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1.
The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c27-c29 diasteranes [13β(H),17α(H); 20R + S] and C28-C29 regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C27-C29 regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.  相似文献   

2.
Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C1, C2–C5, C6–C15 and C15+). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.  相似文献   

3.
A large suite of natural gases (93) from the North West Shelf and Gippsland and Otway Basins in Australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases. About 26% of these gases have anomalous stable carbon isotope compositions in the C1–C4 hydrocarbons and CO2 components, and are interpreted to have a secondary biogenic history. The characteristics include unusually large isotopic separations between successive n-alkane homologues (up to +29‰ PDB) and isotopically heavy CO2 (up to +19.5‰ PDB). Irrespective of geographic location, these anomalous gases are from the shallower accumulations (600–1700 m) where temperatures are lower than 75°C. The secondary biogenic gases are readily distinguishable from thermogenic gases (74% of this sample suite), which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m. While dissolution effects may have contributed to the high 13C enrichment of the CO2 component in the secondary biogenic gases, the primary signature of this CO2 is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis. Correlation between biodegraded oils and biodegraded “dry” gas supports the concept that gas is formed from the bacterial destruction of oil, resulting in “secondary biogenic gas”. Furthermore, the prominence of methanogenic CO2 in these types of accumulations along with some isotopically-depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked. It is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis.  相似文献   

4.
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.  相似文献   

5.
Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C16–C29 range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.  相似文献   

6.
Hydrocarbon mixtures too complex to resolve by traditional capillary gas chromatography display gas chromatograms with dramatically rising baselines or “humps” of coeluting compounds that are termed unresolved complex mixtures (UCMs). Because the constituents of UCMs are not ordinarily identified, a large amount of geochemical information is never explored. Gas chromatograms of saturated/unsaturated hydrocarbons extracted from Late Archean argillites and greywackes of the southern Abitibi Province of Ontario, Canada contain UCMs with different appearances or “topologies” relating to the intensity and retention time of the compounds comprising the UCMs. These topologies appear to have some level of stratigraphic organization, such that samples collected at any stratigraphic formation collectively are dominated by UCMs that either elute early- (within a window of C15–C20 n-alkanes), early- to mid- (C15–C30 n-alkanes), or have a broad UCM that extends through the entire retention time of the sample (from C15–C42 n-alkanes). Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC–MS) was used to resolve the constituents forming these various UCMs. Early- to mid-eluting UCMs are dominated by configurational isomers of alkyl-substituted and non-substituted polycyclic compounds that contain up to six rings. Late eluting UCMs are composed of C36–C40 mono-, bi-, and tricyclic archaeal isoprenoid diastereomers. Broad UCMs spanning the retention time of compound elution contain nearly the same compounds observed in the early-, mid-, and late-retention time UCMs. Although the origin of the polycyclic compounds is unclear, the variations in the UCM topology appear to depend on the concentration of initial compound classes that have the potential to become isomerized. Isomerization of these constituents may have resulted from hydrothermal alteration of organic matter.  相似文献   

7.
Insights into oil cracking based on laboratory experiments   总被引：3，自引：0，他引：3  
The objectives of this pyrolysis investigation were to determine changes in (1) oil composition, (2) gas composition and (3) gas carbon isotope ratios and to compare these results with hydrocarbons in reservoirs. Laboratory cracking of a saturate-rich Devonian oil by confined, dry pyrolysis was performed at T=350–450 °C, P=650 bars and times ranging from 24 h to 33 days. Increasing thermal stress results in the C15+ hydrocarbon fraction cracking to form C6–14 and C1–5 hydrocarbons and pyrobitumen. The C6–14 fraction continues to crack to C1–5 gases plus pyrobitumen at higher temperatures and prolonged heating time and the δ 13Cethane–δ13Cpropane difference becomes greater as oil cracking progresses. There is considerable overlap in product generation and product cracking. Oil cracking products accumulate either because the rate of generation of any product is greater than the rate of removal by cracking of that product or because the product is a stable end member under the experimental conditions. Oil cracking products decrease when the amount of product generated from a reactant is less than the amount of product cracked. If pyrolysis gas compositions are representative of gases generated from oil cracking in nature, then understanding the processes that alter natural gas composition is critical.  相似文献   

