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1.
Analysis of oil samples from the Niger Delta (Nigeria) revealed a range of structurally related hopanes, including 25-norhopanes, and hopanoic and 25-norhopanoic acids. 25-Norhopanes were detected in all medium and heavily biodegraded oils and were most abundant in the heavily degraded oils. Hopanoic acids (C30-C33) and 25-norhopanoic acids (C30-C31) were most abundant in moderately degraded oils and occurred in reduced concentration in heavily degraded oils but were absent from, or in trace concentration in, slightly degraded oils. Consideration of the structures suggests that 25-norhopanoic acids form via carboxylation of 25-norhopanes or demethylation of hopanoic acids. Mass balance for the onshore Niger Delta oils suggests that formation of 25-norhopanes operates independently of 25-norhopanoic acid formation and that 25-norhopanoic acids are likely transient intermediates for only a small proportion of the 25-norhopanes.  相似文献   

2.
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   

3.
In addition to the previously reported 25-norhopanes and 25-norhopanoic acids, for the first time we report the identification of 25-norbenzohopanes. The hydrocarbon composition of the bitumen from Palaeozoic carbonates in northern Alberta displays molecular evidence for severe levels of biodegradation characterised by the removal of C30–C35 hopanes. Biodegradation is also indicated by the removal of C32 and C33 benzohopanes. The appearance of C31 and C32 25-norbenzohopanes corresponds to the decrease in C32 and C33 benzohopanes, suggesting that 25-norbenzohopanes originate by demethylation of benzohopane counterparts. Demethylation at C-10 in the hopanoids affects a broader class of compounds that so far includes the hopanes and hopanoic acids, as well as the benzylated hopanoid species.  相似文献   

4.
Origin and occurrence of 25-norhopanes: a statistical study   总被引：1，自引：0，他引：1  
The alkane fraction of more than 200 rocks, biodegraded oils and non-biodegraded oils, have been analysed by means of computerized GC-MS, in order to investigate the effect of natural biodegradation on the occurrence of “demethylated hopanes”, i.e. 17α-25-norhopanes. The results obtained indicate that 25-norhopanes are preexisting biomarkers the concentration of which is enhanced by selective biodegradation of more readily degradable homologs, i.e. regular hopanes, rather than by demethylation of hopanes in reservoirs. However, the use of 25-norhopane enrichment as a palaebiodegradation indicator in apparently non-biodegraded oils is still valuable providing the initial background content in the corresponding source rocks is known. Furthermore, 25-norhopanes appear to be diagnostic of specific environmental conditions (marine and lacustrine source rocks, dysoxic and not very hypersaline). Lastly, one other (novel) bacterially resistant rearranged hopanoic compound, namely a C29 neohopane, is applicable for both biodegradation and maturation evaluation.  相似文献   

5.
The aliphatic hydrocarbon composition (acyclic isoprenoids, hopanoids and steroids) of oils from the most productive fields in the southern geological Province of Cuba have been studied. This province is defined by its position with respect to the Cretaceous overthrust belt generated during the formation of oceanic crust along the axis of the proto-Caribbean Basin. The relative abundances of 18α(H)-22,29,30-trisnorneohopane, gammacerane and diasteranes suggest that Pina oils are related to the carbonate oils from the Placetas Unit in the northern province (low Ts/(Ts+Tm) and C27,29 rr/(rr+sd) ratios). The Cristales and Jatibonico oils exhibit some differentiating features such as higher Ts/(Ts+Tm) and absence of gammacerane. The oils from this province do not exhibit significant differences in either hopane, C32 22S/(S+R) and C30 αβ/(αβ+βα), or sterane, C29 αα 20S/(S+R), maturity ratios. However, the relative content of 5α(H),14β(H),17β(H)-cholestanes (C29 ββ/(ββ+αα) ratio) indicates that Pina oils are more mature than Cristales and Jatibonico oils. Several of these oils (Cristales, Jatibonico and Pina 26) are heavily biodegraded, lacking n-alkanes, norpristane, pristane and phytane (the two former oils do not contain acyclic isoprenoid hydrocarbons). Other biodegradation products, the 25-norhopanes, are found in all the oils. Their occurrence is probably due to mixing of severely biodegraded oil residues with undegraded crude oils during accumulation in the reservoir.  相似文献   

6.
An unusual series of C22–C27 monounsaturated sterenes and C24–C30 tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ13C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (Ts/Tm = 0.23; Ro = 0.44%; Tmax = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment.  相似文献   

