ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-9-4727-2009 Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry Pan X. 1 Underwood J. S. 1 2 Xing J.-H. 1 3 Mang S. A. 1 4 Nizkorodov S. A. 1 Department of Chemistry, University of California – Irvine, Irvine, CA 92697–2025, USA Department of Chemistry, Loyola University, New Orleans, LA 70118, USA Kyoto University Pioneering Research Unit for Next Generation, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 2125, USA 24 02 2009 9 1 4727 4767 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/9/4727/2009/acpd-9-4727-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/9/4727/2009/acpd-9-4727-2009.pdf

Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone and D-limonene concentrations (0.1–300 ppm) used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO<sub>2</sub>+HO<sub>2</sub>/RO<sub>2</sub> reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA material. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O<sub>3</sub>-initiated oxidation of biogenic volatile organic compounds in clean air.

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