8.
Suberinite, and subereous components of amorphous nature, comprise largely unrecognized, proficient sources of liquid hydrocarbons. Due to difficulties in recognizing the presence of subereous components and suberinite in organic sediments, the contributions of these liptinitic components to the organic input of source rocks are easily underestimated. Severe chemical alterations of suberinite in the vitrinite reflectance range of Ro = 0.35–0.60% are demonstrated. Organic geochemical data, obtained from samples subjected to natural maturation, reveal that subereous components/suberinite undergoes early thermal degradation to generate large amounts of hydrocarbons below Ro = 0.60%. Data obtained from laboratory maturation of immature, suberinite-rich coals indicate that about 50% of the potential of suberinite for generating C12+ hydrocarbons has already been exhausted during natural maturation of the samples, prior to the onset of the traditionally defined “oil window”. The present data (a) contradict the assumption that suberinite is mainly sourced by selective preservation/enrichment of a stable, highly aliphatic biopolymer, i.e. “suberan” and (b) suggest that suberinite contains appreciable amounts of aliphatic and aromatic moieties which are released at low thermal stress.  相似文献   

9.
Leping coal is known for its high content of “barkinite”, which is a unique liptinite maceral apparently found only in the Late Permian coals of South China. “Barkinite” has previously identified as suberinite, but on the basis of further investigations, most coal petrologists conclude that “barkinite” is not suberinite, but a distinct maceral. The term “barkinite” was introduced by (State Bureau of Technical Supervision of the People's Republic of China, 1991, GB 12937-91 (in Chinese)), but it has not been recognized by ICCP and has not been accepted internationally.In this paper, elemental analyses (EA), pyrolysis-gas chromatography, Rock-Eval pyrolysis and optical techniques were used to study the optical features and the hydrocarbon-generating model of “barkinite”. The results show that “barkinite” with imbricate structure usually occurs in single or multiple layers or in a circular form, and no definite border exists between the cell walls and fillings, but there exist clear aperture among the cells.“Barkinite” is characterized by fluorescing in relatively high rank coals. At low maturity of 0.60–0.80%Ro, “barkinite” shows strong bright orange–yellow fluorescence, and the fluorescent colors of different cells are inhomogeneous in one sample. As vitrinite reflectance increases up to 0.90%Ro, “barkinite” also displays strong yellow or yellow–brown fluorescence; and most of “barkinite” lose fluorescence at the maturity of 1.20–1.30%Ro. However, most of suberinite types lose fluorescence at a vitrinite reflectance of 0.50% Ro, or at the stage of high volatile C bituminous coal. In particular, the cell walls of “barkinite” usually show red color, whereas the cell fillings show yellow color under transmitted light. This character is contrary to suberinite.“Barkinite” is also characterized by late generation of large amounts of liquid oil, which is different from the early generation of large amounts of liquid hydrocarbon. In addition, “barkinite” with high hydrocarbon generation potential, high elemental hydrogen, and low carbon content. The pyrolysis products of “barkinite” are dominated by aliphatic compounds, followed by low molecular-weight aromatic compounds (benzene, toluene, xylene and naphthalene), and a few isoprenoids. The pyrolysis hydrocarbons of “barkinite” are mostly composed of light oil (C6–C14) and wet gas (C2–C5), and that heavy oil (C15+) and methane (C1) are the minor hydrocarbon.In addition, suberinite is defined only as suberinized cell walls—it does not include the cell fillings, and the cell lumens were empty or filled by corpocollinites, which do not show any fluorescence. Whereas, “barkinite” not only includes the cell walls, but also includes the cell fillings, and the cell fillings show bright yellow fluorescence.Since the optical features and the hydrocarbon-generating model of “barkinite” are quite different from suberinite. We suggest that “barkinite” is a new type of maceral.  相似文献   

10.
《Applied Geochemistry》2006,21(5):833-838
Some hydrocarbons occluded inside asphaltene structures can be considered to be “original oil”, and are very important especially for severely post-altered crude oil in related geochemical studies such as oil/oil, oil/source correlation. The use of oxidising reagents could properly release these occluded hydrocarbons, and make possible direct study of these compounds without interference from the segments chemically bonded to the asphaltene molecule. Interference from adsorbed and/or co-precipitated compounds can be avoided by applying an asphaltene purification procedure.  相似文献   

