References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-7165-2008

Simulation of atmospheric mercury depletion events (AMDEs) during polar springtime using the MECCA box model

Xie

Z.-Q.

¹ ³ Sander

² Pöschl

¹ Slemr

Biogeochemistry Department, Max Planck Institute for Chemistry, P.O. Box 3060, 55020 Mainz, Germany

Air Chemistry Department, Max Planck Institute for Chemistry, P.O. Box 3060, 55020 Mainz, Germany

also at: Institute of Polar Environment, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China

09 12 2008

8 23 7165 7180

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/8/7165/2008/acp-8-7165-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/7165/2008/acp-8-7165-2008.pdf

Atmospheric mercury depletion events (AMDEs) during polar springtime are closely correlated with bromine-catalyzed tropospheric ozone depletion events (ODEs). To study gas- and aqueous-phase reaction kinetics and speciation of mercury during AMDEs, we have included mercury chemistry into the box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere), which enables dynamic simulation of bromine activation and ODEs. We found that the reaction of Hg with Br atoms dominates the loss of gaseous elemental mercury (GEM). To explain the experimentally observed synchronous depletion of GEM and O3, the reaction rate of Hg+BrO has to be much lower than that of Hg+Br. The synchronicity is best reproduced with rate coefficients at the lower limit of the literature values for both reactions, i.e. kHg+Br≈3×10−13 and kHg+BrO≤1×10−15 cm3 molecule−1 s−1, respectively. Throughout the simulated AMDEs, \chem{BrHgOBr} was the most abundant reactive mercury species, both in the gas phase and in the aqueous phase. The aqueous-phase concentrations of BrHgOBr, HgBr2, and HgCl2 were several orders of magnitude larger than that of Hg(SO3)22−. Considering chlorine chemistry outside depletion events (i.e. without bromine activation), the concentration of total divalent mercury in sea-salt aerosol particles (mostly HgCl42−) was much higher than in dilute aqueous droplets (mostly Hg(SO3)22−), and did not exhibit a diurnal cycle (no correlation with HO2 radicals).

References 1

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.

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, 56B, 397–403, 2004.

Aspmo, K., Gauchard, P.-A., 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.

Barrie, L A., Bottenheim, J W., Schnell, R C., Crutzen, P J., and Rasmussen, R A.: Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere, Nature, 334, 138–141, 1988.

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

Bottenheim, J W., Gallant, A G., and Brice, K A.: Measurements of NOy species and \chemO_3 at 82\degree N latitude, Geophys. Res. Lett., 13, 113–116, 1986.

Brezonik, P L. (Ed.): Chemical Kinetics and Process Dynamics in Aquatic Systems, CRC Press, Boca Raton, FL, 1994.

Calvert, J G. and Lindberg, S E.: A modeling study of the mechanism of the halogen-ozone-mercury homogeneous reactions in the troposphere during the polar spring, Atmos. Environ., 37, 4467–4481, 2003.

Calvert, J G. and Lindberg, S E.: Potential influence of iodine-containing compounds on the chemistry of the troposphere in the polar spring. I. Ozone depletion, Atmos. Environ., 38, 5087–5104, 2004a.

Calvert, J G. and Lindberg, S E.: The potential influences of iodine-containing compounds on the chemistry of the troposphere in the polar spring. II. Mercury depletion, Atmos. Environ., 38, 5105–5116, 2004b.

Canosa-Mas, C E., King, M D., Lopez, R., Percival, C J., Wayne, R P., Shallcross, D E., Pyle, J A., and Daele, V.: Is the reaction between \chemCH_3(O)O_2 and \chemNO_3 important in the night-time troposphere?, J. Chem. Soc. Faraday Trans., 92, 2211–2222, 1996.

Christensen, J H., Brandt, J., Frohn, L M., and Skov, H.: Modelling of mercury in the Arctic with the Danish Eulerian Hemispheric Model, Atmos. Chem. Phys., 4, 2251–2257, 2004.

