Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 5 2008 10.5194/acp-8-1403-2008 http://www.atmos-chem-phys.net/8/1403/2008/ http://www.atmos-chem-phys.net/8/1403/2008/acp-8-1403-2008.html http://www.atmos-chem-phys.net/8/1403/2008/acp-8-1403-2008.pdf 1403 1421 2008-03-11 Seasonal and diurnal variations of Hg° over New England H. Mao hmao@typhoon.sr.unh.edu R. W. Talbot J. M. Sigler B. C. Sive J. D. Hegarty Institute for the Study of Earth, Oceans and Space, Climate Change Research Center, University of New Hampshire, Durham, NH 03824, USA Factors influencing diurnal to interannual variability in Hg° over New England were investigated using multi-year measurements conducted by AIRMAP at the Thompson Farm (TF) coastal site, an inland elevated site at Pac Monadnock (PM), and two month measurements on Appledore Island (AI) in the Gulf of Maine. Mixing ratios of Hg° at TF showed distinct seasonality with maxima in March and minima in October. Hg° at AI tracked the trend at TF but with higher minima, while at PM the diurnal and annual cycles were dampened. In winter, Hg° was correlated most strongly with CO and NO_y, indicative of anthropogenic emissions as their primary source. Our analysis indicates that Hg° had a regional background level of ~160 fmol/mol in winter, a dry deposition velocity of ~0.20 cm s^−1 with a ~16 day lifetime in the coastal boundary layer in summer. The influence of oceanic emissions on ambient Hg° levels was identified using the Hg°-CHBr₃ correlation at both TF and AI. Moreover, the lower Hg° levels and steeper decreasing warm season trend at TF (0.5–0.6 fmol/mol d^−1) compared to PM (0.2–0.3 fmol/mol d^−1) likely reflected the impact of marine halogen chemistry. Large interannual variability in warm season Hg° levels in 2004 versus 2005/2006 may be due to the role of precipitation patterns in influencing surface evasion of Hg°. In contrast, changes in wintertime maximum levels of Hg° were small compared to drastic reductions in CO, CO₂, NO_y, and SO₂ from 2004/2005 to 2006/2007. These trends could be explained by a homogeneous distribution of Hg° over North American in winter due to its long lifetime and/or rapid removal of reactive mercury from anthropogenic sources. We caution that during warmer winters, the Hg°-CO slope possibly reflects Hg° loss relative to changes in CO more than their emission ratio. Ambrose, J. L., Mao, H., Mayne, H. R., Stutz, J., Talbot, R. W., and Sive, B. C.: Nighttime nitrate radical chemistry at Appledore Island, ME during ICARTT 2004, J. Geophys. Res., 112, D21302, doi:10.1029/2007JD008756, 2007. Ariya, P. A., Khalizov, A., and Gidas, A.: Reactions of gaseous mercury with atomic and molecular halogens: kinetics, product studies, and atmospheric implications, J. Phys. Chem. A, 106, 7310–7320, 2002. Bash, J. O. and Miller, D. R.: A relaxed eddy accumulation system for measuring surface fluxes of total gaseous mercury (TGM), J. Atmos. Oceanic Technol., 25(2), 244–257, doi:10.1175/2007JTECHA908.1, 2008. Berg, T. and Aspmo, K.: Atmospheric mercury at the Zeppelin station, 889/2003, Norwegian Institute for Air Research, Statlig program for forurensnigsovervåking, NILU OR 86/2003, 2003. Bergan, T., Gallardo, L., and Rodhe, H.: Mercury in the global troposphere: a three-dimensional model study, Atmos. Environ., 