Geoscientific Model Development Discussions www.geosci-model-dev-discuss.net 1991-9611 1991-962X 2 2 2009 10.5194/gmdd-2-1335-2009 http://www.geosci-model-dev-discuss.net/2/1335/2009/ http://www.geosci-model-dev-discuss.net/2/1335/2009/gmdd-2-1335-2009.html http://www.geosci-model-dev-discuss.net/2/1335/2009/gmdd-2-1335-2009.pdf 1335 1374 2009-12-04 Simulating emission and chemical evolution of coarse sea-salt particles in the Community Multiscale Air Quality (CMAQ) model J. T. Kelly jkelly@arb.ca.gov P. V. Bhave C. G. Nolte U. Shankar K. M. Foley Atmospheric Modeling and Analysis Division, National Exposure Research Laboratory, Office of Research and Development, US Environmental Protection Agency, RTP, NC, USA Institute for the Environment, University of North Carolina, Chapel Hill, NC, USA now at: Planning and Technical Support Division, Air Resources Board, California Environmental Protection Agency, Sacramento, CA, USA Chemical processing of sea-salt particles in coastal environments significantly impacts concentrations of particle components and gas-phase species and has implications for human exposure to particulate matter and nitrogen deposition to sensitive ecosystems. Emission of sea-salt particles from the coastal surf zone is known to be elevated compared to that from the open ocean. Despite the importance of sea-salt emissions and chemical processing, the US EPA's Community Multiscale Air Quality (CMAQ) model has traditionally treated coarse sea-salt particles as chemically inert and has not accounted for enhanced surf-zone emissions. In this article, updates to CMAQ are described that enhance sea-salt emissions from the coastal surf zone and allow dynamic transfer of HNO3, H2SO4, HCl, and NH3 between coarse particles and the gas phase. Predictions of updated CMAQ models and the previous release version, CMAQv4.6, are evaluated using observations from three coastal sites during the Bay Regional Atmospheric Chemistry Experiment (BRACE) in Tampa, FL in May 2002. Model updates improve predictions of NO3−, SO42−, NH4+, Na+, and Cl− concentrations at these sites with only a 8% increase in run time. In particular, the chemically interactive coarse particle mode dramatically improves predictions of nitrate concentration and size distributions as well as the fraction of total nitrate in the particle phase. Also, the surf-zone emission parameterization improves predictions of total sodium and chloride concentration. Results of a separate study indicate that the model updates reduce the mean absolute error of nitrate predictions at coastal CASTNET and SEARCH sites in the eastern US. Although the new model features improve performance relative to CMAQv4.6, some persistent differences exist between observations and predictions. Modeled sodium concentration is biased low and causes under-prediction of coarse particle nitrate. Also, CMAQ over-predicts geometric mean diameter and standard deviation of particle modes at the BRACE sites. These over-predictions may cause too rapid particle dry deposition and partially explain the low bias in sodium predictions. Despite these shortcomings, the updates to CMAQ enable more realistic simulations of chemical processes in environments where marine air mixes with urban pollution. The model updates described in this article are included in the public release of CMAQv4.7 (<a href="http://www.cmaq-model.org" target="_blank">http://www.cmaq-model.org</a>). Allen, A. G., Harrison, R. M., and Erisman, J. W.: Field-measurements of the dissociation of ammonium-nitrate and ammonium-chloride aerosols, Atmos. Environ., 23(7), 1591–1599, 1989. Arnold, J. R., Hartsell, B. E., Luke, W. T., Ullah, S. M. R., Dasgupta, P. K., Huey, L. G., and Tate, P.: Field test of four methods for gas-phase ambient nitric acid, Atmos. Environ., 41(20), 4210–4226, 2007. Asgharian, B., Hoffman, W., and Bergmann, R.: Particle deposition in a multiple-path