Atmospheric Chemistry and Physics Discussions
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2009
10.5194/acpd-9-19939-2009
http://www.atmos-chem-phys-discuss.net/9/19939/2009/
http://www.atmos-chem-phys-discuss.net/9/19939/2009/acpd-9-19939-2009.html
http://www.atmos-chem-phys-discuss.net/9/19939/2009/acpd-9-19939-2009.pdf
19939
19966
2009-09-24
Chirality and origin of atmospheric humic-like substances
I. Salma
salma@chem.elte.hu
T. Mészáros
W. Maenhaut
E. Vass
Zs. Majer
Eötvös University, Institute of Chemistry, Budapest, Hungary
Ghent University, Institute for Nuclear Sciences, Ghent, Belgium
Aerosol water extracts and atmospheric humic-like substances (HULIS)
obtained from PM<sub>2.5</sub>-fraction aerosol samples collected in
a rural/continental background environment and in an urban
environment in spring and summer, and at a tropical site that was
heavily impacted by biomass burning were studied. Mean organic
matter-to-organic carbon mass conversion factor and standard deviation
of 2.04±0.06 were derived for HULIS from biomass burning. Mean
atmospheric concentrations of HULIS for the rural and urban
environments, and for the biomass burning during daylight periods and
nights were 1.65, 2.2, 43, and 60 μg m<sup−3</sup>,
respectively. This indicates that intense emission sources and/or
formation mechanisms of HULIS operate in biomass burning. Mean
contributions of C in HULIS (HULIS-C) to water-soluble organic carbon
(WSOC) were 35, 48, 63, and 76%, respectively, for the sample set
listed. The data suggest that HULIS-C is the major component of the
WSOC in tropical biomass burning, and that HULIS most likely do not
share common origin in the three environments studied. Differentiation
among the possible formation processes was attempted by investigating
the optical activity of HULIS through their (electronic and
vibrational) circular dichroism properties. The urban HULIS did not
show optical activity, which is in line with the concept of their
major airborne formation from anthropogenic aromatics. The rural HULIS
revealed weak optical activity, which may be associated with one of
their important formation pathways by photo-oxidation and
oligomerisation, i.e., with the formation from chiral biogenic
precursors with one of the enantiomers slightly enriched. The biomass
burning HULIS exhibited strong effect in the vibrational circular
dichroism as a clear distinction from the other two types. This was
related to the contribution of the thermal degradation products of
lignins and cellulose. The biomass burning HULIS resemble Suwannee
River Fulvic Acid standard more closely in some aspects than the urban
and rural types of HULIS, which may be related to their common origin
from plant material.
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