Bulk and intramolecular carbon isotopic compositions of hydrocarbon gases from laboratory pyrolysis of oil shale of the Green River Formation: Implications for isotope structures of kerogens

Evaluation of intramolecular isotope distributions within organic compounds can provide important insights into gas formation processes and structural properties of gas-generating precursors, such as kerogen, bitumen, and oil, in natural reservoirs. Until recently, little has been known about the intramolecular isotope distributions within kerogens. In this study, we conducted systematic pyrolysis experiments of gas generation from a lacustrine oil shale of the Eocene Green River Formation under hydrous and anhydrous conditions (equivalent maturity or Easy %R_o: 0.76 to 3.27 at 310 to 480 °C for 3 to 50 days), measuring gas yields and compositions, as well as bulk and position-specific (PS) carbon isotope compositions. Gas generation processes were investigated in combination with kinetic Monte Carlo (kMC) simulations on a model Type I kerogen based on the chemical structures of oil shale of the Green River Formation. The comparison of our experimental results with kMC modelling indicates a series of β-scission, radical isomerization, and recombination reactions better represent the bulk isotope compositions of propane in the pyrolysis of the oil shale of the Green River Formation, but the ΔC_c-t (= δ¹³C_cen – δ¹³C_ter) values of propane at Easy %R_o > 1.5 can be better simulated by a simple combination of propyl groups with H radicals. Combining our previous works on marine shale of the Woodford Formation and Springfield Coal Member of the Carbondale Formation, PS carbon isotopes of propane indicate that in the lacustrine shales of the Green River Formation and the marine Woodford Shale, propane is sourced from CC bond cleavage, while CO bond cracking generates propane from coal at the initial kerogen cracking stage. At high maturity, the differences of late-stage propane production among the source rocks lead to the different bulk and PS C kinetic isotope effects of propane. Our findings suggest that the δ¹³C at the terminal position of propane precursors is likely up to 3.6‰ higher than at the central position in the Green River kerogen, while they are similar in the marine shale of Woodford Formation. In addition, the δ¹³C at the central position of propyl groups attached to heteroatom compounds is relatively more positive in the Springfield Coal Member of the Carbondale Formation than in Green River kerogen. A comparison of intramolecular C isotopes of propyl groups in the kerogens with their bulk δ¹³C, based on the PS δ¹³C of early-generated propane, contributes to our understanding of heterogeneities of isotopic structures of sedimentary organic matter.