ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-4399-2012 Sulfuric acid nucleation: power dependencies, variation with relative humidity, and effect of bases Zollner J. H. 1 Glasoe W. A. 1 Panta B. 1 Carlson K. K. 1 McMurry P. H. 2 Hanson D. R. 1 Department of Chemistry, Augsburg College, Minneapolis, MN 55454, USA Department of Mechanical Engineering, University of Minnesota, Minneapolis, MN 55455, USA 16 05 2012 12 10 4399 4411 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/12/4399/2012/acp-12-4399-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/4399/2012/acp-12-4399-2012.pdf

Nucleation of particles composed of sulfuric acid, water, and nitrogen base molecules was studied using a continuous flow reactor. The particles formed from these vapors were detected with an ultrafine condensation particle counter, while vapors of sulfuric acid and nitrogen bases were detected by chemical ionization mass spectrometry. Variation of particle numbers with sulfuric acid concentration yielded a power dependency on sulfuric acid of 5 ± 1 for relative humidities of 14–68% at 296 K; similar experiments with varying water content yielded power dependencies on H<sub>2</sub>O of ~7. The critical cluster contains about 5 H<sub>2</sub>SO<sub>4</sub> molecules and a new treatment of the power dependency for H<sub>2</sub>O suggests about 12 H<sub>2</sub>O molecules for these conditions. Addition of 2-to-45 pptv of ammonia or methyl amine resulted in up to millions of times more particles than in the absence of these compounds. Particle detection capabilities, sulfuric acid and nitrogen base detection, wall losses, and the extent of particle growth are discussed. Results are compared to previous laboratory nucleation studies and they are also discussed in terms of atmospheric nucleation scenarios.

 References Ayers, G. P., Gillet, R. W., and Gras, J. L.: On the vapor pressure of sulfuric acid, Geophys. Res. Lett., 7, 433–436, 1980. Ball, S. M., Hanson, D. R., Eisele, F. L., and McMurry, P. H.: Laboratory studies of particle nucleation: Initial results for H<sub>2</sub>SO<sub>4</sub>, H<sub>2</sub>O, and NH<sub>3</sub> vapors, J. Geophys. Res., 104, 23709–23718, 1999. Bein, K. J. and Wexler, A. S.: Interpreting activity in H<sub>2</sub>O-H<sub>2</sub>SO<sub>4</sub> binary nucleation, J. Chem. Phys., 127, 124316, http://dx.doi.org/10.1063/1.2768925doi:10.1063/1.2768925, 2007. Benson, D. R., Erupe, M. E., and Lee, S. H.: Laboratory-measured H<sub>2</sub>SO<sub>4</sub>-H<sub>2</sub>O-NH<sub>3</sub> ternary homogeneous nucleation rates: Initial observations, Geophys. Res. Lett., 36, L15818, http://dx.doi.org/10.1029/2009gl038728doi:10.1029/2009gl038728, 2009. 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 SO<sub>2</sub> + OH reaction, Geophys. Res. Lett., 35, L11801, http://dx.doi.org/10.1029/2008GL033387doi:10.1029/2008GL033387, 2008. Benson, D. R., Yu, J. H., Markovich, A., and Lee, S.-H.: Ternary homogeneous nucleation of H<sub>2</sub>SO<sub>4</sub>, NH<sub>3</sub>, and H<sub>2</sub>O under conditions relevant to the lower troposphere, Atmos. Chem. Phys., 11, 4755–4766, http://dx.doi.org/10.5194/acp-11-4755-2011doi:10.5194/acp-11-4755-2011, 2011. Berndt, T., Böge, O., Stratmann, F., Heintzenberg, J., and Kulmala, M.: Rapid formation of sulfuric acid particles at near-atmospheric conditions, Science, 307, 698–700, 2005. Berndt, T., Boge, O., and Stratmann, F.: Formation of atmospheric H<sub>2</sub>SO<sub>4</sub>/H<sub>2</sub>O particles in the absence of organics: A laboratory study, Geophys. Res. Lett., 