Liquid elemental mercury (Hg0
L)
pollution
can remain in soils for decades and, over time, will undergo corrosion,
a process in which the droplet surface oxidizes soil constituents
to form more reactive phases, such as mercury oxide (HgO). While these
reactive coatings may enhance Hg migration in the subsurface, little
is known about the transformation potential of corroded Hg0
L in the presence of reduced inorganic sulfur species
to form sparingly soluble HgS particles, a process that enables the
long-term sequestration of mercury in soils and generally reduces
its mobility and bioavailability. In this study, we investigated the
dissolution of corroded Hg0
L in the presence
of sulfide by quantifying rates of aqueous Hg release from corroded
Hg0
L droplets under different sulfide concentrations
(expressed as the S:Hg molar ratio). For droplets corroded in ambient
air, no differences in soluble Hg release were observed among all
sulfide exposure levels (S:Hg mole ratios ranging from 10–4 to 10). However, for droplets oxidized in the presence of a more
reactive oxidant (hydrogen peroxide, H2O2),
we observed a 10- to 25-fold increase in dissolved Hg when the oxidized
droplets were exposed to low sulfide concentrations (S:Hg ratios from
10–4 to 10–1) relative to droplets
exposed to high sulfide concentrations. These results suggest two
critical factors that dictate the release of soluble Hg from Hg0
L in the presence of sulfide: the extent of surface
corrosion of the Hg0
L droplet and sufficient
sulfide concentration for the formation of HgS solids. The mobilization
of Hg0
L in porous media, therefore, largely
depends on aging conditions in the subsurface and chemical reactivity
at the Hg0
L droplet interface.