Photolytic fractionation of seven singly and doubly substituted nitrous oxide isotopocules measured by quantum cascade laser absorption spectroscopy
dc.contributor.author
Kantnerova, Kristyna
dc.contributor.author
Jespersen, Malte F.
dc.contributor.author
Bernasconi, Stefano M.
dc.contributor.author
Emmenegger, Lukas
dc.contributor.author
Johnson, Matthew S.
dc.contributor.author
Mohn, Joachim
dc.date.accessioned
2021-03-04T10:49:14Z
dc.date.available
2020-10-23T02:56:52Z
dc.date.available
2020-10-23T07:00:08Z
dc.date.available
2021-03-04T10:49:14Z
dc.date.issued
2020-12
dc.identifier.other
10.1016/j.aeaoa.2020.100094
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/447393
dc.identifier.doi
10.3929/ethz-b-000447393
dc.description.abstract
There is strong interest in using isotopic analysis to better constrain the budget of atmospheric nitrous oxide (N2O). This interest is supported by emerging instruments that allow analysis of multiply substituted species. We have studied fractionation during UV photolysis of singly and doubly isotopically substituted molecules (isotopocules) of N2O. N2O was photolyzed in an electropolished stainless-steel reactor using a broadband laser-driven light source with bandpass filters. Isotopocule ratios were quantified at different stages of photolysis using a quantum cascade laser absorption spectroscopy (QCLAS) system. Wavelength-dependent fractionation constants were determined using the Rayleigh distillation model. The fractionation constants for photolysis with 200 nm and 214 nm bandpass filters, respectively, for the seven most abundant isotopocules of N2O (after 14N14N16O) are: 14N15N16O (456): (−48.9 ± 7.4) ‰ /(−82.4 ± 22.3) ‰, 15N14N16O (546): (−22.2 ± 5.3) ‰ /(−36.1 ± 19.6) ‰, 14N14N17O (447): (−12.7 ± 4.5) ‰ /(−21.9 ± 15.7) ‰, 14N14N18O (448): (−33.5 ± 12.0) ‰ /(−44.1 ± 29.8) ‰, 14N15N18O (458): (−80.9 ± 6.5) ‰ /(−120.9 ± 23.7) ‰, 15N14N18O (548): (−52.7 ± 10.8) ‰ /(−79.1 ± 28.5) ‰, 15N15N16O (556): (−66.9 ± 9.8) ‰ /(−110.9 ± 27.5) ‰. The fractionation constants determined here for isotopocules 456, 546, 447, 448, and 556 are in agreement with previous theoretical models employed in this study and previous experiments. For 458 and 548, the fractionation constants were determined for the first time, confirming the prediction of more negative fractionation for 15N substitution in the central position. The effect of stratospheric photolysis on the clumped isotope Δ values of tropospheric N2O was found to be modest with Δ458 = (4.0 ± 1.0) ‰, Δ548 = (−4.0 ± 1.0) ‰, and Δ556 = (−1.5 ± 1.0) ‰ at 9% photolysis. Therefore, atmospheric variations of doubly substituted N2O isotopocules will likely be dominated by the characteristics of the N2O sources, which strongly supports their value for source attribution and quantification.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
Elsevier
en_US
dc.rights.uri
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject
UV photolysis
en_US
dc.subject
Nitrous oxide
en_US
dc.subject
Clumped isotopes
en_US
dc.subject
QCLAS
en_US
dc.title
Photolytic fractionation of seven singly and doubly substituted nitrous oxide isotopocules measured by quantum cascade laser absorption spectroscopy
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
dc.date.published
2020-10-09
ethz.journal.title
Atmospheric Environment: X
ethz.journal.volume
8
en_US
ethz.pages.start
100094
en_US
ethz.size
13 p.
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Amsterdam
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02330 - Dep. Erd- und Planetenwissenschaften / Dep. of Earth and Planetary Sciences::02704 - Geologisches Institut / Geological Institute::09601 - Stoll, Heather / Stoll, Heather::08806 - Bernasconi, Stefano (Tit.-Prof.)
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02330 - Dep. Erd- und Planetenwissenschaften / Dep. of Earth and Planetary Sciences::02704 - Geologisches Institut / Geological Institute::09601 - Stoll, Heather / Stoll, Heather
en_US
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02330 - Dep. Erd- und Planetenwissenschaften / Dep. of Earth and Planetary Sciences::02704 - Geologisches Institut / Geological Institute::09601 - Stoll, Heather / Stoll, Heather::08806 - Bernasconi, Stefano (Tit.-Prof.)
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02330 - Dep. Erd- und Planetenwissenschaften / Dep. of Earth and Planetary Sciences::02704 - Geologisches Institut / Geological Institute::09601 - Stoll, Heather / Stoll, Heather
ethz.date.deposited
2020-10-23T02:56:57Z
ethz.source
SCOPUS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2020-10-23T07:00:19Z
ethz.rosetta.lastUpdated
2024-02-02T13:14:04Z
ethz.rosetta.exportRequired
true
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true
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