Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-9-3921-2009
http://www.atmos-chem-phys-discuss.net/9/3921/2009/
http://www.atmos-chem-phys-discuss.net/9/3921/2009/acpd-9-3921-2009.html
http://www.atmos-chem-phys-discuss.net/9/3921/2009/acpd-9-3921-2009.pdf
3921
3943
2009-02-05
Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles
J. F. Hamilton
jfh2@york.ac.uk
A. C. Lewis
T. J. Carey
J. C. Wenger
E. Borrás i Garcia
A. Muñoz
Department of Chemistry, University of York, Heslington, York, UK, YO10 5DD, UK
Department of Chemistry and Environmental Research Institute, University College Cork, Cork, Ireland
Fundación Centro de Estudios Ambientales del Mediterráneo (CEAM), EUPHORE laboratories, C/Charles Darwin, 14 – Parque Tecnológico, Paterna, Valencia, Spain
Green leaf volatiles (GLVs) are an important group of chemicals released by
vegetation which have emission fluxes that can be significantly increased
when plants are damaged or stressed. A series of simulation chamber
experiments has been conducted at the European Photoreactor in Valencia,
Spain, to investigate secondary organic aerosol (SOA) formation from the
atmospheric oxidation of the major GLVs <i>cis</i>-3-hexenylacetate and
<i>cis</i>-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to
identify chemical species present in the SOA. <i>Cis</i>-3-hexen-1-ol proved to be a
more efficient SOA precursor due to the high reactivity of its first
generation oxidation product, 3-hydroxypropanal, which can hydrate and
undergo further reactions with other aldehydes resulting in SOA dominated by
higher molecular weight oligomers. The lower SOA yields produced from
<i>cis</i>-3-hexenylacetate are attributed to the acetate functionality, which
inhibits oligomer formation in the particle phase. Based on observed SOA
yields and best estimates of global emissions, these compounds may be
calculated to be a substantial unidentified global source of SOA,
contributing 1–5 TgC yr<sup>−1</sup>, equivalent to around a third of that
predicted from isoprene. Molecular characterization of the SOA, combined
with organic mechanistic information, has provided evidence that the
formation of organic aerosols from GLVs is closely related to the reactivity
of their first generation atmospheric oxidation products, and indicates that
this may be a simple parameter that could be used in assessing the aerosol
formation potential for other unstudied organic compounds in the atmosphere.
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