Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 2 2009 10.5194/acpd-9-5289-2009 http://www.atmos-chem-phys-discuss.net/9/5289/2009/ http://www.atmos-chem-phys-discuss.net/9/5289/2009/acpd-9-5289-2009.html http://www.atmos-chem-phys-discuss.net/9/5289/2009/acpd-9-5289-2009.pdf 5289 5320 2009-03-02 Modelling multi-phase halogen chemistry in the remote marine boundary layer: investigation of the influence of aerosol size resolution on predicted gas- and condensed-phase chemistry D. Lowe douglas.lowe@manchester.ac.uk D. Topping G. McFiggans School of Earth, Atmospheric and Environmental Science, University of Manchester, Manchester, UK A coupled box model of photochemistry and aerosol microphysics which explicitly accounts for size-dependent chemical properties of the condensed-phase has been developed to simulate the multi-phase chemistry of chlorine, bromine and iodine in the marine boundary layer (MBL). The model contains separate seasalt and non-seasalt modes, each of which may be composed of 1–16 size-sections. By comparison of gaseous and aerosol compositions predicted using different size-resolutions with both fixed and size-dependent aerosol turnover rates, it was found that, for halogen-activation processes, the physical property initialisation of the aerosol-mode has a significant influence on gas-phase chemistry. Failure to adequately represent the appropriate physical properties can lead to substantial errors in gas-phase chemistry. The size-resolution of condensed-phase composition has a less significant influence on gas-phase chemistry. Bott, A., Trautmann, T., and Zdunkowski, W.: A numerical model of the cloud-topped planetary boundary-layer: Radiation, turbulence and spectral microphysics in marine stratus, Q. J. Roy. Meteorol. Soc., 122, 635–667, 1996. Carver, G D., Brown, P D., and Wild, O.: The ASAD atmospheric chemistry integration package and chemical reaction database, Comput. Phys. Commun., 105, 197–215, 1997. Damian, V., Sandu, A., Damian, M., Potra, F., and Carmichael, G R.: The Kinetic PreProcessor KPP – A Software Environment for Solving Chemical Kinetics, Comput. Chem. Eng., 26, 1567–1579, 2002. Graedel, T E. and Keene, W C.: Tropospheric budget of reactive chlorine, Global Biogeochem. Cy., 9, 47–77, 1995. Jacobson, M Z.: Development and Application of a new Air Pollution Modeling System – II. Aerosol Module Structure and Design, Atmos. Environ., 31, 131–144, 1997. Keene, W C., Khalil, M. A K., Erickson, D J., McCulloch, A., Graedel, T E., Lobert, J M., Aucott, M L., Gong, S L., Harper, D B., Kleiman, G., Midgley, P., Moore, R M., Seuzaret, C., Turges, W T., Benkovitz, C M., Koropalov, V., Barrie, L A., and Li, Y F.: Composite global emissions of reactive chlorine from anthropogenic and natural sources: Reactive Chlorine Emissions Inventory, J. Geophys. Res., 104, 8429–8440, 1999. Keene, W C., Pszenny, A. A P., Maben, J R., and Sander, R.: Variation of marine aerosol acidity with particle size, Geophys. Res. Lett., 29, 1101, doi:10.1029/2001GL013881, 2002. Keene, W C., Pszenny, A. A P., Maben, J R., Stevenson, E., and Wall, A.: Closure evaluation of size-resolved aerosol pH in the New England coastal atosphere during summer, J. Geophys. Res., 109, D23307, doi:10.1029/2004JD004801, 2004. Kerkweg, A., Sander, R., Tost, H., Jöckel, P., and Lelieveld, J.: Technical Note: Simulation of detailed aerosol chemistry on the global scale using MECCA-AERO, Atmos. Chem. Phys., 7, 2973–2985, 2007. Pechtl, S., Lovejoy, E. R., Burkholder, J. B., and von Glasow, R.: Modeling the possible role of iodine oxides in atmospheric new particle formation, Atmos. Chem. Phys., 6, 505–523, 2006. Porter, J N. and Clarke, A D.: Aerosol size distribution models based on in situ measurements, J. Geophys. Res., 102, 6035–6045, 1997. Pszenny, A. A. P., Moldanová, J., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P. J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian marine boundary layer, Atmos. Chem. Phys., 4, 147–168, 2004. Read, K A., Mahajan, A S., Carpenter, L J., Evans, M J., Faria, B. V E., Heard, D E., Hopkins, J R., Lee, J D., Moller, S J., Lewis, A C., Mendes, L., McQuaid, J B., Oetjen, H., Saiz-Lopez, A., Pilling, M J., and Plane, J. M C.: Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean, Nature, 453, 1232–1235, doi:10.1038/nature07035, 2008. Sander, R. and Crutzen, P J.: Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea, J. Geophys. Res., 101, 9121–9138, 1996. Sander, R., Keene, W. C., Pszenny, A. A. P., Arimoto, R., Ayers, G. P., Baboukas, E., Cainey, J. M., Crutzen, P. J., Duce, R. A., Hönninger, G., Huebert, B. J., Maenhaut, W., Mihalopoulos, N., Turekian, V. C., and Van Dingenen, R.: Inorganic bromine in the marine boundary layer: a critical review, Atmos. Chem. Phys., 3, 1301–1336, 2003. Schwartz, S E.: Mass-transport considerations pertinent to aqueous phase reactions of gases in liquid-water clouds, in: Chemistry of Multiphase Atmospheric Systems, edited by: Jaeschke, W., Springer-Verlag, New York, USA, 415–471, 1986. Slinn, S A. and Slinn, W. G N.: Predictions for particle deposition on natural waters, Atmos. Environ., 14, 1013–1016, 1980. Sportisse, B.: An Analysis of Operator Splitting Techinques in the Stiff Case, J. Comput. Phys., 161, 140–168, 2000. Topping, D., McFiggans, G., and Lowe, D.: A hybrid mixing rule/explicit thermodynamic approach for calculating gas/liquid equilibria in atmospheric aerosol particles – 1 Inorganic compounds, J. Geophys. Res., 114, D04304, doi:10.1029/2008JD010099, 2009. Torres, A L. and Thompson, A M.: Nitric Oxide in the Equatorial Pacific Boundary Layer: SAGA 3 Measurements, J. Geophys. Res., 98, 16949–16954, 1993. Toyota, K., Takahashi, M., and Akimoto, H.: Modeling multi-phase halogen chemistry in the marine boundary layer with size-segregated aerosol module: Implications for quasi-size-dependent approach, Geophys. Res. Lett., 28, 2899–2902, 2001. von Glasow, R., Sander, R., Bott, A., and Crutzen, P J.: Modeling halogen chemistry in the marine boundary layer 1. Cloud-free MBL, J. Geophys. Res., 107, 4341, doi:10.1029/2001JD000942, 2002.