Formation pathway of secondary inorganic aerosol and its influencing factors in Northern China: Comparison between urban and rural sites

Secondary inorganic aerosol, including sulfate, nitrate, and ammonium (SNA), is a significant source of PM2.5 during haze episodes in Northern China. A series of high-time-resolution instruments were used in collecting PM2.5 chemical components and gaseous pollutants during a regional heavy pollution process from January 12-25, 2018, at urban and rural sites. SNA, accounting for >50% of PM2.5 at both sites, had greater importance on haze formation. Gas-phase and N2O5 hydrolysis reactions were the main formation pathways of nitrate during the daytime and nighttime, respectively. The OH radical was the primary factor for gas-phase reactions. HONO photolysis played a more critical role in OH radical formation when O3 concentration decreased during the haze episode. N2O5 hydrolysis reaction was mainly affected by O3 and aerosol water content. High relative humidity, aerosol water content, and N2O5 concentrations at the urban site enhanced the hydrolysis reactions more than those at the rural site. The aqueous-phase reactions dominated the sulfate formation with the highest rate of transition metal ion catalytic and H2O2 oxidation reactions at the urban and rural sites, respectively. Elevated relative humidity and particle acidity at the urban site resulted in a higher formation rate of aqueous-phase sulfate than at the rural site. The gas-particle partition coefficient of NH3 had a negative correlation with the particle pH, and the presence of NH3 could promote the increase of SNA concentration. Thus, more attention should be paid to the differences in SNA formation between urban and rural regions when formulating air quality policies.