Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 7 15 2007 10.5194/acp-7-4001-2007 http://www.atmos-chem-phys.net/7/4001/2007/ http://www.atmos-chem-phys.net/7/4001/2007/acp-7-4001-2007.html http://www.atmos-chem-phys.net/7/4001/2007/acp-7-4001-2007.pdf 4001 4013 2007-08-01 GEM/POPs: a global 3-D dynamic model for semi-volatile persistent organic pollutants – Part 1: Model description and evaluations of air concentrations S. L. Gong sunling.gong@ec.gc.ca P. Huang T. L. Zhao L. Sahsuvar L. A. Barrie J. W. Kaminski Y. F. Li T. Niu Air Quality Research Division, Science {&} Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario M3H 5T4, Canada Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, Canada, M5S 3E5, Canada Department of Earth and Space Science and Engineering, York University, 4700 Keele Street, Toronto, Ontario, M3J 1P3, Canada Atmospheric Research and Environment Program, World Meteorological Organization, 7 bis, avenue de la Paix, BP2300, 1211 Geneva 2, Switzerland Certre for Atmosphere Watch & Services (CAWAS), Chinese Academy of Meteorological Sciences, China Meteorological Administration (CMA), Beijing 100081, China GEM/POPs was developed to simulate the transport, deposition and partitioning of semi-volatile persistent organic pollutants (POPs) in the atmosphere within the framework of Canadian weather forecasting model GEM. In addition to the general processes such as anthropogenic emissions, atmosphere/water and atmosphere/soil exchanges, GEM/POPs incorporates a dynamic aerosol module to provide the aerosol surface areas for the semi-volatile POPs to partition between gaseous and particle phases and a mechanism for particle-bound POPs to be removed. Simulation results of three PCBs (28, 153 and 180) for the year 2000 indicate that the model captured the main features of global atmospheric PCBs when compared with observations from EMEP, IADN and Alert stations. The annual averaged concentrations and the fractionation of the three PCBs as a function of latitudes agreed reasonably well with observations. The impacts of atmospheric aerosols on the transports and partitioning of the three PCBs are reasonably simulated. The ratio of particulate to gaseous PCBs in the atmospheric column ranges from less than 0.1 for PCB28 to as high as 100 for PCB180, increasing from the warm lower latitudes to the cold high latitudes. Application of GEM/POPs in a study of the global transports and budgets of various PCBs accompanies this paper. Achman, D. R., Hornbuckle, K. C., and Eisenreich, S. J.: Volatilization of Polychlorinated Biphenyls from Green Bay, Lake Michigan, Environ. Sci. Technol., 27, 75–87, 1993. Anderson, P. N. and Hites, R. A.: OH Radical Reactions: The Major Removal Pathway for Polychlorinated Biphenyls from the Atmosphere, Environ. Sci. Technol., 30, 1756–1763, 1996. Atkinson, R. and Aschmann, S. M.: Rate Constants for the Gas-Phase Reaction of Hydroxyl Radicals with Biphenyl and the Monochlorobiphenyls at 295K, Environ. Sci. Technol., 19, 462–464, 1985. Bidleman, T. F., Falconer, R. L., and Harner, T. (Eds.): Particle/Gas Distribution of Semivolatile Organic Compounds: Field and Laboratory Experiments with Filtration Samplers. Gas and Particle Partition Measurements of Atmospheric Organic Compounds, Gordon and Breach Publishers, Newark, New Jersey, 1998. Breivik, K., Sweetman, A., Pacyna, J. M., and Jones, K. C.: Towards a global historical emission inventory for selected PCB congeners – a mass balance approach 1. Global production and consumption, Sci. Total Environ., 290, 181–198, 2002a. Breivik, K., Sweetman, A., Pacyna, J. M., and Jones, K. C.: Towards a global historical emission inventory for selected PCB congeners - a mass balance approach 2. Emissions, Sci. Total Environ., 290, 199–224, 2002b. Côté, J., Gravel, S., Méthot, A., Patoine, A., Roch, M., and Staniforth, A.: The operational CMC-MRB Global Environmental Multiscale (GEM) model: Part I – Design considerations and formulation, Mon. Wea. Rev., 126, 1373–1395, 1998. de Cuevas, B. A., Webb, D. J., Coward, A. C., Richmond, C. S., and Rourke, E.: The UK Ocean Circulation and Advanced Modelling Project (OCCAM), in: High Performance Computing, Proceedings of HPCI Conference 1998, edited by: Allan, R. J., Guest, M. F., Simpson, A. D., Henty, D. S., and Nicole, D. A.,Plenum Press, Manchester, 325–335, 1999. Falconer, R. L., Bidleman, T. F., and Cotham, W. E.: Preferential Sorption of Non-and-Mono-ortho-polychlorinated Biphenyls to Urban Aerosols, Environ. Sci. Technol., 29, 1666–1673, 1995. Finizio, A., Mackay, D., Bidleman, T., and Harner, T.: Octanol-air partition coefficient as a predictor of partitioning of semi-volatile organic chemicals to aerosols, Atmos. Environ., 31, 2289–2296, 1997. Foujols, M.