Geochemistry and mineralogy of legacy tailings under a composite cover

Remediation by a composite cover was implemented on partly oxidized sulfide-rich tailings in northern Ontario, Canada to reduce the production and release of acid mine drainage (AMD). The impact of the cover on sulfide oxidation rates and trace element mobility was initiated a decade after cover placement via multi-year measurements of pore-gas concentrations, pore-water and groundwater sampling and analysis, mineralogical studies of the tailings, selective chemical extractions, and synchrotron-based X-ray absorption experiments. Depleted pore-gas O2 concentrations, circumneutral pH, and improvement in water quality were observed at one detailed sampling location, suggesting the cover decreased AMD generation and transport. Carbon and sulfur isotope ratios indicate sulfate reduction occurred at the base of the tailings. In contrast, near-atmospheric pore-gas O2 concentrations, low pH, and elevated aqueous concentrations of Fe, sulfate, Zn, Cu, As, and Pb were observed at another location, suggesting localized sulfide oxidation. Trace elements in the tailings are associated with secondary crystalline and amorphous Fe(III) oxyhydroxides, covellite, and Fe(III) hydroxysulfate phases, formed prior to the installation of the cover. Substantial reductive dissolution of Fe(III) oxyhydroxides due to isolation of the tailings from the atmosphere by the cover was not observed. Concentrations of Zn and Mn remained elevated due to limited sequestration under the current acidic to circumneutral pH. Although secondary Fe(III) oxyhydroxides contain As(V) and As(III), which was released by oxidation of arsenopyrite, dissolved As persists. Due to localized sulfide oxidation, element remobilization, and limited capacity for sulfate reduction, diminished water quality, with elevated aqueous concentrations of sulfate, Zn, As, and Mn, may persist. •Intact cover location has higher pH and lower contaminant concentrations.•Localized sulfide oxidation continued at location with cover defect.•Substantial reductive dissolution of Fe(III) oxyhydroxides was not observed.•Dissolved Zn and Mn remained elevated due to limited secondary sequestration.•Fe(III) oxyhydroxides contains As (III) and As(V), but dissolved As persists.