ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-6597-2009 Source regions of some persistent organic pollutants measured in the atmosphere at Birkenes, Norway Eckhardt S. 1 Breivik K. 1 2 Li Y. F. 3 4 Manø S. 1 Stohl A. 1 Norwegian Institute for Air Research, P.O. Box 100, 2027 Kjeller, Norway University of Oslo, Department of Chemistry, P.O. Box 1033, 0315 Oslo, Norway Air Quality Research Division, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario M3H 5T4, Canada International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, China 11 09 2009 9 17 6597 6610 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/9/6597/2009/acp-9-6597-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/6597/2009/acp-9-6597-2009.pdf

A key feature of POPs (Persistent Organic Pollutants) is their potential for long-range atmospheric transport. In order to better understand and predict atmospheric source-receptor relationships of POPs, we have modified an existing Lagrangian transport model (FLEXPART) to include some of the key processes that control the atmospheric fate of POPs. We also present four years (2004–2007) of new atmospheric measurement data for polychlorinated biphenyls (PCBs) and hexachlorocyclohexanes (HCHs) obtained at Birkenes, an EMEP (European Monitoring and Evaluation Programme) site in southern Norway. The model overestimates measured PCB-28 and γ-HCH concentrations by factors of 2 and 8, respectively, which is most likely because the emissions used as input to the model are overestimated. FLEXPART captures the temporal variability in the measurements very well and, depending on season, explains 31–67% (14–62%) of the variance of measured PCB-28 (γ-HCH) concentrations. FLEXPART, run in a time-reversed (adjoint) mode, was used to identify the source regions responsible for the POP loading at the Birkenes station. Emissions in Central Europe and Eastern Europe contributed 32% and 24%, respectively, to PCB-28 at Birkenes, while Western Europe was found to be the dominant source (50%) for γ-HCH. Intercontinental transport from North America contributed 13% γ-HCH. While FLEXPART has no treatment of the partitioning of POPs between different surface media, it was found a very useful tool for studying atmospheric source-receptor relationships for POPs and POP-like chemicals that do not sorb strongly to atmospheric particles and whose atmospheric levels are believed to be mainly controlled by primary sources.

 References Ahling, B. and Lindskog, A.: Thermal destruction of PCB and hexachlorobenzene, Sci. Total Environ., 10, 51–59, 1978. AMAP, A. M. A. P.: Amap assessment 1998: Arctic pollution issues, Oslo, Norway, xii+859 pp., 1998. ECMWF, E. C. f. M.-R. W. F.: User guide to ECMWF products 2.1, Meteorol. Bull., Reading, England, UK, 1995. Amundsen, C. E., Hanssen, J. E., Semb, A., and Steinnes, E.: Long-range atmospheric transport of trace-elements to southern Norway, Atmos. Environ. A-Gen., 26, 1309–1324, 1992. 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. Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore, A. M., Li, Q. B., Liu, H. G. Y., Mickley, L. J., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res.-Atmos., 106, 23073–23095, 2001. Breivik, K., Pacyna, J. M., and Munch, J.: Use of alpha-, beta- and gamma-hexachlorocyclohexane in Europe, 1970-1996, Sci. Total Environ., 239, 151–163, 1999. 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. 