天然气丙烷位置特异性同位素地球化学：烷烃形成、演化与次生改造过程示踪

doi:10.3799/dqkx.2026.055

天然气丙烷位置特异性同位素地球化学：烷烃形成、演化与次生改造过程示踪

doi: 10.3799/dqkx.2026.055

刘鹏¹,
刘翰林^2,3,4,,
邹才能^2,3,4,,
赵群^2,3,4,
陈艳鹏^2,3,4,
邓泽^2,3,4,
周国晓⁵,
郭睿良⁶,
刘昌杰⁷,
宋董军⁸,
王晓锋⁹

1. 西安科技大学安全科学与工程学院，陕西西安 710054
2. 中国石油勘探开发研究院，北京 100083
3. 中国石油天然气集团有限公司煤岩气重点实验室，河北廊坊 065007
4. 国家能源页岩气研发（实验）中心，河北廊坊 065007
5. 中国石油长庆油田分公司勘探开发研究院，陕西西安 710018
6. 西安石油大学地球科学与工程学院，陕西西安 710065
7. 中国科学院西北生态环境资源研究院，甘肃兰州 730000
8. 兰州大学地质科学与矿产资源学院，甘肃兰州 730000
9. 西北大学地质学系，陕西西安 710069

基金项目:

深地国家科技重大专项《油气田有关天然气藏中氦气富集与探测》青年科学家项目《富氦煤岩优势组构与氦气赋存及聚集机制》（2025ZD1010507）

详细信息

作者简介:
刘鹏（1990-），副教授，博士，主要从事非常规油气地质和同位素地球化学研究。E-mail：pliu52@hotmail.com

通讯作者:
刘翰林（1992-），高级工程师，博士，主要从事非常规油气地质和油气能源战略研究。E-mail: lhldmc@163.com

邹才能（1963-），中国科学院院士，博士，主要从事事常规—非常规油气地质学理论与勘探、新能源技术、能源战略、碳中和等领域的研究工作。E-mail: zcn@petrochina.com.cn

中图分类号: P593
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出版历程
- 收稿日期: 2026-01-12
- 网络出版日期: 2026-03-11

Position-specific isotopes in propane of natural gas: tracing of hydrocarbons generation, evolution, and secondary alteration

Peng Liu¹,
Hanlin Liu^{2,3,4
,},
Caineng Zou^{2,3,4
,},
Qun Zhao^2,3,4,
Yanpeng Chen^2,3,4,
Ze Deng^2,3,4,
Guoxiao⁵,
Zhou⁶,
Ruiliang Guo⁷,
Changjie Liu⁸,
Dongjun Song⁹

1. College of Safety Science and Engineering, Xi'an University of Science and Technology, Xi'an 710054, China;
2. Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, 100083, China;
3. China National Petroleum Corporation Key Laboratory of Coal-Rock Gas, Langfang 065007, China;
4. National Energy Shale Gas R & D (Experiment) Center, Langfang 065007, China;
5. Exploration and Development Research Institute of PetroChina Changqing Oilfield Company, Xi'an 710018, China;
6. School of Earth Sciences and Engineering, Xi'an Shiyou University, Xi'an, 710065, China;
7. Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China;
8. School of Earth Sciences, Lanzhou University, Lanzhou 730000, China;
9. Department of Geology, Northwest University, Xi'an, 710069, China

摘要

摘要: 天然气中丙烷位置特异性同位素研究是当前油气地球化学的前沿热点。本文系统介绍了丙烷位置特异性同位素组成的测试技术进展，探讨了其在天然气中分布的控制机理，并阐述了该技术对烷烃形成路径、排烃过程及次生改造作用的示踪原理与应用。此外，通过应用烃源岩热脱附气的丙烷位置特异性同位素特征，成功实现了气藏与多套邻近烃源岩的精细气源对比。该技术为研究天然气的形成、演化与改造提供了新型示踪工具。最后展望了未来需结合实验与数值模拟，以推动其在复杂地质条件下的进一步应用。
- 天然气 /
- 丙烷 /
- 位置特异性同位素组成 /
- 形成路径 /
- 排滞过程 /
- 次生改造
Abstract: The study of position-specific isotopes in natural gas propane is an emerging hotspot in petroleum geochemistry. This review summarizes advancements in analytical techniques for determining position-specific isotope compositions of propane in natural gas and and examines the controlling mechanisms of position-specific isotope distributions in natural gases. The approach provides a novel means to trace hydrocarbon generation pathways, expulsion-retention processes and secondary alteration.By applying position-specific isotope signatures of propane desorbed from source rock, refined gas source correlation can be achieved, especially in basins with multiple adjacent source rock intervals. In summary, position-specific isotopes of propane provide a powerful tool for elucidating the formation, evolution, and alteration processes of natural gases. Further studies should integrate experimental and modeling approaches to extend its application to more complex geological systems.
- Natural gas /
- Propane /
- Position-specific isotope composition /
- Formation pathway /
- Expulsion and retention processes /
- Secondary alteration