Dastoor, A P. and Larocque, Y.: Global circulation of atmospheric mercury: a modeling study, Atmos. Environ., 38, 147–161, 2004.

Donohoue, D L., Bauer, D., and Hynes, A J.: Temperature and pressure dependent rate coefficients for the reaction of Hg with Cl and the reaction of Cl with Cl: a pulsed laser photolysis-pulsed laser induced fluorescence study, J. Phys. Chem. A, 109, 7732–7741, 2005.

Donohoue, D L., Bauer, D., Cossairt, B., and Hynes, A J.: Temperature and pressure dependent rate coefficients for the reaction of \chemHg with \chemBr and the reaction of \chemBr with \chemBr: a pulsed laser photolysis-pulsed laser induced fluorescence study, J. Phys. Chem. A, 110, 6623–6632, 2006.

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.

Gårdfeldt, K. and Jonsson, M.: Is bimolecular reduction of Hg(II) complexes possible in aqueous systems of environmental importance, J. Phys. Chem. A, 107, 4478–4482, 2003.

Goodsite, M., Plane, J. M C., and Skov, H.: A theoretical study of the oxidation of \chemHg^0 to \chemHgBr_2 in the troposphere, Environ. Sci. Technol., 38, 1772–1776, 2004.

Hedgecock, I M. and Pirrone, N.: Mercury and photochemistry in the marine boundary layer-modelling studies suggest the in situ production of reactive gas phase mercury, Atmos. Environ., 35, 3055–3062, 2001.

Hedgecock, I M. and Pirrone, N.: Chasing quicksilver: Modeling the atmospheric lifetime of \chemHg^0_(g) in the marine boundary layer at various latitudes, Environ. Sci. Technol., 38, 69–76, 2004.

Hedgecock, I M., Pirrone, N., Sprovieri, F., and Pesenti, E.: Reactive gaseous mercury in the marine boundary layer: modelling and experimental evidence of its formation in the Mediterranean region, Atmos. Environ., 37, S41–S49, 2003.

Hedgecock, I M., Trunfio, G A., Pirrone, N., and Sprovieri, F.: Mercury chemistry in the MBL: Mediterranean case and sensitivity studies using the AMCOTS (Atmospheric Mercury Chemistry over the Sea) model, Atmos. Environ., 39, 7217–7230, 2005.

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

Hepler, L G. and Olofsson, G.: Mercury. Thermodynamic properties, chemical equilibriums, and standard potentials, Chem. Rev., 75, 585–602, 1975.

Holmes, C D., Jacob, D J., and Yang, X.: Global lifetime of elemental mercury against oxidation by atomic bromine in the free troposphere, Geophys. Res. Lett., 33, L20808, \doi10.1029/2006GL027176, 2006.

Khalizov, A F., Viswanathan, B., Larregaray, P., and Ariya, P A.: A theoretical study on the reactions of \chemHg with halogens: Atmospheric implications, J. Phys. Chem. A, 107, 6360–6365, 2003.

Lin, C.-J. and Pehkonen, S O.: Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol, Atmos. Environ., 31, 4125–4137, 1997.

Lin, C.-J. and Pehkonen, S O.: Oxidation of elemental mercury by aqueous chlorine (\chemHOCl/\chemOCl^-): Implications for tropospheric mercury chemistry, J. Geophys. Res., 103D, 28 093–28 102, 1998.

Lin, C.-J., Pongprueksa, P., Lindberg, S E., Pehkonen, S O., Byune, D., and Jang, C.: Scientific uncertainties in atmospheric mercury models I: Model science evaluation, Atmos. Environ., 40, 2911–2928, 2006.

Lindberg, S E., Brooks, S., Lin, C.-J., Scott, K., Meyers, T., Chambers, L., Landis, M., and Stevens, R.: Formation of reactive gaseous mercury in the Arctic: Evidence of oxidation of \chemHg^0 to gas-phase \chemHg-II compounds after Arctic sunrise, Water Air Soil Pollut. Focus, 1, 295–302, 2001.

