Potentially Important Contribution of Gas-Phase Oxidation of Naphthalene and Methylnaphthalene to Secondary Organic Aerosol during Haze Events in Beijing

Naphthalene (Nap) and methylnaphthalene (MN) are the most abundant polycyclic aromatic hydrocarbons (PAHs) in atmosphere and have been proposed to be important precursors of anthropogenic secondary organic aerosol (SOA) derived from laboratory chamber experiments. In this study, atmospheric Nap/MN and their gas-phase photooxidation products were quantified by a Proton Transfer Reaction-Quadrupole interface Time-of-Flight Mass Spectrometer (PTR-QiTOF) during the 2016 winter in Beijing. Phthalic anhydride, a late generation product from Nap under high-NOx conditions, appeared to be more prominent than 2-formylcinnamaldehyde (early generation product), possibly due to more sufficient oxidation during the haze. 1,2-Phthalic acid (1,2-PhA), the hydrated form of phthalic anhydride, was capable of partitioning into aerosol phase and served as a tracer to explore the contribution of Nap to ambient SOA. The measured fraction in particle phase (Fp) of 1,2-PhA averaged at 73 ± 13% with OA mass loadings of 52.5–87.8 μg/m3, lower than the value predicted by the absorptive partitioning model (100%). Using tracer product-based and precursor consumption-based methods, 2-ring PAHs (Nap and MN) were estimated to produce 14.9% (an upper limit) of the SOA formed in the afternoon during the wintertime haze, suggesting a comparable contribution of Nap and MN with monocyclic-aromatics on urban SOA formation.