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参考文献(64)

Cai, C., Li, H., Li, K., et al. 2022. Thermochemical Sulfate Reduction in Sedimentary Basins and Beyond: A Review. Chemical Geology, 607: 121018
Cai, C., Zhang, C., He, H., et al. 2013. Carbon Isotope Fractionation During Methane-Dominated Tsr in East Sichuan Basin Gasfields, China: A Review. Marine and Petroleum Geology, 48: 100-110
Dai, J. 1992. Identification and Distinction of Various Alkane Gases. Science in China(Series B), 35(10): 1246-1257
Feng, D., Wang, X., Liu, P., et al. 2025. Differential Geochemical Characteristics and Control Mechanism of Source Rocks in the Shuixigou Group, Turpan–Hami Basin. Geological Journal, n/a(n/a).https://doi.org/10.1002/gj.70163
Gai, H., Tian, H., Cheng, P., et al. 2019. Influence of Retained Bitumen in Oil-Prone Shales on the Chemical and Carbon Isotopic Compositions of Natural Gases: Implications from Pyrolysis Experiments. Marine and Petroleum Geology, 101: 148-161
Gao, L., He, P., Jin, Y., et al. 2016. Determination of Position-Specific Carbon Isotope Ratios in Propane from Hydrocarbon Gas Mixtures. Chemical Geology, 435: 1-9.https://doi.org/10.1016/j.chemgeo.2016.04.019
Gilbert, A., Nakagawa, M., Taguchi, K., et al. 2022. Hydrocarbon Cycling in the Tokamachi Mud Volcano (Japan): Insights from Isotopologue and Metataxonomic Analyses. Microorganisms, 10(7): 1417.https://doi.org/10.3390/microorganisms10071417
Gilbert, A., Sherwood Lollar, B., Musat, F., et al. 2019. Intramolecular Isotopic Evidence for Bacterial Oxidation of Propane in Subsurface Natural Gas Reservoirs. Proceedings of the National Academy of Sciences, 116(14): 6653-6658.doi: 10.1073/pnas.1817784116
Gilbert, A., Yamada, K., Suda, K., et al. 2016. Measurement of Position-Specific 13c Isotopic Composition of Propane at the Nanomole Level. Geochimica et Cosmochimica Acta, 177: 205-216.https://doi.org/10.1016/j.gca.2016.01.017
Guo, R., Zhou, X., Lei, X., et al. 2025. Intramolecular Isotopic Distributions of Associated Propane in Shale Oil Determined by an Improved Gc-Pyrolysis-Gc-Irms Approach: Insights into Influence of Kerogen Structures on Enrichment of Hydrocarbon Deposits. Journal of Analytical and Applied Pyrolysis, 188: 107023
Hu, W.-X., Kang, X., Cao, J., et al. 2018. Thermochemical Oxidation of Methane Induced by High-Valence metal Oxides in a Sedimentary Basin. Nature Communications, 9(1): 5131. doi: 10.1038/s41467-018-07267-x
Jaekel, U., Vogt, C., Fischer, A., et al. 2014. Carbon and Hydrogen Stable Isotope Fractionation Associated with the Anaerobic Degradation of Propane and Butane by Marine Sulfate-Reducing Bacteria. Environmental microbiology, 16(1): 130-140. doi: 10.1111/1462-2920.12251
James, A. T. 1983. Correlation of Natural Gas by Use of Carbon Isotopic Distribution between Hydrocarbon Components. AAPG Bulletin, 67(7): 1176-1191. doi: 10.1306/03b5b722-16d1-11d7-8645000102c1865d
James, A. T. 1990. Correlation of Reservoired Gases Using the Carbon Isotopic Compositions of Wet Gas Components1. AAPG Bulletin, 74(9): 1341-1458. doi: 10.1306/0c9b24f7-1710-11d7-8645000102c1865d
Kniemeyer, O., Musat, F., Sievert, S. M., et al. 2007. Anaerobic Oxidation of Short-Chain Hydrocarbons by Marine Sulphate-Reducing Bacteria. Nature, 449(7164): 898-901
Li, F.-J., Liu, P., Yang, W.-W., et al. 2026. Kerogen Aromatization and Late Hydrocarbon Generation: Evidence from Position-Specific Isotope Composition of Propane. Petroleum Science.https://doi.org/10.1016/j.petsci.2026.01.024
