Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 1 2009 10.5194/acpd-9-59-2009 http://www.atmos-chem-phys-discuss.net/9/59/2009/ http://www.atmos-chem-phys-discuss.net/9/59/2009/acpd-9-59-2009.html http://www.atmos-chem-phys-discuss.net/9/59/2009/acpd-9-59-2009.pdf 59 80 2009-01-05 Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics E. L. Shapiro J. Szprengiel N. Sareen C. N. Jen M. R. Giordano V. F. McNeill vfm2103@columbia.edu Department of Chemical Engineering, Columbia University, NY, 10027, USA Light-absorbing and high-molecular-weight secondary organic products were observed to result from the reaction of glyoxal in mildly acidic (pH=4) aqueous inorganic salt solutions mimicking aqueous tropospheric aerosol particles. High-molecular-weight (500–600 amu) products were observed when ammonium sulfate ((NH₄)₂SO₄) or sodium chloride (NaCl) was present in the aqueous phase. The products formed in the (NH₄)₂SO₄ solutions absorb light at UV and visible wavelengths. Substantial absorption at 300–400 nm develops within two hours, and absorption between 400–600 nm develops within days. Pendant drop tensiometry measurements show that the products are not surface-active. The experimental results along with ab initio predictions of the UV/Vis absorption of potential products suggest that an aldol condensation mechanism is active in the glyoxal-(NH₄)₂SO₄system, resulting in the formation of pi-conjugated products. If similar products are formed in atmospheric aerosol particles, they could change the optical properties of the seed aerosol over its lifetime. Anastasiadis,~S H., Chen,~J K., Koberstein,~J T., Siegel,~A F., Sohn, J E., and Emerson,~J A.: The determination of interfacial tension by video image processing of pendant fluid drops, J. Colloid Interf. Sci., 119(1), 55–66, 1987. Badger,~C L., Griffiths,~P T., George,~I. , Abbatt,~J P D., and Cox,~R. A.: Reactive uptake of \chemN_2O_5 by aerosol particles containing mixtures of humic acid and ammonium sulfate, J. Phys. Chem. A, 110(21), 6986–6994, 2006. Baker,~J., Arey,~J., and Atkinson,~R.: Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene, Environ. Sci. Technol., 39(11), 4091–4099, 2005. Carlton,~A G., Turpin,~B J., Altieri,~K E., Seitzinger,~S., Reff,~A., Lim,~H J., and Ervens,~B.: Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments, Atmos. Environ., 41(35), 7588–7602, 2007. 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. Dorogan,~I V.: Theoretical methods of investigation of excited states of organic molecules, Russ J. Gen. Chem., 78(4), 774–783, 2008. 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(2), L02816, doi:10.1029/2007GL031828, 2008. 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.-Atmos., 109, D15205, doi:10.1029/2003JD004387, 2004. Facchini,~M C., Mircea,~M., Fuzzi,~S., and Charlson,~R J.: Cloud albedo enhancement by surface-active organic solutes in growing droplets, Nature, 401(6750), 257–259, 1999. Foresman,~J B., Head-Gordon,~M., Pople,~J A., and Frisch,~M J.: Toward a~systematic molecular orbital theory for excited states, J. Phys. Chem., 96, 135–149, 1992. Fridlind,~A M. and Jacobson,~M Z.: A~study of gas-aerosol equilibrium and aerosol pH in the remote marine boundary layer during the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res.-Atmos., 105(D13), 17325–17340, 2000. Fu,~T.-M., Jacob,~D J., Wittrock,~F., Burrows,~J P., Vrekoussis,~M., and Henze,~D K.: Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols, J. Geophys. Res.-Atmos., 113, D15303, doi:10.1029/2007JD009505, 2008. Gao,~S., Surratt,~J D., Knipping,~E M., Edgerton,~E S., Shahgholi,~M., and Seinfeld,~J H.: Characterization of polar organic components in fine aerosols in the southeastern United States: Identity, origin, and evolution, J. Geophys. Res.-Atmos., 111(D14), D14314, doi:10.1029/2005JD006601, 2006. 