ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-4939-2011 Atmospheric new particle formation: real and apparent growth of neutral and charged particles Leppä J. 1 Anttila T. 1 Kerminen V.-M. 1 Kulmala M. 2 Lehtinen K. E. J. 3 Finnish Meteorological Institute, P.O. Box 503, 00101 Helsinki, Finland Department of Physics, P.O. Box 64, 00014, University of Helsinki, Finland Finnish Meteorological Institute, Kuopio Unit, and University of Eastern Finland, Department of Physics and Mathematics, P.O. Box 1627, 70211 Kuopio, Finland 27 05 2011 11 10 4939 4955 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/11/4939/2011/acp-11-4939-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4939/2011/acp-11-4939-2011.pdf

In this study we have provided simple analytical formulae to estimate the growth rate of a nucleation mode due to self-coagulation and the apparent growth rate due to coagulation scavenging by larger particles. These formulae were used on a set of simulations covering a wide range of atmospheric conditions. The modal growth rates were determined from the simulation results by summing the contribution of each process, by calculating the increase rate in the count mean diameter of the mode and by following the peak concentration of the mode. The results of these three methods were compared with each other and the means used to estimate the growth rate due to self-coagulation and coagulation scavenging were found to give accurate values. We also investigated the role of charged particles and electric interactions in the growth of a nucleation mode. Charged particles were found to increase the growth rate due to both self-coagulation and coagulation scavenging by a factor of ~1.5 to 2. In case of increased condensation onto charged particles, the total condensational growth rate of a nucleation mode may increase significantly in the very early steps of the growth. The analytical formulae provided by this paper were designed to provide the growth rates due to different processes from aerosol dynamic simulations, but the same principles can be used to determine the growth rates from measurement data.

 References %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. 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, http://dx.doi.org/10.5194/acp-3-361-2003doi:10.5194/acp-3-361-2003, 2003. 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 Env. Res., 10, 323–336, 2005. Dal Maso, M., Sogacheva, L., Aalto, P. P., Riipinen, I., Komppula, M., Tunved, P., Korhonen, L., Suur-Uski, V., Hirsikko, A., Kurtén, T., Kerminen, V.-M., Lihavainen, H., Viisanen, Y., Hansson, H. C., and Kulmala, M.: Aerosol size distribution measurements at four Nordic field stations: identification, analysis and trajectory analysis of new particle formation bursts, Tellus, 59B, 350–361, 2007. Fuchs, N.: The Mechanics of Aerosols, Dover, Mineola, N.Y., USA, 408~pp., 1964. Fuchs, N. A. and Sutugin, A. G.: Highly dispersed aerosols, in: Topics in current aerosol research, edited by: Hidy G. M. and Brock J. R., Pergamon Press, 1–60, 1971. Gagné, S., Laakso, L., Petäjä, T., Kerminen, V.-M., and Kulmala, M.: Analysis of one year of Ion-DMPS data from the SMEAR II station, Finland, Tellus, 60B, 318–329, 2008. Gagné,~S., Nieminen,~T., Kurtén,~T., Manninen,~H E., Petäjä,~T., Laakso,~L., Kerminen,~V.