Identifying Criegee intermediates as potential oxidants in the troposphere

Hdl Handle:
http://hdl.handle.net/10034/609570
Title:
Identifying Criegee intermediates as potential oxidants in the troposphere
Authors:
Novelli, Anna; Hens, Korbinian; Tatum-Ernest, Cheryl; Martinez, Monica; Noelscher, Anke C.; Sinha, Vinayak; Paasonen, Paasonen; Petaja, Tuukka; Sipila, Mikko; Elste, Thomas; Plass-Dulmer, Christian; Phillips, Gavin J. ( 0000-0003-4443-0822 ) ; Kubistin, Dagmar; Williams, Jonathan; Vereecken, Luc; Lelieveld, Jos; Harder, Hartwig
Abstract:
Criegee intermediates (CI) are formed during the ozonolysis of unsaturated compounds and have been intensively studied in the last few years due to their possible role as oxidants in the troposphere. Stabilised CI (SCI) are now known to react very rapidly, k(298 K) = 10-12 to 10-10 cm3 molecule-1 s-1, with a large number of trace gases (SO2, NO2, organic acids, water dimers). Still, it remains challenging to assess their effective oxidative capacity, as CI chemistry is complex, spans a large range of rate coefficients for different SCI conformers reacting with water dimers and trace gases, and in addition no reliable measurement technique able to detect ambient SCI concentrations is currently available. In this study, we examine the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns, aided by literature data, to estimate the abundance of SCI in the lower troposphere. The budget of SCI is analyzed using four different approaches: 1) based on an observed yet unexplained H2SO4 production; 2) from the measured concentrations of unsaturated volatile organic compounds (VOC); 3) from OH reactivity measurements; 4) from the unexplained production rate of OH. A SCI concentration range between 5 x 103 and 2 x 106 molecule cm-3 is calculated for the two environments. The central weighted estimate of the SCI concentration over the boreal forest of ~ 5 x 104 molecules cm-3 implies a significant impact on the conversion of SO2 into H2SO4. In addition, we present measurements obtained using our inlet pre-injector laser-induced fluorescence assay by gas expansion technique (IPI-LIF-FAGE) for the above-mentioned campaigns. A recent laboratory study performed with the same instrumental setup showed that the IPI-LIF-FAGE system is sensitive to the detection of the OH formed from unimolecular decomposition of SCI. Building on these measurements, the background OH (OHbg) measured during the two field campaigns is investigated in comparison with many other trace gases to assess if the observations in controlled conditions are transferable to ambient conditions.
Affiliation:
Max Planck Institute for Chemistry, IEK-8 Forschungzentrum Juelich, University of Helsinki, University of Chester, Deutscher Wetterdienst
Citation:
Novelli, A., et al. (2015, December). Identifying Criegee intermediates as potential oxidants in the troposphere, Abstract A21B-0119. Poster session presented at 2015 Fall Meeting, AGU, San Francisco, CA.
Publisher:
American Geophysical Union
Publication Date:
Oct-2015
URI:
http://hdl.handle.net/10034/609570
Additional Links:
https://agu.confex.com/agu/fm15/meetingapp.cgi/Paper/80255
Type:
Presentation; Meetings and Proceedings
Language:
en
Description:
Abstract and poster presented at the AGU Fall meeting, San Francisco 2015.
ISSN:
NA
Appears in Collections:
Natural Sciences

Full metadata record

DC FieldValue Language
dc.contributor.authorNovelli, Annaen
dc.contributor.authorHens, Korbinianen
dc.contributor.authorTatum-Ernest, Cherylen
dc.contributor.authorMartinez, Monicaen
dc.contributor.authorNoelscher, Anke C.en
dc.contributor.authorSinha, Vinayaken
dc.contributor.authorPaasonen, Paasonenen
dc.contributor.authorPetaja, Tuukkaen
dc.contributor.authorSipila, Mikkoen
dc.contributor.authorElste, Thomasen
dc.contributor.authorPlass-Dulmer, Christianen
dc.contributor.authorPhillips, Gavin J.en
dc.contributor.authorKubistin, Dagmaren
dc.contributor.authorWilliams, Jonathanen
dc.contributor.authorVereecken, Lucen
dc.contributor.authorLelieveld, Josen
dc.contributor.authorHarder, Hartwigen
dc.date.accessioned2016-05-17T15:41:40Zen
dc.date.available2016-05-17T15:41:40Zen
dc.date.issued2015-10en
dc.identifier.citationNovelli, A., et al. (2015, December). Identifying Criegee intermediates as potential oxidants in the troposphere, Abstract A21B-0119. Poster session presented at 2015 Fall Meeting, AGU, San Francisco, CA.en
dc.identifier.issnNAen
dc.identifier.urihttp://hdl.handle.net/10034/609570en
dc.descriptionAbstract and poster presented at the AGU Fall meeting, San Francisco 2015.en
dc.description.abstractCriegee intermediates (CI) are formed during the ozonolysis of unsaturated compounds and have been intensively studied in the last few years due to their possible role as oxidants in the troposphere. Stabilised CI (SCI) are now known to react very rapidly, k(298 K) = 10-12 to 10-10 cm3 molecule-1 s-1, with a large number of trace gases (SO2, NO2, organic acids, water dimers). Still, it remains challenging to assess their effective oxidative capacity, as CI chemistry is complex, spans a large range of rate coefficients for different SCI conformers reacting with water dimers and trace gases, and in addition no reliable measurement technique able to detect ambient SCI concentrations is currently available. In this study, we examine the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns, aided by literature data, to estimate the abundance of SCI in the lower troposphere. The budget of SCI is analyzed using four different approaches: 1) based on an observed yet unexplained H2SO4 production; 2) from the measured concentrations of unsaturated volatile organic compounds (VOC); 3) from OH reactivity measurements; 4) from the unexplained production rate of OH. A SCI concentration range between 5 x 103 and 2 x 106 molecule cm-3 is calculated for the two environments. The central weighted estimate of the SCI concentration over the boreal forest of ~ 5 x 104 molecules cm-3 implies a significant impact on the conversion of SO2 into H2SO4. In addition, we present measurements obtained using our inlet pre-injector laser-induced fluorescence assay by gas expansion technique (IPI-LIF-FAGE) for the above-mentioned campaigns. A recent laboratory study performed with the same instrumental setup showed that the IPI-LIF-FAGE system is sensitive to the detection of the OH formed from unimolecular decomposition of SCI. Building on these measurements, the background OH (OHbg) measured during the two field campaigns is investigated in comparison with many other trace gases to assess if the observations in controlled conditions are transferable to ambient conditions.en
dc.language.isoenen
dc.publisherAmerican Geophysical Unionen
dc.relation.urlhttps://agu.confex.com/agu/fm15/meetingapp.cgi/Paper/80255en
dc.subjectatmospheric chemistryen
dc.subjectcriegee intermediatesen
dc.subjectlaser induced fluorescenceen
dc.titleIdentifying Criegee intermediates as potential oxidants in the troposphereen
dc.typePresentationen
dc.typeMeetings and Proceedingsen
dc.contributor.departmentMax Planck Institute for Chemistry, IEK-8 Forschungzentrum Juelich, University of Helsinki, University of Chester, Deutscher Wetterdiensten
dc.date.accepted2000-01-01en
or.grant.openaccessNoen
rioxxterms.funderxxen
rioxxterms.identifier.projectxxen
rioxxterms.versionAMen
rioxxterms.licenseref.startdate2016-05-23en
This item is licensed under a Creative Commons License
Creative Commons
All Items in ChesterRep are protected by copyright, with all rights reserved, unless otherwise indicated.