Oxidation of Elemental Mercury in the Atmosphere; Constraints Imposed by Global Scale Modelling

We use the global mercury model published by Bergan et al. (1999) to evaluate the potential role of ozone and the hydroxyl radical as gas phase oxidants for the oxidation of elemental mercury in the atmosphere. The magnitude of natural and man-made mercury emissions are taken from recent literature estimates. We consider only two mercury reservoirs, elemental mercury, Hg⁰, and the more soluble divalent form, HgII. Wet and dry deposition of HgII is explicitly treated.Applying monthly mean fields of ozone for the oxidation of gas phase Hg⁰ and using the reaction rate by Hall (1995) yields a global transformation of Hg⁰ to HgII which is too slow to keep the simulated concentration of Hg⁰ near observed values. This shows that there must be additional important removal processes for Hg⁰ or that the reaction rate proposed by Hall (1995) is too slow. A simulation in which the oxidation rate was artificially increased, so that the global turn-over time of Hg⁰ is one year and the simulated average concentration of Hg⁰ realistic, produces latitudinal and seasonal variations in Hg⁰ that do not support the hypothesis that gas phase reaction with O₃ is the major oxidation process for Hg⁰.Recent studies indicate that OH may be an important gas phase oxidant for Hg⁰ (Sommar et al., 2001). Using OH as the sole oxidantand applying the oxidation rate by Sommar et al., we calculate aconcentration of Hg⁰ well below (about a factor of three) the observations. By prescribing a slower rate, corresponding to a turn-over time of Hg⁰ of one year, we calculate concentrations of both Hg⁰ in surface air and HgII in precipitation which correspond reasonably well, both in magnitude and temporal variation, with seasonal observations in Europe and North America. This result supports the suggestion that the oxidation by OH is an important pathway for the removal of Hg⁰. In view of the uncertainties associated with our calculations, this conclusion should still be regarded as tentative.