-M., Boy,~M., and Kulmala,~M.: Factors influencing the contribution of ion-induced nucleation in a boreal forest, Finland, Atmos. Chem. Phys., 10, 3743–3757, http://dx.doi.org/10.5194/acp-10-3743-2010doi:10.5194/acp-10-3743-2010, 2010. Gong, Y., Hu, M., Cheng, Y., Su, H., Yue, D., Liu, F., Wiedensohler, A., Wang, Z., Kalesse, H., Liu, S., Wu, Z., Xiao, K., Mi, P., and Zhang, Y.: Competition of coagulation sink and source rate: New particle formation in the Pearl River Delta of China, Atmos. Environ., 44, 3278–3285, 2010. Held, A., Nowak, A., Birmili, W., Wiedensohler, A., Forkel, R., and Klemm, O.: Observations of particle formation and growth in a mountainous forest region in central Europe, J. Geophys. Res., 109, D23204, http://dx.doi.org/10.1029/2004JD005346doi:10.1029/2004JD005346, 2004. 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. %Hirsikko, A., Nieminen, T., Gagné, S., Lehtipalo, K., Manninen, H. E., %Ehn, M., Hõrrak, U., Kerminen, V.-M., Laakso, L., McMurry, P. H., Mirme, %A., Mirme, S., Petäjä, T., Tammet, H., Vakkari, V., Vana, M., and %Kulmala, M.: Atmospheric ions and nucleation: a review of observations, %Atmos. Chem. Phys., 11, 767-798, 2011. Hirsikko, A., Nieminen, T., Gagné, S., Lehtipalo, K., Manninen, H. E., Ehn, M., Hõrrak, U., Kerminen, V.-M., Laakso, L., McMurry, P. H., Mirme, A., Mirme, S., Petäjä, T., Tammet, H., Vakkari, V., Vana, M., and Kulmala, M.: Atmospheric ions and nucleation: a review of observations, Atmos. Chem. Phys., 11, 767–798, http://dx.doi.org/10.5194/acp-11-767-2011doi:10.5194/acp-11-767-2011, 2011. Hoppel, W. A. and Frick, G. M.: Ion-aerosol attachment coefficients and the steady-state charge distribution on aerosol in a bipolar environment, Aerosol Sci. Technol., 5, 1–21, 1986. %Hõrrak, U., Aalto, P. P., Salm, J., Komsaare, K., Tammet, H., %Mäkelä, J. M., Laakso, L., and Kulmala, M.: Variation and balance of %positive air ion concentrations in a boreal forest, Atmos. Chem. Phys., 8, %655–675, 2008. Hõrrak, U., Aalto, P. P., Salm, J., Komsaare, K., Tammet, H., Mäkelä, J. M., Laakso, L., and Kulmala, M.: Variation and balance of positive air ion concentrations in a boreal forest, Atmos. Chem. Phys., 8, 655–675, http://dx.doi.org/10.5194/acp-8-655-2008doi:10.5194/acp-8-655-2008, 2008. Howard, J., Wersborg, B., and Williams, G.: Coagulation of carbon particles in premixed flames, Faraday Symp. Chem. Soc.,~7, 109–119, 1973. Hussein,~T., Puustinen,~A., Aalto,~P P., Mäkelä,~J M., Hämeri,~K., and Kulmala,~M.: Urban aerosol number size distributions, Atmos. Chem. Phys., 4, 391–411, http://dx.doi.org/10.5194/acp-4-391-2004doi:10.5194/acp-4-391-2004, 2004. Iida, K., Stolzenburg, M. R., McMurry, P. H., and Smith, J. N.: Estimating nanoparticle growth rates from size-dependent charged fractions: Analysis of new particle formation events in Mexico City, J. Geophys. Res., 113, D05207, http://dx.doi.org/10.1029/2007JD009260doi:10.1029/2007JD009260, 2008. Jacobson, M. Z.: Fundamentals of Atmospheric Modeling, Cambridge University Press, 2005. Kerminen, V.-M., Pirjola, L., and Kulmala, M.: How significantly does coagulational scavenging limit atmospheric particle production?, J. Geophys. Res., 106, 24119–24126, 2001. Kerminen, V.-M., Lehtinen, K. E. J., Anttila, T., and Kulmala, M.: Dynamics of atmospheric nucleation mode particles: a timescale analysis, Tellus, 56B, 135–146, 2004. Kerminen, V.-M., Anttila, T., Petäjä, T., Laakso, L., Gagné, S., Lehtinen, K. E. J., and Kulmala, M.: Charging state of the atmospheric nucleation mode: Implications for separating neutral and ion-induced nucleation, J. Geophys. Res., 112, D21205, http://dx.doi.org/10.1029/2007JD008649doi:10.1029/2007JD008649, 2007. Kristensson, A., Dal Maso, M., Swietlicki, E., Hussein, T., Zhou, J., Kerminen, V.