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

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

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

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.     

Terpenoid biomarker distributions in low maturity crude oils

Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C₂₇, C₂₈, and C₂₉ sterane isomers. The useful maturity indicators include the C₂₉ 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C₂₇, C₂₈, and C₂₉ steranes, and the rearranged to normal sterane ratio. In addition, C₂₇ rearranged steran es appear to form at a faster rate than C₂₈ or C₂₉ rearranged steranes. However, the isomerization of the C₂₇ biological component appears to occur at a slower rate than the C₂₉ counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C₂₇ trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C₃₁₊ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C₃₁–C₃₄).     

Occurrences and distributions of branched alkylbenzenes in the Dongsheng sedimentary uranium ore deposits,China

A series of branched alkylbenzene ranging from C₁₅ to C₁₉ with several isomers (2–5) at each carbon number were identified in sediments from the Dongsheng sedimentary uranium ore deposits, Ordos Basin, China. The distribution patterns of the branched alkylbenzenes show significant differences in the sample extracts. The branched alkylbenzenes from organic-rich argillites and coals range from C₁₅ to C₁₉ homologues, in which the C₁₇ or C₁₈ dominated. On the other hand, the C₁₉ branched alkylbenzenes dominated in the sandstone/siltstone extracts. The obvious differences of the branched alkylbenzene distributions between the uranium-host sandstones/siltstones and the interbedded barren organic-rich mudstones/coals probably indicate their potential use as biological markers associated with particular depositional environments and/or maturity diagenetic processes. Possible origins for these branched alkylbenzenes include interaction of simple aromatic compounds with, or cyclization and aromatization reactions of, these linear lipid precursors such as fatty acids, methyl alkanoates, wax esters or alkanes/alkenes that occur naturally in carbonaceous sediments. The possible simple aromatic compounds may include substituted benzenes, functionalized compounds such as phenols that are bound to kerogen at the benzyl position, and phenols that are decomposition products derived from aquatic and terrestrial sources. The distributions of methyl alkanoates and n-alkanes were found to be different between organic-rich mudstone/coal and sandstone/siltstone. From this result, it can be concluded that such differences of the alkylbenzene distributions were mainly resulting from the differences of organic precursors, although maturity effect and radiolytic alteration cannot be completely excluded.     

The effect of biodegradation on polycyclic aromatic hydrocarbons in reservoired oils from the Liaohe basin, NE China

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 C_0–5-alkylnaphthalenes and the C_0–3-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 C_26–28 long side-chained counterparts. The C_21–22-monoaromatic steroid hydrocarbons (MAS) appear to be more resistant to biodegradation than the C_27–29-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.     

Efficiency of extraction of polycyclic aromatic hydrocarbons from the Paleoproterozoic Here’s Your Chance Pb/Zn/Ag ore deposit and implications for a study of Bitumen II

Demineralisation of a sedimentary rock with HF liberates a fraction of extractable organic matter (OM) that is not accessible with standard extraction techniques, which is known as Bitumen II. This fraction displays lower maturity parameters than the free extractable OM (Bitumen I). Studies of successive conventional extraction have found that the later steps show a decrease in maturity similar to that observed for Bitumen II. We aimed to investigate whether or not Bitumen II is simply the result of residual Bitumen I left over from the initial extraction.A series of successive Soxhlet extraction steps was performed on a highly mineralised sample from the Paleoproterozoic Here’s Your Chance (HYC) Pb–Zn–Ag deposit in the Northern Territory of Australia. The study showed that the extraction efficiency for polycyclic aromatic hydrocarbons (PAHs) decreased with increasing molecular weight. Maturity parameters based on methyl phenanthrenes generally decreased with successive extraction steps. This is because the thermodynamically more stable β isomers were preferentially extracted over the α isomers, so later extraction steps contained a greater proportion of α isomers. Bitumen II was prepared from a previously-studied sample from the same sample pit. It showed a decrease in maturity parameters relative to Bitumen I, but the distribution of PAHs did not match those of the later Bitumen I extraction steps. We conclude that Bitumen II did not result from incomplete extraction of Bitumen I. As Bitumen II is preserved within the kerogen–mineral matrix, it has potential for tracing the migration and maturation history of ancient or thermally altered systems.     

Organic geochemical evaluation of organic acids to assess anthropogenic soil deposits of Central Amazon,Brazil

Terra Preta de Índio (TPI) and Terra Mulata (TM) are anthropogenic soils from the Amazon region and are rich in stable organic matter (OM). The formation and incorporation of OM in these soils has recently been under investigation. Organic geochemical analysis is an appropriated tool for the assessment of the sources of OM. Therefore, we have used the distribution of different acid classes preserved in the free and bound soil fractions of 12 samples from two contrasting anthropogenic soils (TPI, TM) and an adjacent soil, in order to infer the sources of OM and the magnitude of non-cultural influence on the formation of anthropogenic soils. The major acids in both fractions (i.e. free and bound) were n-saturated, branched and unsaturated alkanoic acids, hydroxyalkanoic acids, bile acids and lignin/suberin derived aromatic acids. In general, the acids in the free and bound fractions appeared to be complementary and together provided valuable information about OM incorporation into anthropogenic soils. Different incorporation of ω-hydroxyalkanoic acids (C₂₂, C₂₄ and C₂₈) and 9(10),16-dihydroxyhexadecanoic acid, and presence/absence of bile acid showed a distinct genesis for the soils. The influence of modern vegetation was revealed by bound ω-hydroxyalkanoic acid (C₂₂, C₂₄ and C₂₈) distributions only in the topsoil profiles of TPI and TM, indicating that organic geochemical analysis is a useful approach in the investigation of ancient human deposits in tropical archaeological soils.     

Geochemical study on a well in the Western Canada Basin: relation of the aromatic distribution pattern to maturity of organic matter

Thirty-one rock samples from a Western Canada Basin well have been analysed for aromatics, using glass capillary gas chromatography with simultaneous flame ionization and sulfur-selective flame photometric detection. A uniform aromatic distribution pattern with a marked predominance of di- and tricyclic aromatic hydrocarbons was observed throughout a depth interval of 3000 meters comprising Cretaceous and Jurassic sediments. The very high relative abundance of sulfur aromatics at two narrow intervals in the Triassic and Mississippian is attributed to a major change in facies. Gradual changes with increasing depth have been observed for a series of compound ratios, which had been calculated from the isomers of methyl- and dimethylphenanthrene, and their parent compounds. These changes reflect the increasing thermal maturation of the sedimentary organic matter. A Methylphenanthrene Index (MPI) has been introduced, which exhibited a very good correlation with vitrinite reflectance data. The MPI is the first maturity parameter which is based on a series of aromatic hydrocarbons. This hydrocarbon internal maturity parameter permits the recognition and definition of maturity levels in extracts which can be compared to the maturity (e.g. vitrinite reflectance) of source rocks.     

A comparison of the distributions of carbazoles and dibenzothiophenes in western Qaidam Basin,Northwest China

Variations in the distributions of carbazoles and dibenzothiophenes were investigated in a set of source rocks, which differ mainly in their maturity levels during immature-mature stages. A comparison of the distributions of carbazoles and dibenzothiophenes has revealed the main results as follows- ① variations in the relative amounts of C0-, C1-, C2-dibenzothiophenes show a low correlation with that of the corresponding carbazoles, with the for- mer＇s being much higher than the latter＇s; ② variations in the relative amounts of methyldibenzothiophene isomers also display a low correlation with that of the corresponding methylcarbazoles, with 4-/4- ＋1-methyldibenzothio- phene ratio ranging from 0.52 to 0.96, while the corresponding carbazole ratio of 1-/1- ＋4-methylcarbazole only being 0.71-0.05; ③ the maturity parameter for 4,6-/4,6- ＋l,4-dimethyldibenzothiohene, ranging from 0.34 to 0.75, shows a remarkable linear correlation with the corresponding ratio of 1,8-/1,8- ＋1,4-dimethylcarbazole （R2〉0.84）. The un-correlation may indicate some different geological-geochemical fates for some isomers of dibenzothiophenes and carbazoles. The high correlation may reveal a strong maturation dependence on the dimethylcarbazole distribu- tions, indicating that attention should be paid when 1,8-/1,8- ＋1,4-dimethylcarbazole is used as a petroleum migra- tion indicator.     

