References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-3035-2006

Homogeneous nucleation rates of nitric acid dihydrate (NAD) at simulated stratospheric conditions – Part II: Modelling

Möhler

¹ Bunz

¹ Stetzer

Forschungszentrum Karlsruhe, Institute for Meteorology and Climate Research (IMK-AAF), Germany

24 07 2006

6 10 3035 3047

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Activation energies ΔGact for the nucleation of nitric acid dihydrate (NAD) in supercooled binary HNO3/H2O solution droplets were calculated from volume-based nucleation rate measurements using the AIDA (Aerosol, Interactions, and Dynamics in the Atmosphere) aerosol chamber of Forschungszentrum Karlsruhe. The experimental conditions covered temperatures T between 192 and 197 K, NAD saturation ratios SNAD between 7 and 10, and nitric acid molar fractions of the nucleating sub-micron sized droplets between 0.26 and 0.28. Based on classical nucleation theory, a new parameterisation for ΔGact=A×(T ln SNAD)−2+B is fitted to the experimental data with A=2.5×106 kcal K2 mol−1 and B=11.2−0.1(T−192) kcal mol−1. A and B were chosen to also achieve good agreement with literature data of ΔGact. The parameter A implies, for the temperature and composition range of our analysis, a mean interface tension σsl=51 cal mol−1 cm−2 between the growing NAD germ and the supercooled solution. A slight temperature dependence of the diffusion activation energy is represented by the parameter B. Investigations with a detailed microphysical process model showed that literature formulations of volume-based (Salcedo et al., 2001) and surface-based (Tabazadeh et al., 2002) nucleation rates significantly overestimate NAD formation rates when applied to the conditions of our experiments.

References 1

Bertram, A K. and Sloan, J J.: Temperature-dependent nucleation rate constants and freezing behavior of submicron nitric acid dihydrate aerosol particles under stratospheric conditions, J. Geophys. Res., 103, 3553–3561, 1998a.

Bertram, A K. and Sloan, J J.: The nucleation rate constants and freezing mechanism of nitric acid trihydrate aerosol under stratospheric conditions, J. Geophys. Res., 103, 13 261–13 265, 1998b.

Bertram, A K., Dickens, D B., and Sloan, J J.: Supercooling of type 1 polar stratospheric clouds: The freezing of submicron nitric acid aerosols having \chemHNO_3 mol fractions less than $0.5$, J. Geophys. Res., 105, 9283–9290, 2000.

Brooks, S D., Baumgardner, D., Gandrud, B., Dye, J E., Northway, M J., Fahey, D W., Bui, T P., Toon, O B., and Tolbert, M A.: Measurements of large stratospheric particles in the Arctic polar vortex, J. Geophys. Res., 108, 4652, doi:10.1029/2002JD003278, 2003.

Bunz, H. and Dlugi, R.: Numerical-Studies on the Behavior of Aerosols in Smog Chambers, J. Aerosol Sci., 22, 441–465, 1991.

Carslaw, K S., Clegg, S L., and Brimblecombe, P.: A Thermodynamic Model of the System \chemHCl-HNO_3-H_2SO_4-H_2O, Including Solubilities of \chemHBr, from $<$$200$ to $328$ \unitK, J. Phys. Chem., 99, 11 557–11 574, 1995.

Carslaw, K S., Peter, T., Bacmeister, J T., and Eckermann, S D.: Widespread solid particle formation by mountain waves in the Arctic stratosphere, J. Geophys. Res., 104, 1827–1836, 1999.

Clegg, S., Brimbleconbe, P., and Wexler, A.: Thermodynamic model of the system \chemH^+-NH_4^+-SO_4^2-NO_3^–H_2O at tropospheric temperatures, J. Phys. Chem. A, 102, 2137–2154, doi:10.1021/jp973042r, 1998.

Curtius, J., Weigel, R., Vössing, H.-J., Wernli, H., Werner, A., Volk, C.-M., Konopka, P., Krebsbach, M., Schiller, C., Roiger, A., Schlager, H., Dreiling, V., and Borrmann, S.: Observations of meteoritic material and implications for aerosol nucleation in the winter Arctic lower stratosphere derived from in situ particle measurements, Atmos. Chem. Phys., 5, 3053–3069, 2005.

Deshler, T., Larsen, N., Weissner, C., Schreiner, J., Mauersberger, K., Cairo, F., Adriani, A., Di~Donfrancesco, G., Ovarlez, J., Ovarlez, H., Blum, U., Fricke, K H., and Dörnbrack, A.: Large nitric acid particles at the top of an Arctic stratospheric cloud, J. Geophys. Res., 108, 4517, doi:10.1029/2003JD003479, 2003.

