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Title: 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

Abstract

Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (“clumped”) such as 13CH3D and 12CH2D2. In order to place methaneclumped isotope measurements into a thermodynamic reference frame that allows calculations of clumped isotope-based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150 °C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped isotope-based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of 13CH3D and 12CH2D2 from 1 to 500 °C using a combination of γ-Al2O3- and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC)more » methods and find 1:1 agreement (within ±1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1 to 500 °C, providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): Δ13CH3D ≅ 1000 × ln(K13CH3D) = (1.47348 × 1019)/T7 – (2.08648 × 1017)/T6 + (1.19810 × 1015)/T5 – (3.54757 × 1012)/T4 + (5.54476 × 109)/T3 – (3.49294 × 106)/T2 + (8.89370 × 102)/T and Δ12CH2D2 ≅ 1000 × ln(8/3K12CH2D2) = –(9.67634 × 1015)/T6 + (1.71917 × 1014)/T5 – (1.24819 × 1012)/T4 + (4.30283 × 109)/T3 – (4.48660 × 106)/T2 + (1.86258 × 103)/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations.« less

Authors:
ORCiD logo [1];  [2];  [3];  [3]; ORCiD logo [4]; ORCiD logo [2];  [1]
  1. Energy Geosciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States, Department of Earth and Planetary Science, University of California, Berkeley, California 94720, United States
  2. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
  3. Department of Earth and Planetary Science, University of California, Berkeley, California 94720, United States
  4. Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1575296
Alternate Identifier(s):
OSTI ID: 1580033
Grant/Contract Number:  
AC02-05CH11231; EAR-1911296; CHE-1611581
Resource Type:
Published Article
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Name: ACS Earth and Space Chemistry Journal Volume: 3 Journal Issue: 12; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Methane Clumped Isotopes; Methane Isotope Equilibration; Methane Geochemistry; Path Integral Monte Carlo Calculations; 253 Ultra

Citation Formats

Eldridge, Daniel L., Korol, Roman, Lloyd, Max K., Turner, Andrew C., Webb, Michael A., Miller, III, Thomas F., and Stolper, Daniel A. 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. United States: N. p., 2019. Web. doi:10.1021/acsearthspacechem.9b00244.
Eldridge, Daniel L., Korol, Roman, Lloyd, Max K., Turner, Andrew C., Webb, Michael A., Miller, III, Thomas F., & Stolper, Daniel A. 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. United States. doi:10.1021/acsearthspacechem.9b00244.
Eldridge, Daniel L., Korol, Roman, Lloyd, Max K., Turner, Andrew C., Webb, Michael A., Miller, III, Thomas F., and Stolper, Daniel A. Mon . "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". United States. doi:10.1021/acsearthspacechem.9b00244.
@article{osti_1575296,
title = {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},
author = {Eldridge, Daniel L. and Korol, Roman and Lloyd, Max K. and Turner, Andrew C. and Webb, Michael A. and Miller, III, Thomas F. and Stolper, Daniel A.},
abstractNote = {Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (“clumped”) such as 13CH3D and 12CH2D2. In order to place methaneclumped isotope measurements into a thermodynamic reference frame that allows calculations of clumped isotope-based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150 °C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped isotope-based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of 13CH3D and 12CH2D2 from 1 to 500 °C using a combination of γ-Al2O3- and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC) methods and find 1:1 agreement (within ±1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1 to 500 °C, providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): Δ13CH3D ≅ 1000 × ln(K13CH3D) = (1.47348 × 1019)/T7 – (2.08648 × 1017)/T6 + (1.19810 × 1015)/T5 – (3.54757 × 1012)/T4 + (5.54476 × 109)/T3 – (3.49294 × 106)/T2 + (8.89370 × 102)/T and Δ12CH2D2 ≅ 1000 × ln(8/3K12CH2D2) = –(9.67634 × 1015)/T6 + (1.71917 × 1014)/T5 – (1.24819 × 1012)/T4 + (4.30283 × 109)/T3 – (4.48660 × 106)/T2 + (1.86258 × 103)/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations.},
doi = {10.1021/acsearthspacechem.9b00244},
journal = {ACS Earth and Space Chemistry},
number = 12,
volume = 3,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1021/acsearthspacechem.9b00244