Organic geochemical characteristics and depositional environments of the Jurassic coals in the eastern Taurus of Southern Turkey

In this study, organic matter content, type and maturity as well as some petrographic and physical characteristics of the Jurassic coals exposed in the eastern Taurus were investigated and their depositional environments were interpreted.The total organic carbon (TOC) contents of coals in the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc areas are 24.54, 66.78 and 49.15%, respectively. The Feke–Akkaya and Kozan–Kizilinc coals have low Hydrogen Index (HI) values while the Kozan–Gedikli coals show moderate HI values. All coal samples display very low Oxygen Index (OI) values. The Kozan–Gedikli coals contain Type II organic matter (OM), the Feke–Akkaya coals contain a mixture of type II and type III OM; and the Kozan–Kizilinc coals are composed of Type III OM. Sterane distribution was calculated as C₂₇ > C₂₉ > C₂₈ from the m/z 217 mass chromatogram for all coal samples.T_max values for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 439, 412 and 427 °C. Vitrinite reflectance values (%R_o) for the Feke–Akkaya and Kozan–Kizilinc coal samples were measured as 0.65 and 0.51 and these values reveal that the Feke–Akkaya and Kozan–Kizilinc coals are at subbituminous A or high volatile C bituminous coal stage. On the basis of biomarker maturity parameters, these coals have a low maturity.The pristane/phytane (Pr/Ph) ratios for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 1.53, 1.13 and 1.25, respectively. In addition, all coals show a homohopane distribution which is dominated by low carbon numbers, and C₃₅ homohopane index is very low for all coal samples. All these features may indicate that these coals were deposited in a suboxic environment.The high sterane/hopane ratios with high concentrations of steranes, low Pr/Ph ratios and C₂₅/C₂₆ tricyclic ratios > 1 may indicate that these coals formed in a swamp environment were temporarily influenced by marine conditions.     

Organic geochemistry of Miocene source rocks from the Banat Depression (SE Pannonian Basin, Serbia)

The origin, depositional environment and maturity of petroleum source rocks were determined via conventional whole rock and biomarker analysis of samples from wells in the Banat Depression, where the most important Serbian oil and gas fields are located. The organic matter (OM) in organic-rich upper Tertiary siltstones and marls consists predominantly of Type II kerogen. Numerous biomarker parameters indicated mixed algal-terrestrial OM, related to a brackish or freshwater environment, whose salinity decreased from Middle to Upper Miocene. The OM was deposited under variable redox conditions, reducing to sub-oxic.The wells in the Banat Depression experienced variable high rates of rapid heating, providing an opportunity for examining the applicability of different thermal indicators in a hyperthermal basin. Rock-Eval and numerous biomarker parameters indicate that the main stage of oil generation begins at ca.130 °C and vitrinite reflectance (Rc) ca. 0.63% and reaches a maximum at ca.145-150 °C and Rc ca. 0.72-0.75%, while the late stage of oil generation starts at ca.155 °C and ca. Rc 0.78%, which corresponds, depending on geothermal gradient, to relative depths of 2100-2300 m, 2600-2900 m and 3050-3100 m, respectively. The naphthalene and phenanthrene maturity parameters proved to be less applicable than the biomarker ratios, particularly in the early to moderate maturation range. The newly proposed parameter C(14a)-homo-26-nor-17α(H)-hopane/C₃₀hopane (C₃₀HH/C₃₀H) proved applicable to a wide range of maturity.     

Evolution of tricyclic alkanes in the Espirito Santo Basin,Brazil

The distributions of tricyclic isoprenoid alkanes were characterized in the Neocomian sequence from the Espirito Santo Basin, Brazil, by high-resolution gas chromatography-mass spectrometry and co-injection with synthetic standards where available. A suite of homologous components ranging from C₂₀ to C₂₈ were present throughout the sequence as a mixture of stereoisomers whose relative abundance changed with depth. The epimerization rates were similar for the various tricyclic compounds irrespective of side-chain length, achieving equilibrium ratios before the main stage of oil generation. This new maturity parameter should be useful as a supplement to sterane/hopane measurements.     

Novel aryl polycyclic aromatic hydrocarbons: Phenylphenanthrene and phenylanthracene identification, occurrence and distribution in sedimentary rocks

