% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Ehn:22984,
author = {Ehn, M. and Kleist, E. and Junninen, H. and Petäjä, T.
and Lönn, G. and Schobesberger, S. and Dal Maso, M. and
Trimborn, A. and Kulmala, M. and Worsnop, D. and Wahner, A.
and Wildt, J. and Mentel, Th.F.},
title = {{G}as phase formation of extremely oxidized pinene reaction
products in chamber and ambient air},
journal = {Atmospheric chemistry and physics},
volume = {12},
issn = {1680-7316},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {PreJuSER-22984},
pages = {5113 - 5127},
year = {2012},
note = {M. E. gratefully acknowledges financial support by the Emil
Aaltonen foundation. This work was supported by the ERC
Advanced Grant EU-FP7-ATMNUCLE (project no 227463), and by
the Academy of Finland Center of Excellence program (project
no 1118615).},
abstract = {High molecular weight (300-650 Da) naturally charged
negative ions have previously been observed at a boreal
forest site in Hyytiala, Finland. The long-term measurements
conducted in this work showed that these ions are observed
practically every night between spring and autumn in
Hyytiala. The ambient mass spectral patterns could be
reproduced in striking detail during additional measurements
of alpha-pinene (C10H16) oxidation at low-OH conditions in
the Julich Plant Atmosphere Chamber (JPAC). The ions were
identified as clusters of the nitrate ion (NO3-) and
alpha-pinene oxidation products reaching oxygen to carbon
ratios of 0.7-1.3, while retaining most of the initial ten
carbon atoms. Attributing the ions to clusters instead of
single molecules was based on additional observations of the
same extremely oxidized organics in clusters with HSO4-
(Hyytiala) and C3F5O2- (JPAC). The most abundant products in
the ion spectra were identified as C10H14O7, C10H14O9,
C10H16O9, and C10H14O11. The mechanism responsible for
forming these molecules is still not clear, but the initial
reaction is most likely ozone attack at the double bond, as
the ions are mainly observed under dark conditions.
beta-pinene also formed highly oxidized products under the
same conditions, but less efficiently, and mainly C-9
compounds which were not observed in Hyytiala, where
beta-pinene on average is 4-5 times less abundant than
alpha-pinene. Further, to explain the high O/C together with
the relatively high H/C, we propose that geminal diols
and/or hydroperoxide groups may be important. We estimate
that the night-time concentration of the sum of the neutral
extremely oxidized products is on the order of 0.1-1 ppt
(similar to 10(6)-10(7) molec cm(-3)). This is in a similar
range as the amount of gaseous H2SO4 in Hyytiala during
day-time. As these highly oxidized organics are roughly 3
times heavier, likely with extremely low vapor pressures,
their role in the initial steps of new aerosol particle
formation and growth may be important and needs to be
explored in more detail in the future.},
keywords = {J (WoSType)},
cin = {IEK-8 / IBG-2},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013 / I:(DE-Juel1)IBG-2-20101118},
pnm = {Atmosphäre und Klima},
pid = {G:(DE-Juel1)FUEK491},
shelfmark = {Meteorology $\&$ Atmospheric Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000305281600020},
doi = {10.5194/acp-12-5113-2012},
url = {https://juser.fz-juelich.de/record/22984},
}