Geochemical characteristics and origin of gases from the Upper,Lower Paleozoic and the Mesozoic reservoirs in the Ordos Basin,China

The Ordos Basin, the second largest sedimentary basin in China, contains the broad distribution of natural gas types. So far, several giant gas fields have been discovered in the Upper and Lower Paleozoic in this basin, each having over 1000×10⁸m³ of proven gas reserves, and several gas pools have also been discovered in the Mesozoic. This paper collected the data of natural gases and elucidated the geochemical characteristics of gases from different reservoirs, and then discussed their origin. For hydrocarbons preserved in the Upper Paleozoic, the elevated δ ¹³C values of methane, ethane and propane indicate that the gases would be mainly coal-formed gases; the singular reversal in the stable carbon isotopes of gaseous alkanes suggests the mixed gases from humic sources with different maturity. In the Lower Paleozoic, the δ ¹³C₁ values are mostly similar with those in the Upper Paleozoic, but the δ ¹³C₂ and δ ¹³C₃ values are slightly lighter, suggesting that the gases would be mixing of coal-type gases as a main member and oil-type gases. There are multiple reversals in carbon isotopes for gaseous alkanes, especially abnormal reversal for methane and ethane (i.e. δ ¹³C₁>δ ¹³C₂), inferring that gases would be mixed between high-mature coal-formed gases and oil-type gases. In the Mesozoic, the δ ¹³C values for gaseous alkanes are enriched in ¹²C, indicating that the gases are mainly derived from sapropelic sources; the carbon isotopic reversal for propane and butane in the Mesozoic is caused by microbial oxidation and mixing of gases from sapropelic sources with different maturity. In contrast to the Upper Paleozoic gases, the Mesozoic gases are characterized by heavier carbon isotopes of iso-butane than normal butane, which may be caused by gases generated from different kerogen types. Finally, according to δ ¹³C₁-R ₀ relationship and extremely low total organic carbon contents, the Low Paleozoic gases would not be generated from the Ordovician source as a main gas source, bycontrast, the Upper Paleozoic source as a main gas source is contributed to the Lower Paleozoic gases.     

Geochemical characteristics of pyrolysis gas from epimetamorphic rocks in the northern basement of Songliao Basin,Northeast China

The Xushen gas field, located in the north of Songliao Basin, is a potential giant gas area for China in the future. Its proved reserves have exceeded 1000×10⁸ m³ by the end of 2005. But, the origin of natural gases from the deep strata is still in debating. Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin. According to pyrolysis experiments for these rocks in the semi-confined system, gas production and geochemistry of alkane gases are discussed in this paper. The Carboniferous-Permian epimetamorphic rocks were heated from 300°C to 550°C, with temperature interval of 50°C. The gas production was quantified and measured for chemical and carbon isotopic compositions. Results show that δ ¹³C₁ is less than −20‰, carbon isotope trend of alkane gas is δ ¹³C₁<δ ¹³C₂<δ ¹³C₃ or δ ¹³C₁<δ ¹³C₂>δ ¹³C₃, these features suggest that the gas would be coal-type gas at high-over maturity, not be inorganic gas with reversal trend of gaseous alkanes (δ ¹³C₁>δ ¹³C₂>δ ¹³C₃). These characteristics of carbon isotopes are similar with the natural gas from the basin basement, but disagree with gas from the Xingcheng reservoir. Thus, the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes. The gas generation intensity for epimetamorphic rocks is 3.0×10⁸–23.8×10⁸ m³/km², corresponding to R _o from 2.0% to 3.5% for organic matter.

     

Hydrogen isotope composition of natural gases from the Tarim Basin and its indication of depositional environments of the source rocks

