Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
9
4
2009
10.5194/acpd-9-15181-2009
http://www.atmos-chem-phys-discuss.net/9/15181/2009/
http://www.atmos-chem-phys-discuss.net/9/15181/2009/acpd-9-15181-2009.html
http://www.atmos-chem-phys-discuss.net/9/15181/2009/acpd-9-15181-2009.pdf
15181
15214
2009-07-14
Toward a general parameterization of N<sub>2</sub>O<sub>5</sub> reactivity on aqueous particles: the competing effects of particle liquid water, nitrate and chloride
T. H. Bertram
J. A. Thornton
thornton@atmos.washington.edu
Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA
now at: Department of Chemistry; University of California San Diego, La Jolla, CA, USA
The heterogeneous reaction of N<sub>2</sub>O<sub>5</sub> on mixed organic-inorganic aerosol particles
was investigated using an entrained aerosol flow tube coupled to a custom-built chemical
ionization mass spectrometer. Laboratory results on aqueous particles confirm a strong
dependence of the reactive uptake coefficient (γ) on particle liquid water, for
particle water concentrations below 15 M, and the molar ratio of particle water to
nitrate. Measurements of γ(N<sub>2</sub>O<sub>5</sub>) on mixed chloride-nitrate particles
indicate that the presence of trace chloride can negate the suppression of
γ(N<sub>2</sub>O<sub>5</sub>) at high nitrate loadings with implications for polluted coastal
regions. These results are used to construct a new parameterization for γ(N<sub>2</sub>O<sub>5</sub>), that when coupled to an aerosol thermodynamics model, can be used
within regional and/or global chemical transport models.
Anttila, T., Kiendler-Scharr, A., Tillmann, R., and Mentel, T F.: On the reactive uptake of gaseous compounds by organic-coated aqueous aerosols: Theoretical analysis and application to the heterogeneous hydrolysis of \chemN_2O_5, J. Phys. Chem. A, 110, 10435–10443, 2006.
Badger, C L., Griffiths, P T., George, I., Abbatt, J P D., and Cox, R A.: Reactive uptake of \chemN_2O_5 by aerosol particles containing mixtures of humic acid and ammonium sulfate, J. Phys. Chem. A, 110, 6986–6994, 2006.
Behnke, W., George, C., Scheer, V., and Zetzsch, C.: Production and decay of \chemClNO_2, from the reaction of gaseous \chemN_2O_5 with \chemNaCl solution: Bulk and aerosol experiments, J. Geophys. Res., 102, 3795–3804, 1997.
Bertram, T H., Thornton, J A., and Riedel, T P.: An experimental technique for the direct measurement of \chemN_2O_5 reactivity on ambient particles, Atmos. Meas. Tech., 2, 231–242, 2009.
Braban, C F. and Abbatt, J P D.: A~study of the phase transition behavior of internally mixed ammonium sulfate~– malonic acid aerosols, Atmos. Chem. Phys., 4, 1451–1459, 2004.
Brown, R. L.: Tubular Flow Reactors with 1st-Order Kinetics, Journal of Research of the National Bureau of Standards, 83, 1–8, 1978.
Brown, S S., Ryerson, T B., Wollny, A G., Brock, C A., Peltier, R., Sullivan, A P., Weber, R J., Dube, W P., Trainer, M., Meagher, J F., Fehsenfeld, F C., and Ravishankara, A R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, 2006.
Carslaw, K S., Clegg, S L., and Brimblecombe, P.: A~thermodynamic model of the system \chemHCl-\chemHNO_3-\chemH_2SO_4-\chemH_2O, including solubilities of \chemHBr, from less than 200 to 328 \unitK, J. Phys. Chem., 99, 11557–11574, 1995.
Clegg, S L., Brimblecombe, P., and Wexler, A S.: Thermodynamic model of the system \chemH^+-\chemNH_4^+-\chemNa^+-\chemSO_4^2-\chemNO_3^-\chemCl^-\chemH_2O at 298.15 \unitK, J. Phys. Chem. A., 102, 2155–2171, 1998.
Cosman, L M. and Bertram, A K.: Reactive uptake of \chemN_2O_5 on aqueous \chemH_2SO_4 solutions coated with 1-component and 2-component monolayers, J. Phys. Chem. A, 112, 4625–4635, 2008.
