Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 21 2008 10.5194/acp-8-6365-2008 http://www.atmos-chem-phys.net/8/6365/2008/ http://www.atmos-chem-phys.net/8/6365/2008/acp-8-6365-2008.html http://www.atmos-chem-phys.net/8/6365/2008/acp-8-6365-2008.pdf 6365 6374 2008-11-06 SO₂ oxidation products other than H₂SO₄ as a trigger of new particle formation. Part 1: Laboratory investigations T. Berndt berndt@tropos.de F. Stratmann S. Bräsel J. Heintzenberg A. Laaksonen M. Kulmala Leibniz-Institut für Troposphärenforschung e.V., Leipzig, Germany University of Kuopio, Kuopio, Finland University of Helsinki, Helsinki, Finland Mechanistic investigations of atmospheric H₂SO₄ particle formation have been performed in a laboratory study taking either H₂SO₄ from a liquid reservoir or using the gas-phase reaction of OH radicals with SO₂. Applying both approaches for H₂SO₄ generation simultaneously it was found that H₂SO₄ evaporated from the liquid reservoir acts considerably less effective for the process of particle formation and growth than the products originating from the reaction of OH radicals with SO₂. Furthermore, for NO_x concentrations >5×10¹¹ molecule cm^−3 the formation of new particles from the reaction of OH radicals with SO₂ is inhibited. This suggests that substances other than H₂SO₄ (potentially products from sulphur-containing peroxy radicals) trigger lower tropospheric new particle formation and growth. The currently accepted mechanism for SO₂ gas-phase oxidation does not consider the formation of such substances. The analysis of new particle formation for different reaction conditions in our experiment suggests that a contribution of impurities to the nucleation process is unlikely. Atkinson, R., Bauch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkins, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of O$_x$, HO$_x$, NO$_x$ and SO$_x$ species, Atmos. Chem. Phys., 4, 1461–1738, 2004. Ball, S. M., Hanson, D. R., Eisele, F. L., and McMurry, P. H.: Laboratory studies of particle nucleation: Initial results for H₂SO₄, H₂O, and NH₃ vapors, J. Geophys. Res., 104, 23 709–23 718, doi:10.1029/1999JD900411, 1999. 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 SO₂+OH reaction, Geophys. Res. Lett., 35, L11801, doi:10.1029/2008GL033387, 2008. Berndt, T., Böge, O., and Stratmann, F.: Atmospheric particle formation from the ozonolysis of alkenes in the presence of SO₂, Atmos. Environ., 38, 2145–2153, 2004. 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., Böge, O., and Stratmann, F.: Formation of atmospheric H₂SO₄/H₂O particles in the absence of organics: A laboratory study, Geophys. Res. Lett., 33, L15817, doi:10.1029/2006GL026660, 2006. Burkholder, J. B., Baynard, T., Ravishankara, A. R., and Lovejoy, E. R.: Particle nucleation following the O₃ and OH initiated oxidation of α-pinene and β-pinene between 278 and 320 K, J. Geophys. Res., 112, D10216, 2007. Burrows, J. P., Cliff, D. I., Harris, G. W., Thrush, B. A., and Wilkinson, J. P. T.: Atmospheric reactions of the HO₂ radical studied by laser magnetic resonance spectroscopy, Proc. R. Soc. Lond. A, 368, 463–481, 1979. Finlayson-Pitts, B. J. and Pitts Jr., J. N., and references therein: Chemistry of the Upper and Lower Atmosphere, Academic Press, San Diego, CA, USA, 2000. Friend, J. P., Barnes, R. A. and Vasta, R. M.: Nucleation by free-radicals from the photo-oxidation of sulfur-dioxide in air, J. Phys. Chem., 84, 2423–2436, 1980. Gleason, J. F., Sinha, A., and Howard, C. J.: Kinetics of the gas-phase reaction HOSO₂+O$_2\to$ HO₂+SO₃, J. Phys. Chem., 91, 719–724, 1987. Hanson, D. R. and Eisele, F.: Diffusion of H₂SO₄ in humidified nitrogen: Hydrated H₂SO₄, J. Phys. Chem. A, 104, 1715–1719, 2000. Hoffmann T., Bandur, R., Marggraf, U., and Linscheid, M.: Molecular composition of organic aerosols formed in the α-pinene/O₃ reaction: Implications for new particle