ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-4033-2012 Changing sources and environmental factors reduce the rates of decline of organochlorine pesticides in the Arctic atmosphere Becker S. 1 Halsall C. J. 1 Tych W. 1 Kallenborn R. 2 3 Schlabach M. 2 Manø S. 2 Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK Norwegian Institute for Air Research (NILU), P.O. Box 100, 2007 Kjeller, Norway The Norwegian University of Life Sciences (UMB), Department of Chemistry, Biotechnology and Food Scienc, P.O. Box 5003, 1432 Aas, Norway 08 05 2012 12 9 4033 4044 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/12/4033/2012/acp-12-4033-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/4033/2012/acp-12-4033-2012.pdf

An extensive database of organochlorine (OC) pesticide concentrations measured at the Norwegian Arctic monitoring station at Ny-Ålesund, Svalbard, was analysed to assess longer-term trends in the Arctic atmosphere. Dynamic Harmonic Regression (DHR) is employed to investigate the seasonal and cyclical behaviour of chlordanes, DDTs and hexachlorobenzene (HCB), and to isolate underlying inter-annual trends. Although a simple comparison of annual mean concentrations (1994–2005) suggest a decline for all of the OCs investigated, the longer-term trends identified by DHR only show a significant decline for <i>p</i>,<i>p</i>'-DDT. Indeed, HCB shows an increase from 2003–2005. This is thought to be due to changes in source types and the presence of impurities in current use pesticides, together with retreating sea ice affecting air-water exchange. Changes in source types were revealed by using isomeric ratios for the chlordanes and DDTs. Declining trends in ratios of <i>trans</i>-chlordane/<i>cis</i>-chlordane (TC/CC) indicate a shift from primary sources, to more "weathered" secondary sources, whereas an increasing trend in <i>o</i>,<i>p</i>'-DDT/<i>p</i>,<i>p</i>'-DDT ratios indicate a shift from use of technical DDT to dicofol. Continued monitoring of these OC pesticides is required to fully understand the influence of a changing climate on the behaviour and environmental cycling of these chemicals in the Arctic as well as possible impacts from "new" sources.

 References AMAP, Arctic Monitoring and Assessment Programme: Arctic Pollution 2002: Persistent Organic Pollutants, Heavy Metals, Radioactivity, Human Health, Changing Pathways, AMAP, Oslo, Norway, 2002. Bailey, R., Barrie, L. A., Halsall, C. J., Fellin, P., and Muir, D. C. G.L Atmospheric organochlorine pesticides in the western Canadian Arctic: Evidence of transpacific transport, J. Geophys. Res., 105, 11805–11811, 2000. Bailey, R. E.: Global hexachlorobenzene emissions, Chemosphere, 43, 167–182, 2001. Barber, J. L., Sweetman, A. J., van Wijk, D., and Jones, K. C.: Hexachlorobenzene in the global environment: Emissions, levels, distribution, trends and processes, Sci. Total Environ., 349, 1–44, 2005. Becker, S., Halsall, C. J., Tych, W., Hung, H., Attewell, S., Blanchard P., Li, H., Fellin, P., Stern, G., Billeck, B., and Friesen, S.: Resolving the long-term trends of polycyclic aromatic hydrocarbons in the Canadian Arctic Atmosphere, Environ. Sci. Technol., 40, 3217–3222, 2006. Becker, S., Halsall, C. J., Tych, W., Kallenborn, R., Su, Y., and Hung, H.: Long-term trends in atmospheric concentrations of α- and γ-HCH in the Arctic provide insight into the effects of legislation and climatic fluctuations on contaminant levels, Atmos. Environ., 42, 8225–8233, 2008. Berg, T., Kallenborn, R., and Stein, M.: Temporal trends in atmospheric heavy metal and organochlorine concentrations at Zeppelin, Svalbard. Arctic, Antarct. Alp. Res., 36, 284–291, 2004. Bidleman, T. F., Widekvist, U., Jansson, B., and Söderlund, R.: Organochlorine pesticides and PCBs in the atmosphere of Southern Sweden, Atmos. Environ. 