-A., Levy, M., Aumont, O. and Madec, G.: OPA8.1 Tracer reference manual, Institut Pierre-Simon Laplace, 2000. Gong, S. L., Barrie, L. A., Blanchet, J.-P., Salzen, K. v., 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. Gusev, A., Mantseva, E., Shatalov, V., and Strukov, B.: Regional Multicompartment Model MSCE-POP, EMEP/MSC-E Technical Report 5/2005, Moscow, 2005.. Halsall, C. J.: Investigating the occurence of pesistent organic pollutants (POPs) in the Arctic: Their atmospheric behaviour and interaction with the seasonal snow pack, Env. Poll., 128, 163–175, 2004. Hansen, K. M., Christensen, J. H., Brandt, J., Frohn, L. M., and Geels, C.: Modelling atmospheric transport persistent organic pollutants in Northern Hemisphere with a 3-D dynamical model: DEHM-POP, Atmos. Chem. Phys., 4, 1125–1137, 2004. Harner, T. and Bidleman, T. F.: Measurement of Octanol-Air Partition Coefficients for Polychlorinated Biphenyls, J. Chem. Eng. Data, 41, 895–899, 1996. Harner, T. and Bidleman, T. F.: Octanol-Air Partition Coefficient for Describing Particle/Gas Partitioning of Aromatic Compounds in Urban Air, Environ. Sci. Technol., 32, 1494–1502, 1998. Harner, T., Pozo, K., Gouin, T., Macdonald, A.-M., Hung, H., Cainey, J., and Peters, A.: Global pilot study for persistent organic pollutants (POPs) using PUF disk passive air samplers, Environ. Poll., 144, 445–452 2006. Huang, P., Gong, S. L., Zhao, T. L., Neary, L., and Barrie, L. A.: GEM/POPs: a global 3-D dynamic model for semi-volatile persistent organic pollutants – 2. Global transports and budgets of PCBs, Atmos. Chem. Phys., \blackboxCompanion paper. Will be inserted by PO!, 2007. Hung, H., Blanchard, P., Halsall, C. J., Bidleman, T. F., Stern, G. A., Fellin, P., Muir, D. C. G., Barrie, L. A., Jantunen, L. M., Helm, P. A., Ma, J., and Konoplev, A.: Temporal and spatial variabilities of atmospheric polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and polycyclic aromatic hydrocarbons (PAHs) in the Canadian Arctic: Results from a decade of monitoring, Sci. Total Environ., 342, 119–144, 2005a. Hung, H., Halsall, C. J., Blanchard, P., Li, H. H., Fellin, P., Stern, G. and Rosenberg, B.: Temporal trends of organochlorine pesticides in the Canadian Arctic atmosphere, Env. Sci. Technol., 36, 862–868, 2002. Hung, H., Lee, S. C., Wania, F., Blanchard, P., and Brice, K.: Measuring and simulating atmospheric concentration trends of polychlorinated biphenyls in the Northern Hemisphere, Atmos. Environ., 39, 6502–6512, 2005b. Junge, C. E. (Ed.): Fate of Pollutants in the Air and Water Environments, 1. J. Wiley, New York, 7–26, 1977. Jury, W. A.: Volatilization From soil, in:Vadose Zone Modeling of Organic Pollutants, 3rd ed., edited by: Hern, S. C. and Melancon, S. M., Lewis Publishers Inc., Michigan, 1989. Jury, W. A., Spencer, W. F., and Farmer, W. J.: Behavior Assessment Model for Trace Organics in Soil: I.Model Description, J. Environ. Qual., 12, 558–564, 1983. Karickhoff, S. W.: Semi-Empirical Estimation of Sorption of Hydrophobic Pollutants on Natural Sediments and Soils, Chemosphere, 10, 833–846, 1981. Koziol, A. S. and Pudykiewicz, J. A.: Global-scale environmental transport of persistent organic pollutants, Chemosphere, 45, 1181–1200, 2001. Kwok, E. S. C., Atkinson, R., and Arey, J.: Rate Constants for the Gas_Phase Reactions of the OH Radical with Dichlorobiphenyls, 1-Chlorodibenzo-p-dioxin, 1,2-Dimethoxybenzene, and Diphenyl Ether: Estimation of OH Radical Reaction Rate Constants for PCBs, PCDDs, and PCDFs, Environ. Sci. Technol., 29, 1591–1598, 1995. Li, Y.-F.: Global Population Distribution Database, A Report to the United Nations Environment Programme, under UNEP Sub-Project FP/1205-95-12, 1996. Liss, P. S. and Slater, P. G.: Flux of Gases across the Air-Sea Interface, Nature, 247, 181–197, 1974. Ma, J., Daggupaty, S., Harner, T., and Li, Y.