Amplified role of potential HONO sources in O-3 formation in North China Plain during autumn haze aggravating processes

Co-occurrences of high concentrations of PM2.5 and ozone (O-3) have been frequently observed in haze-aggravating processes in the North China Plain (NCP) over the past few years. Higher O-3 concentrations on hazy days were hypothesized to be related to nitrous acid (HONO), but the key sources of HONO enhancing O-3 during haze-aggravating processes remain unclear. We added six potential HONO sources, i.e., four groundbased (traffic, soil, and indoor emissions, and the NO2 heterogeneous reaction on ground surface (Het(ground))) sources, and two aerosol-related (the NO2 heterogeneous reaction on aerosol surfaces (Het(aerosol)) and nitrate photolysis (Phot(nitrate))) sources into the WRF-Chem model and designed 23 simulation scenarios to explore the unclear key sources. The results indicate that ground-based HONO sources producing HONO enhancements showed a rapid decrease with height, while the NO C OH reaction and aerosol-related HONO sources decreased slowly with height. Photnitrate contributions to HONO concentrations were enhanced with aggravated pollution levels. The enhancement of HONO due to Phot(nitrate) on hazy days was about 10 times greater than on clean days and Phot(nitrate) dominated daytime HONO sources (similar to 30 %-70% when the ratio of the photolysis frequency of nitrate (J(nitrate)) to gas nitric acid (JHNO(3)) equals 30) at higher layers (>800 m). Compared with that on clean days, the Phot(nitrate) contribution to the enhanced daily maximum 8 h averaged (DMA8) O-3 was increased by over 1 magnitude during the haze-aggravating process. Phot(nitrate) contributed only similar to 5% of the surface HONO in the daytime with a J(nitrate) =JHNO(3) ratio of 30 but contributed similar to 30 %-50% of the enhanced O-3 near the surface in NCP on hazy days. Surface O-3 was dominated by volatile organic compound-sensitive chemistry, while O-3 at higher altitudes ( >800 m) was dominated by NOx-sensitive chemistry. Phot(nitrate) had a limited impact on nitrate concentrations (<15 %) even with a J(nitrate)=JHNO(3) ratio of 120. These results suggest the potential but significant impact of Phot(nitrate) on O-3 formation, and that more comprehensive studies on Phot(nitrate) in the atmosphere are still needed.