33, L15817, http://dx.doi.org/10.1029/2006GL026660doi:10.1029/2006GL026660, 2006. Berndt, T., Stratmann, F., Sipilä, M., Vanhanen, J., Petäjä, T., Mikkilä, J., Grüner, A., Spindler, G., Lee Mauldin III, R., Curtius, J., Kulmala, M., and Heintzenberg, J.: Laboratory study on new particle formation from the reaction OH + SO<sub>2</sub>: influence of experimental conditions, H<sub>2</sub>O vapour, NH<sub>3</sub> and the amine tert-butylamine on the overall process, Atmos. Chem. Phys., 10, 7101–7116, http://dx.doi.org/10.5194/acp-10-7101-2010doi:10.5194/acp-10-7101-2010, 2010. Birmili, W., Stratmann, F., Wiedensohler, A., Covert, D., Russell, L. M., and Berg, O.: Determination of Differential Mobility Analyzer Transfer Functions Using Identical Instruments in Series, Aerosol Sci. Technol., 27, 215–223, 1997. Brus, D., Hyvärinen, A.-P., Viisanen, Y., Kulmala, M., and Lihavainen, H.: Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results, Atmos. Chem. Phys., 10, 2631–2641, http://dx.doi.org/10.5194/acp-10-2631-2010doi:10.5194/acp-10-2631-2010, 2010. Brus, D., Neitola, K., Hyvärinen, A.-P., Petäjä, T., Vanhanen, J., Sipilä, M., Paasonen, P., \mboxKulmala, M., and Lihavainen, H.: Homogenous nucleation of sulfuric acid and water at close to atmospherically relevant conditions, Atmos. Chem. Phys., 11, 5277–5287, http://dx.doi.org/10.5194/acp-11-5277-2011doi:10.5194/acp-11-5277-2011, 2011. Carlson, K. K., Panta, B., Glasoe, W. A., and Hanson, D. R.: Ammonia and Amine Permeation Tubes: Quantification, Use in AmPMS Calibrations and in Nucleation Experiments, in preparation, 2012. Coffman, D. J. and Hegg, D. A.: A preliminary study of the effect of ammonia on particle nucleation in the MBL, J. Geophys. Res., 100, 7147–7160, 1995. Doyle, G. J.: Self-Nucleation in the Sulfuric Acid-Water System, J. Chem. Phys., 35, 795–799, 1961. Erupe, M. E., Viggiano, A. A., and Lee, S.-H.: The effect of trimethylamine on atmospheric nucleation involving H<sub>2</sub>SO<sub>4</sub>, Atmos. Chem. Phys., 11, 4767–4775, http://dx.doi.org/10.5194/acp-11-4767-2011doi:10.5194/acp-11-4767-2011, 2011. Fuchs, N. A.: On the stationary charge distribution on aerosol particles in a bipolar ionic atmosphere, Geofis. Pura. Appl., 56, 185–193, 1963. Ge, X., Wexler, A. S., and Clegg, S. L.: Atmospheric amines – Part I. A review, Atmos. Environ., 45, 524–546, 2011. Hanson, D.: Mass accommodation of H<sub>2</sub>SO<sub>4</sub> and CH<sub>3</sub>SO<sub>3</sub>H on water-sulfuric acid solutions from 6 to 97 % RH, J. Phys. Chem. A., 109, 6919–6927, http://dx.doi.org/10.1021/jp0510443doi:10.1021/jp0510443, 2005. Hanson, D. R. and Eisele, F. L.: Diffusion of H<sub>2</sub>SO<sub>4</sub> in humidified nitrogen: Hydrated H<sub>2</sub>SO<sub>4</sub>, J. Phys. Chem. A, 104, 1715–1719, 2000. Hanson, D. R. and Eisele, F. L.: Measurement of prenucleation molecular clusters in the NH<sub>3</sub>, H<sub>2</sub>SO<sub>4</sub>, H<sub>2</sub>O system, J. Geophys. Res., 107, http://dx.doi.org/10.1029/2001JD001100doi:10.1029/2001JD001100, 2002. Hanson, D. R. and Kosciuch, E.: The NH<sub>3</sub> mass accommodation coefficient for uptake onto sulfuric acid solutions, J. Phys. Chem. A, 107, 2199–2208, 2003. 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, http://dx.doi.org/10.1021/jp062844wdoi:10.1021/jp062844w, 2006. Hanson, D. R., Eisele, F. L., Ball, S. M., and McMurry, P. M.: Sizing small sulfuric acid particles with an ultrafine particle condensation nucleus counter, Aerosol Sci. Tech., 36, 554–559, 2002. Hanson, D. R, McMurry, P. H., Jiang, J., Tanner, D., and Huey, L. G.: Ambient Pressure Proton Transfer Mass Spectrometry: Detection of Amines and Ammonia, Environ. Sci. Technol., 45, 8881–8888, http://dx.doi.org/10.1021/es201819adoi:10.1021/es201819a, 2011. Hermann, E., Brus, D., Hyvärinen, A.