-F.: Impacts of Lindane usage in the Canadian prairies on the Great Lakes ecosystem, 1. Coupled atmospheric transport model and modeled concentrations in air and soil, Environ. Sci. Technol., 37, 3774–3781, 2003. Mackay, D.: Multimedia Environmental Models, The Fugacity Approach, Lewis Publishers, 1991. Mackay, D., Shiu, W. Y., and Ma, K. C.: Illustrated Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals, I. Lewis Publishers Inc., Michigan, 1992. MacLeod, M., Woodfine, D., Mackay, D., McKone, T., Bennett, D., and Maddalena, R.: BETR North America: A Regionally Segmented Multimedia Contaminant Fate Model for North America, Environ. Sci. Pollut. Res., 8, 156–163, 2001. Malanichev, A., Mantseva, E., Shatalov, V., Strukov, B., and Vulykh, N.: Numerical evaluation of the PCB transport over the Northern Hemisphere, Environ. Poll., 128, 279–289, 2004. Mandalakis, M. and Stephanou, E. G.: Polychlorinated biphenyls associated with fine particles (pm2.5) in the urban environment of Chile: concentration levels, and sampling volatilization losses, Environ. Toxicol. Chem., 21, 2270–2275, 2002. Meijer, S. N., Ockenden, W. A., Sweetman, A. J., Breivik, K., Grimalt, J. O. and Jones, K. C.: Global distribution and budget of PCBs and HCB in background surface soils: implications for sources and environmental processes, Environ. Sci. Technol., 37, 667–672, 2003. Pankow, J. F.: Review and Comparative Analysis of the Theories on Partitioning Between the Gas and Aerosol Particulate Phases in the Atmosphere, Atmos. Environ., 21, 2275–2283, 1987. Sahsuvar, L.: Modelling Physical Chemical Properties and Pathways of Polychlorinated Biphenyls in the Atmosphere, MSc Thesis, York University, Toronto, 140 pp., 1999. Sahsuvar, L., Helm, P. A., Jantunen, L. M., and Bidleman, T. F.: Henry's law constants for alpha-, beta-, and gamma-hexachlorocyclohexanes (HCHs) as a function of temperature and revised estimates of gas exchange in Arctic regions, Atmos. Environ., 37, 983–992, 2003. Schnoor, J. L.: Environmental Modeling. Fate and Transport of Pollutants in Water, Air, and Soil, Environmental Science and Technology, John Wiley & Sons, Inc., New York, 1996. Semeena, V. S., Feichter, J., and Lammel, G.: Impact of the regional climate and substance properties on the fate and atmospheric long-range transport of persistent organic pollutants – exampled of DDT and $\gamma $-HCH, Atmos. Chem. Phys., 6, 1231–1248, 2006. Semeena, V. S. and Lammel, G.: The significance of the grasshopper effect on the atmospheric distribution of president organic substances, Geophys. Res. Lett., 32, L07804, doi:10.1029/2004GL022229, 2005. Shen, L., Wania, F., Lei, Y. D., Teixeira, C., Muir, D. C. G., and Xiao, H.: Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere, Environ. Poll., 144, 434–444, 2006. Sobek, A. and Gustafsson, O.: Latitudinal fractionation of polychlorinated biphenyls in surface seawater along a 62 degrees N-89 degrees N transect from the southern Norwegian Sea to the North Pole area, Environ. Sci. Technol., 38, 2746–2751, 2004. Strand, A. and Hov, Ø.: A model strategy for the simulation of chlorinated hydrocarbon distributions in the global environment, Water Air Soil Poll., 86, 283–316, 1996. Sun, P., Backus, S., Blanchard, P., and Hites, R. A.: Annual variation of polycyclic aromatic hydrocarbon concentrations in precipitation collected near the Great Lakes, Environ. Sci. Technol., 40, 696–701, 2006. Toose, L., Woodfine, D. G., MacLeod, M., Mackay, D., and Gouin, J.: BETR-World: a geographically explicit model of chemical fate: application to transport of alpha-HCH to the Arctic, Environ. Poll., 128, 223–240, 2004. van Jaarsveld, J. A., van Pul, W. A. J., and de Leeuw, F. A. A. M.: Modelling transport and deposition of persistent organic pollutants in the European region, Atmos. Env., 31, 1011–1024, 1997. Venkatram, A., Karamchandani, P. K., and Misra, P. K.: Testing a comprehensive acid deposition model, Atmos. Environ., 22, 737–747, 1988. Wania, F. and Daly, G. L.: Estimating the contribution of degradation in air and deposition to the deep sea to the global loss of PCBs, Atmos. Environ., 36, 5581–5593, 2002. Wania, F. and Mackay, D.: A global distribution model for persistent organic chemicals, Sci. Total Environ., 160/161, 211–232, 1995.