11.
This paper deals with natural temperature records in the heavy (asphaltenes) and the light fractions (C7—light hydrocarbons) of petroleum. Two sets of marine oils formed from different source rocks and petroleum systems were studied using asphaltene kinetics and light hydrocarbon analysis. Both fractions have been reported to contain information about the temperature the respective oils have been exposed to in the subsurface. These indicated temperatures generally correspond to the conditions in the source rock when expulsion occurred. Bulk kinetic analysis of reservoir oil asphaltenes as well as light hydrocarbon (LH) analysis (of dimethylpentanes) were used here in order to evaluate the expulsion temperatures. Surprisingly, when considering information coming from both fractions, an inverse trend between LHs expulsion temperatures (Ctemp) and asphaltenes (Tasph.) can be observed—high Tasph (asphaltene temperatures) occur with low LH Ctemp (light hydrocarbon expulsion temperatures) and low Tasph can be observed when Ctemp is high. These differences are of fundamental importance for the use of such geochemical data in calibrating numerical basin models. The reason for this inverse behaviour is possibly due to the different expulsion behaviour of light hydrocarbons and the heavy fraction of oils, especially when the source rocks contain only moderate amounts of organic matter. In addition it has to be considered that the temperature predictions obtained using asphaltene kinetic analysis are related to the onset temperature of petroleum expulsion, while light hydrocarbons provide, at best, average expulsion temperatures.  相似文献   

12.
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   

13.
The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state 13C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C19), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C1–C6 alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.  相似文献   

14.
Organic inclusions could be formed at the stages of either primary or secondary migration of hydrocarbons so long as mineral crystallization or recrystallization takes place in the sediments, presenting a direct indicator of oil/gas evolution, migration and abundance. Based on the study of organic inclusions in carbonate-type reservoir beds of commercial importance from North China, Xingjing, North Jiangsu, Jianghan, Sichuan and Guizhou in China, many inclusion parameters for oil/gas potential assessment of carbonate reservoir beds are summarized in this paper, including: 1) Types of organic inclusion: Commercially important oil beds are characterized by inclusions consisting of either pure liquid hydrocarbons or liquid plus minor gaseous hydrocarbons, while commercially important gas reservoirs are characterized by inclusions consisting of either pure gaseous hydrocarbons or gas plus minor liquid hydrocarbons. 2) Quantity of organic inclusions: The number of organic inclusions in commercially important oil/gas reservoirs is over 60% of the total inclusion percentage. 3) Temperature of saline inclusions: The homogenization temperatures of contemporaneous saline inclusions in oil reservoirs range from 91–161 °C, while in gas reservoirs from 150–250 °C). 4) Inclusion composition: In commercially important oil reservoirs, C1/C2=2−10, C1/C3=2−4, C1/C4=2−21, (C2−C4)/(C1−C4)(%)>20, (CH4+CO+H2)/CO2 (molecules/g)=0.5−1.0, and in C2−C3−nC4 triangle diagram there should be an upside-down triangle with the apex within the ellipse, while in commercial gas reservoirs, C1/C2=10−35, C1/C3=14−82, C1/C4=21−200, (C2−C4)/(C1−C4)(%)<20, (CH4+CO+H2)/CO2>1, and there would be an upright triangle with the apex within the ellipse. The above-mentioned parameters have been used to evaluate a number of other unknown wells or regions and the results are very satisfactory. It is valid to use organic inclusions as an indicator to assess the oil/gas potential during oil/gas exploration and prospecting. This approach is effective, economic, rapid, and easy to popularize.  相似文献   

15.
To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C28–C32 thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C28–C32 diols and alkenols, characteristic lipids of N. salina. C1–C2 alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.  相似文献   

16.
Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C4 and C3 plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C11 to C31, and the C4-derived n-alkenes/alkanes were approx. 8‰ more enriched in 13C than the C3-derived compounds. Both the C4 and C3-derived n-alkenes/alkanes (C20-C30) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in 13C than the lower mol. wt (C1111-C19) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C4 and C3-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.  相似文献   

