References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-8-11363-2008

Aerosol dynamics simulations on the connection of sulphuric acid and new particle formation

Sihto

S.-L.

¹ Vuollekoski

¹ Leppä

² Riipinen

¹ Kerminen

V.-M.

² Korhonen

³ Lehtinen

K. E. J.

³ ⁴ Boy

¹ Kulmala

Univ. of Helsinki, Dept. of Physics, P.O. Box 64, FI-00014 University of Helsinki, Finland

Finnish Meteorological Institute, Climate and Global Change, P.O. Box 503, FI-00101 Helsinki, Finland

University of Kuopio, Department of Physics, P.O. Box 1627, FI-70211 Kuopio, Finland

Finnish Meteorological Institute, Kuopio Unit, P.O. Box 1627, FI-70211 Kuopio, Finland

10 06 2008

8 3 11363 11394

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-discuss.net/8/11363/2008/acpd-8-11363-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/8/11363/2008/acpd-8-11363-2008.pdf

We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. We investigated the factors that affect the sulphuric acid dependence during the early stages of particle growth, and tried to find conditions which would yield the linear dependence between the particle number concentration at 3–6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3–6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. The simulations yielded a linear dependence between the particle number concentration at 3 nm and sulphuric acid, when a low saturation vapour pressure for the condensable organic vapour was assumed, or when nucleation took place at ~2 nm instead of ~1 nm. Comparison of results with activation and ternary nucleation showed that ternary nucleation cannot explain the experimentally observed linear or square dependence on sulphuric acid.

References 1

Baker, M. B. and Peter, T.: Small-scale cloud processes and climate, Nature, 451, 299–300, 2008.

Boy, M., Kulmala, M., Ruuskanen, T. M., Pihlatie, M., Reissell, A., Aalto, P. P., Keronen, P., Dal Maso, M., Hellen, H., Hakola, H., Jansson, R., Hanke, M., and Arnold, F.: Sulphuric acid closure and contribution to nucleation mode particle growth, Atmos. Chem. Phys., 5, 863–878, 2005.

Boy, M., Hellmuth, O., Korhonen, H., Nilsson, E. D., ReVelle, D., Turnipseed, A., Arnold, F., and Kulmala, M.: MALTE – model to predict new aerosol formation in the lower troposphere, Atmos. Chem. Phys., 6, 4499–4517, 2006.

Fuchs, N. A., and Sutugin, A. G., High dispersed aerosols, in: Topics in Current Aerosol Research (Part 2), edited by G. M. Hidy and J. R. Brock, Pergamon, New York, 1–200, 1971.

Heaton, K. J., Dreyffus, M. A., Wang, S., and Johnston, M. V.: Oligomers in the early stage of biogenic secondary organic aerosol formation and growth, Environ. Sci. Technol., 41, 6129–6136, 2007.

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 Env. Res., 10, 357–369, 2005.

IPCC (Intergovernmental Panel on Climate Change); Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the IPCC, http://www.ipcc.ch/ipccreports/ar4-wg1.htm, 2007.

Kerminen, V.-M., Lehtinen, K. E. J., Anttila, T., and Kulmala, M.: Dynamics of atmospheric nucleation mode particles: a time scale analysis, Tellus, 56B, 135–146, 2004.

Kerminen, V.-M., Lihavainen, H., Komppula, M., Viisanen, Y., and Kulmala, M.: Direct observational evidence linking atmospheric aerosol formation and cloud droplet activation, Geophys. Res. Lett., 32, L14803, doi:10.1029/2005GL023130, 2005.

Komppula, M., Sihto, S.-L., Korhonen, H., Lihavainen, H., Kerminen, V.-M., Kulmala, M., and Viisanen, Y.: New particle formation in air mass transported between two measurement sites in Northern Finland, Atmos. Chem. Phys., 6, 2811–2824, 2006.

Korhonen, H., Lehtinen, K. E. J., and Kulmala, M.: Multicomponent aerosol dynamics model UHMA: model development and validation, Atmos. Chem. Phys., 4, 757–771, 2004.

Korhonen, H., Kerminen, V.-M., Lehtinen, K. E. J., and Kulmala, M.: CCN activation and cloud processing in sectional aerosol models with low size resolution, Atmos. Chem. Phys., 5, 2561–2570, 2005.

