Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 10 5 2010 10.5194/acpd-10-12371-2010 http://www.atmos-chem-phys-discuss.net/10/12371/2010/ http://www.atmos-chem-phys-discuss.net/10/12371/2010/acpd-10-12371-2010.html http://www.atmos-chem-phys-discuss.net/10/12371/2010/acpd-10-12371-2010.pdf 12371 12431 2010-05-11 Glyoxal processing outside clouds: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles B. Ervens R. Volkamer Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA Chemical Sciences Division, Earth System Research Laboratory, NOAA, Boulder, Colorado, USA Department of Biochemistry and Chemistry, University of Colorado, Boulder, CO, USA This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions in aqueous aerosol particles that form secondary organic aerosol (SOA). Recent laboratory results on glyoxal reactions are reviewed and a consistent set of reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds to form (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles compared to cloud droplets and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry. The application of this new module in a chemical box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the atmospheric relevance of SOA formation from glyoxal. During day time a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ~5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5<pH<7). Reversible glyoxal oligomerization, parameterized by an equilibrium constant Kolig=1000 (in ammonium sulfate solution), contributes <1% to total predicted SOA masses at any time. 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