-P., Stratmann, F., Wilck, M., Lihavainen, H., and Kulmala, M.: A Computational Fluid Dynamics Approach to Nucleation in the Water-Sulfuric Acid System, J. Phys. Chem. A, 114, 8033–8042, 2010. IPCC: Fourth Assessment Report, Climate Change 2007: Working Group I: The Physical Science Basis, Technical Summary 2.2, Cambridge University Press, New York, USA available at: http://www.ipcc.ch/publications_and_data/ar4/wg1/en/tssts-2-2.html, 2007. Kirkby, J., Curtius, J., Almeida, J., Dunne, E., Duplissy, J., Ehrhart, S., Franchin, A., Gagne, S., Ickes, L., Kurten, A., Kupc, A., Metzger, A., Riccobono, F., Rondo, L., Schobesberger, S., Tsagkogeorgas, G., Wimmer, D., Amorim, A., Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Downard, A., Ehn, M., Flagan, R. C., Haider, S., Hansel, A., Hauser, D., Jud, W., Junninen, H., Kreissl, F., Kvashin, A., Laaksonen, A., Lehtipalo, K., Lima, J., Lovejoy, E. R., Makhmutov, V., Mathot, S., Mikkila, J., Minginette, P., Mogo, S., Nieminen, T., Onnela, A., Pereira, P., Petaja, T., Schnitzhofer, R., Seinfeld, J. H., Sipila, M., Stozhkov, Y., Stratmann, F., Tome, A., Vanhanen, J., Viisanen, Y., Vrtala, A., Wagner, P. E., Walther, H., Weingartner, E., Wex, H., Winkler, P. M., Carslaw, K. S., Worsnop, D. R., Baltensperger, U., and Kulmala, M.: Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation, Nature, 476, 429, http://dx.doi.org/10.1038/nature10343doi:10.1038/nature10343, 2011. Kuang, C.: Atmospheric nucleation: Measurements, mechanisms, and dynamics, in Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, 2009. Kuang, C., Chen, M., McMurry, P. H., and Wang, J.: Optimization of laminar flow ultrafine condensation particle counters for the enhanced detection of 1 nm condensation nuclei, Aerosol Sci. Technol., 46, 309–315, http://dx.doi.org/10.1080/02786826.2011.626815 doi:10.1080/02786826.2011.626815, 2012. Kulmala, M., Vehkamäki, H., Petaja, 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. Kurtén, T., Loukonen, V., Vehkamäki, H., and Kulmala, M.: Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia, Atmos. Chem. Phys., 8, 4095–4103, http://dx.doi.org/10.5194/acp-8-4095-2008 doi:10.5194/acp-8-4095-2008, 2008. Laaksonen, A., Talanquer, V., and Oxtoby, D.: Nucleation: Theory and atmospheric applications, Annu. Rev. Phys. Chem., 46, 489–524, 1995. McGraw, R. and Wu, D. T.: Kinetic extensions of the nucleation theorem, J. Chem. Phys., 118, 9337–9347, 2003. McMurry, P. H., Woo, K. S., Weber, R., Chen, D. R., and Pui, D. Y. H.: Size distributions of 3-10 nm atmospheric particles: implications for nucleation mechanisms, Phil. Trans. R. Soc. Lond. A, 358, 2625–2642, 2000. Metzger, A., Verheggen, B., Dommen, J., Duplissy, J., Prevot, A. S. H., Weingartner, E., Riipinen, I., Kulmala, M., Spracklen, D. V., Carslaw, K. S., and Baltensperger, U.: Evidence for the role of organics in aerosol particle formation under atmospheric conditions, P. Natl. Acad. Sci., 107, 6646–6651, 2010. Mirabel, P. and Ponche, J. L.: Studies of gas-phase clustering of water on sulphuric acid molecules, Chem. Phys. Lett., 183, 21–24, 1991. Nel, A.: Air Pollution-Related Illness: Effects of Particles Science, Science, 308, 804–806, 2005. Noppel, M.: Ethnalpy and entropy changes in formation of gas-phase sulfuric acid hydrates and dehydrates as a result of fitting to experimental pressure