References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-293-2011

Modeling natural emissions in the Community Multiscale Air Quality (CMAQ) model – Part 2: Modifications for simulating natural emissions

Mueller

S. F.

¹ Mao

¹ Mallard

J. W.

Tennessee Valley Authority, P.O. Box 1010, Muscle Shoals, Alabama 35662-1010, USA

14 01 2011

11 1 293 320

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The Community Multiscale Air Quality (CMAQ) model version 4.6 has been revised with regard to the representation of chlorine (HCl, ClNO2) and sulfur (dimethylsulfide, or DMS, and H2S), and evaluated against observations and earlier published models. Chemistry parameterizations were based on published reaction kinetic data and a recently developed cloud chemistry model that includes heterogeneous reactions of organic sulfur compounds. Evaluation of the revised model was conducted using a recently enhanced data base of natural emissions that includes ocean and continental sources of DMS, H2S, chlorinated gases and lightning NOx for the continental United States and surrounding regions. Results using 2002 meteorology and emissions indicated that most simulated "natural" (plus background) chemical and aerosol species exhibit the expected seasonal variations at the surface. Ozone exhibits a winter and early spring maximum consistent with ozone data and an earlier published model. Ozone distributions reflect the influences of atmospheric dynamics and pollutant background levels imposed on the CMAQ simulation by boundary conditions derived from a global model. A series of model experiments reveals that the consideration of gas-phase organic sulfur chemistry leads to sulfate aerosol increases over most of the continental United States. Cloud chemistry parameterization changes result in widespread decreases in SO2 across the modeling domain and both increases and decreases in sulfate. Most cloud-mediated sulfate increases occurred mainly over the Pacific Ocean (up to about 0.1 μg m−3) but also over and downwind from the Gulf of Mexico (including parts of the eastern US). Geographic variations in simulated SO2 and sulfate are due to the link between DMS/H2S and their byproduct SO2, the heterogeneity of cloud cover and precipitation (precipitating clouds act as net sinks for SO2 and sulfate), and the persistence of cloud cover (the largest relative sulfate increases occurred over the persistently cloudy Gulf of Mexico and western Atlantic Ocean). Overall, the addition of organic sulfur chemistry increased hourly surface sulfate levels by up to 1–2 μg m−3 but reduced sulfate levels in the vicinity of high SO2 emissions (e.g., wildfires). Simulated surface levels of DMS compare reasonably well with observations in the marine boundary layer where DMS oxidation product levels are lower than observed. This implies either a low bias in model oxidation rates of organic sulfur species or a low bias in the boundary conditions for DMS oxidation products. This revised version of CMAQ provides a tool for realistically simulating the influence of natural emissions on air quality.

References 1

% vor jede Referenz Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, doi:10.5194/acp-4-1461-2004, 2004.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, doi:10.5194/acp-6-3625-2006, 2006.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens, Atmos. Chem. Phys., 7, 981–1191, doi:10.5194/acp-7-981-2007, 2007.

Ayers, G. P. and Gillett, R. W.: DMS and its oxidation products in the remote marine atmosphere: implications for climate and atmospheric chemistry, J. Sea Res., 43, 275–286, 2000.

Behnke, W., George, C., Scheer, V., and Zetzsch, C.: Production and decay of ClNO2 from the reaction of gaseous N2O$_5$ with NaCl solution: bulk and aerosol experiments, J. Geophys. Res., 102, 3795–3804, 1997.

Berntsen, T. K. and Isaksen, I. S. A.: A global 3D chemical transport model for the troposphere: model description and CO and O3 results, J. Geophys. Res, 102, 21239–21280, 1997.

Berntsen, T. K., Karlsdóttir, S., and Jaffe, D. A.: Influence of Asian emissions on the composition of air reaching the north western United States, Geophys. Res. Let., 26, 2171–2174, 1999.

Bonifacic, M., Mockel, H., Bahnemann, D., and Asmus, K. D.: Formation of positive-ions and other primary species in oxidation of sulfides by hydroxyl radicals, Journal of the Chemical Society-Perkin Transactions 2(7), 675–685, 1975.

Byers, H. R.: Elements of Cloud Physics, The University of Chicago Press, Chicago, 142–146, 1965.

Chameides, W., Lindsay, R., Richardson, J., and Kiang, C.: The role of biogenic hydrocarbons in urban photochemical smog: Atlanta as a case study, Science, 241, 1473–1475, 1988.

Chawla, O. P. and Fessenden, R. W.: Electron-spin resonance and pulse-radiolysis studies of some reactions of SO$_4^-$, J. Phys. Chem., 79, 2693–2700, 1975.

