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1.
Compound-specific isotope analysis has become an important tool in environmental studies and is an especially powerful way to evaluate biodegradation of hydrocarbons. Here, carbon isotope ratios of light hydrocarbons were used to characterise in-reservoir biodegradation in the Gullfaks oil field, offshore Norway. Increasing biodegradation, as characterised, for example, by increasing concentration ratios of Pr/n-C17 and Ph/n-C18, and decreasing concentrations of individual light hydrocarbons were correlated to 13C-enrichment of the light hydrocarbons. The δ13C values of C4 to C9n-alkanes increase by 7-3‰ within the six oil samples from the Brent Group of the Gullfaks oil field, slight changes (1-3‰) being observed for several branched alkanes and benzene, whereas no change (<1‰) in δ13C occurs for cyclohexane, methylcyclohexane, and toluene. Application of the Rayleigh equation demonstrated high to fair correlation of concentration and isotope data of i- and n-pentane, n-hexane, and n-heptane, documenting that biodegradation in reservoirs can be described by the Rayleigh model. Using the appropriate isotope fractionation factor of n-hexane, derived from laboratory experiments, quantification of the loss of this petroleum constituent due to biodegradation is possible. Toluene, which is known to be highly susceptible to biodegradation, is not degraded within the Gullfaks oil field, implying that the local microbial community exhibits rather pronounced substrate specificities. The evaluation of combined molecular and isotopic data expands our understanding of the anaerobic degradation processes within this oil field and provides insight into the degradative capabilities of the microorganisms. Additionally, isotope analysis of unbiodegraded to slightly biodegraded crude oils from several oil fields surrounding Gullfaks illustrates the heterogeneity in isotopic composition of the light hydrocarbons due to source effects. This indicates that both source and also maturity effects have to be well constrained when using compound-specific isotope analysis for the assessment of biodegradation.  相似文献   

2.
A consequence of the biodegradation of petroleum is that lower molecular weight compounds are removed preferentially to higher molecular weight (HMW) compounds greater than triacontane (n-C30). The extent to which the latter compounds are biodegraded has rarely been studied. Reasons for this include the technical difficulties associated with carrying out biodegradability tests with solid, water-insoluble substances and the limits of the analytical techniques, such as gas chromatography (GC).A quantitative high temperature GC (HTGC) method was developed to monitor the biodegradation of the aliphatic fraction of a waxy Indonesian oil by Pseudomonas fluorescens. Recoveries of over 90% were obtained for n-alkanes up to hexacontane (C60) using liquid-liquid continuous extraction. After only 14 days, 80% of the aliphatic hydrocarbons had been degraded. At the end of the 136-day study, 14% of the original fraction remained. This comprised mainly C40+ compounds. No decrease in the concentrations of compounds above C45 was observed. However, the use of a rapid screening biodegradation method provided tentative proof that Pseudomonas fluorescens was capable of utilising n-alkanes up to C60 once the bacteria had acclimated to HMW alkanes.  相似文献   

3.
A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C13-C21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ13C values increase by ∼4‰ and δD values increase by ∼50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH‡) and entropy (ΔΔS‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C20 (n-icosane), the changes in enthalpy are calculated to be ∼1340 J mol-1 (320 cal mol-1) and 230 J mol-1 (55 cal mol-1) for D-H and 13C-12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration.  相似文献   

