Kinetic-simulating experiment combined with GC-IRMS analysis: application to identification and assessment of coal-derived methane from Zhongba Gas Field (Sichuan Basin, China)

The main purpose of this study is to model the δ13C values of methane derived from coal by combining kinetic-simulating experiment with the gas chromatography–isotope ratio mass spectrum (GC-IRMS) analysis. The stable carbon isotopic variation of methane in pyrolysates with heating temperature indicates that the assumptions for both a constant kinetic isotope effect (α) and a uniform initial isotopic composition (δ13Co) are impractical for explaining the carbon isotopic fractionation during coalification. For purposes of simplification, two approaches are used in this paper to deal with the heterogeneity of terrestrial organic matter. One is that, assuming a uniform initial isotopic composition (i.e., δ13Ci, o=δ13Co) for all methane-generating precursors in coal, the isotopic variation of methane is fitted by adjusting ΔEa, i (Ea13C, i−Ea12C, i) for each hypothetical reaction. The other is that, assuming a constant kinetic isotope effect during the whole gas formation, that is all ΔEa, i values are identical, the modeling of methane isotopic composition is achieved by changing the 13CH4 generation potential of each reaction (fi, 13C), namely, by adjusting the initial δ13C value (δ13Ci, o) for each methane-generating precursor. Results of the kinetic calculation shows that the two simulating methods can yield a similar result at a geological heating rate of 2 °C/My, which further demonstrates that those natural gases with methane δ13C value being approximately −36‰ are possibly sourced from the upper Triassic coal measure strata in the Northwestern Sichuan Basin.