Process-based interpretation of groundwater arsenic mobility via oxidative and reductive dissolution in a complex...

The Giant Mine operated from 1948 to 1999 to recover Au from arsenopyrite-hosted ore and is undergoing one of the largest remediation projects in Canadian history. Mine-waste containing flotation tailings and As-bearing roaster-generated Fe oxides was deposited in the Northwest Tailings Containment Area (NW-TCA) from 1988 to 1999. Since 2017, a longitudinal study has been undertaken at the NW-TCA to examine hydrogeological and geochemical controls. A comprehensive conceptual model was derived from integrating 8 years of field measurements (2017-2024) through an 18-m depth profile (GM7). Tailings exhibited circumneutral pH porewater, excess neutralization capacity, and elevated dissolved As concentrations (>25 mg L^-1), predominantly in the saturated tailings. Currently, As-rich tailings porewaters at GM7 infiltrate to the base of the NW-TCA and discharge through the underlying fractured bedrock. Field measurements of the tailings hydrogeology, isotope geochemistry, mineralogy and microbiology, coupled with multicomponent reactive transport modelling, indicate that: (i) reductive dissolution of As-bearing Fe oxides controls As mobility in the NW-TCA, (ii) As released from oxidative dissolution of arsenopyrite is primarily attenuated by Fe-arsenate phases at the near-surface, and (iii) adsorption of arsenite onto existing Fe oxides is a likely As attenuation mechanism in the saturated tailings. This has profound implications for the assessment of the Giant Mine tailings, where Fe oxides represent the most abundant As-bearing phase and thus constitute a long-term source of As, driven by microbial activity and available C sources in the tailings. These findings provide direction to optimize remediation efforts of As-bearing roaster residues and sulfidic flotation tailings.