4.
Although no commercial oil or gas occurrences have been found in the Barrandian Basin, residual oils and petroleum inclusions give evidence about the petroleum history of this Lower Palaeozoic Basin. Petroleum inclusions are hosted in six generations of calcite and quartz cements that can be attributed to different stages of a basinal cycle and associated diagenetic events. They were analysed using an on-line crushing and an off-line crush-and-leach approach. Five different groups (PI-A to PI-E) and intermediate mixtures (PI-M) could be differentiated based on the relative distribution of n-alkanes. All oils had a calculated aromatic maturity Rc ranging between 0.9 and 1.6%. PI-A shows a molecular weight maximum in the range of n-C8–11 with a constant attenuation towards higher carbon numbered n-alkanes. This distribution is interpreted as the pristine precursor oil for other petroleum inclusion groups. PI-B has a maximum weight abundance at n-C15–20. The genetic relationship between PI-B and PI-A can tentatively be explained by mixing effects or by gas stripping. PI-C is bimodal and characterised by a molecular weight maximum at n-C32–34, and also a molecular weight maximum at n-C15–20 similar to that of group PI-B. PI-D shows a normally distributed molecular weight maximum in the range n-C25–28 and is interpreted as a wax precipitate from ascending gas saturated in n-alkanes. PI-E contains predominantly gaseous compounds with only a few higher hydrocarbons. Thompson's aromaticity values are elevated for condensates of group PI-E, and also for group PI-C that is dominated by long-chained n-alkanes. This gives evidence that fault-bound petroleum migration in the Barrandian Basin was associated with evaporative fractionation for group PI-C and PI-E. Samples of group PI-E yielded gas-range compounds only, and all come from a last generation of vein-filling whitish calcite that was formed in a late uplift phase of the basin. For other petroleum inclusion groups, only a vague preferential occurrence in specific mineralisation phases or stratigraphic intervals of the host rock has been found. This reflects the predominance of fracture-bound migration in the Barrandian Basin. Aromatic maturity values also showed no correlation between either crystal type or PI-group. In six of the investigated petroleum inclusion samples alk-1-enes are present. These terminal olefins are interpreted to be the result of the natural pyrolysis of petroleum due to the intrusion of volcanic dykes or hydrothermal processes. An artificial generation of olefins during sample work-up and analysis is unlikely. The preservation of alk-1-enes from Palaeozoic times was possible due to the protecting environment of petroleum inclusions.  相似文献   

5.
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.  相似文献   

6.
Biodegradation, one of the most important weathering processes, alters the composition of spilled oil, making it difficult to identify the source of the release and to monitor its fate in the environment. A laboratory experiment was conducted to simulate oil spill weathering process of microbial degradation to investigate compositional changes in a range of source- and weathering-dependent molecular parameters in oil residues, and the conventional diagnostic ratios for oil spill identification were also evaluated. The conventional diagnostic ratios of n-alkane displayed obvious changes after biodegradation, especially for Pr/n-C17 and Ph/n-C18 with relative standard deviation more than 118.84 %, which suggests they are invalid for oil source identification of the middle-serious spill. Many polycyclic aromatic hydrocarbons (PAHs) are more resistant to biodegradation process than their saturated hydrocarbon counterparts, thus making PAHs to be one of the most valuable fingerprinting classes of hydrocarbons for oil identification. Biomarker ratios of hopanes and steranes were also useful for source identification even after moderate biodegradation, and the diagnostic ratios from them could be used in tracking origin and sources of hydrocarbon pollution. Finally, the carbon isotopic type curve may provide another diagnostic means for correlation and differentiation of spilled oils, and be particularly valuable for lighter refined products or severely biodegraded oils, the source of which may be difficult to identify by routine biomarker techniques.  相似文献   

7.
《Applied Geochemistry》1998,13(7):851-859
Emerging acceptance of the limitations of separate phase product recovery has spawned interest in the intrinsic alteration of residual separate phase petroleum products. In this study the geochemical changes in a continuous core through soil containing a separate phase diesel fuel #2 (SPD) in contact with groundwater are investigated. Chemical heterogeneities are shown to exist which can be attributed to weathering, particularly intrinsic biodegradation. The results show that the aliphatic hydrocarbon content is reduced and the δ13C ratio of the aliphatic hydrocarbons increased from top to bottom in the core. Both changes are thought to be due to preferential biodegradation of (isotopically lighter) n-alkanes. A slight increase in the relative abundance of shorter chain n-alkanes (<n-C17) was also observed. The distribution of the dominant aromatic hydrocarbons (C0–C3 alkyl-naphthalenes) is remarkably consistent throughout the core, although naphthalene is depleted below the oil–water interface. In spite of low oil saturation (S0), little or no evidence of biodegradation is noted at the uppermost boundary of the SPD. However, intrinsic biodegradation is evident approximately 0.3 m above the oil–water interface in spite of higher S0. The extent of the chemical changes attributable to biodegradation (described above) gradually increases below the oil–water interface, eventually reaching a maximum at the bottom of the SPD profile (∼1.2 m below the interface) where S0 is again reduced. The relatively higher level of biodegradation observed at and below the oil–water interface may be attributed to the reduced S0 in this zone. An estimate of the mass reduction in diesel fuel between the uppermost and bottommost parts of the core is calculated to be 23% (by weight), due predominantly to the biodegradation of n-alkanes.  相似文献   