21, 641–654, 1987. Bidleman, T. F., Jantunen, L. M. M., Helm, P. A., Brorström-Lunden, E., and Juntto, S.: Chlordane Enantiomers and Temporal Trends of Chlordane Isomers in Arctic Air, Environ. Sci. Technol., 36, 539–544, 2002. Bidleman, T. F., Wong, F., Backe, C., Södergren, A., Brorström-Lundén, E., Helm, P. A., and Stern, G. A.: Chiral signatures of chlordanes indicate changing sources to the atmosphere over the past 30 years. Atmos. Environ., 38, 5963–5970, 2004. Bidleman, T. F. and Leone, A. D.: Soil-air exchange of organochlorine pesticides in the Southern United States, Environ. Pollut., 128, 49–57, 2004. Chaves, A., Shea, D., and Cope, W. G.: Environmental fate of chlorothalonil in a Costa Rican banana plantation, Chemosphere, 69, 1166–1174, 2007. Connor, M. S., Davis, J. A., Leatherbarrow, J., Greenfield, B. K., Gunther, A., Hardin, D., Murnley, T., Oram, J. J., and Werme, C.: The slow recovery of San Francisco Bay from the legacy of organochlorine pesticides, Environ. Res., 105, 87–100, 2006. Dougherty, C. P., Holtz, S. H., Reinert, J. C., Panyacosit, L., Axelrad, D. A. and Woodruff, T. J.: Dietary exposures to food contaminants across the United States. Environmental Research A 84, 170–185, 2000. 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, http://dx.doi.org/10.5194/acp-7-4527-2007doi:10.5194/acp-7-4527-2007, 2007. Gouin, T., Wania, F., Ruepert, C., and Castillo, L. E.: Field testing passive air samplers for current use pesticides in a tropical environment, Environ. Sci. Technol., 42, 6625–6630, 2008. Halsall, C. J., Bailey, R., Stern, G. A., Barrie, L. A., Fellin, P., Muir, D. G. C., Rosenberg, B., Rovinsky, F. Ya., Kononov, E. Ya., and Pastukhov, B.: Multi-year observations of organohalogen pesticides in the Arctic atmosphere, Environ. Pollut., 102, 51–62, 1998. 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, Environ. Sci. Technol. 36, 862–868, 2002. Hung, H., Blanchard, P., Halsall, C. J., Bidleman, T. F., Stern, G. A., Fellin, P., Muir, D. G. C., 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, 2005. Jantunen, L. M. M., Bidleman, T. F., Harner, T., and Parkhurst, W. J.: Toxaphene, Chlordane, and other organochlorine pesticides in Alabama air, Environ. Sci. Technol., 34, 5097–5105, 2000. Kallenborn, R., Christensen, G., Evenset, A., Schlabach, M., and Stohl, A.: Atmospheric transport of persistent organic pollutants (POPs) to Bjørnøya (Bear island), J. Environ. Monitor., 9, 1082–1091, 2007. Kawano, M., Inoue, T., Wada, T., Hidaka, H., and Tatsukawa, R.: Bioconcentration and residue patterns of chlordane compounds in marine animals: invertebrates, fish, mammals and seabirds, Environ. Sci. Technol., 22, 792–797, 1988. Li, J., Zhang, G., Qi, S., Li, X., and Peng, X.: Concentrations, enantiomeric compositions and sources of HCH, DDT and chlordane in soils from the Pearl River Delta, South China. Sci. Total Environ., 372, 215–224, 2006. Li, J., Zhang, G., Guo, L., Xu, W., Li, W., Lee, C. S. L., Ding, A., and Wang, T.: Organochlorine pesticides in the atmosphere of Guangzhou and Hong Kong: Regional sources and long-range atmospheric transport, Atmos. Environ., 41, 3889–3903, 2007. Oehme, M.: Further evidence for long range air transport of polychlorinated aromatics and pesticides from North America and Eurasia to the Arctic, Ambio, 20, 293–297, 1991. Oehme, M., Haugen, J.-E., and Schlabach, M.: Ambient air levels of persistent organochlorines in spring 1992 at Spitsbergen and the Norwegian mainland: comparison with 1984 results and quality control measures, Sci. Total Environ., 160–161, 139–152, 1995. Oehme, M., Haugen, J.-E., and Schlabach, M.: Seasonal Changes and Relations between Levels of Organochlorines in Arctic Ambient Air: First Results of an All-Year-Round Monitoring Program at Ny-Ålesund, Svalbard, Norway, Environ. Sci. Technol. 