Selenite Stable Isotope Fractionation during Abiotic Reduction by Sodium Sulfide.

Reduction of Se(IV) by sulfur reducing bacteria (SRB) can remove Se from groundwater either by direct respiration or the production of H2S(g) and subsequent abiotic reduction. This study examined abiotic Se(IV) reduction by H2S(g) to determine the associated Se isotope fractionation. The extent of fractionation was compared to the results with studies of Se(IV) reduction in systems containing microorganisms to assess whether these processes could be distinguished. A solution containing Na2S was added in increasing concentrations to solutions containing Se(IV) as SeO32- to reduce and precipitate Se. Precipitates with three distinct colors were observed. Powder X-ray diffraction (PXRD) results yielded three distinct spectra for each of the three colors of precipitate, which corresponded to SenS8-n (orange) or Se(0) (red) and S(0) (yellow). The δ82Se values of the residual dissolved Se increased as the aqueous Se concentration decreased. The S/Se in solution affected the isotopic fractionation, with an 82ε of 10.1 ± 0.6‰ observed for solutions with S/Se < 1.7, and of 7.9 ± 0.3‰ for solutions with S/Se > 1.7.

Reactive transport modelling of tailings hydrogeochemistry under a composite cover.

Quantitative forecasts of acid mine drainage (AMD) production are important for remediation planning. Reactive transport simulations corresponding to a detailed sampling location at a covered legacy tailings impoundment in northern Ontario, Canada, were conducted to quantitatively assess the predominant hydrogeochemical reactions. The simulations span the period from the end of tailings deposition (circa 1970) to early 2020, 12 years after remediation by a five-layer composite cover. The conceptual model of uncovered tailings weathering and subsequent geochemistry of the covered tailings system was implemented in 1D using the multi-component reactive transport code MIN3P. Transient monthly infiltration, post-cover boundary condition changes, and a dynamic temperature regime were incorporated. The shrinking core model, including parallel O2(aq) and Fe3+ oxidation reactions for the waste rock in the cover and the underlying tailings, was implemented to simulate the oxidation of As-bearing pyrite, chalcopyrite, and sphalerite. Primary carbonate and aluminosilicate host minerals promoted acid-neutralization reactions. Precipitation of secondary phases and sorption/desorption of Cu, Zn, and arsenite were incorporated into the model. The overall agreement between key simulated and field-measured post-cover aqueous geochemical parameters suggests that the conceptual model captured the primary hydrogeochemical processes in the covered tailings. A lack of reliable data on initial tailings mineralogy and pre-cover hydrogeochemistry increased simulation uncertainty. Simulated reaction rates indicate that where intact, the cover decreased sulfide oxidation rates by both O2(aq) and Fe3+ and improved pore-water quality over time. Simulation results indicate that elevated concentrations of Zn and As are likely to persist in the tailings regardless of cover performance, whereas concentrations of Cu and Al are the parameters most sensitive to cover effectiveness.

Microbiological and geochemical characterization of As-bearing tailings and underlying sediments.

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (∼400 mg L-1), SO42-, Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ34S-SO4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

Microbial processes with the potential to mobilize As from a circumneutral-pH mixture of flotation and roaster tailings.

The Northwest Tailings Containment Area at the inactive Giant Mine (Canada) contains a complex mixture of arsenic-containing substances, including flotation tailings (84.8 wt%; with 0.4 wt% residual S), roaster calcine wastes (14.4 wt% Fe oxides), and arsenic trioxide (0.8 wt%) derived from an electrostatic precipitator as well as As-containing water (21.3 ± 4.1 mg L-1 As) derived from the underground mine workings. In the vadose zone the tailings pore water has a pH of 7.6 and contains elevated metal(loid)s (2.37 ± 5.90 mg L-1 As); mineral oxidizers account for 2.5% of total 16S rRNA reads in solid samples. In the underlying saturated tailings, dissolved Fe and As concentrations increase with depth (up to 72 and 20 mg L-1, respectively), and the mean relative abundance of Fe(III)-reducers is 0.54% of total reads. The potential for As mobilization via both reductive and oxidative (bio)processes should be considered in Giant Mine remediation activities. The current remediation plan includes installation of an engineered cover that incorporates a geosynthetic barrier layer.