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@ARTICLE{Holzinger:868174,
author = {Holzinger, Rupert and Acton, W. Joe F. and Bloss, William
J. and Breitenlechner, Martin and Crilley, Leigh R. and
Dusanter, Sébastien and Gonin, Marc and Gros, Valerie and
Keutsch, Frank N. and Kiendler-Scharr, Astrid and Kramer,
Louisa J. and Krechmer, Jordan E. and Languille, Baptiste
and Locoge, Nadine and Lopez-Hilfiker, Felipe and Materić,
Dušan and Moreno, Sergi and Nemitz, Eiko and Quéléver,
Lauriane L. J. and Sarda Esteve, Roland and Sauvage,
Stéphane and Schallhart, Simon and Sommariva, Roberto and
Tillmann, Ralf and Wedel, Sergej and Worton, David R. and
Xu, Kangming and Zaytsev, Alexander},
title = {{V}alidity and limitations of simple reaction kinetics to
calculate concentrations of organic compounds from ion
counts in {PTR}-{MS}},
journal = {Atmospheric measurement techniques},
volume = {12},
number = {11},
issn = {1867-8548},
address = {Katlenburg-Lindau},
publisher = {Copernicus},
reportid = {FZJ-2019-06746},
pages = {6193 - 6208},
year = {2019},
abstract = {In September 2017, we conducted a proton-transfer-reaction
mass-spectrometry (PTR-MS) intercomparison campaign at the
CESAR observatory, a rural site in the central Netherlands
near the village of Cabauw. Nine research groups deployed a
total of 11 instruments covering a wide range of instrument
types and performance. We applied a new calibration method
based on fast injection of a gas standard through a sample
loop. This approach allows calibrations on timescales of
seconds, and within a few minutes an automated sequence can
be run allowing one to retrieve diagnostic parameters that
indicate the performance status. We developed a method to
retrieve the mass-dependent transmission from the fast
calibrations, which is an essential characteristic of PTR-MS
instruments, limiting the potential to calculate
concentrations based on counting statistics and simple
reaction kinetics in the reactor/drift tube. Our
measurements show that PTR-MS instruments follow the simple
reaction kinetics if operated in the standard range for
pressures and temperature of the reaction chamber (i.e.
1–4 mbar, 30–120∘, respectively), as well as a
reduced field strength E∕N in the range of 100–160 Td.
If artefacts can be ruled out, it becomes possible to
quantify the signals of uncalibrated organics with
accuracies better than $±30 \%.$ The simple reaction
kinetics approach produces less accurate results at E∕N
levels below 100 Td, because significant fractions of
primary ions form water hydronium clusters. Deprotonation
through reactive collisions of protonated organics with
water molecules needs to be considered when the collision
energy is a substantial fraction of the exoergicity of the
proton transfer reaction and/or if protonated organics
undergo many collisions with water molecules.},
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:000499728300001},
doi = {10.5194/amt-12-6193-2019},
url = {https://juser.fz-juelich.de/record/868174},
}