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@ARTICLE{Fuchs:807652,
author = {Fuchs, Hendrik and Tan, Zhaofeng and Hofzumahaus, Andreas
and Broch, Sebastian and Dorn, Hans-Peter and Holland, Frank
and Künstler, Christopher and Gomm, Sebastian and Rohrer,
Franz and Schrade, Stephanie and Tillmann, Ralf and Wahner,
Andreas},
title = {{I}nvestigation of potential interferences in the detection
of atmospheric {RO}x radicals by laser-induced fluorescence
under dark conditions},
journal = {Atmospheric measurement techniques},
volume = {9},
number = {4},
issn = {1867-8548},
address = {Katlenburg-Lindau},
publisher = {Copernicus},
reportid = {FZJ-2016-02138},
pages = {1431 - 1447},
year = {2016},
abstract = {Direct detection of highly reactive, atmospheric hydroxyl
radicals (OH) is widely accomplished by laser-induced
fluorescence (LIF) instruments. The technique is also
suitable for the indirect measurement of HO2 and RO2 peroxy
radicals by chemical conversion to OH. It requires sampling
of ambient air into a low-pressure cell, where OH
fluorescence is detected after excitation by 308 nm laser
radiation. Although the residence time of air inside the
fluorescence cell is typically only on the order of
milliseconds, there is potential that additional OH is
internally produced, which would artificially increase the
measured OH concentration. Here, we present experimental
studies investigating potential interferences in the
detection of OH and peroxy radicals for the LIF instruments
of Forschungszentrum Jülich for nighttime conditions. For
laboratory experiments, the inlet of the instrument was over
flowed by excess synthetic air containing one or more
reactants. In order to distinguish between OH produced by
reactions upstream of the inlet and artificial signals
produced inside the instrument, a chemical titration for OH
was applied. Additional experiments were performed in the
simulation chamber SAPHIR where simultaneous measurements by
an open-path differential optical absorption spectrometer
(DOAS) served as reference for OH to quantify potential
artifacts in the LIF instrument. Experiments included the
investigation of potential interferences related to the
nitrate radical (NO3, N2O5), related to the ozonolysis of
alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene,
α-pinene, limonene, isoprene), and the laser photolysis of
acetone. Experiments studying the laser photolysis of
acetone yield OH signals in the fluorescence cell, which are
equivalent to 0.05 × 106 cm−3 OH for a mixing ratio
of 5 ppbv acetone. Under most atmospheric conditions, this
interference is negligible. No significant interferences
were found for atmospheric concentrations of reactants
during ozonolysis experiments. Only for propene, α-pinene,
limonene, and isoprene at reactant concentrations, which are
orders of magnitude higher than in the atmosphere, could
artificial OH be detected. The value of the interference
depends on the turnover rate of the ozonolysis reaction. For
example, an apparent OH concentration of approximately
1 × 106 cm−3 is observed when 5.8 ppbv limonene
reacts with 600 ppbv ozone. Experiments with the nitrate
radical NO3 reveal a small interference signal in the OH,
HO2, and RO2 detection. Dependencies on experimental
parameters point to artificial OH formation by surface
reactions at the chamber walls or in molecular clusters in
the gas expansion. The signal scales with the presence of
NO3 giving equivalent radical concentrations of
1.1 × 105 cm−3 OH, 1 × 107 cm−3 HO2, and
1.7 × 107 cm−3 RO2 per 10 pptv NO3.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {243 - Tropospheric trace substances and their
transformation processes (POF3-243) / HITEC - Helmholtz
Interdisciplinary Doctoral Training in Energy and Climate
Research (HITEC) (HITEC-20170406)},
pid = {G:(DE-HGF)POF3-243 / G:(DE-Juel1)HITEC-20170406},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000375616100001},
doi = {10.5194/amt-9-1431-2016},
url = {https://juser.fz-juelich.de/record/807652},
}