Arsenic and antimony geochemistry of historical roaster waste from the Giant Mine, Yellowknife, Canada.

Historical mining and mineral processing at the former Giant Mine (Yellowknife, NT, Canada) created an enduring legacy of arsenic (As) and antimony (Sb) contamination. Approximately 237,000 tonnes of arsenic trioxide roaster waste (ATRW) generated between 1948 and 1999 remains stored on-site in underground chambers. We studied the chemical forms and phase associations of As and Sb to improve understanding of ATRW environmental behavior. Although arsenolite [As2O3] is the principal As and Sb host, we also observed minor associations of As with Fe oxides. Arsenic K-edge X-ray absorption spectroscopy (XAS) revealed As(III) dominated ATRW, with some As(V) and As(-I) also present. Arsenic coordination and bonding is consistent with arsenolite, while scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) showed minor As association with Fe oxides and arsenopyrite [FeAsS]. Antimony K-edge XAS revealed variable proportions of Sb(III) and Sb(V), with Sb-O, Sb-Sb and Sb-As bonding consistent with stibioclaudetite [AsSbO3] or Sb-substituted arsenolite. Electron microprobe analysis (EMPA) results showed variable but quantitative Sb substitution for As in arsenolite grains, possibly influencing ATRW solubility and reactivity under environmental conditions. Overall, our results reveal complex As and Sb phase associations with important implications for ongoing remediation efforts and long-term environmental fate of ATRW solids.