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 3. An update, Sci. Total Environ., 377, 296–307, doi:10.1016/j.scitotenv.2007.02.026, 2007. Brubaker, W. W. and Hites, R. A.: OH reaction kinetics of gas-phase alpha- and gamma-hexachlorocyclohexane and hexachlorobenzene, Environ. Sci. Technol., 32, 766–769, 1998. Cousins, I. T., Mackay, D., and Jones, K. C.: Measuring and modelling the vertical distribution of semivolatile organic compounds in soils. II: Model development, Chemosphere, 39, 2519–2534, 1999. Currado, G. M. and Harrad, S.: Comparison of Polychlorinated Biphenyl concentrations in indoor and outdoor air and the potential significance of inhalation as a human exposure pathway, Environ. Sci. Technol., 32, 3043–3047, 1998. Currado, G. M. and Harrad, S.: Factors influencing atmospheric concentrations of polychlorinated biphenyls in Birmingham, UK, Environ. Sci. Technol., 34, 78–82, 2000. Du, S. Y. and Rodenburg, L. A.: Source identification of atmospheric PCBs in Philadelphia/Camden using positive matrix factorization followed by the potential source contribution function, Atmos. Environ., 41, 8596–8608, doi:10.1016/j.atmosenv.2007.07.042, 2007. Eckhardt, S., Stohl, A., Beirle, S., Spichtinger, N., James, P., Forster, C., Junker, C., Wagner, T., Platt, U., and Jennings, S. G.: The North Atlantic Oscillation controls air pollution transport to the Arctic, Atmos. Chem. Phys., 3, 1769–1778, 2003. Eckhardt, S., Breivik, K., Man\o, S., and Stohl, A.: Record high peaks in PCB concentrations in the Arctic atmosphere due to long-range transport of biomass burning emissions, Atmos. Chem. Phys., 7, 4527–4536, 2007. Emanuel, K. A. and Živković-Rothman, M.: Development and evaluation of a convection scheme for use in climate models, J. Atmos. Sci., 56, 1766–1782, 1999. Forster, C., Stohl, A., and Seibert, P.: Parameterization of convective transport in a Lagrangian particle dispersion model and its evaluation, J. Appl. Meteorol. Clim., 46, 403–422, doi:10.1175/jam2470.1, 2007. Gong, S. L., Huang, P., Zhao, T. L., Sahsuvar, L., Barrie, L. A., Kaminski, J. W., Li, Y. F., and Niu, T.: GEM/POPs: a global 3-D dynamic model for semi-volatile persistent organic pollutants – Part 1: Model description and evaluations of air concentrations, Atmos. Chem. Phys., 7, 4001–4013, 2007. Gouin, T., Thomas, G. O., Cousins, I., Barber, J., Mackay, D., and Jones, K. C.: Air-surface exchange of polybrominated biphenyl ethers and polychlorinated biphenyls, Environ. Sci. Technol., 36, 1426–1434, doi:10.1021/es011105k, 2002. Hafner, W. D. and Hites, R. A.: Potential sources of pesticides, PCBs, and PAHs to the atmosphere of the Great Lakes, Environ. Sci. Technol., 37, 3764–3773, doi:10.1021/es034021f, 2003. Halsall, C. J.: Investigating the occurrence of persistent organic pollutants (pops) in the Arctic: Their atmospheric behaviour and interaction with the seasonal snow pack, Environ. Pollut., 128, 163–175, doi:10.1016/j.envpol.2003.08.026, 2004. Hansen, K. M., Christensen, J. H., Brandt, J., Frohn, L. M., and Geels, C.: Modelling atmospheric transport of α-hexachlorocyclohexane in the Northern Hemispherewith a 3-D dynamical model: DEHM-POP, Atmos. Chem. Phys., 4, 1125–1137, 2004. Hansen, K. M., Prevedouros, K., Sweetman, A. J., Jones, K. C., and Christensen, J. H.: A process-oriented inter-comparison of a box model and an atmospheric chemistry transport model: Insights into model structure using alpha-HCH as the modelled substance, Atmos. Environ., 40, 2089–2104, doi:10.1016/j.atmosenv.2005.11.050, 2006. Harner, T., Shoeib, M., Kozma, M., Gobas, F., and Li, S. M.: Hexachlorocyclohexanes and endosulfans in