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., Van Alsenoy,~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(3), 371–382, 2008. Graber,~E R. and Rudich,~Y.: Atmospheric HULIS: How humic-like are they? A~comprehensive and critical review, Atmos. Chem. Phys., 6, 729–753, 2006. 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, 2005a. Heald,~C L., Jacob,~D J., Park,~R J., Russell,~L M., Huebert,~B J. , Seinfeld,~J H., Liao,~H., and Weber,~R J.: A~large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32(18), L18809, doi:10.1029/2005GL023831, 2005. Henze,~D K. and Seinfeld,~J H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976, 2006. Hoffer, A., Gelencsér, A., Guyon, P., Kiss, G., Schmid, O., Frank, G. P., Artaxo, P., and Andreae, M. O.: Optical properties of humic-like substances (HULIS) in biomass-burning aerosols, Atmos. Chem. Phys., 6, 3563–3570, 2006. Hudson,~B. and Kohler,~B.: Linear polyene electronic structure and spectroscopy, Ann. Rev. Phys. Chem., 25, 437–460, 1974. Jang,~M S. and Kamens,~R M.: Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a~sulfuric acid aerosol catalyst, Environ. Sci. Technol., 35(24), 4758–4766, 2001. Kalberer,~M., Paulsen,~D., Sax,~M., Steinbacher,~M., Dommen,~J., Prevot,~A. S H., Fisseha,~R., Weingartner,~E., Frankevich,~V., Zenobi,~R., and Baltensperger,~U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303(5664), 1659–1662, 2004. Karas,~M., Ehring,~H., Nordhoff,~E., Stahl,~B., Strupat,~K., Hillenkamp,~F., Grehl,~M., and Krebs,~B. Matrix-assisted laser-desorption ionization mass-spectrometry with additives to 2,5-dihydroxybenzoic acid, Org. Mass Spectrom., 28(12), 1476–1481, 1993. Keene,~W C., Sander,~R., Pszenny,~A A P., Vogt,~R., Crutzen,~P J., and Galloway,~J N.: Aerosol pH in the marine boundary layer: a~review and model evaluation, J. Aerosol Sci., 29(3), 339–356, 1998. Keene,~W C. and Savoie,~D L.: The pH of deliquesced sea-salt aerosol in polluted marine air, Geophys. Res. Lett., 25(12), 2181–2184, 1998. Keene,~W C., Pszenny,~A A P., Maben,~J R., and Sander,~R.: Variation of marine aerosol acidity with particle size, Geophys. Res. Lett., 29(7), 1101, doi:10.1029/2001GL013881, 2002. Keene,~W C., Pszenny,~A A P., Maben,~J R., Stevenson,~E., and Wall,~A.: Closure evaluation of size-resolved aerosol pH in the New England coastal atmosphere during summer, J. Geophys. Res.-Atmos., 109, D23202, doi:10.1029/2004JD004801, 2004. Kendall,~R A., Dunning,~T H., and Harrison,~R J.: Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions., J. Chem. Phys., 96(9), 6796–6806, 1992. Kiss,~G., Tombacz,~E., and Hansson,~H C.: Surface tension effects of humic-like substances in the aqueous extract of tropospheric fine aerosol, J. Atmos. Chem., 50(3), 279–294, 2005. Kroll,~J H., Ng,~N L., Murphy,~S M., Flagan,~R C., and Seinfeld,~J H.: Secondary organic aerosol formation from isoprene photoxidation, Environ. Sci. Technol., 40, 1869–1877, 2006. 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.-Atmos., 110(D23), 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. Liggio,~J., Li,~S M., and McLaren,~R.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res.-Atmos., 110(D10), 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(6), 1532–1541, 2005b. Loeffler,~K W., Koehler,~C A., Paul,~N M., and De Haan,~D O.: Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions, Environ. Sci. Technol., 40(20), 6318–6323, 2006. Malik,~M. and Joens,~J A.: Temperature dependent near-UV molar absorptivities of glyoxal and gluteraldehyde in aqueous solution, Spectrochim. Acta A, 56(14), 2653–2658, 2000. McNeill, V. F., Patterson, J., Wolfe, G. M., and Thornton, J. A.: The effect of varying levels of surfactant on the reactive uptake of N₂O$_5$ to aqueous aerosol, Atmos. Chem. Phys., 6, 1635–1644, 2006. Müller, L., Reinnig, M.