7.
The black shale samples collected from two Neogene formations in the Klias Peninsula area, West Sabah, have been assessed and characterized in details by gas chromatography, gas chromatography-mass spectrometry and a variety of organic geochemical parameters. The aims of this study are to describe the characteristics of organic matter of these sediments in terms of source/type of the organic matter, assess its thermal maturity and paleoenvironment of deposition, based primarily on biomarker distributions. The results of both formations do not reveal significant differences within the rock extracts. The gas chromatograms of the saturated hydrocarbon fractions of the Setap Shale and the Belait formations displayed monomodal n-alkane distributions and nearly identical regular sterane compositions with a predominance of C27 regular steranes. These are consistent with open marine depositional environments dominated by marine biological matter. Another related feature of these rock extracts is the presence of a high relative abundance of gammacerane, indicating anoxic marine hypersaline source depositional environment. The relatively high abundance of common land plant-derived biomarkers, such as bicadinanes and oleananes, is a clear indication of a major terrigenous input to the source of the extractable organic matter. The predominance of oleanane biomarkers in both formations is indicative of angiospermis input and Tertiary source rocks. The high C29/C30 hopane ratios, moderate development of C33–C35 hopanes, high abundance of tricyclic terpanes and a slight predominance of C27 regular sterane over C28 and C29 steranes are characteristic features tending to suggest a significant marine influence on these source rocks, thereby suggesting a mixed source input. The 22S/(22S+22R)C32 hopane ratio has reached equilibrium, and this is supported by the high maturity level as indicated by the 22S/22SC31–33 extended hopane ratios and 20S/(20S+20R)C29 regular steranes ratios.  相似文献   

8.
A suite of reservoir cores (oil sands) from a single well in Bohai Bay Basin, East China, displayed a progressive increase in petroleum biodegradation extent on the basis of bulk composition and 25-norhopane content. This fits with the proposal that subsurface petroleum biodegradation is dominantly an anaerobic process and usually occurs at the oil–water contact. It is likely that sequential microbial degradation of hydrocarbons under anoxic conditions does not occur in a true stepwise fashion, but is controlled by various factors such as concentration and solubility of hydrocarbons and their diffusion rate to the oil/water contact. In fact, 25-norhopanes were formed prior to the complete elimination of the acyclic, and mono- and bicyclic alkanes. An inverse response of the 22S/(22S + 22R) ratio between each extended 17α(H)-hopane and its corresponding 25-norhopane was observed as severe biodegradation occurred, supporting the proposal that the 25-norhopanes originate from demethylation of hopanes. Field observation revealed that biomarkers without extended alkyl side chains, such as oleanane, gammacerane and β-carotane, have significant resistance to biodegradation and can be used as naturally occurring “internal standards” to evaluate variations in other biomarkers. The results suggest that the quantity of 25-norhopanes showed a minor increase as the hopanes decreased significantly, i.e. only partial hopane conversion to the corresponding 25-norhopanes. Alternative degradation pathways for hopanes might occur in reservoirs, in addition to C-25 demethylation.  相似文献   

9.
The isoprenoid alkanes present in a seep oil from Costa Rica have been examined using gas chromatography and mass spectrometry. In addition to the predominance of the C16 and C18-C20 regular isoprenoid alkanes, the C21 and C23-C25 regular isoprenoid alkanes were identified. The C26, C28 and C30 regular isoprenoid alkanes were tentatively identified. No evidence for the regular C17, C22 or C27 isoprenoid alkanes was found. The compounds 3,7,11- trimethyltetradecane and 3,7,11-trimethylhexadecane were tentatively identified. It is suggested that a higher regular isoprenoid structure (or structures) is required in addition to phytol to account for the distribution of isoprenoid alkanes.  相似文献   

10.
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   

11.
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   

12.
The distributions of hopanoic acids, ranging from C30 to C34, in the Messel oil shale were characterized in both the free and bound states. The bound acids were released by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). These were compared with the distributions of the hopanoic acids and hopanes released or generated from Messel oil shale kerogen following closed system microscale pyrolysis. This comparison revealed that epimerization had occurred at C-17, C-21 and C-22 during heating. It was also clear that the residual bound hopanoic acids had undergone configurational isomerization. During the pyrolysis there is a large loss of hopanoic acids following their rapid release from the kerogen into the free fraction even at 250 °C. In these particular experiments this loss does not appear to result in exclusive formation of hopanes, by way of decarboxylation or reduction reactions, unless the resulting hopanes are either themselves rapidly transformed into other compounds or the reaction rates are a function of the total number of carbon atoms in each hopanoic acid precursor.  相似文献   

13.
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   

14.
A complete series of C32–C35 benzohopanes and corresponding C31–C34 25-norbenzohopanes were tentatively identified in Devonian and Jurassic bitumen sands from the northwestern Sichuan Basin in southwestern China. Although other origins cannot be excluded, the relative distributions of C32–C35 benzohopanes and C31–C34 25-norbenzohopanes, along with other biomarker parameters, suggest that the 25-norbenzohopanes formed by demethylation of the corresponding benzohopanes.  相似文献   

