Effects of Aerosol Water Content on the formation of secondary inorganic aerosol during a Winter Heavy PM_2.5 Pollution Episode in Xi'an, China

Sulfate, nitrate and ammonium are the most abundant secondary inorganic aerosols (SIA) in atmospheric fine particle matter (PM_2.5). Meteorological conditions, gas-particle transportation process, and aerosol acidity (pH) can influence SIA formation. In this study, we conducted semi-continuous measurements of water-soluble inorganic ions during a winter extreme pollution event (from January 9th to January 17th, 2015, average PM_2.5 concentrations of ~250 μg m⁻³ and peak concentrations of ~700 μg m⁻³) in Xi'an to elucidate on the SIA formation mechanism. The hourly mean level of the total water-soluble ion was 137.4 μg m⁻³, accounting for 55.3% of PM_2.5 on average. The dominant ions concentrations of SO₄²⁻, NO₃⁻ and NH₄⁺ accounted for 15.8%, 19.0% and 13.2% of PM_2.5 mass, respectively. PM_2.5 was moderately acidic, with an average pH of 4.8 ± 0.4. Compared to the clean periods, sulfate content decreased by 6.9% during the polluted periods, while those of nitrate and ammonium increased by 2.2% and 5.0%, respectively. The increase in nitrogen oxidation ratios (NOR) and ammonia conversion ratio (NHR) from normal days to haze days were greater when comparison to sulfur oxidation ratios (SOR). In the polluted periods, sulfate and nitrate formations were facilitated by water content increase. Strong linear correlation coefficients between SOR (R² = 0.81) and NOR (R² = 0.55) with aerosol water content indicated that the gas-liquid reaction of SO₂ and NO₂ is the major pathway of sulfate and nitrate formation during severe haze episodes. In contrast, the NHR and aerosol water content exhibited a logarithmic relationship, which reveals that when water content was greater than 100 μg m⁻³, the gas-particle partitioning ratio of ammonium was basically unchanged following an increase in water content.