ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-8-5899-2008 Consistent simulation of bromine chemistry from the marine boundary layer to the stratosphere – Part 1: Model description, sea salt aerosols and pH Kerkweg A. 1 2 Jöckel P. 1 Pozzer A. 1 Tost H. 1 Sander R. 1 Schulz M. 3 Stier P. 4 Vignati E. 5 Wilson J. 5 Lelieveld J. 1 MPI for Chemistry (Otto Hahn Institute), Atmospheric Chemistry Department, P.O. Box 3060, 55020 Mainz, Germany Institute for Atmospheric Physics, University of Mainz, Mainz, Germany Laboratoire des Sciences du Climat et de l'Environnement, CEA-IPSL, Saclay, France Atmospheric, Oceanic and Planetary Physics, University of Oxford, Oxford, UK Joint Research Centre, Institute of Environment and Sustainability, Ispra, Italy 15 10 2008 8 19 5899 5917 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/8/5899/2008/acp-8-5899-2008.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/5899/2008/acp-8-5899-2008.pdf

This is the first article of a series presenting a detailed analysis of bromine chemistry simulated with the atmospheric chemistry general circulation model ECHAM5/MESSy. Release from sea salt is an important bromine source, hence the model explicitly calculates aerosol chemistry and phase partitioning for coarse mode aerosol particles. Many processes including chemical reaction rates are influenced by the particle size distribution, and aerosol associated water strongly affects the aerosol pH. Knowledge of the aerosol pH is important as it determines the aerosol chemistry, e.g., the efficiency of sulphur oxidation and bromine release. Here, we focus on the simulated sea salt aerosol size distribution and the coarse mode aerosol pH. <br><br> A comparison with available field data shows that the simulated aerosol distributions agree reasonably well within the range of measurements. In spite of the small number of aerosol pH measurements and the uncertainty in its experimental determination, the simulated aerosol pH compares well with the observations. The aerosol pH ranges from alkaline aerosol in areas of strong production down to pH-values of 1 over regions of medium sea salt production and high levels of gas phase acids, mostly polluted regions over the oceans in the Northern Hemisphere.

 References Balkanski, Y., Schulz, M., Claquin, T., Moulin, C., and Ginoux, P.: Global emissions of mineral aerosol: Formulation and validation using satellite imagery, Emission of Atmospheric Tracer Compounds, Kluwer Academic Publisher, Norwell, 253–282, 2003. Bates, T S., Kapustin, V N., Quinn, P K., Covert, D S., Coffman, D J., Mari, C., Dirkee, P A., Bruyn, W. J D., and Saltzman, E S.: Processes controlling the distribution of aerosol particles in the lower marine boundary layer during the First Aerosol Charaterization Experiment (ACE1), J. Geophys. Res., 103, 16 369–16 383, 1998. Brasseur, G P. and Solomon, S.: Aeronomy of the middle atmosphere, Springer-Verlag, Dordecht, The Netherlends, 2005. Buchholz, J.: Simulations of Physics and Chemistry of Polar Stratospheric Clouds with a General Circulation Model, Ph.D. thesis, Johannes Gutenberg-Universität, Fachbereich Physik, http://nbn-resolving.de/urn/resolver.pl?urn=urn:nbn:de:hebis:77-8187, 2005. Damian, V., Sandu, A., Damian, M., Potra, F., and Carmichael, G R.: The kinetic preprocessor KPP – a software enviroment for solving chemical kinetics, Comput. Chem. Eng., 26, 1567–1579, 2002. Dentener, F., Kinne, S., Bond, T., Boucher, O., Cofala, J., Generoso, S., Ginoux, P., Gong, S., Hoelzemann, J. J., Ito, A., Marelli, L., Penner, J. E., Putaud, J.