Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

This content will become publicly available on Sat Jul 13 00:00:00 EDT 2024

Title: Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C

Abstract

Methane clumped isotope compositions signify the relative natural abundances of rare, doubly substituted isotopic species of methane (13CH3D and 12CH2D2) and have emerged as a new isotopic tool to trace the sources, sinks, and lifecycles of methane in the environment. Such measurements can identify equilibration (or reequilibration) temperatures if found to be in isotopic equilibrium or non-equilibrium processes (e.g., kinetically controlled reactions or mixing) if not in isotopic equilibrium. Naturally occurring thermogenic methane—formed by the thermally activated breakdown of larger organic molecules—has been found to have clumped isotope compositions consistent with equilibrium at reasonable gas formation temperatures in some settings and non-equilibrium processes occurring during either formation, migration, storage, or extraction in others. To explore the potential controls on the isotopic composition of thermogenic methane, we conducted isothermal time-series ethane pyrolysis experiments at 550 and 600 °C to measure methane and ethane 13C/12C and D/H fractionations and methane clumped isotope compositions (resolved 13CH3D and 12CH2D2). We explore the effects of modifying the initial clumped isotope composition of ethane and the addition of water vapor to pyrolysis experiments. We observe that ethane and methane 13C/12C are controlled by kinetic isotope effects and Rayleigh distillation processes. In contrast, ethane and methane D/Hmore » and methane clumped isotope compositions appear to be controlled by a combination of these processes and hydrogen isotope exchange. The hydrogen isotope exchange processes lead to isotopic equilibrium as reaction completion is approached for both D/H (ethane/methane) and methane clumped isotope compositions. Here, we develop a chemical model based on a mass balance approach that accounts for inheritance vs. hydrogen-abstraction formation pathways for singly and doubly substituted isotopologues of ethane and methane that is compared to the experimental data. The model allows the determination of carbon and hydrogen kinetic isotope effects associated with ethane cracking and hydrogen abstraction reactions that, where applicable, we compare to prior theoretical constraints. From the comparison of the model to the experimental data, we infer that the kinetically controlled ethane and methane bulk isotope compositions and methane clumped isotope compositions are controlled by kinetic isotope effects (both primary and secondary) associated with both C–C bond and C–H bond cleavage reactions. Specifically, the methane clumped isotope compositions likely result from a combination of clumped isotope effects associated with ethane breakdown and/or assembly of methane isotopologues (expressed in terms of γ-factor parameters ≠ 1) and combinatorial effects that arise probabilistically. We discuss our experimental results in the context of recent pyrolysis experiments and observations of naturally occurring thermogenic methane. We consider a proposal consistent with observations from nature that the hydrogen isotope exchange reactions that promote equilibration of methane isotopic molecules at or near formation temperature may be facilitated by free radicals generated by pyrolysis reactions. In this framework, isotope exchange effectively ceases when pyrolysis effectively ceases locking in compositions that can be consistent with peak formation temperatures.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [3];  [4]
+ Show Author Affiliations
  1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
  2. University of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1997185
Alternate Identifier(s):
OSTI ID: 1992540
Report Number(s):
LA-UR-23-26087
Journal ID: ISSN 0016-7037
Grant/Contract Number:  
89233218CNA000001; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 355; Journal ID: ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Earth sciences; Clumped isotopes, Methane, Natural gas, Thermogenic methane, Pyrolysis, Kinetic isotope effect

