Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 10 2009 10.5194/acp-9-3317-2009 http://www.atmos-chem-phys.net/9/3317/2009/ http://www.atmos-chem-phys.net/9/3317/2009/acp-9-3317-2009.html http://www.atmos-chem-phys.net/9/3317/2009/acp-9-3317-2009.pdf 3317 3330 2009-05-25 Applying the Condensation Particle Counter Battery (CPCB) to study the water-affinity of freshly-formed 2–9 nm particles in boreal forest I. Riipinen ilona.riipinen@helsinki.fi H. E. Manninen T. Yli-Juuti M. Boy M. Sipilä M. Ehn H. Junninen T. Petäjä M. Kulmala Department of Physics, University of Helsinki, Helsinki, Finland Helsinki Institute of Physics, University of Helsinki, Helsinki, Finland Measurements on the composition of nanometer-sized atmospheric particles are the key to understand which vapors participate in the secondary aerosol formation processes. Knowledge on these processes is crucial in assessing the climatic effects of secondary aerosol formation. We present data of >2 nm particle concentrations and their water-affinity measured with the Condensation Particle Counter Battery (CPCB) at a boreal forest site in Hyytiälä, Finland, during spring 2006. The data reveal that during new particle formation events, the smallest particles activate for growth at clearly smaller sizes in water than in butanol vapor. However, even at 2–4 nm, there are days when the particles seem to be less hygroscopic than ammonium sulfate or sulfuric acid, which are often referred to as the most likely compounds present in atmospheric nucleation. This observation points to the possible presence of water-soluble organics, even at the very first steps on particle formation. The water-affinity of the particles decreases with size, indicating that the vapors that participate in the first steps of the particle formation and growth are more hygroscopic than the vapors contributing to the later stages of the growth. This suggests that the relative role of less hygroscopic organics in atmospheric particle growth increases as a function of particle size. Aalto, P. P., Hämeri, K., Becker, E., Weber, R., Salm, J., Mäkelä, J. M., Hoell, C., O'Dowd, C. D., Karlsson, H., Hansson, H.- C., Väkevä, M., Koponen, I. K., Buzorius, G., and Kulmala, M.: Physical characterization of aerosol particles during nucleation events, Tellus B, 53, 344–348, 2001. Allan, J. D., Alfarra, M. R., Bower, K. N., Coe, H., Jayne, J. T., Worsnop, D. R., Aalto, P. P., Kulmala, M., Hyötyläinen, T., Cavalli, F., and Laaksonen, A.: Size and composition measurements of background aerosol and new particle growth in a Finnish forest during QUEST 2 using an Aerodyne Aerosol Mass Spectrometer, Atmos. Chem. Phys., 6, 315–327, 2006. Asmi, E., Sipilä, M., Manninen, H. E., Vanhanen, J., Lehtipalo, K., Gagné, S., Neitola, K., Mirme, A., Mirme, S., Tamm, E., Uin, J., Komsaare, K., Attoui, M., and Kulmala, M.: Results of the first air ion spectrometer calibration and intercomparison workshop, Atmos. Chem. Phys., 9, 141–154, 2009. Berndt, T., Böge, O., Stratmann, F., Heitzenberg, J., and Kulmala, M.: Rapid formation of sulfuric acid particles at near-atmospheric conditions, Science, 307, 697–700, 2005. Birmili, W., Berresheim, H., Plass-Dülmer, C., Elste, T., Gilge, S., Wiedensohler, A., and Uhrner, U.: The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved aerosol, H₂SO₄, OH, and monoterpenes measurements, Atmos. Chem. Phys., 3, 361–376, 2003. Boy, M., Kulmala, M., Ruuskanen, T. M., Pihlatie, M., Reissell, A., Aalto, P. P., Keronen, P., Dal Maso, M., Hellén, H., Hakola, H., Jansson, R., Hanke, M., and Arnold, F.: Sulfuric acid closure and contribution to nucleation mode particle growth, Atmos. Chem. Phys., 5, 863–878, 2005. Dal Maso, M., Kulmala, M., Riipinen, I., Wagner, R., Hussein, T., Aalto, P. P., and Lehtinen, K. E. J.: Formation and growth of fresh atmospheric aerosols: eight years of aerosol size distribution data from SMEAR II, Hyytiälä, Finland, Boreal Environ. Res., 10, 323–336, 2005. Ehn, M., Petäjä, T., Afmhoff, H., Aalto, P. P., Hämeri, K., Arnold, F., Laaksonen, A., and Kulmala, M.: Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid, Atmos. Chem. Phys., 7, 211–222, 2007a. Ehn, M., Petäjä, T., Birmili, W., Junninen, H., Aalto, P., and Kulmala, M.: Non-volatile residuals of newly formed atmospheric particles in the boreal forest, Atmos. Chem. Phys., 7, 677–684, 2007b. Fiedler, V., Dal Maso, M., Boy, M., Aufmhoff, H., Schuck, T., Birmili, W., Hanke, M., Uecker, J., Arnold, F., and Kulmala, M.: The contribution of sulfuric acid to atmospheric particle formation and growth: a comparison between boundary layers in Northern and Central Europe, Atmos. Chem. Phys., 5, 1773–1785, 2005. Fuchs, N. A. and Sutugin, A. G.: Highly Dispersed Aerosols, London, Ann Arbor Science Publishers, 1–60, 1970. Hanson, D. R. and Eisele, F. L.: Measurement of prenucleation molecular clusters in the NH₃, H₂SO₄, H₂O system, J. Geophys. Res., 107, 4158–4166, 2002. Hari, P. and Kulmala, M.: Station for Measuring Ecosystem–Atmosphere Relations (SMEAR II), Boreal Environ. Res., 10, 315–322, 2005. Hering, S. V., Stoltzenburg, M. R., Quant, F. R., Oberreit, D. R., and Keady, P. B.: A laminar-flow, water-based condensation particle counter (WCPC), Aerosol Sci. Technol., 39, 659–672, 2005. Hirsikko, A., Laakso, L., Hõrrak, U., Aalto, P. P., Kerminen, V.-M., and Kulmala, M.: Annual and size dependent variation of growth rates and ion concentrations in boreal forest, Boreal Environ. Res., 10, 357–369, 2005. Hoppel, W. A., Frick, G. M., Fitzgerald, J. W., and Larson, R. E.: Marine boundary layer measurements of new particle formation and the effects nonprecipitating clouds have on aerosol size distribution, J. Geophys. Res., 99, 14443–14460, 1994. Hussein, T., Junninen, H., Tunved, P., Kristensson, A., Dal Maso, M., Riipinen, I., Aalto, P. P., Hansson, H.-C., Swietlicki, E., and Kulmala, M.: Time-span and spatial-scale of regional new particle formation events over Finland and Southern Sweden, Atmos. Chem. Phys. Discuss., 9, 135–173, 2009. Hämeri, K., Väkevä, M., Hansson, H.-C., and Laaksonen, A.: Hygroscopic growth of ultrafine ammonium sulfate aerosol measured using a ultrafine tandem differential mobility analyzer, J. Geophys. Res., 105, 22231–22242, 2001. IPCC (Intergovernmental Panel on Climate Change). Climate Change 2007: The Physical Science Basis. Summary for Policymakers; IPCC Secretariat: Geneva, Switzerland, http://www.ipcc.ch/ipccreports/assessments-reports.htm last accessed: 14 April 2009, 2007. Jang, M., Czoschke, N. M., Lee, S., Kamens, R. M.: Identification of Polymers as Major Components of Atmospheric Organic Aerosols, Science, 298, 814–817, 2002. Jokinen, V. and Mäkelä, J. M.: Closed loop arrangement with critical orifices for DMA sheath/excess flow system, J. Aerosol Sci., 28, 643–648, 1997. Kalberer, M., Paulse, D., Sax, M., Steinbecher. M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingertner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric aerosols, Science, 303, 1659–1662, 2004. Kulmala, M.: How particles nucleate and grow, Science, 302, 1000–1001, 2003. Kulmala, M., Vehkamäki, H., Petäjä, T., Dal Maso, M., Lauri, A., Kerminen, V.-M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine atmospheric particles: A review of observations, J. Aerosol Sci., 35, 143–176, 2004a. Kulmala, M., Laakso, L., Lehtinen, K. E. J., Riipinen, I., Dal Maso, M., Anttila, T., Kerminen, V.