model of the human lung, Aerosol Sci. Tech., 34, 332–339, 2001. Athanasopoulou, E., Tombrou, M., Pandis, S. N., and Russell, A. G.: The role of sea-salt emissions and heterogeneous chemistry in the air quality of polluted coastal areas, Atmos. Chem. Phys., 8, 5755–5769, 2008. Atkeson, T., Greening, H., and Poor, N.: Bay Region Atmospheric Chemistry Experiment (BRACE), Atmos. Environ., 41(20), 4163–4164, 2007. Beichert, P. and Finlayson-Pitts, B. J.: Knudsen cell studies of the uptake of gaseous HNO3 and other oxides of nitrogen on solid NaCl: The role of surface-adsorbed water, J. Phys. Chem., 100(37), 15218–15228, 1996. Bessagnet, B., Hodzic, A., Vautard, R., Beekmann, M., Cheinet, S., Honoré, C., Liousse, C., and Rouil, L.: Aerosol modeling with CHIMERE – preliminary evaluation at the continental scale, Atmos. Environ., 38(18), 2803–2817, 2004. Binkowski, F. S. and Roselle, S. J.: Models-3 community multiscale air quality (CMAQ) model aerosol component – 1. Model description, J. Geophys. Res., 108(D6), 4183–4201, 2003. Bricker, S., Longstaff, B., Dennison, W., Jones, A., Boicourt, K., Wicks, C., and Woerner, J.: Effects of Nutrient Enrichment in the Nation's Estuaries: A Decade of Change, NOAA Coastal Ocean Program Decision Analysis Series No 26, National Centers for Coastal Ocean Science, Silver Spring, MD, 2007. Binkowski, F. and Shankar, U.: The Regional Particulate Matter Model 1. Model description and preliminary results, J. Geophys. Res., 100(D12), 26191–26209, 1995. Brunekreef, B. and Forsberg, B.: Epidemiological evidence of effects of coarse airborne particles on health, Eur. Respir. J., 26(2), 309–318, 2005. Byun, D. and Ching, J. K. S.: Science algorithms of the EPA Models-3 Community Multiscale Air Quality (CMAQ) modeling system, Tech. Rep. EPA-600/R-99/030, US Government Printing Office, US Environmental Protection Agency, Washington, DC, 1999. Byun, D. and Schere, K. L.: Review of the governing equations, computational algorithms, and other components of the Models-3 Community Mulitiscale Air Quality (CMAQ) modeling system, Appl. Mech. Rev., 59, 51–77, 2006. Capaldo, K. P., Pilinis, C., and Pandis, S. N.: A computationally efficient hybrid approach for dynamic gas/aerosol transfer in air quality models, Atmos. Environ., 34(21), 3617–3627, 2000. Carter, W. P. L.: Implementation of the SAPRC-99 chemical mechanism into the Models-3 framework, Tech. Rep., US Environmental Protection Agency, available at: http://www.cert.ucr.edu/~carter/absts.htm#s99mod3, 2000. Chan, C. K., Ha, Z. Y., and Choi, M. Y.: Study of water activities of aerosols of mixtures of sodium and magnesium salts, Atmos. Environ., 34(28), 4795–4803, 2000. Clarke, J. F., Edgerton, E. S., and Martin, B. E.: Dry deposition calculations for the clean air status and trends network, Atmos. Environ., 31(21), 3667–3678, 1997. Clarke, A. D., Owens, S. R., and Zhou, J. C.: An ultrafine sea-salt flux from breaking waves: Implications for cloud condensation nuclei in the remote marine atmosphere, J. Geophys. Res., 111, D06202, doi:10.1029/2005JD006565, 2006. Cohen, M. D., Flagan, R. C., and Seinfeld, J. H.: Studies of concentrated electrolyte-solutions using the electrodynamic balance.1. Water activities for single-electrolyte solutions, J. Phys. Chem., 91(17), 4563–4574, 1987. Dasgupta, P. K., Campbell, S. W., Al-Horr, R. S., Ullah, S. M. R., Li, J. Z., Amalfitano, C., and Poor, N. D.: Conversion of sea salt aerosol to NaNO3 and the production of HCl: analysis of temporal behavior of aerosol chloride/nitrate and gaseous HCl/HNO3, Atmos. Environ., 41(20), 4242–4257, 2007. Dassios, K. G. and Pandis, S. N.: The mass accommodation coefficient of ammonium nitrate aerosol, Atmos. Environ., 33(18), 2993–3003, 1999. de Leeuw, G., Neele, F. P., Hill, M., Smith, M. H., and Vignati, E.: Production of sea spray aerosol in the surf zone, J. Geophys. Res., 105(D24), 29397–29409, 