Citation Formats

Eldridge, Daniel Lee, Turner, Andrew C., Bill, Markus, Conrad, Mark E., and Stolper, Daniel A. Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C. United States: N. p., 2023. Web. doi:10.1016/j.gca.2023.06.006.
Copy to clipboard
Eldridge, Daniel Lee, Turner, Andrew C., Bill, Markus, Conrad, Mark E., & Stolper, Daniel A. Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C. United States. https://doi.org/10.1016/j.gca.2023.06.006
Copy to clipboard
Eldridge, Daniel Lee, Turner, Andrew C., Bill, Markus, Conrad, Mark E., and Stolper, Daniel A. Thu . "Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C". United States. https://doi.org/10.1016/j.gca.2023.06.006.
Copy to clipboard
@article{osti_1997185,
title = {Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C},
author = {Eldridge, Daniel Lee and Turner, Andrew C. and Bill, Markus and Conrad, Mark E. and Stolper, Daniel A.},
abstractNote = {Methane clumped isotope compositions signify the relative natural abundances of rare, doubly substituted isotopic species of methane (13CH3D and 12CH2D2) and have emerged as a new isotopic tool to trace the sources, sinks, and lifecycles of methane in the environment. Such measurements can identify equilibration (or reequilibration) temperatures if found to be in isotopic equilibrium or non-equilibrium processes (e.g., kinetically controlled reactions or mixing) if not in isotopic equilibrium. Naturally occurring thermogenic methane—formed by the thermally activated breakdown of larger organic molecules—has been found to have clumped isotope compositions consistent with equilibrium at reasonable gas formation temperatures in some settings and non-equilibrium processes occurring during either formation, migration, storage, or extraction in others. To explore the potential controls on the isotopic composition of thermogenic methane, we conducted isothermal time-series ethane pyrolysis experiments at 550 and 600 °C to measure methane and ethane 13C/12C and D/H fractionations and methane clumped isotope compositions (resolved 13CH3D and 12CH2D2). We explore the effects of modifying the initial clumped isotope composition of ethane and the addition of water vapor to pyrolysis experiments. We observe that ethane and methane 13C/12C are controlled by kinetic isotope effects and Rayleigh distillation processes. In contrast, ethane and methane D/H and methane clumped isotope compositions appear to be controlled by a combination of these processes and hydrogen isotope exchange. The hydrogen isotope exchange processes lead to isotopic equilibrium as reaction completion is approached for both D/H (ethane/methane) and methane clumped isotope compositions. Here, we develop a chemical model based on a mass balance approach that accounts for inheritance vs. hydrogen-abstraction formation pathways for singly and doubly substituted isotopologues of ethane and methane that is compared to the experimental data. The model allows the determination of carbon and hydrogen kinetic isotope effects associated with ethane cracking and hydrogen abstraction reactions that, where applicable, we compare to prior theoretical constraints. From the comparison of the model to the experimental data, we infer that the kinetically controlled ethane and methane bulk isotope compositions and methane clumped isotope compositions are controlled by kinetic isotope effects (both primary and secondary) associated with both C–C bond and C–H bond cleavage reactions. Specifically, the methane clumped isotope compositions likely result from a combination of clumped isotope effects associated with ethane breakdown and/or assembly of methane isotopologues (expressed in terms of γ-factor parameters ≠ 1) and combinatorial effects that arise probabilistically. We discuss our experimental results in the context of recent pyrolysis experiments and observations of naturally occurring thermogenic methane. We consider a proposal consistent with observations from nature that the hydrogen isotope exchange reactions that promote equilibration of methane isotopic molecules at or near formation temperature may be facilitated by free radicals generated by pyrolysis reactions. In this framework, isotope exchange effectively ceases when pyrolysis effectively ceases locking in compositions that can be consistent with peak formation temperatures.},
doi = {10.1016/j.gca.2023.06.006},
journal = {Geochimica et Cosmochimica Acta},
number = ,
volume = 355,
place = {United States},
year = {Thu Jul 13 00:00:00 EDT 2023},
month = {Thu Jul 13 00:00:00 EDT 2023}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 13, 2024
Publisher's Version of Record
https://doi.org/10.1016/j.gca.2023.06.006
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The catalytic decomposition of petroleum into natural gas
journal, December 1997

Precise Measurements of 12CH2D2 by Tunable Infrared Laser Direct Absorption Spectroscopy
journal, October 2019

Methane thermometry in deep-sea hydrothermal systems: Evidence for re-ordering of doubly-substituted isotopologues during fluid cooling
journal, November 2020

Carbon isotope fractionation during natural gas generation from kerogen
journal, May 1991

Mathematical modeling of stable carbon isotope ratios in natural gases
journal, August 2000

Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures
journal, April 1985

Origin of gaseous hydrocarbons in subsurface environments: Theoretical considerations of carbon isotope distribution
journal, December 1988

An accurate ab initio quartic force field and vibrational frequencies for CH 4 and isotopomers
journal, January 1995

  • Lee, Timothy J.; Martin, Jan M. L.; Taylor, Peter R.
  • The Journal of Chemical Physics, Vol. 102, Issue 1
  • DOI: 10.1063/1.469398

The hydrogen and carbon isotopic composition of methane from natural gases of various origins
journal, May 1980

Methane oxidation in sediment and water column environments—Isotope evidence
journal, January 1986

Exploring deep microbial life in coal-bearing sediment down to  2.5 km below the ocean floor
journal, July 2015

The thermodynamic properties of isotopic substances
journal, January 1947

Calculation of Equilibrium Constants for Isotopic Exchange Reactions
journal, May 1947

