Formation And Stability Of Atmospherically Relevant Isoprene-derived Organosulfates And Organonitrates

Title:
Formation And Stability Of Atmospherically Relevant Isoprene-derived Organosulfates And Organonitrates
Authors:
Darer, Adam I.; Cole-Filipiak, Neil C.; O'Connor, Alison E.; Elrod, Matthew J.
Abstract:
Isoprene is the precursor for number of alcohol, organosulfate, and organonitrate species observed in ambient secondary organic aerosol (SOA). Recent laboratory and field work has suggested that isoprene-derived epoxides may be crucial intermediates that can explain the existence of these compounds in SOA. To confirm this hypothesis, the specific hydroxy epoxides observed in gas phase isoprene photooxidation experiments (as well as several other related species) were synthesized and the bulk phase aqueous reactions of these species in the presence of sulfate and nitrate were studied via nuclear magnetic resonance (NMR) techniques. The results indicate that both primary and tertiary organosulfates and organonitrates are efficiently formed from the potential SOA reactions of isoprene-derived epoxides. However, the tertiary organonitrates are shown to undergo rapid nucleophilic substitution reactions (in which nitrate is substituted for by water or sulfate) over the whole range of SOA pH, while the tertiary organosulfates are found to undergo a much slower acid-dependent hydrolysis reaction. The primary organonitrates and organosulfates under study were found to be stable against nudeophilic substitution reactions, even at low pH. This finding provides a potential explanation for the fact that organosulfates are more commonly detected in ambient SOA than are organonitrates.
Citation:
Darer, Adam I., Neil C. Cole-Filipiak, Alison E. O'Connor, and Matthew J. Elrod. 2011. "Formation And Stability Of Atmospherically Relevant Isoprene-derived Organosulfates And Organonitrates." Environmental Science & Technology 45(5): 1895-1902.
Publisher:
American Chemical Society
DATE ISSUED:
2011-03
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/es103797z
PERMANENT LINK:
http://hdl.handle.net/11282/310099

Full metadata record

DC FieldValue Language
dc.contributor.authorDarer, Adam I.en_US
dc.contributor.authorCole-Filipiak, Neil C.en_US
dc.contributor.authorO'Connor, Alison E.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:25:17Zen
dc.date.available2013-12-23T16:25:17Zen
dc.date.issued2011-03en
dc.identifier.citationDarer, Adam I., Neil C. Cole-Filipiak, Alison E. O'Connor, and Matthew J. Elrod. 2011. "Formation And Stability Of Atmospherically Relevant Isoprene-derived Organosulfates And Organonitrates." Environmental Science & Technology 45(5): 1895-1902.en_US
dc.identifier.issn0013-936Xen_US
dc.identifier.urihttp://hdl.handle.net/11282/310099en
dc.description.abstractIsoprene is the precursor for number of alcohol, organosulfate, and organonitrate species observed in ambient secondary organic aerosol (SOA). Recent laboratory and field work has suggested that isoprene-derived epoxides may be crucial intermediates that can explain the existence of these compounds in SOA. To confirm this hypothesis, the specific hydroxy epoxides observed in gas phase isoprene photooxidation experiments (as well as several other related species) were synthesized and the bulk phase aqueous reactions of these species in the presence of sulfate and nitrate were studied via nuclear magnetic resonance (NMR) techniques. The results indicate that both primary and tertiary organosulfates and organonitrates are efficiently formed from the potential SOA reactions of isoprene-derived epoxides. However, the tertiary organonitrates are shown to undergo rapid nucleophilic substitution reactions (in which nitrate is substituted for by water or sulfate) over the whole range of SOA pH, while the tertiary organosulfates are found to undergo a much slower acid-dependent hydrolysis reaction. The primary organonitrates and organosulfates under study were found to be stable against nudeophilic substitution reactions, even at low pH. This finding provides a potential explanation for the fact that organosulfates are more commonly detected in ambient SOA than are organonitrates.en_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/es103797zen
dc.subject.departmentChemistryen_US
dc.titleFormation And Stability Of Atmospherically Relevant Isoprene-derived Organosulfates And Organonitratesen_US
dc.typearticleen_US
dc.identifier.journalEnvironmental Science and Technologyen_US
dc.subject.keywordSecondary organic aerosolen_US
dc.subject.keywordMass-spectrometryen_US
dc.subject.keywordTropospheric aerosolsen_US
dc.subject.keywordAmbient aerosolen_US
dc.subject.keywordSOA formationen_US
dc.subject.keywordPhotooxidationen_US
dc.subject.keywordNitratesen_US
dc.subject.keywordEpoxidesen_US
dc.subject.keywordKineticsen_US
dc.identifier.volume45en_US
dc.identifier.issue5en_US
dc.identifier.startpage1895en_US
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