ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-4085-2010 Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments Baduel C. 1 Voisin D. 1 Jaffrezo J.-L. 1 Université Joseph Fourier – Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, rue Molière, 38402 Saint-Martin-d'Hères, France 03 05 2010 10 9 4085 4095 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/10/4085/2010/acp-10-4085-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/4085/2010/acp-10-4085-2010.pdf

Major contributors to the organic aerosol include water-soluble macromolecular compounds (e.g. HULIS<sub>WS</sub>: Water Soluble Humic LIke Substances). The nature and sources of HULIS<sub>WS</sub> are still largely unknown. This work is based on a monitoring in six different French cities performed during summer and winter seasons. HULIS<sub>WS</sub> analysis was performed with a selective method of extraction complemented by carbon quantification. UV spectroscopy was also applied for their chemical characterisation. HULIS<sub>WS</sub> carbon represent an important contribution to the organic aerosol mass in summer and winter, as it accounts for 12–22% of Organic Carbon and 34–40% of Water Soluble Organic Carbon. We found strong differences in the optical properties (specific absorbance at 250, 272, 280 nm and E2/E3 ratio) and therefore in the chemical structure between HULIS<sub>WS</sub> from samples of summer- and wintertime. These differences highlight different processes responsible for emissions and formation of HULIS<sub>WS</sub> according to the season, namely biomass burning in winter, and secondary processes in summer. Specific absorbance can also be considered as a rapid and useful indicator of the origin of HULIS<sub>WS</sub> in urban environment.

 References % vor jede Referenz Asa-Awuku, A., Sullivan, A. P., Hennigan, C. J., Weber, R. J., and Nenes, A.: Investigation of molar volume and surfactant characteristics of water-soluble organic compounds in biomass burning aerosol, Atmos. Chem. Phys., 8, 799–812, 2008. Aymoz, G., Jaffrezo, J. L., Chapuis, D., Cozic, J., and Maenhaut, W.: Seasonal variation of PM$_10 $ main constituents in two valleys of the French Alps. I: EC/OC fractions, Atmos. Chem. Phys., 7, 661–675, 2007. Baduel, C., Voisin, D., and Jaffrezo, J. L.: Comparison of analytical methods for Humic Like Substances (HULIS) measurements in atmospheric particles, Atmos. Chem. Phys., 9, 5949–5962, 2009. 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, 2005. Cavalli, F., Viana, M., Yttri, K. E., Genberg, J., and Putaud, J.-P.: Toward a standardised thermal-optical protocol for measuring atmospheric organic and elemental carbon: the EUSAAR protocol, Atmos. Meas. Tech., 3, 79–89, 2010. Chin, Y., Aiken, G., and O'Loughlin, E.: Molecular Weight, Polydispersity, and Spectroscopic Properties of Aquatic Humic Substances, Environ. Sci. Technol., 28(11), 1853–1858, doi:10.1021/es00060a015, 1994. Decesari, S., Facchini, M. C., Matta, E., Lettini, F., Mircea, M., Fuzzi, S., Tagliavini, E., and Putaud, J. -P.: Chemical features and seasonal variation of fine aerosol water-soluble organic compounds in the Po Valley, Italy, Atmos. Environ., 35(21), 3691–3699, doi:10.1016/S1352-2310(00)00509-4, 2001. Decesari, S., Facchini, M. C., Matta, E., Mircea, M., Fuzzi, S., Chughtai, A. R., and Smith, D. M.: Water soluble organic compounds formed by oxidation of soot, Atmos. Environ., 36(11), 1827–1832, doi:10.1016/S1352-2310(02)00141-3, 