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dc.contributor.authorGiorio, Chiaraen
dc.contributor.authorCampbell, SJen
dc.contributor.authorBruschi, Men
dc.contributor.authorArchibald, Alexanderen
dc.contributor.authorKalberer, Markusen
dc.date.accessioned2017-05-24T13:16:53Z
dc.date.available2017-05-24T13:16:53Z
dc.date.issued2017-03-06en
dc.identifier.issn1359-6640
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/264400
dc.description.abstractOzonolysis of alkenes is a key reaction in the atmosphere, playing an important role in determining the oxidising capacity of the atmosphere and acting as a source of compounds that can contribute to local photochemical “smog”. The reaction products of the initial step of alkene-ozonolysis are Criegee intermediates (CIs), which have for many decades eluded direct experimental detection because of their very short lifetime. We use an innovative experimental technique, stabilisation of CIs with spin traps and analysis with proton transfer reaction mass spectrometry, to measure the gas phase concentration of a series of CIs formed from ozonolysis of a range of both biogenic and anthropogenic alkenes in flow tube experiments. Density functional theory (DFT) calculations were used to assess the stability of the CI-spin trap adducts and showed that the reaction of the investigated CIs with the spin trap occurs very rapidly except for the large β-pinene CI. Our measurement method was used successfully to measure all the expected CIs, emphasising that this new technique is applicable to a wide range of CIs with different molecular structures previously unidentified experimentally. In addition, for the first time it was possible to study CIs simultaneously in an even more complex reaction system consisting of more than one olefinic precursor. Comparison between our new experimental measurements, calculations of stability of the CI-spin trap adducts and results from numerical modelling, using the master chemical mechanism (MCM), showed that our new method can be used for quantification of CIs produced in situ in laboratory experiments.
dc.description.sponsorshipThis work was funded by the European Research Council (ERC starting grant 279405) and NERC (NE/K008218/1). ATA thanks NERC for funding through NCAS.
dc.language.isoenen
dc.publisherRoyal Society of Chemistry
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectCriegee intermediatesen
dc.subjectVOCen
dc.subjectPTR-MSen
dc.subjectspin trapsen
dc.subjectMCMen
dc.subjectDFTen
dc.titleDetection and identification of Criegee intermediates from the ozonolysis of biogenic and anthropogenic VOCs: comparison between experimental measurements and theoretical calculationsen
dc.typeArticle
prism.publicationDate2017en
prism.publicationNameFaraday Discussionsen
dc.identifier.doi10.17863/CAM.9888
dcterms.dateAccepted2017-03-06en
rioxxterms.versionofrecord10.1039/C7FD00025Aen
rioxxterms.versionAMen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2017-03-06en
dc.contributor.orcidGiorio, Chiara [0000-0001-7821-7398]
dc.contributor.orcidArchibald, Alexander [0000-0001-9302-4180]
dc.contributor.orcidKalberer, Markus [0000-0001-8885-6556]
dc.identifier.eissn1364-5498
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEPSRC (EP/K039520/1)
pubs.funder-project-idEuropean Research Council (279405)


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International