Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 6 2009 10.5194/acp-9-1929-2009 http://www.atmos-chem-phys.net/9/1929/2009/ http://www.atmos-chem-phys.net/9/1929/2009/acp-9-1929-2009.html http://www.atmos-chem-phys.net/9/1929/2009/acp-9-1929-2009.pdf 1929 1942 2009-03-19 Gaseous elemental and reactive mercury in Southern New Hampshire J. M. Sigler jsigler@gust.sr.unh.edu H. Mao R. Talbot Institute for the Study of Earth, Oceans and Space, Climate Change Research Center, University of New Hampshire, Durham, New Hampshire 03824, UK We conducted measurements of Hg⁰ and RGM at two inland sites, Thompson Farm (TF) and Pac Monadnock (PM), and a marine site (Appledore Island (AI)) from the UNH AIRMAP observing network in New Hampshire in 2007. Measurements of other important trace gases and meteorological variables were used to help understand influences on the atmospheric Hg budget in New England. Seasonal variation in both species observed at TF and PM is attributable to such factors as seasonal variation in deposition strength, meteorological conditions and biogenic emissions. Hg⁰ and RGM varied diurnally at TF, particularly in spring, following the trend in air temperature and <i>j</i>NO₂ and suggesting photochemical production of RGM. The diurnal patterns of Hg⁰ and RGM at AI during summer were nearly opposite in phase, with Hg⁰ decreasing through late afternoon, suggesting more significant photochemical oxidation of Hg⁰ to RGM in the marine environment, likely due to the presence of marine halogen compounds. A significant relationship of RGM with SO₂ at TF suggests a strong contribution of RGM from anthropogenic sources. Significant levels of halogen compounds measured at TF in previous studies, as well as similar Hg⁰ levels and Hg⁰-CO ratios at TF and AI may suggest that similar air masses are prevalent at these sites. % vor jede Referenz Aspmo, K., Gauchard, P., Steffen, A., Temme, C., Berg, T., Bahlmann, E., Banic, C., Dommergue, A., Ebinghaus, R., Ferrari, C., Pirrone, N., Sprovieri, F., and Wibetoe, G.: Measurements of atmospheric mercury species during an international study of mercury depletion events at Ny-Ålesund, Svalbard, spring 2003. How reproducible are our present methods?, Atmos. Environ., 39, 7607–7619, 2005. Bash, J. O. and Miller, D. R.: A relaxed eddy accumulation system for measuring surface fluxes of total gaseous mercury, J. Atmos. Ocean. Tech., 25, 244–257, 2008. Calvert, J. G. and Lindberg, S. E.: Mechanisms of mercury removal by O₃ and OH in the atmosphere, Atmos. Environ., 39, 3355–3367, 2005. Carpi, A.: Mercury from combustion sources: A review of the chemical species emitted and their transport in the atmosphere, Water Air Soil Pollut., 56, 745–767, 1997. Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via: http://www.arl.noaa.gov/ready/hysplit4.html, NOAA Air Resources Laboratory, Silver Spring, MD, USA, 2003. Engle, M. A., Tate, M. T., Krabbenhoft, D. P., Kolker, A, Olson, M. L., Edgerton, E. S., DeWild, J. F., and McPherson, A. K.: Characterization and cycling of atmospheric mercury along the central US Gulf Coast, Appl. Geochem., 23, 419–437, 2008. EPA (United States Environmental Protection Agency): Mercury Study Report to Congress, online available at: www.epa.gov/mercury.html, 1997. EPA: US Greenhouse Gas Inventory Reports, online available at: http://www.epa.gov/climatechange/emissions/usinventoryreport.html, 2008a. EPA: National Emissions Inventory, online available at: http://www.epa.gov/ttn/chief/net/2002inventory.html, 2008b. Evers, D. C., Han, Y., Driscoll, C. T., Kamman, N. C., Goodale, M. W., Lambert, K. F., Holsen, T. M., Chen, C. Y., Clair, T. A., and