Numerous reports have recognised the presence of compounds with molecular weight 254 a.m.u. in aromatic fractions. However, their unequivocal identification has not been achieved due to a lack of reference substances. In geological samples, such m/z 254 compounds could potentially be represented by a number of structural isomers of binaphthyl, phenylphenanthrene, phenylanthracene and indenofluorene with each compound type possessing several positional isomers. In this work, all these m/z 254 compounds, with the exception of the tentatively recognised indenofluorenes, have been unequivocally identified in sedimentary rocks for the first time. Comparison of the mass spectra and the gas chromatography (GC) retention times of synthesised standards with the natural compounds in rocks shows that the major components of aromatic fractions are phenylphenanthrene isomers and, to a lesser extent, binaphthyls and 9-phenylanthracene. The elution sequence expressed as standard retention indices of all these m/z 254 isomers were determined by using high resolution capillary GC with three stationary phases: 5%, 35% and 50% (mole fraction) phenyl substituted methylpolysiloxane on HP-5MS, DB-35MS and DB-17MS columns, respectively. A survey of more than 350 sedimentary rock samples of varying origins and maturity (R_r 0.3–1.4%) reveals that relative abundances of the m/z 254 isomers depend on the maturity of the organic matter. The isomers initially appear at the onset of oil generation (R_r > 0.5%) exclusively in diagenetically/catagenetically oxidised samples containing varying proportions of Types II and III kerogen. Interestingly, all five possible positional phenylphenanthrene isomers (including the most sterically hindered isomer 4-phenylphenanthrene) are present from the beginning of the oil generation window. Such a distribution suggests that low-regioselectivity reactions are likely to be involved in the formation. Interaction, during maturation, of phenyl radicals from primary cracking with aromatic moieties of more resistant terrigenic components of kerogen in an oxidising diagenetic realm is postulated to be responsible for the neoformation of phenylated aromatics in geological samples. Up to the final stages of oil generation, the evolution of the phenyl PAH distributions presumably involve 1,2-phenyl shift reactions and cyclisation, if allowed by the molecular geometry. A near thermodynamically-controlled distribution, with only 3- and 2-phenylphenanthrene and minor 2,2′-binaphthyl remaining, is approached when vitrinite reflectance reaches 1.2% (R_r). The three compounds seem to be persistent beyond the oil window as is suggested by their presence in hydrothermal oil formed at T > 300 °C.     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state C NMR spectroscopy

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R₀ from 0.29% to 1.27%). Specific functional groups such as CH₃, CH₂, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as “oil prone” and “gas prone” carbons, have been quantified by ¹³C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (∼30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ∼30 carbons, and of ∼20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range ¹H-¹³C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters.     

An assessment of paleodepositional environment and maturity of organic matter in sediments of the Setap Shale and Belait formations in West Sabah,East Malaysia by organic geochemical methods

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/22SC_31–33 extended hopane ratios and 20S/(20S+20R)C₂₉ regular steranes ratios.     

New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

Characteristics and Natural Gas Origin of Middle−Late Triassic Marine Source Rocks of the Western Sichuan Depression, SW China

A scientific exploration well(CK1) was drilled to expand the oil/gas production in the western Sichuan depression, SW, China. Seventy-three core samples and four natural gas samples from the Middle–Late Triassic strata were analyzed to determine the paleo-depositional setting and the abundance of organic matter(OM) and to evaluate the hydrocarbon-generation process and potential. This information was then used to identify the origin of the natural gas. The OM is characterized by medium n-alkanes(n C_(15)–n C_(19)), low pristane/phytane and terrigenous aquatic ratios(TAR), a carbon preference index(CPI) of ～1, regular steranes with C_(29) C_(27) C_(28), gammacerane/C_(30) hopane ratios of 0.15–0.32, and δD_(org) of-132‰ to-58‰, suggesting a marine algal/phytoplankton source with terrestrial input deposited in a reducing–transitional saline/marine sedimentary environment. Based on the TOC, HI index, and chloroform bitumen "A" the algalrich dolomites of the Leikoupo Formation are fair–good source rocks; the grey limestones of the Maantang Formation are fair source rocks; and the shales of the Xiaotangzi Formation are moderately good source rocks. In addition, maceral and carbon isotopes indicate that the kerogen of the Leikoupo and Maantang formations is type Ⅱ and that of the Xiaotangzi Formation is type Ⅱ–Ⅲ. The maturity parameters and the hopane and sterane isomerization suggest that the OM was advanced mature and produced wet–dry gases. One-dimensional modeling of the thermal-burial history suggests that hydrocarbon-generation occurred at 220–60 Ma. The gas components and C–H–He–Ar–Ne isotopes indicate that the oilassociated gases were generated in the Leikoupo and Maantang formations, and then, they mixed with gases from the Xiaotangzi Formation, which were probably contributed by the underlying Permian marine source rocks. Therefore, the deeply-buried Middle–Late Triassic marine source rocks in the western Sichuan depression and in similar basins have a great significant hydrocarbon potential.