-P., Textor, C., Schulz, M., van der Werf, G. R., and Wilson, J.: Emissions of primary aerosol and precursor gases in the years 2000 and 1750 prescribed data-sets for AeroCom, Atmos. Chem. Phys., 6, 4321–4344, 2006. Duce, R A.: Sea/air exchange of pollution and natural substances: The SEAREX Program, Proceedings of the WMO Technical Conference on Regional and Global Observation of Atmospheric Pollution Relative to Climate, Report, No 14, WMO No 549, World Meteorological Organization, Geneva, 1982. Fitzgerald, J W.: Marine Aerosols: A Review, Atmos. Environ., 25A, 533–545, 1991. Fridlind, A. and Jacobson, M.: A study of gas-aerosol equilibrium and aerosol pH in the remote marine boundary layer during the First Aerosol Characterization Experiment (ACE~1), J. Geophys. Res., 105, 17 325–17 340, 2000. %% %%Ganzeveld, L. and Lelieveld, J.: Dry deposition parameterization in a chemistry %% general circulation model and its influence on the distribution of reactive %% trace gases, J. Geophys. Res., 100, 20 999–21 012, 1995. Giorgetta, M A., Manzini, E., and Roeckner, E.: Forcing of the quasi-biennial oscillation from a broad spectrum of atmospheric waves, Geophys. Res. Lett., 29, 1245, doi:10.1029/2002GL014756, 2002. Giorgetta, M A., Manzini, E., Roeckner, E., Esch, M., and Bengtson, L.: Climatology and forcing of the quasi-biennial oscillation in the MAECHAM5 model, J. Clim., 19, 3882–3901, 2006. Gong, S L., Barrie, L A., Blanchet, J.-P., von Salzen, K., Lohmann, U., Lesins, G., Spacek, L., Zhang, L M., Girard, E., Lin, H., Leaitch, R., Leighton, H., Chylek, P., and Huang, P.: Canadian Aerosol Module: A size-segregated simulation of atmospheric aerosol processes for climate and air quality models 1. Module development, J. Geophys. Res., 108, 4007, doi:10.1029/2001JD002002, 2003. Guazzotti, S A., Coffee, K R., and Parther, K A.: Continuous measurements of size-resolved particle chemistry during INDOEX-Intensive Field Phase~99, J. Geophys. Res., 106, 28 607–28 627, 2001. Guelle, W., Schulz, M., Balkanski, Y., and Dentener, F.: Influence of the source formulation on modeling the atmospheric global distribution of sea salt aerosol, J. Geophys. Res., 106, 27 509–27 524, 2001. Jeuken, A., Siegmund, P., Heijboer, L., Feichter, J., and Bengtson, L.: On the potential of assimilating meteorological analysis in a climate model for the purpose of model validation, J. Geophys. Res., 101, 16 939–16 950, 1996. Jöckel, P., Sander, R., Kerkweg, A., Tost, H., and Lelieveld, J.: Technical Note: The Modular Earth Submodel System (MESSy) – a new approach towards Earth System Modeling, Atmos. Chem. Phys., 5, 433–444, 2005. Jöckel, P., Tost, H., Pozzer, A., Brühl, C., Buchholz, J., Ganzeveld, L., Hoor, P., Kerkweg, A., Lawrence, M. G., Sander, R., Steil, B., Stiller, G., Tanarhte, M., Taraborrelli, D., van Aardenne, J., and Lelieveld, J.: The atmospheric chemistry general circulation model ECHAM5/MESSy1: consistent simulation of ozone from the surface to the mesosphere, Atmos. Chem. Phys., 6, 5067–5104, 2006. Keene, W C. and Galloway, J.: Consideration Regarding Sources for Formic and Acetic Acids in the Troposphere, J. Geophys. Res., 91, 14 466–14 474, 1986. Keene, W. and Savoie, D.: The pH of deliquesced sea-salt aerosol in polluted air, Geophys. Res. Lett., 25, 2181–2184, 1998. Keene, W. and Savoie, D.: Correction to "The pH of deliquesced sea-salt aerosol in polluted air", Geophys. Res. Lett., 26, 1315–1316, 1999. Keene, W., Pszenny, A., Maben, J., Stevenson, E., and Wall, A.: Closure evaluation of size-resolved aerosol pH in the New England coastal atmosphere during summer, J. Geophys. Res., 109, D23307, doi:10.1029/2004JD004801, 2004. Keene, W C., Sander, R., Pszenny, A A., Vogt, R., Crutzen, P J., and Galloway, J N.: Aerosol pH in the marine boundary layer: A review and model evaluation, J. Aerosol Sci., 29, 339–356, 1998. 