Xiaoqiang Li | Search USGS

USGS2023

Intramolecular carbon isotope geochemistry of butane isomers from laboratory maturation and Monte-Carlo simulations of kerogen types I, II, and III

Position-specific (PS) carbon isotope compositions of light hydrocarbons such as propane and butane isomers (n-butane and i-butane) can provide a wealth of information on the history of natural gases in the subsurface reservoirs and other environments. For PS carbon isotope analysis of butane isomers, we have established a GC-pyrolysis-GC-isotope ratio mass spectrometry method with demonstrated accuracy. With this method, we analyzed PS δ 13 C values of butane isomers generated from the systematic laboratory pyrolysis experiments of three different kerogen types (I, II, and III) at temperatures of 310–430 °C with corresponding thermal maturity (Easy %R o ) ranging from 0.7 to 3.3. The observed evolution in the abundances of butane isomers can be interpreted and semi-quantitatively modeled based on the abundances of different C C bonds within the kerogens at low maturity and thermal degradation of butane isomers at high maturity. The δ 13 C values at the central sites of both nC 4 and iC 4 were heavier than those at the terminal positions, similar to our previous observations of propane. Their isotopic evolution with the maturity were controlled largely by kinetic isotope effects associated with breaking of different C C bonds during the generation and degradation of butane isomers. Kinetic Monte Carlo (kMC) simulations of n-butane generated from thermal cracking of model kerogens (I, II, and III) and an oil with a series of reactions (homolytic cleavage, β-scission, radical isomerization, H-abstraction, and termination by radical recombination) provided generally consistent results with the experimental observations, although the difference in PS δ 13 C values between the central and terminal positions are somewhat overestimated. On the other hand, the kMC simulation with homolytic cleavage and capping reactions alone produced significant deviations from the experimental results. Re-assessment of very limited data of PS δ 13 C values of natural butanes with our experimental and simulation results show that biodegradation significantly increased δ 13 C values at the central positions, not only of propane, but also of both butane isomers. This study lays a foundation and demonstrates the potential of PS isotope geochemistry of butane isomers to further improve our understanding of the sources, and geochemical and microbial processes of light hydrocarbons in the subsurface and other natural environments.

Geochimica et Cosmochimica Acta↗

USGS2022

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 (= δ 13 C cen – δ 13 C 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 C C bond cleavage, while C O 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 δ 13 C 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 δ 13 C 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 δ 13 C, based on the PS δ 13 C of early-generated propane, contributes to our understanding of heterogeneities of isotopic structures of sedimentary organic matter.

International Journal of Coal Geology↗