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 at polar sunrise, Environ. Sci. Technol., 36, 1245–1256, 2002.

Lu, J Y. and Schroeder, W H.: Annual time-series of total filterable atmospheric mercury concentrations in the Arctic, Tellus, 56B, 213–222, 2004.

Lu, J Y., Schroeder, W H., Barrie, L A., Steffen, A., Welch, H E., Martin, K., Lockhart, L., Hunt, R V., Boila, G., and Richter, A.: Magnification of atmospheric mercury deposition to polar regions in springtime: the link to tropospheric ozone depletion chemistry, Geophys. Res. Lett., 28, 3219–3222, 2001.

Munthe, J.: The aqueous oxidation of elemental mercury by ozone, Atmos. Environ., 26A, 1461–1468, 1992.

Munthe, J., Xiao, Z F., and Lindqvist, O.: The aqueous reduction of divalent mercury by sulfite, Water Air Soil Pollut., 56, 621–630, 1991.

Pal, B. and Ariya, P A.: Gas-phase \chemHO-initiated reactions of elemental mercury: Kinetics, product studies, and atmospheric implications, Environ. Sci. Technol., 38, 5555–5566, 2004a.

Pal, B. and Ariya, P A.: Studies of ozone initiated reactions of gaseous mercury: Kinetics, product studies, and atmospheric implications, Phys. Chem. Chem. Phys., 6, 572–579, 2004b.

Pan, L. and Carmichael, G R.: A two-phase box model to study mercury atmospheric mechanisms, Environ. Chem., 2, 205–214, 2005.

Pehkonen, S O. and Lin, C J.: Aqueous photochemistry of divalent mercury with organic acids, J. Air Waste Manage. Assoc., 48, 144–150, 1998.

Perovich, D K. and Richter-Menge, J A.: Surface characteristics of lead ice, J. Geophys. Res., 99C, 16 341–16 350, 1994.

Peterson, G., Munthe, J., Pleijel, K., Bloxam, R., and Kumar, A V.: A comprehensive Eulerian modelling framework for airborne mercury species: development and testing of the tropospheric chemistry module (TCM), Atmos. Environ., 32, 829–843, 1998.

Pleijel, K. and Munthe, J.: Modelling the atmospheric mercury cycle – Chemistry in fog droplets, Atmos. Environ., 29, 1441–1457, 1995.

Poissant, L. and Pilote, M.: Time series analysis of atmospheric mercury in Kuujjuarapik/Whapmagoostui (Québec), J. Phys. IV France, 107, 1079–1082, 2003.

Rankin, A M., Wolff, E W., and Martin, S.: Frost flowers: Implications for tropospheric chemistry and ice core interpretation, J. Geophys. Res., 107, 4683, \doi10.1029/2002JD002492, 2002.

Raofie, F. and Ariya, P A.: Kinetics and products study of the reaction of BrO radicals with gaseous mercury, J. Phys. IV France, 107, 1119–1121, 2003.

Raofie, F. and Ariya, P A.: Product study of the gas-phase \chemBrO-initiated oxidation of \chemHg^0: Evidence for stable \chemHg^1+ compounds, Environ. Sci. Technol., 38, 4319–4326, 2004.

Ryaboshapko, A., Bullock, R., Ebinghaus, R., Ilyin, I., Lohman, K., Munthe, J., Petersen, G., Seigneur, C., and Wängberg, I.: Comparison of mercury chemistry models, Atmos. Environ., 36, 3881–3898, 2002.

Sander, R., Kerkweg, A., Jöckel, P., and Lelieveld, J.: Technical note: The new comprehensive atmospheric chemistry module MECCA, Atmos. Chem. Phys., 5, 445–450, 2005.

