1Department of Chemistry, University of California, Irvine, Irvine, California 92697-2025, USA
*currently at: Department of Chemistry, Loyola University, New Orleans, LA 70118, USA
**currently at: Kyoto University Pioneering Research Unit for Next Generation, Kyoto University, Gokasho, Uji, Kyoto, 611-0011 Japan
***currently at: Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250, USA
Received: 07 Jan 2009 – Published in Atmos. Chem. Phys. Discuss.: 24 Feb 2009
Abstract. 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 (0.1–300 ppm) and D-limonene (0.02–3 ppm) concentrations 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 RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.
Revised: 18 May 2009 – Accepted: 25 May 2009 – Published: 15 Jun 2009
Pan, X., Underwood, J. S., Xing, J.-H., Mang, S. A., and Nizkorodov, S. A.: Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry, Atmos. Chem. Phys., 9, 3851-3865, doi:10.5194/acp-9-3851-2009, 2009.