References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-5031-2010

Circumpolar measurements of speciated mercury, ozone and carbon monoxide in the boundary layer of the Arctic Ocean

Sommar

¹ Andersson

M. E.

² Jacobi

H.-W.

³ ⁴

State key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China

Department of Chemistry, Göteborg University, 41296 Göteborg, Sweden

CNRS/Université Joseph Fourier – Grenoble 1, Laboratoire de Glaciologie et Géophysique de l'Environnement, 54 Rue Molière, 38400 St Martin d'Hères, France

Alfred Wegener Institute for Polar and Marine Research, Am Handelshafen 12, 27570 Bremerhaven, Germany

01 06 2010

10 11 5031 5045

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Using the Swedish icebreaker Oden as a platform, continuous measurements of airborne mercury (gaseous elemental mercury (Hg0), divalent gaseous mercury species HgIIX2(g) (acronym RGM) and mercury attached to particles (PHg)) and some long-lived trace gases (carbon monoxide CO and ozone O3) were performed over the North Atlantic and the Arctic Ocean. The measurements were performed for nearly three months (July–September 2005) during the Beringia 2005 expedition (from Göteborg, Sweden via the proper Northwest Passage to the Beringia region Alaska – Chukchi Penninsula – Wrangel Island and in-turn via a north-polar transect to Longyearbyen, Spitsbergen). The Beringia 2005 expedition was the first time that these species have been measured during summer over the Arctic Ocean going from 60° to 90° N. During the North Atlantic transect, concentration levels of Hg0, CO and O3 were measured comparable to typical levels for the ambient mid-hemispheric average. However, a rapid increase of Hg0 in air and surface water was observed when entering the ice-covered waters of the Canadian Arctic archipelago. Large parts of the measured waters were supersaturated with respect to Hg0, reflecting a strong disequilibrium. Heading through the sea ice of the Arctic Ocean, a fraction of the strong Hg0 pulse in the water was transferred with some time-delay into the air samples collected ~20 m above sea level. Several episodes of elevated Hg0 in air were encountered along the sea ice route with higher mean concentration (1.81±0.43 ng m−3) compared to the marine boundary layer over ice-free Arctic oceanic waters (1.55±0.21 ng m−3). In addition, the bulk of the variance in the temporal series of Hg0 concentrations was observed during July. The Oden Hg0 observations compare in this aspect very favourably with those at the coastal station Alert. Atmospheric boundary layer O3 mixing ratios decreased when initially sailing northward. In the Arctic, an O3 minimum around 15–20 ppbV was observed during summer (July–August). Alongside the polar transect during the beginning of autumn, a steady trend of increasing O3 mixing ratios was measured returning to initial levels of the expedition (>30 ppbV). Ambient CO was fairly stable (84±12 ppbV) during the expedition. However, from the Beaufort Sea and moving onwards steadily increasing CO mixing ratios were observed (0.3 ppbV day−1). On a comparison with coeval archived CO and O3 data from the Arctic coastal strip monitoring sites Barrow and Alert, the observations from Oden indicate these species to be homogeneously distributed over the Arctic Ocean. Neither correlated low ozone and Hg0 events nor elevated concentrations of RGM and PHg were at any extent sampled, suggesting that atmospheric mercury deposition to the Arctic basin is low during the Polar summer and autumn.

References 1

Andersson, M. E.: Transport of Mercury Species in the Environment - Exchange between Oceanic Waters and the Atmosphere, Ph.D thesis, Department of Chemistry, Göteborg University, Sweden, 59 pp., 2008.

Andersson, M. E.: Speciation of aqueous mercury species in a cross section of the Arctic Ocean, in preparation, 2010.

Andersson, M. E., Gårdfeldt, K., Wängberg, I., and Strömberg, D.: Determination of Henry's law constant for elemental mercury, Chemosphere, 73, 587–592, 2008a.

Andersson, M. E., Sommar, J., Gårdfeldt, K., and Lindqvist, O.: Enhanced concentrations of dissolved gaseous mercury in the surface waters of the Arctic Ocean, Mar. Chem., 110, 190–194, 2008b.

Andersson, M. E., Gårdfeldt, K., and Wängberg, I.: A description of an automatic continuous equilibrium system for the measurement of dissolved gaseous mercury, Anal. Bioanal. Chem. 391, 2277–2282, 2008c.