data, J. Geophys. Res., 105, 19779–19785, 2000. Nowak, J. B., Huey, L. G., Russell, A. G., Tian, D., Neuman, J. A., Orsini, D., Sjostedt, S. J., Sullivan, A. P., Tanner, D. J., Weber, R. J., Nenes, A., Edgerton, E., and Fehsenfeld, F. C.: Analysis of urban gas phase ammonia measurements from the 2002 Atlanta Aerosol Nucleation and Real-Time Characterization Experiment (ANARChE), J. Geophys. Res, 111, D17308, http://dx.doi.org/10.1029/2006JD007113doi:10.1029/2006JD007113, 2006. Oberdorster, G., Ferin, J., Gelein, R., Soderholm, S. C., and Finkelstein, J.: Role of the alveolar macrophage in lung injury-Studies with ultrafine particles, Environ. Health Perspect., 97, 193–199, 1992. O'Dowd, C. D., Aalto, P. P., Yoon, Y. J., and Hamerib, K.: The use of the pulse height analyser ultrafine condensation particle counter (PHA-UCPC) technique applied to sizing of nucleation mode particles of differing chemical composition, J. Aerosol Sci., 35, 205–216, 2004. Oxtoby, D. W. and Kashchiev, D.: A general relation between the nucleation work and the size of the nucleus in multicomponent nucleation, J. Chem. Phys., 100, 7665–7671, 1994. Panta, B., Glasoe, W. A., Zollner, J. A., Carlson, K. K., and Hanson, D. R.: Computational Fluid Dynamics of a Cylindrical Nucleation Flow Reactor with Detailed Cluster Thermodynamics, submitted to J. Phys. Chem. A, 2012. Reiss, H.: The Kinetics of Phase Transitions in Binary Systems, J. Chem. Phys., 18, 840–848, 1950. Saros, M. T., Weber, R. J., Marti, J. J., and McMurry, P. H.: Ultrafine aerosol measurement using a condensation nucleus counter with pulse height analysis, Aerosol Sci. Tech., 25, 200–213, 1996. Sipilä, M., Berndt, T., Petäjä, T., Brus, D., Vanhanen, J., Stratmann, F., Patokoski, J., Mauldin III, R. L., Hyvärinen, A. P., Lihavainen, H., and Kulmala, M.: The role of sulfuric acid in atmospheric nucleation, Science, 327, 1243–1246, http://dx.doi.org/10.1126/science.1180315doi:10.1126/science.1180315, 2010. Stoltzenburg, M. R. and McMurry, P. H.: An ultrafine aerosol condensation nucleus counter, Aerosol Sci. Technol., 14, 48–65, 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, 4622, http://dx.doi.org/10.1029/2002JD002184doi: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. Weber, R. J., McMurry, P. H., Mauldin, L., Tanner, D. J., Eisele, F. L., Brechtel, F. J., Kreidenweis, S. M., Kok, G. L., Schillawski, R. D., and Baumgardner, D.: A study of new particle formation and growth involving biogenic trace gas species measured during ace-1, J. Geophys. Res., 103, 16385–16396, 1998. Weber, R. J., McMurry, P. H., Mauldin, 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, 307–310, 1999. Wyslouzil, B. E., Seinfeld, J. H., Flagan, R. C., and Okiuyama, K.: Binary nucleation in acid-water systems ii. Sulfuric acid-water and a comparison with methanesulfonic acid-water, J. Chem. Phys., 94, 6842–6850, 1991. Yu, H., McGraw, R., and Lee, S. H.: Effects of amines on formation of sub-3 nm particles and their subsequent growth, Geophys. Res. Lett., 39, L02807, http://dx.doi.org/10.1029/2011GL050099doi:10.1029/2011GL050099, 2012. Young, L. H., Benson, D. R., Kameel, F. R., Pierce, J. R., Junninen, H., Kulmala, M., and Lee, S.-H.: Laboratory studies of H<sub>2</sub>SO<sub>4</sub>/H<sub>2</sub>O binary homogeneous nucleation from the SO<sub>2</sub>+OH reaction: evaluation of the experimental setup and preliminary results, Atmos. Chem. Phys., 8, 4997–5016, http://dx.doi.org/10.5194/acp-8-4997-2008doi:10.5194/acp-8-4997-2008, 2008. Zhang, R. H., 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.