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1.
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 DEcis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.  相似文献   

2.
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   

3.
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   

4.
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   

5.
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   

6.
Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.  相似文献   

7.
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   

8.
Siliceous sourced Tertiary oils from the Circum-Pacific area of Japan, Russia and the U.S.A. have a heavy carbon isotope composition, monomodal n-alkane distributions, and nearly identical regular sterane compositions with a predominance of C27 homologues. These are consistent with open marine depositional environments dominated by diatomaceous organic matter. However, a number of alkane and biomarker parameters such as Pr/Ph, CPI, relative concentration of 28,30-bisnorhopane, and the C35/C34 homohopane ratio indicate more oxic depositional environments for the source rocks of Japan and Russia. In contrast to the California Monterey Formation sourced oils, petroleums with low maturity levels from the North Sakhalin basin, Russia and the Akita basin, Japan have lower concentrations of asphaltenes and sulphur and are characterized by higher API gravities. A correlation of extractable organic matter from source rocks vs the least matured petroleums demonstrates that oil expulsion in siliceous shales of the Akita basin occurs at a maturity level corresponding to Ro≥0.65%, which is in the range of the conventional oil window (Ro = 0.6−1.1%).  相似文献   

9.
China has a number of petroliferous lacustrine sedimentary basins of varying salinity and age (mainly Eocene). A geochemical investigation has been undertaken on several oils and source rocks from the Eocene lacustrine Biyang Basin. The distributions of n-alkanes, isoprenoids, steranes, and terpanes have been studied and used to characterize the sedimentary environment of deposition, maturity, biodegradation and undertake possible correlations. The ratios of C30-hopane/gammacerane, 4-methyl-steranes/regular steranes, steranes/hopanes, C21 tricyclic/C30 hopane are proposed to be indicative of the depositional environment whereas ß-carotane appears to be a source related indicator. The geochemical data obtained in this study suggest that the major source rocks in the Biyang Basin were deposited in a saline/hypersaline depositional environment.  相似文献   

10.
各类生物标志物的组成特征表明:柴达木盆地北缘的冷湖油田原油具有姥植比高(Pr/Ph>2.0),重排甾烷(C27重排甾烷/规则甾烷=0.5~0.7)、重排藿烷(diaC30H/C30H=0.2~0.4)和新藿烷(C29Ts/C29H=0.4~0.7)含量中等,伽马蜡烷含量低(伽马蜡烷指数<0.05)的特征,它们源于该地区发育的下侏罗统淡水湖沼相烃源岩;而柴西北区咸水湖相原油的姥植比低(Pr/Ph<0.8),重排甾烷(C27重排甾烷/规则甾烷<0.1)、重排藿烷(diaC30H/C30H<0.05)和新藿烷(C29Ts/C29H=0.2~0.4)含量低和伽马蜡烷含量高(伽马蜡烷指数=0.4~0.8),这一系列特征与柴西地区发育的古近系-新近系咸水湖相烃源岩一致。但是,东坪地区原油呈现完全不同的生物标志物组合,主要表现为丰富的伽马蜡烷(伽马蜡烷指数=1.2~3.0)与高含量的新藿烷(C29Ts/C29H>1.5)、重排藿烷(diaC30H/C30H>0.7)和重排甾烷(C27重排甾烷/规则甾烷>0.4)并存,这与地质样品中伽马蜡烷和重排类标志物的分布特征相矛盾,因为依据现有的认识无法解释这一特殊地球化学现象。生物标志物组成特征表明东坪地区原油所具有的特殊生物标志物组合并非源于不同类型原油之间的混合,而是一种客观存在,尽管其确切的地球化学意义和形成条件目前并不清楚。由此可见,东坪地区原油为柴达木盆地一个新的原油类型,推测其烃源岩可能形成于偏酸性的咸水环境。  相似文献   

11.
The triterpenoid hydrocarbons of some West Australian shales have been examined by GC-MS. In addition to the common 17α(H),21β(H)-hopanes, 17β(H),21β(H)-hopanes and 17β(H),21α(H)-moretanes, 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes were identified in the organic extracts. In contrast, pyrolysates of the solvent-extracted sediments contained only the common hopane and moretane series, indicating that 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes are not bonded to kerogen, but rather are present in the sediments as free hydrocarbons.  相似文献   

