It is widely accepted that organic–inorganic interactions involving hydrogen-rich fluids (H2O and H2) play a significant role in hydrocarbon (HC) generation in sedimentary basins, and the effects of hydrogenation of organic matter (OM) by H2O/H2 on C/H isotope fractionation remain poorly understood. This study investigates these effects through a series of pyrolysis experiments conducted at 330–420 °C and 50 MPa, encompassing three groups: (1) anhydrous pyrolysis with kerogen only (Group 1), (2) kerogen and H2O (Group 2), and (3) kerogen, H2O, and Fe1-xS (Group 3). Groups 2 and 3 were designed to simulate hydrogenation of OM by H2O and H2, respectively. Results show that HC gas yields in Group 3 experiments are 1.8 to 3.2 times of those in Group 1, while yields in Group 2 are lower than Group 1. Moreover, hydrogenation by H2 produces HC gases with smaller 13C fractionation and more negative δ2H values compared to hydrogenation by H2O. These findings suggest distinct mechanisms for HC gas generation during H2-OM and H2O-OM reactions. Further analysis demonstrates that the equilibrium isotope effect (EIE) governs 13C and 2H isotope fractionation during hydrogenation of OM by H2. Importantly, the EIE for 2H isotope fractionation of H2O-H2, CH4-H2, and OM-H2 is evaluated under both experimental and geological conditions. This study provides crucial insights into the significant influence of hydrogenation of OM by H2 on the generation and C/H isotopic fractionation of HC gases, as well as the evolution and preservation of H2 in organic-rich shales.
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