2000. Evans, M. S. C., Campbell, S. W., Bhethanabotla, V., and Poor, N. D.: Effect of sea salt and calcium carbonate interactions with nitric acid on the direct dry deposition of nitrogen to Tampa Bay, Florida, Atmos. Environ., 38(29), 4847–4858, 2004. Elleman, R. A. and Covert, D. S.: Aerosol size distribution modeling with the Community Multiscale Air Quality modeling system (CMAQ) in the Pacific Northwest: 1 Model comparison to observations, J. Geophys. Res., 114, D11206, doi:10.1029/2008 JD010791, 2009. Foley, K. M., Roselle, S. J., Appel, K. W., Bhave, P. V., Pleim, J. E., Otte, T. L., Mathur, R., Sarwar, G., Young, J. O., Gilliam, R. C., Nolte, C. G., Kelly, J. T., Gilliland, A. B., and Bash, J. O.: Incremental testing of the community multiscale air quality (CMAQ) modeling system version 4.7, Geosci. Model Dev. Discuss., 2, 1245–1297, 2009. Foltescu, V. L., Pryor, S. C., and Bennet, C.: Sea salt generation, dispersion and removal on the regional scale, Atmos. Environ., 39(11), 2123–2133, 2005. Gard, E. E., Kleeman, M. J., Gross, D. S., Hughes, L. S., Allen, J. O., Morrical, B. D., Fergenson, D. P., Dienes, T., Galli, M. E., Johnson, R. J., Cass, G. R., and Prather, K. A.: Direct observation of heterogeneous chemistry in the atmosphere, Science, 279, 1184–1187, 1998. Gaydos, T. M., Koo, B., Pandis, S. N., and Chock, D. P.: Development and application of an efficient moving sectional approach for the solution of the atmospheric aerosol condensation/evaporation equations, Atmos. Environ., 37(23), 3303–3316, 2003. Gong, S. L.: A parameterization of sea-salt aerosol source function for sub- and super-micron particles, Global Biogeochem. Cy., 17(4), 1097, doi:10.1029/2003GB002079, 2003. Grell, G., Dudhia, J., and Stauffer, D.: A description of the fifth-generation Penn State/NCAR mesoscale model (MM5), Tech. Rep. NCAR/TN-398+STR, National Center for Atmospheric Research, Boulder, CO, 1994. Grell, G. A., Peckham, S. E., Schmitz, R., McKeen, S. A., Frost, G., Skamarock, W. C., and Eder, B.: Fully coupled "online" chemistry within the WRF model, Atmos. Environ., 39(37), 6957–6975, 2005. Hansen, D. A., Edgerton, E .S., Hartsell, B. E., Jansen, J. J., Kandasamy, N., Hidy, G. M., and Blanchard, C. L.: The southeastern aerosol research and characterization study: Part 1-Overview, J. Air Waste Manag. Assoc., 53(12), 1460–71, 2003. Hopkins, R. J., Desyaterik, Y., Tivanski, A. V., Zaveri, R. A., Berkowitz, C. M., Tyliszczak, T., Gilles, M. K., and Laskin, A.: Chemical speciation of sulfur in marine cloud droplets and particles: Analysis of individual particles from the marine boundary layer over the California current, J. Geophys. Res., 113, D04209, doi:10.1029/2007JD008954, 2008. Hsu, S.-C., Liu, S. C., Kao, S.-J., Jeng, W.-L., Huang, Y.-T., Tseng, C.-M., Tsai, F., Tu, J.-Y., and Yang, Y.: Water-soluble species in the marine aerosol from the northern South China Sea: High chloride depletion related to air pollution, J. Geophys. Res., 112, D19304, doi:10.1029/2007JD008844, 2007. Jacobson, M. Z.: Development and application of a new air pollution modeling system.3. Aerosol-phase simulations, Atmos. Environ., 31(4), 587–608, 1997. Jacobson, M. Z.: A solution to the problem of nonequilibrium acid/base gas-particle transfer at long time step, Aerosol Sci. Technol., 39(2), 92–103, 2005. Jiang, W., Smyth, S., Giroux, É, Roth, H., and Yin, D.: Differences between CMAQ fine mode particle and PM2.5 concentrations and their impact on model performance evaluation in the lower Fraser valley, Atmos. Environ., 40(26), 4973–4985, 2006 Keene W. C., Stutz, J., Pszenny, A. A. P., Maben, J. R., Fischer, E. V., Smith, A. M., von Glasow, R., Pechtl, S., Sive, B. C., and Varner, R. K.: Inorganic chlorine and bromine in coastal New England air during summer, J. Geophys. Res., 112, D10S12, doi:10.1029/2006JD007689, 2007. Kelly, J. T. and Wexler, A. S.: Water uptake by aerosol: Water activity in supersaturated