33, 1575–1585, 1999. Brown, S. S., Dibb, J. E., Stark, H., et al.: Nighttime removal of NO_x in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GLo19412, 2004. Brunke, E., Labuschagne, C., and Slemr, F.: Gaseous mercury emissions from a fire in the Cape Peninsula, South Africa, during January 2000, Geophys. Res. Lett., 28(8), 1483–1486, 2001. Calvert, J. G. and Lindberg, S. E.: Mechanisms of mercury removal by O₃ and OH in the atmosphere, Atmos. Environ., 39, 3355–3367, 2005. Chen, M., Talbot, R., Mao, H., Sive, B., Chen, J., and Griffin, R. J.: Air mass classification in coastal New England and its relationship to meteorological conditions, J. Geophys. Res., 112, D10S05, doi:10.1029/2006JD007687, 2007. DeBell, L. J., Talbot, R. W., Dibb, J. E., Munger, J. W., Fischer, E. V., and Frolking, S. E.: A major regional air pollution event in the northeastern United States caused by extensive forest fires in Quebec, Canada, J. Geophys. Res., 109, D19305, doi:10.1029/2004JD004840, 2004. Dickerson, R. R., Rhoads, K. P., Carsey, T. P., Oltmans, S. J., Burrows, J. P., and Crutzen, P. J.: Ozone in the remote marine boundary layer: A possible role for halogens, J. Geophys. Res., 104(D17), 21 385–21 395, 1999. Draxler, R. R.: HYSPLIT_4 (HYbrid Single-Particle Lagrangian Integrated Trajectory Version 4) User's Guide, NOAA Technical Memorandum ERL ARL-230, June 1999. Fehsenfeld, F. C., Ancellet, G., and Bates, T. S., et al.: International Consortium for Atmospheric Research on Transport and Transformation (ICARTT): North America to Europe – Overview of the 2004 summer field study, J. Geophys. Res., 111, D23S01, doi:10.1029/2006JD007829, 2006. Fischer, E., Pszenny, A., Keene, W., Maben, J., Smith, A., Stohl, A., and Talbot, R.: Nitric acid phase partitioning and cycling in the New England coastal atmosphere, J. Geophys. Res., 111, D23S09, doi:10.1029/2006JD007328, 2006. Fischer, E. V., Ziemba, L. D., Talbot, R. W., Dibb, J. E., Griffin, R. J., Husain, L., and Grant, A. N.: Aerosol major ion record at Mount Washington, J. Geophys. Res., 112, D02303, doi:10.1029/2006JD007253, 2007. Friedli, H. R., Radke, L. F., and Lu, J. Y.: Mercury in smoke from biomass fires, Geophys. Res. Lett., 28(17), 3223–3226, 2001. Friedli, H. R., Tadke, L. F., Prescott, R., Li, P., Woo, J.-H., and Carmichael, G. R.: Mercury in the atmosphere around Japan, Korea, and China as observed during the 2001 ACE-Asia field campaign: Measurements, distributions, sources, and implications, J. Geophys. Res., 109, D19S25, doi:10.1029/2003JD004244, 2004. Hall, B.: The gas phase oxidation of elemental mercury by ozone, Water, Air, Soil Pollution, 80(1–4), 301–315, doi:10.1007/BF01189680, 1995. Hogrefe, C., Rao, S. T., Zurbenko, I. G., and Porter, P. S.: Interpreting the information in ozone observations and model predictions relevant to regulatory policies in the eastern United States, B. Am. Meteorol. Soc., 81, 2083–2106, 2000. Jacob, D. J.: Introduction to atmospheric chemistry, Princeton University Press, Princeton, New Jersey, 25–26, 1999. Kindler, T. P., Chameides, W. L., Wine, P. H., Cunnold, D. M., Alyea, F. N., and Franklin, J. A.: The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl₄, C₂Cl₄, C₂HCl₃, CH₃CCl₃, and CHCl₃, J. Geophys. Res., 100(Dl), 1235–1251, 1995. Kellerhals, M., Beauchamp, St., Belzer, W., et al.: Temporal and spatial variability of total gaseous mercury in Canada: results from the Canadian Atmospheric Mercury Measurement Network (CAMNet), Atmos. Environ., 37, 1003–1011, 2003. Kim, K.