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@ARTICLE{Glowania:893098,
author = {Glowania, Marvin and Rohrer, Franz and Dorn, Hans-Peter and
Hofzumahaus, Andreas and Holland, Frank and Kiendler-Scharr,
Astrid and Wahner, Andreas and Fuchs, Hendrik},
title = {{C}omparison of formaldehyde measurements by {H}antzsch,
{CRDS} and {DOAS} in the {SAPHIR} chamber},
journal = {Atmospheric measurement techniques},
volume = {14},
number = {6},
issn = {1867-8548},
address = {Katlenburg-Lindau},
publisher = {Copernicus},
reportid = {FZJ-2021-02557},
pages = {4239 - 4253},
year = {2021},
abstract = {Three instruments that use different techniques to measure
gaseous formaldehyde (HCHO) concentrations were compared in
experiments in the atmospheric simulation chamber SAPHIR at
Forschungszentrum Jülich. One instrument (AL4021,
Aero-Laser GmbH) detects HCHO using the wet-chemical
Hantzsch reaction (for efficient gas-phase stripping),
chemical conversion and fluorescence measurement. An
internal HCHO permeation source allows for daily
calibrations. This instrument was characterized by sulfuric
acid titration (overall accuracy $8.6 \%)$ and yields
measurements with a time resolution of 90 s and a limit of
detection (3σ) of 0.3 ppbv. In addition, a new commercial
instrument that makes use of cavity ring-down spectroscopy
(CRDS) determined the concentrations of HCHO, water vapour,
and methane (G2307, Picarro, Inc.). Its limit of detection
(3σ) is specified as 0.3 ppbv for an integration time of
300 s, and its accuracy is limited by the drift of the
zero signal (manufacturer specification 1.5 ppbv). A
custom-built high-resolution laser differential optical
absorption spectroscopy (DOAS) instrument provided HCHO
measurements with a limit of detection (3σ) of 0.9 ppbv
and an accuracy of $7 \%$ using an
optical multiple reflection cell. The measurements were
conducted from June to December 2019 in experiments in which
either ambient air flowed through the chamber or the
photochemical degradation of organic compounds in synthetic
air was investigated. Measured HCHO concentrations were up
to 8 ppbv. Various mixtures of organic compounds, water
vapour, nitrogen oxides and ozone were present in these
experiments. Results demonstrate the need to correct the
baseline in measurements performed by the Hantzsch
instrument to compensate for drifting background signals.
Corrections were equivalent to HCHO mixing ratios in the
range of 0.5–1.5 ppbv. The baseline of the CRDS
instrument showed a linear dependence on the water vapour
mixing ratio with a slope of
$(−11.20±1.60) ppbv \%−1$ below and
$(−0.72±0.08) ppbv \%−1$ above a water vapour
mixing ratio of $0.2 \%.$ In addition, the intercepts of
these linear relationships drifted within the specification
of the instrument (1.5 ppbv) over time but appeared to be
equal for all water mixing ratios. Regular zero measurements
are needed to account for the changes in the instrument
zero. After correcting for the baselines of measurements by
the Hantzsch and the CRDS instruments, linear regression
analysis of measurements from all three instruments in
experiments with ambient air indicated good agreement, with
slopes of between 0.98 and 1.08 and negligible intercepts
(linear correlation coefficients R2>0.96). The new small
CRDS instrument measures HCHO with good precision and is
accurate if the instrument zero is taken into account.
Therefore, it can provide measurements with similar accuracy
to the DOAS instrument but with slightly reduced precision
compared to the Hantzsch instrument.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {211 - Die Atmosphäre im globalen Wandel (POF4-211)},
pid = {G:(DE-HGF)POF4-211},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000661421100001},
doi = {10.5194/amt-14-4239-2021},
url = {https://juser.fz-juelich.de/record/893098},
}