Cosman, L M., Knopf, D A., and Bertram, A K.: \chemN_2O_5 reactive uptake on aqueous sulfuric acid solutions coated with branched and straight-chain insoluble organic surfactants, J. Phys. Chem. A, 112, 2386–2396, 2008.
Cziczo, D J., Nowak, J B., Hu, J H., and Abbatt, J P D.: Infrared spectroscopy of model tropospheric aerosols as a~function of relative humidity: Observation of deliquescence and crystallization, J. Geophys. Res., 102, 18843–18850, 1997.
Davis, J M., Bhave, P V., and Foley, K M.: Parameterization of \chemN_2O_5 reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate, Atmos. Chem. Phys., 8, 5295–5311, 2008.
Dentener, F J. and Crutzen, P J.: Reaction of \chemN_2O_5 on tropospheric aerosols~– Impact on the global distributions of \chemNO_x, \chemO_3, and \chemOH, J. Geophys. Res., 98, 7149–7163, 1993.
Evans, M J. and Jacob, D J.: Impact of new laboratory studies of \chemN_2O_5 hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone, and \chemOH, Geophys. Res. Let., 32, L09813, doi:10.1029/2005GL022469, 2005.
Finlayson-Pitts, B J., Ezell, M J., and Pitts, J N.: Formation of chemically active chlorine compounds by reactions of atmospheric \chemNaCl particles with gaseous \chemN_2O_5 and ClO\chemNO_2, Nature, 337, 241–244, 1989.
Folkers, M., Mentel, T F., and Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of \chemN_2O_5, Geophys. Res. Lett., 30(12), 1644, doi:10.1029/2003GL017168, 2003.
Fountoukis, C. and Nenes, A.: ISORROPIA II: a computationally efficient thermodynamic equilibrium model for \chemK^+-\chemCa^2+-\chemMg^2+-\chemNH^4+-\chemNa^+- \chemSO_4^2-\chemNO_3^-\chemCl^-\chemH_2O aerosols, Atmos. Chem. Phys., 7, 4639–4659, 2007.
Fried, A., Henry, B E., Calvert, J G., and Mozurkewich, M.: The reaction probability of \chemN_2O_5 with sulfuric-acid aerosols at stratospheric temperatures and compositions, J. Geophys. Res., 99, 3517–3532, 1994.
Griffiths, P T., Badger, C L., Cox, R A., Folkers, M., Henk, H H., and Mentel, T F.: Reactive uptake of \chemN_2O_5 by aerosols containing dicarboxylic acids, effect of particle phase, composition, and nitrate content, J. Phys. Chem. A, 113, 5082–5090, 2009.
Hallquist, M., Stewart, D J., Stephenson, S K., and Cox, R A.: Hydrolysis of \chemN_2O_5 on sub-micron sulfate aerosols, PCCP, 5, 3453–3463, 2003.
Hanson, D. and Kosciuch, E.: The \chemNH_3 mass accommodation coefficient for uptake onto sulfuric acid solutions, J. Phys. Chem. A., 107, 2199–2208, 2003.
Hu, J H. and Abbatt, J P D.: Reaction probabilities for \chemN_2O_5 hydrolysis on sulfuric acid and ammonium sulfate aerosols at room temperature, J. Phys. Chem. A, 101, 871–878, 1997.
Kane, S M., Caloz, F., and Leu, M T.: Heterogeneous uptake of gaseous \chemN_2O_5 by (\chemNH_4)(2)\chemSO_4, \chemNH_4HSO_4, and \chemH_2SO_4 aerosols, J. Phys. Chem. A, 105, 6465–6470, 2001.
Kercher, J P., Riedel, T P., and Thornton, J A.: Chlorine activation by \chemN_2O_5: simultaneous, in situ detection of \chemClNO_2 and \chemN_2O_5 by chemical ionization mass spectrometry, Atmos. Meas. Tech., 2, 193–204, 2009.
McNeill, V. F., Patterson, J., Wolfe, G. M., and Thornton, J. A.: The effect of varying levels of surfactant on the reactive uptake of \chemN_2O_5 to aqueous aerosol, Atmos. Chem. Phys., 6, 1635–1644, 2006.
Mentel, T F., Sohn, M., and Wahner, A.: Nitrate effect in the heterogeneous hydrolysis of dinitrogen pentoxide on aqueous aerosols, PCCP, 1, 5451–5457, 1999.
