Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 6 2007 10.5194/acpd-7-16119-2007 http://www.atmos-chem-phys-discuss.net/7/16119/2007/ http://www.atmos-chem-phys-discuss.net/7/16119/2007/acpd-7-16119-2007.html http://www.atmos-chem-phys-discuss.net/7/16119/2007/acpd-7-16119-2007.pdf 16119 16153 2007-11-19 Parameterization of N₂O₅ reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate J. M. Davis davisj@ncsu.edu P. V. Bhave K. M. Foley Atmospheric Modeling Division, U.S. Environmental Protection Agency, Research Triangle Park, NC, USA Atmospheric Sciences Modeling Division, Air Resources Laboratory, National Oceanic and Atmospheric Administration, Research Triangle Park, NC, USA now at: North Carolina State University, Department of Marine, Earth, and Atmospheric Sciences, Raleigh, NC, USA A comprehensive parameterization was developed for the heterogeneous reaction probability (γ) of N₂O₅ as a function of temperature, relative humidity, particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH₄HSO₄, (NH₄)₂SO₄, and NH₄NO₃ were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH₄HSO₄ and (NH₄)₂SO₄ particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 79% of the laboratory data within a factor of two and 53% within a factor of 1.25. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, relative humidity, sulfate, nitrate, and ammonium, obtained from a recent Community Multiscale Air Quality model simulation. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our results highlight a critical need for more laboratory measurements of γ at low temperature and high relative humidity to improve model simulations of N₂O₅ hydrolysis during wintertime conditions. Akaike, H.: Information theory and an extension of the maximum likelihood principle. In Proc. 2nd Int. Symp. Information Theory, eds B. N. Petrov and F. Csáki, Budapest, 267–281, 1973. Aldener, M., Brown, S. S., Stark, H., Williams, E. J., Lerner, B. M., Kuster, W. C., Goldan, P. D., Quinn, P. K., Bates, T. S., Fehsenfeld, F. C., and Ravishankara, A. R.: Reactivity and loss mechanisms of NO₃ and N₂O$_5$ in a polluted marine environment: Results from in situ measurements during New England Air Quality Study 2002, J. Geophys. Res., 111, D23S73, doi:10.1029/2006JD007252, 2006. 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 N₂O$_5$, J. Phys. Chem. A, 110, 10 435–10 443, 2006. % %Appel, K. W., Bhave, P. V., Gilliland, A. B., Sarwar, G., and Roselle, S. %J.: Evaluation of the Community Multiscale Air Quality (CMAQ) model version %4.5: Uncertainties and sensitivities impacting model performance. Part II: %Particulate matter, Atmos. Environ., in review\blackbox\bf status?, 2007. Ayers, J. D. and Simpson, W. R.: Measurements of N₂O$_5$ near Fairbanks, Alaska, J. Geophys. Res., 111, D14309, doi:10.1029/2006JD007070, 2006. Badger, C. L., Griffiths, P. T., George, I., Abbatt, J. P. D., and Cox, R. A.: Reactive uptake of N₂O$_5$ by aerosol particles containing mixtures of humic acid and ammonium sulfate, J. Phys. Chem. A, 110, 6986–6994, 2006a. Badger, C. L., George, I., Griffiths, P. T., Braban, C. F., Cox, R. A., and Abbatt, J. P. D.: Phase transitions and hygroscopic growth of aerosol particles containing humic acid and mixtures of humic acid and ammonium sulphate, Atmos. Chem. Phys., 6, 755–768, 2006b. Binkowski, F. S. and Roselle, S. J.: Models-3 Community Multiscale Air Quality (CMAQ) model aerosol component – 1. Model description, J. Geophys. Res., 108, 4183, doi:10.1029/2001JD001409, 2003. Brown, S. S., Stark, H., Ciciora, S. J., and