De Valk, J. P. J. M. M. and van der Hage, J. C. H.: A model for cloud chemistry processes suitable for use in long range transport models: a sensitivity study, Atmos. Environ., 28, 1653–1663, 1994.

EPA: Guidance for Tracking Progress under the Regional Haze Rule, Office of Air Quality Planning and Standards, Research Triangle Park, NC, EPA-454/B-03-004, 2003.

EPA: Review of the National Ambient Air Quality Standards for Particulate Matter: Policy Assessment of Scientific and Technical Information, Office of Air Quality Planning and Standards, Research Triangle Park, NC, EPA-452/R-05-005, 2005.

Erickson III, D. J., Seuzaret, C., Keene, W. C., and Gong, S. L.: A general circulation model based calculation of HCl and ClNO2 production from sea salt dechlorination: reactive chlorine emissions inventory, J. Geophys. Res, 104, 8347–8372, 1999.

Ervens, B., Carlton, A. G., Turpin, B. J., Altieri, K. E., Kreidenweis, S. M., and Feingold, G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, L02816, doi:10.1029/2007GL031828, 2008.

Finlayson-Pitts, B. J. and Pitts Jr., J. N.: Chemistry of the Upper and Lower Atmosphere, Academic Press, San Diego, CA, 2000.

Friedl, R. R., Brune, W. H., and Anderson, J. G.: Kinetics of SH with NO2, O3, O2, and H2O2, J. Phys. Chem., 89, 5505–5510, 1985.

Gershenzon, M., Davidovits, P., Jayne, J. T., Kolb, C. E., and Worsnop, D. R.: Simultaneous uptake of DMS and ozone on water, J. Phys. Chem. A, 105, 7031–7036, 2001.

Graedel, T. E., Bates, T. S., Bouwman, A. F., Cunnold, D., Dignon, J., Fung, I., Jacob, D. J., Lamb, B. K., Logan, J. A., Marland, G., Middleton, P., Pacyna, J. M., Placet, M., and Veldt, C.: A compilation of inventories of emissions to the atmosphere, Global Biogeochem. Cy., 7, 1–26, 1993.

Grell, G. A., Dudhia, J., and Stauffer, D. R.: A description of the fifth-generation Penn State/NCAR Mesoscale Model (MM5), NCAR Tech. Note, NCAR/TN-398+STR, 122~pp., 1994.

Henze, D. K. and Seinfeld, J. H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976, 2006.

Herrmann, H., Ervens, B., Jacobi, H.-W., Wolke, R., Nowacki, P., and Zellner, R.: CAPRAM 2.3: a chemical aqueous phase radical mechanism for tropospheric chemistry, J. Atmos. Chem., 36, 231–284, 2000.

Hoffman, M. R.: On the kinetics and mechanism of oxidation of aquated sulfur-dioxide by ozone, Atmos. Environ., 20, 1145–1154, 1986.

Huie, R. E. and Clifton, C. L.: Temperature-dependence of the rate constants for reactions of the sulfate radical, SO$_4^-$, with anions, J. Phys. Chem, 94, 8561–8567, 1990.

Jacob, D. J., Park, R., and Logan, J. A.: Documentation and Evaluation of the GEOS-Chem Simulation for 2002 Provided to the VISTAS Group, Harvard University, available at: http://vistassesarm.org/documents/Harvard_GEOS-CHEM_FinalReport_20050624.doc, 2005.

Jourdain, B., Legrand, M., and Preunkert, S.: Multiple year-round atmospheric records of DMS, DMSO, sea-salt and sulfur (MSA and non-sea-salt sulfate) aerosols at Dumont D'Urville (Antarctica) (December 1998–August 2002), EGS-AGU-EUG Joint Assembly, Nice, France, 6–11 April, 2003.

Kaminski, J. W., Neary, L., Struzewska, J., McConnell, J. C., Lupu, A., Jarosz, J., Toyota, K., Gong, S. L., Côté, J., Liu, X., Chance, K., and Richter, A.: GEM-AQ, an on-line global multiscale chemical weather modelling system: model description and evaluation of gas phase chemistry processes, Atmos. Chem. Phys., 8, 3255–3281, doi:10.5194/acp-8-3255-2008, 2008.

Karamchandani, P. and Venkatram, A.: The role of non-precipitating clouds in producing ambient sulfate during summer: results from simulations with the Acid Deposition and Oxidant Model (ADOM), Atmos. Environ., 26A, 1041–1052, 1992.

Kaynak, B., Hu, Y., Martin, R. V., Russell, A. G., Choi, Y., and Wang, Y.: The effect of lightning NOx production on surface ozone in the continental United States, Atmos. Chem. Phys., 8, 5151–5159, doi:10.5194/acp-8-5151-2008, 2008.

