Demethylated hopanes in crude oils and their applications in petroleum geochemistry

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.     

Sulphur-containing compounds in sulphur-rich crude oils from hypersaline lake sediments and their geochemical implications

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.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Study on secondary migration of hydrocarbons in Tazhong area of Tarim Basin in terms of carbazole compounds

Fractionated carbazoles have been detected for the first time in crude oils from the Tazhong area of the Tarim Basin, and these nitrogen compounds were successfully utilized in the study of petroleum migration. Alkylcarbazoles are quite abundant in all the samples analyzed; small amounts of benzocarbazoles were detected only in some of the sample, and dibenzocarbazoles were not found in the oils. Based on the distributions of G1, G2 and G3 types of C₂-alkylcarbazoles, the ratio of C₃-/C₂-carbazoles and the relative concentrations of alkylcarbazole and alkylbenzocarbazole, oils in the Carboniferous C_III reservoir in the Tazhong uplift are thought to have laterally migrated to the high level of Tazhong structure No. 4 from both northwest and southeast. The study here also shows that oils in the area may have undergone long-distance migration. This project is financially supported by the China National Petroleum Corporation and the State Educational Commission.     

On the depth,time and mechanism of origin of the heavy to medium-gravity naphthenic crude oils

Paraffinic crude oils are designated ‘primary’ because their composition is very close or identical to that of the hydrocarbons extracted from the corresponding oil source rocks. Heavy and medium-gravity naphthenic crude oils, on the other hand, typically are quite different compositionally from hydrocarbon mixtures in either mature or immature shales.The normal paraffin carbon number odd/even ratio 2C₂₉/(C₂₈ + C₃₀) of all the heavy to medium-gravity crude oils which could be analysed are in exactly the same range as is observed for the primary paraffinic crude oils, namely 0.95–1.42. The naphthene indices of the medium to heavy gravity naphthenic crude oils and of the primary paraffinic crude oils from the same area are identical or close. These facts are significant because both the n-paraffin carbon number odd/even ratio and the naphthene index of shale hydrocarbons are strongly depth and subsurface temperature dependent. The facts observed demonstrate beyond question that, in the same area, the paraffinic precursors of the heavy to medium-gravity naphthenic crude oils are generated and expelled in the identical depth range, and from the same mature relatively deep oil source beds as the primary paraffinic crude oils. Later, during and/or after a generally upward migration into oil reservoirs, the primary crude may be transformed compositionally into a naphthenic crude oil.In none of the five widely scattered oil basins studied are medium to heavy naphthenic crude oils found at temperatures greater than a limiting subsurface temperature. The abruptness of the temperature cutoff of the change in oil compositions in all five oil basins, as well as the average value of the cutoff temperature of 66°C (150°F), leaves no doubt that the mechanism of this crude oil transformation process is microbial.Optical activity, which was observed in narrow saturate hydrocarbon fractions of the 80–325°C range of all microbially transformed crude oils, but not in the primary untransformed oils, is strong additional evidence for the microbial nature of the crude oil transformation process. The observed optical activity is explained by the microbial digestion at different rates of optical antipodes present in the primary paraffinic crude oils.To gain perspective the vast scale of the microbial oil transformation process in nature is pointed out. Billions of tons of heavy to medium-gravity naphthenic crude oils, originating from the microbial transformation of primary paraffinic oils, are present in oil fields and tar sands all over the world.     

Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H2O2/CH3COOH

Being the heaviest fraction of crude oils, asphaltenes are liable to aggregate, and other molecules in the oils can be steadily adsorbed onto, and even occluded inside the macromolecular structures of the asphaltenes. These occluded compounds inside the asphaltenes can survive over geological time in oil reservoirs owing to effective protection by the macromolecular structures of the asphaltenes. The asphaltenes of a crude oil (ZG31) from the central Tarim Basin, NW China, were hierarchically degraded by increasing the amount of H₂O₂/CH₃COOH to release the occluded compounds. Besides the common components, series of even numbered n-alk-1-enes and 3-ethylalkanes were detected among the occluded compounds. Comparison of the biomarker distributions and the compound-specific C isotopic results between the compounds from the maltenes and those from the occluded fraction, the ZG31 reservoir was suggested to have been charged multiple times, with different charges being derived from different strata of source rocks.     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

Delineating compositional variabilities among crude oils from Central Montana, USA, using light hydrocarbon and biomarker characteristics

