Water-soluble organic nitrogen (WSON) is an important component of PM_2.5 which may affect air quality, climate and human health. Herein, one-year field samples of atmospheric PM_2.5 (June 2017–May 2018) were collected in northern Nanjing. Chemical characterization of PM_2.5 major components as well as WSON were conducted, and WSON composition and sources were further investigated via measurements by a Aerodyne soot particle aerosol mass spectrometer (SP-AMS) as well as positive matrix factorization (PMF). Inorganic ions, mainly consisting of ammonium, sulfate, and nitrate, were found to dominate PM_2.5 mass (58.7%), followed by organic matter (OM) (22.6%), and elemental carbon (EC) (2.1%). Water-soluble OM dominated OM (65.1%), and its temporal variation was closely correlated with that of secondary organic matter, while time series of water-insoluble OM concentrations correlated tightly with that of primary organic matter. Average WSON concentration was 2.15 μg/m³, which was highest in winter and lowest in summer. Correlation analysis of WSON with PM_2.5 components also indicated that WSON was mainly from secondary sources. SP-AMS revealed that WSON mass spectrum was composed of C_xH_yN_p⁺ (91.2%) and C_xH_yO_zN_p⁺ (8.8%), indicating dominance of amines and other oxygenated ON compounds. PMF analysis resolved two primary sources (traffic, biomass burning) and two secondary sources (less-oxidized and more-oxidized factors) of WSOM and WSON, and the secondary source dominated both WSOM and WSON. Contribution of the more-oxidized ON factor was very high in winter, and the less-oxidized factor was significant in summer, indicating a likely important role of aqueous-phase processing in winter as well as photochemical oxidation in summer to WSON.

Intermediate-volatility organic compounds (IVOCs) have been recognized as an important contributor to the secondary organic aerosol (SOA) formation via gas-phase reactions. However, it is unclear whether or not IVOCs-SOA can be produced in the aqueous phase. This work investigated aqueous oxidation of one model compound of IVOCs, dibenzothiophene (DBT). Results show that DBT can be degraded by both hydroxyl radical and the triplet excited states of organic light chromophores (³C*). Aqueous dark oxidation of DBT was also possible. SOA yields of 32% and 15% were found for hydroxyl radical (OH)-mediated photo-oxidation and dark oxidation, respectively. A continuous and significant increase of oxidation degree of SOA was observed during OH photo-oxidation, but not during the dark oxidation. Factor analyses revealed that there was a persistent production of highly oxygenated compounds from the less oxygenated species. OH-initiated photochemical reactions can also produce species with a relatively large light-absorbing ability, while such photo-enhancement due to direct light irradiation and ³C*-initiated oxidation could occur, but is much less important. In the future, studies on the second-order rate constants, molecular characterization of the oxidation products from this and other IVOCs precursors are needed to better understand the role of this reaction pathway in SOA budget, air quality and climate change.