2002. Decesari, S., Mircea, M., Cavalli, F., Fuzzi, S., Moretti, F., Tagliavini, E., and Facchini, M. C.: Source Attribution of Water-Soluble Organic Aerosol by Nuclear Magnetic Resonance Spectroscopy, Environ. Sci. Technol., 41(7), 2479–2484, doi:10.1021/es061711l, 2007. Dinar, E., Riziq, A. A., Spindler, C., Erlick, C., Kiss, G., and Rudich, Y.: The complex refractive index of atmospheric and model humic-like substances (HULIS) retrieved by a cavity ring down aerosol spectrometer (CRD-AS), Faraday Discuss., 137, 279–295, 2008. Dinar, E., Taraniuk, I., Graber, E. R., Katsman, S., Moise, T., Anttila, T., Mentel, T. F., and Rudich, Y.: Cloud Condensation Nuclei properties of model and atmospheric HULIS, Atmos. Chem. Phys., 6, 2465–2482, 2006. Duarte, R. M., Pio, C. A., and Duarte, A. C.: Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions, Anal. Chim. Acta, 530(1), 7–14, 2005. Duarte, R. M. B. O., Silva, A. M. S., and Duarte, A. C.: Two-Dimensional NMR Studies of Water-Soluble Organic Matter in Atmospheric Aerosols, Environ. Sci. Technol., 42(22), 8224–8230, doi:10.1021/es801298s, 2008. Duarte, R. M., Santos, E. B., Pio, C. A., and Duarte, A. C.: Comparison of structural features of water-soluble organic matter from atmospheric aerosols with those of aquatic humic substances, Atmos. Environ., 41(37), 8100–8113, doi:10.1016/j.atmosenv.2007.06.034, 2007. El Haddad, I., Marchand, N., Dron, J., Temime-Roussel, B., Quivet, E., Wortham, H., Jaffrezo, J. L., Baduel, C., Voisin, D., Besombes, J. L., and Gille, G.: Comprehensive primary particulate organic characterization of vehicular exhaust emissions in France, Atmos. Environ., 43(39), 6190–6198, doi:10.1016/j.atmosenv.2009.09.001, 2009. Feczko, T., Puxbaum, H., Kasper-Giebl, A., Handler, M., Limbeck, A., Gelencsér, A., Pio, C., Preunkert, S., and Legrand, M.: Determination of water and alkaline extractable atmospheric humic-like substances with the TU Vienna HULIS analyzer in samples from six background sites in Europe, J. Geophys. Res., 112(D23), D23S10, doi:10.1029/2006JD008331, 2007. Gelencsér, A., Hoffer, A., Kiss, G., Tombácz, E., Kurdi, R., and Bencze, L.: In-situ Formation of Light-Absorbing Organic Matter in Cloud Water, J. Atmos. Chem., 45(1), 25–33, doi:10.1023/A:1024060428172, 2003. 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. Graham, B., Mayol-Bracero, O., Guyon, P., Roberts, G., Decesari, S., Facchini, M. C., Artaxo, P., Maenhaut, W., Köll, P., and Andreae, M.: Water-soluble organic compounds in biomass burning aerosols over Amazonia1. Characterization by NMR and GC-MS, J. Geophys. Res., 107(D20), 8047, doi:10.1029/2001JD000336, 2002. Gross, D. S., Galli, M. E., Kalberer, M., Prevot, A. S. H., Dommen, J., Alfarra, M. R., Duplissy, J., Gaeggeler, K., Gascho, A., Metzger, A., and Baltensperger, U.: Real-Time Measurement of Oligomeric Species in Secondary Organic Aerosol with the Aerosol Time-of-Flight Mass Spectrometer, Anal. Chem., 78(7), 2130–2137, doi:10.1021/ac060138l, 2006. Guzman, M. I., Colussi, A. J., and Hoffmann, M. R.: Photoinduced Oligomerization of Aqueous Pyruvic Acid, J. Phys. Chem. A, 110(10), 3619–3626, doi:10.1021/jp056097z, 2006. Hatch, C., Gierlus, K., Schuttlefield, J., and Grassian, V.: Water adsorption and cloud condensation nuclei activity of calcite and calcite coated with model humic and fulvic acids, Atmos. Environ., 42(22), 5672–5684, doi:10.1016/j.atmosenv.2008.03.005, 2008. Hautala, K., Peuravuori, J., and Pihlaja, K.: Measurement of aquatic humus content by spectroscopic analyses, Water Research, 