8.
The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C17 alkane (Pr/n-C17) and/or phytane/n-C18 alkane (Ph/n-C18) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C17 and Ph/n-C18 values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C14–C22) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C15) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.  相似文献   

9.
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.  相似文献   

10.
Light hydrocarbons (LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation (rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here, 23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C6–C7 LHs. The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils, such biodegradation scale could not sufficiently affect C6–C7 cycloalkanes. For branched C6–C7 alkanes, generally, monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings. The degree of alkylation is one of the primary controlling factors on the biodegradation of C6–C7 LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C6–C7 alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation, which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango’s LH parameters K1 values decrease and K2 values increase, the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase. LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the “Biodegraded” zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the “Biodegraded” zone.  相似文献   

11.
Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C15+ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C15+ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C15+ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m3/m3 during bitumen generation and remain essentially constant (81–84 m3/m3) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C17 and phytane/n-C18) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.  相似文献   

12.
<正>The oil source of the Tarim Basin has been controversial over a long time.This study characterizes the crude oil and investigates the oil sources in the Lunnan region,Tarim Basin by adopting compound specific isotopes of n-alkanes and biomarkers approaches.Although the crude oil has a good correlation with the Middle-Upper Ordovician(O_(2+3)) source rocks and a poor correlation with the Cambrian-Lower Ordovician((?)-O_1) based on biomarkers,theδ~(13)C data of n-alkanes of the Lunnan oils show an intermediate value between(?)-O_1 and O_(2+3) genetic affinity oils,which suggests that the Lunnan oils are actually of an extensively mixed source.A quantification of oil mixing was performed and the results show that the contribution of the Cambrian-Lower Ordovician source rocks ranges from 11%to 70%(averaging 36%),slightly less than that of the Tazhong uplift.It is suggested that the inconsistency between the biomarkers andδ~(13)C in determining the oil sources in the Lunnan Region results from multiple petroleum charge episodes with different chemical components in one or more episode(s) and different sources.The widespread marine mixed-source oil in the basin indicates that significant petroleum potential in deep horizons is possible.To unravel hydrocarbons accumulation mechanisms for the Lunnan oils is crucial to further petroleum exploration and exploitation in the region.  相似文献   

