Molecular Distribution and Stable Carbon Isotopic Composition of Dicarboxylic Acids, Ketocarboxylic Acids, and alpha-Dicarbonyls in Size-Resolved Atmospheric Particles From Xi'an City, China

Size-resolved airborne particles (9-stages) in urban Xi&#39;an, China, during summer and winter were measured for molecular distributions and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and alpha-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 +/- 200 ng m(-3)) and glyoxylic acids (omega C-2, 235 +/- 134 ng m(-3)) in Xi&#39;an 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 (&lt;2.1 mu m) in both seasons peaking at 0.7-2.1 mu m. However, summertime concentrations of malonic (C-3), succinic (C-4), azelaic (C-9), phthalic (Ph), pyruvic (Pyr), 4-oxobutanoic (omega C-4), and 9-oxononanoic (omega C-9) acids, and glyoxal (Gly) in the coarse mode (&gt;2.1 mu m) are comparable to and even higher than those in the fine mode (&lt;2.1 mu m). Stable carbon isotopic compositions of the major organics are higher in winter than in summer, except oxalic acid (C-2), omega C-4, and Ph. delta C-13 of C-2 showed a clear difference in sizes during summer, with higher values in fine mode (ranging from -22.8 parts per thousand to -21.9 parts per thousand) and lower values in coarse mode (-27.1 parts per thousand to -23.6 parts per thousand). The lower delta C-13 of C-2 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 C-2, sulfate and omega C-2 and their delta C-13 values suggest that omega C-2 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 C-2.</p

Chemical composition and size distribution of wintertime aerosols in the atmosphere of Mt. Hua in central China

TSP, PM(10) and size-segregated aerosols were collected at the summit (2060 m, a.s.l.) of Mt. Hua in central China during the winter of 2009, and determined for organic (OC) and elemental carbon (EC), pH of water-extracts and inorganic ions. OC in TSP and PM(10) are 6.9 +/- 2.9 and 5.9 +/- 2.5 mu g m(-3), while EC in TSP and PM(10) are 0.9 +/- 0.6 and 0.9 +/- 0.5 mu g m(-3), respectively. SO(4)(2-), NO(3)(-), NH(4)(+) and Ca(2)(+) are major ions in PM(10) with concentrations of 5.8 +/- 3.7, 2.7 +/- 1.6, 1.6 +/- 0.9 and 1.5 +/- 0.7 mu g m(-3), respectively. OC/EC ratios (8.2 +/- 3.1 in TSP and 6.6 +/- 1.8 in PM(10)) at the mountaintop are 2-4 times higher than those in lowland surface, suggesting an enhanced transformation of organics from gas- to solid- phase because of an increased photochemical oxidation and/or an increased condensation due to lower temperature, as well as an increased organic input from mountain plant emission. Air mass backward trajectories showed that compared with those derived from north/northwest China aerosols transported from the south contained higher concentrations of SO(4)(2-) and NH(4)(+) and lower concentrations of Ca(2+). Size distributions of NH(4)(+) and K(+) presented as an accumulation mode with a peak at 0.7-1.1 mu m, in contrast to Ca(2+) and Mg(2+), which maximized at the size 4.7-5.8 mu m as a coarse mode. SO(4)(2-) and NO(3)(-) showed a bimodal pattern with a large peak at the range 0.7-1.1 mu m and a small peak at the size of 4.7-5.8 mu m, whereas Na(+) and Cl(-) displayed a bimodal pattern with two equivalent peaks in the fine (&lt; 2.1 mu m) and coarse (&gt;= 2.1 mu m) ranges. pH values of the water-extracts demonstrate that aerosols originate from southern China are more acidic than those from the north/northwest, and the particles with a diameter of 0.7-11 mu m are most acidic.</p