Three compositionally distinctive groups of oils identified in central Montana by biomarker analyses are also recognized by the unique compositions of their light hydrocarbon (gasoline range) fraction. The majority of oils produced from Paleozoic pools (Pennsylvanian Tyler–Amsden interval) group into one broad category based on the distribution of C₂₀–C₄₀ biomarkers. These oils not only have the lowest Paraffin Indices and relative concentrations of normal heptane, but are readily distinguishable from the other compositional groups by using selected “Mango” parameters. However, the biomarker-based subdivision of this group into at least two sub-families is not reflected in the gasoline range fraction, suggesting little effect of source rock host lithology on the distribution of C₅–C₈ hydrocarbons. Oils occurring predominantly in Jurassic–Cretaceous reservoirs display different biomarker and gasoline range characteristics, including Paraffin Indices, K1 parameter and relative concentrations of C₇ compounds, and are classified in two separate compositional categories. In contrast to oils from the Tyler–Amsden interval, the oils produced from the Mesozoic strata are amongst the most mature oils in the study area. The unique biomarker/light hydrocarbon signatures are likely due to different source organic matter. Secondary alteration of oil due to biodegradation and migration, although recognized, appears less significant. The results indicate the overall usefulness of gasoline range compositions in delineating compositional affinities of crude oils in central Montana, clearly suggesting that the oils found in Paleozoic and Mesozoic reservoirs belong to different petroleum systems.     

Charactristics of the Biomarkers from Nonmarine Crude Oils in China—A Review

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.     

Distribution of diaromatic nitrogen bases in crude oils

Azanaphthalene derivatives were identified in 9 petroleum samples. In all investigated crude oils; the number of alkyl substituents was found to extend up to C₉ with a maximum most often for C₆; unsubstituted parent compounds are absent. Two distinct types of azanaphthalenes occur: solely methylated derivatives which are abundant in most crude oils of Cretaceous or Miocene ages, and compounds bearing alkyl chains of up to 4 carbon atoms, with a majority of 8-isopropyl quinoline derivatives, which dominate in a California crude oil of Pliocene age.     

The occurrence of norlupanes and bisnorlupanes in oils of Tertiary deltaic basins

Lupanoid hydrocarbons are known to occur in several petroleum systems, and lupane (C₃₀) has recently been confirmed to exist in several crude oils. In contrast, norlupanes (C₂₉) and bisnorlupanes (C₂₈) are rarely observed in oil. All of these compounds are considered to derive from natural products of angiosperms, and numerous examples of their functionalized analogs are known. The occurrence of C₂₈ and C₂₉ lupanoids in biochemical and geochemical systems is reviewed here, and the presence and origin of their hydrocarbon analogs in crude oils are examined in detail. Although direct biochemical precursors for the lupane of crude oil are evident, such precursors for norlupane and bisnorlupane are not obvious. Nor is it clear if the C₂₈ and C₂₉ analogs are diagenetic descendants from the lupane structure. Adding additional confusion is the occurrence of these analogs in oils which show numerous indications of post-source molecular addition during migration and entrapment, making it unclear if they originate from a conventional source rock or from carrier or seal rock. Despite these uncertainties, there is extensive potential – some of which has already been realized – to use these compounds in oil–oil and oil-source rock correlations, particularly in instances where extensive biodegradation has occurred. Deconvolution of the time(s) of introduction of norlupane and bisnorlupane into the fluid – as well as various other hydrocarbons, including olefins – also provides great potential as a tool for mapping the migration history of an oil.     

Correlation of crude oils with their oil source formation,using high resolution GLC C6-C7 component analyses

A new method has been devised, based on high resolution GLC component analyses of the C₆-C₇ hydrocarbons from shales and from crude oils, whereby composition parameters in an oil are compared with the corresponding parameters in a shale. Ideally, a given composition parameter should have the same value for a crude oil and the source rock which generated and expelled that crude oil. A Similarity Coefficient has been devised, to measure the degree of correlation between crude oil and source rock hydrocarbons or between the hydrocarbons from different groups of crude oils. The maximum value of the Similarity Coefficient is 1.00, and the theoretical minimum is a positive fraction close to zero. Based on the natural variation in composition of primary (not biodegraded) crude oils of the same basin and origin, it was found that if the Similarity Coefficient is about 0.80 or higher, correlation between the natural hydrocarbons considered is good. If the Similarity Coefficient is less than 0.73, correlation is poor.Based on strict rules for sample selection (e.g. maturity of shales and lack of biodegradation in the oils), ten presumed crude oil-source formation pairs were selected. Most of these pairs have high Similarity Coefficients of 0.80 or more. Erroneous crude oil-source rock combinations from areas with more than one source formation, as in West Texas, have low Similarity Coefficients. This indicates that the crude oil-source formation correlation method based on the Similarity Coefficient generally is functioning properly.     