By measuring carbon and hydrogen isotope compositions for C1, C2 and C3 of 74 gas samples, natural gases from the Tarim Basin can be divided into six groups on the basis of their origins: (1) coal-type gas derived from coal measures; (2) coal-type gas generated from the T-J lacustrine mudstones; (3) oil-type gas derived from the Cambrian and low Ordovician marine source rocks; (4) oil-type gas from the source rocks deposited in the marine-transitional facies; (5) mixing gas between gas derived from the Carboniferous transitional source rocks and the Mesozoic humic gas, and (6) mixing gases of thermal genetic gas and little deep gas in the Southwest depression of the Tarim Basin. The δ D values of methane in natural gases originating from different type kerogens are affected by both palaeo-environments of the source rock formation (kerogen types) and thermal maturity, with sedimentary environment (kerogen type) as the main controlling factor. Under the similar thermal maturity, the hydrogen isotope composition of methane is more enriched in deuterium in marine environments than lacustrine one. With the increase of thermal maturity and the increase of carbon atomic numbers of gaseous alkanes, the hydrogen isotopes become enriched in deuterium. The δ D values of ethane and propane (δ D2, δ D3) are controlled mainly by thermal maturity and to a lesser degree by sedimentary environment of the source rock formation. The partial reversal of hydrogen isotopes for gaseous alkanes would be related to the microbial oxidation, mixing of sapropelic and humic gases and / or mixing of gases from similar kerogen sources with various thermal maturities. In the oil-type gas, the sulfate reduction reaction would result in the reversed order of δ D1 and δ D2 (e.g. δ D1>δ D2).     

Natural gas geochemistry and its origins in Kuqa depression

According to gas compositional and carbon isotopic measurement of 114 gas samples from the Kuqa depression, accumulation of the natural gases in the depression is dominated by hydrocarbon gases, with high gas dryness (C₁/C_1–4) at the middle and northern parts of the depression and low one towards east and west sides and southern part. The carbon isotopes of methane and its homologues are relatively enriched in ¹³C, and the distributive range of δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ is ?32‰–?36‰, ?22‰–?24‰ and ?20‰–?22‰, respectively. In general, the carbon isotopes of gaseous alkanes become less negative with the increase of carbon numbers. The δ ¹³ \(C_{CO_2 } \) value is less than ?10‰ in the Kuqa depression, indicating its organogenic origin. The distributive range of ³He/⁴He ratio is within n × 10^?8 and a decrease in ³He/⁴He ratio from north to south in the depression is observed. Based on the geochemical parameters of natural gas above, natural gas in the Kuqa depression is of characteristics of coal-type gas origin. The possible reasons for the partial reversal of stable carbon isotopes of gaseous alkanes involve the mixing of gases from one common source rock with different thermal maturity or from two separated source rock intervals of similar kerogen type, multistages accumulation of natural gas under high-temperature and over-pressure conditions, and sufficiency and diffusion of natural gas.     

Geochemical characteristics of pyrolysis gas from epimetamorphic rocks in the northern basement of Songliao Basin,Northeast China

The Xushen gas field, located in the north of Songliao Basin, is a potential giant gas area for China in the future. Its proved reserves have exceeded 1000×10⁸ m³ by the end of 2005. But, the origin of natural gases from the deep strata is still in debating. Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin. According to pyrolysis experiments for these rocks in the semi-confined system, gas production and geochemistry of alkane gases are discussed in this paper. The Carboniferous-Permian epimetamorphic rocks were heated from 300°C to 550°C, with temperature interval of 50°C. The gas production was quantified and measured for chemical and carbon isotopic compositions. Results show that δ ¹³C₁ is less than ?20‰, carbon isotope trend of alkane gas is δ ¹³C₁<δ ¹³C₂<δ ¹³C₃ or δ ¹³C₁<δ ¹³C₂>δ ¹³C₃, these features suggest that the gas would be coal-type gas at high-over maturity, not be inorganic gas with reversal trend of gaseous alkanes (δ ¹³C₁>δ ¹³C₂>δ ¹³C₃). These characteristics of carbon isotopes are similar with the natural gas from the basin basement, but disagree with gas from the Xingcheng reservoir. Thus, the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes. The gas generation intensity for epimetamorphic rocks is 3.0×10⁸–23.8×10⁸ m³/km², corresponding to R _o from 2.0% to 3.5% for organic matter.     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than −44‰, −29‰ and −26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \( C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than −10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.

     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than ?44‰, ?29‰ and ?26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \(C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than ?10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ²₅ reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ²₇ reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.

