Unexpected epoxide formation in the gas-phase photooxidation of isoprene.
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.
Paulot
Fabien
F
Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA 91125, USA. paulot@caltech.edu
Crounse
John D
JD
Kjaergaard
Henrik G
HG
Kürten
Andreas
A
St Clair
Jason M
JM
Seinfeld
John H
JH
Wennberg
Paul O
PO