Sander, R., Burrows, J., and Kaleschke, L.: Carbonate precipitation in brine – a potential trigger for tropospheric ozone depletion events, Atmos. Chem. Phys., 6, 4653–4658, 2006.

Sandu, A. and Sander, R.: Technical note: Simulating chemical systems in Fortran90 and Matlab with the Kinetic PreProcessor KPP-2.1, Atmos. Chem. Phys., 6, 187–195, 2006.

Schroeder, W H. and Munthe, J.: Atmospheric mercury – An overview, Atmos. Environ., 32, 809–822, 1998.

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.

Schwartz, S E.: Mass-transport considerations pertinent to aqueous phase reactions of gases in liquid-water clouds, in: Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, Vol. G6, edited by Jaeschke, W., pp. 415–471, Springer Verlag, Berlin, 1986.

Seigneur, C., Wrobel, J., and Constantinou, E.: A chemical kinetic mechanism for atmospheric inorganic mercury, Environ. Sci. Technol., 28, 1589–1597, 1994.

Seigneur, C., Vijayaraghavan, K., and Lohman, K.: Atmospheric mercury chemistry:sensitivity of global model simulations to chemical reactions, J. Geophys. Res., 111, D22 306, 2006.

Selin, N E., Jacob, D., Park, R., Yantosca, R M., Strode, S., Jaeglé, L., Holmes, C., and Jaffe, D A.: Chemical cycling and deposition of atmospheric mercury: constraints from observations, J. Geophys. Res., 112, D02308, doi:10.1029/2006JD007450, 2007.

Shepler, B C., Balabanov, N B., and Peterson, K A.: Hg+Br→HgBr recombination and collision-induced dissociation dynamics, J. Chem. Phys., 127, 164 304, \doi10.1063/1.2777142, 2007.

Shon, Z.-H., Kim, K.-H., Kim, M.-Y., and Lee, M.: Modeling study of reactive gaseous mercury in the urban air, Atmos. Environ., 39, 749–761, 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, 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., 38, 2373–2382, 2004.

Slemr, F., Brunke, E., Ebinghaus, R., Temme, C., Munthe, J., Wangberg, I., Schroeder, W H., Steffen, A., and Berg, T.: Worldwide trend of atmospheric mercury since 1977, Geophys. Res. Lett., 30, 1516, \doi10.1029/2003GL016954, 2003.

Sommar, J., Gardfeldt, K., Stromberg, 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.

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, 2008.

Tokos, J. J S., Hall, B., Calhoun, J A., and Prestbo, E M.: Homogeneous gas-phase reaction of \chemHg^0 with \chemH_2O_2, \chemO_3, \chemCH_3I, and \chem(CH_3)_2S: Implications for atmospheric \chemHg cycling, Atmos. Environ., 32, 823–827, 1998.

Travnikov, O.: Contribution of the intercontinental atmospheric transport to mercury pollution in the Northern Hemisphere, Atmos. Environ., 39, 7541–7548, 2005.

van Loon, L., Mader, E., and Scott, S L.: Reduction of the aqueous mercuric ion by sulfite: UV spectrum of \chemHgSO_3 and its intramolecular redox reaction, J. Phys. Chem. A, 104, 1621–1626, 2000.

van Loon, L L., Mader, E A., and Scott, S L.: Sulfite stabilization and reduction of the aqueous mercuric ion: Kinetic determination of sequential formation constants, J. Phys. Chem. A, 105, 3190–3195, 2001.

Wang, Z. and Pehkonen, S O.: Oxidation of elemental mercury by aqueous bromine: atmospheric implications, Atmos. Environ., 38, 3675–3688, 2004.

Xiao, Z F., Munthe, J., Stromberg, D., and Lindqvist, O.: Photochemical behavior of inorganic mercury compounds in aqueous solution, in: Mercury as a Global Pollutant – Integration and Synthesis, edited by Watras, C J. and Huckabee, J W., pp. 581–592, Lewis Publishers, 1994.