     

Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010,a total of 15 large tight gas fields have been found in China,located in the Ordos,Sichuan,and Tarim basins.The annual production and total reserves of these fields in 2010 were 222.5×108and 28657×108m3,respectively,accounting for 23.5%and 37.3%,respectively,of the total annual production and reserves of natural gases in China.They took a major part of all natural gas production and reserves in China.According to the analyses of 81 gas samples,the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics:(1)Plots of 13C1-13C2-13C3,13C1-C1/C2+3and 13C1-13C2demonstrate the coal-derived origin of tight gases in China;(2)For the primary alkane gases,both carbon and hydrogen isotopic values increase with increasing molecular mass,i.e.,13C113C213C313C4and2H12H22H3;(3)The isotopic differences of 13C2-13C1,13C3-13C1,2H2-2H1and 2H3-2H1decrease with increasing Ro(%)and C1/C1–4;(4)There are seven causes for the carbon and hydrogen isotopic reversal,however,the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ₅ ² reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ₇ ² reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.     

Identification of marine natural gases with different origin sources

Kinetic experiments of gas generation for typical samples of marine gas precursors including low-maturity kerogen, residual kerogen and oil as well as dispersed liquid hydrocarbon (DLH) in source rocks were performed by closed system, and the evolution trends of molecular and isotopic compositions of natural gases from different precursors against the maturity (R ₀%) at laboratory conditions were analyzed. Several diagrams of gas origin were calibrated by using the experimental data. A diagram based on the ratio of normal and isomerous butane and pentane (i/nC₄ ? i/nC₅) was proposed and used to identify the origins of the typical marine natural gases in the Sichuan Basin and the Tarim Basin, China. And the maturities of natural gases were estimated by using the statistical relationships between the gaseous molecular carbon isotopic data and maturities (δ¹³C-R ₀%) with different origins. The results indicate that the molecular and isotopic compositions of simulated gases from different precursors are different from each other. For example, the dryness index of the oil-cracking gas is the lowest; the dryness indices of gases from DLH and kerogen in closed system are almost the same; and the dryness index of gases from residual kerogen is extremely high, indicating that the kerogen gases are very dry; the contents of non-hydrocarbon gases in kerogen-cracking gases are far higher than those in oil-cracking and DLH-cracking gases. The molecular carbon isotopes of oil-cracking gases are the lightest, those of kerogen in closed system and GLH-cracking gases are the second lightest, and those of cracking gases from residual kerogen are the heaviest. The calibration results indicate that the diagrams of In(C₁/C₂)-In(C₂/C₃) and δ^{4 3}C₂-δ^{4 3}C₃-In(C₂/C₃) can discriminate primary and secondary cracking gases, but cannot be used to identify gas origin sources, while the diagram of i/nC₄ ? i/nC₅ can differentiate the gases from different precursors. The application results of these diagrams show that gas mixtures extensively exist in China, which involved the gases from multiple precursors and those from different maturity stages. For example, marine gases in the Sichuan Basin involve the mixture of oil-cracking gases and high-over-maturated kerogen gases, while those in the Tarim Basin involve not only the mixture of gases from multiple precursors, but also those from different maturity gases and post-reservoir alternations such as oxidized degradation and gas intrusion processes.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China — Application of fluid inclusion gases

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.

     

Preliminary study on the origin identification of natural gas by the parameters of light hydrocarbon

The light hydrocarbon composition of 209 natural gas samples and individual light hydrocarbon carbon isotopes of 53 natural gas samples from typical humic-sourced gas and sapropelic-sourced gas in the four basins of China have been determined and analyzed. Some identification parameters for humic-sourced gas and sapropelic-sourced gas are proposed or corrected. The differences of compound-specific δ ¹³C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded. The humic-sourced gas has the distribution of δ ¹³C_benzene> ?24‰, δ ¹³C_toluene >?23‰, δ ¹³C_cyclohexane > ?24‰ and δ ¹³C_{methyl cyclohexane}> ?24‰, while the sapropelic-sourced gas has the distribution of δ ¹³C_benzene <?24‰, δ ¹³C_toluene< ?24‰, δ ¹³C_cyclohexane< ?24‰ and δ ¹³C_{methyl cyclohexane}< ?24‰. Among the components of C₇ light hydrocarbon compound, such as normal heptane (nC₇), methyl cyclohexane (MCH) and dimethyl cyclopentane (ΣDMCP), etc, relative contents of nC₇ and MCH are influenced mainly by the source organic matter type of natural gas. Therefore, it is suggested that the gas with relative content of nC₇ of more than 30% and relative content of MCH of less than 70% is sapropelic-sourced gas, while gas with relative content of nC₇ of less than 35% and relative content of MCH of more than 50% is humic-sourced gas. Among components of C_5–7 aliphatics, the gas with relative content of C_5–7 normal alkane of more than 30% is sapropelic-sourced gas, while the gas with relative content of C_5–7 normal alkane of less than 30% is humic-sourced gas. These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.     