-H., Ebinghaus, R., and Schroeder, W. H., et al.: Atmospheric mercury concentrations from several observatory sites in the Northern Hemisphere, J. Atmos. Chem., 50, 1–24, 2005. Lamarque, J.-F. and Hess, P. G.: Model analysis of the temporal and geographical origin of the CO distribution during the TOPSE campaign, J. Geophys. Res., 108(D4), 8354, doi:10.1029/2002JD002077, 2003. Laurier, F. J. G., Mason, R. P., and Whalin, L.: Reactive gaseous mercury formation in the North Pacific Ocean's marine boundary layer: A potential role of halogen chemistry, J. Geophys. Res., 108(D17), 4529, doi:10.1029/2003JD003625, 2003. Laurier, F. and Mason, R.: Mercury concentration and speciation in the coastal and open ocean boundary layer, J. Geophys. Res., 112, D06302, doi:10.1029/2006JD007320, 2007. Lee, D. S., Dollard, G. J., and Pepler, S.: Gas phase mercury in the atmosphere of the United Kingdom, Atmos. Environ., 32, 855–864, 1998. Lee, D. S., Nemitz, E., Fowler, D., and Kingdon, R. D.: Modeling atmospheric mercury transport and deposition across Europe and the UK, Atmos. Environ., 35, 5455–5466, 2001. Lin, C.-J., Pongprueksa, P., Lindberg, S. E., Pehkonen, S. O., Byun, D., and Jang, C.: Scientific uncertainties in atmospheric mercury models I: Model science evaluation, Atmos. Environ., 40, 2911–2928, 2006. Lindberg, S. E., Meyers, T. P., Taylor, G. E., Turner, R. R., and Schroeder, W. H.: Atmosphere-surface exchange of mercury in a forest: Results of modeling and gradient approaches, J. Geophys. Res., 97, 2519–2528, 1992. Lindberg, S. E. and Stratton, W. J.: Atmospheric mercury speciation: concentrations and behavior of reactive gaseous mercury in ambient air, Environ. Sci. Technol., 32(1), 49–57, 1998. Lindberg, S. E., Hanson, P. J., Meyers, T. P., and Kim, K.-H.: Air/surface exchange of mercury vapor over forests – The need for a reassessment of continental biogenic emissions, Atmos. Environ., 32(5), 895–908, 1998. Lindberg, S. E., Zang, H., and Gustin, M., et al.: Increases in mercury emission from desert soils in response to rainfall and irrigation, J. Geophys. Res., 104(D17), 21 879–21 888, 1999. Mao, H. and Talbot, R.: O₃ and CO in New England: Temporal variations and relationships, J. Geophys. Res., 109, D21304, doi:10.1029/2004JD004913, 2004a. Mao, H. and Talbot, R.: Role of meteorological processes in two New England ozone episodes during summer 2001, J. Geophys. Res.,~109,~D20305, doi:10.1029/2004JD004850, 2004b. Mao, H. and Talbot, R.: Relationship of surface O₃ to large-scale circulation patterns during two recent winters, Geophys. Res. Lett., 31, L06108, doi:10.1029/2003GL018860, 2004c. Mason, R. P. and Sheu, G.