Kuang, C., McMurry, P. H., McCormick, A. V., and Eisele, F.: Dependence of nucleation rates on sulfuric acid vapor concentrations in diverse atmospheric locations, J. Geophys. Res., in press, 2008.

Kulmala, M., Toivonen, A., Mäkelä, J., and Laaksonen, A.: Analysis of the growth of nucleation mode particles observed in Boreal forest, Tellus, 50B, 449–462, 1998.

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., Suni, T., Lehtinen, K. E. J., Dal Maso, M., Boy, M., Reissell, A., Rannik, Ü., Aalto, P., Keronen, P., Hakola, H., Bäck, J., Hoffmann, T., Vesala, T., and Hari, P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, 2004b.

Kulmala, M., Kerminen, V. M., Anttila, T., Laaksonen, A., and O'Dowd, C. D.: Organic aerosol formation via sulphate cluster activation, J. Geophys. Res., 109, D04205, doi:10.1029/2003JD003961, 2004c.

Kulmala, M., Lehtinen, K. E. J., and Laaksonen, A.: Cluster activation theory as an explanation of the linear dependence of the formation rate of 3 nm particles and sulphuric acid concentrations, 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., Kerminen, V.-M.: Toward Direct Measurement of Atmospheric Nucleation, Science, 318, 89–92, 2007.

Laaksonen, A., Hamed, A., Joutsensaari, J., Hiltunen, L, Cavalli, F., Junkermann, W., Asmi, A., Fuzzi, S., and Facchini, M. C.: Cloud condensation nucleus production from nucleation events at a highly polluted region, Geophys. Res. Lett., 32, L06812, doi:10.1029/2004GL022092, 2005.

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, 251–257, 2003.

Limbeck, A., Kulmala, M., and Puxbaum, H.: Secondary organic aerosol formation in the atmosphere via heterogenous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett., 30, 1996, 2003.

McMurry, P. H.: New partcle formation in the presence of an aerosol: Rates, time scales and sub-0.01 um size distributions, J. Colloid Interface Sci., 95, 72–80, 1983.

McMurry, P. H., Fink, M. A., Sakurai, H., Stolzenburg, M. R., Mauldin, L., Moore, K., Smith, J. N., Eisele, F. L., Sjostedt, S., Tanner, D., Huey, L. G., Nowak, J. B., Edgerton, E., and Voisin, D.: A criterion for new particle formation in the sulfur-rich Atlanta atmosphere, J. Geophys. Res., 110, D22S02, doi:10.1029/2005JD005901, 2005.

I. Napari, M. Noppel, H. Vehkamäki, and M. Kulmala, An improved model for ternary nucleation of sulfuric acid-ammonia-water, J. Chem. Phys. 116, 4221, 2002.

Penner, J. E., Quaas, J., Storelvmo, T., Takemura, T., Boucher, O., Guo, H., Kirkevåg, A., Kristjansson, J. E., and Seland, Ø: Model intercomparison of indirect aerosol effects, Atmos. Chem. Phys., 6, 3391–3405, 2006.

Rannik, Ü., Aalto, P., Keronen, P., Vesala, T., and Kulmala, M.: Interpretation of aerosol particle fluxes over a pine forest: Dry deposition and random errors, J. Geophys. Res., 108(D17), 4544, 2003.

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 sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä, Atmos. Chem. Phys., 7, 1899–1914, 2007.

Rosenfeld, D.: Aerosol, clouds, and climate, Science, 312, 1323–1324, 2006.

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.

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.

Spracklen, D. V., Carslaw, K. S., Merikanto, J., Mann, G. W., Chipperfield, M. P., Kulmala, M., Sihto, S.-L., Riipinen, I., Kerminen V.-M., Lihavainen, H., Wiedensohler, A., and Birmili, W.: The contribution of particle formation to global cloud condensation nuclei concentrations, Geophys. Res. Lett., in press, 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.

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 can stratospheric conditions, J. Geophys. Res., 107, 4622, 2002.

Weber, R. J., Marti, J. J., McMurry, P. H., Eisele, F. L., Tanner, D. J., and Jefferson, A.: Measured atmospheric new particle formation rates: implications for nucleation mechanisms, Chem. Eng. Comm., 151, 53–64, 1996.

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.

Zhang, K. M. and Wexler, A. S: A hypothesis for growth of fresh atmospheric nuclei, J. Geophys. Res., 107(D21), 4577, 2002.