The Upper Valanginian (Early Cretaceous) positive carbon-isotope event recorded in terrestrial plants

Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon-isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon-isotope excursion is expressed in the atmosphere. δ¹³C_plant values fluctuate around − 23‰ to − 22‰ for the Valanginian-Hauterivian, except during the Upper Valanginian where δ¹³C_plant values record a positive excursion to ∼− 18‰. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine δ¹³C_carb curve, several conclusions can be drawn: (1) the δ¹³C_plant record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon-isotope fractionation, caused by a decrease in atmospheric pCO₂, occurred during the Upper Valanginian positive δ¹³C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought.     

Carbon and hydrogen isotopic characteristics of natural gases from the Luliang and Baoshan basins in Yunnan Province, China

The Luliang and Baoshan basins are two small ba- sins in Yunnan Province. In the recent ten years or so, there have been found a number of natural gas pools of commercial importance in the two basins. Although the gas pools are small in size, the natural …     

Stable carbon isotope signatures of cellulose in macrophytes collected from three eutrophic lakes in China

Aquatic plants are essential for maintaining the diversity and stability of a lake ecosystem. Stable carbon isotopes (δ¹³C) of macrophytes have been widely used as a powerful tool to study ecological processes and paleoenvironmental evolution in lakes. Varying results are obtained when using the δ¹³C of macrophytes to study the changes in the lake environment at different spatio-temporal scales. Thus, sample preparation and subsequent laboratory analyses are crucial for studying environmental changes using the isotopic signal retained in the macrophytes, and are essential for the interpretation of isotope-environment relationships. This study analyzed the δ¹³C of different tissue components of macrophytes in three lakes of the lower Yangtze River basin, and a correlation analysis was performed on aquatic environments influencing the δ¹³C values in the different tissue components of macrophytes. The test results showed the difference between the δ¹³C values of the whole sample and cellulose. Relative analyses indicated that the major factors contributing to the δ¹³C variability in macrophytes were pH and the concentration of dissolved inorganic carbon (DIC). The δ¹³C of α-cellulose (δ¹³C_AC) is more sensitive to environmental variables than that of the whole sample (δ¹³C_W) and holocellulose (δ¹³C_HC). The results of this study imply that extraction of α-cellulose is a prerequisite for research on the changes in lake environment using δ¹³C of macrophytes. This study aims to provide theoretical and data basis for further research on the environmental and ecological change using stable carbon isotopes of aquatic plants.     

Discrimination of abiogenic and biogenic alkane gases

We have combined the analytical data of the carbon isotope distribution pattern, R/Ra and CH4/3He values of abiogenic and biogenic (referring to the thermogenic and bacterial or microbial) alkane gases in China with those of alkane gases from USA, Russia, Germany, Australia and other countries. Four discrimination criteria are derived from this comparative study: 1) Carbon isotopic composition is generally greater than -30‰ for abiogenic methane and less than -30‰ for biogenic methane; 2) Abiogenic alkane gases have a carbon isotopic reversal trend (δ 13C1> δ 13C2> δ 13C3> δ 13C4) with δ 13C1>-30‰ in general; 3) Gases with R/Ra >0.5 and δ 13C11 δ 13C2>0 are of abiogenic origin; 4) Gases (meth- ane) with CH4/3He≤106 are of abiogenic origin, whereas gases with CH4/3He≥1011 are of biogenic origin.     

