Atmospheric mercury simulation using the CMAQ model: formulation description and analysis of wet deposition results

The community multiscale air quality (CMAQ) modeling system has been adapted to simulate the emission, transport, transformation and deposition of atmospheric mercury (Hg) in three distinct forms: elemental Hg gas, reactive gaseous Hg, and particulate Hg. Emissions of Hg are currently defined from information published in the Environmental Protection Agency's Mercury Study Report to Congress. The atmospheric transport of these three forms of Hg is simulated in the same manner as for all other substances simulated by the CMAQ model to date. Transformations of Hg are simulated with four new chemical reactions within the standard CMAQ gaseous chemistry framework and a highly modified cloud chemistry mechanism which includes a compound-specific speciation for oxidized forms of Hg, seven new aqueous-phase Hg reactions, six aqueous Hg chemical equilibria, and a two-way mechanism for the sorption of dissolved oxidized Hg to elemental carbon particles. The CMAQ Hg model simulates the partitioning of reactive gaseous Hg between air and cloud water based on the Henry's constant for mercuric chloride. Henry's equilibrium is assumed for elemental Hg also. Particulate Hg is assumed to be incorporated into the aqueous medium during cloud nucleation. Wet and dry deposition is simulated for each of the three forms of Hg. Wet deposition rate is calculated based on precipitation information from the CMAQ meteorological processor and the physicochemical Hg speciation in the cloud chemistry mechanism. Dry deposition rate is calculated based on dry deposition velocity and air concentration information for each of the three forms of Hg. The horizontal modeling domain covers the central and eastern United States and adjacent southern Canada. An analysis of simulated Hg wet deposition versus weekly observations is performed. The results are described for two evaluation periods: 4 April–2 May 1995, and 20 June–18 July 1995.