Abnormal stable carbon isotopic (δ13C) compositions, deviating from the conventional order of δ13C1 < δ13C2 < δ13C3, are frequently observed in natural gas reservoirs. For thermogenic gas, these anomalies, such as δ13C1 < δ13C3 < δ13C2 or δ13C1 > δ13C2 > δ13C3, have multiple formation mechanisms including gas mixing in conventional systems and desorption processes of gaseous hydrocarbons in unconventional shale gas systems due to their inconsistency with Rayleigh fractionation processes. Considering distinct reaction pathways (e.g., C1 polymerized to C2), these aberrant δ13C signatures are often construed as intrinsic hallmarks of extensively evolved natural gas. However, on the basis of gas generation simulation, not all findings exhibit abnormal δ13C values, hinting at multifaceted and intricate mechanisms governing the isotopic fractionation of alkane gas components. This study conducted gold tube pyrolysis of an Australian torbanite, revealing four distinct types of δ13C anomalies in hydrocarbon classes. Polycyclic aromatic hydrocarbons (PAHs) exhibited δ13C values more negative than co-occurring n-alkanes. δ13C3 displayed a negative trend shift from EasyRo = 3.5 %, resulting in a partially δ13C-reversed gas (δ13C1 < δ13C3 < δ13C2) formed at EasyRo ≈ 4.1 %. Moreover, intramolecular δ13C3 (both terminal and central carbons, termed δ13Ca and δ13Cb, respectively) reversed alongside the overall δ13C3 trend. Additionally, the evolution of site preference in δ13C3 (termed ‰SP = δ13Ca – δ13Cb) transitioned from progressively negative to positive. The results of this study demonstrate that the potential conversion between saturated hydrocarbons, aromatic hydrocarbons, and alkane gases is at least partially responsible for δ13C anomalies, but also that gaseous hydrocarbons formed from other fractions at high maturity cannot be ruled out, such as kerogen and pyrobitumen.
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