Intramolecular carbon isotope of propane from coal-derived gas reservoirs of sedimentary basins: Implications for source, generation and post-generation of hydrocarbons

An intramolecular isotopic study was conducted on natural gases collected from coal-derived gas reservoirs in sedimentary basins of China to determine their position-specific isotope distributions. The propane from the Turpan-Hami Basin exhibited negative Δ_C-T (δ¹³C_central-δ¹³C_terminal) values ranging from −3.9‰ to −0.3‰, with an average of −2.1‰. Propane from the Ordos Basin, Sichuan Basin, and Tarim Basin showed positive Δ_C-T values, with averages of 1.3‰, 5.4‰ and 7.6‰, respectively. Position-specific carbon isotope compositions reveal the precursors and the propane generation pathways in the petroliferous basins. Propane formed from the thermal cracking of Type III kerogen has larger δ¹³C_central and δ¹³C_terminal values than propane from Type I/II kerogen. The precursor for natural gases collected in this study is identified to be Type III kerogen. Comparing our data to calculated results for thermal cracking of Type III kerogen, we found that propane from the low-maturity gas reservoir in the Turpan Basin was generated via the i-propyl radical pathway, whereas propane from the Sulige tight gas reservoir in the Ordos Basin was formed via the n-propyl radical pathway. δ¹³C_terminal values covered a narrow range across basins, in contrast to δ¹³C_central. The terminal carbon position in propane is less impacted by microbial oxidation and more relevant to maturity levels and precursors. Thus, δ¹³C_terminal has a good potential to infer the origin and maturity level of natural gas. In examining post-generation processes, we proposed an improved identification strategy for microbial oxidation of natural gases, based on the position-specific carbon isotope distributions of propane. Samples from the Liaohe Depression of the Bohai Bay Basin and the Sichuan Basin were detected of post-generation microbial oxidation. Overall, position-specific carbon isotope composition of propane provides new insights into the generation mechanism and post-generation processes of natural gas in the geological period at the atomic level.