urban, rural, and high altitude air samples in the fraser valley, british columbia: Evidence for trans-pacific transport, Environ. Sci. Technol., 39, 724–731, doi:10.1029/2004jd004286, 2005. Harrad, S. J., Sewart, A. P., Alcock, R., Boumphrey, R., Burnett, V., Duartedavidson, R., Halsall, C., Sanders, G., Waterhouse, K., Wild, S. R., and Jones, K. C.: Polychlorinated-biphenyls (PCBs) in the british environment – sinks, sources and temporal trends, Environ. Pollut., 85, 131–146, 1994. Haugen, J. E., Wania, F., and Lei, Y. D.: Polychlorinated biphenyls in the atmosphere of southern norway, Environ. Sci. Technol., 33, 2340–2345, 1999. Hertel, O., Christensen, J., Runge, E. H., Asman, W. A. H., Berkowicz, R., Hovmand, M. F., and Hov, O.: Development and testing of a new variable scale air-pollution model – ACDEP, Atmos. Environ., 29, 1267–1290, 1995. Hoff, R. M., Brice, K. A., and Halsall, C. J.: Nonlinearity in the slopes of Clausius-Clapeyron plots for SVOCs, Environ. Sci. Technol., 32, 1793–1798, 1998. 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 – Part 2: Global transports and budgets of PCBs, Atmos. Chem. Phys., 7, 4015–4025, 2007. Hung, H., Halsall, C. J., Blanchard, P., Li, H. H., Fellin, P., Stern, G., and Rosenberg, B.: Are PCBs in the Canadian Arctic atmosphere declining? Evidence from 5 years of monitoring, Environ. Sci. Technol., 35, 1303–1311, 2001. 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, doi:10.1016/j.atmosenv.2005.07.012, 2005. Jamshidi, A., Hunter, S., Hazrati, S., and Harrad, S.: Concentrations and chiral signatures of polychlorinated biphenyls in outdoor and indoor air and soil in a major UK conurbation, Environ. Sci. Technol., 41, 2153–2158, doi:10.1021/es062218c, 2007. Kocan, A., Petrik, J., Chovancova, J., Neubauerova, L., and Bezacinsky, M.: Pcdd, pcdf and pcb levels in stack emissions from czechoslovak waste burning facilities, ISI:A1991HB10400050, 1473–1480, 1991. Li, N. Q., Wania, F., Lei, Y. D., and Daly, G. L.: A comprehensive and critical compilation, evaluation, and selection of physical-chemical property data for selected polychlorinated biphenyls, J. Phys. Chem. Ref. Data, 32, 1545–1590, doi:10.1063/1.1562632, 2003a. Li, Y. F., McMillan, A., and Scholtz, M. T.: Global HCH usage with 1 degrees x1 degrees longitude/latitude resolution, Environ. Sci. Technol., 30, 3525–3533, 1996. Li, Y. F., Bidleman, T. F., Barrie, L. A., and McConnell, L. L.: Global hexachlorocyclohexane use trends and their impact on the Arctic atmospheric environment, Geophys. Res. Lett., 25, 39–41, 1998a. Li, Y. F., Cai, D. J., and Singh, A.: Technical hexachlorocyclohexane use trends in China and their impact on the environment, Arch. Environ. Con. Tox., 35, 688–697, 1998b. Li, Y. F.: Global technical hexachlorocyclohexane usage and its contamination consequences in the environment: From 1948 to 1997, Sci. Total Environ., 232, 121–158, 1999a. Li, Y. F.: Global gridded technical hexachlorocyclohexane usage inventories using a global cropland as a surrogate, J. Geophys. Res.-Atmos., 104, 23785–23797, 1999b. Li, Y. F., Scholtz, M. T., and van Heyst, B. J.: Global gridded emission inventories of alpha-hexachlorocyclohexane, J. Geophys. Res.