Bacterial degradation of crude oil: Comparison of field and experimental data

It has been reported that the composition of crude oils in the subsurface may be altered by bacterial action to the extent that oil correlations (Winters and Williams, 1969) and the value of the crude (Evans et al., 1971) are severely affected. Experimental documentation of these effects is provided by this study.A crude oil was degraded in a 21-day laboratory experiment by a culture of four aerobic bacteria isolated from an oil-contaminated soil. The progress of the experiment was measured by the changes induced in the chemical composition of the oil fraction boiling above 270°C. These changes were similar to the variations in composition found in the MC5 oils of Saskatchewan, Canada.Normal paraffins through to at least nC₃₄ were severely depleted although the attack was temporarily blocked at nC₂₅ (Jobson et al., 1972). The position of this blockage is a function of the isolate employed. The isoprenoids, pristane and phytane, were metabolised after the disappearance of the n-paraffins. Lower-ring naphthenes and aromatics were attacked at the same time as the lighter normal paraffins and before the heavier ones.The more condensed cyclic hydrocarbons were apparently unaffected. Additional non-hydrocarbon NSO, and particularly asphaltene (both defined under section “Methods”), compounds were formed by the metabolism of the hydrocarbons.The residual oil after attack was heavier by approximately 30° API than the initial crude oil.     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

Sterane isomerisation and moretane/hopane ratios in crude oils derived from Tertiary source rocks

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.     

Study on the geochemical correlation of crude oils of Palaeocene and Jurassic ages from the Potowar Indus Basin in northern Pakistan

This study deals with a detailed geochemical characterization of three crude oils from the Upper Indus Basin, Punjab, Pakistan. The samples were obtained from three productive oil fields of the Datta Formation (Jurassic), Lochhart (Palaeocene) and the Dhak Pass zone (Palaeocene). The GC parameters for and the bulk properties of Datta Formation oils are essentially coincident with those of the oils from the Dhak Pass Formation in the Upper Indus Basin, Pakistan and the oils likely originate from a marine source rock. In contrast, the Lockhart Formation oils show different behaviors and seem to be originated from dirty carbonate rocks although all three crude oils are mature, being of non-biodegraded and somewhat mixed organic matter origin. Low Pr/Ph values and high C₃₅ homohopane index for the Lockhart Formation oils suggest a source of anoxic environment with low Eh while oils from the Datta Formation and Dhak Pass Formation showed different trends, i.e., lower values of C₃₅ homohopane index indicating different depositional environment than oil from the Lockhart Formation. All three crude oils from the Upper Indus Basin are mature for the hopane ratios, i.e., Ts/Ts+Tm, C₃₂22S/(S+R) and C₃₀ αβ/(αβ+βα) and sterane ratios, i.e., C₂₉22S/(S+R) and C₂₉ββ/(ββ+αα) but oils from the Lockhart Formation seem to be less mature than those from the Palaeocene and Datta Formation according to plots like API° vs. homohopane Index, Pr/Ph vs. sterane. The relative composition of 5α(H), 14β(H), 17β(H)-24-ethylecholestanes and the C₂₉20S/20S+20R index, indicate that all three crude oils are equally mature, which makes it unlikely with respect to the above said plots. This difference is may be due to the migratory chromatography which alters the concentrations of sterane and hoapnes and hence gives different results. These oils do not exhibit UCM and have complete n-alkane profiles indicating non-biodegradation.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).     

Chemical composition and stable carbon isotopic ratios of crude oils from Southern Germany

Thirty crude oils were sampled in the South German Molasse Basin. The crude oils were chemically separated into five component groups and their stable carbon isotopic ratios were determined by mass spectrometry. A distinct differentiation of four regionally connected groups can be inferred from the results of the δ¹³C values and chemical analyses. This grouping is in accordance with the present geologic information on the origin of crude oils in the Molasse Basin.The chemistry of crude oils seems to have been influenced by secondary processes in the eastern part of the Molasse Basin.     

Molecular correlation of free oil,adsorbed oil and inclusion oil of reservoir rocks in the Tazhong Uplift of the Tarim Basin,China

The free, adsorbed and inclusion oils were recovered by sequential extraction from eleven oil and tar containing reservoir rocks in the Tazhong Uplift of Tarim Basin. The results of gas chromatography (GC) and GC–mass spectrometry analyses of these oil components and seven crude oils collected from this region reveal multiple oil charges derived from different source rocks for these oil reservoirs. The initially charged oils show strong predominance of even over odd n-alkanes in the range n-C₁₂ to n-C₂₀ and have ordinary maturities, while the later charged oils do not exhibit any predominance of n-alkanes and have high maturities. The adsorbed and inclusion oils of the reservoir rocks generally have high relative concentrations of gammacerane and C₂₈ steranes, similar to the Cambrian-Lower Ordovician source rocks. In contrast, the free oils of these reservoir rocks generally have low relative concentrations of gammacerane and C₂₈ steranes, similar to the Middle-Upper Ordovician source rocks. There are two interpretations of this result: (1) the initially charged oils are derived from the Cambrian-Lower Ordovician source rocks while the later charged oils are derived from the Middle-Upper Ordovician source rocks; and (2) both the initially and later charged oils are mainly derived from the Cambrian-Lower Ordovician source rocks but the later charged oils are contaminated by the oil components from the Silurian tar sandstones and the Middle-Upper Ordovician source rocks.