  • Bigeleisen, Jacob; Mayer, Maria Goeppert
  • The Journal of Chemical Physics, Vol. 15, Issue 5
  • DOI: 10.1063/1.1746492

Distinguishing and understanding thermogenic and biogenic sources of methane using multiply substituted isotopologues
journal, July 2015

KINETIC ISOTOPE EFFECTS IN THE REACTION OF METHYL RADICALS WITH ETHANE, ETHANE-d6 AND ETHANE-1,1,1-d3
journal, November 1960

Der thermische Zerfall des Äthans bei Zusatz von Fremdgasen
journal, January 1939

  • Küchler, L.; Τheile, Η.
  • Zeitschrift für Physikalische Chemie, Vol. 42B, Issue 1
  • DOI: 10.1515/zpch-1939-4226

Geochemistry of clumped isotopologues of CH4 within fluid inclusions in Alpine tectonic quartz fissures
journal, May 2021

  • Mangenot, Xavier; Tarantola, Alexandre; Mullis, Josef
  • Earth and Planetary Science Letters, Vol. 561
  • DOI: 10.1016/j.epsl.2021.116792

Primary cracking of algal and landplant kerogens: Kinetic models of isotope variations in methane, ethane and propane
journal, December 1995

Δ13CH3D and Δ12CH2D2 signatures of methane aerobically oxidized by Methylosinus trichosporium with implications for deciphering the provenance of methane gases
journal, September 2022

  • Krause, Sebastian J. E.; Liu, Jiarui; Young, Edward D.
  • Earth and Planetary Science Letters, Vol. 593
  • DOI: 10.1016/j.epsl.2022.117681

Microscale oxygen isotope variations in 1.9Ga Gunflint cherts: Assessments of diagenesis effects and implications for oceanic paleotemperature reconstructions
journal, January 2010

  • Marin, Johanna; Chaussidon, Marc; Robert, François
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 1
  • DOI: 10.1016/j.gca.2009.09.016

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues
journal, September 2016

A model for 12 CH 2 D 2 and 13 CH 3 D as complementary tracers for the budget of atmospheric CH 4: Model 12 CH 2 D 2 and 13 CH 3 D Budget in Air
journal, September 2017

  • Haghnegahdar, Mojhgan A.; Schauble, Edwin A.; Young, Edward D.
  • Global Biogeochemical Cycles, Vol. 31, Issue 9
  • DOI: 10.1002/2017GB005655

Inter-laboratory calibration of natural gas round robins for δ2H and δ13C using off-line and on-line techniques
journal, June 2012

Equilibrium clumped-isotope effects in doubly substituted isotopologues of ethane
journal, January 2017

  • Webb, Michael A.; Wang, Yimin; Braams, Bastiaan J.
  • Geochimica et Cosmochimica Acta, Vol. 197
  • DOI: 10.1016/j.gca.2016.10.001

Position-Specific and Clumped Stable Isotope Studies: Comparison of the Urey and Path-Integral Approaches for Carbon Dioxide, Nitrous Oxide, Methane, and Propane
journal, January 2014

  • Webb, Michael A.; Miller, Thomas F.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 2
  • DOI: 10.1021/jp411134v

Clumped isotope constraints on the origins of reservoir methane from the Barents Sea
journal, April 2022

  • Thiagarajan, Nivedita; Pedersen, Jon Halvard; Brunstad, Harald
  • Petroleum Geoscience, Vol. 28, Issue 2
  • DOI: 10.1144/petgeo2021-037

Kinetics of propane cracking and position-specific isotope fractionation: Insights into the origins of natural gases
journal, May 2021

The kinetic modeling of oil cracking by hydrothermal pyrolysis experiments
journal, March 1999

Evidence for methane isotopic bond re-ordering in gas reservoirs sourcing cold seeps from the Sea of Marmara
journal, January 2021

Kinetic clumped isotope fractionation during the thermal generation and hydrogen exchange of methane
journal, March 2019

Thermal reactions of kerogen with added water, heavy water and pure organic substances
journal, January 1984

High-resolution, long-term isotopic and isotopologue variation identifies the sources and sinks of methane in a deep subsurface carbon cycle
journal, February 2021

Clumped isotope effects of thermogenic methane formation: Insights from pyrolysis of hydrocarbons
journal, June 2021

Mathematical simulation of the carbon isotopic fractionation between huminitic coals and related methane
journal, May 1992

Modeling the Kinetics and Mechanisms of Petroleum and Natural Gas Generation: A First Principles Approach
journal, January 2001