12.
The present paper deals with the biomarker characteristics of crude oils and source rocks from different environments(fresh,fresh-brackish and salt waters)of nonmarine depositional basins of different ages in China.Their characters are summarized as follows:1)Souce rocks and crude oils derived from fresh-water lacustrine facies have an odd/even predominance of n-alkanes and high pristine/phytane ratios.Oils from the fresh-water lacustrine facies differ from typical marine oils in the relative contents of total steranes and terpanes,the concentrations of hopanes and organic sul-phur compounds and the values of methylphenanthrene indices and C,H,S stable isotopes.2)The source rocks and crude oils derived from saline lacustrine facies possess an even/odd predominance of n-alkanes and high phytane/pristine ratios.There are also some differences between saline lacustrine oils and freshwater lacustrine oils in the concentrations of steranes,tricyclic terpanes and organic sulphur compounds,as well as in the values of methylphenanthrene indices and C,H,S stable isotopes.3)Oils derived from fresh-brackish water lake facies differ from oils from fresh-water lacustrine or samline lacustrine environments in respect of some biomarkers.According to the various distributions of these biomarkers,a number of geochemical parameters can be applied synthetically to differentiating and identifying the nature of original depositional environments of crude oils and source rocks and that of organisms-primary source materials present in those environments.  相似文献   

13.
Based on the systematic analyses of fifteen typical crude oils and ten typical potential source rocks col-lected from the Qaidam,Tarim and Turpan basins,Northwest China,the geochemical characteristics of the oils and source rocks were investigated and oil-source rock correlations undertaken.The oils and source rocks deposited in saline lacustrine environment from the western Qaidam Basin were characterized by n-alkanes with even car-bon-number preference in the C20-C28 range,low pristane/phytane(Pr/Ph) ratios(less than 0.5),and high abundances of C27 steranes,gammacerane and C35 hopanes.The oils and source rocks deposited in marine environment from the Tarim Basin were characterized by n-alkanes with even carbon-number preference in the C14-C18 range,relatively low Pr/Ph ratios(near to 1),high abundance of C28 steranes,and relatively high gammacerane.In contrast,the oils and source rocks deposited in terrigenous bog environment from the Turpan Basin were characterized by relatively high Pr/Ph ratios(oil samples greater than 6) high abundance of C29 steranes,and relatively low gammacerane and C31-35 hopanes.The higher amounts of C37 and C38 n-alkanes of source rocks from the western Qaidam Basin and the Tarim Basin suggest an origin of these alkanes from functionalized C37 and C38 n-alkadienes and alkenones in prymnesiophytes living in lacustrine and marine environments.Oil-source rock correlations suggest oils in the west-ern Qaidam Basin were derived from the Oligocene Lower Ganchaigou Formation(E3),oils in the Tabei and Tazhong uplifts from the Tarim Basin have a genetic relationship with the Middle-Upper Ordovician source beds.Oils in the Turpan Basin generally fall into two genetic types.Most oils in the Taibei depression from the Turpan Basin were derived from the Lower-Middle Jurassic coal measures,but the fewer oils in this region are a mixed source derived from the Lower-Middle Jurassic coal measure and the Upper Permian source rocks.  相似文献   

14.
Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C26 to C34 and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.  相似文献   

15.
Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy (13C-enriched) carbon isotopic compositions spanning a narrow range (δ13C = ?22.2 to ?23.4‰), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.  相似文献   

16.
Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C15-C20 isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C15/C16 < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C19-C21) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C29Ts and an unknown C30 compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C23 in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.  相似文献   