Ravishankara, A. R.: In-situ measurement of atmospheric NO₃ and N₂O$_5$ via cavity ring-down spectroscopy, Geophys. Res. Lett., 28, 3227–3230, 2001. Brown, S. S., Stark, H., Ryerson, T. B., Williams, E. J., Nicks, D. K., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nitrogen oxides in the nocturnal boundary layer: Simultaneous in situ measurements of NO₃, N₂O$_5$, NO₂, NO, and O₃, J. Geophys. Res., 108, 4299, doi:10.1029/2002JD002917, 2003a. Brown, S. S., Stark, H., and Ravishankara, A. R.: Applicability of the steady state approximation to the interpretation of atmospheric observations of NO₃ and N₂O$_5$, J. Geophys. Res., 108, 4539, doi:10.1029/2003JD003407, 2003b. Brown, S. S., Dibb, J. E., Stark, H., Aldener, M., Vozella, M., Whitlow, S., Williams, E. J., Lerner, B. M., Jakoubek, R., Middlebrook, A. M., DeGouw, J. A., Warneke, C., Goldan, P. D., Kuster, W. C., Angevine, W. M., Sueper, D. T., Quinn, P. K., Bates, T. S., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Nighttime removal of NO_x in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GL019412, 2004. 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. Brown, S. S., Dubé, W. P., Osthoff, H. D., Wolfe, D. E., Angevine, W. M., and Ravishankara, A. R.: High resolution vertical distributions of NO₃ and N₂O$_5$ through the nocturnal boundary layer, Atmos. Chem. Phys., 7, 139–149, 2007. Casella, G. and Berger, R. L.: Statistical Inference, 2$^nd$ edition, Duxbury, Pacific Grove, CA, 2002. Dentener, F. J. and Crutzen, P. J.: Reaction of N₂O$_5$ on tropospheric aerosols: Impact on the global distributions of NO_x, O₃, and OH, J. Geophys. Res., 98, 7149–7163, 1993. Evans, M. J. and Jacob, D. J.: Impact of new laboratory studies of N₂O$_5$ hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone and OH, Geophys. Res. Lett., 32, L09813, doi:10.1029/2005GL022469, 2005. Folkers, M.: Bestimmung der reaktionswahrscheinlichkeit von N₂O$_5$ an troposhärisch relevanten aerosolen, Ph.D. Thesis, Universität Köln, 2001. Folkers, M., Mentel, Th. F., and Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of N₂O$_5$, Geophys. Res. Lett., 30, 1644, doi:10.1029/2003GL017168, 2003. Fried, A., Henry, B. E., Calvert, J. G., and Mozurkewich, M.: The reaction probability of N₂O$_5$ with sulfuric acid aerosols at stratospheric temperatures, J. Geophys. Res., 99, 3517–3532, 1994. Gilliland, A. B., Appel, K. W., Pinder, R. W., and Dennis, R. L.: Seasonal NH₃ emissions for the continental United States: Inverse model estimation and evaluation, Atmos. Environ., 40, 4986–4998, 2006. Goff, J. A. and Gratch, S.: Low-pressure properties of water from −160 to 212F, in Transactions of the American society of heating and ventilating engineers, presented at the 52nd annual meeting of the American society of heating and ventilating engineers, New York, 95–122, 1946. Hallquist, M., Stewart, D. J., Stephenson, S. K., and Cox, R. A.: Hydrolysis of N₂O$_5$ on sub-micron sulfate aerosols, Phys. Chem. Chem. Phys., 5, 3453–3463, 2003. Hanson, D. R. and Ravishankara, A. R.: The reaction probabilities of ClONO₂ and N₂O$_5$ on polar stratospheric cloud materials, J. Geophys. Res., 96, 5081–5090, 1991. Hu, J. H. and Abbatt, J. P. D.: Reaction probabilities for N₂O$_5$ hydrolysis on sulfuric acid and ammonium sulfate aerosols at room temperature, J. Phys. Chem. A, 101, 871–878, 1997. IUPAC Subcommittee on gas kinetic data evaluation: Data sheet H23, http://www.iupac-kinetic.ch.cam.ac.uk/, revised 15 August, 2006. Kane, S. M., Caloz, F., and Leu, M.