34(1), 246–258, doi:10.1016/S0043-1354(99)00137-2, 2000. Hoffer, A., Kiss, G., Blazso, M., and Gelencsér, A.: Chemical characterization of humic-like substances (HULIS) formed from a lignin-type precursor in model cloud water, Geophys. Res. Lett., 31(6), L06115, doi:10.1029/2003GL018962, 2004. Jammoul, A., Gligorovski, S., George, C., and D'Anna, B.: Photosensitized Heterogeneous Chemistry of Ozone on Organic Films, J. Phys. Chem. A, 112(6), 1268–1276, doi:10.1021/jp074348t, 2008. Kiss, G., Varga, B., Galambos, I., and Ganszky, I.: Characterization of water-soluble organic matter isolated from atmospheric fine aerosol, J. Geophys. Res., 107(D21), 8339, doi:10.1029/2001JD000603, 2002. Krivácsy, Z., Kiss, G., Ceburnis, D., Jennings, G., Maenhaut, W., Salma, I., and Shooter, D.: Study of water-soluble atmospheric humic matter in urban and marine environments, Atmos. Res., 87(1), 1–12, doi:10.1016/j.atmosres.2007.04.005, 2008. Legrand, M., Preunkert, S., Oliveira, T., Pio, C. A., Hammer, S., Gelencsér, A., Kasper-Giebl, A., and Laj, P.: Origin of C2-C5 dicarboxylic acids in the European atmosphere inferred from year-round aerosol study conducted at a west-east transect, J. Geophys. Res., 112, D23S07 doi:10.1029/2006JD008019, 2007. Li, A., Hu, J., Li, W., Zhang, W., and Wang, X.: Polarity based fractionation of fulvic acids, Chemosphere, 77(10), 1419–1426, doi:10.1016/j.chemosphere.2009.09.002, 2009. Limbeck, A., Handler, M., Neuberger, B., Klatzer, B., and Puxbaum, H.: Carbon-Specific Analysis of Humic-like Substances in Atmospheric Aerosol and Precipitation Samples, Anal. Chem., 77(22), 7288–7293, doi:10.1021/ac050953l, 2005. Limbeck, A., Kulmala, M., and Puxbaum, H.: Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett., 30(19), 1996, doi:10.1029/2003GL017738, 2003. Marchand, N., Besombes, J. L., Chevron, N., Masclet, P., Aymoz, G., and Jaffrezo, J. L.: Polycyclic aromatic hydrocarbons (PAHs) in the atmospheres of two French alpine valleys: sources and temporal patterns, Atmos. Chem. Phys., 4, 1167–1181, 2004. Mayol-Bracero, O. L., Guyon, P., Graham, B., Roberts, G., Andreae, M., Decesari, S., Fuzzi, S., and Artaxo, P.: Water-soluble organic compounds in biomass burning aerosols over Amazonia 2. Apportionment of the chemical composition and importance of the polyacidic fraction, J. Geophys. Res., 107(D20), 8091, doi:10.1029/2001JD000522, 2002. Moretti, F., Tagliavini, E., Decesari, S., Facchini, M. C., Rinaldi, M., and Fuzzi, S.: NMR Determination of Total Carbonyls and Carboxyls: A Tool for Tracing the Evolution of Atmospheric Oxidized Organic Aerosols, Environ. Sci. Technol., 42(13), 4844–4849, doi:10.1021/es703166v, 2008. Peuravuori, J. and Pihlaja, K.: Molecular size distribution and spectroscopic properties of aquatic humic substances, Anal. Chim. Acta, 337(2), 133–149, doi:10.1016/S0003-2670(96)00412-6, 1997. Pio, C., Legrand, M., Alves, C., Oliveira, T., Afonso, J., Caseiro, A., Puxbaum, H., Sanchez-Ochoa, A., and Gelencsér, A.: Chemical composition of atmospheric aerosols during the 2003 summer intense forest fire period, Atmos. Environ., 42(32), 7530–7543, doi:10.1016/j.atmosenv.2008.05.032, 2008. Pissot, N., Besombes, J. L., Jaffrezo, J. L., Voisin, D., and Baduel, C.: Wood smoke impact on the ambient air quality of four large French cities using levoglucosan as principal biomass burning tracer, Atmos. Environ., in preparation, 2010. Puxbaum, H., Caseiro, A., Sánchez-Ochoa, A., Kasper-Giebl, A., Claeys, M., Gelencsér, A., Legrand, M., Preunkert, S. and