Li, J., Liu, C., He, X., et al. 2019. Aerobic Microbial Oxidation of Hydrocarbon Gases: Implications for Oil and Gas Exploration. Marine and Petroleum Geology, 103: 76-86
Li, X., Birdwell, J. E., & Horita, J. 2022a. Bulk and Intramolecular Carbon Isotopic Compositions of Hydrocarbon Gases from Laboratory Pyrolysis of Oil Shale of the Green River Formation: Implications for Isotope Structures of Kerogens. International Journal of Coal Geology, 264: 104141.https://doi.org/10.1016/j.coal.2022.104141
Li, X., & Horita, J. 2022. Kinetic and Equilibrium Reactions on Natural and Laboratory Generation of Thermogenic Gases from Type Ii Marine Shale. Geochimica et Cosmochimica Acta, 333: 263-283.https://doi.org/10.1016/j.gca.2022.07.020
Li, X., Mastalerz, M., & Horita, J. 2022b. Gas Generation and Intramolecular Isotope Study in Laboratory Pyrolysis of the Springfield Coal from the Illinois Basin. Organic Geochemistry, 171: 104466.https://doi.org/10.1016/j.orggeochem.2022.104466
Li, X., McGovern, G. P., & Horita, J. 2021. Kinetics of Propane Cracking and Position-Specific Isotope Fractionation: Insights into the Origins of Natural Gases. Organic Geochemistry, 155: 104234.https://doi.org/10.1016/j.orggeochem.2021.104234
Li, Y., Jiang, W., Liu, W., et al. 2024. Contribution of Abiotic Methane Polymerization of C2+ Hydrocarbons in Highly Mature Natural Gas Reservoirs. Organic Geochemistry, 192: 104798.https://doi.org/10.1016/j.orggeochem.2024.104798
Li, Y., Zhang, L., Xiong, Y., et al. 2018. Determination of Position-Specific Carbon Isotope Ratios of Propane from Natural Gas. Organic Geochemistry, 119: 11-21.https://doi.org/10.1016/j.orggeochem.2018.02.007
Liu, C., Liu, P., McGovern, G. P., et al. 2019. Molecular and Intramolecular Isotope Geochemistry of Natural Gases from the Woodford Shale, Arkoma Basin, Oklahoma. Geochimica et Cosmochimica Acta, 255: 188-204.https://doi.org/10.1016/j.gca.2019.04.020
Liu, C., Liu, P., Wang, X., et al. 2023a. Establishing Accuracy of Position-Specific Carbon Isotope Analysis of Propane by Gc-Pyrolysis-Gc-Irms. Rapid Communications in Mass Spectrometry: e9494.https://doi.org/10.1002/rcm.9494
Liu, C., McGovern, G. P., Liu, P., et al. 2018. Position-Specific Carbon and Hydrogen Isotopic Compositions of Propane from Natural Gases with Quantitative Nmr. Chemical Geology, 491: 14-26.https://doi.org/10.1016/j.chemgeo.2018.05.011
Liu, P., Wang, X.-F., Wang, J., et al. 2025a. Deciphering Origins of Hydrocarbon Deposits by Means of Intramolecular Carbon Isotopes of Propane Adsorbed on Sediments. Petroleum Science, 22(2): 546-556
Liu, P., Wang, X., Liu, C., et al. 2024. Intramolecular Carbon Isotopic Rollover in Propane from Natural Gas Reservoirs of the Santanghu Basin: Insights into Chemical Structure of Kerogen. Organic Geochemistry, 188: 104740.https://doi.org/10.1016/j.orggeochem.2024.104740
Liu, P., Wang, X., Liu, C., et al. 2023b. Kinetic Isotope Effects and Reaction Pathways of Thermogenic Propane Generation at Early Maturation Stage: Insights from Position-Specific Carbon Isotope Analysis. Marine and Petroleum Geology, 153: 106252.https://doi.org/10.1016/j.marpetgeo.2023.106252
Liu, P., Wang, X., Liu, H., et al. 2025b. Intramolecular Carbon Isotopic Fractionation of Propane Via Thermochemical Sulfate Reduction (TSR) in Natural Gas Reservoirs. Natural Gas Industry B.https://doi.org/10.1016/j.ngib.2025.12.001
