Rapid oxidation of mercury (Hg) at volcanic vents: insights from high temperature thermodynamic models of Mt Etna's emissions

A major uncertainty regarding the environmental impacts of volcanic Hg is the extent to which Hg is deposited locally or transported globally. An important control on dispersion and deposition is the oxidation state of Hg compounds: Hg(0) is an inert, insoluble gas, while Hg(II) occurs as reactive gases or in particles, which deposit rapidly and proximally, near the volcanic vent. Using a new high temperature thermodynamic model, we show that although Hg in Etna's magmatic gases is almost entirely Hg(0) (i.e., gaseous elemental mercury), significant quantities of Hg(II) are likely formed at Etna's vents as gaseous HgCl2, when magmatic gases are cooled and oxidised by atmospheric gases. These results contrast with an earlier model study and allow us to explain recent measurements of Hg speciation at the crater rim of Etna without invoking rapid (b1 min) low temperature oxidation processes. We further model Hg speciation for a series of additional magmatic gas compositions. Compared to Etna, Hg(II) production (i.e., Hg(II)/Hgtot) is enhanced in more HCl-rich magmatic gases, but is independent of the Hg, HBr and HI content of the magmatic gases. Hg(II)production is not strongly influenced by the initial oxidation state of magmatic gases above NNO, although production is hindered in more reduced magmatic gases. The model and results are widely applicable to other open-vent volcanoes and may be used to improve the accuracy of chemical kinetic models for low temperature Hg speciation in volcanic plumes.