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@ARTICLE{Fuchs:22396,
author = {Fuchs, H. and Dorn, H.-P. and Bachner, M. and Bohn, B. and
Brauers, T. and Gomm, S. and Hofzumahaus, H. and Holland, F.
and Nehr, S. and Rohrer, F. and Tillmann, R. and Wahner, A.},
title = {{C}omparison of {OH} concentration measurements by {DOAS}
and {LIF} during {SAPHIR} chamber experiments at high {OH}
reactivity and low {NO} concentration},
journal = {Atmospheric measurement techniques},
volume = {5},
issn = {1867-1381},
address = {Katlenburg-Lindau},
publisher = {Copernicus},
reportid = {PreJuSER-22396},
pages = {1611 - 1626},
year = {2012},
note = {This work was supported by the EU FP-7 program EUROCHAMP-2
(grant agreement no. 228335) and by the EU FP-7 program
PEGASOS (grant agreement no. 265307). S. Nehr and B. Bohn
thank the Deutsche Forschungsgemeinschaft for funding under
grant BO 1580/3-1. We thank M. Kaminski, R. Wegener, K. D.
Lu, X. Li, A. Buchholz, P. Schlag, H.-C. Wu, S. Dixneuf, P.
Musgen and R. Haseler for additional measurements during
this campaign and technical support.},
abstract = {During recent field campaigns, hydroxyl radical (OH)
concentrations that were measured by laser-induced
fluorescence (LIF) were up to a factor of ten larger than
predicted by current chemical models for conditions of high
OH reactivity and low NO concentration. These discrepancies,
which were observed in forests and urban-influenced rural
environments, are so far not entirely understood. In summer
2011, a series of experiments was carried out in the
atmosphere simulation chamber SAPHIR in Julich, Germany, in
order to investigate the photochemical degradation of
isoprene, methyl-vinyl ketone (MVK), methacrolein (MACR) and
aromatic compounds by OH. Conditions were similar to those
experienced during the PRIDE-PRD2006 campaign in the Pearl
River Delta (PRD), China, in 2006, where a large difference
between OH measurements and model predictions was found.
During experiments in SAPHIR, OH was simultaneously detected
by two independent instruments: LIF and differential optical
absorption spectroscopy (DOAS). Because DOAS is an
inherently calibration-free technique, DOAS measurements are
regarded as a reference standard. The comparison of the two
techniques was used to investigate potential artifacts in
the LIF measurements for PRD-like conditions of OH
reactivities of 10 to 30 s(-1) and NO mixing ratios of 0.1
to 0.3 ppbv. The analysis of twenty experiment days shows
good agreement. The linear regression of the combined data
set (averaged to the DOAS time resolution, 2495 data points)
yields a slope of 1.02 +/- 0.01 with an intercept of (0.10
+/- 0.03) x 10(6) cm(-3) and a linear correlation
coefficient of R-2 = 0.86. This indicates that the
sensitivity of the LIF instrument is well-defined by its
calibration procedure. No hints for artifacts are observed
for isoprene, MACR, and different aromatic compounds. LIF
measurements were approximately $30-40\%$ (median) larger
than those by DOAS after MVK (20 ppbv) and toluene (90 ppbv)
had been added. However, this discrepancy has a large
uncertainty and requires further laboratory investigation.
Observed differences between LIF and DOAS measurements are
far too small to explain the unexpected high OH
concentrations during the PRIDE-PRD2006 campaign.},
keywords = {J (WoSType)},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {Atmosphäre und Klima / EUROCHAMP-2 - Integration of
European Simulation Chambers for Investigating Atmospheric
Processes - Part 2 (228335) / BROWSE - Bystanders,
Residents, Operators and WorkerS Exposure models for plant
protection products (265307)},
pid = {G:(DE-Juel1)FUEK491 / G:(EU-Grant)228335 /
G:(EU-Grant)265307},
shelfmark = {Meteorology $\&$ Atmospheric Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000306975500008},
doi = {10.5194/amt-5-1611-2012},
url = {https://juser.fz-juelich.de/record/22396},
}