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@ARTICLE{Kaminski:830478,
author = {Kaminski, Martin and Fuchs, Hendrik and Acir, Ismail-Hakki
and Bohn, Birger and Brauers, Theo and Dorn, Hans-Peter and
Häseler, Rolf and Hofzumahaus, Andreas and Li, Xin and
Lutz, Anna and Nehr, Sascha and Rohrer, Franz and Tillmann,
Ralf and Vereecken, Luc and Wegener, Robert and Wahner,
Andreas},
title = {{I}nvestigation of the β-pinene photooxidation by {OH} in
the atmosphere simulation chamber {SAPHIR}},
journal = {Atmospheric chemistry and physics},
volume = {17},
number = {11},
issn = {1680-7324},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2017-04019},
pages = {6631 - 6650},
year = {2017},
abstract = {Besides isoprene, monoterpenes are the non-methane volatile
organic compounds (VOCs) with the highest global emission
rates. Due to their high reactivity towards OH, monoterpenes
can dominate the radical chemistry of the atmosphere in
forested areas. In the present study the photochemical
degradation mechanism of β-pinene was investigated in the
Jülich atmosphere simulation chamber SAPHIR (Simulation of
Atmospheric PHotochemistry In a large Reaction Chamber). One
focus of this study is on the OH budget in the degradation
process. Therefore, the SAPHIR chamber was equipped with
instrumentation to measure radicals (OH, HO2, RO2), the
total OH reactivity, important OH precursors (O3, HONO,
HCHO), the parent VOC β-pinene, its main oxidation
products, acetone and nopinone and photolysis frequencies.
All experiments were carried out under low-NO conditions
( ≤ 300 ppt) and at atmospheric β-pinene
concentrations ( ≤ 5 ppb) with and without
addition of ozone. For the investigation of the OH budget,
the OH production and destruction rates were calculated from
measured quantities. Within the limits of accuracy of the
instruments, the OH budget was balanced in all β-pinene
oxidation experiments. However, even though the OH budget
was closed, simulation results from the Master Chemical
Mechanism (MCM) 3.2 showed that the OH production and
destruction rates were underestimated by the model. The
measured OH and HO2 concentrations were underestimated by up
to a factor of 2, whereas the total OH reactivity was
slightly overestimated because the model predicted a
nopinone mixing ratio which was 3 times higher than
measured. A new, theory-derived, first-generation product
distribution by Vereecken and Peeters (2012) was able to
reproduce the measured nopinone time series and the total OH
reactivity. Nevertheless, the measured OH and HO2
concentrations remained underestimated by the numerical
simulations. These observations together with the fact that
the measured OH budget was closed suggest the existence of
unaccounted sources of HO2. Although the mechanism of
additional HO2 formation could not be resolved, our model
studies suggest that an activated alkoxy radical
intermediate proposed in the model of Vereecken and Peeters
(2012) generates HO2 in a new pathway, whose importance has
been underestimated so far. The proposed reaction path
involves unimolecular rearrangement and decomposition
reactions and photolysis of dicarbonyl products, yielding
additional HO2 and CO. Further experiments and quantum
chemical calculations have to be made to completely unravel
the pathway of HO2 formation.},
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:000402958000003},
doi = {10.5194/acp-17-6631-2017},
url = {https://juser.fz-juelich.de/record/830478},
}