13.
A suite of 18 oils from the Barrow Island oilfield, Australia, and a non-biodegraded reference oil have been analysed compositionally in order to detail the effect of minor to moderate biodegradation on C5 to C9 hydrocarbons. Carbon isotopic data for individual low molecular weight hydrocarbons were also obtained for six of the oils. The Barrow Island oils came from different production wells, reservoir horizons, and compartments, but have a common source (the Upper Jurassic Dingo Claystone Formation), with some organo-facies differences. Hydrocarbon ratios based on hopanes, steranes, alkylnaphthalenes and alkylphenanthrenes indicate thermal maturities of about 0.8% Rc for most of the oils. The co-occurrence in all the oils of relatively high amounts of 25-norhopanes with C5 to C9 hydrocarbons, aromatic hydrocarbons and cyclic alkanes implies that the oils are the result of multiple charging, with a heavily biodegraded charge being overprinted by fresher and more pristine oil. The later oil charge was itself variably biodegraded, leading to significant compositional variations across the oilfield, which help delineate compartmentalisation. Biodegradation resulted in strong depletion of n-alkanes (>95%) from most of the oils. Benzene and toluene were partially or completely removed from the Barrow Island oils by water washing. However, hydrocarbons with lower water solubility were either not affected by water washing, or water washing had only a minor effect. There are three main controls on the susceptibility to biodegradation of cyclic, branched and aromatic low molecular weight hydrocarbons: carbon skeleton, degree of alkylation, and position of alkylation. Firstly, ring preference ratios at C6 and C7 show that isoalkanes are retained preferentially relative to alkylcyclohexanes, and to some extent alkylcyclopentanes. Dimethylpentanes are substantially more resistant to biodegradation than most dimethylcyclopentanes, but methylhexanes are depleted faster than methylpentanes and dimethylcyclopentanes. For C8 and C9 hydrocarbons, alkylcyclohexanes are more resistant to biodegradation than linear alkanes. Secondly, there is a trend of lower susceptibility to biodegradation with greater alkyl substitution for isoalkanes, alkylcyclohexanes, alkylcyclopentanes and alkylbenzenes. Thirdly, the position of alkylation has a strong control, with adjacent methyl groups reducing the susceptibility of an isomer to biodegradation. 1,2,3-Trimethylbenzene is the most resistant of the C3 alkylbenzene isomers during moderate biodegradation. 2-Methylalkanes are the most susceptible branched alkanes to biodegradation, 3-methylalkanes are the most resistant and 4-methylalkanes have intermediate resistance. Therefore, terminal methyl groups are more prone to bacterial attack compared to mid-chain isomers, and C3 carbon chains are more readily utilised than C2 carbon chains. 1,1-Dimethylcyclopentane and 1,1-dimethylcyclohexane are the most resistant of the alkylcyclohexanes and alkylcyclopentanes to biodegradation. The straight-chained and branched C5–C9 alkanes are isotopically light (depleted in 13C) relative to cycloalkanes and aromatic hydrocarbons. The effects of biodegradation consistently lead to enrichment in 13C for each remaining hydrocarbon, due to preferential removal of 12C. Differences in the rates of biodegradation of low molecular weight hydrocarbons shown by compositional data are also reflected in the level of enrichment in 13C. The carbon isotopic effects of biodegradation show a decreasing level of isotopic enrichments in 13C with increasing molecular weight. This suggests that the kinetic isotope effect associated with biodegradation is site-specific and often related to a terminal carbon, where its impact on the isotopic composition becomes progressively ‘diluted’ with increasing carbon number.  相似文献   

14.
Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C30 diahopane/C29Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C19-tricyclic and C24-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ13C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C23-tricyclic/C30 hopane, C28-tricyclic/C30 hopane, total tricyclic terpanes/hopanes and C31(R + S)/C30 hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C41+) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C17, Ph/n-C18 and low API gravities.  相似文献   

15.
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16.
Experimental studies of the effects of thermochemical sulfate reduction (TSR) on light hydrocarbons were conducted in sealed gold tubes for 72 h at 400 °C and 50 MPa. A variety of pyrolysis experiments were carried out, including anhydrous, hydrous without MgSO4 (hydrous experiments) and hydrous with MgSO4 (TSR experiments). Common reservoir minerals including montmorillonite, illite, calcite and quartz were added to various experiments. Measurements of the quantities of n-C9+ normal alkanes (high molecular weight, HMW), n-C6-8 normal alkanes (low molecular weight, LMW), C7-8 isoalkanes, C6-7 cycloalkanes and C6-9 monoaromatics and compound specific carbon isotope analyses were made. The results indicate that TSR decreases hydrocarbon thermal stability significantly as indicated by chemically lower concentrations and isotopically heavier LMW saturated hydrocarbons in the TSR experiments compared to the hydrous and anhydrous experiments. In the LMW saturated hydrocarbon fraction, cycloalkanes tend to be more resistant to TSR than n-alkanes and isoalkanes. TSR promotes aromatization reactions and favors the generation of monoaromatics, resulting in higher chemical concentrations and isotopically equivalent compositions of monoaromatics in the anhydrous, hydrous and TSR experiments. This indicates that LMW monoaromatics are thermally stable during the pyrolysis experiments. Acid rather than basic catalyzed ionic reactions probably play a major role in TSR. This is suggested by the promotion effects of acid-clay minerals including illite and particularly montmorillonite. The basic mineral calcite retards the destruction of n-C9+ normal alkanes within the TSR experiments. Furthermore, clay minerals have a minor influence on the generation of LMW monoaromatics and play a negative role in regulating the concentrations of LMW saturated hydrocarbons; calcite does not favor the generation of LMW monoaromatics and plays a positive role in controlling the concentrations of LMW saturates relative to clay minerals. Quartz has a negligible role in the TSR experiments.Due to their differential responses to TSR, LMW hydrocarbon parameters, such as Schaefer [Schaefer, R.G., Littke, R., 1988. Maturity-related compositional changes in the low-molecular-weight hydrocarbon fraction of Toarcian Shale. Organic Geochemistry 13, 887-892], Thompson [Thompson, K.F.M., 1988. Gas-condensate migration and oil fractionation in deltaic systems. Marine and Petroleum Geology 5, 237-246], Halpern [Halpern, H., 1995. Development and application of light-hydrocarbon-based star diagrams. American Association of Petroleum Geologists Bulletin 79, 801-815] and Mango [Mango, F.D., 1997. The light hydrocarbons in petroleum: a critical review. Organic Geochemistry 26, 417-440] parameters and stable carbon isotopic compositions of individual LMW saturated hydrocarbons in TSR affected oils should be used with caution. In addition, water promotes thermal cracking of n-C9+ normal alkanes and favors the generation of LMW cycloalkanes and monoaromatics. The result is lower concentrations of n-C9+ HMW normal alkanes and higher concentrations of LMW cycloalkanes and monoaromatics in hydrous experiments relative to anhydrous experiments with or without minerals.This investigation provides a better understanding of the effects of TSR on LMW hydrocarbons and the influence of reservoir minerals on TSR in natural systems. The paper shows how LMW hydrocarbon indicators in TSR altered oils improve understanding of the processes of hydrocarbon generation, migration and secondary alteration in subsurface petroleum reservoirs.  相似文献   