Liu, Q., Worden, R., Jin, Z., et al. 2013. Tsr Versus Non-Tsr Processes and Their Impact on Gas Geochemistry and Carbon Stable Isotopes in Carboniferous, Permian and Lower Triassic Marine Carbonate Gas Reservoirs in the Eastern Sichuan Basin, China. Geochimica et Cosmochimica Acta, 100: 96-115
Meng, Q., Wang, X., Wang, X., et al. 2017. Gas Geochemical Evidences for Biodegradation of Shale Gases in the Upper Triassic Yanchang Formation, Ordos Basin, China. International Journal of Coal Geology, 179: 139-152.https://doi.org/10.1016/j.coal.2017.05.018
Milkov, A. V., Schwietzke, S., Allen, G., et al. 2020. Using Global Isotopic Data to Constrain the Role of Shale Gas Production in Recent Increases in Atmospheric Methane. Scientific Reports, 10(1): 4199
Musat, F., Chen, S.-C., Musat, N., et al. 2025. Anaerobic Oxidation of Short-Chain Volatile Alkanes. Trends in Microbiology
Piasecki, A., Sessions, A., Lawson, M., et al. 2016a. Analysis of the Site-Specific Carbon Isotope Composition of Propane by Gas Source Isotope Ratio Mass Spectrometer. Geochimica et Cosmochimica Acta, 188: 58-72.https://doi.org/10.1016/j.gca.2016.04.048
Piasecki, A., Sessions, A., Lawson, M., et al. 2018. Position-Specific 13c Distributions within Propane from Experiments and Natural Gas Samples. Geochimica et Cosmochimica Acta, 220: 110-124.https://doi.org/10.1016/j.gca.2017.09.042
Piasecki, A., Sessions, A., Peterson, B., et al. 2016b. Prediction of Equilibrium Distributions of Isotopologues for Methane, Ethane and Propane Using Density Functional Theory. Geochimica et Cosmochimica Acta, 190: 1-12.https://doi.org/10.1016/j.gca.2016.06.003
Rooney, M. A., Claypool, G. E., & Moses Chung, H. 1995. Modeling Thermogenic Gas Generation Using Carbon Isotope Ratios of Natural Gas Hydrocarbons. Chemical Geology, 126(3): 219-232.https://doi.org/10.1016/0009-2541(95)00119-0
Schoell, M. 1983. Genetic Characterization of Natural Gases. AAPG Bulletin, 67(12): 2225-2238.10.1306/ad46094a-16f7-11d7-8645000102c1865d
Seewald, J. S. 2003. Organic–Inorganic Interactions in Petroleum-Producing Sedimentary Basins. Nature, 426(6964): 327-333
Shuai, Y., Bai, B., Liu, X., et al. 2024. Position-Specific Carbon Isotopes of Propane in Coal Systems in China. Fuel, 360: 130515
Shuai, Y., Li, J., Tao, X., et al. 2024. High-valence metal oxide reduction reaction， identification， and its impact on petroleum accumulation. Natural Gas Geoscience, 2024, 35(12): 2228-2239 https://doi.org/10.11764/j.issn.1672-1926.2024.05.008 (In Chinese with English Abstract)
Shuai Y H, Peng PA, Tao X W, et al. Intramolecular 13C isotope distributions in propane from natural gases and produced in the laboratory. Chin Sci Bull, 2023, 68: 4995-5008, doi: 10.1360/TB-2023-0210 (In Chinese with English Abstract)
Shuai, Y., Xiong, Y., Li, J., et al. 2023. Unusual 13c Depletion in the Central Carbon of Propane in the Gases of Longmaxi Shale in the Sichuan Basin. Organic Geochemistry, 184: 104658
Song, D., Liu, P., Horita, J., et al. 2025. Position-Specific Carbon Isotope Compositions of Propane as a Novel Proxy for Tracing Sealing Integrity of Shale Systems. GSA Bulletin.10.1130/b38616.1
Song, D., Tuo, J., Dai, S., et al. 2022. New Insights into the Role of System Sealing Capacity in Shale Evolution under Conditions Analogous to Geology: Implications for Organic Matter Evolution and Petroleum Generation. Marine and Petroleum Geology, 140: 105659