Butler, T.: Biological mercury hotspots in the northeastern United States and southeastern Canada, BioScience, 57, 29–43, 2007. Fischer, E. and Talbot, R.: Regional NO$_3^-$ events in the northeastern United States related to seasonal climate anomalies, Geophys. Res. Lett., 32, L16804, doi:10.1029/2005GL023490, 2005. Gabriel, M. C., Williamson, D. G., Brooks, S., and Lindberg, S. E.: Atmospheric speciation of mercury in two contrasting southeastern U.S. airsheds, Atmos. Environ., 39, 4947–4958, 2005. Gustin, M. S. and Stamenkovic, L.: Effect of watering and soil moisture on mercury emissions from soils, Biogeochemistry, 76, 215–232, 2005. Han, Y.-J., Holsen, T. M., Lai, S. O., Hopke, P. K., Yi, S. M., Liu, W., Pagano, J., Falanga, L., Milligan, M., and Andolina, C.: Atmospheric gaseous mercury concentrations in New York State: relationships with meteorological data and other pollutants, Atmos. Environ., 38, 6431–6446, 2004. Kellerhals, Beauchamp, S., Belzer, W., Blanchard, P., Froude, F., Harvey, B., McDonald, K., Pilote, M., Poissant, L., Puckett, K., Schroeder, B., Steffen, A., and Tordon, R.: 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., Lindberg, S. E., and Meyers, T. P.: Micrometeorological measurements of mercury vapor fluxes over background forest soils in eastern Tennessee, Atmos. Environ., 29, 267–282, 1995. Kim, K.-H., Ebinghaus, R., Schroeder, W. H., Blanchard, P., Kock, H. H., Steffen, A., Froude, F. A., Kim, M. Y., Hong, S. M., and Kim, J. H.: Atmospheric mercury concentrations from several observatory sites in the Northern Hemisphere, J. Atmos. Chem., 50, 1–24, 2005. Knipping, E. M., Lakin, M. J., Foster, K. L., Jungwirth, P., Tobias, D. J., Gerber, R. B., Dabdub, D., and Finlayson-Pitts, B. J.: Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols, Science, 288, 301–306, 2000. Landis, M. S., Stevens, R. K., Schaedlich, F., and Prestbo, E. M.: Development and characterization of an annular denuder methodology for the measurement of divalent inorganic reactive gaseous mercury in ambient air, Environ. Sci. Technol., 36(13), 3000–3009, 2002. Laurier, F. J. G., Mason, R. P., Whalin, L., and Kato, S.: 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. 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, 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., Zhang, H., Gustin, M., Vette, A., Marsik, F., Owens, J., Casimir, A., Ebinghaus, R., Edwards, G., Fitzgerald, C., Kemp, J., Kock, H. H., London, J., Majewski, M., Poissant, L., Pilote, M., Rasmussen, P., Schaedlich, F., Schneeberger, D., Sommar, J., Turner, R., Wallschläger, D., and Xiao, Z.: Increases in mercury emission from desert soils in response to rainfall and irrigation, J. Geophys. Res., 104(D17), 21879–21888, 1999. Lindberg, S. E., Brooks, S., Lin, C. J., Scott, K. J., Landis, M. S., Stevens, R. K., Goodsite, M., and Richter, A.: Dynamic oxidation of gaseous mercury in the arctic troposphere during polar sunrise, Environ. Sci. Technol., 36(6), 1245–1256, 2002. Liu, B., Keeler, G. J., Dvonch, J. T., Barres, J. A., Lynam, M. M., Marsik, F. J., and Morgan, J. T.: Temporal variability of mercury speciation in urban air, Atmos. Environ., 41, 1911–1923, 2007. Lynam, M. M. and Keeler, G. J.: Automated speciated mercury measurements in Michigan, Environ. Sci. Technol., 39, 9253–9262, 2005. Malcolm, E. G., Keeler, G. J., and Landis, M. S.: The effects of the coastal environment on the atmospheric mercury cycle, J. Geophys. Res., 108, 4357, doi:10.1029/2002JD003084, 2003. Manolopoulos, H., Schauer, J. J., Purcell, M. D., Rudolph, T. M., Olson, M. L., Rodger, B., and Krabbenhoft, D. P.: Local and regional factors affecting atmospheric mercury speciation at a remote location, J. Environ. Eng. Sci., 6, 491–501, 2007a. Manolopoulos, H., Snyder, D. C., Schauer, J. J., Hill, J. S., Turner, J. R., Olson, M. L., and Krabbenhoft, D. P.: Sources of speciated atmospheric mercury at a residential neighborhood impacted by industrial sources, Environ. Sci. Technol., 41, 5626–5633, 2007b. 