13β(H),17α(H); 20R + S] and C28-C29 regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C27-C29 regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.  相似文献   

14.
The distribution of ring-C monoaromatic and triaromatic steroid hydrocarbons of about fifty crude oils and sediments of various origins and ages were studied in order to test their validity as geochemical source and maturity parameters. Three ratios appeared to be useful maturity parameters, i.e. A/B cis to trans isomers in non-rearranged monoaromatics, mono/triaromatics and shortvs long-chain homologues. Four other variations may be considered as source parameters depending upon lithology or other palaeo-environmental conditions, i.e. rearranged vs non-rearranged monoaromatics, 5β/5α -methyl rearranged monoaromatics, carbon number distribution and occurrence of a yet unknown series of methylated triaromatic steroids. 5α-Methyl rearranged monoaromatics seem to be particularly important in anhydrites from sabkha environments. Recent identification of most aromatic steroid constituents occurring in geological samples confers on this class of compounds an increasing value as correlation parameters in geochemical studies.  相似文献   

15.
  相似文献   

16.
Recent sediments from Bransfield Strait, Antarctica have been analyzed for triterpenoid and steroid hydrocarbons, sterols and steroid ketones to consider the effects of hydrothermal fluids on the sedimentary organic matter. The steroid distributions in unaltered and altered sediments are controlled more by inputs from source organisms than by the effects of hydrothermal activity, which is suggested to be limited to low temperature alteration. Nevertheless, chemical reactions occurred in altered sediments and include dehydration of sterols to sterenes, isomerization of triterpenes and sterenes, rearrangement of sterenes to diasterenes and reductive processes leading to generation of phytane from phytol via phytenes.  相似文献   

17.
Molecular mechanics calculations of rearranged cholestenes revealed that diacholest-13(17)-enes with 10α stereochemistry are more stable than their 10β counterparts and that a partly rearranged sterene with a Δ8 double bond and 10β, 14β stereochemistry (compound 7) is relatively stable at thermodynamic equilibrium. The calculated data are in good agreement with sedimentary and experimental data and thus reinforce recent propositions for early-stage diagenesis of steroids.  相似文献   

18.
19-Norisopimarane and isopimarane have been synthesized from isopimara-9(11), 15-diene-3β, 19-diol. Analysis of the alkane fractions of an Australian crude oil by GC-MS showed the presence of nine diterpenoid hydrocarbons (diterpanes), of which one was bicyclic two were tricyclic and six were tetracyclic.19-Norisopimarane and isopimarane were identified by comparison of their mass spectra and GC retention times with those of the synthetic standards. ent-Beyerane, 16a(H)-phyllocladane, 16)β(H)-phyllocladane, ent-16α(H)-kaurane and labdane were also identified by comparison with authentic reference compounds. The remaining two compounds were tentatively identified as rimuane and as a 17-nortetracyclic diterpane on the basis of mass spectral evidence. The diterpanes are probably derived from conifer resins.  相似文献   

19.
A suite of samples from the Funan Mine, N.E. China, has allowed a comparison to be made between hydrocarbon-rich coals and coaly shales. These are immature coals and the known geological history suggests that they have experienced only a mild geothermal history. Analyses of the di- and sesquiterpenoid components show that compounds based on the kaurane skeleton are absent unlike Australian brown coals; and the diterpenes isopimarane, pimarane and 16α (H)-phyllocladane relate to a different community of higher plants such as Pinaceae and Taxodiaceae from those recognized in Australian brown coals. A consideration of geochimical parameters and biomarker composition leads to the conclusion that the geolipid concentrations in the sample suite are environmentally determined. It is concluded, therefore, that 22R-17β (H),21β (H)-bishomohopanoic acid and the 22R-17α (H),21β (H)-homohopane, both predominant components in their respective classes, are derived from different sources. Labdanic acids have been identified in these coals. They are likely to be derived from resin constituents of the coal and not from microbial biomass. They could potentially be developed as a maturation parameter. Cis and trans isomers of a triaromatic hydrocarbon based on the oleanane skeleton which has been previously identified in Victorian brown coal are present in the Funan coals. The more oxidizing the environment the less advanced is the isomerization of cis to trans and again the environment of deposition is the controlling factor. This study emphasizes the importance of understanding pathways of early diagenesis for the interpretation of data derived from more mature samples.  相似文献   

20.
This study provides information on non-aromatic hydrocarbons contained in thick Palaeogene halite sequences in the Bresse region (France). The presence of almost uniquely biological markers and the absence of thermogenic compounds denote the low maturity of the corresponding samples consistent with Rock-Eval pyrolysis data. The distribution of n-alkanes enables the distinction of three main biological signatures: algal (mode in nC17–nC18); terrestrial (mode in nC29–nC31) and bacterial (mode in nC25–nC26 with no odd-even carbon number predominance). As to the cyclic biomarkers, hopanes and hopenes are largely predominant over steranes and diasterenes in samples having received appreciable amounts of terrestrial inputs (Type B) and conversely for the samples containing high proportions of algal debris (Type A, Type C).  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号