Unexpected epoxide formation in the gas-phase photooxidation of isoprene

Fabien Paulot; John D Crounse; Henrik G Kjaergaard; Andreas Kürten; Jason M St Clair; John H Seinfeld; Paul O Wennberg

doi:10.1126/science.1172910

Unexpected epoxide formation in the gas-phase photooxidation of isoprene

Fabien Paulot, John D Crounse, Henrik G Kjaergaard, Andreas Kürten, Jason M St Clair, John H Seinfeld, Paul O Wennberg

Department of Chemistry

564 Citations (Scopus)

Abstract

Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceed

those from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% of

these emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxyl

radical OH. We report here that under pristine conditions isoprene is oxidized primarily to

hydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficiently

to the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormous

flux-nearly 100 teragrams of carbon per year-of these epoxides to the atmosphere. The

discovery of these highly soluble epoxides provides a missing link tying the gas-phase degradation

of isoprene to the observed formation of organic aerosols.

Original language	English
Journal	Science
Volume	325
Issue number	5941
Pages (from-to)	730-733
Number of pages	4
ISSN	0036-8075
DOIs	https://doi.org/10.1126/science.1172910
Publication status	Published - 2009

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title = "Unexpected epoxide formation in the gas-phase photooxidation of isoprene",

abstract = " Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceedthose from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% ofthese emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxylradical OH. We report here that under pristine conditions isoprene is oxidized primarily tohydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficientlyto the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormousflux-nearly 100 teragrams of carbon per year-of these epoxides to the atmosphere. Thediscovery of these highly soluble epoxides provides a missing link tying the gas-phase degradationof isoprene to the observed formation of organic aerosols.",

author = "Fabien Paulot and Crounse, {John D} and Kjaergaard, {Henrik G} and Andreas K{\"u}rten and {St Clair}, {Jason M} and Seinfeld, {John H} and Wennberg, {Paul O}",

year = "2009",

doi = "10.1126/science.1172910",

language = "English",

volume = "325",

pages = "730--733",

journal = "Science",

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TY - JOUR

T1 - Unexpected epoxide formation in the gas-phase photooxidation of isoprene

AU - Paulot, Fabien

AU - Crounse, John D

AU - Kjaergaard, Henrik G

AU - Kürten, Andreas

AU - St Clair, Jason M

AU - Seinfeld, John H

AU - Wennberg, Paul O

PY - 2009

Y1 - 2009

N2 - Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceedthose from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% ofthese emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxylradical OH. We report here that under pristine conditions isoprene is oxidized primarily tohydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficientlyto the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormousflux-nearly 100 teragrams of carbon per year-of these epoxides to the atmosphere. Thediscovery of these highly soluble epoxides provides a missing link tying the gas-phase degradationof isoprene to the observed formation of organic aerosols.

AB - Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceedthose from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% ofthese emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxylradical OH. We report here that under pristine conditions isoprene is oxidized primarily tohydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficientlyto the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormousflux-nearly 100 teragrams of carbon per year-of these epoxides to the atmosphere. Thediscovery of these highly soluble epoxides provides a missing link tying the gas-phase degradationof isoprene to the observed formation of organic aerosols.

U2 - 10.1126/science.1172910

DO - 10.1126/science.1172910

M3 - Journal article

C2 - 19661425

SN - 0036-8075

VL - 325

SP - 730

EP - 733

JO - Science

JF - Science

IS - 5941

ER -

Unexpected epoxide formation in the gas-phase photooxidation of isoprene

Abstract

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