17.
The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) has been studied in oil columns from the Liaohe basin, NE China, characterized by varied degrees of biodegradation. The Es3 oil column has undergone light to moderate biodegradation – ranging from levels 2 to 5 on the [Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Cliffs, NJ, p. 363] scale (abbreviated as ‘PM level’) – while the shallower Es1 column has undergone more severe biodegradation, ranging from PM level 5 to 8. Both columns show excellent vertical biodegradation gradients, with degree of biodegradation increasing with increasing depth toward the oil–water contact (OWC). The compositional gradients in the oil columns imply mass transport control on degradation rates, with degradation occurring primarily at the OWC. The diffusion of hydrocarbons to the OWC zone will be the ultimate control on the maximum degradation rate. The chemical composition and physical properties of the reservoired oils, and the ‘degradation sequence’ of chemical components are determined by mixing of fresh oil with biodegraded oil.The PAH concentrations and molecular distributions in the reservoired oils from these biodegraded columns show systematic changes with increasing degree of biodegradation. The C3+-alkylbenzenes are the first compounds to be depleted in the aromatic fraction. Concentrations of the C0–5-alkylnaphthalenes and the C0–3-alkylphenanthrenes decrease markedly during PM levels 3–5, while significant isomer variations occur at more advanced stages of biodegradation (>PM level 4).The degree of alkylation is a critical factor controlling the rate of biodegradation; in most cases the rate decreases with increasing number of alkyl substituents. However, we have observed that C3-naphthalenes concentrations decrease faster than those of C2-naphthalenes, and methylphenanthrenes concentrations decrease faster than that of phenanthrene. Demethylation of a substituted compound is inferred as a possible reaction in the biodegradation process.Differential degradation of specific alkylated isomers was observed in our sample set. The relative susceptibility of the individual dimethylnaphthalene, trimethylnaphthalene, tetramethylnaphthalene, pentamethylnaphthalene, methylphenanthrene, dimethylphenanthrene and trimethylphenanthrene isomers to biodegradation was determined. The C20 and C21 short side-chained triaromatic steroid hydrocarbons are degraded more readily than their C26–28 long side-chained counterparts. The C21–22-monoaromatic steroid hydrocarbons (MAS) appear to be more resistant to biodegradation than the C27–29-MAS.Interestingly, the most thermally stable PAH isomers are more susceptible to biodegradation than less thermally stable isomers, suggesting that selectivity during biodegradation is not solely controlled by thermodynamic stability and that susceptibility to biodegradation may be related to stereochemical structure. Many commonly used aromatic hydrocarbon maturity parameters are no longer valid after biodegradation to PM level 4 although some ratios change later than others. The distribution of PAHs coupled with knowledge of their biodegradation characteristics constitutes a useful probe for the study of biodegradation processes and can provide insight into the mechanisms of biodegradation of reservoired oil.  相似文献   

18.
Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ13C values are found in the Tarim and Qaidam basins (δ13C1: − 19.0 to − 29.9‰; δ13C2: − 18.8 to − 27.1‰), and those with lowest δ13C values occur in the Turpan-Harmi and Junggar basins (δ13C1: − 40.1 to − 44.0‰; δ13C2: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ13C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.  相似文献   

19.
A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S2=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S2=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S2=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.  相似文献   

20.
A new maturity parameter determined on both oil and bitumen samples, the asphaltene Tmax, is proposed and discussed. This parameter could be very useful to address the maturity of the source rock. The asphaltene Tmax is measured by programmed Rock-Eval pyrolysis, using a modified temperature program. Some phases of the experimental procedure, such as the asphaltene preparation and the Rock-Eval measurement substratum choice, are crucial in order to achieve reliable data. Laboratory simulations were carried out in order to assess the possible effects of both primary and secondary migration on asphaltene Tmaxin the expelled oil: the original value of the asphaltene Tmax in the bitumen is not substantially modified and it is very close to that measured on kerogen. Examples of the determination of asphaltene Tmax on many samples, collected from different areas and with different organic matter composition, are given. Results show that Tmax values from oil asphaltenes are reasonable indicators of source rock maturity.  相似文献   

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