Ariya, P. A., Dastoor, A. P., Amyot, M., Schroeder, W. H., Barrie, L., Anlauf, K., Raofie, F., Ryzhkov, A., Davignon, D., Lalonde, J., and Steffen, A.: The Arctic: a sink for mercury, Tellus Ser. B-Chem. Phys. Meteorol., 56, 397–403, 2004.

Aspmo, K., Temme, C., Berg, T., Ferrari, C., Gauchard, P.-A., Fain, X., and Wibetoe, G.: Mercury in the Atmosphere, Snow and Melt Water Ponds in the North Atlantic Ocean during Arctic Summer, Environ. Sci. Technol., 40, 4083–4089, 2006.

Banic, C. M., Beauchamp, S. T., Tordon, R. J., Schroeder, W. H., Steffen, A., Anlauf, K. A., and Wong, H. K. T.: Vertical distribution of gaseous elemental mercury in Canada, J. Geophys. Res.-Atmos., 108, 4264, doi:10.1029/2002JD002116, 2003.

Berg, T., Sekkesæter, S., Steinnes, E., Valdal, A.-K., and Wibetoe, G.: Arctic springtime depletion of mercury in the European Arctic as observed at Svalbard, Sci. Total Environ., 304, 43–51, 2003.

Brooks, S. B., Saiz-Lopez, A., Skov, H., Lindberg, S. E., Plane, J. M. C., and Goodsite, M. E.: The mass balance of mercury in the springtime arctic environment, Geophys. Res. Lett., 33, LI3812, doi:10.1029/2005GL025525, 2006.

Calvert, J. G., and Lindberg, S. E.: Mechanisms of mercury removal by O3 and OH in the atmosphere, Atmos. Environ., 39, 3355–3367, 2005.

Dastoor, A. P., Davignon, D., Theys, N., Van Roozendael, M., Steffen, A., and Ariya, P. A.: Modeling Dynamic Exchange of Gaseous Elemental Mercury at Polar Sunrise, Environ. Sci. Technol., 42, 5183–5188, 2008.

Donohoue, D. L., Bauer, D., Cossairt, B., and Hynes, A. J.: Temperature and Pressure Dependent Rate Coefficients for the Reaction of Hg with Br and the Reaction of Br with Br: A Pulsed Laser Photolysis-Pulsed Laser Induced Fluorescence Study, J. Phys. Chem. A, 110, 6623–6632, 2006.

Draxler, R. R., and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD. 2003.

Ebinghaus, R., Kock, H. H., Temme, C., Einax, J. W., Löwe, A. G., Richter, A., Burrows, J. P., and Schroeder, W. H.: Antarctic springtime depletion of atmospheric mercury, Environ. Sci. Technol., 36, 1238–1244, 2002.

Ebinghaus, R., Slemr, F., Brenninkmeijer, C. A. M., van Velthoven, P., Zahn, A., Hermann, M., O'Sullivan, D. A., and Oram, D. E.: Emissions of gaseous mercury from biomass burning in South America in 2005 observed during CARIBIC flights, Geophys. Res. Lett., 34, L08813, doi:10.1029/2006GL028866, 2007.

Eneroth, K., Holmén, K., Berg, T., Schmidbauer, N., and Solberg, S.: Springtime depletion of tropospheric ozone, gaseous elemental mercury and non-methane hydrocarbons in the European Arctic, and its relation to atmospheric transport, Atmos. Environ., 41, 8511–8526, 2007.

Gallagher, M. W., Beswick, K. M., and Coe, H.: Ozone deposition to coastal waters, Quart. J. R. Met. Soc. 127, 539–558, 2001.

Gerbig, C., Schmitgen, S., Kley, D., Volz-Thomas, A., Dewey, K., and Haaks, D.: An improved fast-response vacuum-UV resonance fluorescence CO instrument, J. Geophys. Res.-Atmos., 104, 1699–1704, 1999.

Hedgecock, I. M., Pirrone, N., and Sprovieri, F.: Chasing quicksilver northward: mercury chemistry in the Arctic troposphere, Environ. Chem., 5, 131–134, 2008.

Helmig, D., Oltmans, S. J., Carlson, D., Lamarque, J.-F., Jones, A., Labuschagne, C., Anlauf, K., and Hayden, K.: A review of surface ozone in the polar regions, Atmos. Environ., 41, 5138–5161, 2007.

Helmig, D., Cohen, L. D., Bocquet, F., Oltmans, S., Grachev, A., and Neff W.: Spring and summertime diurnal surface ozone fluxes over the polar snow at Summit, Greenland, Geophys. Res. Lett., 36, L08809, doi:10.1029/2008GL036549, 2009.

