Atmospheric Chemistry and Physics
www.atmos-chem-phys.net
1680-7316
1680-7324
6
12
2006
10.5194/acp-6-4079-2006
http://www.atmos-chem-phys.net/6/4079/2006/
http://www.atmos-chem-phys.net/6/4079/2006/acp-6-4079-2006.html
http://www.atmos-chem-phys.net/6/4079/2006/acp-6-4079-2006.pdf
4079
4091
2006-09-11
Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms
S.-L. Sihto
M. Kulmala
V.-M. Kerminen
M. Dal Maso
T. Petäjä
I. Riipinen
H. Korhonen
F. Arnold
R. Janson
M. Boy
A. Laaksonen
K. E. J. Lehtinen
University of Helsinki, Department of Physical Sciences, P.O. Box 64, 00014 University of Helsinki, Finland
Finnish Meteorological Institute, Climate and Global Change, Erik Palmenin Aukio 1, P.O. Box 503, 00101 Helsinki, Finland
Atmospheric Physics Division, Max-Planck Institute for Nuclear Physics (MPIK), P.O. Box 103980, 69029 Heidelberg, Germany
University of Stockholm, Department of Applied Environmental Science, Air Pollution Laboratory, Frescativägen 54, 10691 Stockholm, Sweden
University of Kuopio, Department of Applied Physics, P.O. Box 1627, 70211 Kuopio, Finland
Finnish Meteorological Institute and University of Kuopio, Department of Applied Physics, P.O. Box 1627, 70211 Kuopio, Finland
We have investigated the formation and early growth of atmospheric secondary
aerosol particles building on atmospheric measurements. The measurements were
part of the QUEST 2 campaign which took place in spring 2003 in
Hyytiälä (Finland). During the campaign numerous aerosol particle
formation events occurred of which 15 were accompanied by gaseous sulphuric
acid measurements. Our detailed analysis of these 15 events is focussed on
nucleation and early growth (to a diameter of 3 nm) of fresh particles. It
revealed that new particle formation seems to be a function of the gaseous
sulphuric acid concentration to the power from one to two when the time delay
between the sulphuric acid and particle number concentration is taken into
account. From the time delay the growth rates of freshly nucleated particles
from 1 nm to 3 nm were determined. The mean growth rate was 1.2 nm/h and it
was clearly correlated with the gaseous sulphuric acid concentration. We
tested two nucleation mechanisms – recently proposed cluster activation and
kinetic type nucleation – as possible candidates to explain the observed
dependences, and determined experimental nucleation coefficients. We found
that some events are dominated by the activation mechanism and some by the
kinetic mechanism. Inferred coefficients for the two nucleation mechanisms
are the same order of magnitude as chemical reaction coefficients in the gas
phase and they correlate with the product of gaseous sulphuric acid and
ammonia concentrations. This indicates that besides gaseous sulphuric acid
also ammonia has a role in nucleation.
Bernd, T., Böge, O., Stratmann, F., Heintzenberg, J., and Kulmala, M.: Rapid formation of new sulfuric acid particles at near-atmospheric conditions, Science, 307(5710), 698–700, 2005.
Birmili, W. and Wiedensohler, A.: The influence of meteorological parameters on ultrafine particle production at a continental site, J. Aerosol Sci., 29, S1015–1016, 1998.
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, H<sub>2</sub>SO<sub>4</sub>, 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., 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.
Cabada, J. C., Khlystov, A., Wittig, A. E., Pilinis, C., and Pandis, S. N.: Light scattering by fine particles during the Pittsburgh Air Quality Study: Measurements and modelling, J. Geophys. Res., 109, D16S03, doi:10.1029/2003JD004155, 2004.
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.
Donaldson, K., Li, X. Y., and MacNee, W.: Ultra-fine (nanometre) particle mediated lung injury, J. Aerosol. Sci., 29, 553–560, 1998.
Dunn, M. J., Jimenez, J.-L., Baumgartner, D., Castro, T., McMurry, P. H., and Smith, J. N.: Measurements of Mexico City nanoparticle size distributions: Observations of new particle formation and growth, Geophys. Res. Lett., 31, L10102, doi:10.1029/2004GL019483, 2004.
