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SimonichStaciEMTHeterogeneousReactionsParticulate.pdf

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https://ir.library.oregonstate.edu/concern/articles/0v838529b

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  • The heterogeneous reactions of ambient particulate matter (PM)-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) with NO₃/N₂O₅, OH radicals, and O₃ were studied in a laboratory photochemical chamber. Ambient PM[subscript 2.5] and PM₁₀ samples were collected from Beijing, China and Riverside, California, and exposed under simulated atmospheric long-range transport conditions for O₃ and OH and NO₃ radicals. Changes in the masses of 23 PAHs and 20 NPAHs, as well as the direct and indirect-acting mutagenicity of the PM (determined using the Salmonella mutagenicity assay with TA98 strain), were measured prior to and after exposure to NO₃/N₂O₅, OH radicals, and O₃. In general, O₃ exposure resulted in the highest relative degradation of PM-bound PAHs with more than four rings (benzo[a]pyrene was degraded equally well by O₃ and NO₃/N₂O₅). However, NPAHs were most effectively formed during the Beijing PM exposure to NO₃/N₂O₅. In ambient air 2-nitrofluoranthene (2-NF) is formed from gas-phase NO₃ radical- and OH radical-initiated reactions of fluoranthene, and 2-nitropyrene (2-NP) is formed from gas-phase OH radical-initiated reaction of pyrene. There was no formation of 2-NF or 2-NP in any of the heterogeneous exposures, suggesting that gas-phase formation of NPAHs did not play an important role during chamber exposures. Exposure of Beijing PM to NO₃/N₂O₅ resulted in an increase in direct-acting mutagenic activity which was associated with the formation of mutagenic NPAHs. No NPAH formation was observed in any of the exposures of the Riverside PM. This was likely due to the accumulation of atmospheric degradation products from gas phase reactions of volatile species onto the surface of PM collected in Riverside prior to exposure in the chamber, thus decreasing the availability of PAHs for reaction.
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