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Molecular Distribution and Stable Carbon Isotopic Composition of Dicarboxylic Acids, Ketocarboxylic Acids, and 伪-Dicarbonyls in Size-Resolved Atmospheric Particles From Xi鈥檃n City, China
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文摘
Size-resolved airborne particles (9-stages) in urban Xi鈥檃n, China, during summer and winter were measured for molecular distributions and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and 伪-dicarbonyls. To our best knowledge, we report for the first time the size-resolved differences in stable carbon isotopic compositions of diacids and related compounds in continental organic aerosols. High ambient concentrations of terephthalic (tPh, 379 卤 200 ng m鈥?) and glyoxylic acids (蠅C2, 235 卤 134 ng m鈥?) in Xi鈥檃n aerosols during winter compared to those in other Chinese cities suggest significant emissions from plastic waste burning and coal combustions. Most of the target compounds are enriched in the fine mode (<2.1 渭m) in both seasons peaking at 0.7鈥?.1 渭m. However, summertime concentrations of malonic (C3), succinic (C4), azelaic (C9), phthalic (Ph), pyruvic (Pyr), 4-oxobutanoic (蠅C4), and 9-oxononanoic (蠅C9) acids, and glyoxal (Gly) in the coarse mode (>2.1 渭m) are comparable to and even higher than those in the fine mode (<2.1 渭m). Stable carbon isotopic compositions of the major organics are higher in winter than in summer, except oxalic acid (C2), 蠅C4, and Ph. 未13C of C2 showed a clear difference in sizes during summer, with higher values in fine mode (ranging from 鈭?2.8鈥?to 鈭?1.9鈥? and lower values in coarse mode (鈭?7.1鈥?to 鈭?3.6鈥?. The lower 未13C of C2 in coarse particles indicate that coarse mode of the compound originates from evaporation from fine mode and subsequent condensation/adsorption onto pre-existing coarse particles. Positive linear correlations of C2, sulfate and 蠅C2 and their 未13C values suggest that 蠅C2 is a key intermediate, which is formed in aqueous-phase via photooxidation of precursors (e.g., Gly and Pyr), followed by a further oxidation to produce C2.

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