ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-8219-2010 Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles Ervens B. 1 2 Volkamer R. 1 3 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 02 09 2010 10 17 8219 8244 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/10/8219/2010/acp-10-8219-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/8219/2010/acp-10-8219-2010.pdf

This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical 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. Products of these processes include (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 and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). <br><br> The application of the new module including detailed chemical processes in a 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 predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming &sim;5 μg m<sup>−3</sup> 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). <br><br> Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter <i>k</i><sub>effupt</sub> that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by <i>k</i><sub>effupt</sub>, and can be parameterized by an effective Henry's law constant including an equilibrium constant <i>K</i><sub>olig</sub> = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes <1% to total predicted SOA masses at any time. <br><br> Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. <br><br> Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

 References Aiken, A. C., Salcedo, D., Cubison, M. J., Huffman, J. A., DeCarlo, P. F., Ulbrich, I. M., Docherty, K. S., Sueper, D., Kimmel, J. R., Worsnop, D. R., Trimborn, A., Northway, M., Stone, E. A., Schauer, J. J., Volkamer, R. M., Fortner, E., de Foy, B., Wang, J., Laskin, A., Shutthanandan, V., Zheng, J., Zhang, R., Gaffney, J., Marley, N. A., Paredes-Miranda, G., Arnott, W. P., Molina, L. T., Sosa, G., and Jimenez, J. L.: Mexico City aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) – Part 1: Fine particle composition and organic source apportionment, Atmos. Chem. Phys., 9, 6633–6653, doi:10.5194/acp-9-6633-2009, 2009. Altieri, K., Carlton, A. G., Lim, H., Turpin, B. J., and Seitzinger, S. P.: Evidence for oligomer formation in clouds: reaction of isoprene oxidation products, Environ. Sci. Technol., 40(16), 4956–4960, 2006. Bahreini, R., Ervens, B., Middlebrook, A. M., Warneke, C., DeGouw, J. A., DeCarlo, P., Jimenez, J. L., Brock, C. A., Neuman, J. A., Ryerson, T. B., Stark, H., Atlas, E., Brioude, J., Fried, A., Holloway, J. S., Peischl, J., Richter, D., Walega, J., Weibring, P., Wollny, A. G., and Fehsenfeld, F. C.: Organic aerosol formation in urban and industrial plumes in Houston, TX, J. Geophys. Res., 114, D00F16, doi:10.1029/2008JD011493, 2009. Bao, L., Matsumoto, M., Kubota, T., Kazuhiko, S., Wang, Q., and Sakamoto, K.: Gas/particle partitioning of low-molecular-weight dicarboxylic acids at a suburban site in Saitama, Japan, Atmos. Environ., in press, 2009. Barnard, J. C., Volkamer, R., and Kassianov, E. I.: Estimation of the mass absorption cross section of the organic carbon component of aerosols in the Mexico City Metropolitan Area, Atmos. Chem. Phys., 8, 6665–6679, doi:10.5194/acp-8-6665-2008, 2008. Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions – Part 2 Dialdehydes, methylglyoxal, and diketones, Atmos. Environ., 39, 6597–6607, 2005. Betterton, E. A. and Hoffmann, M. R.: Henry's law constants of some environmentally important aldehydes, Environ. Sci. Technol., 22, 1415–1418, 1988. Bielski, B. H. J., Cabell, D. E., Arudi, R. L., and Ross, A. B.: Reactivity of HO<sub>2</sub>/O$_2^-$ radicals in aqueous solution, J. Phys. Chem. Ref. Data, 14(4), 1041–1100, 1985. Bloss, C., Wagner, V., Jenkin, M. E., Volkamer, R., Bloss, W. J., Lee, J. D., Heard, D. E., Wirtz, K., Martin-Reviejo, M., Rea, G., Wenger, J. C., and