References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-2631-2010

Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results

Brus

¹ ² Hyvärinen

A.-P.

² Viisanen

² Kulmala

³ 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

18 03 2010

10 6 2631 2641

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/10/2631/2010/acp-10-2631-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/2631/2010/acp-10-2631-2010.pdf

In this study we introduce a new 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 detail. Wall losses were estimated from the measured sulfuric acid concentration profiles along the flow tube and compared to a theoretical prediction. In this investigation the experimental evidence of new particle formation was observed at a concentration of 109 molecules cm−3 of sulfuric acid and the nucleation rates measured at three relative humidities (RH) 10, 30 and 50%, cover six orders of magnitude, from 10−3 to 103 particles cm−3. Particle free air was used as a carrier gas. Our initial results are compared to the theoretical prediction of binary homogeneous nucleation, to results obtained by other investigators, and to atmospheric nucleation.

References 1

Ball, S. M., Hanson, D. R., 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.

Liu, B. Y H. and Pui, D. Y. H.: Electrical neutralization of aerosol, J. Aerosol Sci., 5, 465–472, 1974.

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 Interface 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, USA, 464–470., 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.

Wiedensohler, A.: An approximation of the bipolar charge distribution for particles in submicron size range, J. Aerosol Sci., 19, 387–389, 1988.

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.