-T.: Heterogeneous uptake of gaseous N₂O$_5$ by (NH$_4)_2$SO₄, NH₄HSO₄, and H₂SO₄ aerosols, J. Phys. Chem. A, 105, 6465–6470, 2001. Khlystov, A., Stanier, C. O., Takahama, S., and Pandis, S. N.: Water content of ambient aerosol during the Pittsburgh Air Quality Study, J. Geophys. Res., 110, D07S10, doi:10.1029/2004JD004651, 2005. Kutner, M. H., Nachtshein, C. J., Neter, J., and Li, W.: Applied Linear Statistical Models, 5th edition, McGraw-Hill, New York, 2005. Leu, M.-T.: Heterogeneous reactions of N₂O$_5$ and HCl on ice surfaces: implications for Antarctic ozone depletion, Geophys. Res. Lett., 15, 851–854, 1988. Martin, S. T.: Phase transitions of aqueous atmospheric particles, Chem. Rev., 100, 3403–3453, 2000. Martin, S. T., Schlenker, J. C., Malinowski, A., Hung, H.-M., and Rudich, Y.: Crystallization of atmospheric sulfate-nitrate-ammonium particles, Geophys. Res. Lett., 30, 2102, doi:10.1029/2003GL017930, 2003. Matsumoto, J., Imagawa, K., Imai, H., Kosugi, N., Ideguchi, M., Kato, S., and Kajii, Y.: Nocturnal sink of NO_x via NO₃ and N₂O$_5$ in the outflow from a source area in Japan, Atmos. Environ., 40, 6294–6302, 2006. Mentel, T. F., Sohn, M., and Wahner, A.: Nitrate effect in the heterogeneous hydrolysis of dinitrogen pentoxide on aqueous aerosols, Phys. Chem. Chem. Phys., 1, 5451–5457, 1999. Mozurkewich, M. and Calvert, J. G.: Reaction probability of N₂O$_5$ on aqueous aerosols, J. Geophys. Res., 93, 15 889–15 896, 1988. Riemer, N., Vogel, H., Vogel, B., Schell, B., Ackermann, I., Kessler, C., and Hass, H.: Impact of the heterogeneous hydrolysis of N₂O$_5$ on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions, J. Geophys. Res., 108, 4144, doi:10.1029/2002JD002436, 2003. Robinson, G. N., Worsnop, D. R., Jayne, J. T., Kolb, C. E., Davidovits, P.: Heterogeneous uptake of ClONO₂ and N₂O$_5$ by sulfuric acid solutions, J. Geophys. Res., 102, 3583–3601, 1997. Rood, M. J., Shaw, M. A., Larson, T. V., and Covert, D. S.: Ubiquitous nature of ambient metastable aerosol, Nature, 337, 537–539, 1989. Santarpia, J. L., Li, R., and Collins, D. R.: Direct measurement of the hydration state of ambient aerosol populations, J. Geophys. Res., 109, D18209, doi:10.1029/2004JD004653, 2004. Schlenker, J. C., Malinowski, A., Martin, S. T., Hung, H.-M., and Rudich, Y.: Crystals formed at 293 K by aqueous sulfate-nitrate-ammonium-proton aerosol particles, J. Phys. Chem. A, 108, 9375–9383, 2004. Stelson, A. W. and Seinfeld, J. H.: Relative humidity and temperature dependence of the ammonium nitrate dissociation constant, Atmos. Environ., 16, 983–992, 1982. Stutz, J., Alicke, B., Ackermann, R., Geyer, A., White, A., and Williams, E.: Vertical profiles of NO₃, N₂O$_5$, O₃, and NO_x in the nocturnal boundary layer: 1. Observations during the Texas Air Quality Study 2000, J. Geophys. Res., 109, D12306, doi:10.1029/2003JD004209, 2004. Tang, I. N. and Munkelwitz, H. R.: Water activities, densities, and refractive indices of aqueous sulfates and sodium nitrate droplets of atmospheric importance, J. Geophys. Res., 99, 18 801–18 808, 1994. Wahner, A., Mentel, T. F., Sohn, M., and Stier, J.: Heterogeneous reaction of N₂O$_5$ on sodium nitrate aerosol, J. Geophys. Res., 103, 31 103–31 112, 1998. Wexler, A. S., Lurmann, F. W., and Seinfeld, J. H.: Modelling urban and regional aerosols – I. Model development. Atmos. Environ., 28, 531–546, 1994. Wood, E. C., Bertram, T. H., Wooldridge, P. J., and Cohen, R. C.: Measurements of N₂O$_5$, NO₂, and O₃ east of the San Francisco Bay, Atmos. Chem. Phys., 5, 483–491, 2005.