Knipping, E. M. and Dabdub, D.: Impact of chlorine emissions from sea-salt aerosol on coastal urban ozone, Environ. Sci. Technol., 37, 275–284, 2003.

Koo, B., Chien, C.-J., Tonnesen, G., Morris, R., Johnson, J., Sakulyanontvittaya, T., Piyachaturawat, P., and Yarwood, G.: Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies, Atmos. Environ., 44, 2372–2382, doi:10.1016/j.atmosenv.2010.02.041, 2010.

Kreidenweis, S. M., Penner, J. E., Yin, F., and Seinfeld, J. H.: The effects of dimethylsulfide upon marine aerosol concentrations, Atmos. Environ., 25A, 2501–2511, 1991.

Kreidenweis, S. M., Walcek, C. J., Feingold, G., Gong, W. M., Jacobson, M. Z., Kim, C. H., Liu, X. H., Penner, J. E., Nenes, A., and Seinfeld, J. H.: Modification of aerosol mass and size distribution due to aqueous-phase SO2 oxidation in clouds: comparisons of several models, J. Geophys. Res.-Atmos., 108, 4213, doi:10.1029/2002JD002697, 2003.

Kukui, A., Bossoutrot, V., Laverdet, G., and Le Bras, G.: Mechanism of the reaction of CH3SO with NO2 in relation to atmospheric oxidation of dimethyl sulfide: experimental and theoretical study, J. Phys. Chem., 104, 935–946, 2000.

Kukui, A., Borissenko, D., Laverdet, G., and Le Bras, G.: Gas phase reactions of OH radicals with dimethyl sulfoxide and methane sulfinic acid using turbulent flow reactor and chemical ionization mass spectrometry, J. Phys. Chem. A, 107, 5732–5742, 2003.

Lee, Y. N. and Zhou, X. L.: Aqueous reaction-kinetics of ozone and dimethylsulfide and its atmospheric implications, J. Geophys. Res.-Atmos. 99, 3597–3605, 1994.

Levasseur, M., Sharma, S., Cantin, G., Michaud, S., Gosselin, M., and Barrie, L.: Biogenic sulfur emissions from the Gulf of Saint Lawrence and assessment of its impact on the Canadian east coast, J. Geophys. Res, 102(D23), 28025–28039, 1997.

Lin, C.-Y. C., Jacob, D. J., Munger, J. W., and Fiore, A. M.: Increasing background ozone in surface air over the United States, Geophys. Res. Lett., 27, 3465–3468, 2000.

Lucas, D. D. and Prinn, R. G.: Sensitivities of gas-phase dimethylsulfide oxidation products to the assumed mechanisms in a chemical transport model, J. Geophys. Res, 110, D21312, doi:10.1029/2004JD005386, 2005.

Mansell, G. E., Lau, S., Russell, J., and Omary, M.: Final Report: Fugitive Wind Blown Dust Emissions and Model Performance Evaluation, Phase II. Prepared for the Western Governors Association by ENVIRON International Corporation, Novato, CA and the University of California at Riverside Center for Environmental Research and Technology, Riverside, CA, 2006.

Möller, D. and Mauersberger, G.: Cloud chemistry effects on tropospheric photooxidants in polluted atmosphere – model results, J. Atmos. Chem., 14, 153–165, 1992.

Morris, R. E., Koo, B., Guenther, A., Yarwood, G., McNally, D., Tesche, T. W., Tonnesen, G., Boylan, J., and Brewer, P.: Model sensitivity evaluation for organic carbon using two multi-pollutant air quality models that simulate regional haze in the southeastern United States, Atmos. Environ., 40, 4960–4972, 2006.

Mueller, S. F., Bailey, E. M., Cook, T. M., and Mao, Q.: Treatment of clouds and the associated response of atmospheric sulfur in the Community Multiscale Air Quality (CMAQ) modeling system, Atmos. Environ., 40, 6804–6820, 2006.

National Aeronautics and Space Administration: Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling – Evaluation Number 12, Jet Propulsion Laboratory, Publication 97-4, 266~pp., available at: http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/19970037557_1997085720.pdf, 1997.

National Acid Precipitation Assessment Program: The Regional Acidic Deposition Model and Engineering Model, Report 4, in: Acid Deposition: State of Science and Technology, edited by: Irving P. M., Vol. 1, Emissions, Atmospheric Processes, and Deposition, Office of the Director, Washington, DC, 67–69, 1991.

Oltmans, S. J., Lefohn, A. S., Harris, J. M., and Shadwick, D. S.: Background ozone levels of air entering the west coast of the US and assessment of longer-term changes, Atmos. Environ., 42, 6020–6038, 2008.