Pilling, M. J.: Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons, Atmos. Chem. Phys., 5, 641–664, doi:10.5194/acp-5-641-2005, 2005. Bowman, F. M. and Melton, J. A.: Effect of activity coefficient models on predictions of secondary organic aerosol partitioning, J. Aerosol Sci., 35, 1415–1438, 2004. Buxton, G. V., Malone, T. N., and Salmon, G. A.: Oxidation of glyoxal initiated by OH in oxygenated aqueous solutions, J. Chem. Soc. Faraday Trans., 93(16), 2889–2891, 1997. Carlton, A. G., Turpin, B. J., Altieri, K. E., Reff, A., Seitzinger, S., Lim, H., and Ervens, B.: Atmospheric oxalic acid and SOA production from glyoxal: results of aqueous photooxidation experiments, Atmos. Environ., 41, 7588–7602, 2007. Chen, J., Griffin, R. J., Grini, A., and Tulet, P.: Modeling secondary organic aerosol formation through cloud processing of organic compounds, Atmos. Chem. Phys., 7, 5343–5355, doi:10.5194/acp-7-5343-2007, 2007. Christensen, H., Sehested, K., and Corfitzen, H.: Reactions of hydroxyl radicals with hydrogen peroxide at ambient and elevated temperatures, J. Phys. Chem., 86(9), 1588–1590, doi:10.1021/j100206a023, 1982. Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols, Science, 303, 1173–1176, 2004. Clegg, S. L. and Brimblecombe, P.: Thermodynamic model for the system H$^+$-NH$_4^+$-Na$^+$-SO$_4^2-$-NO$_3^-$-Cl$^-$-H<sub>2</sub>O at 298.15 K, J. Phys. Chem. A, 102, 2155–2171, 1998. Corrigan, A. L., Hanley, S. W., and De Haan, D. O.: Uptake of glyoxal by organic and inorganic aerosol, Environ. Sci. Technol., 42(12), 4428–4433, 2008. Creighton, D. J., Migliorini, M., Pourmotabbed, T., and Guha, M. K.: Optimization of efficieny in the glyoxylase pathway, Biochem., 27, 7376–7384, 1988. Davidovits, M., Hu, J. H., Worsnop, D. R., Zahniser, M. S., and Kolb, C. E.: Entry of Gas Molecules into Liquids, Faraday Discuss., 100, 65–82, 1995. Davidovits, P.: Mass accommodation and Chemical Reactions at Gas-Liquid Interfaces, Chem. Reviews, 2006. De Haan, D. O., Corrigan, A. L., Smith, K. W., Stroik, D. R., Turley, J. J., Lee, F. E., Tolbert, M. A., Jimenez, J. L., Cordova, K. E., and Ferrell, G. R.: Secondary organic aerosol-forming reactions of glyoxal with amino acids, Environ. Sci. Technol., 43(8), 2818–2824, 2009a. De Haan, D. O., Corrigan, A. L., Tolbert, M. A., Jimenez, J. L., Wood, S. E., and Turley, J. J.: Secondary Organic Aerosol Formation by Self-Reactions of Methylglyoxal and Glyoxal in Evaporating Droplets, Environ. Sci. Technol., 43(21), 8184–8190, 10.1021/es902152t, 2009b. De Haan, D. O., Tolbert, M. A., and Jimenez, J. L.: Atmospheric condensed phase reactions of glyoxal with methylamine, Geophys. Res. Lett., 36, L11819, doi:10.1029/2009GL037441, 2009c. Debus, H.: Ãœber die Einwirkung des Ammoniaks auf Glyoxal, Annalen der Chemie und Pharmacie, doi:10.1002/jlac.18581070209, 107, 199–208, 1858. DeGouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertram, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: results from the New England Air Quality Study in 2002, J. Geophys. Res., 110, D16305, doi:10.1029/2004JD005623, 2005. Denkenberger, K. A., Moffet, R. C., Holecek, J. C., Robetier, T. P., and Prather, K. A.: Real-time, single-particle measurements of oligomers in aged ambient aerosol particles, Environ. Sci. Technol., 41(15), 5439–5446, 2007. Dix, B., Barnard, J. C., and Volkamer, R.: Implications of the in-situ measured mass absorption cross section of organic aerosols in Mexico City on the atmospheric energy balance, satellite retrievals, and photochemistry, Proceedings of the International Radiation Symposium (IRS2008), Foz do Iguaçu, Brazil, 2008. Dzepina, K., Volkamer, R. M., Madronich, S., Tulet, P., Ulbrich, I. M., Zhang, Q., Cappa, C. D., Ziemann, P. J., and Jimenez, J. L.: Evaluation of recently-proposed secondary organic aerosol models for a case study in Mexico City, Atmos. Chem. Phys., 9, 5681–5709, doi:10.5194/acp-9-5681-2009, 2009. Elliot, A. J. and Buxton, G. V.: Temperature dependence of the reactions OH + O$_2^-$ and OH + HO$_2 $ in water up to 200 °C, J. Chem. Soc. Faraday Trans., 88, 2465–2470, 1992. Ervens, B., George, C., Williams, J. E., Buxton, G. V., Salmon, G. A., Bydder, M., Wilkinson, F., Dentener, F., Mirabel, P., Wolke, R., and Herrmann, H.: CAPRAM2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application, J. Geophys. Res., 108(D14), 4426, doi:10.1029/2002JD002202, 2003a. Ervens, B., Gligorovski, S., and Herrmann, H.: Temperature dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solution, Phys. Chem. Chem. Phys., 5, 1811–1824, 2003b. Ervens, B., Feingold, G., Frost, G. J., and Kreidenweis, S. M.: A modeling study of aqueous production of dicarboxylic acids, 1. Chemical pathways and speciated organic mass production, J. Geophys. Res., 109, D15205, doi:10.1029/2003JD004387, 2004a. Ervens, B., Feingold, G., Clegg, S. L., and Kreidenweis, S. M.: A modeling study of aqueous production of dicarboxylic acids, 2. Implications for cloud microphysics, J. Geophys. Res., 109, D15206, doi:10.1029/2004JD004575, 2004b. Ervens, B., Carlton, A. G., Turpin, B. J., Altieri, K. E., Kreidenweis, S. M., and Feingold, G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, L02816, doi:10.1029/2007GL031828, 2008. Ervens, B., Cubison, M. J., Andrews, E., Feingold, G., Ogren, J. A., Jimenez, J. L., Quinn, P. K., Bates, T. S., Wang, J., Zhang, Q., Coe, H., Flynn, M., and Allan, J. D.: CCN predictions using simplified assumptions of organic aerosol composition and mixing state: a synthesis from six different locations, Atmos. Chem. Phys., 10, 4795–4807, doi:10.5194/acp-10-4795-2010, 2010. Feingold, G. and Kreidenweis, S.: Does cloud processing of aerosol enhance droplet concentrations?, J. Geophys. Res., 105(D19), 24351–24361, 2000. Fratzke, A. R. and Reilly, P. J.: Thermodynamic and kinetic analysis of the dimerization of aqueous glyoxal, Int. J. Chem. Kinet., 18, 775–789, 1986. Fu, T., Jacob, D. J., Wittrock, F., Burrows, J. P., Vrekoussis, M., and Henze, D. K.: Global budgets of atmospheric glyoxal, methylglyoxal, and implications for formation of secondary organic aerosol, J. Geophys. Res., 113, D15303, doi:10.1029/2007JD009505, 2008. Fu, T., Jacob, D. J., and Heald, C. L.: Aqueous-phase reactive uptake of dicarbonyls as a source of organic aerosol over eastern North America, Atmos. Environ., 43, 1814–1822, 2009. Galloway, M. M., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Flagan, R. C., Seinfeld, J. H., and Keutsch, F. N.: Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions, Atmos. Chem. Phys., 9, 3331–3345, doi:10.5194/acp-9-3331-2009, 2009. Gao, S., Keywood, M., Ng, N. L., Surratt, J., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low-molecular-weight and oligomeric components in secondary organic aerosols from the ozonolysis of cycloalkenes and $\alpha $-pinene, J. Phys. Chem. A, 108(46), doi:10.1021/jp047466e, 2004. Gelencser, A.: Carbonaceous Aerosol, Atmospheric and Oceanographic Sciences Library, edited by: Mysak, L. A., and Hamilton, K., Springer, Dordrecht (NL), 350~pp., 2004. Gibb, S. W., Mantoura, R. F. C., and Liss, P. S.: Ocean-atmosphere exchange and atmospheric speciation of ammonia and methylamines in the region of the NW Arabian Sea, Global Biochem. Cy., 13(1), 161–178, 1999. Gomez-Gonzalez, Y., Surratt, J. D., Cuyckens, F., Szmigielski, R., Vermeylen, R., Jaoui, M., Lewandowski, M., Offenberg, J. H., Kleindienst, T. E., Edney, E. O., Blockhuys, F., VanAlsenoy, C., Maenhaut, W., and Claeys, M.: Characterization of organosulfates from the photooxidation of isoprene and unsaturated fatty acids in ambient aerosol using liquid chromatography/(−) electrospray ionization mass spectrometry, J. Mass. Spectrom., 43, 371–382, 2008. Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbon, J. Geophys. Res., 104, D3, 3555–3567, 1999. Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Development and initial evaluation of a dynamic species-resolved model for gas phase chemistry and size-resolved gas/particle partitioning associated with secondary organic aerosol formation, J. Geophys. Res., 110, D05304, doi:10.1029/2004JD005219, 2005. Hanson, D., Burkholder, J. B., Howard, C. J., and Ravishankara, A. R.: Measurement of OH and HO<sub>2</sub> Radical Uptake Coefficients on Water and Sulfuric Acid Surfaces, J. Phys. Chem., 96, 4979–4985, 1992. Hastings, W. P., Koehler, C. A., Bailey, E. L., and De Haan, D. O.: Secondary organic aerosol formation by glyoxal hydration and oligomer formation: humidity effects and equilibrium shifts during analysis, Environ. Sci. Technol., 39(22), 8728–8735, 2005. Hennigan, C. J., Bergin, M. H., Russell, A. G., Nenes, A., and Weber, R. J.: Gas/particle partitioning of water-soluble organic aerosol in Atlanta, Atmos. Chem. Phys., 9, 3613–3628, doi:10.5194/acp-9-3613-2009, 2009. Herrmann, H.: Kinetics of aqueous phase reactions relevant for atmospheric chemistry, Chem. Reviews, 103(12), 4691–4716, 2003. Hodzic, A., Jimenez, J. L., Madronich, S., Canagaratna, M. R., DeCarlo, P. F., Kleinman, L., and Fast, J.: Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation, Atmos. Chem. Phys., 10, 5491–5514, doi:10.5194/acp-10-5491-2010, 2010. Igawa, M., Munger, J. W., and Hoffmann, M. R.: Analysis of aldehydes in cloud- and fogwater samples by HPLC with a postcolumn reaction detector, Environ. Sci. Technol., 23, 556–561, 1989. Ip, H. S. S., Huang, X. H. H., and Yu, J. Z.: Effective Henry's law constants of glyoxal, glyoxylic acid and glycolic acid, Geophys. Res. Lett., 36, L01802, doi:10.1029/2008GL036212, 2009. Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken, A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L., Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y. L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara, P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J., Dunlea, E. J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P. I., Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A., Miyoshi, T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K., Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A. M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E., Baltensperger, U., and Worsnop, D. R.: Evolution of organic aerosols in the atmosphere, Science, 326, 5959, 1525–1529, doi:10.1126/science.1180353, 2009. Karpel vel Leitner, N. and Doré, M.: Mecanisme d'action des Radicaux OH sur les Acides glycolique, glyoxylique, acetique et oxalique en solution aqueouse: Incidence sur la consammation de peroxyde d'hydrogene dans les systeme H<sub>2</sub>O<sub>2</sub>/UV et O<sub>3</sub>/ H<sub>2</sub>O<sub>2</sub>, Wat. Res. , 6, 1383–1397, 1997. Kläning, U. K., Sehested, K., and Holcman, J.: Standard Gibbs energy of formation of the hydroxyl radical in aqueous solution. Rate constants for the reaction ClO$_2^-$ + O<sub>3</sub> = O$_3^-$ + ClO<sub>2</sub>, J. Phys. Chem., 89, 760–763, 1985. Kleinman, L. I., Springston, S. R., Wang, J., Daum, P. H., Lee, Y.-N., Nunnermacker, L. J., Senum, G. I., Weinstein-Lloyd, J., Alexander, M. L., Hubbe, J., Ortega, J., Zaveri, R. A., Canagaratna, M. R., and Jayne, J.: The time evolution of aerosol size distribution over the Mexico City plateau, Atmos. Chem. Phys., 9, 4261–4278, doi:10.5194/acp-9-4261-2009, 2009. Kroll, J. H., Ng, N. L., Murphy, S. M., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds, J. Geophys. Res., 110, D23207, doi:10.1029/2005JD006004, 2005. Kua, J., Hanley, S. W., and De Haan, D. O.: Thermodynamics and kinetics of glyoxal dimer formation: a computational study, J. Phys. Chem. A, 112(1), 66–72, 2008. Lide, D. R. (ed.): CRC Handbook of Chemistry and Physics, 89th ed., CRC Press/Taylor and Francis, Boca Raton, FL, 2009. Liggio, J., Li, S.