Hirdman, D., Aspmo, C., Burkhart, J.F., Eckhardt, S., Sodemann, H., and Stohl, A.: 2009, Transport of mercury in the Arctic atmosphere: Evidence for a spring-time net sink and summer-time source, Geophys. Res. Lett., 36, L12814, doi:10.1029/2009GL038345, 2009.

Holland, M. M., Bitz, C. M., and Tremblay, B.: Future abrupt reductions in the summer Arctic sea ice, Geophys. Res. Lett., 33, L23503, doi:10.1029/2006GL028024, 2006.

Holloway, T., Levy II, H., and Kasibhatla, P.: Global distribution of carbon monoxide, J. Geophys. Res., 105, 12123–12147, 2000.

Hollwedel, J., Wenig, M., Beirle, S., Kraus, S., Kuhl, S., Wilms-Grabe, W., Platt, U., and Wagner, T.: Year-to-year variations of spring time polar tropospheric BrO as seen by GOME, Trace Constituents in the Troposphere and Lower Stratosphere, 34, 804–808, doi:10.1016/j.asr.2003.08.060, 2004.

Hönninger, G.: Halogen Oxide Studies in the Boundary Layer by Multi Axis Differential Optical Absorption Spectroscopy and Active Longpath-DOAS., Ph D. Thesis, Institute of Environmental Physics, University of Heidelberg, Germany, 262 pp., 2002.

IHO, 1953: Limits of Oceans and Seas, Special Publication 23, International Hydrographic Organization, Monaco.

Jacobi, H. W. and Schrems, O.: Peroxyacetyl nitrate (PAN) distribution over the South Atlantic Ocean, Phys. Chem. Chem. Phys., 1, 5517–5521, 1999.

Jacobi, H. W., Kaleschke, L., Richter, A., Rozanov, A., and Burrows, J. P.: Observation of a fast ozone loss in the marginal ice zone of the Arctic Ocean, J. Geophys. Res.-Atmos., 111, D15309, doi:10.1029/2005JD006715, 2006.

Jaffe, D., Prestbo, E., Swartzendruber, P., Weiss-Penzias, P., Kato, S., Takami, A., Hatakeyama, S., and Kajii, Y.: Export of atmospheric mercury from Asia, Atmos. Environ., 39, 3029–3038, 2005.

Kaleschke, L., Richter, A., Burrows, J., Afe, O., Heygster, G., Notholt, J., Rankin, A. M., Roscoe, H. K., Hollwedel, J., Wagner, T., and Jacobi, H. W.: Frost flowers on sea ice as a source of sea salt and their influence on tropospheric halogen chemistry, Geophys. Res. Lett., 31, L16114, doi:10.1029/2004GL020655, 2004.

Kellerhals, M., 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., 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.

Kock, H. H., Bieber, E., Ebinghaus, R., Spain, T. G., and Thees, B.: Comparison of long-term trends and seasonal variations of atmospheric mercury concentrations at the two European coastal monitoring stations Mace Head, Ireland, and Zingst, Germany, Atmos. Environ., 39, 7549–7556, 2005.

Lahoutifard, N., Poissant, L., and Scott, S. L.: Scavenging of gaseous mercury by acidic snow at Kuujjuarapik, Northern Quebec, Sci. Total Environ., 355, 118–126, 2006.

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.-Atmos., 108, L16114, doi:10.1029/2003JD003625, 2003.

Lemke, P., J. Ren, R.B. Alley, I. Allison, J. Carrasco, G. Flato, Y. Fujii, G. Kaser, P. Mote, R.H. Thomas and T. Zhang, 2007: Observations: Changes in Snow, Ice and Frozen Ground. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA.

Lockhart, W. L., Stern, G. A., Wagemann, R., Hunt, R. V., Metner, D. A., DeLaronde, J., Dunn, B., Stewart, R. E. A., Hyatt, C. K., Harwood, L., and Mount, K.: Concentrations of mercury in tissues of beluga whales (Delphinapterus leucas) from several communities in the Canadian Arctic from 1981 to 2002, Sci. Total Environ., 351, 391–412, 2005.

Mason, R. P., Laurier, F. J. G., Whalin, L., and Sheu, G. R.: The role of ocean-atmosphere exchange in the global mercury cycle, J. Phys. IV, 107, 835–838, 2003.

