Origin of light hydrocarbon gases from the Matsukawa geothermal area in Japan

Light hydrocarbon and isotope compositions of methane were analyzed in well steam samples from the Matsukawa vapour-dominated type geothermal system. Alkanes (C₁-C₄) and alkene (C₂) were detected in all samples. Light hydrocarbon contents of CO₂-type steam are slightly higher than those of CO₂-H₂S-type steam. The isotope composition of methane and the relationship between methane/ethane ratio and δ¹³C-value of methane suggest that these light hydrocarbon gases are mixtures of thermogenic and abiogenic components. The abiogenic hydrocarbon may be attributed to magmatic hydrocarbon gases equilibrated with carbon dioxide at f_o2 defined by the fayalite-magnetite-quartz buffer (FMQ).     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.     

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C₂₄ with (1) MgSO₄; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C₂₄ with MgSO₄ was initiated at 431 °C, coincident with the evolution of C₂–C₅ hydrocarbons. Whereas the yields of H₂S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very ¹³C depleted, but became progressively heavier with pyrolysis temperature and were more ¹³C enriched than the values of a control treatment conducted on just n-C₂₄ above 475 °C. TSR of MgSO₄ also led to progressively higher concentrations of CO₂ showing relatively low δ¹³C values, possibly due to input of isotopically light CO₂ derived from gaseous hydrocarbon oxidation (e.g., more depleted CH₄).     

Variations in the carbon isotope composition and production yield of various pyrolysis products under open and closed system conditions

Production rates and carbon isotopic compositions of various pyrolysis products were investigated for three sediments from the Williston Basin under open and closed pyrolysis conditions in the temperature range of 300–600°C.Both parameters do not show any significant differences for kerogens and carbon dioxides with the analytical procedure. Contrary to open system pyrolysis, however, decreasing yields of pyrolysates and higher amounts of gaseous hydrocarbons (C_2–4 compounds) at temperatures of 500 and 600°C, point to their decomposition to give ultimately methane.Moreover, these pyrolysis products display distinct carbon isotopic variations under open and closed pyrolysis conditions. They are due to a kinetic isotope effect, i.e. the preferential cleavage of ¹²C-¹²C over ¹³C-¹²C bonds, but the extent of the shift in isotopic composition seems to depend primarily on the reservoir size and the type of source material.     

Mathematical models for petroleum-forming processes: carbon isotope fractionation

A mathematical model has been developed in which carbon isotope fractionation during thermal cracking of n-paraffins can be simulated. The model has been calibrated based on data from laboratory cracking experiments carried out on n-octadecane. Relative rate constants for cleavage of C¹²-C¹², C¹²-C¹³ and C¹³-C¹³ bonds agree with the experimental values obtained by other workers.Application of this model to the process of petroleum formation gives good agreement with some existing experimental data, but suggests that a review of our understanding of isotope fractionation during thermal cracking may be necessary. The relative importance of the degree to which the organic material has been cracked and of the type of the organic material in influencing δC¹³ values is discussed.The present model predicts that cracking of n-paraffin distributions having initial odd or even carbon number predominances can induce isotopic inhomogeneity among the homologs of the resulting distribution. The model exhibits some deficiencies in explaining or predicting the δC¹³ values of ethane and propane in relation to methane in gases and of oils and associated methane. Explanations for these discrepancies may lie in the simplicity of our mathematical model, in our assumption of initial isotopic homogeneity within molecules and in our use of only n-paraffins as the source molecules for the cracking reactions.     