Pio, C.: Levoglucosan levels at background sites in Europe for assessing the impact of biomass combustion on the European aerosol background, J. Geophys. Res., 112, D23S05, doi:10.1029/2006JD008114, 2007. Ricard, V., Jaffrezo, J. -L., Kerminen, V., Hillamo, R. E. J., Sillanpaa, M., Ruellan, S., Liousse, C., and Cachier, H.: Two years of continuous aerosol measurements in northern Finland, J. Geophys. Res., 107(D11), 4129, doi:10.1029/2001JD000952, 2002. Salma, I., Ocskay, R., and Láng, G. G.: Properties of atmospheric humic-like substances – water system, Atmos. Chem. Phys., 8, 2243–2254, 2008. Salma, I., Ocskay, R., Chi, X., and Maenhaut, W.: Sampling artefacts, concentration and chemical composition of fine water-soluble organic carbon and humic-like substances in a continental urban atmospheric environment, Atmos. Environ., 41(19), 4106–4118, doi:10.1016/j.atmosenv.2007.01.027, 2007. Samburova, V., Zenobi, R., and Kalberer, M.: Characterization of high molecular weight compounds in urban atmospheric particles, Atmos. Chem. Phys., 5, 2163–2170, 2005. Sannigrahi, P., Sullivan, A. P., Weber, R. J., and Ingall, E. D.: Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state 13C NMR spectroscopy, Environ. Sci. Technol., 40(3), 666–672, 2006. Sullivan, A. P. and Weber, R. J.: Chemical characterization of the ambient organic aerosol soluble in water: 1. Isolation of hydrophobic and hydrophilic fractions with a XAD-8 resin, J. Geophys. Res., 111(9), D05314, doi:10.1029/2005JD006485, 2006. Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R. C., et al.: Chemical Composition of Secondary Organic Aerosol Formed from the Photooxidation of Isoprene, J. Phys. Chem. A, 110(31), 9665–9690, doi:10.1021/jp061734m, 2006. Szidat, S., Ruff, M., Perron, N., Wacker, L., Synal, H.-A., Hallquist, M., Shannigrahi, A. S., Yttri, K. E., Dye, C., and Simpson, D.: Fossil and non-fossil sources of organic carbon (OC) and elemental carbon (EC) in Göteborg, Sweden, Atmos. Chem. Phys., 9, 1521–1535, 2009. Szidat, S., Jenk, T. M., Synal, H., Kalberer, M., Wacker, L., Hajdas, I., Kasper-Giebl, A., and Baltensperger, U.: Contributions of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by 14C, J. Geophys. Res., 111(D7), D07206, doi:10.1029/2005JD006590, 2006. Tagliavini, E., Moretti, F., Decesari, S., Facchini, M. C., Fuzzi, S., and Maenhaut, W.: Functional group analysis by H NMR/chemical derivatization for the characterization of organic aerosol from the SMOCC field campaign, Atmos. Chem. Phys., 6, 1003–1019, 2006. Tolocka, M. P., Jang, M., Ginter, J. M., Cox, F. J., Kamens, R. M., and Johnston, M. V.: Formation of Oligomers in Secondary Organic Aerosol, Environ. Sci. Technol., 38(5), 1428–1434, doi:10.1021/es035030r, 2004. Traina, S., Novak, J., and Smeck, N.: An Ultraviolet Absorbance Method of Estimating the Percent Aromatic Carbon Content of Humic Acids, J. Environ. Qual., 19(1), 151–153, 1990. Vione, D., Maurino, V., Minero, C., Pelizzetti, E., Harrison, M. A. J., Olariu, R., and Arsene, C.: Photochemical reactions in the tropospheric aqueous phase and on particulate matter, Chem. Soc. Rev., 35(5), 441–453, 2006. Wyche, K. P., Monks, P. S., Ellis, A. M., Cordell, R. L., Parker, A. E., Whyte, C., Metzger, A., Dommen, J., Duplissy, J., Prevot, A. S. H., Baltensperger, U., Rickard, A. R., and Wulfert, F.: Gas phase precursors to anthropogenic secondary organic aerosol: detailed observations of 1,3,5-trimethylbenzene photooxidation, Atmos. Chem. Phys., 9, 635–665, 2009.