Seasonal differences in sources and formation processes of PM2.5 nitrate in an urban environment of North China

Abstract

Nitrate (NO₃^-) has been the dominant ion of secondary inorganic aerosols (SIAs) in PM_2.5 in North China. Tracking the formation mechanisms and sources of particulate nitrate are vital to mitigate air pollution. In this study, PM_2.5 samples in winter (January 2020) and in summer (June 2020) were collected in Jiaozuo, China, and water-soluble ions and (δ¹⁵N, δ¹⁸O)-NO₃^- were analyzed. The results showed that the increase of NO₃^- concentrations was the most remarkable with increasing PM_2.5 pollution level. δ¹⁸O-NO₃^- values for winter samples (82.7‰ to 103.9‰) were close to calculated δ¹⁸O-HNO₃ (103‰ ± 0.8‰) values by N₂O₅ pathway, while δ¹⁸O-NO₃^- values (67.8‰ to 85.7‰) for summer samples were close to calculated δ¹⁸O-HNO₃ values (61‰ ± 0.8‰) by OH oxidation pathway, suggesting that PM_2.5 nitrate is largely from N₂O₅ pathway in winter, while is largely from OH pathway in summer. Averaged fractional contributions of P_N2O5+H2O were 70% and 39% in winter and summer sampling periods, respectively, those of P_OH were 30% and 61%, respectively. Higher δ¹⁵N-NO₃^- values for winter samples (3.0‰ to 14.4‰) than those for summer samples (-3.7‰ to 8.6‰) might be due to more contributions from coal combustion in winter. Coal combustion (31% ± 9%, 25% ± 9% in winter and summer, respectively) and biomass burning (30% ± 12%, 36% ± 12% in winter and summer, respectively) were the main sources using Bayesian mixing model. These results provided clear evidence of particulate nitrate formation and sources under different PM_2.5 levels, and aided in reducing atmospheric nitrate in urban environments.

Keywords: Bayesian mixing model; Dual isotopes; Nitrate formation pathways; PM(2.5).