Gas- and particle-phase products from the photooxidation of acenaphthene and acenaphthylene by OH radicals

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Riva, Matthieu
Healy, Robert M.
Flaud, Pierre-Marie
Perraudin, Emilie
Wenger, John C.
Villenave, Eric
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This work is focused on the gas-phase oxidation of acenaphthylene and acenaphthene by OH radicals and associated secondary organic aerosol (SOA) formation under low and high-NOx conditions. Experiments were carried out in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) to chemically characterize the gas- and particle-phase products, respectively. Due to the structures of these two aromatic compounds, the proposed chemical mechanisms exhibit some differences. In the case of acenaphthene, H-atom abstraction from the saturated cyclopenta-fused ring was found to be competitive with the OH-addition to the aromatic rings. During the photooxidation of acenaphthene using nitrous acid (HONO), aromatic ring-opening products such as indanone and indanone carbaldehyde, generated through OH addition to the aromatic ring, were formed in higher yields compared to low-NOx conditions. In the case of acenaphthylene, OH addition to the unsaturated cyclopenta-fused ring was strongly favored. Hence, ring-retaining species such as acenaphthenone and acenaphthenequinone, were identified as the main reaction products in both gas- and particle-phases, especially under high-NOx conditions. Subsequent SOA formation was observed in all experiments and SOA yields were determined under low/high-NOx conditions to be 0.61/0.46 and 0.68/0.55 from the OH-initiated oxidation of acenaphthylene and acenaphthene, respectively.
PAHs , Gas-phase , Atmospheric oxidation , Photooxidation , OH radicals
Riva, M., Healy, R. M., Flaud, P.-M., Perraudin, E., Wenger, J. C. and Villenave, E. (2017) 'Gas- and particle-phase products from the photooxidation of acenaphthene and acenaphthylene by OH radicals', Atmospheric Environment, 151, pp. 34-44. doi:10.1016/j.atmosenv.2016.11.063
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