Primary and secondary organic aerosols (POA and SOA) contain a complex mixture of multifunctional chemicals, many of which are photolabile. Much of the previous work that aimed to understand the chemical evolution (aging) of POA and SOA has focused on the reactive uptake of gas-phase oxidants by particles. By stripping volatile compounds and ozone from α-pinene ozonolysis SOA with three 1-m-long denuders, and exposing the residual particles in a flow cell to near-ultraviolet (λ>300 nm) radiation, we find that condensed-phase photochemistry can induce significant changes in SOA particle size and chemical composition. The particle-bound organic peroxides, which are highly abundant in α-pinene ozonolysis SOA (22 ± 5% by weight), have an atmospheric photolysis lifetime of about 6 days at a 24-h average solar zenith angle (SZA) of 65° experienced at 34° latitude (Los Angeles) in the summer. In addition, the particle diameter shrinks 0.56% per day under these irradiation conditions as a result of the loss of volatile photolysis products. Experiments with and without the denuders show similar results, suggesting that condensed-phase processes dominate over heterogeneous reactions of particles with organic vapors, excess ozone, and gas-phase free radicals. These condensed-phase photochemical processes occur on atmospherically relevant time scales and should be considered when modeling the evolution of organic aerosol in the atmosphere.
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