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@ARTICLE{Fuchs:849792,
author = {Fuchs, Hendrik and Albrecht, Sascha and Acir,
Ismail–Hakki and Bohn, Birger and Breitenlechner, Martin
and Dorn, Hans-Peter and Gkatzelis, Georgios and
Hofzumahaus, Andreas and Holland, Frank and Kaminski, Martin
and Keutsch, Frank N. and Novelli, Anna and Reimer, David
and Rohrer, Franz and Tillmann, Ralf and Vereecken, Luc and
Wegener, Robert and Zaytsev, Alexander and Kiendler-Scharr,
Astrid and Wahner, Andreas},
title = {{I}nvestigation of the oxidation of methyl vinyl ketone
({MVK}) by {OH} radicals in the atmospheric simulation
chamber {SAPHIR}},
journal = {Atmospheric chemistry and physics},
volume = {18},
number = {11},
issn = {1680-7324},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2018-03904},
pages = {8001 - 8016},
year = {2018},
abstract = {The photooxidation of methyl vinyl ketone (MVK) was
investigated in the atmospheric simulation chamber SAPHIR
for conditions at which organic peroxy radicals (RO2) mainly
reacted with NO ("high NO" case) and for conditions at which
other reaction channels could compete ("low NO" case).
Measurements of trace gas concentrations were compared to
calculated concentration time series applying the Master
Chemical Mechanism (MCM version 3.3.1). Product yields of
methylglyoxal and glycolaldehyde were determined from
measurements. For the high NO case, the methylglyoxal yield
was $(19±3)\%$ and the glycolaldehyde yield was
$(65±14)\%,$ consistent with recent literature studies. For
the low NO case, the methylglyoxal yield reduced to
$(5±2)\%$ because other RO2 reaction channels that do not
form methylglyoxal became important. Consistent with
literature data, the glycolaldehyde yield of $(37±9)\%$
determined in the experiment was not reduced as much as
implemented in the MCM, suggesting additional reaction
channels producing glycolaldehyde. At the same time, direct
quantification of OH radicals in the experiments shows the
need for an enhanced OH radical production at low NO
conditions similar to previous studies investigating the
oxidation of the parent VOC isoprene and methacrolein, the
second major oxidation product of isoprene. For MVK the
model–measurement discrepancy was up to a factor of 2.
Product yields and OH observations were consistent with
assumptions of additional RO2 plus HO2 reaction channels as
proposed in literature for the major RO2 species formed from
the reaction of MVK with OH. However, this study shows that
also HO2 radical concentrations are underestimated by the
model, suggesting that additional OH is not directly
produced from RO2 radical reactions, but indirectly via
increased HO2. Quantum chemical calculations show that HO2
could be produced from a fast 1,4-H shift of the second most
important MVK derived RO2 species (reaction rate constant
0.003s−1). However, additional HO2 from this reaction was
not sufficiently large to bring modelled HO2 radical
concentrations into agreement with measurements due to the
small yield of this RO2 species. An additional reaction
channel of the major RO2 species with a reaction rate
constant of (0.006±0.004)s−1 would be required that
produces concurrently HO2 radicals and glycolaldehyde to
achieve model–measurement agreement. A unimolecular
reaction similar to the 1,5-H shift reaction that was
proposed in literature for RO2 radicals from MVK would not
explain product yields for conditions of experiments in this
study. A set of H-migration reactions for the main RO2
radicals were investigated by quantum chemical and
theoretical kinetic methodologies, but did not reveal a
contributing route to HO2 radicals or glycolaldehyde.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {243 - Tropospheric trace substances and their
transformation processes (POF3-243)},
pid = {G:(DE-HGF)POF3-243},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000434422200002},
doi = {10.5194/acp-18-8001-2018},
url = {https://juser.fz-juelich.de/record/849792},
}