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. Kerkweg, A., Buchholz, J., Ganzeveld, L., Pozzer, A., Tost, H., and Jöckel, P.: Technical Note: An implementation of the dry removal processes DRY DEPosition and SEDImentation in the Modular Earth Submodel System (MESSy), Atmos. Chem. Phys., 6, 4617–4632, 2006a. Kerkweg, A., Sander, R., Tost, H., and Jöckel, P.: Technical note: Implementation of prescribed (OFFLEM), calculated (ONLEM), and pseudo-emissions (TNUDGE) of chemical species in the Modular Earth Submodel System (MESSy), Atmos. Chem. Phys., 6, 3603–3609, 2006b. 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. Landgraf, J. and Crutzen, P.: An Efficient Method for Online Calculation of Photolysis and Heating Rates, J. Atmos. Sci., 55, 863–878, 1998. Lauer, A., Hendricks, J., Ackermann, I., Schell, B., Hass, H., and Metzger, S.: Simulating aerosol microphysics with the ECHAM/MADE GCM - Part~I: Model description and comparison with observations, Atmos. Chem. Phys., 5, 3251–3276, 2005. Lewis, E R. and Schwartz, S E.: Sea Salt Aerosol Production: Mechanisms, Methods, Measurements and Models – A Critical Review, American Geophysical Union, Washington, D.C., 2004. Maring, H., Savioe, D., Izaguirre, M., and Custals, L.: Vertical distribution of dust and sea-salt aerosol over Puerto Rico during PRIDE measured from a light aircraft, J. Geophys. Res., 108, 8587, \doi10.1029/2002JD002544, 2003. Monahan, E C.: The Role of Air-Sea Exchange in Geochemical Cycling, chap. The Ocean as a Source for Atmospheric Particles, D. Reidel Publishing Company, 129–163, 1986. Murphy, D., Thomson, D., Middlebrook, A., and Schein, M.: In situ single-particle characterization at Cape Grim, J. Geophys. Res., 103, 16 485–16 491, 1998. O'Dowd, C D. and Smith, M H.: Physicochemical Properties of Aerosols Over the Northeast Atlantic: Evidence for Wind-Speed-Related Submicron Sea-Salt Aerosol Production, J. Geophys. Res., 98, 1137–1149, 1993. Phinney, L., Leaitch, W R., Lohmann, U., Boudires, H., Worsnop, D R., Jayne, J T., Toom-Sauntry, D., Wadleigh, M., Sharma, S., and Shantz, N.: Characterization of the aerosol over the sub-arctic north east Pacific Ocean, Deep-Sea Res., 53, 2410–2433, 2006. Pierce, J R. and Adams, P J.: Global evaluation of CCN formation by direct emission of sea salt and growth of ultrafine sea salt, J. Geophys. Res., 111, D06203, doi:10.1029/2005JD006186, 2006. Pozzer, A., Jöckel, P., Sander, R., Williams, J., Ganzeveld, L., and Lelieveld, J.: Technical Note: The MESSy-submodel AIRSEA calculating the air-sea exchange of chemical species, Atmos. Chem. Phys., 6, 5435–5444, 2006. Pozzer, A., Jöckel, P., Tost, H., Sander, R., Ganzeveld, L., Kerkweg, A., and Lelieveld, J.: Simulating organic species with the global atmospheric chemistry general circulation model ECHAM5/MESSy1: a comparison of model results with observations, Atmos. Chem. Phys., 7, 2527–2550, 2007. 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. Roeckner, E., Bäuml, G., Bonaventura, L., Brokopf, R., Esch, M., Giorgetta, M., Hagemann, S., Kirchner, I., Kornblueh, L., Manzini, E., Rhodin, A., Schlese, U., Schulzweida, U., and Tompkins, A.: The atmospheric general circulation model ECHAM5, Tech. Rep. MPI-Report~349, Max Planck-Institute for Meteorology, Hamburg, http://www.mpimet.mpg.de/fileadmin/publikationen/Reports/max_scirep_349.pdf , 2003. Roeckner, E., Brokopf, R., Esch, M., Giorgetta, M., Hagemann, S., Kornblueh, L., Manzini, E., Schlese, U., and Schulzweida, U.: The atmospheric general circulation model ECHAM5. PART II: Sensitivity of Simulated Climate to Horizontal and Vertical Resolution, Tech. Rep. MPI-Report~354, MPI for Meteorology, Hamburg, http://www.mpimet.mpg.de/fileadmin/publikationen/Reports/max_scirep_354.pdf , 2004. Sander, R. and