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@ARTICLE{Vereecken:840312,
author = {Vereecken, L. and Novelli, A. and Taraborrelli, D.},
title = {{U}nimolecular decay strongly limits the atmospheric impact
of {C}riegee intermediates},
journal = {Physical chemistry, chemical physics},
volume = {47},
number = {19},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2017-07854},
pages = {31599--31612},
year = {2017},
abstract = {Stabilized Criegee intermediates (SCI) are reactive
oxygenated species formed in the ozonolysis of hydrocarbons.
Their chemistry could influence the oxidative capacity of
the atmosphere by affecting the HOx and NOx cycles, or by
the formation of low-volatility oxygenates enhancing
atmospheric aerosols known to have an important impact on
climate. The concentration of SCI in the atmosphere has
hitherto not been determined reliably, and very little is
known about their speciation. Here we show that the
concentration of biogenic SCI is strongly limited by their
unimolecular decay, based on extensive theory-based
structure–activity relationships (SARs) for the reaction
rates for decomposition. Reaction with water vapor, H2O and
(H2O)2 molecules, is the second most important loss process;
SARs are also proposed for these reactions. For SCI derived
from the most common biogenic VOCs, we find that
unimolecular decay is responsible for just over half of the
loss, with reaction with water vapor the main remaining loss
process. Reactions with SO2, NO2, or acids have negligible
impact on the atmospheric SCI concentration. The ambient SCI
concentrations are further characterized by analysis of
field data with speciated hydrocarbon information, and by
implementation of the chemistry in a global chemistry model.
The results show a highly complex SCI speciation, with an
atmospheric peak SCI concentrations below 1 × 105 molecule
cm−3, and annual average SCI concentrations less than 7 ×
103 molecule cm−3. We find that SCI have only a negligible
impact on the global gas phase H2SO4 formation or removal of
oxygenates, though some contribution around the equatorial
belt, and in select regions, cannot be excluded.},
cin = {IEK-8 / JARA-HPC},
ddc = {540},
cid = {I:(DE-Juel1)IEK-8-20101013 / $I:(DE-82)080012_20140620$},
pnm = {243 - Tropospheric trace substances and their
transformation processes (POF3-243) / Chemical processes in
the troposphere and their impact on climate
$(jicg23_20151101)$},
pid = {G:(DE-HGF)POF3-243 / $G:(DE-Juel1)jicg23_20151101$},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:29182168},
UT = {WOS:000417295800009},
doi = {10.1039/C7CP05541B},
url = {https://juser.fz-juelich.de/record/840312},
}