ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-7859-2010 Seasonal cycle and temperature dependence of pinene oxidation products, dicarboxylic acids and nitrophenols in fine and coarse air particulate matter Zhang Y. Y. 1 Müller L. 2 Winterhalter R. 1 Moortgat G. K. 1 Hoffmann T. 2 Pöschl U. 1 Max Planck Institute for Chemistry, P.O. Box 3060, 55020 Mainz, Germany Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg Univ., Duesbergweg 10-14, 55128 Mainz, Germany 25 08 2010 10 16 7859 7873 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/10/7859/2010/acp-10-7859-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/7859/2010/acp-10-7859-2010.pdf

Filter samples of fine and coarse air particulate matter (PM) collected over a period of one year in central Europe (Mainz, Germany) were analyzed for water-soluble organic compounds (WSOCs), including the α- and β-pinene oxidation products pinic acid, pinonic acid and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA), as well as a variety of dicarboxylic acids and nitrophenols. Seasonal variations and other characteristic features in fine, coarse, and total PM (TSP) are discussed with regard to aerosol sources and sinks in comparison to data from other studies and regions. The ratios of adipic acid and phthalic acid to azelaic acid indicate that the investigated aerosol samples were mainly influenced by biogenic sources. A strong Arrhenius-type correlation was found between the 3-MBTCA concentration and inverse temperature (<i>R</i><sup>2</sup> = 0.79, <i>n</i> = 52, <i>E</i><sub>a</sub> = 126 &plusmn; 10 kJ mol<sup>−1</sup>, temperature range 275–300 K). Model calculations suggest that the temperature dependence observed for 3-MBTCA can be explained by enhanced photochemical production due to an increase of hydroxyl radical (OH) concentration with increasing temperature, whereas the influence of gas-particle partitioning appears to play a minor role. The results indicate that the OH-initiated oxidation of pinonic acid is the rate-limiting step in the formation of 3-MBTCA, and that 3-MBTCA may be a suitable tracer for the chemical aging of biogenic secondary organic aerosol (SOA) by OH radicals. An Arrhenius-type temperature dependence was also observed for the concentration of pinic acid (<i>R</i><sup>2</sup> = 0.60, <i>n</i> = 56, <i>E</i><sub>a</sub> = 84 &plusmn; 9 kJ mol<sup>−1</sup>); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation.

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