NOMADSS Aircraft Observations Suggest Rapid Oxidation of Elemental Mercury in the Subtropical Free Troposphere

Abstract:

Oxidized mercury species constitute a small fraction of the total atmospheric burden of mercury, but play an important role in the cycling of mercury in the environment. They dominate the deposition flux of mercury from the atmosphere to the Earth’s surfaces, because of their high solubility and low vapor pressure. Their primary source is in-situ oxidation of elemental mercury, but our understanding of these oxidation mechanisms is limited. The Nitrogen, Oxidants, Mercury, and Aerosol Distribution, Sources, and Sinks (NOMADSS) experiment was designed with the aim of addressing these limitations, using aircraft-based speicated measurements of mercury in the troposphere over the eastern US in the summer of 2013. We observed high concentrations of oxidized mercury in clean, dry pockets of air originating in the upper troposphere. We analyze these observations with the GEOS-Chem model, which simulates oxidation of mercury by bromine radicals. The modeled concentrations of oxidized mercury are found to be low, by up to a factor of ten, compared to the observations. This indicates that the oxidation rate of mercury is much faster than that calculated in the model. We perform two simulations to test the sensitivity of the modeled oxidation: (i) by increasing bromine radical concentrations by a factor of three in the 45°S-45°N latitude band, and (ii) by using an oxidation rate constant that is higher by a factor of five. We find that the model performance improves considerably in both these simulations. Here, we present a comparison of the standard and the sensitivity simulations to the NOMADSS and the surface-based Mercury Deposition Network (MDN) observations. We further discuss the potential implications of the faster oxidation on the global transport, distribution, and burden of oxidized mercury.