Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol

J Phys Chem A. 2008 Sep 11;112(36):8337-44. doi: 10.1021/jp804376c. Epub 2008 Aug 14.

Abstract

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 1-butene. The absorption spectrum of SOA material collected onto CaF2 windows was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-I photocleavage of carbonyls. Both spectra had a band at approximately 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 nm, 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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Acetaldehyde / chemistry
  • Acetone / chemistry
  • Aerosols / chemistry*
  • Air Pollutants / chemistry*
  • Chromatography, Gas / methods
  • Cyclohexenes / chemistry
  • Filtration / instrumentation
  • Filtration / methods
  • Limonene
  • Organic Chemicals / chemistry*
  • Ozone / chemistry
  • Particle Size
  • Photochemistry*
  • Quartz / chemistry
  • Terpenes / chemistry
  • Time Factors
  • Ultraviolet Rays
  • Volatilization

Substances

  • Aerosols
  • Air Pollutants
  • Cyclohexenes
  • Organic Chemicals
  • Terpenes
  • Acetone
  • Quartz
  • Ozone
  • Limonene
  • Acetaldehyde