Molecular-scale investigation on the composition, sources and secondary generation of organic aerosols in polluted central China

Abstract

Molecular analyses help to better understand the overall picture of characteristics, meteorological effects, sources, and secondary transformations of organic aerosols (OA). A two-year observation campaign was conducted in polluted central China during 2019–2021, and 130 compounds of molecular OA (quantified organic compounds, QOCs) were quantified. The average concentration of QOCs was 1971 ng/m3, showing the highest normalized QOCs in PM2.5 (31 ng/μg) compared to others. Among the QOCs, the polar category contributed 84%, with the dominated abundant fatty acids observed. The enhanced acid ratios of malonic/succinic and octadecanoic/oleic in summer indicated higher aerosol age, significantly promoted by temperature. Three benzenetricarboxylic acids, mostly from secondary formation, also exhibited quite high concentrations in summer. The noticeable presence of carcinogenic polycyclic aromatic hydrocarbons (PAHs) (45% of ∑28PAHs) highlighted severe health risks associated with human exposure, particularly in winter (56 ng/m3, approximately 7 times that in summer). According to the random forest model assessments, meteorological conditions in summer were most conducive to eliminating pollutants, while that in winter contributed 19% of QOC concentration. The Positive Matrix Factorization analysis revealed that anthropogenic secondary organic aerosols (ASOA) and biogenic SOA (BSOA) jointly accounted for 32% of QOCs, followed by biomass burning (20%), coal combustion (17%), vehicle emissions (16%), and cooking (15%). ASOA was positively correlated with O3 (r = 0.58) and aerosol acidity facilitated ASOA production at 40% < relative humidity <80%. On polluted days, BSOA increased as NO2 and PM2.5 increased, contributing to worsened aerosol pollution. In spring and summer, gas-phase oxidation contributed more saturated dicarboxylic acids (52 and 55%), while aqueous-phase conversion predominated in autumn and winter (59 and 66%). This study provides new information on particulate molecular organic compounds as well as the secondary transformation, which is of great significance for formulating the prevention and control measures of aerosol pollution.