potassium solutions and deliquescence as a function of temperature, Atmos. Environ., 40(24), 4450–4468, 2006. Kleeman, M. J. and Cass, G. R.: A 3D Eulerian source-oriented model for an externally mixed aerosol, Environ. Sci. Technol., 35, 4834–4848, 2001. Koo, B., Gaydos, T. M., and Pandis, S. N.: Evaluation of the equilibrium, dynamic, and hybrid aerosol modeling approaches, Aerosol Sci. Technol., 37(1), 53–64, 2003. Lee, T., Yu, X. Y., Ayres, B., Kreidenweis, S. M., Malm, W. C., and Collett, J. L.: Observations of fine and coarse particle nitrate at several rural locations in the United States, Atmos. Environ., 42(11), 2720–2732, 2008. Lewis, E. R. and Schwartz, S. E.: Sea-Salt Aerosol Production: Mechanisms, Methods, Measurements, and Models–A Critical Review. American Geophysical Union, Washington, DC, 2004. Lurmann, F. W., Wexler, A. S., Pandis, S. N., Musarra, S., Kumar, N., and Seinfeld, J. H.: Modelling urban and regional aerosols. 2. Application to California's South Coast Air Basin, Atmos. Environ., 31(17), 2695–2715, 1997. McInnes, L. M., Covert, D. S., Quinn, P. K., and Germani, M. S.: Measurements of chloride depletion and sulfur enrichment in individual sea-salt particles collected from the remote marine boundary-layer, J. Geophys., 99(D4), 8257–8268, 1994. Meng, Z. Y., Dabdub, D., and Seinfeld, J. H.: Size-resolved and chemically resolved model of atmospheric aerosol dynamics, J. Geophys. Res., 103(D3), 3419–3435, 1998. Meng, Z. Y. and Seinfeld, J. H.: Time scales to achieve atmospheric gas-aerosol equilibrium for volatile species, Atmos. Environ., 30(16), 2889–2900, 1996. Monahan, E. C., Spiel, D. E., and Davidson, K. L.: A model of marine aerosol generation via whitecaps and wave disruption, in: Oceanic Whitecaps, edited by: Monahan, E. C. and MacNiocaill, G., D Reidel Publishing Company, Norwell, Mass., 167–174, 1986. Nenes, A., Pandis, S. N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquatic Geochem., 4(1), 123–152, 1998. Nicholls, R. J. and Small, C.: Improved estimates of coastal population and exposure to hazards released, EOS Transactions, July, 83(28), p 301 and p 305, 2002. Nolte, C. G., Bhave, P. V., Arnold, J. R., Dennis, R. L., Zhang, K. M., and Wexler, A. S.: Modeling urban and regional aerosols – Application of the CMAQ-UCD Aerosol Model to Tampa, a coastal urban site, Atmos. Environ., 42(13), 3179–3191, 2008. 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, Nat. Geosci., 1(5), 324–328, 2008. Pandis, S. N., Wexler, A. S., and Seinfeld, J. H.: Secondary organic aerosol formation and transport.2. predicting the ambient secondary organic aerosol-size distribution, Atmos. Environ., 27(15), 2403–2416, 1993. Park, S. K., Marmur, A., Kim, S. B., Tian, D., Hu, Y. T., McMurry, P. H., and Russell, A. G.: Evaluation of fine particle number concentrations in CMAQ, Aerosol. Sci. Tech., 40(11), 985–996, 2006. Petelski, T. and Chomka, M.: Marine aerosol fluxes in the coastal zone – BAEX experimental data, Oceanologia, 38, 469–484, 1996. 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. Pilinis, C., Capaldo, K. P., Nenes, A., and Pandis, S. N.: MADM – A new multicomponent aerosol dynamics model, Aerosol Sci. Tech., 32(5), 482–502, 2000. Pleim, J., Wong, D., Mathur, R., Young, J., Otte, T., Gilliam, R., Binkowski, F., and Xiu, A.: Development of the coupled 2-way WRF-CMAQ system, 7th Annual CMAS Conference, 6–8 October, Chapel Hill, NC, http://www.cmascenter.org, 2008. Pryor, S. C., Barthelmie, R. J., Schoof, J. T., Binkowski, F. S., Delle Monache, L., and Stull, R.: Modeling the impact of sea-spray on particle concentrations in a coastal city, Sci. Tot. Environ., 391, 132–142, 2008. Pryor, S. C. and Sorensen, L. L.: Nitric acid-sea salt reactions: Implications for nitrogen deposition to water surfaces, J. Appl. Meteorol., 39(5), 725–731, 2000. Sandstrom, T., Nowak, D., and van Bree, L.: Health effects of coarse particles