-R.: Role of the ocean in the global mercury cycle, Global Biochem. Cycles, 16(4), 1093, doi:10.1029/2001GB001440, 2002. Miller, S. T. K., Keim, B. D., Talbot, R. W., and Mao, H.: Sea breeze: Structure, forecasting, and impacts, Rev. Geophys., 41(3), 1011, doi:10.1029/2003RG000124, 2003. Munger, J. W., Fan, S. M., Bakwin, P. S., Goulden, M. L., Goldstein, A. H., Colman, A. S., and Wofsy, S. C.: Regional budgets for nitrogen oxides from continental sources: Variations of rates for oxidation and deposition with season and distance from source regions, J. Geophys. Res., 103, 8355–8368, 1998. NESCAUM: Economic Valuation of Human Health Benefits of Controlling Mercury Emissions from U.S. Coal-Fired Power Plants, Northeast States for Coordinated Air Use Management, Boston, MA, 2005a. NESCAUM: Inventory of Anthropogenic Mercury Emissions in the Northeast, Northeast States for Coordinated Air Use Management, Boston, MA, 2005b. NOAA GMD: Annual Report #26, http://www.esrl.noaa.gov/gmd/publications/annrpt26/, 2000. Obrist, D., Conen, F., Vogt, R., Siegwolf, R., and Alewell, C.: Estimation of Hg° exchange between ecosystems and the atmosphere using $^222$Rn and Hg° concentration changes in the stable nocturnal boundary layer, Atmos. Environ., 40, 856–866, 2006. Olaguer, E. P.: The distribution of the chlorinated solvents dichloromethane, perchloroethylene, and trichloroethylene in the global atmosphere, Environ. Sci. Pollut. Res., 9, 175–182, 2002. Pai, P., Karamchandani, P., Seigneur, C., and Allan, M.: Sensitivity of simulated atmospheric mercury concentrations and deposition to model input parameters, Atmos. Environ., 31, 2717–2732, 1997. Pacyna, E. G. and Pacyna, J. M.: Global emission of mercury from anthropogenic sources in 1995, Water, Air, Soil Pollut., 137, 149–165, 2002. Parrish, D. D., Holloway, J. S., Trainer, M., Murphy, P. C., Forbes, G. L., and Fehsenfeld, F. C.: Export of North American ozone pollution to the North Atlantic Ocean, Science, 259, 1436–1439, 1993. Poissant, L., Pilote, M., Xu, X., Zhang, H., and Beauvais, C.: Atmospheric mercury speciation and deposition in the Bay of St. Francois wetlands, J. Geophys. Res., 109, D11301, doi:10.1029/2003JD004364, 2004. Poissant, L., Pilote, M., Constant, P., Beauvais, C., and Zhang, H. H.: A year of continuous measurements of three atmospheric mercury species (GEM, RGM, and Hg$_p)$ in southern Québec, Canada, Atmos. Environ., 39, 1275–1287, 2005. Schroeder, W. H. and Munthe, J.: Atmospheric mercury – an overview, Atmos. Environ., 5, 809–822, 1998. Seigneur, C., Vijayaraghavan, K., Lohman, K., Karamchandani, P., and Scott, C.: Global source attribution for mercury deposition in the United States, Environ. Sci. Technol. 38, 555–569, 2004. Sheu, G.-R.: Speciation and distribution of atmospheric mercury: Significance of reactive gaseous mercury in the global mercury cycle, Ph.D. Thesis, University of Maryland, College Park, pp. 170, 2001. Shipham, M. C., Bartlett, K. B., Crill, P. M., Harriss, R. C., and Blaha, D.: Atmospheric methane measurements in central New England: An analysis of the long-term trend and the seasonal and diurnal cycles, J. Geophys. Res., 103(D9), 10 621–10 630, 1998a. Shipham, M. C., Crill, P. M., Bartlett, K. B., Goldstein, A. H., Czepiel, P. M., Harriss, R. C., and Blaha, D.: Methane measurements in central New England: An assessment of regional transport from surrounding sources, J. Geophys. Res., 103, 21 985–22 000, 1998b. Sigler, J. M., Lee, X.-H., and Munger, J. W.: Emission and long-range transport of mercury from a Canadian boreal forest fire, Environ. Sci. Technol. 37(19), 4343–4347, 2003. Sigler, J. M. and Lee, X.