Stable isotope reversal and evolution of gas during the hydrous pyrolysis of continental kerogen in source rocks under supercritical conditions

Abstract

Semi-closed hydrous pyrolysis experiments were conducted to investigate the isotopic evolution of shale gas produced from continental organic-rich shales with increasing thermal maturity and prospecting potential. The δ13C values of methane, ethane, propane and n-butane became heavier with increasing thermal maturity and showed good relationships with vitrinite reflectance (VR). Gases expelled from type-I, type-II, and type-III kerogens followed the normal carbon sequence (δ13CC1 < δ13CC2 < δ13CC3 < δ13CnC4) and the hydrogen isotopic sequence (δ2HC1 < δ2HC2 < δ2HC3 < δ2HnC4 < δ2HiC4) among the alkanes at VRs lower than 2.14% Ro, 2.42% Ro, and 1.87% Ro respectively. The isotopically reversed gases (δ13CC1 < δ13CC2 < δ13CnC4 < δ13CC3) were observed in type-I kerogen with a VRs above 2.14% Ro and in type-II kerogen with a VR above 2.42% Ro. In type-III kerogen, isotopically reversed gases (δ13CC1 < δ13CnC4 < δ13CC3 < δ13CC2) were observed with a VR above 2.94% Ro. These results suggest four stages in the stable carbon isotope reversal of ethane, propane, and n-butane with increasing maturity. The isotopically reversed gases (δ13CC1 < δ13CC2 < δ13CnC4 < δ13CC3) may represent lower maturity and higher productivity shale gas than the isotopically reversed gases (δ13CC1 < δ13CnC4 < δ13CC3 < δ13CC2), indicating that continental type-I kerogen has the highest potential productivity for shale gas, and continental type-III kerogen has the lowest. Stable hydrogen isotope composition did not respond to the stable carbon isotope reversal in isotopically reversed gases. We suggest that indigenous generation and mixing may be the dominant mechanisms responsible for the stable carbon isotope reversal, and adsorption/desorption during hydrocarbon expulsion may promote the stable isotope reversal under semi-closed conditions. Overall, these results suggest that this study is an important contribution to continental shale gas exploration.