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Works referenced in this record:

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


A Review of Hydrogen, Carbon, Nitrogen, Oxygen, Sulphur, and Chlorine Stable Isotope Fractionation Among Gaseous Molecules
journal, May 1977


Formation temperatures of thermogenic and biogenic methane
journal, June 2014


Method for calibrating methane clumped isotope measurements via catalytic equilibration of methane isotopologues on γ‐alumina
journal, March 2020

  • Wang, David T.; Sattler, Aaron; Paccagnini, Michele
  • Rapid Communications in Mass Spectrometry, Vol. 34, Issue 10
  • DOI: 10.1002/rcm.8555

Nonequilibrium clumped isotope signals in microbial methane
journal, March 2015


Biodegradation of oil in uplifted basins prevented by deep-burial sterilization
journal, June 2001

  • Wilhelms, A.; Larter, S. R.; Head, I.
  • Nature, Vol. 411, Issue 6841
  • DOI: 10.1038/35082535

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

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


Methods and limitations of ‘clumped’ CO 2 isotope (Δ 47 ) analysis by gas-source isotope ratio mass spectrometry
journal, September 2009

  • Huntington, K. W.; Eiler, J. M.; Affek, H. P.
  • Journal of Mass Spectrometry, Vol. 44, Issue 9
  • DOI: 10.1002/jms.1614

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

Emerging Topics in Marine Methane Biogeochemistry
journal, January 2011


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


Prediction of equilibrium distributions of isotopologues for methane, ethane and propane using density functional theory
journal, October 2016


Clumped-isotope signatures at equilibrium of CH4, NH3, H2O, H2S and SO2
journal, February 2016


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


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

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


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

Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases
journal, December 2004

  • Wang, Zhengrong; Schauble, Edwin A.; Eiler, John M.
  • Geochimica et Cosmochimica Acta, Vol. 68, Issue 23
  • DOI: 10.1016/j.gca.2004.05.039

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


On the proper use of the Bigeleisen–Mayer equation and corrections to it in the calculation of isotopic fractionation equilibrium constants
journal, December 2010


Theoretical estimation of the equilibrium distribution of clumped isotopes in nature
journal, January 2012


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


A high-resolution gas-source isotope ratio mass spectrometer
journal, February 2013

  • Eiler, John M.; Clog, Matthieu; Magyar, Paul
  • International Journal of Mass Spectrometry, Vol. 335
  • DOI: 10.1016/j.ijms.2012.10.014

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

Equilibrium Oxygen, Hydrogen and Carbon Isotope Fractionation Factors Applicable to Geologic Systems
journal, January 2001

  • Chacko, T.; Cole, D. R.; Horita, J.
  • Reviews in Mineralogy and Geochemistry, Vol. 43, Issue 1
  • DOI: 10.2138/gsrmg.43.1.1

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

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


Direct path integral estimators for isotope fractionation ratios
journal, December 2014

  • Cheng, Bingqing; Ceriotti, Michele
  • The Journal of Chemical Physics, Vol. 141, Issue 24
  • DOI: 10.1063/1.4904293

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

Formation and abundance of doubly-substituted methane isotopologues (13CH3D) in natural gas systems
journal, November 2008


Convenient and accurate discretized path integral methods for equilibrium quantum mechanical calculations
journal, August 1981

  • Schweizer, Kenneth S.; Stratt, Richard M.; Chandler, David
  • The Journal of Chemical Physics, Vol. 75, Issue 3
  • DOI: 10.1063/1.442141

Efficient molecular dynamics and hybrid Monte Carlo algorithms for path integrals
journal, August 1993

  • Tuckerman, Mark E.; Berne, Bruce J.; Martyna, Glenn J.
  • The Journal of Chemical Physics, Vol. 99, Issue 4
  • DOI: 10.1063/1.465188

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

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


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

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

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


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