Kinetic and equilibrium reactions on natural and laboratory generation of thermogenic gases from Type II marine shale

The phenomenon that laboratory pyrolysis experiments produce much wetter gases than those in natural reservoirs is a long-recognized and debated problem in the investigation of natural gases in sedimentary basins. In this study, we explore the discrepancy by pyrolyzing a type II kerogen from the Woodford Shale in Oklahoma, compared with the previous results on the produced natural gases from the Arkoma Basin generated from the same source rock (Liu et al., 2019) with the discussion of gas and isotopic compositions at bulk and position-specific (PS) levels. An improved GC-pyrolysis-GC IRMS method is applied for the determination of PS δ13C of propane produced in the pyrolysis of the Woodford Shale at Easy %Ro from 0.76 to 3.27. Kinetic and thermodynamic considerations of the chemical and isotopic compositions of the natural and laboratory pyrolysis gases suggest that the generation of light hydrocarbons involves uni-directional cracking reactions, exchange reactions with water, and likely reversible reactions among light hydrocarbons and other H-containing volatiles. After the gas generation in the unconventional Woodford Shale reservoirs, the C1-C4 gases might have approached close to chemical equilibrium of C1-C3 and isotope equilibrium of C2-C1 and C3-C1 pairs at their peak temperatures. The capping H for the generation of C1-C4 in the Woodford Shale gases appears to have experienced at least partial exchange with the water, while that in the pyrolysis gases is only originated from organic-bound compounds with large kinetic isotope effects (KIE). Our findings indicate that elevated compound-specific and PS δ13C values of propane in the wet-gas cracking stage are significantly influenced by the breakdown of the thermally stable compounds (e.g., remaining kerogen, residues). A first synthesis of PS δ13C and δ2H isotopic compositions of propane from this study and the literature data suggests relatively similar isotopic structures of propane precursors in kerogens. This study demonstrates that PS isotope analysis of propane can contribute to identifying various geological (e.g., maturation, wet-gas cracking, H exchange, diffusion) and biodegradation processes.