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@ARTICLE{Cho:999168,
author = {Cho, Changmin and Fuchs, Hendrik and Hofzumahaus, Andreas
and Holland, Frank and Bloss, William J. and Bohn, Birger
and Dorn, Hans-Peter and Glowania, Marvin and Hohaus,
Thorsten and Liu, Lu and Monks, Paul S. and Niether, Doreen
and Rohrer, Franz and Sommariva, Roberto and Tan, Zhaofeng
and Tillmann, Ralf and Kiendler-Scharr, Astrid and Wahner,
Andreas and Novelli, Anna},
title = {{E}xperimental chemical budgets of {OH}, {HO} 2 , and {RO}
2 radicals in rural air in western {G}ermany during the
{JULIAC} campaign 2019},
journal = {Atmospheric chemistry and physics},
volume = {23},
number = {3},
issn = {1680-7316},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2023-01202},
pages = {2003 - 2033},
year = {2023},
abstract = {Photochemical processes in ambient air were studied using
the atmospheric simulation chamber SAPHIR at
Forschungszentrum Jülich, Germany. Ambient air was
continuously drawn into the chamber through a 50 m high
inlet line and passed through the chamber for 1 month in
each season throughout 2019. The residence time of the air
inside the chamber was about 1 h. As the research center
is surrounded by a mixed deciduous forest and is located
close to the city Jülich, the sampled air was influenced by
both anthropogenic and biogenic emissions. Measurements of
hydroxyl (OH), hydroperoxyl (HO2), and organic peroxy (RO2)
radicals were achieved by a laser-induced fluorescence
instrument. The radical measurements together with
measurements of OH reactivity (kOH, the inverse of the OH
lifetime) and a comprehensive set of trace gas
concentrations and aerosol properties allowed for the
investigation of the seasonal and diurnal variation of
radical production and destruction pathways. In spring and
summer periods, median OH concentrations reached
6 × 106 cm−3 at noon, and median concentrations of
both HO2 and RO2 radicals were 3 × 108 cm−3. The
measured OH reactivity was between 4 and 18 s−1 in both
seasons. The total reaction rate of peroxy radicals with NO
was found to be consistent with production rates of odd
oxygen (Ox= NO2 + O3) determined from NO2 and O3
concentration measurements. The chemical budgets of radicals
were analyzed for the spring and summer seasons, when peroxy
radical concentrations were above the detection limit. For
most conditions, the concentrations of radicals were mainly
sustained by the regeneration of OH via reactions of HO2 and
RO2 radicals with nitric oxide (NO). The median diurnal
profiles of the total radical production and destruction
rates showed maxima between 3 and 6 ppbv h−1 for OH,
HO2, and RO2. Total ROX (OH, HO2, and RO2) initiation and
termination rates were below 3 ppbv h−1. The highest
OH radical turnover rate of 13 ppbv h−1 was observed
during a high-temperature (max. 40 ∘C) period in August.
In this period, the highest HO2, RO2, and ROX turnover rates
were around 11, 10, and 4 ppbv h−1, respectively. When
NO mixing ratios were between 1 and 3 ppbv, OH and HO2
production and destruction rates were balanced, but
unexplained RO2 and ROX production reactions with median
rates of 2 and 0.4 ppbv h−1, respectively, were
required to balance their destruction. For NO mixing ratios
above 3 ppbv, the peroxy radical reaction rates with NO
were highly uncertain due to the low peroxy radical
concentrations close to the limit of NO interferences in the
HO2 and RO2 measurements. For NO mixing ratios below
1 ppbv, a missing source for OH and a missing sink for HO2
were found with maximum rates of 3.0 and 2.0 ppbv h−1,
respectively. The missing OH source likely consisted of a
combination of a missing inter-radical HO2 to OH conversion
reaction (up to 2 ppbv h−1) and a missing primary
radical source (0.5–1.4 ppbv h−1). The dataset
collected in this campaign allowed analyzing the potential
impact of OH regeneration from RO2 isomerization reactions
from isoprene, HO2 uptake on aerosol, and RO2 production
from chlorine chemistry on radical production and
destruction rates. These processes were negligible for the
chemical conditions encountered in this study.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000931124700001},
doi = {10.5194/acp-23-2003-2023},
url = {https://juser.fz-juelich.de/record/999168},
}