Crutzen, P.: 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., H\"önninger, 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. Sander, R., Kerkweg, A., J\"öckel, P., and Lelieveld, J.: Technical note: The new comprehensive atmospheric chemistry module MECCA, Atmos. Chem. Phys., 5, 445–450, 2005. Sandu, A. and Sander, R.: Technical note: Simulating chemical systems in Fortran90 and Matlab with the Kinetic PreProcessor KPP-2.1, Atmos. Chem. Phys., 6, 187–195, 2006. Schulz, M., de~Leeuw, G., and Balkanski, Y.: Emission of atmospheric trace compounds, Sea-salt aerosol source functions and emissions, Kluwer Academic, 333–359, 2004. Smith, M H. and Harrison, M.: The Sea Spray Generation Function, J. Aerosol Sci., 29, Suppl 1, S189–S190, 1998. Spracklen, D. V., Pringle, K. J., Carslaw, K. S., Chipperfield, M. P., and Mann, G. W.: A global off-line model of size-resolved aerosol microphysics: I. Model development and prediction of aerosol properties, Atmos. Chem. Phys., 5, 2227–2252, 2005. Stier, P., Feichter, J., Kinne, S., Kloster, S., Vignati, E., Wilson, J., Ganzeveld, L., Tegen, I., Werner, M., Balkanski, Y., Schulz, M., Boucher, O., Minikin, A., and Petzold, A.: The aerosol-climate model ECHAM5-HAM, Atmos. Chem. Phys., 5, 1125–1156, 2005. Textor, C., Schulz, M., Guibert, S., Kinne, S., Balkanski, Y., Bauer, S., Berntsen, T., Berglen, T., Boucher, O., Chin, M., Dentener, F., Diehl, T., Easter, R., Feichter, H., Fillmore, D., Ghan, S., Ginoux, P., Gong, S., Grini, A., Hendricks, J., Horowitz, L., Huang, P., Isaksen, I., Iversen, I., Kloster, S., Koch, D., Kirkev&aring;g, A., Kristjansson, J. E., Krol, M., Lauer, A., Lamarque, J. F., Liu, X., Montanaro, V., Myhre, G., Penner, J., Pitari, G., Reddy, S., Seland, Ø., Stier, P., Takemura, T., and Tie, X.: Analysis and quantification of the diversities of aerosol life cycles within AeroCom, Atmos. Chem. Phys., 6, 1777–1813, 2006. Tost, H., Jöckel, P., Kerkweg, A., Sander, R., and Lelieveld, J.: Technical note: A new comprehensive SCAVenging submodel for global atmospheric chemistry modelling, Atmos. Chem. Phys., 6, 565–574, 2006. Tost, H., Jöckel, P., and Lelieveld, J.: Influence of different convection parameterisations in a GCM, Atmos. Chem. Phys., 6, 5475–5493, 2006. Tost, H., Jöckel, P., and Lelieveld, J.: Lightning and convection parameterisations – uncertainties in global modelling, Atmos. Chem. Phys., 7, 4553–4568, 2007. Vehkamäki, H., nad I Napari, M K., Lehtinen, K., Timmreck, C., Noppel, M., and Laaksonen, A.: An improved parameterization for sulfuric acid-water nucleation rates for tropospheric and stratospheric conditions, J. Geophys. Res., 107, 4622, doi:10.1029/2002JD002184, 2002. Vignati, E., Wilson, J., and Stier, P.: M7: An efficient size-resolved aerosol microphysics module for large-scale aerosol transport, J. Geophys. Res., 109, D22202, doi:10.1029/2003JD004486, 2004. von~Glasow, R. and Sander, R.: Variation of sea salt aerosol pH with relative humidity, Geophys. Res. Lett., 28, 247–250, 2001. von~Glasow, R., Sander, R., Bott, A., and Crutzen, P.: Modeling halogen chemistry in the marine boundary layer~1. Cloud-free MBL, J. Geophys. Res., 107, 4341, doi:10.1029/2001JD000942, 2002. Wagner, T., Leue, C., Wenig, M., Pfeilsticker, K., and Platt, U.: Spatial and temporal distribution of enhanced boundary layer BrO concentrations measured by GOME instrument onboard ERS-2, J. Geophys. Res., 106, 24 225–24 235, 2001. %% %% Wesely, M.: Parameterization of the surface resistances to gaseous dry %% depposition in regional-scale numerical models, Atmos. Environ., 23, %% 1293–1304, 1989. Wilson, J., Cuvelier, C., and Raes, F.: A modeling study of global mixed aerosol fields, J. Geophys. Res., 106, 34 081–34 108, 2001.