Formation and impacts of nitryl chloride in Pearl River Delta

Here we present a field measurement of ClNO2 (nitryl chloride) and N2O5 (dinitrogen pentoxide) by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with the Filter Inlet for Gas and AEROsols (FIGAERO) at a regional site in the Pearl River Delta during a photochemical pollution season from 26 September to 17 November 2019. Three patterns of air masses are sampled during this campaign, including the dominating air masses from the north and northeast urban regions (Type A), the southeast coast (Type B), and the South China Sea (Type C). The concentration of ClNO2 and N2O5 was observed to be much higher in Type A and B than in Type C, indicating that the urban nighttime chemistry is more active than the background marine regions. The N2O5 uptake coefficient and ClNO2 production yield were estimated based on the field measurement, and the performance of the previously derived parameterizations was assessed. The nighttime ClNO2 correlated with particulate chloride and the mass concentration of fine particles (most likely due to aerosol surface area) suggested that the ClNO2 formation was limited by the N2O5 uptake at this site. By examining the relationship between particulate chloride and other species, we implied that anthropogenic emissions (e.g., biomass burning) rather than sea salt particles dominate the origin of particulate chloride, although the site was only about 100 km away from the ocean. A box model with detailed chlorine chemistry is used to investigate the impacts of ClNO2 chemistry on atmospheric oxidation. Model simulations showed that the chlorine radical liberated by ClNO2 photolysis during the next day had a slight increase in concentrations of OH, HO2, and RO2 radicals, as well as minor contributions to RO2 radical and O-3 formation (< 5 %, on daytime average), in all the three types of air masses. Relatively high contributions were observed in Type A and B. The overall low contributions of ClNO2 to atmospheric oxidation are consistent with those reported recently from wintertime observations in China (including Shanghai, Beijing, Wangdu, and Mt. Tai). This may be attributed to the following: (1) relatively low particle mass concentration limited ClNO2 formation; (2) other reactions channels, like nitrous acid (HONO), oxygenated volatile organic compounds (OVOCs, including formaldehyde), and ozone photolysis had a more significant radical formation rate during the ozone pollution episodes and weakened the ClNO2 contribution indirectly. The results provided scientific insights into the role of nighttime chemistry in photochemical pollution under various scenarios in coastal areas.