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@ARTICLE{Gensch:16945,
author = {Gensch, I. and Laumer, W. and Stein, O. and Kammer, B. and
Hohaus, T. and Saathoff, H. and Wegener, R. and Wahner, A.
and Kiendler-Scharr, A.},
title = {{T}emperature dependence of the kinetic isotope effect in
ß-pinene ozonolysis},
journal = {Journal of Geophysical Research},
volume = {116},
issn = {0148-0227},
address = {Washington, DC},
publisher = {Union},
reportid = {PreJuSER-16945},
pages = {D20301},
year = {2011},
note = {We thank Jochen Rudolph (York University, Toronto) for
fruitful discussions and valuable suggestions. We also
gratefully acknowledge the AIDA scientific team for constant
advice and assistance during the measurement campaign. This
work was supported by the EU within the EUROCHAMP project.
We thank Angelika Heil for providing us with IGBP Moderate
resolution Imaging Spectroradiometer (MODIS) Land Cover
data.},
abstract = {The temperature dependence of the kinetic isotope effect
(KIE) of beta-pinene ozonolysis was investigated
experimentally at 258, 273 and 303 K in the AIDA atmospheric
simulation chamber. Compound specific carbon isotopic
analysis of gas phase samples was performed off-line with a
Thermo Desorption-Gas Chromatography-Isotope Ratio Mass
Spectrometry (TD-GC-IRMS) system. From the temporal behavior
of the delta C-13 of beta-pinene a KIE of 1.00358 +/-
0.00013 was derived at 303 K, in agreement with literature
data. Furthermore, KIE values of 1.00380 +/- 0.00014 at 273
K and 1.00539 +/- 0.00012 at 258 K were determined, showing
an increasing KIE with decreasing temperature. A
parameterization of the observed KIE temperature dependence
was deduced and used in a sensitivity study carried out with
the global chemistry transport model MOZART-3. Two scenarios
were compared, the first neglecting, the second implementing
the KIE temperature dependence in the simulations.
beta-Pinene stable carbon isotope ratio and concentration
were computed, with emphasis on boreal zones. For early
spring it is shown that when neglecting the temperature
dependence of KIE, the calculated average age of beta-pinene
in the atmosphere can be up to two times over-or
underestimated. The evolution of the isotopic composition of
the major beta-pinene oxidation product, nopinone, was
examined using Master Chemical Mechanism (MCM) simulations.
The tested hypothesis that formation of nopinone and its
associated KIE are the determining factors for the observed
delta C-13 values of nopinone is supported at high
beta-pinene conversion levels.},
keywords = {J (WoSType)},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {Atmosphäre und Klima},
pid = {G:(DE-Juel1)FUEK491},
shelfmark = {Meteorology $\&$ Atmospheric Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000296159800008},
doi = {10.1029/2011JD016084},
url = {https://juser.fz-juelich.de/record/16945},
}