Hao Xie

Nanjing University

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John M. Eiler

California Institute of Technology

Michael J Formolo

ExxonMobil (United States)

Michael Lawson

ExxonMobil (United States)

Camilo Ponton

California Institute of Technology

Alex L. Sessions

California Institute of Technology

Nivedita Thiagarajan

California Institute of Technology

Brian K. Peterson

ExxonMobil (United States)

Yanhua Shuai

Research Institute of Petroleum Exploration and Development

Max K. Lloyd

California Institute of Technology

Xavier Mangenot

Sustainable Europe Research Institute

Cooperative Institutions

California Institute of Technology

Planetary Science Institute

Research Institute of Petroleum Exploration and Development

China National Petroleum Corporation (China)

Centre National de la Recherche Scientifique

United States Geological Survey

University of Oxford

ExxonMobil (United States)

University of Manchester

Woods Hole Oceanographic Institution

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Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Geochimica et Cosmochimica Acta (2020)

Hao Xie Camilo Ponton Michael J Formolo Michael Lawson Geoffrey S. Ellis

Propane

Kinetic isotope effect

Equilibrium fractionation

10.1016/j.gca.2020.09.009

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Citations (16)

Corrigendum to “Theoretical and experimental constraints on hydrogen isotope equilibrium in C1–C5 alkanes” [Geochim. Cosmochim. Acta 386 (2024) 63–73]

Geochimica et Cosmochimica Acta (2025)

Hao Xie Michael J Formolo Alex L. Sessions John M. Eiler

Hydrogen isotope

10.1016/j.gca.2025.01.044

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Isotopic evidence for quasi-equilibrium chemistry in thermally mature natural gases

Proceedings of the National Academy of Sciences (2020)

Nivedita Thiagarajan Hao Xie Camilo Ponton Nami Kitchen Brian K. Peterson

Natural gas is a key energy resource, and understanding how it forms is important for predicting where it forms in economically important volumes. However, the origin of dry thermogenic natural gas is one of the most controversial topics in petroleum geochemistry, with several differing hypotheses proposed, including kinetic processes (such as thermal cleavage, phase partitioning during migration, and demethylation of aromatic rings) and equilibrium processes (such as transition metal catalysis). The dominant paradigm is that it is a product of kinetically controlled cracking of long-chain hydrocarbons. Here we show that C2+n-alkane gases (ethane, propane, butane, and pentane) are initially produced by irreversible cracking chemistry, but, as thermal maturity increases, the isotopic distribution of these species approaches thermodynamic equilibrium, either at the conditions of gas formation or during reservoir storage, becoming indistinguishable from equilibrium in the most thermally mature gases. We also find that the pair of CO2 and C1 (methane) exhibit a separate pattern of mutual isotopic equilibrium (generally at reservoir conditions), suggesting that they form a second, quasi-equilibrated population, separate from the C2 to C5 compounds. This conclusion implies that new approaches should be taken to predicting the compositions of natural gases as functions of time, temperature, and source substrate. Additionally, an isotopically equilibrated state can serve as a reference frame for recognizing many secondary processes that may modify natural gases after their formation, such as biodegradation.

Propane

Alkane

Butane

Pentane

Equilibrium thermodynamics

10.1073/pnas.1906507117

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Identifying thermogenic and microbial methane in deep water Gulf of Mexico Reservoirs

Geochimica et Cosmochimica Acta (2020)

Nivedita Thiagarajan Nami Kitchen Hao Xie Camilo Ponton Michael Lawson

Abiogenic petroleum origin

Atmospheric methane

Isotopic signature

10.1016/j.gca.2020.02.016

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Citations (43)

Formation mechanism of deep natural hydrogen in the Sichuan Basin

Science China Earth Sciences (2025)

Xiaomei Wang Kun He Chunlong Yang Hao Xie Xiaobo Wang

10.1007/s11430-024-1463-1

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The isotopic structures of geological organic compounds

Geological Society London Special Publications (2017)

John M. Eiler Matthieu Clog Michael Lawson Max K. Lloyd Alison Piasecki

Abstract Organic compounds are ubiquitous in the Earth's surface, sediments and many rocks, and preserve records of geological, geochemical and biological history; they are also critical natural resources and major environmental pollutants. The naturally occurring stable isotopes of volatile elements (D, 13 C, 15 N, 17,18 O, 33,34,36 S) provide one way of studying the origin, evolution and migration of geological organic compounds. The study of bulk stable isotope compositions (i.e. averaged across all possible molecular isotopic forms) is well established and widely practised, but frequently results in non-unique interpretations. Increasingly, researchers are reading the organic isotopic record with greater depth and specificity by characterizing stable isotope ‘structures’ – the proportions of site-specific and multiply substituted isotopologues that contribute to the total rare-isotope inventory of each compound. Most of the technologies for measuring stable isotope structures of organic molecules have been only recently developed and to date have been applied only in an exploratory way. Nevertheless, recent advances have demonstrated that molecular isotopic structures provide distinctive records of biosynthetic origins, conditions and mechanisms of chemical transformation during burial, and forensic fingerprints of exceptional specificity. This paper provides a review of this young field, which is organized to follow the evolution of molecular isotopic structure from biosynthesis, through diagenesis, catagenesis and metamorphism.

10.1144/sp468.4

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Citations (17)

Clumped isotope effects of thermogenic methane formation: Insights from pyrolysis of hydrocarbons

Geochimica et Cosmochimica Acta (2021)

Guannan Dong Hao Xie Michael J Formolo Michael Lawson Alex L. Sessions

10.1016/j.gca.2021.03.009

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Citations (36)

CH4 isotopic ordering records ultra-slow hydrocarbon biodegradation in the deep subsurface

Earth and Planetary Science Letters (2021)

Josué J. Jautzy Peter Douglas Hao Xie John M. Eiler Ian D. Clark