-M., Hõrrak, U., Vana, M., and Tammet, H.: Initial steps of aerosol growth, Atmos. Chem. Phys., 4, 2553–2560, 2004b. Kulmala, M., Suni, T., Lehtinen, K. E. J., Dal Maso, M., Boy, M., Reissell, A., Rannik, Ü., Aalto, P., Keronen, P., Hakola, H., Bäck, J., Hoffman, T., Vesala, T., and Hari, P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, 2004c. Kulmala, M., Lehtinen, K. E. J., and Laaksonen, A.: Cluster activation theory as an explanation of the linear dependence between formation rate of 3 nm particles and sulfuric acid concentration, Atmos. Chem. Phys., 6, 787–793, 2006. Kulmala, M., Riipinen, I., Sipilä, M., Manninen, H. E., Petäjä, T., Junninen, H., Dal Maso, M., Mordas, G., Mirme, A., Vana, M., Hirsikko, A., Laakso, L., Harrison, R. M., Hanson, I., Leung, C., Lehtinen, K. E. J., and Kerminen, V.-M.: Toward direct measurement of atmospheric nucleation, Science, 318, 89–92, 2007a. Kulmala, M., Mordas, G., Petäjä, T., Grönholm, T., Aalto, P. P., Vehkamäki, H., Hienola, A., Herrmann, E., Sipilä, M., Riipinen, I., Manninen, H. E., Hämeri, K., Stratmann, F., Bilde, M., Winkler, P. M., Birmili, W., and Wagner, P. E.: The condensation particle counter battery (CPCB): A new tool to investigate the activation properties of nanoparticles, J. Aerosol Sci., 38, 289–304, 2007b. Laakso, L., Grönholm, T., Kulmala, L., Haapanala, S., Hirsikko, A., Lovejoy, E. N., Kazil, J., Kurtén, T., Boy, M., Nilsson, E. D., Sogachev, A., Riipinen, I., Stratmann, F., and Kulmala, M.: Hot-air balloon as a platform for boundary-layer profile measurements during particle formation, Boreal Environ. Res., 12, 279–294, 2007. Lee, S.-H., Reeves, J. M., Wilson, J. C., Hunton, D. E., Viggiano, A. A., Miller, T. M., Ballentin, T. H., and Lait, L. M.: Particle formation by ion nucleation in the upper troposphere and lower stratosphere, Science, 301, 1886–1889, 2003. Lehtinen, K. E. J. and Kulmala, M.: A model for particle formation and growth in the atmosphere with molecular resolution in size, Atmos. Chem. Phys., 3, 251–258, 2003. Lohmann, U. and Feichter, J.: Global indirect aerosol effects: A review, Atmos. Chem. Phys., 5, 715–737, 2005. McMurry, P. H.: The history of CPCs, Aerosol Sci. Tech., 33, 297–322, 2000. Mirme, A., Tamm, E., Mordas, G., Vana, M., Uin, J., Mirme, S., Bernotas, T., Laakso, L., Hirsikko, A., and Kulmala, M.: A wide-range multi-channel Air Ion Spectrometer, Boreal Environ. Res., 12, 247–264, 2007. Mordas, G., Kulmala, M., Petäjä, T., Aalto, P. P., Matulevicius, V., Grigoraitis, V., Ulevicius, V., Grayslus, V., Ukkonen, A., and Hämeri, K.: Design and performance characteristics of a condensation particle counter UF02proto, Boreal Environ. Res., 10, 543–552, 2005. Mäkelä, J. M., Yli-Koivisto, S., Hiltunen, V., Seidl, W., Swietlicki, E., Teinilä, K., Sillanpää, M., Koponen, I. K., Paatero, P., Rosman, K., and Hämeri, K.: Chemical composition of aerosol during particle formation events in boreal forest, Tellus B, 53, 380–393, 2001. O'Dowd, C. D., Aalto, P., Hämeri, K., Kulmala, M., and Hoffmann, T.: Atmospheric particles from organic vapors, Nature, 416, 497–498, 2002. O'Dowd, C. D., Yoon, Y. J., Junkermann, W., Aalto, P., Kulmala, M., Lihavainen, H., and Viisanen, Y.: Airborne measurements of nucleation mode particles II: boreal forest nucleation events, Atmos. Chem. Phys., 9, 937–944, 2009. Petäjä, T., Mordas, G., Manninen, H., Aalto, P. P., Hämeri, K., and Kulmala, M.: Detection efficiency of a water-based TSI Condensation Particle Counter 3785, Aerosol Sci. Tech., 40, 1090–1097, 2006. Ramanathan, V., Crutzen, P. J., Kiehl, J. T., and Rosenfeld, D.: Aerosol, climate and the hydrological cycle, Science, 294, 2119–2124, 2001. Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Saarnio, K., Teinilä, K., Kerminen, V.