30, 2294–2304, 1996. PAN (Pesticide Action Network). Active Ingredient Fact Sheets: Dicofol. http://www.pan-uk.org/pestnews/Actives/dicofol.htm, last access: April 2012. Patton, G. W., Walla, M. D., Bidleman, T. F., and Barrie, L. A.: Polycyclic Aromatic and Organochlorine Compounds in the Atmosphere of Northern Ellesmere Island, Canada, J. Geophys. Res., 96, 10867–10877, 1991. Pesticide Usage Survey (PUS). The Food & Environment Research Agency, UK (formerly the Central Science Laboratory, CSL), http://pusstats.csl.gov.uk, last access: April 2012. Qiu, X., Zhu, T., Yao, B., Hu, J., and Hu, S.: Contribution of Dicofol to the current DDT pollution in China, Environ. Sci. Technol. 39, 4385–4390, 2005. Shen, L., Wania, F., Lei, Y. D., Teixeira, C., Muir, D. C. G., and Bidleman, T. F.: Atmospheric Distribution and Long-Range Transport Behaviour of organochlorine pesticides in North America, Environ. Sci. Technol. 39, 409–420, 2005. Shigenaka, G.: Chlordane in the marine environment of the United States: review and results from the National Status and Trends Programme. Technical Memorandum NOS OMA 55, NOAA, Seattle, WA, USA, 1990. Su, Y., Hung, H., Blanchard, P., Patton, G. W., Kallenborn, R., Konoplev, A., Fellin, P., Li, H., Geen, C., Stern, G., Rosenberg, B., and Barrie, L. A.: Spatial and seasonal variations of hexachlorocyclohexanes (HCHs) and Hexachlorobenzene (HCB) in the Arctic Atmosphere, Environ. Sci. Technol. 40, 6601–6607, 2006. Su, Y., Hung, H., Blanchard, P., Patton, G. W., Kallenborn, R., Konoplev, A., Fellin, P., Li, H., Geen, C., Stern, G., Rosenberg, G., and Barrie, L. A.: A circumpolar perspective of atmospheric organochlorine pesticides (OCPs): Results from six arctic monitoring stations in 2000–2003. Atmos. Environ., http://dx.doi.org/10.1016/j.atmosenv.2008.01.054doi:10.1016/j.atmosenv.2008.01.054, 2008. Tych, W., Pedegral, D. J., Young, P. C. and Davies, J.: An unobserved component model for multi-rate forecasting of telephone call demand: the design of a forecasting support system, Int. J. Forecast., 18, 673–695, 2002. UNECE Protocol to the 1979 convention on long range transboundary air pollution on persistent organic pollutants and executive body decision 1998/2 on information to be submitted and the procedure for adding substances to annex I, II or III to the protocol on persistent organic pollutants, ECE/EB.AIR/60, United Nations, New York and Geneva, 1998. US EPA: Office for Prevention, Pesticides & Toxic Substances (OPPTS), Re-registration Eligibility Decision (RED): Chlorothalonil, http://www.epa.gov/oppsrrd1/REDs/0097red.pdf, last accessed: April 2012. Van de Plassche, E. J., Schwegler, M., Rasenberg, M., and Schouten, G.: DDT in Dicofol, UN-ECE report, http://www.unece.org/fileadmin/DAM/env/lrtap/TaskForce/popsxg/2000-2003/ddt_in_dicofol.pdf, Accessed: April 2012, 2003. Van Oostdam, J., Donaldson, S. G., Feeley, M., Arnold, D., Ayotte, P., Bondy, G., Chan, L., Dewailly, É., Furgal, C. M., Kuhnlein, H., Loring, E., Muckle, G., Myles, E., Receveur, O., Tracy, B., Gill, U., and Kalhok, S.: Human health implications of environmental contaminants in Arctic Canada: A review. Sci. Total Environ., 351–352, 165–246, 2005. Wang, X. P., Xu, B. Q., Kang, S. C., Cong, Z. Y., and Yao, T. D.: The historical residue trends of DDT, Hexachlorocyclohexanes and polycyclic aromatic hydrocarbons in an ice core from Mt. Everest, central Himalayas, China, Atmos. Environ., 42, 6699–6709, 2008. Young, P., Pedegral, D. J., and Tych, W.: Dynamic Harmonic Regression, J. Forecast., 18, 369–394, 1999. Young, P. C.: Nonstationary time series analysis and forecasting, Prog. Environ. Sci., 1, 3–48, 1999. Xu, D., Deng, L., Chai, Z., and Mao, X.: Organohalogenated compounds in pine needles from Beijing City, China. Chemosphere, 57, 1343–1353, 2004. Yang, X., Wang, S., Bian, Y., Chen, F., Yu, G., Gu, C., and Jiang, X.: Dicofol application resulted in high DDTs residue in cotton fields from northern Jiangsu province, China, J. Haz. Mat., 150, 92-98, 2007. Zhang, G., Parker, A., House, A., Mai, B., Li, X., Kang, Y., and Wang, Z. Sedimentary records of DDT and HCH in the Pearl River Delta, South China, Environ. Sci. Technol., 36, 3671–3677, 2002.