Mercury specation during thermal remediation and in post-treatment environments

Mercury is a toxic metal that has been released to the environment through numerous industrial activities. It can exist in various solid, aqueous, and gaseous forms. Volatile Hg(0) is frequently present at the source of a spill where it behaves as a dense non-aqueous phase liquid (DNAPL) contaminant that can change oxidation state and speciation via chemical or biological reactions. Mercury speciation is a key factor determining the mobility, bioavailability, and toxicity of Hg in the environment. Previous research has demonstrated that In Situ Thermal Desorption (ISTD) can be used in various modes to treat soil contaminants including Hg(0). The application of ISTD and other remediation processes must incorporate potential speciation during remediation and assess mobility of any mercury remaining in the soil post-remediation. However, research examining the impact of mercury speciation on ISTD processes is limited. The goals of this research are to investigate the fate and transport of mercury in soils from the source where concentrations are expected to be high to dilute solutions associated with down gradient groundwater, lakes, and rivers. For high concentrations of mercury, equilibrium speciation has been investigated to identify potential transformations at high temperatures consistent with those applied in ISTD processes. A model has been developed that describes mercury speciation over a range of environmental conditions. At low mercury concentrations, competitive Hg(II) adsorption on the soil minerals, goethite and gibbsite, has been evaluated over a range of experimental conditions. Models describing Hg(II) adsorption and aqueous speciation have been developed to provide a tool for predicting the fate and transport of residual mercury after thermal remediation applications. The results of these studies demonstrate that ISTD is feasible, but the off-gas speciation will depend on both the applied temperatures and the soil composition and redox conditions of the site. Pure phase mercury was predicted to be vaporized at temperatures well within the range of typical ISTD processes. The adsorption of trace levels of Hg(II) remaining after ISTD was successfully modeled on goethite and gibbsite using the 1-pK CD-MUSIC model.