Characteristics and accumulation mechanisms of the Dongfang 13-1 high temperature and overpressured gas field in the Yinggehai Basin,the South China Sea

The Dongfang 13-1 is located in the diapiric structure belt of the Yinggehai Basin. The formation pressure of its main gas reservoir in the Miocene Huangliu Formation is up to 54.6 MPa(pressure coefficient=1.91) and the temperature is as high as 143°C(geothermal gradient 4.36°C/100 m), indicating that it is a typical high-temperature and overpressured gas reservoir. The natural gas is interpreted to be coal-type gas derived from the Miocene mature source rocks containing type II2-III kerogens as evidenced by high dryness index of up to 0.98 and heavy carbon isotopes, i.e., the δ13C1 ranging from -30.76‰ to -37.52‰ and δ13C2 ranging from -25.02‰ to -25.62‰. The high temperature and overpressured Miocene petroleum system is related mainly to diapir in the Yinggehai Basin and contains more pore water in the overpressured reservoirs due to undercompaction process. The experimental and calculated results show that the solubility of natural gas in formation water is as high as 10.5 m3/m3 under the temperature and pressure conditions of the Sanya Formation, indicating that at least part of the gas may migrate in the form of water-soluble phase. Meanwhile, the abundant gas source in the Basin makes it possible for the rapid saturation of natural gas in formation water and exsolution of soluble gas. Therefore, the main elements controlling formation of the Dongfang 13-1 gas pool include that(1) the diapir activities and accompanying changes in temperature and pressure accelerate the water-soluble gas exsolution and release a lot of free gas;(2) submarine fan fine sandstone in the Huangliu Formation provides good gas-water segregation and accumulation space; and(3) the overlying overpressured mud rocks act as effective caps. The accumulation mechanism reveals that the high temperatural and high pressure structure belt near the diapir structures has a good potential for large and medium-sized gas field exploration.     

Abiogenic hydrocarbons in commercial gases from the Songliao Basin, China

This paper discusses the kinetic fractionation, composition and distribution characteristics of carbon and hydrogen isotopes for various alkane gases formed in different environments, by different mecha- nisms and from different sources in nature. It is demonstrated that the biodegradation or thermode- gradation of complex high-molecule sedimentary organic material can form microbial gas or thermogenic gas. The δ 13C1 value ranges from -110‰ to -50‰ for microbial gases but from -50‰ to -35‰ (even heavier) f...     

Organic facies and geochemical aspects in Neogene neritic sediments of the Takafu syncline area of central Japan: Paleoenvironmental and sedimentological reconstructions

Abstract Organic petrological observations of kerogen macerals and organic geochemical analyses of carbon isotopes of kerogen macerals and biomarkers were conducted on Neogene neritic sediments of the Takafu syncline area of central Japan. The Senmi, Sakainomiya and Lower Shigarami Formations in that area were deposited at the neritic provinces on the southern edge of the paleo‐Japan Sea during the Late Miocene to Early Pliocene. Sedimentary organic matter in these formations was almost terrigenous in origin. Changes in kerogen maceral compositions reflect sedimentological and tectonic histories evaluated in previous studies from sedimentary facies and paleontology. It was found that carbon isotope ratios (δ¹³C) of kerogen macerals increased from ?28‰ to ?25‰ from the Sakainomiya to the lower part of the Lower Shigarami Formations. The cause of that increase was presumably the expansion of C₄ plants into southwest Japan. The timing was concordant with that of the expansion of C₄ plant grasslands in East Asia. The oxicity (oxic to anoxic) conditions of sea bottoms evaluated from pristane/phytane ratios varied. Particularly, in the lower part of the Senmi Formation, layers in which no steroid biomarkers could be detected were found, and had presumably formed under oxic conditions when strong biodegradation had occurred. Concentrations of regular (C₂₇–C₂₉) steranes and dinosteranes were higher in the Sakainomiya and Lower Shigarami Formations. This indicates that dinoflagellates‐dominant primary productions were higher at those stages. In addition, concentrations of diatomaceous biomarkers such as C₂₆ norsterane increased from the Lower Shigarami Formation, thus adding diatoms to the major producers. Furthermore, similar associations between the increases of δ¹³C values of kerogen macerals and concentrations of diatomaceous biomarkers were observed in the Takafu syncline area. Thus, the expansion of C₄ plants was possibly associated with the high production of diatom in the shallow‐marine areas of the paleo‐Japan Sea during the Neogene Period.