Closed system Fischer-Tropsch synthesis over meteoritic iron,iron ore and nickel-iron alloy

Meteoritic iron, iron ore and nickel-iron alloy (either alone or in some cases mixed with alumina, carbonaceous chondrite, potassium carbonate or sodium carbonate) were used to catalyze the reaction of deuterium and carbon monoxide in a closed reaction vessel. The mole ratio of deuterium to carbon monoxide ranged from 1/2:1 to 10:1, the reaction temperature from 195 to 370°C, and the reaction time from 6 to 480 hr. Analysis of the reaction products showed that normal alkanes and alkenes (C₁₁-C₂₅), their monomethyl substituted isomers and aromatic hydrocarbons (e.g. naphthalene, acenaphthene, fluorene, phenanthrene and the methyl derivatives of these hydrocarbons) were synthesized. In addition to the aforementioned hydrocarbons, one reaction product was shown to contain perdeutero normal fatty acids (10:0–16:0).     

Experimental study of the effects of thermochemical sulfate reduction on low molecular weight hydrocarbons in confined systems and its geochemical implications

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-C_6-8 normal alkanes (low molecular weight, LMW), C_7-8 isoalkanes, C_6-7 cycloalkanes and C_6-9 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.     

Diagnostic lipid biomarker and stable carbon isotope signatures of microbial communities mediating the anaerobic oxidation of methane with sulphate

The anaerobic oxidation of methane (AOM) with sulphate is the most important sink for methane in marine environments. This process is mediated by a consortium of methanotrophic archaea and sulphate reducing bacteria. So far, three groups of anaerobic methane oxidisers (ANME-1, -2 and -3) related to the methanogenic Methanosarcinales and Methanomicrobiales were discovered. The sulphate reducing partner of ANME-1 and -2 are two different eco-types of SRB related to the Desulfosarcina/Desulfococcus cluster (Seep-SRB1), whereas ANME-3 is associated with Desulfobulbus spp. (DBB). In this article, we reviewed literature data to assign statistically significant lipid biomarker signatures for a chemotaxonomic identification of the three known AOM communities. The lipid signatures of ANME-2/Seep-SRB1 and ANME-3/DBB are intriguingly similar, whereas ANME-1/Seep-SRB1 shows substantial differences to these AOM communities. ANME-1 can be distinguished from ANME-2 and -3 by a low ratio of the isoprenoidal dialkyl glycerol diethers sn2-hydroxyarchaeol and archaeol combined with a comparably low stable carbon isotope difference of archaeol relative to the source methane. Furthermore, only ANME-1 contains substantial amounts of isoprenoidal glycerol dialkyl glycerol tetraethers (GDGTs), however, with the probable exception of the ANME-2c sub-cluster. In contrast to the ANME-1 archaea, the tail to tail linked hydrocarbon tetramethylhexadecane (crocetane) is unique to ANME-2, whereas pentamethylicosenes (PMIs) with 4 and 5 double bonds without any higher saturated homologues were only found in ANME-3. The sulphate reducing partner of ANME-1 can be discerned from those of ANME-2 and -3 by a low ratio of the fatty acids (FAs) C_16:1ω5 relative to i-C_15:0 and, although to a lesser degree, by a high abundance of ai-C_15:0 relative to i-C_15:0. Furthermore, substantial amounts of ¹³C depleted non-isoprenoidal monoalkyl glycerol ethers (MAGEs) were only found in the sulphate reducing partners of ANME-2 and -3. A differentiation of these SRB is possible based on the characteristic presence of the FAs cy-C_17:0ω5,6 and C_17:1ω6, respectively. Generally, the data analysed here show overlaps between the different AOM communities, which highlights the need to use multiple lipid signatures for a robust identification of the dominating microbes involved.     

Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

Kinetic Model of Gaseous Alkanes Formed from Coal in a Confined System and Its Application to Gas Filling History in Kuqa Depression, Tarim Basin, Northwest China

Based on the pyrolysis products for the Jurassic low-mature coal under programmed temperature,and chemical and carbon isotopic compositions of natural gas from the Kuqa Depression, the genetic origin of natural gas was determined,and then a gas filling model was established,in combination with the geological background of the Kuqa Depression.The active energy of CH_4,C_2H_6 and C_3H_8 was gotten after the data of pyrolysis gas products under different heating rates(2℃/h and 20℃/h)were fitted by the Gas O...     