15.
The Qinjiatun and Qikeshu oilfields are new Mesozoic petroleum exploration targets in Lishu Fault Depression of Songliao Basin, northeastern China. Currently, researches on geochemistry of crude oils from Qinjiatun and Qikeshu oilfields have not been performed and the genesis of oils is still uncertain. Based on bulk analyses, the crude oils in the Qinjiatun and Qikeshu oilfields of Lishu Fault Depression from the Lower Cretaceous can be classified as three types. TypeⅠoils, from Quantou and Denglouku formations of Qikeshu oilfield, are characterized by high C24tetracyclic terpane/C26tricyclic terpanes ratios, low gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29norhopane ratios and 17α(H)-diahopane/17α(H)-hopane ratios, indicating a brackish lacustrine facies. TypeⅡoils, from Shahezi Formation of Qikeshu oilfield show low C24tetracyclic terpane/C26tricyclic terpanes, high gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29 norhopane and C30diahopane/C30hopane ratios, thus suggesting that they originated from source rocks deposited in a weak reducing brackish lacustrine environment, or clay-rich sediments. Type oilsⅢ, from some wells of Qikeshu oilfield have geochemical characteristics intermediate between those two types and may be mixture of typeⅠand Ⅱoils.  相似文献   

16.
Unusual short chain lanostanes (C24 and C25) and C30 lanostane were identified in sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, northern China. Besides the regular steranes (C27-30), a series of 4-methyl steranes (C22−23, C27−30), 4,4-dimethyl steranes (C22−24, C28−30), short chain steranes (C23−26), abundant pregnanes (C21−22) and androstanes (C19−20), together with sulfur containing steroids (20-thienylpregnanes and thienylandrostanes) were detected in the aliphatic and branched-cyclic hydrocarbon fraction of these crude oils. A literature survey of some long chain sterane analogues (e.g., A-nor-steranes, norcholestanes, C30 steranes, lanostanes) and pregnanes seems to point to a sponge and/or dinoflagellate source. 4-Methyl, 4,4-dimethyl steroids and lanosterols (4,4,14-trimethyl steroids as the basic skeleton of lanostanes) can be derived from methanotrophic bacteria. Thus, a biological origin from a prokaryotic methylotroph can be used to explain the common source of abundant short chain steranes (C23-26), 4-methyl (C22-23) and 4,4-dimethyl steranes (C22-24), as well as lanostanes (C24-25 and C30 analogues) in our oil samples. Generally, the steroids appear to have been extensively sulfurized with sulfur substitution at the C-22 position in the side chain during the early stage of diagenesis, which was readily subject to attack by bacterial degradation (enzymatic cleavage) and/or abiotic oxidation. As a consequence, short chain sterane analogues (e.g., abundant pregnanes and androstanes in this study) and short chain lanostanes (C24−C25) might later be released through cleavage of weak C-S bonds at the C-22 carbon in the sulfurized steroids and lanostane sulfides. Finally, the formation of the short chain C24−C25 lanostanes and distinctive occurrence of short chain steranes in this study can be well explained by microbial biodegradation of sulfurized lanostanoids and steroids in the reservoir.  相似文献   

17.
The formation or generation of hopanes are important processes during both the natural heating of organic-rich sediments and laboratory pyrolysis experiments. Molecular maturity parameters as well as the amounts (ng/g rock) of the C31 hopanes and C30–C32 hopanoic acids were quantified in a Jurassic silty shale horizon (Isle of Skye, Scotland) as a function of distance from an igneous intrusion. The maturity profiles of the homohopanes and the hopanoic acids are comparable. There is also a correlation between the decreasing amounts of C30–C32 hopanoic acids and concomitant increases in C29–C31 hopanes suggesting that free hopanoic acids could be one potential source of hopanes in this particular horizon. Other possible sources could include hopanoic acids that are bound into the macromolecular fraction.  相似文献   

18.
Based on gas chromatography and gas chromatography-mass spectrometry analyses, an amazing amount of hopanoids was detected in the peat deposits in the Dajiuhu National Wetland Park in central China. The hopanoids identified included hopanes (C27-C31 αβ, C27-C32 ββ, C29 βα), hopenes (hop-22(29)-ene, 22,29,30-trinorhop-17(21)-ene, hop-17(21)-ene, hop-13(18)-ene, etc.), hopanoic acids (C31-C34 ββ, C32-C33 βα, C32 αβ), hopanols (C32 ββ and αβ) and hopanone (22,29,30-trinorhop-21-one). C31 αβ-22R hopane was found to be the dominant hopanoid, more abundant than individual nalkanes derived from higher plants. These hopanoids, exclusive of some hopenes, are proposed to be primarily from bacteria. The dominant C31 αβ-22R hopane in young sediments, without any thermal maturation, might be formed through microbial epimerization under acidic conditions in the peatland as suggested before, or directly from aerobic bacteria. This finding highlights the importance of microbes in the formation of peatland as well as in the reconstruction of paleoenvironments.  相似文献   

19.
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   

20.
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   

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