in ambient air: messages for research and decision-making, Eur. Respir. J., 26(2), 187–188, 2005. Sartelet, K. N., Hayami, H., Albriet, B., and Sportisse, B.: Development and preliminary validation of a modal aerosol model for tropospheric chemistry: MAM, Aerosol Sci. Tech., 40(2), 118–127, 2006. Sartelet, K. N., Hayami, H., and Sportisse, B.: Dominant aerosol processes during high-pollution episodes over Greater Tokyo, J. Geophys. Res., 112, D14214, doi:10.1029/2006JD007885, 2007. Sarwar, G. and Bhave, P. V.: Modeling the effect of chlorine emissions on ozone levels over the eastern United States, J. Appl. Meteorol. Clim., 46(7), 1009–1019, 2007. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley & Sons, Inc., New York, 1998. Simon, H., Kimura, Y., McGaughey, G., Allen, D. T., Brown, S. S., Osthoff, H. D., Roberts, J. M., Byun, D., and Lee, D.: Modeling the impact of ClNO2 on ozone formation in the Houston area, J. Geophys. Res., 114, D00F03, doi:10.1029/2008JD010732, 2009. Smyth, S. C., Jiang, W. M., Roth, H., Moran, M. D., Makar, P. A., Yang, F. Q., Bouchet, V. S., and Landry, H.: A comparative performance evaluation of the AURAMS and CMAQ air-quality modelling systems, Atmos. Environ., 43(5), 1059–1070, 2009. Spyridaki, A., Lazaridis, M., Eleftheriadis, K., Smolik, J., Mihalopoulos, N., and Aleksandropoulou, V.: Modelling and evaluation of size-resolved aerosol characteristics in the eastern Mediterranean during the SUB-AERO project, Atmos. Environ., 40, 6261–6275, 2006. Sullivan, R. C. and Prather, K. A.: Investigations of the diurnal cycle and mixing state of oxalic acid in individual particles in Asian aerosol outflow, Environ. Sci. Technol., 41(23), 8062–8069, 2007. Sun, Q. and Wexler, A. S.: Modeling urban and regional aerosols - Condensation and evaporation near acid neutrality, Atmos. Environ., 32(20), 3527–3531, 1998a. Sun, Q. and Wexler, A. S.: Modeling urban and regional aerosols near acid neutrality – Application to the 24–25~June SCAQS episode, Atmos. Environ., 32(20), 3533–3545, 1998b. Tang, I., Tridico, A., and Fung, K.: Thermodynamic and optical properties of sea salt aerosols, J. Geophys. Res., 102(D19), 23269–23275, 1997. Volckens, J., Dailey, L., Walters, G., and Devlin R. B.: Direct particle-to-cell deposition of coarse ambient particulate matter increases the production of inflammatory mediators from cultured human airway epithelial cells, Environ. Sci. Technol., 43(12), 4595–4599, 2009. Wexler, A. S. and Seinfeld, J. H.: The distribution of ammonium-salts among a size and composition dispersed aerosol, Atmos. Environ., 24(5), 1231–1246, 1990. Wexler, A. S. and Seinfeld, J. H.: Analysis of aerosol ammonium-nitrate - departures from equilibrium during SCAQS, Atmos. Environ., 26(4), 579–591, 1992. 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. Zhang, K. M., Knipping, E. M., Wexler, A. S., Bhave, P. V., and Tonnesen, G. S.: Size distribution of sea-salt emissions as a function of relative humidity, Atmos. Environ., 39(18), 3373–3379, 2005. Zhang, K. M. and Wexler, A. S.: An asynchronous time-stepping (ATS) integrator for atmospheric applications: Aerosol dynamics, Atmos. Environ., 40(24), 4574–4588, 2006. Zhang, K. M. and Wexler, A. S.: Modeling urban and regional aerosols – Development of the UCD Aerosol Module and implementation in CMAQ model, Atmos. Environ., 42(13), 3166–3178, 2008. Zhang, Y., Liu, P., Pun, B., and Seigneur, C.: A comprehensive performance evaluation of MM5-CMAQ for the summer 1999 southern oxidants study episode- Part III: diagnostic and mechanistic evaluations, Atmos. Environ., 40(26), 4856–4873, 2006. Zhang, Y., Pun, B., Vijayaraghavan, K., Wu, S. Y., Seigneur, C., Pandis, S. N., Jacobson, M. Z., Nenes, A., and Seinfeld, J. H.: Development and application of the model of aerosol dynamics, reaction, ionization, and dissolution (MADRID), J. Geophys. Res., 109, D01202, doi:10.1029/2003JD003501, 2004.