Mozurkewich, M. and Calvert, J G.: Reaction probability of \chemN_2O_5 on aqueous aerosols, J. Geophys. Res., 93, 15889–15896, 1988.
Murphy, D M., Cziczo, D J., Froyd, K D., Hudson, P K., Matthew, B M., Middlebrook, A M., Peltier, R E., Sullivan, A., Thomson, D S., and Weber, R J.: Single-particle mass spectrometry of tropospheric aerosol particles, J. Geophys. Res., 111, D23S32, doi:10.1029/2006JD007340, 2006.
Osthoff, H D., Roberts, J M., Ravishankara, A R., Williams, E J., Lerner, B M., Sommariva, R., Bates, T S., Coffman, D., Quinn, P K., Dibb, J E., Stark, H., Burkholder, J B., Talukdar, R K., Meagher, J., Fehsenfeld, F C., and Brown, S S.: High levels of nitryl chloride in the polluted subtropical marine boundary layer, Nature Geoscience, 1, 324–328, 2008.
Park, S C., Burden, D K., and Nathanson, G M.: The inhibition of \chemN_2O_5 hydrolysis in sulfuric acid by 1-butanol and 1-hexanol surfactant coatings, J. Phys. Chem. A, 111, 2921–2929, 2007.
Quinn, P K., Bates, T S., Baynard, T., Clarke, A D., Onasch, T B., Wang, W., Rood, M J., Andrews, E., Allan, J., Carrico, C M., Coffman, D., and Worsnop, D.: Impact of particulate organic matter on the relative humidity dependence of light scattering: A~simplified parameterization, Geophys. Res. Let., 32, L22809, doi:10.1029/2005GL024322, 2005.
Riemer, N., Vogel, H., Vogel, B., Anttila, T., Kiendler-Scharr, A., and Mentel, T F.: The relative importance of organic coatings for the heterogeneous hydrolysis of \chemN_2O_5, in preparation, 2009.
Riemer, N., Vogel, H., Vogel, B., Schell, B., Ackermann, I., Kessler, C. and Hass, H.: Impact of the heterogeneous hydrolysis of \chemN_2O_5 on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions, J. Geophys. Res., 108(D4), 4144, doi:10.1029/2002JD002436, 2003.
Robinson, G N., Worsnop, D R., Jayne, J T., Kolb, C E. and Davidovits, P.: Heterogeneous uptake of \chemClONO_2 and \chemN_2O_5 by sulfuric acid solutions, J. Geophys. Res., 102, 3583–3601, 1997.
Schweitzer, F., Mirabel, P., and George, C.: Multiphase chemistry of \chemN_2O_5, \chemClNO_2, and Br\chemNO_2, J. Phys. Chem. A., 102, 3942–3952, 1998.
Thornton, J A. and Abbatt, J P D.: \chemN_2O_5 reaction on submicron sea salt aerosol: Kinetics, products, and the effect of surface active organics, J. Phys. Chem. A, 109, 10004–10012, 2005.
Thornton, J A., Braban, C F., and Abbatt, J P D.: \chemN_2O_5 hydrolysis on sub-micron organic aerosols: the effect of relative humidity, particle phase, and particle size, PCCP, 5, 4593–4603, 2003.
Wagner, C., Hanisch, F., Holmes, N., de Coninck, H., Schuster, G., and Crowley, J N.: The interaction of \chemN_2O_5 with mineral dust: aerosol flow tube and Knudsen reactor studies, Atmos. Chem. Phys., 8, 91–109, 2008.
Wahner, A., Mentel, T F., Sohn, M., and Stier, J.: Heterogeneous reaction of \chemN_2O_5 on sodium nitrate aerosol, J. Geophys. Res., 103, 31103–31112, 1998.
Wexler, A S. and Clegg, S L.: Atmospheric aerosol models for systems including the ions \chemH^+, \chemNH_4^+, \chemNa^+, \chemSO_4^2-, \chemNO_3^-,\chemCl^-, \chemBr^-, and \chemH_2O, J. Geophys. Res., 107(D14), 4207, doi:10.1029/2001JD000451, 2002.
Zaveri, R A., Easter, R C., Fast, J D., and Peters, L K.: Model for simulating aerosol interactions and chemistry (MOSAIC), J. Geophys. Res., 113, D13204, doi:10.1029/2007JD008782, 2008.