Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol
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The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored in situ by infrared cavity ring-down spectroscopy. A number of additional gas-phase products of SOA photodegradation were observed by gas chromatography, including methane, ethene, acetaldehyde, acetone, methanol, and I-butene. The absorption spectrum of SOA material collected onto CaF, windows was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-1 photocleavage of carbonyls. Both spectra had a band at similar to 300 nm corresponding to the overlapping n -> pi* transitions in nonconjugated carbonyls. The effective extinction coefficient of freshly prepared SOA was estimated to be on the order of' 15 L mol(-1) cm(-1) at 300 rim, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result of condensation reactions that increased the degree of conjugation in the SOA constituents. These observations suggest that photolysis of carbonyl functional groups represents a significant sink for monoterpene SOA compounds in the troposphere, with an estimated lifetime of several hours over the continental United States.
Originalsprog | Engelsk |
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Tidsskrift | Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory |
Vol/bind | 112 |
Udgave nummer | 36 |
Sider (fra-til) | 8337-8344 |
Antal sider | 8 |
ISSN | 1089-5639 |
DOI | |
Status | Udgivet - 2008 |
ID: 44568028