Microscale mineralogical characterization of As, Fe, and Ni in uranium mine tailings

Uranium (U) ores can contain high concentrations of elements of concern (EOCs), such as arsenic (As) and nickel (Ni) present in sulfide and arsenide minerals. The U in these ores is often solubilized by adding H₂SO₄ to attain a pH ∼1 under oxic conditions. This process releases some EOCs from the primary minerals into solution. The barren raffinate (solution remaining after U extraction) is subsequently neutralized with Ca(OH)₂ to a terminal pH of ∼10.5, resulting in a reduction in the aqueous concentrations of the EOCs. These neutralized raffinates are mixed with the non-reacted primary minerals and discharged as tailing into tailings management facilities (TMFs). To aid in the accurate characterization and quantification of the mineralogical controls on the concentrations of EOCs in the tailings porewater, their spatial distribution and speciation were studied at the micron scale in tailings samples collected from the Deilmann U Tailings Management Facility (DTMF), northern Saskatchewan, Canada. Backscattered electron images of the tailings samples generated using an electron microprobe show the presence of nodules (10–200μm size) surrounded by bright rims. Wavelength dispersive spectrometric (WDS) and synchrotron-based micro-X-ray fluorescence (μ-XRF) elemental mapping show that the nodules are dominated by Ca and S (as gypsum) and the bright rims are dominated by Fe, As, and Ni. Micro-X-ray absorption near-edge structure (μ-XANES) spectra collected within and near the rims indicate that the Fe and Ni are present mainly in the +3 and +2 oxidation states, respectively; for As, the +5 oxidation state dominates but significant amounts of the +3 oxidation state are present in some areas. Linear combination fit analyses of the K-edges for the Fe, As, and Ni μ-XANES spectra to reference compounds suggest the Fe in the rims is present as ferrihydrite with As and Ni are adsorbed to it. Energy dispersive spectrometric (EDS) data indicate that isolated, highly reflective particles distributed throughout the tailings matrix are primary As-, Cu-, Fe-, and Ni-bearing minerals. Geochemical modeling of the neutralization process shows that the nodules (gypsum) formed at pH ∼1 and acted as a substrate for the precipitation of ferrihydrite at pH ∼3.4. The As and Ni subsequently adsorb to the ferrihydrite. Overall, the microscale data suggest that the As and Ni adsorbed onto the ferrihydrite should remain stable for many years and continue to the control the Fe, As, and Ni concentrations in the tailings porewater.