The hydrocarbon gases in the L1 gas field of the Lishui-Jiaojiang Sag have been commonly interpreted to be an accumulation of pure sapropelic-type thermogenic gas.In this study,chemical components,stable isotopic comp...The hydrocarbon gases in the L1 gas field of the Lishui-Jiaojiang Sag have been commonly interpreted to be an accumulation of pure sapropelic-type thermogenic gas.In this study,chemical components,stable isotopic compositions,and light hydrocarbons were utilized to shed light on the origins of the hydrocarbon fluids in the L1gas pool.The hydrocarbon fluids in the L1 gas pool are proposed to be a mixture of three unique components:mid-maturity oil from the middle Paleocene coastal marine Lingfeng source rock,oil-associated(late oil window)gas generated from the lower Paleocene lacustrine Yueguifeng source rock,and primary microbial gas from the paralic deposits of the upper Paleocene Mingyuefeng source rock.Here,for the first time,the hydrocarbon gases in the L1 gas pool are diagnosed as mixed oil-associated sapropelic-type gas and microbial gas via four pieces of principal evidence:(1)The abnormal carbon isotopic distributions of all methane homologues from C_(1)(CH_(4)or methane)to C_(5)(C_(5)H_(12)or pentane)shown in the Chung plot;(2)the diagnostic~(13)C-depleted C_(1)compared with the thermogenic sapropelic-type gas model,whileδ^(13)C_(2)(C_(2)H_(6)or ethane)andδ^(13)C_(3)(C_(3)H_(8)or propane)both fit perfectly;(3)the excellent agreement of the calculated carbon isotopic compositions of the pure thermogenic gas with the results of the thermal simulated gas from the type-II1 kerogen-rich Yueguifeng source rock;and(4)the oil-associated gas inferred from various binary genetic diagrams with an abnormally elevated gas oil ratio.Overall,the natural gases of the L1 gas pool were quantified in this study to comprise approximately 13%microbial gas,nearly 48%oil-associated sapropelic-type gas,and 39%of nonhydrocarbon gas.The microbial gas is interpreted to have been codeposited and entrained in the humic-kerogen-rich Mingyuefeng Formation under favorable lowtemperature conditions during the late Paleocene-middle Eocene.The microbial gas subsequently leaked into the structurally and stratigraphically complex L1 trap with oil-associated sapropelic-type gas from the Yueguifeng source rock during the late Eocene-Oligocene uplifting event.A small amount of humic-kerogen-generated oil in the L1 gas pool is most likely to be derived from the underlying Lingfeng source rock.The detailed geological and geochemical considerations of source rocks are discussed to explain the accumulation history of hydrocarbon fluids in the L1 gas pool.This paper,therefore,represents an effort to increase the awareness of the pitfalls of various genetic diagrams,and an integrated geochemical and geological approach is required for hydrocarbonsource correlation.展开更多
There have been many achievements in the research on carbon isotopes of alkane hydrocarbon gases in oil and gas bearing basins in China. Because of the limited molecular types and the simple molecular structures of C&...There have been many achievements in the research on carbon isotopes of alkane hydrocarbon gases in oil and gas bearing basins in China. Because of the limited molecular types and the simple molecular structures of C<sub>1-4</sub> alkane hydrocarbon gases, the information provided by these carbon isotopes is limited. C<sub>5-8</sub> light hydrocarbons are found more often in wet gas, and their molecules have more complex structures and展开更多
Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five...Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.展开更多
The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abun...The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.展开更多
Natural gases were widely distributed in the Jiyang Depression with complicated component composition, and it is difficult to identify their genesis. Based on investigation of gas composition, carbon isotope ratios, l...Natural gases were widely distributed in the Jiyang Depression with complicated component composition, and it is difficult to identify their genesis. Based on investigation of gas composition, carbon isotope ratios, light hydrocarbon properties, as well as geological analysis, natural gases in the Jiyang Depression are classified into two types, one is organic gas and the other is abiogenic gas. Abiogenic gas is mainly magmatogenic or mantlederived CO2. Organic gases are further divided into coaltype gas, oil-type gas, and biogas according to their kero- gen types and formation mechanisms. The oil-type gases are divided into mature oil-type gas （oil-associated gas） and highly mature oil-type gas. The highly mature oil-type gases can be subdivided into oil-cracking gas and kerogen thermal degradation gas. Identification factors for each kind of hydrocarbon gas were summarized. Based on genesis analysis results, the genetic types of gases buried in different depths were discussed. Results showed that shallow gases （〈1,500 m） are mainly mature oil-type gases, biogas, or secondary gases. Secondary gases are rich in methane because of chromatographic separation during migration and secondary biodegradation. Secondary biodegradation leads to richness of heavy carbon isotope ratios in methane and propane. Genesis of middle depth gases （1,500-3,500 m） is dominated by mature oil-type gases.Deep gases （3,500-5,500 m） are mainly kerogen thermal degradation gas, oil-cracking gas, and coal-type gas.展开更多
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 C...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-specificδ13C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded.The humic-sourced gas has the distribution ofδ13C benzene > -24‰,δ13C toluene >-23‰,δ13C cyclohexane >-24‰andδ13C methyl cyclohexane >-24‰,while the sapropelicsourced gas has the distribution ofδ13C benzene <-24‰,δ13C toluene <-24‰,δ13C cyclohexane <-24‰and δ13C 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 C5-7 aliphatics, the gas with relative content of C5-7 normal alkane of more than 30%is sapropelic-sourced gas,while the gas with relative content of C5-7 normal alkane of less than 30%is humic-sourced gas.These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.展开更多
Abundant carbon isotopic information of single molecule can be obtained from the trace samples (chromatographic grade) on the basis of carbon isotopic on-line analytical technique developed in the late 1980s. This bri...Abundant carbon isotopic information of single molecule can be obtained from the trace samples (chromatographic grade) on the basis of carbon isotopic on-line analytical technique developed in the late 1980s. This brings the carbon isotopic study of the petroleum and natural gases into a new development stage.展开更多
Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from ...Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon frac-tion obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4—-39.0) and methanotrophic bacteria (-38.4—-46.3). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1? is the heaviest in all studied ste- ranes, showing that the carbon source or growth condition for its precursor, dinoflagellate, may be different from that of regular steranes. The variation trend of d 13C values between isomers of hopanes shows that 13C-enriched precursors take precedence in process of their epimerization. Methanotro-phic hopanes presented reveal the processes of strong trans-formation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.展开更多
基金The“Seven Year Action Plan”East China Sea Special Project of CNOOC under contract No.CNOOC-KJ 135 ZDXM39 SH02。
文摘The hydrocarbon gases in the L1 gas field of the Lishui-Jiaojiang Sag have been commonly interpreted to be an accumulation of pure sapropelic-type thermogenic gas.In this study,chemical components,stable isotopic compositions,and light hydrocarbons were utilized to shed light on the origins of the hydrocarbon fluids in the L1gas pool.The hydrocarbon fluids in the L1 gas pool are proposed to be a mixture of three unique components:mid-maturity oil from the middle Paleocene coastal marine Lingfeng source rock,oil-associated(late oil window)gas generated from the lower Paleocene lacustrine Yueguifeng source rock,and primary microbial gas from the paralic deposits of the upper Paleocene Mingyuefeng source rock.Here,for the first time,the hydrocarbon gases in the L1 gas pool are diagnosed as mixed oil-associated sapropelic-type gas and microbial gas via four pieces of principal evidence:(1)The abnormal carbon isotopic distributions of all methane homologues from C_(1)(CH_(4)or methane)to C_(5)(C_(5)H_(12)or pentane)shown in the Chung plot;(2)the diagnostic~(13)C-depleted C_(1)compared with the thermogenic sapropelic-type gas model,whileδ^(13)C_(2)(C_(2)H_(6)or ethane)andδ^(13)C_(3)(C_(3)H_(8)or propane)both fit perfectly;(3)the excellent agreement of the calculated carbon isotopic compositions of the pure thermogenic gas with the results of the thermal simulated gas from the type-II1 kerogen-rich Yueguifeng source rock;and(4)the oil-associated gas inferred from various binary genetic diagrams with an abnormally elevated gas oil ratio.Overall,the natural gases of the L1 gas pool were quantified in this study to comprise approximately 13%microbial gas,nearly 48%oil-associated sapropelic-type gas,and 39%of nonhydrocarbon gas.The microbial gas is interpreted to have been codeposited and entrained in the humic-kerogen-rich Mingyuefeng Formation under favorable lowtemperature conditions during the late Paleocene-middle Eocene.The microbial gas subsequently leaked into the structurally and stratigraphically complex L1 trap with oil-associated sapropelic-type gas from the Yueguifeng source rock during the late Eocene-Oligocene uplifting event.A small amount of humic-kerogen-generated oil in the L1 gas pool is most likely to be derived from the underlying Lingfeng source rock.The detailed geological and geochemical considerations of source rocks are discussed to explain the accumulation history of hydrocarbon fluids in the L1 gas pool.This paper,therefore,represents an effort to increase the awareness of the pitfalls of various genetic diagrams,and an integrated geochemical and geological approach is required for hydrocarbonsource correlation.
文摘There have been many achievements in the research on carbon isotopes of alkane hydrocarbon gases in oil and gas bearing basins in China. Because of the limited molecular types and the simple molecular structures of C<sub>1-4</sub> alkane hydrocarbon gases, the information provided by these carbon isotopes is limited. C<sub>5-8</sub> light hydrocarbons are found more often in wet gas, and their molecules have more complex structures and
文摘Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.
文摘The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.
文摘Natural gases were widely distributed in the Jiyang Depression with complicated component composition, and it is difficult to identify their genesis. Based on investigation of gas composition, carbon isotope ratios, light hydrocarbon properties, as well as geological analysis, natural gases in the Jiyang Depression are classified into two types, one is organic gas and the other is abiogenic gas. Abiogenic gas is mainly magmatogenic or mantlederived CO2. Organic gases are further divided into coaltype gas, oil-type gas, and biogas according to their kero- gen types and formation mechanisms. The oil-type gases are divided into mature oil-type gas （oil-associated gas） and highly mature oil-type gas. The highly mature oil-type gases can be subdivided into oil-cracking gas and kerogen thermal degradation gas. Identification factors for each kind of hydrocarbon gas were summarized. Based on genesis analysis results, the genetic types of gases buried in different depths were discussed. Results showed that shallow gases （〈1,500 m） are mainly mature oil-type gases, biogas, or secondary gases. Secondary gases are rich in methane because of chromatographic separation during migration and secondary biodegradation. Secondary biodegradation leads to richness of heavy carbon isotope ratios in methane and propane. Genesis of middle depth gases （1,500-3,500 m） is dominated by mature oil-type gases.Deep gases （3,500-5,500 m） are mainly kerogen thermal degradation gas, oil-cracking gas, and coal-type gas.
文摘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-specificδ13C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded.The humic-sourced gas has the distribution ofδ13C benzene > -24‰,δ13C toluene >-23‰,δ13C cyclohexane >-24‰andδ13C methyl cyclohexane >-24‰,while the sapropelicsourced gas has the distribution ofδ13C benzene <-24‰,δ13C toluene <-24‰,δ13C cyclohexane <-24‰and δ13C 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 C5-7 aliphatics, the gas with relative content of C5-7 normal alkane of more than 30%is sapropelic-sourced gas,while the gas with relative content of C5-7 normal alkane of less than 30%is humic-sourced gas.These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.
文摘Abundant carbon isotopic information of single molecule can be obtained from the trace samples (chromatographic grade) on the basis of carbon isotopic on-line analytical technique developed in the late 1980s. This brings the carbon isotopic study of the petroleum and natural gases into a new development stage.
基金This work wassupported by the Knowledge Innovation Program of Chinese Academyof Sciences (Grant No.KZCx3-sw-128), the “973”Programme ofChina (Grant No.2002CB211701), and the Foundation of the State KeyLaboratory of Gas Geochemistry.
文摘Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon frac-tion obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4—-39.0) and methanotrophic bacteria (-38.4—-46.3). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1? is the heaviest in all studied ste- ranes, showing that the carbon source or growth condition for its precursor, dinoflagellate, may be different from that of regular steranes. The variation trend of d 13C values between isomers of hopanes shows that 13C-enriched precursors take precedence in process of their epimerization. Methanotro-phic hopanes presented reveal the processes of strong trans-formation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.