Nightingale, P. D., Malin, G., Law, C. S., Watson, A. J., Liss, P. S., Liddicoat, M. I., Boutin, J., and Upstill-Goddard, R. C.: In situ evaluation of air-sea gas exchange parameterizations using novel conservative and volatile tracers, Glob. Biogeochem. Cycle, 14, 373–387, 2000.

Novelli, P. C., Masarie, K. A., and Lang, P. M.: Distributions and recent changes of carbon monoxide in the lower troposphere, J. Geophys. Res.-Atmos., 103, 19015–19033, 1998.

Obrist, D.: Atmospheric mercury pollution due to losses of terrestrial carbon pools?, Biogeochemistry, 85, 119–123, 2007.

Outridge, P. M., Macdonald, R. W., Wang, F., Stern, G. A., and Dastoor, A. P.: A mass balance inventory of mercury in the Arctic Ocean, Environ. Chem., 5, 89–111, 2008.

Poulain, A. J., Chadhain, S. M. N., Ariya, P. A., Amyot, M., Garcia, E., Campbell, P. G. C., Zylstra, G. J., and Barkay, T.: Potential for mercury reduction by microbes in the high Arctic, Appl. Environ. Microb., 73, 2230–2238, 2007a.

Poulain, A. J., Garcia, E., Amyot, M., Campbell, P. G. C., and Ariya, P. A.: Mercury distribution, partitioning and speciation in coastal vs. inland High Arctic snow, Geochim. Cosmochim. Acta, 71, 3419–3431, 2007b.

Schroeder, W. H., Anlauf, K. G., Barrie, L. A., Lu, J. Y., Steffen, A., Schneeberger, D. R., and Berg, T.: Arctic springtime depletion of mercury, Nature, 394, 331–332, 1998.

Schroeder, W. H., Steffen, A., Scott, K., Bender, T., Prestbo, E., Ebinghaus, R., Lu, J. Y., and Lindberg, S. E.: Summary report: first international Arctic atmospheric mercury research workshop, Atmos. Environ., 37, 2551–2555, 2003.

Sigler, J. M., Lee, X., and Munger, W.: Emission and long-range transport of gaseous mercury from a large-scale Canadian boreal forest fire, Environ. Sci. Technol., 37, 4343–4347, 2003.

Simpson, W., Alvarez-Avilies, L., Douglas, T. A., Sturm, M., and Domine, F.: Halogens in the coastal snow pack near Barrow, Alaska: Evidence for active bromine air-snow chemistry during springtime, Geophys. Res. Lett., 32, L04811, doi:10.1029/2004GL021748, 2005.

Simpson, W. R., von Glasow, R., Riedel, K., Anderson, P., Ariya, P., Bottenheim, J., Burrows, J., Carpenter, L. J., Frieß, U., Goodsite, M. E., Heard, D., Hutterli, M., Jacobi, H.-W., Kaleschke, L., Neff, B., Plane, J., Platt, U., Richter, A., Roscoe, H., Sander, R., Shepson, P., Sodeau, J., Steffen, A., Wagner, T., and Wolff, E.: Halogens and their role in polar boundary-layer ozone depletion, Atmos. Chem. Phys., 7, 4375–4418, doi:10.5194/acp-7-4375-2007, 2007.

Skov, H., Christensen, J. H., Goodsite, M. E., Heidam, N. Z., Jensen, B., Wåhlin, P., and Geernaert, G.: Fate of Elemental Mercury in the Arctic during Atmospheric Mercury Depletion Episodes and the Load of Atmospheric Mercury to the Arctic, Environ. Sci. Technol., 54, 2373–2382, 2004.

Slemr, F., Schuster, G., and Seiler, W.: Distribution, speciation, and budget of atmospheric mercury, J. Atmos. Chem., 3, 407–434, 1985.

Slemr, F., Ebinghaus, R., Simmonds, P. G., and Jennings, S. G.: European emissions of mercury derived from long-term observations at Mace Head, on the western Irish coast, Atmos. Environ., 40, 6966–6974, 2006.

Slemr, F., Brunke, E. G., Labuschagne, C., and Ebinghaus, R.: Total gaseous mercury concentrations at the Cape Point GAW station and their seasonality, Geophys. Res. Lett., 35, L11807, doi:10.1029/2008GL033741, 2008.

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.

Sommar, J., Gårdfeldt, K., Strömberg, D., and Feng, X. B.: A kinetic study of the gas-phase reaction between the hydroxyl radical and atomic mercury, Atmos. Environ., 35, 3049–3054, 2001.