17.
Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated.Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.  相似文献   

18.
Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C15, n-C17, n-C19 alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C21, n-C23, n-C25 homologues from aquatic plants, and the n-C29, n-C31 homologues from vascular plants. In contrast, the n-C27 alkane is not categorized in the n-C29 and n-C31 group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ13Corg), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ13Corg, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ13Corg, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.  相似文献   

19.
A significant quantity of hydrocarbons (including alkanes) is occluded in the skeleton of the asphaltene molecule. The hydrocarbons are probably remnants of the “original oil” which had been retained within the asphaltene matrix and protected from the secondary alteration processes that occurred subsequently in the oil reservoirs. In this work we report that oxidation of asphaltenes by stirring with 30%H2O2–HAc or NaIO4–NaH2PO4 can release nC7-soluble oxidized products, including the occluded hydrocarbons. Characterization of the nC7-soluble fractions of oxidized products can be applied to highlight some geochemical problems, such as in studies of oil–oil correlation, oil–source correlation and secondary alterations of oil reservoirs. It will be especially useful to recover the original geochemical information of some oil reservoirs heavily degraded by post-depositional processes.  相似文献   

20.
《Applied Geochemistry》2005,20(7):1427-1444
Very high S oils (up to 14.7%) with H2S contents of up to 92% in the associated gas have been found in the Tertiary in the Jinxian Sag, Bohai Bay Basin, PR China. Several oil samples were analyzed for C and S stable isotopes and biomarkers to try to understand the origin of these unusual oil samples.The high S oils occur in relatively shallow reservoirs in the northern part of the Jinxian Sag in anhydrite-rich reservoirs, and are characteristic of oils derived from S-rich source rocks deposited in an enclosed and productive stratified hypersaline water body. In contrast, low S oils (as low as 0.03%) in the southern part of the Jinxian Sag occur in Tertiary lacustrine reservoirs with minimal anhydrite. These southern oils were probably derived from less S-rich source rocks deposited under a relatively open and freshwater to brackish lake environment that had larger amounts of higher plant inputs.The extremely high S oil samples (>10%) underwent biodegradation of normal alkanes resulting in a degree of concentration of S in the residual petroleum, although isoprenoid alkanes remain showing that biodegradation was not extreme. Interestingly, the high S oils occur in H2S-rich reservoirs (H2S up to 92% by volume) where the H2S was derived from bacterial SO4 reduction, most likely in the source rock prior to migration. Three oils in the Jinxian Sag have δ34S values from +0.3‰ to +16.2‰ and the oil with the highest S content shows the lightest δ34S value. This δ34S value for that oil is close to the δ34S value for H2S (∼0‰). It is possible that H2S was incorporated into functionalized compounds within the residual petroleum during biodegradation at depth in the reservoir thus accounting for the very high concentrations of S in petroleum.  相似文献   

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