Disselkamp, R S., Anthony, S E., Prenni, A J., Onasch, T B., and Tolbert, M A.: Crystallization kinetics of nitric acid dihydrate aerosols, J. Phys. Chem., 100, 9127–9137, 1996.

Drdla, K. and Browell, E V.: Microphysical modeling of the 1999–2000 Arctic winter: 3. Impact of homogeneous freezing on polar stratospheric clouds, J. Geophys. Res., 109, doi:10.1029/2003JD004352, 2004.

Fahey, D W., Gao, R S., Carslaw, K S., Kettleborough, J., Popp, P J., Northway, M J., Holecek, J C., Ciciora, S C., McLaughlin, R J., Thompson, T L., Winkler, R H., Baumgardner, D G., Gandrud, B., Wennberg, P O., Dhaniyala, S., McKinney, K., Peter, T., Salawitch, R J., Bui, T P., Elkins, J W., Webster, C R., Atlas, E L., Jost, H., Wilson, J C., Herman, R L., Kleinböhl, A., and von König, M.: The detection of large \chemHNO_3-containing particles in the winter arctic stratosphere, Science, 291, 1026–1031, 2001.

Höpfner, M., Larsen, N., Spang, R., Luo, B P., Ma, J., Svendsen, S H., Eckermann, S D., Knudsen, B., Massoli, P., Cairo, F., Stiller, G., Von~Clarmann, T., and Fischer, H.: MIPAS detects Antarctic stratospheric belt of NAT PSCs caused by mountain waves, Atmos. Chem. Phys., 6, 1221–1230, 2006.

Irie, H. and Kondo, Y.: Evidence for the nucleation of polar stratospheric clouds inside liquid particles, Geophys. Res. Lett., 30, 38–1, doi:10.1029/2002GL016493, 2003.

Irie, H., Pagan, K L., Tabazadeh, A., Legg, M J., and Sugita, T.: Investigation of polar stratospheric cloud solid particle formation mechanisms using ILAS and AVHRR observations in the Arctic, Geophys. Res. Lett., 31, L15107, doi:10.1029/2004GL020246, 2004.

Jensen, E J., Toon, O B., and Hamill, P.: Homogeneous Freezing Nucleation of Stratospheric Solution Droplets, Geophys. Res. Lett., 18, 1857–1860, 1991.

Knopf, D A.: Do NAD and NAT form in liquid stratospheric aerosols by pseudoheterogeneous nucleation?, J. Phys. Chem. A, 110, 5745–5750, 2006.

Knopf, D A., Koop, T., Luo, B P., Weers, U G., and Peter, T.: Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification, Atmos. Chem. Phys., 2, 207–214, 2002.

Koop, T., Luo, B., Tsias, A., and Peter, T.: Water activity as the determinant for homogeneous ice nucleation in aqueous solutions, Nature, 406, 611–614, 2000.

Larsen, N., Knudsen, B M., Svendsen, S H., Deshler, T., Rosen, J M., Kivi, R., Weisser, C., Schreiner, J., Mauerberger, K., Cairo, F., Ovarlez, J., Oelhaf, H., and Spang, R.: Formation of solid particles in synoptic-scale Arctic PSCs in early winter 2002/2003, Atmos. Chem. Phys., 4, 2001–2013, 2004.

Luo, B P., Carslaw, K S., Peter, T., and Clegg, S L.: Vapor pressures of \chemH_2SO_4/HNO_3/HCl/HBr/H_2O solutions to low stratospheric temperatures, Geophys. Res. Lett., 22, 247–250, 1995.

Luo, B P., Voigt, C., Fueglistaler, S., and Peter, T.: Extreme NAT supersaturations in mountain wave ice PSCs: A clue to NAT formation, J. Geophys. Res., 108, 4441, doi:10.1029/2002JD003104, 2003.

Pagan, K L., Tabazadeh, A., Drdla, K., Hervig, M E., Eckermann, S D., Browell, E V., Legg, M J., and Foschi, P G.: Observational evidence against mountain-wave generation of ice nuclei as a prerequisite for the formation of three solid nitric acid polar stratospheric clouds observed in the Arctic in early December 1999, J. Geophys. Res., 109, D04312, doi:10.1029/2003JD003846, 2004.

Peter, T.: Microphysics and heterogeneous chemistry of polar stratospheric clouds, Ann. Rev. Phys. Chem., 48, 785–822, 1997.