formation processes, J. Geophys. Res., 103, 25 569–25 578, 1998. Howard, C., Communication at the 17th Symposium on Free Radicals, Granby, 1985; see ref (11) in: Discharge flow measurements of the rate constants for the reactions OH+SO₂+He and HOSO₂+O₂ in relation with the atmospheric oxidation of SO₂, edited by: Martin, D., Jourdain, J. L., and LeBras, G., J. Phys. Chem., 90, 4143–4147, 1986. Jayne, J. T., Pöschl, U., Chen, Y. M., Dai, D., Molina, L. T., Worsnop, D. R., Kolb, C. E., and Molina, M. J.: Pressure and temperature dependence of the gas-phase reaction of SO₃ with H₂O and the heterogeneous reaction of SO₃ with H₂O/H₂SO₄ surfaces, J. Phys. Chem. 101, 10 000–10 011, 1997. Kolditz, L.: Anorganische Chemie, Deutscher Verlag der Wissenschaften, Berlin, 461–482, 1983. Kulmala, M., Laaksonen, A., and Pirjola, L.: Parameterization for sulphuric acid/water nucleation rates, J. Geophys. Res., 103, 8301–8307, 1998. Kulmala, M., Pirjola, L., and Makela, J. M.: Stable sulphate cluster as a source of new atmospheric particles, Nature, 404, 66–69, 2000. Kulmala, M.: How particles nucleate and grow, Science, 302, 1000–1001, 2003. Martin, L. R. and Damschen, D. E.: Aqueous Oxidation of Sulfur Dioxide by Hydrogen Peroxide at Low pH, Atmos. Environ., 15, 1615–1621, 1981. Laaksonen, A., Kulmala, M., Berndt, T., Stratmann, F., Mikkonen, S., Ruuskanen, A., Lehtinen, K. E. J., Dal Maso, M., Aalto, P., Petäjä, T., Riipinen, I., Sihto, S.-L., Janson, R., Arnold, F., Hanke, M., Ãœcker, J., Umann, B., Sellegri, K., O’Dowd, C. D., and Viisanen, Y., Atmos. Chem. Phys. Discuss., 8, 9673–9695, 2008. Lee, S.-H., Reeves, J. M., Wilson, J. C., Hunton, D. E., Viggiano, A. A., Miller, T. M., Ballenthin, J. O., and Lait, L. R.: Science, 301, 1886–1889, 2003. Lovejoy, E. R., Hanson, D. R., and Huey, L. G.: Kinetics and products of the gas-phase reaction of SO₃ with water, J. Phys. Chem., 100, 19 911–19 916, 1996. Lovejoy, E. R., Curtius, J., and Froyd, K. D.: Atmospheric ion-induced nucleation of sulphuric acid and water, J. Geophys. Res., 109, D08204, doi:10.1029/2003JD004460, 2004. Martin, D., Jourdain, J. L., and LeBras, G.: Discharge flow measurements of the rate constants for the reactions OH+SO₂+He and HOSO₂+O₂ in relation with the atmospheric oxidation of SO₂, J. Phys. Chem., 90, 4143–4147, 1986. McMurry, P. H., Fink, M., Sakurai, H., Stolzenburg, M. R., Mauldin III, R. L., Smith, J., Eisele, F., Moore, K., 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. Payne, W. A., Stief, L. J., and Davis, D. D.: A Kinetics Study of the Reaction of HO₂ with SO₂ and NO, J. Am. Chem. Soc., 95, 7614–7619, 1973. Penzhorn, R. D. and Canosa, C. E.: 2nd Derivative UV Spectroscopy Study of the Thermal and Photochemical Reaction of NO₂ with SO₂ and SO₃, Ber. Bunsen Phys. Chem., 87, 648–654, 1983. Reid, R. C., Prausnitz, J. M., and Poling, B. E.: The Properties of Gases and Liquids, McGraw-Hill, New York, 11, 1–20, 1987. Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Teinilä, K., Kerminen, V.-M., Laaksonen, A., and Lehtinen, K. F. 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. Stockwell, W. R. and Calvert, J. G.: The mechanism of the HO-SO₂ reaction, Atmos. Environ., 17, 2231–2235, 1983. Wayne, R.: Chemistry of Atmospheres, Clarendon Press, Oxford, 242–245, 1991. 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. Young, L.-H., Benson, D. R., Kameel, F. R., Pierce, J. R., Junninen, H., Kulmala, M., and Lee, S.-H.: Laboratory studies of H₂SO₄/H₂O binary homogeneous nucleation from the SO₂+OH reaction: evaluation of the experimental setup and preliminary results, Atmos. Chem. Phys., 8, 4997–5016, 2008. Yu, F., Turco, R. P., and Kärcher, B.: The possible role of organics in the formation and evolution of ultrafine aircraft particles, J. Geophys. Res., 104, 4079–4087, 1999. Zhang, R., 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, 1487–1489, 2004.