-H.: Gaseous mercury in background forest soil in the northeastern United States, J. Geophys. Res., 111, G02007, doi:10.1029/2005JG000106, 2006. Sive, B. C., Zhou, Y., Troop, D., Wang, Y., Little, W. C., Wingenter, O. W., Russo, R. S., Varner, R. K., and Talbot, R.: Development of a cryogen-free concentration system for measurements of volatile organic compounds, Anal. Chem., 77(21), 6989–6998, doi:10.1021/ac0506231, 2005. Sommar, J., Gårdfeld, K., Strömberg, D., and Feng, X.: A kinetic study of the gas-phase reaction between the hydroxyl radical and atomic mercury, Atmos. Environ., 35, 3049–3054, 2001. Sommar, J., Hallquist, M., Ljungström, E., and Lindqvist, O.: On the gas phase reactions between volatile biogenic mercury species and the nitrate radical, J. Atmos. Chem., 27, 233–247, 1997. Spivakovsky, C. M., Logan, J. A., Montzka, S. A., et al.: Three-dimensional climatological distribution of tropospheric OH: Update and evaluation, J. Geophys. Res., 105(D7), 8931–8980, 2000. Sprovieri, F., Pirrone, N., and Sommar, J.: Mercury speciation in the marine boundary layer along a 6000 km cruise path around the Mediterranean Sea, Atmos. Environ., 37, suppl. 1, S63–S71, 2003. Stohl, A.: Characteristics of atmospheric transport into the Arctic troposphere, J. Geophys. Res., 111, D11306, doi:10.1029/2005JD006888, 2006. Sullivan, T. M., Adams, J., Milian, L., Subramaniam, S., Feagin, L., Williams, J., and Boyd, A.: Local impacts of mercury emissions from the Monticellow coal fired power plant, BNL-77475-2007-IR, Environmental Sciences Department, Environmental Research & Technology Division, Brookhaven National Laboratory, P.O. Box 5000, Upton, NY 11973-5000, 2006. Talbot, R., Mao, H., and Sive, B.: Diurnal characteristics of surface level O₃ and other important trace gases in New England, J. Geophys. Res., 110, D09307, doi:10.1029/2004JD005449, 2005. Talbot, R. W., Brown, D., Bryce, J., Chen, M., Griffin, R., McDowell, W., Mao, H., Mayne, H., Sive, B., Varner, R., Wake, C., Koermer, J., and Pszenny, A.: AIRMAP: A UNH Air Quality and Climate Program, Semi-Annual Technical Report to Office of Oceanic and Atmospheric Research and NOAA Earth Systems Research Laboratory, National Oceanic and Atmospheric Administration, Silver Spring, MD, 57 pp., December 2006. Valente, R. J., Shea, C., Humes, K. L., and Tanner, R. L.: Atmospheric mercury in the Great Smoky Mountains compared to regional and global levels, Atmos. Environ., 41, 1861–1873, 2007. Wang, Y., Shim, C., Blake, N., et al.: Intercontinental transport of pollution manifested in the variability and seasonal trend of springtime O₃ at northern middle and high latitudes, J. Geophys. Res., 108, 4683, doi:10.1029/2003JD003592, 2003. Xu, X., Yang, X., Miller, D., Helble, J. J., and Carley, R. J.: Formulation of bi-directional atmosphere-surface exchanges of elemental mercury, Atmos. Environ., 33, 4345–4355, 1999. Zhou, Y., Varner, R. K., Russo, R. S., Wingenter, O. W., Haase, K. B., Talbot, R., and Sive, B. C.: Coastal water source of short-lived halocarbons in New England, J. Geophys. Res., 110, D21302, doi:10.1029/2004JD005603, 2005. Zhou, Y., Varner, R. K., Mao, H., Russo, R. S., Blake, D. R., Wingenter, O. W., Haase, K. B., Talbot, R., and Sive, B. C.: Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002–2004, J. Geophys. Res., in press, 2008. Zurbenko, I. G.: The Spectral Analysis of Time Series, North-Holland, 248 pp., 1986.