17.
The triterpenol geochemistry of the Santa Monica Basin from the Southern California Borderland, off the U.S.A., is described from the study of two sets of trap deployments, five box cores (≈30 cm) and a hydroplastic core (≈1 m). The biogenic sources and diagenetic stability of the triterpenols are discussed.The 17β(H), 21β(H)-hopanols (22R isomer) occur in the carbon number range from 30 to 32 and their abundance is nearly uniform in the shallow sediment sections. However, the three hopanols follow the order of abundance, C32 > C31 C30, in deeper sections. Their concentrations spans from trace levels to 156 μg/g organic carbon (<15 ng to 7 μg/g dry sediment). Tetrahymanol (gammaceran-3β-ol) has been identified in all the samples except in one set of trap particles collected at 100 m water depth, from trace level (<1 μg) to 215 μg/g organic carbon (<20 ng to 9 μg/g dry sediment). Diplopterol is also detected in trace amounts in some samples. The triterpenols in the trap material generally increase with the water column depth and decrease with the subbottom depth in the sediment cores.The extended hopanols are either degradation products of polyhydroxybacteriohopanes or are biosynthesized by bacteria. Tetrahymanol is probably the only suggested biological precursor of gammacerane (the reduced counterpart of tetrahymanol), which has been recognized in numerous crude oils and lithified sediments. Although it has been reported earlier from Green River Shale and from a residual Pleistocene lake sediment, tetrahymanol has so far been positively identified from recent marine sediments only in two recent studies. The decreasing content of tetrahymanol in sedimentary depth profiles in the Santa Monica Basin would favor an origin for this compound in the water column or at the sediment surface. The ubiquitous occurrence of this compound throughout the study area suggests that this triterpenol most probably originates from primitive organisms (protozoa, bacteria?), hitherto not identified or, more likely, not yet analyzed for their lipid composition.  相似文献   

18.
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   

19.
热力作用对烃源岩中重排藿烷类化合物形成的作用   总被引:1,自引:1,他引:0  
张敏  李谨  陈菊林 《沉积学报》2018,36(5):1033-1039
通过对87个采自鄂尔多斯盆地煤系烃源岩和松辽盆地湖相烃源岩样品进行的地球化学分析结果显示,热力作用对烃源岩重排藿烷组成特征的影响强烈。随成熟度的变化,来自两套沉积体系的烃源岩中重排藿烷相对丰度的分布相似,随成熟度增大17α(H)-重排藿烷和18α(H)-新藿烷相对丰度均先增大后减小,并在Ro:0.80%~0.90%(生油窗)时达峰值。不同沉积环境的烃源岩中重排藿烷的成熟度与绝对浓度的变化规律一致。在Ro:0.50%~0.70%(未熟-低熟)阶段,重排藿烷绝对浓度较大;在Ro:0.70%~0.80%(成熟)阶段,重排藿烷的绝对浓度显著降低。不同沉积环境中重排藿烷的参数随成熟度的变化规律揭示:在重排藿烷的形成过程中,热力作用的影响要强于沉积环境和生物来源。  相似文献   

20.
从西北地区侏罗纪煤中分离出来的不同显微组分热解油生物标志物总体上比较相似,但在一些特殊生物标志物的分布上存在明显差异。藻类体、孢子体、角质体热解油Pr/Ph比值一般在1.5~2.0之间,镜质体和基质镜质体热解油Pr/Ph比值在3~4之间,但均只有相应原煤抽提物Pr/Ph比值的一半。在常规生物标志物甾烷和萜烷组成中,藻类体和孢子体含有相对丰富的C27甾烷,角质体其次,镜质体和基质镜质体C27甾烷含量很低或者基本不含C27甾烷;藻类体和角质体含有较高的伽马蜡烷,而与藻类体来自相同原煤的孢子体伽马蜡烷含量很低;镜质体和基质镜质体基本上不含伽马蜡烷;分离显微组分的原煤伽马蜡烷含量均很低。由此可见,伽马蜡烷的含量不仅与有机质沉积水体的盐度有关,与母源的成分也有关系。显微组分热解油与煤系原油生物标志物组成特征对比表明,煤系原油是藻类体、孢子体、角质体等富氢组分和相对贫氢的镜质组生成产物的混合物。不同油气藏中的原油,每一类显微组分的贡献可能不尽相同,有些原油可能主要来源于藻类体和孢子体等富氢显微组分,而有些原油除了富氢显微组分有贡献外,镜质组对其也有一定的贡献,但富氢显微组分应该是煤系含油气盆地中主要的生油显微组分。  相似文献   

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