Fiedler, V., Dal Maso, M., Boy, M., Aufmhoff, H., Hoffmann, J., Schuch, T., Birmili, W., Hanke, M., Uecker, J., Arnold, F., and Kulmala, M.: The contribution of sulphuric acid to atmospheric particle formation and growth: a comparison between boundary layers in Northern and Central Europe, Atmos. Chem. Phys., 5, 1773–1785, 2005.
Hanke, M., Uecker, J., Reiner, T., and Arnold, F.: Atmospheric peroxy radicals: ROXMAS, a new mass-spectrometric methodology for speciated measurements of HO2 and Sigma RO2 and first results, Int. J. Mass Spectr., 213(2–3), 91–99, 2002.
Hari, P. and Kulmala, M.: Station for Measuring Ecosystem–Atmosphere Relations (SMEAR II), Boreal Environ. Res., 10, 315–322, 2005.
Janson, R., Rosman, K., Karlsson, A., and Hansson, H.-C.: Biogenic emissions and gaseous precursors to forest aerosols, Tellus 53B, 423–440, 2001.
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, 2002.
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, P., Kulmala, M., Laaksonen, A., Viisanen, Y., McGraw, R., and Seinfeld, J. H.: Ternary nucleation of H<sub>2</sub>SO<sub>4</sub>, NH<sub>3</sub> and H<sub>2</sub>O in the atmosphere, J. Geophys. Res., 104, 26 349–26 353, 1999.
Kulmala, M., Toivonen, A., Mäkelä, J. M., and Laaksonen, A.: Analysis of the growth of nucleation mode particles observed in Boreal forest, Tellus, 50B, 449–462, 1998.
Kulmala, M., Hämeri, K., Aalto, P. P., Mäkelä, J. M., Pirjola, L., Nilsson, E. D., Buzorius, G., Rannik, Ü, Dal Maso, M., Seidl, W., Hoffmann, T., Janson, R., Hansson, H.-C., Viisanen, Y., Laaksonen, A., and O'Dowd, C. D.: Overview of the international project on Biogenic aerosol formation in the boreal forest (BIOFOR), Tellus 53B, 324–343, 2001a.
Kulmala, M., Dal Maso, M., Mäkelä, J. M., Pirjola, L., Väkevä, M., Aalto, P,. Miikkulainen, P., Hämeri, K., and O'Dowd, C. D.: On the formation, growth and composition of nucleation mode particles, Tellus, 53B, 479–490, 2001b.
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., Horrak, U., Vana, M., and Tammet, H.: Initial steps of aerosol growth, Atmos. Chem. Phys., 4, 2553–2560, 2004b.
Kulmala, M., Lehtinen, K. E. J., Laakso, L., Mordas, G., and Hämeri, K.: On the existence of neutral atmospheric clusters, Boreal Environ. Res., 10, 79–87, 2005a.
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 sulphuric acid concentration, Atmos. Chem. Phys., 6, 787–793, 2006.
Laakso, L., Anttila, T., Lehtinen, K. E. J., Aalto, P. P., Kulmala, M., Hõrrak, U., Paatero, J., Hanke, M., and Arnold, F.: Kinetic nucleation and ions in boreal particle formation events, Atmos. Chem. Phys., 4, 2353–2366, 2004a.
Laakso, L., Petäjä, T., Lehtinen, K. E. J., Kulmala, M., Paatero, J., Hõrrak, U., Tammet, H., and Joutsensaari, J.: Ion production rate in a boreal forest based on ion, particle and radiation measurements, Atmos. Chem. Phys., 4, 1933–1943, 2004b.
Laaksonen, A., Hamed, A., Joutsensaari, J., Hiltunen, L., Cavalli, F., Junkermann, W., Asmi, A., Fuzzi, S., and Faccini, 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.
Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, Atmos. Chem. Phys., 5, 715–737, 2005.
Lushnikov, A. A. and Kulmala, M.: Dimers in nucleating vapors, Phys. Rev. E, 58, 3157–3167, 1998.
McMurry, P. H. and Friedlander, S. K.: New particle formation in the presence of an aerosol, Atmos. Environ., 13, 1635–1651, 1979.
