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@ARTICLE{Hua:62343,
author = {Hua, W. and Chen, Z.M. and Jie, C.Y. and Kondo, Y. and
Hofzumahaus, A. and Takegawa, N. and Lu, K. and Miyazaki, Y.
and Kita, K. and Wang, H.L. and Zhang, Y. and Hu, M.},
title = {{A}tmospheric hydrogen peroxide and organic hydroperoxides
during {PRIDE}-{PRD}'06, {C}hina: their concentration,
formation mechanism and contribution to secondary aerosols},
journal = {Atmospheric chemistry and physics / Discussions},
volume = {8},
issn = {1680-7367},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {PreJuSER-62343},
pages = {10481 - 10530},
year = {2008},
note = {Record converted from VDB: 12.11.2012},
abstract = {Atmospheric hydrogen peroxide (H2O2) and organic
hydroperoxides were measured from 18 to 30 July in 2006
during the PRIDE-PRD'06 campaign at Backgarden, a rural site
located 48 km north of Guangzhou, a mega-city in southern
China. A ground-based instrument was used as a scrubbing
coil collector to sample ambient air, followed by on-site
analysis by high-performance liquid chromatography (HPLC)
coupled with post-column derivatization and fluorescence
detection. The H2O2 mixing ratio over the 13 days ranged
from below the detection limit to a maximum of 4.6 ppbv,
with a mean (and standard deviation) of (1.26 +/- 1.24) ppbv
during the daytime (08:00-20:00 LT). Methyl hydroperoxide
(MHP), with a maximum of 0.8 ppbv and a mean (and standard
deviation) of (0.28 +/- 0.10) ppbv during the daytime, was
the dominant organic hydroperoxide. Other organic peroxides,
including bis-hydroxymethyl hydroperoxide (BHMP),
peroxyacetic acid (PAA), hydroxymethyl hydroperoxide (HMHP),
1-hydroxy-ethyl hydroperoxide (1-HEHP) and ethyl
hydroperoxide (EHP), were detected occasionally. The
concentration of H2O2 exhibited a pronounced diurnal
variation on sunny days, with a peak mixing ratio in the
afternoon (12:00-18:00 LT), but lacked an explicit diurnal
cycle on cloudy days. Sometimes a second peak mixing ratio
of H2O2 was observed during the evening, suggesting that
H2O2 was produced by the ozonolysis of alkenes. The diurnal
variation profile of MHP was, in general, consistent with
that of H2O2. The estimation indicated that in the morning
the H2O2 detected was formed mostly through local
photochemical activity, with the rest probably attributable
to vertical transport. It is notable that relatively high
levels of H2O2 and MHP were found in polluted air. The
unexpectedly high level of HO2 radicals detected in this
region can account for the production of hydroperoxides,
while the moderate level of NOx suppressed the formation of
hydroperoxides. High concentrations of hydroperoxides were
detected in samples of rainwater collected in a heavy shower
on 25 July when a typhoon passed through, indicating that a
considerable mixing ratio of hydroperoxides, particularly
MHP, resided above the boundary layer, which might be
transported on a regional scale and further influence the
redistribution of HOx and ROx radicals. It was found that
hydroperoxides, in particular H2O2, play an important role
in the formation of secondary sulfate in the aerosol phase,
where the heterogeneous reaction might contribute
substantially. A negative correlation between hydroperoxides
and water-soluble organic compounds (WSOC), a considerable
fraction of the secondary organic aerosol (SOA), was
observed, possibly providing field evidence for the
importance of hydroperoxides in the formation of SOA found
in previous laboratory studies. We suggest that
hydroperoxides act as an important link between sulfate and
organic aerosols, which needs further study and should be
considered in current atmospheric models.},
keywords = {J (WoSType)},
cin = {ICG-2},
ddc = {550},
cid = {I:(DE-Juel1)VDB791},
pnm = {Atmosphäre und Klima},
pid = {G:(DE-Juel1)FUEK406},
typ = {PUB:(DE-HGF)16},
url = {https://juser.fz-juelich.de/record/62343},
}