Light hydrocarbons geochemistry of surface sediment from petroliferous region of the Mehsana block,North Cambay Basin

A study was carried out to test the usefulness of surface geochemical methods as regional evaluation tools in petroliferous region of the Mehsana block, North Cambay Basin. A suite of 135 soil samples collected from the depth of 2.5 m, were analyzed for adsorbed light gaseous hydrocarbons and carbon isotopes (δ¹³C_methane and δ¹³C_ethane). The light gaseous hydrocarbon analysis show that the concentration ranges 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb of C₁, C₂, C₃, iC₄ and nC₄, respectively. The value of carbon isotopic ranges of methane −29.5 to −43.0‰ (PDB) and ethane −19.1 to −20.9‰ (PDB). This data, when mapped, indicates patterns coinciding with major known oil and/or gas field of Sobhasan/Linch in this study area. The existence of un-altered petroliferous microseeps of catagenetic origin is observed in the study area. A regional study, such as the one described here, can provide important exploration facts concerning the regional hydrocarbon potential in a block. This method has been confirmed and can be applied successfully in frontier basins.     

Geochemical characterization of adsorbed light gaseous alkanes in near surface soils of the eastern Ganga basin for hydrocarbon prospecting

This study aims to assess the hydrocarbon potential of Ganga basin utilizing the near surface geochemical prospecting techniques. It is based on the concept that the light gaseous hydrocarbons from the oil and gas reservoirs reach the surface through micro seepage, gets adsorbed to soil matrix and leave their signatures in soils and sediments, which can be quantified. The study showed an increased occurrence of methane (C₁), ethane (C₂) and propane (C₃) in the soil samples. The concentrations of light gaseous hydrocarbons determined by Gas Chromatograph ranged (in ppb) as follows, C₁: 0–519, C₂: 0–7 and C₃: 0–2. The carbon isotopic (VPDB) values of methane varied between ?52.2 to ?27.1‰, indicating thermogenic origin of the desorbed hydrocarbons. High concentrations of hydrocarbon were found to be characteristic of the Muzaffarpur region and the Gandak depression in the basin, signifying the migration of light hydrocarbon gases from subsurface to the surface and the area’s potential for hydrocarbon resources.     

Near surface manifestation of hydrocarbons in Proterozoic Bhima and Kaladgi Basins: Implications to hydrocarbon resource potential

Reconnaissance surface geochemical survey for adsorbed soil gas analysis conducted in Proterozoic Bhima and Kaladgi Basins, have revealed occurrence of anomalous concentrations of light gaseous hydrocarbons i.e. C₁ to C₄ (CH₄, C₂H₆, C₃H₈, i-C₄H₁₀ and n-C₄H₁₀) in the near surface soils. The concentrations of C₁ and ΣC₂₊(C₂H₆+C₃H₈+ i-C₄H₁₀+ n-C₄H₁₀) in Bhima and Kaladgi Basins are in the range of 1–2594 ppb and 1 to 57 ppb and 1–1142 ppb and 1–490 ppb, respectively. The carbon isotopic data of adsorbed soil gas methane in few selected samples are in the range of −29.9 to −39‰ (PDB). The evaluation of adsorbed soil gas data indicates that all the gas components are cogenetic and hydrocarbon ratios of C₁/(C₂+C₃) < 10 and C₃/C₁*1000 between 60–500 and 20–60 suggest that the adsorbed gases are derived from oil and gas-condensate zones. The carbon isotopic values of methane further support thermogenic origin of these migrated gases. The concentration distribution of C₁ and ΣC₂₊ in the study areas illustrate C₁ and ΣC₂₊ anomalies near Katamadevarhalli, Andola and Talikota in Bhima Basin and near Kaladgi, Lokapur and north of Mudhol in Kaladgi Basin. The hydrocarbon anomalies near the surface coincide with the favourable subsurface structural features and correlate with existing geochemical and geophysical data in these basins suggesting seepage related anomalies.     