-M., and Kulmala, M.: Characterization of new particle formation events at a background site in Southern Sweden: relation to air mass history, Tellus, 60B, 330–344, 2008. Kuang, C., McMurry, P. H., and McCormick, A. V.: Determination of cloud condensation nuclei production from measure new particle formation events, Geophys. Res. Lett., 36, L09822, http://dx.doi.org/10.1029/2009GL037584doi:10.1029/2009GL037584, 2009. Kulmala, M., Pirjola, L., and Mäkelä, J. M.: Stable sulphate clusters as a source of new atmospheric particles, Nature, 404, 66–69, 2000. 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, 2001. Kulmala, M., Laakso, L., Lehtinen, K. E. J., Riipinen, I., Dal Maso, M., Anttila, T., Kerminen, V.-M., Hõrrak, U., Vana, M., and Tammet, H.: Initial steps of aerosol growth, Atmos. Chem. Phys., 4, 2553–2560, http://dx.doi.org/10.5194/acp-4-2553-2004doi:10.5194/acp-4-2553-2004, 2004. Kulmala, M., Petäjä, T., Mönkkönen, P., Koponen, I. K., Dal Maso, M., Aalto, P. P., Lehtinen, K. E. J., and Kerminen, V.-M.: On the growth of nucleation mode particles: source rates of condensable vapor in polluted and clean environments, Atmos. Chem. Phys., 5, 409–416, 2005. 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, 2007. Kulmala, M. and Kerminen, V.-M.: On the formation and growth of atmospheric nanoparticles, Atmos. Res., 90, 132–150, 2008. Laakso, L., Kulmala, M., and Lehtinen, K. E. J.: Effect of condensation rate enhancement factor on 3-nm~(diameter) particle formation in binary ion-induced and homogeneous nucleation, J. Geophys. Res., 108, 4574, http://dx.doi.org/10.1029/2003JD003432doi:10.1029/2003JD003432, 2003. Laakso,~L., Gagné,~S., Petäjä,~T., Hirsikko,~A., Aalto,~P P., Kulmala,~M., and Kerminen,~V.-M.: Detecting charging state of ultra-fine particles: instrumental development and ambient measurements, Atmos. Chem. Phys., 7, 1333–1345, http://dx.doi.org/10.5194/acp-7-1333-2007doi:10.5194/acp-7-1333-2007, 2007. Lehtinen, K. E. J. and Zachariah, M. R.: Self-preserving Theory for the Volume Distribution of Particles Undergoing Brownian Coagulation, J. Colloid Interf. Sci., 242, 314–318, 2001. 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, http://dx.doi.org/10.5194/acp-3-251-2003doi:10.5194/acp-3-251-2003, 2003. Lehtinen, K. E. J., Dal Maso, M., Kulmala, M., and Kerminen, V.-M.: Estimating nucleation rates from apparent particle formation rates and vice versa: Revised formulation of the Kerminen-Kulmala equation, J. Aerosol Sci., 38, 988–994, 2007. Leppä, J., Kerminen, V.-M., Laakso, L., Korhonen, H., Lehtinen, K. E. J., Gagné, S., Manninen, H. E., Nieminen, T., and Kulmala, M.: Ion-UHMA: a model for simulating the dynamics of neutral and charged aerosol particles, Boreal Env. Res., 14, 559–575, 2009. Lushnikov, A. A. and Kulmala, M.: Charging of aerosol particles in the near free-molecule regime, Eur. Phys. J., D29, 345–355, 2004. Manninen, H. E., Nieminen, T., Asmi, E., Gagné, S., Häkkinen, S. K., Lehtipalo, K., Aalto, P., Vana, M., Mirme, A, Mirme, S., Hõrrak, U., Plass-Dülmer, C., Stange, G., Kiss, G., Hoffer, A., Törõ, N., Moerman, M., Henzing, B., de~Leeuw, G., Brinkenberg, M., Kouvarakis,~G N., Bougiatioti,~A., Mihalopoulos,~N., O'Dowd,~C., Ceburnis,~D., Arneth,~A., Svenningsson, B., Swietlicki, E., Tarozzi, L., Decesari, S., Facchini, M. C., Birmili, W., Sonntag, A., Wiedensohler, A., Boulon, J., Sellegri, K., Laj, P., Gysel, M., Bukowiecki, N., Weingartner, E., Wehrle, G., Laaksonen, A., Hamed, A., Joutsensaari, J., Petäjä, T., Kerminen, V.