References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-3447-2007

A semi-analytical method for calculating rates of new sulfate aerosol formation from the gas phase

Kazil

¹ ² Lovejoy

E. R.

NOAA Earth System Research Laboratory, Boulder, CO, USA

NRC Research Associateship Programs, Washington, D.C., USA

02 07 2007

7 13 3447 3459

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/7/3447/2007/acp-7-3447-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/3447/2007/acp-7-3447-2007.pdf

The formation of new aerosol from the gas phase is commonly represented in atmospheric modeling with parameterizations of the steady state nucleation rate. Present parameterizations are based on classical nucleation theory or on nucleation rates calculated with a numerical aerosol model. These parameterizations reproduce aerosol nucleation rates calculated with a numerical aerosol model only imprecisely. Additional errors can arise when the nucleation rate is used as a surrogate for the production rate of particles of a given size. We discuss these errors and present a method which allows a more precise calculation of steady state sulfate aerosol formation rates. The method is based on the semi-analytical solution of an aerosol system in steady state and on parameterized rate coefficients for H2SO4 uptake and loss by sulfate aerosol particles, calculated from laboratory and theoretical thermodynamic data.

References 1

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.

Bates, D R.: Recombination of small ions in the troposphere and lower stratosphere, Planet. Space Sci., 30, 1275–1282, 1982.

Brock, C A., Hamill, P., Wilson, J C., Jonsson, H H., and Chan, K R.: Particle formation in the upper tropical troposphere: a source of nuclei for the stratospheric aerosol, Science, 270, 1650–1653, 1995.

Cavalli, F., Facchini, M C., Decesari, S., Emblico, L., Mircea, M., Jensen, N R., and Fuzzi, S.: Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project, Atmos. Chem. Phys., 6, 993–1002, 2006.

Clarke, A D.: Atmospheric nuclei in the remote free-troposphere, J. Atmos. Chem., 14, 479–488, 1992.

Clegg, S L., Rard, J A., and Pitzer, K S.: Thermodynamic properties of 0–6 mol kg−1 aqueous sulfuric acid from 273.15 to 328.15 K, J. Chem. Soc., Faraday Trans., 90, 1875–1894, \doi10.1039/FT9949001875, 1994.

Coffman, D J. and Hegg, D A.: A preliminary study of the effect of ammonia on particle nucleation in the marine boundary layer, J. Geophys. Res., 100, 7147–7160, \doi10.1029/94JD03253, 1995.

Curtius, J., Froyd, K D., and Lovejoy, E R.: Cluster ion thermal decomposition (I): Experimental kinetics study and ab initio calculations for HSO$_4^-$(H2SO4)$_(x)$(HNO3)$_(y)$, J. Phys. Chem. A, 105, 10 867–10 873, 2001.

Froyd, K D.: Ion induced nucleation in the atmosphere: Studies of NH3, H2SO4, and H2O cluster ions, Ph.D. thesis, Univ. of Colo., Boulder, 2002.

Froyd, K D. and Lovejoy, E R.: Experimental Thermodynamics of Cluster Ions Composed of H2SO4 and H2O. 1. Positive Ions, J. Phys. Chem. A, 107, 9800–9811, 2003a.

Froyd, K D. and Lovejoy, E R.: Experimental Thermodynamics of Cluster Ions Composed of H2SO4 and H2O. 2. Measurements and ab Initio Structures of Negative Ions, J. Phys. Chem. A, 107, 9812–9824, 2003b.

Fuchs, N A.: The Mechanics of Aerosols, Macmillan, 1964.

Giauque, W F., Hornung, E W., Kunzler, J E., and Rubin, T T.: The thermodynamic properties of aqueous sulfuric acid solutions and hydrates from 15 to 300 K, Am. Chem. Soc. J., 82, 62–70, 1960.

Goff, J A.: Saturation pressure of water on the new Kelvin temperature scale, in: Transactions of the American Society of Heating and Ventilating Engineers, pp. 347–354, American Society of Heating and Ventilating Engineers, 1957.

Hanson, D R. and Lovejoy, E R.: Measurement of the thermodynamics of the hydrated dimer and trimer of sulfuric acid, J. Phys. Chem. A, 110, 9525–9528, \doi10.1021/jp062844w, 2006.

Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative forcing due to tropospheric aerosols: A review, Rev. Geophys., 38, 513–543, \doi10.1029/1999RG000078, 2000.

Heintzenberg, J.: Fine particles in the global troposphere, Tellus Series B Chemical and Physical Meteorology B, 41, 149–160, 1989.

Heintzenberg, J., Covert, D S., and Van~Dingenen, R.: Size distribution and chemical composition of marine aerosols: A compilation and review, Tellus, 52B, 1104–1122, 2000.

Jacobson, M C., Hansson, H.-C., Noone, K J., and Charlson, R J.: Organic atmospheric aerosols: Review and state of the science, Rev. Geophys., 38, 267–294, \doi10.1029/1998RG000045, 2000.

Kazil, J., Lovejoy, E R., Jensen, R J., and Hanson, D R.: Is aerosol formation in cirrus clouds possible?, Atmos. Chem. Phys., 7, 2007.

Kerminen, V.-M. and Kulmala, M.: Analytical formulae connecting the "real" and the "apparent" nucleation rate and the nuclei number concentration for atmospheric nucleation events, J. Aerosol Sci., 33, 609–622, \doi10.1016/S0021-8502(01)00194-X, 2002.

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. Aer. Sci., 35, 143–176, \doi10.1016/j.jaerosci.2003.10.003, 2004a.

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, D4205, \doi10.1029/2003JD003961, 2004b.

Lauer, A., Hendricks, J., Ackermann, I., Schell, B., Hass, H., and Metzger, S.: Simulating aerosol microphysics with the ECHAM/MADE GCM – Part I: Model description and comparison with observations, Atmos. Chem. Phys., 5, 3251–3276, 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, 251–258, 2003.

Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, Atmos. Chem. Phys., 5, 715–737, 2005.

Lovejoy, E R., Curtius, J., and Froyd, K D.: Atmospheric ion-induced nucleation of sulfuric acid and water, J. Geophys. Res., 109, D08204, \doi10.1029/2003JD004460, 2004.

Ma, X. and von Salzen, K.: Dynamics of the sulphate aerosol size distribution on a global scale, J. Geophys. Res., 111, D08 206, \doi10.1029/2005JD006620, 2006.

Modgil, M S., Kumar, S., Tripathi, S N., and Lovejoy, E R.: A parameterization of ion-induced nucleation of sulphuric acid and water for atmospheric conditions, J. Geophys. Res., 110, D19205, \doi10.1029/2004JD005475, 2005.

Napari, I., Noppel, M., Vehkamäki, H., and Kulmala, M.: Parametrization of ternary nucleation rates for H2SO4-NH3-H2O vapors, J. Geophys. Res., 107, 6–1, \doi10.1029/2002JD002132, 2002.

Ravishankara, A R.: Heterogeneous and Multiphase Chemistry in the Troposphere, Science, 276, 1058–1065, \doi10.1126/science.276.5315.1058, 1997.

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, \doi10.1029/2005JD005912, 2005.

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, 4622, \doi10.1029/2002JD002184, 2002.