-M., and McLaren, R.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res. , 110, D10304, doi:10.1029/2004JD005113, 2005a. Liggio, J., Li, S.-M., and McLaren, R.: Heterogeneous reactions of glyoxal on particulate matter: identification of acetals and sulfate esters, Environ. Sci. Technol., 39, 1532–1541, 2005b. Lim, H., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol in Atlanta: results from time-resolved measurements during the Atlanta supersite experiment, Environ. Sci. Technol., 39, 4441–4446, 2005. Lim, Y. B., Tan, Y., Perri, M. J., Seitzinger, S. P., and Turpin, B. J.: Aqueous chemistry and its role in secondary organic aerosol (SOA) formation, Atmos. Chem. Phys. Discuss., 10, 14161–14207, doi:10.5194/acpd-10-14161-2010, 2010. Limbeck, A. and Puxbaum, H.: Dependence of in-cloud scavenging of polar organic aerosol compounds on the water solubility, J. Geophys. Res., 105(D15), 19857–19867, 2000. Lind, J. A. and Kok, G. L.: Correction to "Henry's law Determinations for aqueous solutions of hydrogen peroxide, methylhydroperoxide and peroxyacetic acid" by John A. Lind and Gregory L. Kok, J. Geophys. Res. , 99, D10, 21119~pp., 1994. Loeffler, K. W., Koehler, C. A., Paul, N. M., and De Haan, D. O.: Oligomer formation in evaporating aqueous glyoxal and methylglyoxal solutions, Environ. Sci. Technol., 40(20), 6318–6323, 2006. Martin-Reviejo, M. and Wirtz, K.: Is benzene a precursor for secondary organic aerosol?, Environ. Sci. Technol., 39(4), 1045–1054, 2005. Matsunaga, S., Mochida, M., and Kawamura, K.: Variation of the atmospheric concentrations of biogenic carbonyl compounds and their removal processes in the northern forest at Moshiri, Hokkaido Island in Japan, J. Geophys. Res., 109, D04302, doi:10.1029/2003JD004100, 2004. Matsunaga, S. N., Kato, S., Yoshino, A., Greenberg, J. P., Kajii, Y., and Guenther, A. B.: Gas-aerosol partitioning of semi volatile carbonyls in polluted atmosphere in Hachioji, Tokyo, Geophys. Res. Lett., 32(11), L11805, doi:10.1029/2004gl021893, 2005. McElroy, W. J.: The interactions of gases with aqueous aerosol particles, Central Electr., Gen. Board, Part IV, 1997. Myriokefalitakis, S., Vrekoussis, M., Tsigaridis, K., Wittrock, F., Richter, A., Brühl, C., Volkamer, R., Burrows, J. P., and Kanakidou, M.: The influence of natural and anthropogenic secondary sources on the glyoxal global distribution, Atmos. Chem. Phys., 8, 4965–4981, doi:10.5194/acp-8-4965-2008, 2008. Neta, P., Huie, R. E., and Ross, A. B.: Rate constants for reactions of peroxyl radicals in fluid solutions, J. Phys. Chem. Ref. Data, 19(2), 413–513, 1990. Ng, N. L., Kroll, J. H., Chan, A. W. H., Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from m-xylene, toluene, and benzene, Atmos. Chem. Phys., 7, 3909–3922, doi:10.5194/acp-7-3909-2007, 2007. Ng, N. L., Canagaratna, M. R., Zhang, Q., Jimenez, J. L., Tian, J., Ulbrich, I. M., Kroll, J. H., Docherty, K. S., Chhabra, P. S., Bahreini, R., Murphy, S. M., Seinfeld, J. H., Hildebrandt, L., Donahue, N. M., DeCarlo, P. F., Lanz, V. A., Prévôt, A. S. H., Dinar, E., Rudich, Y., and Worsnop, D. R.: Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry, Atmos. Chem. Phys., 10, 4625–4641, doi:10.5194/acp-10-4625-2010, 2010. Noziere, B., Dziedzic, P., and Cordova, A.: Products and kinetics of the liquid-phase reaction of glyoxal catalysed by ammonium ions (NH$_4^+)$, J. Phys. Chem. A, 113, 231–237, 2009a. Nozière, B., Dziedzic, P., and Córdova, A.: Common inorganic ions are efficient catalysts for organic reactions in atmospheric aerosols and other natural environments, Atmos. Chem. Phys. Discuss., 9, 1–21, doi:10.5194/acpd-9-1-2009, 2009b. Nozière, B., Ekström, S., Alsberg, T., and Holmström, S.: Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols, Geophys. Res. Lett., 37(5), L05806, doi:10.1029/2009gl041683, 2010. Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, 1996. Pankow, J. F.: An absorption model of the gas/aerosol partitioning of organic compounds in the atmosphere, Atmos. Environ., 28(2), 185–188, 1994. Perri, M. J., Lim, Y. B., Seitzinger, S. P., and Turpin, B. J.: Organosulfates from glycolaldehyde in aqueous aerosols and clouds: laboratory studies, Atmos. Environ., 44(21–22), 2658–2664, 2010. Petters, M. D. and Kreidenweis, S. M.: A single parameter representation of hygroscopic growth and cloud condensation nucleus activity, Atmos. Chem. Phys., 7, 1961–1971, doi:10.5194/acp-7-1961-2007, 2007. Pun, B. K. and Seigneur, C.: Investigative modeling of new pathways for secondary organic aerosol formation, Atmos. Chem. Phys., 7, 2199–2216, doi:10.5194/acp-7-2199-2007, 2007. Ruiz-Montoya, M., and Rodriguez-Mellado, J. M.: Use of convolutive potential sweep voltammetry in the calculation of hydration equilibrium constants of $\alpha $-dicarbonyl compounds, J. Electroanal. Chem., 370, 183–187, 1994. Ruiz-Montoya, M. and Rodriguez-Mellado, J. M.: Hydration constants of carbonyl and dicarbonyl compounds comparison between electrochemcial and no electrochemcial techniques, Portugaliae Electrochim. Acta, 13, 299–303, 1995. Russell, L. M.: Aerosol organic-mass-to-organic-carbon ratio measurements, Environ. Sci. Technol., 37, 2982-2987, 2003. Sander, R.: Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry (Version 3), http://www.henrys-law.org (last access: April 2010), 1999. Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06–02, Jet Propulsion Laboratory, Pasadena, CA, USA, 2006. Schuchmann, M. N., Zegota, H., and von Sonntag, C.: Acetate peroxyl radicals O<sub>2</sub>CH<sub>2</sub>CO$_2^-$: A study on the radiolysis and pulse radiolysis of acetate in oxygenated aqueous solutions, Z. Naturforschung, 40B, 215–221, 1985. Schwartz, S.: Mass transport considerations pertinent to aqueous phase reactions of gases in liquid water clouds, in: chemistry of Multiphase Atmospheric Systems, edited by: Jaeschke, W., NATO ASI Series, Springer, Berlin, 415–471, 1986. Schweitzer, F., Magi, L., Mirabel, P., and George, C.: Uptake rate constants of methanesulfonic acid and glyoxal by aqueous droplets, J. Phys. Chem. A, 102, 593–600, 1998. Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics, John Wiley & Sons, New York, 1326~pp., 1998. Seinfeld, J. H. and Pankow, J. F.: Organic Atmospheric Particulate Matter, Ann. Rev. Phys. Chem., 54, 121–140, 2003. Shapiro, E. L., Szprengiel, J., Sareen, N., Jen, C. N., Giordano, M. R., and McNeill, V. F.: Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics, Atmos. Chem. Phys., 9, 2289–2300, doi:10.5194/acp-9-2289-2009, 2009. Sinreich, R., Coburn, S., Dix, B., and Volkamer, R.: Ship-based detection of glyoxal over the remote tropical Pacific Ocean, Atmos. Chem. Phys. Discuss., 10, 15075–15107, doi:10.5194/acpd-10-15075-2010, 2010. Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L.: Climate Change 2007 – The Physical Science Basis, Contribution of Working Group I to the Fourth Assessment Report of the IPCC, Intergovernmental Panel on Climate Change, Cambridge, United Kingdom and New York, NY, USA, 2007. Sorooshian, A., Brechtel, F. J., Ervens, B., Feingold, G., Varutbangkul, V., Bahreini, R., Murphy, S., Holloway, J. S., Atlas, E. L., Anlauf, K., Buzorius, G., Jonsson, H., Flagan, R. C., and Seinfeld, J. H.: Oxalic acid in clear and cloudy atmospheres: analysis of data from International Consortium for Atmospheric Research on Transport and Transformation 2004, J. Geophys. Res., 111(D23), D13201, doi:10.1029/2005JD006880, 2006. Sorooshian, A., Murphy, S. M., Hersey, S., Gates, H., Padro, L. T., Nenes, A., Brechtel, F. J., Jonsson, H., Flagan, R. C., and Seinfeld, J. H.: Comprehensive airborne characterization of aerosol from a major bovine source, Atmos. Chem. Phys., 8, 5489–5520, doi:10.5194/acp-8-5489-2008, 2008. Stavrakou, T., Müller, J.