-M., and Kulmala, M.: EUCAARI ion spectrometer measurements at 12 European sites – analysis of new particle formation events, Atmos. Chem. Phys., 10, 7907–7927, http://dx.doi.org/10.5194/acp-10-7907-2010doi:10.5194/acp-10-7907-2010, 2010. Merikanto, J., Spracklen, D. V., Mann, G. W., Pickering, S. J., and Carslaw, K. S.: Impact of nucleation on global CCN. Atmos. Chem. Phys., 9, 8601–8616, 2009. Mick, H. J., Hospital, A., and Roth, P.: Computer simulation of sooth particle coagulation in low pressure flames, J. Aerosol Sci., 22, 8319–841, 1991. Nadykto, A. B. and Yu, F.: Uptake of neutral polar vapor molecules by charged clusters/particles: Enhancement due to dipole-charge interaction, J. Geophys. Res., 108, 4717, http://dx.doi.org/10.1029/2003JD003664doi:10.1029/2003JD003664, 2003. Nieminen, T., Lehtinen, K. E. J., and Kulmala, M.: Sub-10 nm particle growth by vapor condensation – effects of vapor molecule size and particle thermal speed, Atmos. Chem. Phys., 10, 9773–9779, http://dx.doi.org/10.5194/acp-10-9773-2010doi:10.5194/acp-10-9773-2010, 2010. Pierce, J. R. and Adams, P. J.: Efficiency of cloud condensation nuclei formation from ultrafine particles, Atmos. Chem. Phys., 7, 1367–1379, http://dx.doi.org/10.5194/acp-7-1367-2007doi:10.5194/acp-7-1367-2007, 2007. Pierce, J. R. and Adams, P. J.: Uncertainty in global CCN concentrations from uncertain aerosol nucleation and primary emission rates, Atmos. Chem. Phys., 9, 1339–1356, http://dx.doi.org/10.5194/acp-9-1339-2009doi:10.5194/acp-9-1339-2009, 2009. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From air pollution to climate change, John Wiley & Sons, 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, http://dx.doi.org/10.5194/acp-6-5631-2006doi:10.5194/acp-6-5631-2006, 2006. Spracklen, D. V., Carslaw, K. S., Kulmala, M., Kerminen, V.-M., Sihto, S.-L., Riipinen, I., Merikanto, J., Mann, G. W., Chipperfield, M. P., Wiedensohler, A., Birmili, W., Lihavainen, H.: Contribution of particle formation to global cloud condensation nuclei concentrations, Geophys. Res. Lett., 35, L06808, http://dx.doi.org/10.1029/2007GL033038doi:10.1029/2007GL033038, 2008. 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 atmospheric particles in Atlanta, J. Geophys. Res., 110, D22S05, http://dx.doi.org/10.1029/2005JD005935doi:10.1029/2005JD005935, 2005. Verheggen,~B. and Mozurkewich,~M.: An inverse modeling procedure to determine particle growth and nucleation rates from measured aerosol size distributions, Atmos. Chem. Phys., 6, 2927–2942, http://dx.doi.org/10.5194/acp-6-2927-2006doi:10.5194/acp-6-2927-2006, 2006. Wang, L., Khalizov, A. F., Zheng, J., Xu, W., Ma, Y., Lal, V., and Zhang, R.: Atmospheric nanoparticles formed from heterogeneous reactions of organics, Nat. Geosci., 3, 238–242, http://dx.doi.org/10.1038/ngeo778doi:10.1038/ngeo778, 2010. Winkler, P. M., Steiner, G., Virtala, A., Vehkamäki, H., Noppel, M., Lehtinen, K. E. J., Reischl, G. P., Wagner, P. E., and Kulmala, M.: Heterogeneous Nucleation Experiments Bridging the Scale from Molecular Ion Clusters to Nanoparticles, Science, 319, 1374, http://dx.doi.org/10.1126/science. 1149034doi:10.1126/science. 1149034, 2008. Yu, F., Luo, G., Bates, T. S., Anderson, B., Clarke, A., Kapustin, V., Yantosca, R. M., Wang, Y., and Wu, S.: Spatial distributions of particle number concentrations in the global troposphere: Simulations, observations, and implications for nucleation mechanisms, J. Geophys. Res., 115, D17205, http://dx.doi.org/10.1029/2009JD013473doi:10.1029/2009JD013473, 2010.