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Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

Title data

Keppler, Frank ; Bahlmann, Enno ; Greule, Markus ; Schöler, Heinz Friedrich ; Wittmer, Julian ; Zetzsch, Cornelius:
Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl.
In: Atmospheric Chemistry and Physics. Vol. 18 (2018) Issue 9 . - pp. 6625-6635.
ISSN 1680-7324
DOI: https://doi.org/10.5194/acp-18-6625-2018

Abstract in another language

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Further data

Item Type: Article in a journal
Refereed: Yes
Additional notes: BAYCEER151147
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences > Professor Atmospheric Chemistry
Research Institutions
Research Institutions > Research Centres
Research Institutions > Research Centres > Bayreuth Center of Ecology and Environmental Research- BayCEER
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Result of work at the UBT: Yes
DDC Subjects: 500 Science
500 Science > 550 Earth sciences, geology
Date Deposited: 29 Jan 2020 07:57
Last Modified: 29 Jan 2020 07:57
URI: https://eref.uni-bayreuth.de/id/eprint/53938