Prenni, A J., Onasch, T B., Tisdale, R T., Siefert, R L., and Tolbert, M A.: Composition-dependent freezing nucleation rates for \chemHNO_3/H_2O aerosols resembling gravity-wave-perturbed stratospheric particles, J. Geophys. Res., 103, 28 439–28 450, 1998.

Salcedo, D., Molina, L T., and Molina, M J.: Nucleation rates of nitric acid dihydrate in $1 : 2$ \chemHNO_3/H_2O solutions at stratospheric temperatures, Geophys. Res. Lett., 27, 193–196, 2000.

Salcedo, D., Molina, L T., and Molina, M J.: Homogeneous freezing of concentrated aqueous nitric acid solutions at polar stratospheric temperatures, J. Phys. Chem. A, 105, 1433–1439, 2001.

Solomon, S.: Stratospheric ozone depletion: A review of concepts and history, Rev. Geophys., 37, 275–316, 1999.

Stetzer, O., Möhler, O., Wagner, R., Benz, S., Saathoff, H., Bunz, H., and Indris, O.: Homogeneous nucleation rates of nitric acid dihydrate (NAD) at simulated stratospheric conditions – Part~I: Experimental results, Atmos. Chem. Phys., 6, 3023–3033, 2006.

Tabazadeh, A.: Commentary on "Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification" by Knopf et al., Atmos. Chem. Phys., 3, 863–865, 2003.

Tabazadeh, A., Jensen, E J., Toon, O B., Drdla, K., and Schoeberl, M R.: Role of the stratospheric polar freezing belt in denitrification, Science, 291, 2591–2594, 2001.

Tabazadeh, A., Djikaev, Y S., Hamill, P., and Reiss, H.: Laboratory evidence for surface nucleation of solid polar stratospheric cloud particles, J. Phys. Chem. A, 106, 10 238–10 246, 2002.

Tisdale, R T., Middlebrook, A M., Prenni, A J., and Tolbert, M A.: Crystallization kinetics of \chemHNO_3/H_2O films representative of polar stratospheric clouds, J. Phys. Chem. A, 101, 2112–2119, 1997.

Tizek, H., Knözinger, E., and Grothe, H.: X-ray diffraction studies on nitric acid dihydrate, Phys. Chem. Chem. Phys., 4, 5128–5134, 2002.

Turnbull, D.: Formation of crystal nuclei in liquid metals, J. Appl. Phys., 21, 1022–1028, 1950.

Voigt, C., Schreiner, J., Kohlmann, A., Zink, P., Mauersberger, K., Larsen, N., Deshler, T., Kroger, C., Rosen, J., Adriani, A., Cairo, F., Di~Donfrancesco, G., Viterbini, M., Ovarlez, J., Ovarlez, H., David, C., and Dornbrack, A.: Nitric acid trihydrate (NAT) in polar stratospheric clouds, Science, 290, 1756–1758, 2000.

Voigt, C., Larsen, N., Deshler, T., Kröger, C., Schreiner, J., Mauersberger, K., Luo, B P., Adriani, A., Cairo, F., Di~Donfrancesco, G., Ovarlez, J., Ovarlez, H., Dörnbrack, A., Knudsen, B., and Rosen, J.: In situ mountain-wave polar stratospheric cloud measurements: Implications for nitric acid trihydrate formation, J. Geophys. Res., 108, 8331, doi:10.1029/2001JD001185, 2003.

Voigt, C., Schlager, H., Luo, B P., Dörnbrack, A D., Roiger, A., Stock, P., Curtius, J., Vössing, H., Borrmann, S., Davies, S., Konopka, P., Schiller, C., Shur, G., and Peter, T.: Nitric Acid Trihydrate (NAT) formation at low NAT supersaturation in Polar Stratospheric Clouds (PSCs), Atmos. Chem. Phys., 5, 1371–1380, 2005.

Wagner, R., Mangold, A., Möhler, O., Saathoff, H., Schnaiter, M., and Schurath, U.: A quantitative test of infrared optical constants for supercooled sulphuric and nitric acid droplet aerosols, Atmos. Chem. Phys., 3, 1147–1164, 2003.

Wagner, R., Möhler, O., Saathoff, H., Stetzer, O., and Schurath, U.: Infrared spectrum of nitric acid dihydrate: Influence of particle shape, J. Phys. Chem. A, 109, 2572–2581, 2005.

Waibel, A E., Peter, T., Carslaw, K S., Oelhaf, H., Wetzel, G., Crutzen, P J., Poschl, U., Tsias, A., Reimer, E., and Fischer, H.: Arctic ozone loss due to denitrification, Science, 283, 2064–2069, 1999.