-Atmos., 105, 6621–6632, 2000. Li, Y. F., Cai, D. J., Shan, Z. J., and Zhu, Z. L.: Gridded usage inventories of technical hexachlorocyclohexane and lindane for china with 1/6 degrees latitude by 1/4 degrees longitude resolution, Arch. Environ. Con. Tox., 41, 261–266, 2001. Li, Y. F., Scholtz, M. T., and Van Heyst, B. J.: Global gridded emission inventories of 6-hexachlorocyclohexane, Environ. Sci. Technol., 37, 3493–3498, doi:10.1021/es034157d, 2003b. Li, Y. F., Struger, J., Waite, D., and Ma, J.: Gridded Canadian lindane usage inventories with 1/6 degrees x 1/4 degrees latitude and longitude resolution, Atmos. Environ., 38, 1117–1121, doi:10.1016/j.atmosenv.2003.11.022, 2004. Li, Y. F., Ren, N. Q., and Tian, C.: China-North America project on reduction of lindane usage in china and its impact globally and on North America, in: Report to North America Commission for Environmental Cooperation (CEC), Environment Canada and US EPA, 2008. Lohmann, R., Breivik, K., Dachs, J., and Muir, D.: Global fate of pops: Current and future research directions, Environ. Pollut., 150, 150–165, doi:10.1016/j.envpol.2007.06.051, 2007. Ma, J. M., 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, doi:10.1021/es034160x, 2003. Ma, J. M., Venkatesh, S., Li, Y. F., Cao, Z. H., and Daggupaty, S.: Tracking toxaphene in the North American great lakes basin. 2. A strong episodic long-range transport event, Environ. Sci. Technol., 39, 8132–8141, doi:10.1021/es050946e, 2005. Mackay, D.: Multimedia environmental models. The fugacity approach 2nd ed, in: Lewis Publishers, Boca Raton, FL, 2001. Mackay, D. and Reid, L.: Local and distant residence times of contaminants in multi-compartment models. Part I: A review of the theoretical basis, Environ. Pollut., 156, 1196–1203, doi:10.1016/j.envpol.2008.04.012, 2008. MacLeod, M., Riley, W. J., and McKone, T. E.: Assessing the influence of climate variability on atmospheric concentrations of polychlorinated biphenyls using a global-scale mass balance model (BETR-global), Environ. Sci. Technol., 39, 6749–6756, doi:10.1021/es048426r, 2005. Malanichev, A., Mantseva, E., Shatalov, V., Strukov, B., and Vulykh, N.: Numerical evaluation of the PCBs transport over the northern hemisphere, Environ. Pollut., 128, 279–289, doi:10.1016/j.envpol.2003.08.040, 2004. Meyer, T., Wania, F., and Breivik, K.: Illustrating sensitivity and uncertainty in environmental fate models using partitioning maps, Environ. Sci. Technol., 39, 3186–3196, doi:10.1021/es048728t, 2005. Oehme, M.: Further evidence for long-range air transport of polychlorinated aromates and pesticides – North-America and Eurasia to the Arctic, Ambio, 20, 293–297, 1991. 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, doi:10.1016/s1352-2310(02)00936-6, 2003. Seibert, P. and Frank, A.: Source-receptor matrix calculation with a Lagrangian particle dispersion model in backward mode, Atmos. Chem. Phys., 4, 51–63, 2004. Semeena, V. S. and Lammel, G.: The significance of the grasshopper effect on the atmospheric distribution of persistent organic substances, Geophys. Res. Lett., 32, L07804, doi:10.1029/2004GL022229, 2005. Stohl, A., Hittenberger, M., and Wotawa, G.: Validation of the Lagrangian particle dispersion model FLEXPART against large-scale tracer experiment data, Atmos. Environ., 32, 4245–4264, 1998. Stohl, A. and Thomson, D. J.: A density correction for Lagrangian particle dispersion models, Bound.-Lay. Meteorol., 90, 155–167, 1999. Stohl, A., Forster, C., Eckhardt, S., Spichtinger, N., Huntrieser, H., Heland, J., Schlager, H., Wilhelm, S., Arnold, F., and Cooper, O.: A backward modeling study of intercontinental pollution transport using aircraft measurements, J. Geophys. Res.