Subtropical subsidence and surface deposition of oxidized mercury produced in the free troposphere

Oxidized mercury (Hg(II)) is chemically produced in the atmosphere by oxidation of elemental mercury and is directly emitted by anthropogenic activities. We use the GEOS-Chem global chemical transport model with gaseous oxidation driven by Br atoms to quantify how surface deposition of Hg(II) is influenced by Hg(II) production at different atmospheric heights. We tag Hg(II) chemically produced in the lower (surface-750 hPa), middle (750-400 hPa), and upper troposphere (400 hPa-tropopause), in the stratosphere, as well as directly emitted Hg(II). We evaluate our 2-year simulation (2013-2014) against observations of Hg(II) wet deposition as well as surface and free-tropospheric observations of Hg(II), finding reasonable agreement. We find that Hg(II) produced in the upper and middle troposphere constitutes 91% of the tropospheric mass of Hg(II) and 91% of the annual Hg(II) wet deposition flux. This large global influence from the upper and middle troposphere is the result of strong chemical production coupled with a long lifetime of Hg(II) in these regions. Annually, 77-84% of surface-level Hg(II) over the western US, South America, South Africa, and Australia is produced in the upper and middle troposphere, whereas 26-66% of surface Hg(II) over the eastern US, Europe, and East Asia, and South Asia is directly emitted. The influence of directly emitted Hg(II) near emission sources is likely higher but cannot be quantified by our coarse-resolution global model (2 degrees latitude x 2.5 degrees longitude). Over the oceans, 72% of surface Hg(II) is produced in the lower troposphere because of higher Br concentrations in the marine boundary layer. The global contribution of the upper and middle troposphere to the Hg(II) dry deposition flux is 52%. It is lower compared to the contribution to wet deposition because dry deposition of Hg(II) produced aloft requires its entrainment into the boundary layer, while rain can scavenge Hg(II) from higher altitudes more readily. We find that 55% of the spatial variation of Hg wet deposition flux observed at the Mercury Deposition Network sites is explained by the combined variation of precipitation and Hg(II) produced in the upper and middle troposphere. Our simulation points to a large role of the dry subtropical subsidence regions. Hg(II) present in these regions accounts for 74% of Hg(II) at 500 hPa over the continental US and more than 60% of the surface Hg(II) over high-altitude areas of the western US. Globally, it accounts for 78% of the tropospheric Hg(II) mass and 61% of the total Hg(II) deposition. During the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign, the contribution of Hg(II) from the dry subtropical regions was found to be 75% when measured Hg(II) exceeded 250 pgm(-3). Hg(II) produced in the upper and middle troposphere subsides in the anticyclones, where the dry conditions inhibit the loss of Hg(II). Our results highlight the importance the subtropical anticyclones as the primary conduits for the production and export of Hg(II) to the global atmosphere.