-M., Laaksonen, A., and Lehtinen, K. E. J.: Connections between atmospheric sulfuric acid and new particle formation during QUEST III – IV campaigns in Hyytiälä and Heidelberg, Atmos. Chem. Phys., 7, 1899–1914, 2007. Saros, M., Weber, R. J., Marti, J., and McMurry, P. H.: Ultra fine aerosol measurement using a condensation nucleus counter with pulse height analysis, Aerosol Sci. Tech., 25, 200–213, 1996. Sakurai, H., Fink, M. A., McMurry, P. H., Mauldin, L., Moore, K. F., Smith, J. N., and Eisele, F. L.: Hygroscopicity and volatility of 4–10 nm particles during summertime atmospheric nucleation events in urban Atlanta, J. Geophys. Res., 110, D22S04, doi:10.1029/2005JD005918, 2005. Scheibel, H. G. and Porstendörfer, J.: Generation of monodisperse Ag- and NaCl-aerosols with particle diameters between 2 and 300 nm, J. Aerosol Sci., 14, 113–126, 1983. Sem, G. J.: Design and performance characteristics of three continuous-flow condensation particle counters: a summary, Atmos. Res., 62, 267–294, 2002. Sgro, L. A. and Fernández de la Mora, J.: A Simple Turbulent Mixing CNC for Charged Particle Detection Down to 1.2 nm, Aerosol Sci. Tech., 38, 1–11, 2004. Sihto, S.-L., Kulmala, M., Kerminen, V.-M., Dal Maso, M., Riipinen, I., Korhonen, H., Arnold, F., Jansson, R., Boy, M., Laaksonen, A., and Lehtinen, K. E. J.: Atmospheric sulfuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms, Atmos. Chem. Phys., 6, 1–13, 2006. Sipilä, M., Lehtipalo, K., Kulmala, M., Petäjä, T., Junninen, H., Aalto, P. P., Manninen, H. E., Vartiainen, E., Riipinen, I., Kyrö, E.-M., Curtius, J., Kürten, A., Borrman, S., and O'Dowd, C. D.: Applicability of condensation particle counters to measure atmospheric clusters, Atmos. Chem. Phys., 8, 4049–4060, 2008. Smith, J. N., Moore, K. F., Eisele, F. L., Voisin, D., Ghimire, A. K., Sakurai, H., and McMurry, P H.: Chemical composition of atmospheric nanoparticles during nucleation events in Atlanta, J. Geophys. Res., 110, D22S03, doi:10.1029/2005JD005912, 2005. Stoltzenburg, M. R. and McMurry, P. H.: An ultrafine aerosol condensation nucleus counter, Aerosol Sci. Tech., 14, 48–65, 1991. Swietlicki, E., Hansson, H.-C., Hämeri, K., Svenningsson, B., Massling, A., McFiggans, G., McMurry, P.H., Petäjä, T., Tunved, P., Gysel, M., Topping, D., Weingartner, E., Baltensperger, U., Rissler, J., Wiedensohler, A., and Kulmala, M.: Hygroscopic properties of submicrometer atmospheric aerosol particles measured with H-TDMA instruments in various environments – a review, Tellus B., 60, 432–469, 2008. Tunved, P., Hansson, H.-C., Kerminen, V.-M., Ström, J., Dal Maso, M., Lihavainen, H., Viisanen, Y., Aalto, P. P., Komppula, M., and Kulmala, M.: High natural aerosol loading over boreal forests, Science, 312, 261–263, 2006. Varutbangkul, V., Brechtel, F. J., Bahreini, R., Ng, N. L., Keywood, M. D., Kroll, J. H., Flagan, R. C., Seinfeld, J. H., Lee, A., and Goldstein, A. H.: Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, \mboxsesquiterpenes, and related compounds, Atmos. Chem. Phys., 6, 2367–2388, 2006. Weber, R. J., Marti, J. J., McMurry, P. H., Eisele, F. L., Tanner, D. J., and Jefferson, A.: Measurements of new particle formation and ultrafine particle growth rates at a clean continental site, J. Geophys. Res., 102, 4375–4385, 1997. Wehner, B., Petäjä, T., Boy, M., Engler, C., Birmili, W., Tuch, T., Wiedensohler, A., and Kulmala, M.: The contribution of sulfuric acid and non-volatile compounds on the growth of freshly formed atmospheric aerosols, Geophys. Res. Lett., 32, L17810, doi:10.1029/2005GL023827, 2005. Yu, F. and Turco, R. P.: From molecular clusters to nanoparticles: Role of ambient ionization in tropospheric aerosol formation, J. Geophys. Res., 106, 4797–4814, 2001. Zhang, Q., Stanier, C. O., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., Pandis, S. N., and Jimenez, J. L.: Insights into the chemistry of new particle formation and growth events in Pittsburgh based on aerosol mass spectrometry, Environ. Sci. Technol., 38, 4797–4809, 2004.