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., Talbot, R. W., Sigler, J. M., Sive, B. C., and Hegarty, J. D.: Seasonal and diurnal variations of Hg&deg; over New England, Atmos. Chem. Phys., 8, 1403–1421, 2008. Mason, R. P. and Sheu, G.-R.: Role of the ocean in the global mercury cycle, Global Biogeochem. Cy., 16(4), 1093, doi:10.1029/2001GB001440, 2002. NESCAUM (Northeast States for Coordinated Air Use Management): Inventory of anthropogenic mercury emissions in the northeast, online available at: www.nescaum.org, 2005. 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. Poissant, L. and Casimir, A., Water-air and soil-air exchange rate of total gaseous mercury at background sites, Atmos. Environ., 32, 883–893, 1998. 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., Xu, X., Beauvais, C., Constant, P., and Zhang, H., A year of continuous measurements of three atmospheric mercury species in southern Quebec, Canada, Atmos. Environ., 39, 1275–1287, 2005. Pszenny, A. A. P., Keene, W. C., Jacob, D. J., Fan, S., Maben, J. R., Zetwo, M. P., Springer-Young, M., and Galloway, J. N.: Evidence of inorganic chlorine gases other than hydrogen chloride in marine surface air, Geophys. Res. Lett., 20, 699–702, 1993. Saiz-Lopez, A., Shillito, J. A., Coe, H., and Plane, J. M. C.: Measurements and modelling of I₂, IO, OIO, BrO and NO₃ in the mid-latitude marine boundary layer, Atmos. Chem. Phys., 6, 1513–1528, 2006. Sigler, J. M. and Lee, X.: Recent trends in anthropogenic emission in the northeast United States, J. Geophys. Res., 111, D14316, doi:10.1029/2005JD006814, 2006a. Sigler, J. M. and Lee, X.: Gaseous mercury in background forest soil in the northeastern United States, J. Geophys. Res., 111, G02007, doi:10.1029/2005JG000106, 2006b. Sigler, J. M., Mao, H., Sive, B. C., and Talbot, R. W.: Oceanic influence on atmospheric mercury at coastal and inland sites: A springtime nor'easter in New England, Atmos. Chem. Phys. Discuss., in press, 2009. 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. 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. VanArsdale, A., Weiss, J., Keeler, G., Miller, E., Boulet, G., Brulotte, R., and Poissant, L.: Patterns of mercury deposition and concentration in northeastern North America (1996–2002), Ecotoxicology, 14, 37–52, 2005. Weiss-Penzias, P., Jaffe, D. A., McClintick, A., Prestbo, E. M., and Landis, M. S.: Gaseous elemental mercury in the marine boundary layer: Evidence for rapid removal in anthropogenic pollution, Environ. Sci. Technol., 37, 3755–3763, 2003. Yatavelli, R. L. N., Fahrni, J. K., Kim, M., Crist, K. C., Vickers, C. D., Winter, S. E., and Connell, D. P.: Mercury, PM$_2.5$ and gaseous co-pollutants in the Ohio River Valley region: Preliminary results from the Athens supersite, Atmos. Environ., 40, 6650–6665, 2006. 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., Mao, M., Russo, R. S., Blake, D. R., Wingenter, O. W., Haase, K. B., Ambrose, J., Varner, R. K., Talbot, R., and Sive, B. C.: Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002–2004, J. Geophys. Res., 113, D08305, doi:10.1029/2007JD009103, 2008.