Role of minerals in the thermal alteration of organic matter—I: Generation of gases and condensates under dry condition

Pyrolysis experiments were carried out on Monterey formation kerogen and bitumen and Green River formation kerogen (Type II and I, respectively), in the presence and absence of montmorillonite, illite and calcite at 200 and 300°C for 2–2000 hours. The pyrolysis products were identified and quantified and the results of the measurements on the gas and condensate range are reported here.A significant catalytic effect was observed for the pyrolysis of kerogen with montmorillonite, whereas small or no effects were observed with illite and calcite, respectively. Catalytic activity was evident by the production of up to five times higher C₁–C₆ hydrocarbons for kerogen with montmorillonite than for kerogen alone, and by the dominance of branched hydrocarbons in the C₄–C₆ range (up to 90% of the total amount at any single carbon number). This latter effect in the presence of montmorillonite is attributed to cracking via a carbonium-ion [carbocation] intermediate which forms on the acidic sites of the clay. No catalytic effect, however, was observed for generation of methane and C₂ hydrocarbons which form by thermal cracking. The catalysis of montmorillonite was significantly greater during pyrolysis of bitumen than for kerogen, which may point to the importance of the early formed bitumen as an intermediate in the production of low molecular weight hydrocarbons. Catalysis by minerals was also observed for the production of carbon dioxide.These results stress the importance of the mineral matrix in determining the type and amount of gases and condensates forming from the associated organic matter under thermal stress. The literature contains examples of gas distributions in the geologic column which can be accounted for by selective mineral catalysis, mainly during early stages of organic matter maturation.     

Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150–250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used ¹⁴C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C₂ addition occurred, although very small amounts of products corresponding to C₁ addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.     

Stable Carbon Isotopic Compositions of Methylated-MTTC in Crude Oils from Saline Lacustrine Depositional Environment: Source Implications

Significantly high abundant methyl-MethylTrimethylTridecylChromans (MTTCs) have been detected in aromatic hydrocarbon fractions in crude oils from the Jizhong Depression and Jianghan Basin. The distribution of these compounds is dominated by methyl-MTTC and dimethyl-MTTC series, which indicate diagenetic products of a hypersaline depositional environment in the early stage and show a low degree of methylation. The occurrence of significantly high abundant methyl-MTTC depends mainly on good preservation conditions with a strongly reductive, hypersaline and water-columned depositional environment and subsequent non-intensive diagenetic transformations. The stable carbon isotopic compositions of the methyl-MTTCs and dimethyl-MTTCs in two samples are far different from the stable carbon isotopic composition of C30 hopane of apparent bacteria biogenesis (up to 4.11‰ and 5.75‰, respectively). This obviously demonstrates that the methyl-MTTC and dimethyl-MTTCs cannot be of bacteria origin, which is different from the previous point of view about non-photosynthetic bacteria products or possible bacteria-reworked products. On the contrary, the stable carbon isotopic compositions of methyl-MTTC and dimethyl-MTTCs in the two samples were similar to that of the same carbon-numbered n-alkanes (nC27-nC28-nC29), which indicates that they share the same source origin. Especially in the crude oil from the Zhao61 well, stable carbon isotopic compositions are also similar to that of the same carbon-numbered steranes with ααα-20R isomer (mostly less than 0.4‰). In consideration of the results of previous studies on saline lake ecological sedimentation, the authors hold that the methyl-MTTC and dimethyl-MTTCs in the saline lake sediments should be of algal biogenesis origin.     

Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.     

Insights into oil cracking based on laboratory experiments

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 C_6–14 and C_1–5 hydrocarbons and pyrobitumen. The C_6–14 fraction continues to crack to C_1–5 gases plus pyrobitumen at higher temperatures and prolonged heating time and the δ ¹³C_ethane–δ¹³C_propane 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.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

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 (C_5–8) 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.