Photochemistry of 2-butenedial and 4-oxo-2-pentenal under atmospheric boundary layer conditions

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dc.contributor.authorNewland, Mike J.en
dc.contributor.authorRea, Gerard J.en
dc.contributor.authorThüner, Lars P.en
dc.contributor.authorHenderson, Alistair P.en
dc.contributor.authorGolding, Bernard T.en
dc.contributor.authorRickard, Andrew R.en
dc.contributor.authorBarnes, Ianen
dc.contributor.authorWenger, Johnen
dc.contributor.funderHorizon 2020en
dc.contributor.funderNatural Environment Research Councilen
dc.date.accessioned2024-05-20T14:50:32Z
dc.date.available2024-05-20T14:50:32Z
dc.date.issued2018-12-21en
dc.description.abstractUnsaturated 1,4-dicarbonyl compounds, such as 2-butenedial and 4-oxo-2-pentenal are produced in the atmospheric boundary layer from the oxidation of aromatic compounds and furans. These species are expected to undergo rapid photochemical processing, affecting atmospheric composition. In this study, the photochemistry of (E)-2-butenedial and both E and Z isomers of 4-oxo-2-pentenal was investigated under natural sunlight conditions at the large outdoor atmospheric simulation chamber EUPHORE. Photochemical loss rates, relative to j(NO2), are determined to be j((E)-2-butenedial)/j(NO2) = 0.14 (±0.02), j((E)-4-oxo-2-pentenal)/j(NO2) = 0.18 (±0.01), and j((Z)-4-oxo-2-pentenal)/j(NO2) = 0.20 (±0.03). The major products detected for both species are a furanone (30–42%) and, for (E)-2-butenedial, maleic anhydride (2,5-furandione) (12–14%). The mechanism appears to proceed predominantly via photoisomerization to a ketene–enol species following γ-H abstraction. The lifetimes of the ketene–enol species in the dark from 2-butenedial and 4-oxo-2-pentenal are determined to be 465 s and 235 s, respectively. The ketene–enol can undergo ring closure to yield the corresponding furanone, or further unimolecular rearrangement which can subsequently form maleic anhydride. A minor channel (10–15%) also appears to form CO directly. This is presumed to be via a molecular elimination route of an initial biradical intermediate formed in photolysis, with an unsaturated carbonyl (detected here but not quantified) as co-product. α-Dicarbonyl and radical yields are very low, which has implications for ozone production from the photo-oxidation of unsaturated 1,4-dicarbonyls in the boundary layer. Photochemical removal is determined to be the major loss process for these species in the boundary layer with lifetimes of the order of 10–15 minutes, compared to >3 hours for reaction with OH.en
dc.description.sponsorshipHorizon 2020 (Grant agreement No 730997); Natural Environment Research Council (Grant NE/M013448/1)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationNewland, M. J., Rea, G. J., Thüner, L. P., Henderson, A. P., Golding, B. T., Rickard, A. R., Barnes, I. and Wenger, J. (2019) 'Photochemistry of 2-butenedial and 4-oxo-2-pentenal under atmospheric boundary layer conditions', Physical Chemistry Chemical Physics, 2(3), pp.1160-1171. Available at: https://doi.org/10.1039/C8CP06437Gen
dc.identifier.doihttps://doi.org/10.1039/C8CP06437Gen
dc.identifier.eissn1463-9084en
dc.identifier.endpage1171en
dc.identifier.issn1463-9076en
dc.identifier.issued3en
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen
dc.identifier.startpage1160en
dc.identifier.urihttps://hdl.handle.net/10468/15882
dc.identifier.volume2en
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.rights© 2018, the Authors. Published by the Royal Society of Chemistry.en
dc.subject2-butenedial and 4-oxo-2-pentenalen
dc.subjectAtmospheric boundary layer conditionsen
dc.subjectPhotochemistryen
dc.titlePhotochemistry of 2-butenedial and 4-oxo-2-pentenal under atmospheric boundary layer conditionsen
dc.typeArticle (peer-reviewed)en
oaire.citation.issue3en
oaire.citation.volume21en
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