Park, R. J., Jacob, D. J., Field, B. D., and Yantosca, R. M.: Natural and transboundary pollution influences on sulfate-nitrate-ammonium aerosols in the United States: implications for policy, J. Geophys. Res, 109, D15205, doi:10.1029/2003JD004473, 2004.

Pickering, K. E., Wang, Y., Tao, W.-K., Price, C., and Müller, J.-F.: Vertical distributions of lightning NOx for use in regional and global chemical transport models, J. Geophys. Res, 103, 31203–31216, 1993.

Sciare, J., Kanakidou, M., and Mihalopoulos, N.: Diurnal and seasonal variation of atmospheric dimethylsulfoxide at Amsterdam Island in the southern Indian Ocean, J. Geophys. Res, 105(D13), 17257–17265, 2000.

Sciare, J., Baboukas, E., and Mihalopoulos, N.: Short-term variability of atmospheric DMS and its oxidation products at Amsterdam Island during summer time, J. Atmos. Chem., 39, 281–302, doi:10.1023/A:1010631305307, 2001.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, John Wiley & Sons, New York, 627–634, 1998.

Smith, S. N. and Mueller, S. F.: Modeling natural emissions in the Community Multiscale Air Quality (CMAQ) Model�I: building an emissions data base, Atmos. Chem. Phys., 10, 4931–4952, doi:10.5194/acp-10-4931-2010, 2010.

Tanaka, P. L. and Allen, D. T.: Incorporation of chlorine reactions into the carbon bond-IV mechanism: mechanism updates and preliminary performance evaluation, report on contract no 9880077600-18 between the University of Texas and the Texas Natural Resource Conservation Commission, Center for Energy and Environmental Resources, University of Texas, Austin, TX, 2001.

Tesche, T. W., Morris, R., Tonnesen, G., McNally, D., Boylan, J., and Brewer, P.: CMAQ/CAMx annual 2002 performance evaluation over the eastern US, Atmos. Environ., 40, 4906–4919, 2008.

Van den Berg, A. R., Dentener, F. J., and Lelieveld, J.: Modelling the chemistry of the marine boundary layer; sulphate formation and the role of sea salt aerosol particles, J. Geophys. Res, 105, 11671–11698, 2000.

Vingarzan, R.: A review of surface ozone background levels and trends, Atmos. Environ., 38, 3431–3442, 2004.

Watts, S. F., Watson, A., and Brimblecombe, P.: Measurements of the aerosol concentrations of methanesulphonic acid, dimethyl sulphoxide and dimethyl sulphone in the marine atmosphere of the British Isles, Atmos. Environ., 21, 2667–2672, 1987.

Williams, J. E., Dentener, F. J., and van den Berg, A. R.: The influence of cloud chemistry on HOx and NOx in the moderately polluted marine boundary layer: a 1-D modelling study, Atmos. Chem. Phys., 2, 39–54, doi:10.5194/acp-2-39-2002, 2002.

Yang, G.-P., Zhang, H.-H., Su, L.-P., and Zhou, L.-M.: Biogenic emission of dimethylsulfide (DMS) from the North Yellow Sea, China and its contribution to sulfate in aerosol during summer, Atmos. Environ., 43, 2196–2203, 2009.

Yarwood, G., Rao, S., Yocke, M., and Whitten, G.: Updates to the Carbon Bond Chemical Mechanism: CB05. Report to the US EPA, RT-0400675, available at: http://www.camx.com/publ/pdfs/ CB05_Final_Report_120805.pdf, 2005.

Yin, F., Grosjean, D., and Seinfeld, J. H.: Photooxidation of dimethyl sulfide and dimethyl disulfide. I: mechanism development, J. Atmos. Chem., 11, 309–364, 1990.

Yvon, S. A. and Saltzman, E. S.: Atmospheric sulfur cycling in the tropical Pacific marine boundary layer (12° S, 135° W): a comparison of field data and model results 2. sulfur dioxide, J. Geophys. Res, 101(D3), 6911–6918, 1996.

Zaveri, R. A: Development and Evaluation of a Comprehensive Tropospheric Chemistry Model for Regional and Global Applications, Ph.D. dissertation, Virginia Polytechnic Institute and State University, 250~pp., 1997.

Zhu, L.: Aqueous Phase Reaction Kinetics of Organic Sulfur Compounds of Atmospheric Interest, Ph.D. dissertation, School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 261~pp., 2004.

Zhu, L., Nenes, A., Wine, P. H., and Nicovich, J. M.: Effects of aqueous organosulfur chemistry on particulate methanesulfonate to non-sea salt sulfate ratios in the marine atmosphere, J. Geophys. Res., 111, D05316. doi:10.1029/2005JD006326, 2006.