Reactive mercury in the troposphere: Model formation and results for Florida, the northeastern United States, and the Atlantic Ocean

摘要

We describe the development of a model for transport and photochemistry of atmospheric mercury at the regional scale, along with an application to the eastern United States and adjacent Atlantic Ocean and Gulf of Mexico, and comparison with aircraft-based measurements in Florida. The model is the Community Multiscale Air Quality model (CMAQ) with modifications to include an integrated solution for gas phase and aqueous photochemistry. The expanded chemistry includes O3, NOx, organics, sulfur, halogens and mercury. Divalent reactive gaseous mercury (RGM) is formed slowly through gas phase reactions and removed rapidly by aqueous reactions in cloud water. Model results show that elevated RGM (up to 260 pg m?3) forms intermittently over the Atlantic Ocean in air masses that have a cloud-free history. Aircraft measurements in Florida show RGM varying between 10 and 250 pg m?3 and increasing with altitude, a pattern that is consistent with model results. Ambient RGM would increase by 50% if aqueous reduction reactions were omitted. The model predicts that ambient elemental mercury and RGM anticorrelate in regions where RGM is produced photochemically and correlate in regions dominated by direct emissions. Model results also suggest positive correlations between RGM and SO2, reactive nitrogen and H2O2, which may be used to identify photochemically produced versus directly emitted RGM. RGM in the model is strongly correlated with O3 during pollution events, and ozone formation from anthropogenic precursors is predicted to cause a significant increase in RGM.