In this study, a C9+ fraction of saturate-rich Tertiary source rock-derived oil from the South China Sea basin was pyrolyzed in normal and supercritical water using a 25 mL vessel at a range of temperature from 350 to 425 °C for 24 h, to probe pressure effects up to 900 bar on gas yields and their stable carbon isotopic compositions during thermal cracking. Pressure generally retards oil cracking, as evidenced by reduced gas yields, but the trends depend upon the level of thermal evolution. In the early stages of cracking (350 and 373 °C, equivalent vitrinite reflectance of < ∼1.1% R0), the suppression effect increases with pressure from 200 to 900 bar, but it is most marked between 200 and 470 bar. At the later stages in the wet gas window (390, 405, and 425 °C, equivalent vitrinite reflectance of >1.3% R0), pressure still has a strong suppression effect from 200 to 470 bar, which then levels off or is reversed as the pressure is increased further to 750 and 900 bar. Interestingly, the stable carbon isotopic composition of the generated methane becomes enriched in 13C as the pressure increases from 200 to 900 bar. A maximum fractionation effect of ∼3‰ is observed over this pressure range. Due to pressure retardation, the isotopically heaviest methane signature does not coincide with the maximum gas yield, contrary to what might be expected. In contrast, pressure has little effect on ethane, propane, and butane carbon isotope ratios, which show a maximum variation of ∼1‰. The results suggest that the rates of methane-forming reactions affected by pressure control methane carbon isotope fractionation. Based on distinctive carbon isotope patterns of methane and wet gases from pressurized oil cracking, a conceptual model using “natural gas plot” is constructed to identify pressure effect on in situ oil cracking providing other factors excluded. The transition in going from dry conditions to normal and supercritical water does not have a significant effect on oil-cracking reactions as evidenced by gold bag hydrous and anhydrous pyrolysis results at the same temperatures as used in the pressure vessel.

Due to the importance of the Gloeocapsomorpha Prisca (G. prisca)-enriched source rocks, which belong to Kukersite-type source rocks in the Lower Paleozoic Ordovician strata, it has received great attentions during the petroleum exploration as to whether there are the Kukersite-type source rocks developed in the major hydrocarbon source strata of the Upper and Middle Ordovician in the Tarim Basin. Using pyrolysis-gas chromatography-mass spectrography to analyse kerogens from source rocks in the lime- mud mound with moderate maturity, study reveals that there are the Kukersite-type source rocks in the Ordovician strata of the Tarim Basin. The pyrolysis products showed a low content of >n-C19 normal alkanes with a significant odd-even predominance between n-C13 and n-C17, long-chain alky substituted alkylbenzene and alkylthiophene isomers and distinctive distribution of 5-N-alkyl-1, 3-Benzenediol and its homologous. Based on the geographic environment characteristics of G. Prisca, the molecular distributions of crude oil from the Lower Paleozoic petroleum systems in the Tarim Basin and characteristics of kerogen pyrolysis products from the Middle and Upper Ordovician source rocks, the results suggested that it is less possible to develop the G. Prisca-enriched Kukersite-type source rocks in the major hydrocarbon source rocks in the Middle and Upper Ordovician strata in the Tarim Basin. However, the benthic macroalga and planktonic algae-enriched source rocks are the main contributors.

Although the distribution of mono-, di- and trimethylated 2-methyl-2-(4,8,12-Trimethyltrideeyl) chromans (MTTCs) is well understood as an indicator of water salinity, their origin and formation mechanism are still ambiguous and under debate. In this paper, abnormally high levels of MTTCs were detected in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin. Using a two-step column chromatography method, the MTTCs and naphthalenes were separated from other aromatic compounds and concentrated in one fraction, so that the stable carbon isotope compositions of these compounds could be accurately measured. Similar carbon isotope ratios for the mono-, di- and trimethylated 2-methyl-2-(4,8,12-Trimethyltrideeyl) chromans in a given sample suggest the MTTCs may share the same biological source(s). The MTTCs from the Western Qaidam Basin have similar carbon isotope compositions to primary producer-derived pristane and phytane. However, the δ13C values for the MTTCs showed significant differences with other primary producers-derived biomarkers (e.g. C27 and C29 steranes), probably indicating a distinct microalgae source from specific niches for the MTTC compounds. We speculate that the MTTCs distribution patterns may be controlled by the water chemistry dynamics in niches, which, in turn, is affected by hypersaline bottom water.

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

Large amounts of data regarding the influence of temperature and pressure on the thermal stability of crude oil have been published; however, the role of reservoir mediums has received little attention. Experiments involving oil cracking in the presence of montmorillonite, illite, calcite, quartz and water were conducted in closed gold tubes to investigate the effects of these reservoir mediums on oil destruction. This was done by screening variations in the chemical and stable carbon isotopic components of nC10+ and gasoline-range hydrocarbons (nC8−) present in various systems. Results indicated that reservoir mediums have an active role in oil cracking under experimental conditions. The concentrations of nC10+ in the cracked residues progressively decreased in systems containing oil+water+illite, oil+water+montmorillonite, oil+water, oil+water+quartz and oil+water+calcite. In comparison with the system containing oil+water, our results indicated a retardation effect for oil cracking in systems in the presence of illite and montmorillonite, and an acceleration effect on oil destruction in systems in the presence of calcite and quartz. nC10+ became increasingly depleted in 13C in systems with oil+water+illite, oil+water+calcite, oil+water+montmorillonite, oil+water+ quartz and oil+water. No obvious correlation was observed between concentrations and stable carbon isotopic components of nC6-nC8 and nC10+ in the individual systems. The discrepancies in chemical and stable carbon isotopic components of nC6-nC8 and nC10+ in the pyrolyzed residues highlighted the important role of reservoir mediums to control carbon-carbon cleavage of nC10+ and then the isomerization, cyclolization and aromatization reactions; as well as governing the occurrence and thermal destruction of nC6-nC8 under experimental conditions. This research may have critical implications in reconstructing chemical kinetic models for natural oil cracking.