Mäkelä, J. M., Aalto, P., Jokinen, V., Pohja, T., Nissinen, A., Palmroth, S., Markkanen, T., Seitsonen, K., Lihavainen, H., and Kulmala, M.: Observations of ultrafine aerosol particle formation and growth in boreal forest, Geophys. Res. Lett., 24, 1219–1222, 1997.
Mönkkönen, P., Koponen, I. K., Lehtinen, K. E. J., Hämeri, K., Uma, R., and Kulmala, M.: Measurements in a highly polluted Asian mega city: Observations of aerosol aerosol number size distributions, modal parameters and nucleation events, Atmos. Chem. Phys., 5, 57–66, 2005.
O'Dowd, C., McFiggans, G., Creasey, D. J., Pirjola, L., Hoell, C., Smith, M. H., Allan, B. J., Plane, J. M. C., Heard, D. E., Lee, J. D., Pilling, M. J., and Kulmala M.: On the photochemical production of new particles in the coastal boundary layer, Geophys. Res. Lett., 26, 1707–1710, 1999.
Ramanathan, V., Crutzen, P. J., Kiehl, J. T., and Rosenfeld, D.: Aerosol, climate, and the hydrological cycle, Science, 294, 2119–2124, 2001.
Sekiguchi, M., Nakajima, T., Suzuki, K., Kawamoto, K., Higurashi, A., Rosenfeld, D., Sano, I., and Mukai, S.: A study of the direct and indirect effects of aerosols using global satellite data sets of aerosol and cloud parameters, J. Geophys. Res., 108(D22), 4699, doi:10.1029/2002JD003359, 2003.
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.
Stanier, C. O., Khlystov, A. Y., and Pandis, S. N.: Nucleation events during the Pittsburg Air Quality Study: Description and relation to key meteorological, gas phase and aerosol parameters, Aerosol Sci. Technol., 38(S1), 253–264, 2004.
Stolzenburg, M. R., McMurry, P. H., Sakurai, H., Smith, J. N., Mauldin III, R. L., Eisele, F. L., and Clement, C. F.: Growth rates of freshly nucleated particles in Atlanta, J. Geophys. Res., 110, D22S05, doi:10.1029/2005JD005935, 2005.
Stieb, D. M., Judek, S., and Burnett, R.T.: Meta-analysis of time-series studies of air pollution and mortality: Effects of gases and particles and their influence of cause of death, age and season, J. Air & Manage. Assoc., 52, 470–484, 2002.
Vana, M., Kulmala, M., Dal Maso, M., Hõrrak, U., and Tamm, E.: Comparative study of nucleation mode aerosol particles and intermediate air ions formation events at three sites, J. Geophys. Res., 109, D17201, 2004.
Vehkamäki, H., Dal Maso, M., Hussein, T., Flanagan, R., Hyvärinen, A., Lauros, J., Merikanto, J., Mönkkönen, P., Pihlatie, M., Salminen, K., Sogacheva, L., Thum, T., Ruuskanen, T., Keronen, P., Aalto, P., Hari, P., Lehtinen, K., and Kulmala, M.: Atmospheric particle formation events at Värriö measurement station in Finnish Lapland 1998–2002, Atmos. Chem. Phys., 4, 2015–2023, 2004.
Väkevä, M., Hämeri, K., Puhakka, T., Nilsson, E. D., Hohti, H., and Mäkelä, J. M.: Effects of meteorological processes on aerosol particle size distribution in an urban background area, J. Geophys. Res., 105, 9807–9821, 2000.
Weber, R. J., McMurry, P. H., Eisele, F. L., and Tanner, D. J.: Measurement of expected nucleation precursor species and 3–500 nm diameter particles at Mauna Loa Observatory, Hawaii, J. Atmos. Sci., 52, 2242–2257, 1995.
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., Wiedensohler, A., Tuch, T. M., Wu, Z. J., Hu, M., Slanina, J., and Kiang, C. S.: Variability of the aerosol number size distribution in Beijing, China: New particle formation, dust storms, and high continental background, Geophys. Res. Lett., 31, L22108, doi:10.1029/2004GL021596, 2004.
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 Pittsburg based on aerosol mass spectrometry, Environ. Sci. Technol., 38, 4797–4809, 2004.