Atmospheric mercury over sea ice during the OASIS-2009 campaign


Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on sea ice near open leads in the Beaufort Sea near Barrow, Alaska in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) International Polar Year Program. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg over the sea ice averaged 393.5 pg m−3 (range 47.1–900.1 pg m−3) during the two week long study. RGM concentrations averaged 30.1 pg m−3 (range 3.5–105.4 pg m−3). The mean GEM concentration of 0.59 ng m−3 during the entire study (range 0.01–1.51 ng m−3) was depleted compared to annual Arctic ambient boundary layer concentrations. It was shown that when ozone (O3) and bromine oxide (BrO) chemistry are active there is a~linear relationship between GEM, PHg and O3 but there was no correlation between RGM and O3. There was a linear relationship between RGM and BrO and our results suggest that the origin and age of air masses play a role in determining this relationship. These results were the first direct measurements of these atmospheric components over the sea ice. For the first time, GEM was measured simultaneously over the tundra and the sea ice. The results show a significant difference in the magnitude of the emission of GEM from the two locations where significantly higher emission occurs over the tundra. Elevated chloride levels in snow over sea ice are believed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of Hg(II) to Hg(0) (GEM) in snow. These results are important because while GEM is emitted after depletion events on snow inland, less GEM is emitted over sea ice. Since the snow pack on sea ice retains more mercury than inland snow current models of the Arctic mercury cycle, which are based predominantly on land based measurements, may greatly underestimate atmospheric deposition fluxes. Land based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The findings reported in this study improve the current understanding of mercury cycling in the changing Arctic. The predicted changes in sea ice conditions and a~more saline snow pack in the Arctic could lead to even greater retention of atmospherically deposited mercury in the future. This could severely impact the amount of mercury entering the Arctic Ocean and coastal ecosystems.
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