Stahl, W. J., & Carey, B. D. 1975. Source-Rock Identification by Isotope Analyses of Natural Gases from Fields in the Val Verde and Delaware Basins, West Texas. Chemical Geology, 16(4): 257-267.https://doi.org/10.1016/0009-2541(75)90065-0
Taguchi, K., Ueno, Y., Gilbert, A., et al. 2025. Clumped 13c–13c Isotopes of Ethane from Laboratory Pyrolysis of Kerogen: Implications for Intramolecular 13c Distributions. Organic Geochemistry, 204: 104951.https://doi.org/10.1016/j.orggeochem.2025.104951
Tang, Y., Perry, J. K., Jenden, P. D., et al. 2000. Mathematical Modeling of Stable Carbon Isotope Ratios in Natural Gases. Geochimica et Cosmochimica Acta, 64(15): 2673-2687.https://doi.org/10.1016/S0016-7037(00)00377-X
Tian, H., Xiao, X., Wilkins, R. W., et al. 2012. An Experimental Comparison of Gas Generation from Three Oil Fractions: Implications for the Chemical and Stable Carbon Isotopic Signatures of Oil Cracking Gas. Organic Geochemistry, 46: 96-112
Wang, X., Liu, P., Liu, W., et al. 2024. Intramolecular Carbon Isotope of Propane from Coal-Derived Gas Reservoirs of Sedimentary Basins: Implications for Source, Generation and Post-Generation of Hydrocarbons. Geoscience Frontiers: 101806.https://doi.org/10.1016/j.gsf.2024.101806
Webb, M. A., & Miller, T. F., III. 2014. Position-Specific and Clumped Stable Isotope Studies: Comparison of the Urey and Path-Integral Approaches for Carbon Dioxide, Nitrous Oxide, Methane, and Propane. The Journal of Physical Chemistry A, 118(2): 467-474.10.1021/jp411134v
Worden, R., Smalley, P. C., & Oxtoby, N. 1995. Gas Souring by Thermochemical Sulfate Reduction at 140 C. Aapg Bulletin, 79(6): 854-863
Xia, X. 2014. Kinetics of Gaseous Hydrocarbon Generation with Constraints of Natural Gas Composition from the Barnett Shale. Organic geochemistry, 74: 143-149
Xia, X., Chen, J., Braun, R., et al. 2013. Isotopic Reversals with Respect to Maturity Trends Due to Mixing of Primary and Secondary Products in Source Rocks. Chemical Geology, 339: 205-212
Xia, X., & Gao, Y. 2024. Compound-Specific, Intra-Molecular, and Clumped 13c Fractionations in the Thermal Generation and Decomposition of Ethane and Propane: A Dft and Kinetic Investigation. Geochimica et Cosmochimica Acta, 375: 50-63.https://doi.org/10.1016/j.gca.2024.05.001
Xie, H., Ponton, C., Formolo, M. J., et al. 2020. Position-Specific Distribution of Hydrogen Isotopes in Natural Propane: Effects of Thermal Cracking, Equilibration and Biodegradation. Geochimica et Cosmochimica Acta, 290: 235-256.https://doi.org/10.1016/j.gca.2020.09.009
Xu, Y., Liu, W., Shen, P., et al. 2006. Carbon and Hydrogen Isotopic Characteristics of Natural Gases from the Luliang and Baoshan Basins in Yunnan Province, China. Science in China Series D: Earth Sciences, 49(9): 938-946.10.1007/s11430-006-0938-8
Xu, Y., et al. 1994. Origin Theory and Application of Natural Gas. Science Press, Beijing. (In Chinese)
Zhang, L., Li, Y., Jiang, W., et al. 2022. Position-Specific Carbon Isotopic Composition of Thermogenic Propane: Insights from Pyrolysis Experiments. Organic Geochemistry, 166: 104379.https://doi.org/10.1016/j.orggeochem.2022.104379
Zhao, H., Liu, C., Larson, T. E., et al. 2020. Bulk and Position-Specific Isotope Geochemistry of Natural Gases from the Late Cretaceous Eagle Ford Shale, South Texas. Marine and Petroleum Geology, 122: 104659.https://doi.org/10.1016/j.marpetgeo.2020.104659
帅燕华,李剑,陶小晚,等.2024.地质盆地金属氧化物还原作用及其识别和对油气的影响.天然气地球科学,35(12):2228-2239.
帅燕华,彭平安,陶小晚,等.2023.丙烷分子内碳同位素示踪作用.科学通报,68(36):4995-5008.
徐永昌, 等, 1994. 天然气成因理论及应用. 北京: 科学出版社.