•Oil fingerprints failed to differentiate the spilled oil from highly similar suspected oils.•Specific biomarkers can be a quick scanning tool for determining the possible source.•Multidimensional scaling analysis is introduced to pinpoint the source.Oil fingerprints have been a powerful tool widely used for determining the source of spilled oil. In most cases, this tool works well. However, it is usually difficult to identify the source if the oil spill accident occurs during offshore petroleum exploration due to the highly similar physiochemical characteristics of suspected oils from the same drilling platform. In this report, a case study from the waters of the South China Sea is presented, and multidimensional scaling analysis (MDS) is introduced to demonstrate how oil fingerprints can be combined with mathematical methods to identify the source of spilled oil from highly similar suspected sources. The results suggest that the MDS calculation based on oil fingerprints and subsequently integrated with specific biomarkers in spilled oils is the most effective method with a great potential for determining the source in terms of highly similar suspected oils.

•The αβ and βα configurations of hopanes are mainly derived from contamination by fossil fuels or allochthonous sources.•17β(H), 21β(H)-32-hopanoic acid with different δ13C values that point to different archaea/SRB consortia.•The source organism of BHPs probably consist of a combination of both SRB and type I methanotrophs.The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography–mass spectrometer (GC–MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd–even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17β(H), 21β(H)-hopanoid acids were detected with C32 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17β(H), 21β(H)-hopanoic acid among samples (−30.7‰ to −69.8‰). The δ13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.

•We used SaFAs to estimate the proportion of the terrigenous input to Shenhu.•Most SaFAs are of microbe origin while others are from the terrestrial plants.•The marine input is relatively high due to the hydrocarbon seepage.This study examined the distributions and stable carbon isotopic compositions of saturated fatty acids (SaFAs) in one 300 cm long sedimentary profile, which was named as Site4B in Shenhu, northern South China Sea. The concentrations of total SaFAs in sediments ranged from 1.80 to 10.16 μg/g (μg FA/g dry sediment) and showed an even-over-odd predominance in the carbon chain of C12 to C32, mostly with n-C16 and n-C18 being the two major components. The short-chain fatty acids (ScFAs; n-C12 to n-C18) mainly from marine microorganisms had average δ13C values of −26.7‰ to −28.2‰, whereas some terrigenous-sourced long-chain fatty acids (LcFAs; n-C21 to n-C32) had average δ13C values of −29.6‰ to −34.1‰. The other LcFAs (n-C24 & n-C26 ∼ n-C28; average δ13C values are −26.1‰ to −28.0‰) as well as n-C19 and n-C20 SaFAs (average δ13C values are −29.1‰ and −29.3‰, respectively) showed a mixed signal of carbon isotope compositions.The relative bioproductivity calculation (marine vs. terrigenous) demonstrated that most of organic carbon accumulation throughout the sedimentary profile was contributed by marine organism. The high marine productivity in Shenhu, South China Sea may be related to the hydrocarbon seepage which evidenced by diapiric structures. Interestingly, there is a sever fluctuation of terrigenous inputs around the depth of 97 cm below the seafloor (bsf), probably resulting from the influence of the Dansgaard–Oeschger events and the Younger Dryas event as revealed by 14C age measurements.

Polynuclear aromatic hydrocarbons (PAHs) and black carbon (BC) in sediments are powerful tools in the identification of the combustion process throughout geologic history. In this study, combustion-derived PAHs and BC were carefully investigated in sediments from the Global Stratotype Section and Point of the Permian–Triassic (P/Tr) boundary in Meishan, China. Quantitative analyses of combustion-derived PAHs and BC demonstrate anomalously high concentrations in the boundary event beds that coincide with the mass extinction horizon. The prevalence of parent polynuclear aromatics (e.g., phenanthrene) in PAHs, together with non-metric multidimensional scaling analysis, confirms that the PAHs are mainly derived from vegetation burning instead of having a coal and/or oil origin. BC detected in sediment occurs in various forms from large irregular charcoal particles to fine aciniform soot, with an equivalent reflectance of up to 3.5%. The results strongly suggest that a wildfire occurred during the P/Tr boundary, which served as one of the possible triggers of mass extinction on land. The wildfire occurrence indicates that the O2 concentration of the atmosphere during (or before) the P/Tr mass extinction was probably >17%. The temporal coincidence of the mass extinction with intensive volcanic eruption, marine anoxia and wildfire events in the region of the Meishan section provides new insight into the mechanisms of the P/Tr biotic crisis. Our results show that wildfires could have played an important role in the collapse of the ecosystem in the Meishan P/Tr events.