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Isotope Rollover of Gaseous Hydrocarbons Induced by Water Pressure in Laboratory Pyrolysis Experiments: Insights into the Influence of Pressure on Carbon Kinetic Isotope Effects During Methane Generation

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Abstract

Stable carbon isotope (δ13C) rollover of natural gas has attracted recent attention due to its association with highly productive shale gas. However, the mechanistic causes of δ13C rollover are not fully understood. In this investigation, pyrolysis was carried out using calcareous shale and carbonaceous mudstone under high water pressure (WP) (i.e., 5 × 106–1.2 × 108 Pa). It was found that WP induced the isotope rollover of gaseous hydrocarbons. For both sapropelic and humic organic matter, the δ13C rollover of CH4 (methane), C2H6 (ethane), and C3H8 (propane) occurred when the WP ranged from 3.25 × 107 to 1.2 × 108 Pa. This result can be explained by high WP conditions retarding oil cracking, and enhancing hydrocarbon expulsion and oil generation. The promotion of oil generation resulted in increasing trends of vitrinite reflectance, and inhibition of gaseous hydrocarbons generation resulted in decrease in δ13C1 values with increase in WP. Good functions were found between water pressure and the calculated carbon kinetic isotope effect (KIE) for 12CH4 and 13CH4 produced from sapropelic and humic organic matter. Further calculations showed that the increments of activation volume (\({\Delta V}_{{12}_{{\mathrm{CH}}_{4}}}^{\ddagger }\)–\({\Delta V}_{{13}_{{\mathrm{CH}}_{4}}}^{\ddagger }\)) were linearly correlated with the kinetic isotope effect of methane (\(\Delta \mathrm{KIE}\)) produced from sapropelic and humic organic matter, indicating that WP may affect the KIE of 12CH4 and 13CH4 by changing the \(\Delta {V}^{\ddagger }\) of 12CH4 and 13CH4. Overall, these findings suggest that WP affects the carbon isotope fractionation of gaseous hydrocarbons due to the different thermodynamic properties of 12CH4 and 13CH4.

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Data Availability

All data generated or analyzed during this study are included in this published article and its supplementary information files.

Notes

  1. *1 bar = 100 kPa.

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Acknowledgments

This research was jointly supported by the Guangdong Basic and Applied Basic Research Foundation (Grant Number: 2019A1515111211), the China Postdoctoral Science Foundation (Grant Number: 2021M690247), the National Natural Science Foundation of China (Grant Number: 41903060), and the Shenzhen Fund in Special Foundation for Guiding Local Science and Technology Development of the Central Government (2021Szvup001).

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Authors and Affiliations

  1. Shenzhen Institute, Peking University, Shenzhen, 518055, China

    Yuandong Wu

  2. School of Molecular Science and Engineering, South China University of Technology, Guangzhou, 510641, China

    Yuanju Li

  3. Shanwei Institute of Technology, Shanwei, 516600, China

    Yuanju Li

  4. Huabei Petroleum Tiancheng Industrial Group Co. Ltd, Hebei, 062550, China

    Changfeng Wang

  5. Hubei Cooperative Innovation Center of Unconventional Oil and Gas (Yangtze University), Wuhan, 430100, Hubei, China

    Lina Sun

  6. Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou, 730000, China

    Zhongning Zhang, Liming Ji, Mingzhen Zhang & Long Su

  7. Key Laboratory of Petroleum Resources, Lanzhou, 730000, Gansu Province, China

    Zhongning Zhang, Liming Ji, Mingzhen Zhang & Long Su

  8. Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China

    Yuandong Wu

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  1. Yuandong Wu
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Wu, Y., Li, Y., Wang, C. et al. Isotope Rollover of Gaseous Hydrocarbons Induced by Water Pressure in Laboratory Pyrolysis Experiments: Insights into the Influence of Pressure on Carbon Kinetic Isotope Effects During Methane Generation. Nat Resour Res 31, 1523–1537 (2022). https://doi.org/10.1007/s11053-022-10052-9

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