Sommar, J., Wängberg, I., Berg, T., Gårdfeldt, K., Munthe, J., Richter, A., Urba, A., Wittrock, F., and Schroeder, W. H.: Circumpolar transport and air-surface exchange of atmospheric mercury at Ny-Ålesund (79° N), Svalbard, spring 2002, Atmos. Chem. Phys., 7, 151–166, doi:10.5194/acp-7-151-2007, 2007.

St Louis, V. L., Hintelmann, H., Graydon, J. A., Kirk, J. L., Barker, J., Dimock, B., Sharp, M. J., and Lehnherr, I.: Methylated mercury species in Canadian high Arctic marine surface waters and snowpacks, Environ. Sci. Technol., 41, 6433–6441, 2007.

Steffen, A., Schroeder, W. H., Macdonald, R. W., Poissant, L., and Konoplev, A.: Mercury in the Arctic atmosphere: An analysis of eight years of measurements of GEM at Alert (Canada) and a comparison with observations at Amderma (Russia) and Kuujjuarapik (Canada), Sci. Total Environ., 342, 185–198, 2005.

Steffen, A., Douglas, T., Amyot, M., Ariya, P., Aspmo, K., Berg, T., Bottenheim, J., Brooks, S., Cobbett, F., Dastoor, A., Dommergue, A., Ebinghaus, R., Ferrari, C., Gardfeldt, K., Goodsite, M. E., Lean, D., Poulain, A. J., Scherz, C., Skov, H., Sommar, J., and Temme, C.: A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow, Atmos. Chem. Phys., 8, 1445–1482, doi:10.5194/acp-8-1445-2008, 2008.

Stohl, A.: Characteristics of atmospheric transport into the Arctic troposphere, J. Geophys. Res., 111, D11306, doi:10.1029/2005JD006888, 2006.

Stohl, A., Berg, T., Burkhart, J. F., Fjae'raa, A. M., Forster, C., Herber, A., Hov, Ø., Lunder, C., McMillan, W. W., Oltmans, S., Shiobara, M., Simpson, D., Solberg, S., Stebel, K., Ström, J., Tørseth, K., Treffeisen, R., Virkkunen, K., and Yttri, K. E.: Arctic smoke – record high air pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006, Atmos. Chem. Phys., 7, 511–534, doi:10.5194/acp-7-511-2007, 2007.

Sumner, A. L., Shepson, P. B., Grannas, A. M., Bottenheim, J. W., Anlauf, K. G., Worthy, D., Schroeder, W. H., Steffen, A., Domine, F., Perrier, S., and Houdier, S.: Atmospheric chemistry of formaldehyde in the Arctic troposphere at Polar Sunrise, and the influence of the snowpack, Atmos. Environ., 36, 2553–2562, 2002.

Wang, Y. Q., Zhang, X. Y., and Draxler, R.: TrajStat: GIS-based software that uses various trajectory statistical analysis methods to identify potential sources from long-term air pollution measurement data, Environ. Model. Software, 24, 938–939, 2009.

Wängberg, I., Munthe, J., Amouroux, D., Andersson, M. E., Fajon, V., Ferrara, R., Gårdfeldt, K., Horvat, M., Mamane, Y., Melamed, E., Monperrus, M., Ogrinc, N., Yossef, O., Pirrone, N., Sommar, J., and Sprovieri, F.: Atmospheric mercury at Mediterranean coastal stations, Environ. Fluid Mech., 8, 101–116, 2008.

Wängberg, I., Munthe, J., Ebinghaus, R., Gårdfeldt, K., Iverfeldt, Å., and Sommar, J.: Distribution of TPM in Northern Europe, Sci. Total Environ., 304, 53–59, 2003.

Weiss-Penzias, P., Jaffe, D. A., Swartzendruber, P., Hafner, W., Chand, D., and Prestbo, E.: Quantifying atmospheric mercury emissions from biomass burning and East Asian industrial regions based on ratios with carbon monoxide in pollution plumes at the Mount Bachelor Observatory, Atmos. Environ., 41, 4366–4379.

Wilhelm, S. M.: Estimate of mercury emissions to the atmosphere from petroleum, Environ. Sci. Technol., 35, 4704–4710, 2001.

Wilhelm, S. M. and Spitz, P.: Impact of mercury on crude oil quality, World Refining 13, 32–36, 2003.