-C., Warnke, J., and Hoffmann, Th.: Unambiguous identification of esters as oligomers in secondary organic aerosol formed from cyclohexene and cyclohexene/α-pinene ozonolysis, Atmos. Chem. Phys., 8, 1423–1433, 2008. Noziere,~B., Dziedzic,~P., and Cordova,~A.: Formation of secondary light-absorbing \qutfulvic-like oligomers: A~common process in aqueous and ionic atmospheric particles?, Geophys. Res. Lett., 34(21), L21812, doi:10.1029/2007GL031300, 2007. Noziere,~B. and Esteve,~W.: Light-absorbing aldol condensation products in acidic aerosols: Spectra, kinetics, and contribution to the absorption index, Atmos. Environ., 41(6), 1150–1163, 2007. Peltier,~R E., Sullivan,~A P., Weber,~R J., Wollny,~A G., Holloway,~J. S., Brock,~C A., deGouw,~J. A., and Atlas,~E L.: No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia, Geophys. Res. Lett., 34, L06801, doi:10.1029/2006GL028780, 2007. Pszenny, A. A. P., Moldanová, J., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P. J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian marine boundary layer, Atmos. Chem. Phys., 4, 147–168, 2004. Salma,~I., Ocskay,~R., Varga,~I., and Maenhaut,~W.: Surface tension of atmospheric humic-like substances in connection with relaxation, dilution, and solution pH, J. Geophys. Res.-Atmos., 111(D23), D23205, doi:10.1029/2005JD007015, 2006. Setschenow,~J Z.: Über die Konstitution der Salzlösungen auf Grund ihres Verhaltens zu Kohlensäure, Z. Physik. Chem., 4, 117–125, 1889. 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(2), 517–527, 2007. Tabazadeh,~A.: Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles, Atmos. Environ., 39(30), 5472–5480, 2005. Tang,~I N.: Thermodynamic and optical properties of mixed-salt aerosols of atmospheric importance, J. Geophys. Res.-Atmos., 102(D2), 1883–1893, 1997. Tang,~I N. and Munkelwitz,~H R.: Water activities, densities, and refractive-indexes of aqueous sulfates and sodium-nitrate droplets of atmospheric importance, J. Geophys. Res.-Atmos., 99(D9), 18801–18808, 1994. Tang,~I N., Tridico,~A C., and Fung,~K H.: Thermodynamic and optical properties of sea salt aerosols, J. Geophys. Res.-Atmos., 102(D19), 23269–23275, 1997. Tong,~C H., Blanco,~M., Goddard,~W A., and Seinfeld,~J H.: Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: A~quantum mechanical study, Environ. Sci. Technol., 40(7), 2333–2338, 2006. Tuazon,~E C., Atkinson,~R., Macleod,~H., Biermann,~H W., Winer,~A M., Carter,~W P L., and Pitts,~J N.: Yields of Glyoxal and Methylglyoxal from the Nox-Air Photooxidations of Toluene and M-Xylene and P-Xylene, Environ. Sci. Technol., 18(12), 981–984, 1984. Tuazon,~E C., Macleod,~H., Atkinson,~R., and Carter,~W P L.: Alpha-dicarbonyl yields from the nox-air photooxidations of a~series of aromatic-hydrocarbons in air, Environ. Sci. Technol., 20(4), 383–387, 1986. Tuazon,~E C., Aschmann,~S M., Nishino,~N., Arey,~J., and Atkinson,~R.: Kinetics and products of the OH radical-initiated reaction of 3-methyl-2-butenal, Phys. Chem. Chem. Phys., 7(11), 2298–2304, 2005. Volkamer,~R., Platt,~U., and Wirtz,~K.: Primary and secondary glyoxal formation from aromatics: experimental evidence for the bicycloalkyl-radical pathway from benzene, toluene, and p-xylene, J. Phys. Chem. A, 105(33), 7865–7874, 2001. Volkamer,~R., Molina,~L T., Molina,~M J., Shirley,~T., and Brune,~W H.: DOAS measurement of glyoxal as an indicator for fast VOC chemistry in urban air, Geophys. Res. Lett., 32(8), L08806, doi:10.1029/2005GL022616, 2005. Volkamer,~R., Jimenez,~J L., San Martini,~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(17), L17811, doi:10.1029/2006GL026899, 2006. Volkamer,~R., San Martini,~F., Molina,~L T., Salcedo,~D., Jimenez,~J L., and Molina,~M J.: A~missing sink for gas-phase glyoxal in Mexico 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 (C₂H₂): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase, Atmos. Chem. Phys. Discuss., 8, 14841–14892, 2008.