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 »
- Authors:
-
- 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
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
- Department of Earth and Planetary Science, University of California, Berkeley, California 94720, United States
- Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (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:
- Journal Article: 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. https://doi.org/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. 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". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1575296},
journal = {ACS Earth and Space Chemistry},
issn = {2472-3452},
number = 12,
volume = 3,
place = {United States},
year = {Mon Oct 28 00:00:00 EDT 2019},
month = {Mon Oct 28 00:00:00 EDT 2019}
}
Web of Science
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