Reactive Gaseous Mercury Formation Over The North Pacific Ocean: Influence Of Environmental Parameters On Elemental Mercury Oxidation In The Marine Boundary Layer

Global mercury models have identified wet and dry particle deposition and evasion of dissolved gaseous mercury from the ocean and from land as key controls over global mercury cycling (1,2). Recent ocean studies (3,4) however, have indicated that estimated mercury evasion rates from the ocean substantially exceed estimated deposition. Oxidized reactive gaseous mercury species (RGHg) are now known to play a major role in the global mercury cycle (2,5). RGHg species are water-soluble, exhibit a much shorter atmospheric lifetime than elemental mercury, and contribute to a large extent to atmospheric mercury deposition (2,3,6). Although recent global mercury models have accounted for the dry deposition of RGHg derived from point source emissions (6,7), the formation and deposition of RGHg in remote areas have not been incorporated. We suggest that the oxidation of elemental mercury over the ocean, by gas phase or heterogeneous reactions, is an important part the global mercury cycle. In agreement with previous studies (3,8,9) our recent data from atmospheric collections over the North Pacific Ocean support the notion of enhanced oxidation in the marine boundary layer. Our results show an inverse correlation between RGHg production and ozone, and a diurnal cycle with highest concentrations during periods of highest UV irradiation. In addition, the relationship between RGHg and other parameters measured during the cruise will be discussed. Our results clearly show that RGHg deposition to the ocean must be an important Hg source, and a crucial part of the global Hg cycle. (1) Mason R.P., Fitzgerald W.F., and Morel F.M.M. (1994), The biogeochemical cycling of elemental mercury: Anthropogenic influences, Geochim. Cosmochim. Acta, 58: 3191-3198 (2) Shia R.L., Seigneur C., Pai P., Ko M., and Sze N.-D. (1999), Global simulation of atmospheric mercury concentrations and deposition fluxes, J. Geophy. Res., 104(D19), 23, 747-23, 760 (3) Mason, R.P., Lawson N.M., and Sheu G.-R. (2001), Mercury in the Atlantic Ocean: factors controlling air-sea exchange of mercury and its distribution in the upper water, Deep-Sea Res. II, 2829-2853 (4) Lamborg, C.H., Rolfus K.R., and Fitzgerald W.F. (1999), The atmospheric cycling and air-sea exchange of mercury species in the south and equatorial Atlantic Ocean, Deep-Sea Res. II, 957-977 (5) Lindberg S.E., Brooks S., Lin C.-J., Scott K. J., Landis M. S., Stevens R.K., Goodsite M., and Richter A. (2002), Dynamic oxidation of gaseous mercury in the arctic troposphere at polar sunrise, Environ. Sci. Technol., 1245-1256 (6) Bullock O.R. (2000), Modeling assessment of transport and deposition patterns of anthropogenic mercury air emissions in the United States and Canada, Sci Total Environ., 259(1-3), 145-157 (7) Xu X., Yang X., Miller d.R., Helble J.J., and Carley R.J. (2000), a regional scale modelling study of atmospheric transport and formation of mercury. II. Simulation results for the northeast United states, Atmos. Environ., 34: 4945-4955 (8) Sheu G.-R. (2001), Speciation and distribution of atmospheric mercury: Significance of reactive gaseous mercury in the global mercury cycle. PhD. thesis, University of Maryland, College park, pp. 170 (9) Guentzel J.L., Landing W.M., Gill G.A., and Pollman C.D. (2001), Processes influencing rainfall deposition of mercury in Florida, Environ. Sci. Technol., 35: 863-873