-Atmos., 108, 4370, doi:10.1029/2002jd002862, 2003. Stohl, A., Forster, C., Frank, A., Seibert, P., and Wotawa, G.: Technical note: The Lagrangian particle dispersion model FLEXPART version 6.2, Atmos. Chem. Phys., 5, 2461–2474, 2005. Stohl, A., Andrews, E., Burkhart, J. F., Forster, C., Herber, A., Hoch, S. W., Kowal, D., Lunder, C., Mefford, T., Ogren, J. A., Sharma, S., Spichtinger, N., Stebel, K., Stone, R., Strom, J., Torseth, K., Wehrli, C., and Yttri, K. E.: Pan-Arctic enhancements of light absorbing aerosol concentrations due to North American boreal forest fires during summer 2004, J. Geophys. Res.-Atmos., 111, D22214, doi:10.1029/2006jd007216, 2006. Stohl, A., Seibert, P., Arduini, J., Eckhardt, S., Fraser, P., Greally, B. R., Lunder, C., Maione, M., Mühle, J., O'Doherty, S., Prinn, R. G., Reimann, S., Saito, T., Schmidbauer, N., Simmonds, P. G., Vollmer, M. K., Weiss, R. F., and Yokouchi, Y.: An analytical inversion method for determining regional and global emissions of greenhouse gases: Sensitivity studies and application to halocarbons, Atmos. Chem. Phys., 9, 1597–1620, 2009. Thrane, K. E. and Mikalsen, A.: High-volume sampling of airborne polycyclic aromatic-hydrocarbons using glass-fiber filters and polyurethane foam, Atmos. Environ., 15, 909–918, 1981. Tuinstra, W., Hordijk, L., and Kroeze, C.: Moving boundaries in transboundary air pollution co-production of science and policy under the convention on long range transboundary air pollution, Global Environ. Chang., 16, 349–363, doi:10.1016/j.gloenvcha.2006.03.002, 2006. UNECE: The 1979 Geneva convention on long-range transboundary air pollution, available at: http://www.unece.org/env/lrtap, 2009. UNEP: Final act of the conference of plenipotentaries on the Stockholm convention on persistent organic pollutants, in: United Nations Environment Program, Stockholm, Sweden, 2001. Venier, M. and Hites, R. A.: Flame retardants in the atmosphere near the great lakes, Environ. Sci. Technol., 42, 4745–4751, doi:10.1021/es800313z, 2008. Wania, F. and Mackay, D.: Global fractionation and cold condensation of low volatility organochlorine compounds in polar-regions, Ambio, 22, 10–18, 1993. Wania, F. and Mackay, D.: Tracking the distribution of persistent organic pollutants, Environ. Sci. Technol., 30, A390–A396, 1996. Wania, F., Haugen, J. E., Lei, Y. D., and Mackay, D.: Temperature dependence of atmospheric concentrations of semivolatile organic compounds, Environ. Sci. Technol., 32, 1013–1021, 1998. 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 Su, Y. S.: Quantifying the global fractionation of polychlorinated biphenyls, Ambio, 33, 161–168, 2004. Wania, F.: Potential of degradable organic chemicals for absolute and relative enrichment in the Arctic, Environ. Sci. Technol., 40, 569–577, doi:10.1021/es051406k, 2006. Wesely, M. L.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical-models, Atmos. Environ., 23, 1293–1304, 1989. Willett, K. L., Ulrich, E. M., and Hites, R. A.: Differential toxicity and environmental fates of hexachlorocyclohexane isomers, Environ. Sci. Technol., 32, 2197–2207, 1998. Yttri, K. E., Aas, W., Bjerke, A., Cape, J. N., Cavalli, F., Ceburnis, D., Dye, C., Emblico, L., Facchini, M. C., Forster, C., Hanssen, J. E., Hansson, H. C., Jennings, S. G., Maenhaut, W., Putaud, J. P., and Tørseth, K.: Elemental and organic carbon in PM10: a one year measurement campaign within the European Monitoring and Evaluation Programme EMEP, Atmos. Chem. Phys., 7, 5711–5725, 2007. Zhang, L. S., Ma, J. M., Venkatesh, S., Li, Y. F., and Cheung, P.: Modeling evidence of episodic intercontinental long-range transport of lindane, Environ. Sci. Technol., 42, 8791–8797, doi:10.1021/es801271b, 2008.