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@ARTICLE{Rolletter:865539,
author = {Rolletter, Michael and Kaminski, Martin and Acir,
Ismail-Hakki and Bohn, Birger and Dorn, Hans-Peter and Li,
Xin and Lutz, Anna and Nehr, Sascha and Rohrer, Franz and
Tillmann, Ralf and Wegener, Robert and Hofzumahaus, Andreas
and Kiendler-Scharr, Astrid and Wahner, Andreas and Fuchs,
Hendrik},
title = {{I}nvestigation of the α -pinene photooxidation by {OH} in
the atmospheric simulation chamber {SAPHIR}},
journal = {Atmospheric chemistry and physics},
volume = {19},
number = {18},
issn = {1680-7324},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2019-04919},
pages = {11635 - 11649},
year = {2019},
abstract = {The photooxidation of the most abundant monoterpene,
α-pinene, by the hydroxyl radical (OH) was investigated at
atmospheric concentrations in the atmospheric simulation
chamber SAPHIR. Concentrations of nitric oxide (NO) were
below 120 pptv. Yields of organic oxidation products are
determined from measured time series giving values of
0.11±0.05, 0.19±0.06, and 0.05±0.03 for formaldehyde,
acetone, and pinonaldehyde, respectively. The pinonaldehyde
yield is at the low side of yields measured in previous
laboratory studies, ranging from 0.06 to 0.87. These studies
were mostly performed at reactant concentrations much higher
than observed in the atmosphere. Time series of measured
radical and trace-gas concentrations are compared to results
from model calculations applying the Master Chemical
Mechanism (MCM) 3.3.1. The model predicts pinonaldehyde
mixing ratios that are at least a factor of 4 higher than
measured values. At the same time, modeled hydroxyl and
hydroperoxy (HO2) radical concentrations are approximately
$25 \%$ lower than measured values. Vereecken et al.
(2007) suggested a shift of the initial organic peroxy
radical (RO2) distribution towards RO2 species that do not
yield pinonaldehyde but produce other organic products.
Implementing these modifications reduces the
model–measurement gap of pinonaldehyde by $20 \%$ and
also improves the agreement in modeled and measured radical
concentrations by $10 \%.$ However, the chemical oxidation
mechanism needs further adjustment to explain observed
radical and pinonaldehyde concentrations. This could be
achieved by adjusting the initial RO2 distribution, but
could also be done by implementing alternative reaction
channels of RO2 species that currently lead to the formation
of pinonaldehyde in the model.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {899 - ohne Topic (POF3-899)},
pid = {G:(DE-HGF)POF3-899},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000486704600001},
doi = {10.5194/acp-19-11635-2019},
url = {https://juser.fz-juelich.de/record/865539},
}