Modeling mercury in power plant plumes

Measurements of speciated mercury (Hg) downwind of coal-fired power plants suggest that the Hg(II)/(Hg0 + HgII) ratio (where HgII is divalent gaseous Hg and Hg0 is elemental Hg) decreases significantly between the point of emission and the downwind ground-level measurement site, but that the SO2/(Hg0 + HgII) ratio is conserved. We simulated nine power plant plume events with the Reactive & Optics Model of Emissions (ROME), a reactive plume model that includes a comprehensive treatment of plume dispersion, transformation, and deposition. The model simulations fail to reproduce such a depletion in HgII. A sensitivity study of the impact of the HgII dry deposition velocity shows that a difference in dry deposition alone cannot explain the disparity. Similarly, a sensitivity study of the impact of cloud chemistry on results shows that the effect of clouds on Hg chemistry has only minimal impact. Possible explanations include HgII reduction to Hg0 in the plume, rapid reduction of HgII to Hg0 on ground surfaces, and/or an overestimation of the HgII fraction in the power plant emissions. We propose that a chemical reaction not included in current models of atmospheric mercury reduces HgII to Hg0 in coal-fired power plant plumes. The incorporation of two possible reduction pathways for HgII (pseudo-first-order decay and reaction with SO2) shows better agreement between the model simulations and the ambient measurements. These potential HgII to Hg0 reactions need to be studied in the laboratory to investigate this hypothesis. Because the speciation of Hg has a significant effect on Hg deposition, models of the fate and transport of atmospheric Hg may need to be modified to account for the reduction of HgII in coal-fired power plant plumes if such a reaction is confirmed in further experimental investigations.