Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 6 2009 10.5194/acpd-9-23875-2009 http://www.atmos-chem-phys-discuss.net/9/23875/2009/ http://www.atmos-chem-phys-discuss.net/9/23875/2009/acpd-9-23875-2009.html http://www.atmos-chem-phys-discuss.net/9/23875/2009/acpd-9-23875-2009.pdf 23875 23907 2009-11-11 Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results D. Brus brus@icpf.cas.cz A.-P. Hyvärinen Y. Viisanen M. Kulmala H. Lihavainen Laboratory of Aerosol Chemistry and Physics, Institute of Chemical Process Fundamentals Academy of Sciences of the Czech Republic, Rozvojová 135, 165 02 Prague 6, Czech Republic Finnish Meteorological Institute, Erik Palménin aukio 1, P.O. Box 503, 00100 Helsinki, Finland Department of Physical Sciences, University of Helsinki, P.O. Box 64, 00014 Helsinki, Finland In this study we introduce a new laminar flow tube suitable for binary and ternary homogeneous nucleation studies. The production of sulfuric acid and water vapor mixture, the experimental setup and the method of sulfuric acid concentration determination are discussed in details. Wall losses were estimated from the measured sulfuric acid concentration profile along the laminar flow tube and compared to a theoretical prediction. In this investigation the experimental evidence of new particle formation was observed at concentration of 10⁹ molecules of sulfuric acid in cm³ and nucleation rates measured at three relative humidities (RH) 10, 30 and 50% cover six orders of magnitudes from 10^−3 to 10³ particles in cm³. Particle free air was used as a carrier gas. Our first results are compared to theoretical prediction of binary homogeneous nucleation, to results obtained by other investigators and to atmospheric nucleation. Ball, S. M., Hanson, D. R., and Eisele, F. L., and McMurry, P. H.: Laboratory studies of particle nucleation: Initial results for H₂SO₄, H₂O, and NH₃ vapors, J. Geophys. Res., 104 (D19), 23709–23718, 1999. Benson, D. R., Young, L. H., Kameel, F. R., and Lee, S.-H.: Laboratory-measured nucleation rates of sulfuric acid and water binary homogeneous nucleation from the SO₂+OH reaction, Geophys. Res. Lett., 35, L11801, doi:10.1029/2008GL033387, 2008. Berndt, T., Böge, O., and Stratmann, F.: Formation of atmospheric H₂SO₄/H₂O particles in the absence of organics: A laboratory study, Geophys. Res. Lett., 33, L15817, doi:10.1029/2006GL026660, 2006. Boulaud, D., Madelaine, G., Vigla, D., and Bricard, J.: Experimental study on the nucleation of water vapor sulphuric acid binary system, J. Chem. Phys., 66, 4854–4860, 1977. Clarke, A. D., Varner, J. L., Eisele, F., Mauldin, R. L., Tanner, D., and Litchy, M.: Particle production in the remote marine atmosphere: Cloud outflow and subsidence during ACE~1, J. Geophys. Res., 103(D13), 16397–16409, 1998. Davidson, C. I., Phalen, R. F., and Solomon, P. A.: Airborne particulate matter and human health: A review, Aerosol Sci. Tech., 39, 737–749, 2005. Friend, J. P., Barnes, R. A., and Vasta, R. M.: Nucleation by free radicals from the photooxidation of sulfur dioxide in air, J. Phys. Chem., 84, 2423–2436, 1980. Hanson, D. R. and Eisele, F.: Diffusion of H₂SO₄ in humidified nitrogen: Hydrated H₂SO₄, J. Phys. Chem A, 104, 1715–1719, 2000. 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, 2004. 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.: Towards direct measurement of atmospheric nucleation, Science, 318, 89–92, doi:10.1126/science.1144124, 2007. Mirabel, P. and Clavelin, J. L.: Experimental study of nucleation in binary mixtures: The nitric acid-water and sulphuric acid-water systems, J. Chem. Phys., 68, 5020–5027, 1978. Reiss, H., Margolese, D. I., and Schelling, F. J.: Experimental study of nucleation in vapor mixtures of sulphuric acid and water, J. Colloid Interf. Sci., 56, 511–526, 1976. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From air pollution to climate change, Wiley, New York, 1998. Sihto, S.-L., Kulmala, M., Kerminen, V.-M., Dal Maso, M., Petäjä, T., Riipinen, I., Korhonen, H., Arnold, F., Janson, R., Boy, M., Laaksonen, A., and Lehtinen, K. E. J.: Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms, Atmos. Chem. Phys., 6, 4079–4091, 2006. Sipilä, M., Lehtipalo, K., Kulmala, M., Petäjä, T., Junninen, H., Aalto, P. P., Manninen, H. E., Kyrö, E.-M., Asmi, E., Riipinen, I., Curtius, J., Kürten, A., Borrmann, S., and O'Dowd, C. D.: Applicability of condensation particle counters to measure atmospheric clusters, Atmos. Chem. Phys., 8, 4049–4060, 2008. Spracklen, D. V., Carslaw, K. S., Kulmala, M., Kerminen, V.-M., Mann, G. W., and Sihto, S.-L.: The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales, Atmos. Chem. Phys., 6, 5631–5648, 2006. Twomey, A.: Pollution and the planetary albedo, Atmos. Environ., 8, 1251–1256, 1974. Twomey, S.: Aerosols, clouds and radiation, Atmos. Environ., 25A, 2435–2442, 1991. Vehkamäki, H., Kulmala, M., Napari, I., Lehtinen, K. E. J., Timmreck, C., Noppel, M., and Laaksonen, A.: An improved parameterization for sulfuric acid-water nucleation rates for tropospheric and stratospheric conditions, J. Geophys. Res., 107(D22), 4622, doi:10.1029/2002JD002184, 2002. Viisanen, Y., Kulmala, M., and Laaksonen, A.: Experiments on gas-liquid nucleation of sulphuric acid and water, J. Chem. Phys., 107, 920–926, 1997. Weber, R. J., McMurry, P. H., Mauldin III, R. L., Tanner, D. J., Eisele, F. L., Clarke, A. D., and Kapustin, V. N.: New particle formation in the remote troposphere: A comparison of observations at various sites, Geophys. Res. Lett., 26(3), 307–310, 1999. Wyslouzil, B. E., Sienfeld, J. H., Flagan, R. C., and Okuyama, K.: Binary nucleation in acid-water systems, II Sulphuric acid-water and a comparison with methanesulphonic acid-water, J. Chem. Phys., 94, 6842–6850, 1991. Young, L. H., Benson, D. R., Kameel, F. R., Pierce, J. R., Junninen, H., Kulmala, M., and Lee, S.-H.: Laboratory studies of H₂SO₄/H₂O binary homogeneous nucleation from the SO₂+OH reaction: evaluation of the experimental setup and preliminary results, Atmos. Chem. Phys., 8, 4997–5016, 2008. Zhang, R., Suh, I., Zhao, J., Zhang, D., Fortner, E. C., Tie, X., Molina, L. T., and Molina, M. J.: Atmospheric new particle formation enhanced by organic acids, Science, 304, 1487–1490, 2004.