Seasonal cycle and temperature dependence of pinene oxidation products, dicarboxylic acids and nitrophenols in fine and coarse air particulate matter

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 alpha- and beta-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 (R-2 = 0.79, n = 52, E-a = 126 +/- 10 kJ mol(-1), 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 (R-2 = 0.60, n = 56, E-a = 84 +/- 9 kJ mol(-1)); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation.