High abundances of dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in fine aerosols (PM2.5) in Chengdu, China during wintertime haze pollution.

Abstract

Daytime and nighttime fine aerosol (PM2.5) samples were collected during a haze episode in January 2013 within the urban area of Chengdu, southwest China. Aerosol samples were analyzed for low-molecular-weight homologous dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls, as well as organic carbon and elemental carbon. Concentration ranges of diacids, oxoacids, and α-dicarbonyls were 1,400-5,250, 272-1,380, and 88-220ngm(-3), respectively. Molecular distributions of diacids (mean 3,388 ± 943ngm(-3)) were characterized by a predominance of oxalic acid (C2; 1,373 ± 427ngm(-3)), followed by succinic (C4), terephthalic (tPh), and phthalic (Ph) acids. Such high levels of tPh and Ph were different from those in other Asian cities where malonic acid (C3) is the second or third highest species, mostly owing to significant emissions from coal combustion and uncontrolled waste incineration. High contents of diacids, oxoacids, and α-dicarbonyls were detected on hazy days, suggesting an enhanced emission and/or formation of these organics during such a weather condition. Concentrations of unsaturated aliphatic diacids (e.g., maleic acid) and phthalic acids were higher in nighttime than in daytime. Good positive correlations of C2 with C3, C4, ketomalonic (kC3), pyruvic (Pyr), and glyoxylic (ɷC2) acids in daytime suggest secondary production of C2 via the photooxidation of longer chain diacids and ɷC2. This study demonstrated that both primary emissions and secondary production are important sources of dicarboxylic acids and related compounds in atmospheric aerosols in the Sichuan Basin.