Kinetic modeling of individual gaseous component formed from coal in a confined system
journal, August 2006

Experimental determination of hydrogen isotope exchange rates between methane and water under hydrothermal conditions
journal, July 2022

  • Turner, Andrew C.; Pester, Nicholas J.; Bill, Markus
  • Geochimica et Cosmochimica Acta, Vol. 329
  • DOI: 10.1016/j.gca.2022.04.029

Experimental simulation in a confined system and kinetic modelling of kerogen and oil cracking
journal, December 1992

The Thermal Decomposition of Organic Compounds from the Standpoint of Free Radicals. VI. The Mechanism of Some Chain Reactions
journal, February 1934

  • Rice, F. O.; Herzfeld, K. F.
  • Journal of the American Chemical Society, Vol. 56, Issue 2
  • DOI: 10.1021/ja01317a006

The temperatures of oil and gas formation in the sub-surface
journal, June 1988

  • Quigley, T. M.; Mackenzie, A. S.
  • Nature, Vol. 333, Issue 6173
  • DOI: 10.1038/333549a0

Statistical clumped isotope signatures
journal, August 2016

  • Röckmann, T.; Popa, M. E.; Krol, M. C.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep31947

A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases
journal, April 2016

  • Young, Edward D.; Rumble, Douglas; Freedman, Philip
  • International Journal of Mass Spectrometry, Vol. 401
  • DOI: 10.1016/j.ijms.2016.01.006

Role of transition-metal catalysis in the formation of natural gas
journal, April 1994

  • Mango, Frank D.; Hightower, J. W.; James, Alan T.
  • Nature, Vol. 368, Issue 6471
  • DOI: 10.1038/368536a0

Recognizing the pathways of microbial methanogenesis through methane isotopologues in the subsurface biosphere
journal, July 2021

Exchange catalysis during anaerobic methanotrophy revealed by 12CH2D2 and 13CH3D in methane
journal, April 2019

Organic–inorganic interactions in petroleum-producing sedimentary basins
journal, November 2003

Natural gas seepage in the Gulf of Mexico
journal, June 1976

Large Tunnelling Corrections in Chemical Reaction Rates.1 II
journal, January 1961

  • Johnston, Harold S.; Rapp, Donald
  • Journal of the American Chemical Society, Vol. 83, Issue 1
  • DOI: 10.1021/ja01462a001

Combinatorial effects on clumped isotopes and their significance in biogeochemistry
journal, January 2016

Methane sources and sinks in continental sedimentary systems: New insights from paired clumped isotopologues 13CH3D and 12CH2D2
journal, January 2019

Formation temperatures of thermogenic and biogenic methane
journal, June 2014

Nonequilibrium clumped isotope signals in microbial methane
journal, March 2015

Exchange of alkanes with deuterium over γ-alumina. A Brønsted linear free energy relationship
journal, January 1975

  • Robertson, Philip J.; Scurrell, Michael S.; Kemball, Charles
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 71, Issue 0
  • DOI: 10.1039/f19757100903

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons
journal, December 2010

A reconnaissance study of 13C–13C clumping in ethane from natural gas
journal, February 2018

Hydrogen/Deuterium (H/D) Exchange Catalysis in Alkanes
journal, January 2018

Hydrogen Isotopic (D/H) Composition of Organic Matter During Diagenesis and Thermal Maturation
journal, May 2006

Biogenic methane formation in marine and freshwater environments: CO2 reduction vs. acetate fermentation—Isotope evidence
journal, May 1986

Isotopic evidence for quasi-equilibrium chemistry in thermally mature natural gases
journal, February 2020

  • Thiagarajan, Nivedita; Xie, Hao; Ponton, Camilo
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 8
  • DOI: 10.1073/pnas.1906507117

Clumped methane isotopologue-based temperature estimates for sources of methane in marine gas hydrates and associated vent gases
journal, June 2022

Clumped 13CH2D and 12CHD2 compositions of methyl groups from wood and synthetic monomers: Methods, experimental and theoretical calibrations, and initial results
journal, March 2021

  • Lloyd, Max K.; Eldridge, Daniel L.; Stolper, Daniel A.
  • Geochimica et Cosmochimica Acta, Vol. 297
  • DOI: 10.1016/j.gca.2020.10.008

Reaction of Methyl-d3 Radicals with Isobutane, Isobutane-2-d, and Propane
journal, October 1962