-F., De Smedt, I., Van Roozendael, M., Kanakidou, M., Vrekoussis, M., Wittrock, F., Richter, A., and Burrows, J. P.: The continental source of glyoxal estimated by the synergistic use of spaceborne measurements and inverse modelling, Atmos. Chem. Phys., 9, 8431–8446, doi:10.5194/acp-9-8431-2009, 2009. Surratt, J. D., Kroll, J. H., Kleindienst, T. E., Edney, E. O., Claeys, M., Sorooshian, A., Ng, N. L., Offenberg, J. H., Lewandowski, M., Jaoui, M., Flagan, R. C., and Seinfeld, J. H.: Evidence for organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007. Tan, Y., Perri, M. J., Seitzinger, S. P., and Turpin, B. J.: Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol, Environ. Sci. Technol., 43, 8105–8112, 2009. van Pinxteren, D., Plewka, A., Hofmann, D., Müller, K., Kramberger, H., Svrinca, B., Bächmann, K., Jaeschke, W., Mertes, S., J. L. Collett, and Herrmann, H.: Schmücke hill cap cloud and valley stations aerosol characterisation during FEBUKO (II): organic compounds, Atmos. Environ., 39, 4305–4320, 2005. Volkamer, R., Molina, L. T., and Molina, M. J.: DOAS measurement of glyoxal as an indicator for fast VOC chemistry in urban air, Geophys. Res. Lett., 32, L08806, doi:101029/102005GL022616, 2005. Volkamer, R., Jimenez, J. L., SanMartini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary organic aerosol formation from anthropogenic air pollution: rapid and higher than expected, Geophys. Res. Lett., 33, L17811, doi:10.1029/2006GL026899, 2006. Volkamer, R., SanMartini, F., Molina, L. T., Salcedo, D., Jimenez, J., and Molina, M. J.: A missing sink for gas-phase glyoxal in Mexiko City: formation of secondary organic aerosol, Geophys. Res. Lett., 34, L19807, doi:10.1029/2007GL030752, 2007. Volkamer, R., Ziemann, P. J., and Molina, M. J.: Secondary Organic Aerosol Formation from Acetylene (C<sub>2</sub>H$_2)$: seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase, Atmos. Chem. Phys., 9, 1907–1928, doi:10.5194/acp-9-1907-2009, 2009. Volkamer, R., Coburn, S. C., Dix, B. K., and Sinreich, R.: The Eastern Pacific Ocean is a source for short lived atmospheric gases: glyoxal and iodine oxide, CLIVAR Exchanges, 15(2), 30–33, 2010a. Volkamer, R., Sheehy, P., Molina, L. T., and Molina, M. J.: Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective, Atmos. Chem. Phys., 10, 6969–6991, doi:10.5194/acp-10-6969-2010, 2010b. von Sonntag, C. and Schuchmann, H.-P.: Aufklärung von Peroxylradikalreaktionen in wäßriger Lösung mit strahlenchemischen Techniken, Angew. Chem., 103, 1255–1279, 1991. Wang, L., Khalizov, A. F., Zheng, J., Xu, W., Ma, Y., Lal, V., and Zhang, R.: Atmospheric nanoparticles formed from heterogeneous reactions of organics, Nat. Geosci., 3, 238–242, 2010. Warneck, P.: In-cloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere, Atmos. Environ., 37, 2423–2427, 2003. Wasa, T. and Musha, S.: Polarographic behavior of glyoxal and its related compounds, Bull. Univ. Osaka Prefect. Set. A, 19, 169–180, 1970. Weinstein-Lloyd, J. and Schwartz, S. E.: Low-intensity radiolysis study of free-radical reactions in cloudwater: H<sub>2</sub>O<sub>2</sub> production and destruction, Environ. Sci. Technol., 25, 791–800, 1991. Zhou, X. and Mopper, K.: Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater; implications for air-sea exchange, Environ. Sci. Technol., 24(12), 1864–1869, 1990.