High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and alpha-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534m a.s.l., 36.25 degrees N, 117.10 degrees E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low-molecular-weight dicarboxylic acids, ketoacids and alpha-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Molecular distributions of dicarboxylic acids (C-2-C-11, 220-6070 ng m(-3)) were characterized by a predominance of oxalic (C-2) acid (105-3920 ng m(-3)) followed by succinic (C-4) or malonic (C-3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acids, were also detected together with aromatic diacids (phthalic, isophthalic and terephthalic acids). omega-oxocarboxylic acids (C-2-C-9, 24-610 ng m(-3)) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m(-3)), followed by alpha-ketoacid (pyruvic acid, 3-140 ng m(-3)) and alpha-dicarbonyls (glyoxal, 1-230 ng m(-3) and methylglyoxal, 2-120 ng m(-3)). We found that these levels (>6000 ng m(-3) for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June, showing a maximum on 7 June, and then significantly decreased during the period 8-11 June, when the wind direction shifted from southerly to northerly. Similar temporal trends were found for ketocarboxylic acids and alpha-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of volatile and semi-volatile organic precursors emitted from field burning as well as dark ozonolysis of volatile organic compounds and other organics, accretion reactions and oxidation of nonvolatile organics such as unsaturated fatty acids. This study demonstrates that the field burning of agricultural wastes in early summer strongly influenced the air quality of the free troposphere over the North China Plain.