  • Jackson, W. M.; McNesby, J. R.; Darwent, B. deB.
  • The Journal of Chemical Physics, Vol. 37, Issue 8
  • DOI: 10.1063/1.1733349

Experiments on the role of water in petroleum formation
journal, September 1997

The Thermal Decomposition of Ethane: part i. Initiation and Termination Steps
journal, February 1966

  • Lin, M. C.; Back, M. H.
  • Canadian Journal of Chemistry, Vol. 44, Issue 4
  • DOI: 10.1139/v66-068

Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane
journal, September 1999

The relative abundances of resolved l2CH2D2 and 13CH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases
journal, April 2017

Experimental simulation of gas generation from coals and a marine kerogen
journal, December 1995

A steady-state model for sulphur isotope fractionation in bacterial reduction processes
journal, May 1973

Clumped isotope effects during OH and Cl oxidation of methane
journal, January 2017

  • Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan A.
  • Geochimica et Cosmochimica Acta, Vol. 196
  • DOI: 10.1016/j.gca.2016.09.012

The utility of methane clumped isotopes to constrain the origins of methane in natural gas accumulations
journal, December 2017

  • Stolper, Daniel A.; Lawson, Michael; Formolo, Michael J.
  • Geological Society, London, Special Publications, Vol. 468, Issue 1
  • DOI: 10.1144/SP468.3

Kinetic theory of oxygen isotopic exchange between minerals and water
journal, May 1987

The evolution of intra- and inter-molecular isotope equilibria in natural gases with thermal maturation
journal, August 2021

Methane clumped isotopes: Progress and potential for a new isotopic tracer
journal, November 2017

A kinetic model for isotopologue signatures of methane generated by biotic and abiotic CO2 methanation
journal, March 2019

Comparison of Experimental vs Theoretical Abundances of 13 CH 3 D and 12 CH 2 D 2 for Isotopically Equilibrated Systems from 1 to 500 °C
journal, October 2019

Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation
journal, January 2018

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model
journal, December 2002

“Clumped-isotope” geochemistry—The study of naturally-occurring, multiply-substituted isotopologues
journal, October 2007

Kinetic data for hydrogen and deuterium atom abstraction by methyl and trifluoromethyl radicals in the gaseous phase
journal, June 1971

  • Gray, P.; Herod, A. A.; Jones, A.
  • Chemical Reviews, Vol. 71, Issue 3
  • DOI: 10.1021/cr60271a001

Experimental and theoretical determinations of hydrogen isotopic equilibrium in the system CH4H2H2O from 3 to 200 °C
journal, December 2021

  • Turner, Andrew C.; Korol, Roman; Eldridge, Daniel L.
  • Geochimica et Cosmochimica Acta, Vol. 314
  • DOI: 10.1016/j.gca.2021.04.026

Clumped isotopologue constraints on the origin of methane at seafloor hot springs
journal, February 2018

  • Wang, David T.; Reeves, Eoghan P.; McDermott, Jill M.
  • Geochimica et Cosmochimica Acta, Vol. 223
  • DOI: 10.1016/j.gca.2017.11.030

Measurement of a Doubly Substituted Methane Isotopologue, 13 CH 3 D, by Tunable Infrared Laser Direct Absorption Spectroscopy
journal, June 2014

  • Ono, Shuhei; Wang, David T.; Gruen, Danielle S.
  • Analytical Chemistry, Vol. 86, Issue 13
  • DOI: 10.1021/ac5010579

The Thermal Decomposition of Ethane: part iii. Secondary Reactions
journal, October 1966

  • Lin, M. C.; Back, M. H.
  • Canadian Journal of Chemistry, Vol. 44, Issue 20
  • DOI: 10.1139/v66-358

Combined 13C–D and D–D clumping in methane: Methods and preliminary results
journal, February 2014

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems
journal, May 2011

  • Ni, Yunyan; Ma, Qisheng; Ellis, Geoffrey S.
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 10
  • DOI: 10.1016/j.gca.2011.02.016

Studies of the Hydrogen Held by Solids. VII. The Exchange of the Hydroxyl Groups of Alumina and Silica-Alumina Catalysts with Deuterated Methane
journal, September 1965

  • Larson, John G.; Hall, W. Keith
  • The Journal of Physical Chemistry, Vol. 69, Issue 9
  • DOI: 10.1021/j100893a044

Identifying thermogenic and microbial methane in deep water Gulf of Mexico Reservoirs
journal, April 2020

Modelling isotope fractionation during primary cracking of natural gas: a reaction kinetic approach
journal, July 1998

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: