We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
Field investigation combined with detailed petrographic observation indicate that abundant oil,gas,and solid bitumen inclusions were entrapped in veins and cements of sedimentary rocks in the Dabashan foreland,which w...Field investigation combined with detailed petrographic observation indicate that abundant oil,gas,and solid bitumen inclusions were entrapped in veins and cements of sedimentary rocks in the Dabashan foreland,which were used to reconstruct the oil and gas migration history in the context of tectonic evolution.Three stages of veins were recognized and related to the collision between the North China block and the Yangtze block during the Indosinian orogeny from Late Triassic to Early Jurassic(Dl),the southwest thrusting of the Qinling orogenic belt towards the Sichuan basin during the Yanshanian orogeny from Late Jurassic to Early Cretaceous(D2),and extensional tectonics during Late Cretaceous to Paleogene(D3),respectively.The occurrences of hydrocarbon inclusions in these veins and their homogenization temperatures suggest that oil was generated in the early stage of tectonic evolution,and gas was generated later,whereas solid bitumen was the result of pyrolysis of previously accumulated hydrocarbons.Three stages of hydrocarbon fluid inclusions were also identified in cements of carbonates and sandstones of gas beds in the Dabashan foreland belt and the Dabashan foreland depression(northeastern Sichuan basin),which recorded oil/gas formation,migration,accumulation and destruction of paleo-reservoirs during the D2.Isotopic analysis of hydrocarbon fluid inclusions contained in vein minerals shows that δ^(13)C_1 of gas in fluid inclusions ranges from-17.0‰ to-30.4‰(PDB) and δD from-107.7‰ to-156.7‰(SMOW),which indicates that the gas captured in the veins was migrated natural gas which may be correlated with gas from the gas-fields in northern Sichuan basin.Organic geochemical comparison between bitumen and potential source rocks indicates that the Lower Cambrian black shale and the Lower Permian black limestone were the most possible source rocks of the bitumen.Combined with tectonic evolution history of the Dabashan foreland,the results of this study suggest that oil was generated from the Paleozoic source rocks in the Dabashan area under normal burial thermal conditions before Indosinian tectonics and accumulated to form paleo-reservoirs during Indosinian collision between the North China block and the Yangtz block.The paleo-reservoirs were destroyed during the Yanshanian tectonic movement when the Dabashan foreland was formed.At the same time,oil in the paleo-reservoirs in the Dabashan foreland depression was pyrolyzed to transform to dry gas and the residues became solid bitumen.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
基金funded by CNSF(No.41173055)the Research Program of China Geological Survey(No. 1212011121117)
文摘Field investigation combined with detailed petrographic observation indicate that abundant oil,gas,and solid bitumen inclusions were entrapped in veins and cements of sedimentary rocks in the Dabashan foreland,which were used to reconstruct the oil and gas migration history in the context of tectonic evolution.Three stages of veins were recognized and related to the collision between the North China block and the Yangtze block during the Indosinian orogeny from Late Triassic to Early Jurassic(Dl),the southwest thrusting of the Qinling orogenic belt towards the Sichuan basin during the Yanshanian orogeny from Late Jurassic to Early Cretaceous(D2),and extensional tectonics during Late Cretaceous to Paleogene(D3),respectively.The occurrences of hydrocarbon inclusions in these veins and their homogenization temperatures suggest that oil was generated in the early stage of tectonic evolution,and gas was generated later,whereas solid bitumen was the result of pyrolysis of previously accumulated hydrocarbons.Three stages of hydrocarbon fluid inclusions were also identified in cements of carbonates and sandstones of gas beds in the Dabashan foreland belt and the Dabashan foreland depression(northeastern Sichuan basin),which recorded oil/gas formation,migration,accumulation and destruction of paleo-reservoirs during the D2.Isotopic analysis of hydrocarbon fluid inclusions contained in vein minerals shows that δ^(13)C_1 of gas in fluid inclusions ranges from-17.0‰ to-30.4‰(PDB) and δD from-107.7‰ to-156.7‰(SMOW),which indicates that the gas captured in the veins was migrated natural gas which may be correlated with gas from the gas-fields in northern Sichuan basin.Organic geochemical comparison between bitumen and potential source rocks indicates that the Lower Cambrian black shale and the Lower Permian black limestone were the most possible source rocks of the bitumen.Combined with tectonic evolution history of the Dabashan foreland,the results of this study suggest that oil was generated from the Paleozoic source rocks in the Dabashan area under normal burial thermal conditions before Indosinian tectonics and accumulated to form paleo-reservoirs during Indosinian collision between the North China block and the Yangtz block.The paleo-reservoirs were destroyed during the Yanshanian tectonic movement when the Dabashan foreland was formed.At the same time,oil in the paleo-reservoirs in the Dabashan foreland depression was pyrolyzed to transform to dry gas and the residues became solid bitumen.