Online chemical characterization of atmospheric fine secondary aerosols and organic nitrates in summer Nanjing, China

The mechanisms leading to secondary aerosol pollution in the Yangtze Delta region (such as Nanjing) are still poorly constrained. Here we conducted a field campaign to elucidate the chemical characteristics of fine aerosols, with a focus on variations and formation mechanisms of secondary components in summer Nanjing. The average PM1 mass concentration was 18.88 μg m−3 and was dominated by the secondary species (78%). Secondary inorganic species accounted for 30% of PM1 mass and high PM1 loading was closely relevant with nitrate rather than sulfate. Nitrate was mainly produced from nighttime heterogeneous/aqueous process (production rate of 0.38 g/g H2O) and its variation was driven by thermodynamic equilibrium. On the other hand, sulfate was governed by daytime photochemical production (production rate of 0.013 g/g Ox)(Ox=NO2 + O3) while contribution of aqueous process was minor. Positive matrix factorization identified and quantified a traffic-related hydrocarbon OA (HOA), a cooking OA (COA), and four SOA factors including a local secondary OA (LSOA), a less oxygenated OA (LO-OOA), a moderately oxygenated OA (MD-OOA), and a more-oxidized oxygenated OA (MO-OOA). LSOA was likely from local photochemical conversion of HOA and COA; LO-OOA was semi-volatile thus evaporation/diffusion would offset its weak photochemical production. MO-OOA was very clearly linked with photochemistry, based on its afternoon enhancement and tight positive correlations with Ox (0.029 g/g Ox, occupying ∼60% of photochemical SOA production) and sulfate. MD-OOA was a minor contributor of SOA (∼6%) but it was clearly from aqueous process given the strong positive correlation with aerosol liquid water content (ALWC) and nitrate. Both nitrate and MD-OOA concentrations increased against pH while those of sulfate and MO-OOA decreased. We further investigated the organic nitrate (ON) characteristics, and found that ON was a very minor component of OA in summer Nanjing (0.08–0.14 μg m−3, 0.6–1.1% of OA) and it was predominantly associated with aqueous process. Overall, this work reveals in details formation processes of different secondary species, and therefore is insightful for future air pollution modelling and efficient control in similar regions. •Organics and sulfate dominated PM1, yet high PM1 loading was mainly caused by nitrate.•Nitrate was mainly produced from nighttime heterogeneous/aqueous process.•Sulfate was governed by daytime photochemical processes.•MO-OOA was clearly from