Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 5 2009 10.5194/acpd-9-19783-2009 http://www.atmos-chem-phys-discuss.net/9/19783/2009/ http://www.atmos-chem-phys-discuss.net/9/19783/2009/acpd-9-19783-2009.html http://www.atmos-chem-phys-discuss.net/9/19783/2009/acpd-9-19783-2009.pdf 19783 19815 2009-09-23 Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols: implications for photochemical production and degradation in smoke layers S. Kundu K. Kawamura kawamura@lowtem.hokudai.ac.jp T. W. Andreae A. Hoffer M. O. Andreae Institute of Low Temperature Science, Hokkaido University, Sapporo, Japan Graduate School of Environmental Science, Hokkaido University, Sapporo, Japan Biogeochemistry Department, Max Planck Institute for Chemistry, Mainz, Germany Dept. of Earth and Environmental Sciences, University of Pannonia, Veszprém, Hungary Aerosols in the size class <2.5 μm (6 daytime and 9 nighttime samples) were collected at a pasture site in Rondônia, Brazil, during the intensive biomass burning period of 16–26 September 2002 as part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC). Homologous series of dicarboxylic acids (C₂–C₁₁) and related compounds (ketocarboxylic acids and dicarbonyls) were identified using gas chromatography and GC/mass spectrometry (GC/MS). Among the species detected, oxalic acid was found to be the most abundant, followed by succinic, malonic and glyoxylic acids. Average concentrations of total dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the aerosol samples were 2180, 167 and 56 ng m^−3, respectively. These are 2–8, 3–11 and 2–16 times higher, respectively, than those reported in urban aerosols, such as in 14 Chinese megacities. Higher ratios of dicarboxylic acids and related compounds to biomass burning tracers (levoglucosan and K⁺) were found in the daytime than in the nighttime, suggesting an importance of photochemical production. On the other hand, higher ratios of oxalic acid to other dicarboxylic acids and related compounds normalized to biomass burning tracers (levoglucosan and K⁺) in the daytime provide evidence for the possible degradation of dicarboxylic acids (≥C₃) in this smoke-polluted environment. Assuming that these and related compounds are photochemically oxidized to oxalic acid in the daytime and given their linear relationship, they could account for, on average, 77% of the formation of oxalic acid. 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