The secondary formation of inorganic aerosols in the droplet mode through heterogeneous aqueous reactions under haze conditions

摘要

Secondary inorganic aerosols play important roles in visibility reduction and in regional haze pollution. To investigate the characteristics of size distributions of secondary sulfates and nitrates as well as their formation mechanisms under hazes, size-resolved aerosols were collected using a Micro-Orifice Uniform Deposit Impactor (MOUDI) at an urban site in Jinan, China, in all four seasons (December 2007-October 2008). In haze episodes, the secondary sulfates and nitrates primarily formed in fine particles, with elevated concentration peaks in the droplet mode (0.56-1.8 μm). The fine sulfates and nitrates were completely neutralized by ammonia and existed in the forms of (NH_4)SO_4 and NH_4NO_3, respectively. The secondary formation of sulfates, nitrates and ammonium (SNA) was found to be related to heterogeneous aqueous reactions and was largely dependent on the ambient humidity. With rising relative humidity, the droplet-mode SNA concentration, the ratio of droplet-mode SNA to the total SNA, the fraction of SNA in droplet-mode particles and the mass median aerodynamic diameter of SNA presented an exponential, logarithmic or linear increase. Two heavily polluted multi-day haze episodes in winter and summer were analyzed in detail. The secondary sulfates were linked to heterogeneous uptake of SO_2 followed by the subsequent catalytic oxidation by oxygen together with iron and manganese in winter. The fine nitrate formation was strongly associated with the thermodynamic equilibrium among NH_4NO_3, gaseous HNO_3 and NH_3, and showed different temperature-dependences in winter and summer.