Joseph Essilfie-Dughan

Transformation of Two-Line Ferrihydrite to Goethite and Hematite as a Function of pH and Temperature

Under oxic aqueous conditions, two-line ferrihydrite gradually transforms to more thermodynamically stable and more crystalline phases, such as goethite and hematite. This temperature- and pH-dependent transformation can play an important role in the sequestration of metals and metalloids adsorbed onto ferrihydrite. A comprehensive assessment of the crystallization of two-line ferrihydrite with respect to temperature (25, 50, 75, and 100 °C) and pH (2, 7, and 10) as a function of reaction time (minutes to months) was conducted via batch experiments. Pure and transformed phases were characterized by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The rate of transformation of two-line ferrihydrite to hematite increased with increasing temperature at all pHs studied and followed first-order reaction kinetics. XRD and XANES showed simultaneous formation of goethite and hematite at 50 and 75 °C at pH 10, with hematite being the dominant product at all pHs and temperatures. With extended reaction time, hematite increased while goethite decreased, and goethite reaches a minimum after 7 days. Observations suggest two-line ferrihydrite transforms to hematite via a two-stage crystallization process, with goethite being intermediary. The findings of this study can be used to estimate rates of crystallization of pure two-line ferrihydrite over the broad range of temperatures and pH found in nature.

Effects of Adsorbed Arsenate on the Rate of Transformation of 2-Line Ferrihydrite at pH 10

2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic. As ferrihydrite is unstable under oxic conditions and can undergo dissolution and subsequent transformation to hematite and goethite over time, the impact of transformation on the long-term stability of EOC within tailings is of importance from an environmental standpoint. Here, studies were undertaken to assess the rate of 2-line ferrihydrite transformation at varying As/Fe ratios (0.500-0.010) to simulate tailings conditions at the Deilmann Tailings Management Facility of Cameco Corporation, Canada. Kinetics were evaluated under relevant physical (~1 °C) and chemical conditions (pH ~10). As the As/Fe ratio increased from 0.010 to 0.018, the rate of ferrihydrite transformation decreased by 2 orders of magnitude. No transformation of ferrihydrite was observed at higher As/Fe ratios (0.050, 0.100, and 0.500). Arsenic was found to retard ferrihydrite dissolution and transformation as well as goethite formation.

Molybdenum Speciation in Uranium Mine Tailings Using X-Ray Absorption Spectroscopy

Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.

Mineralogical controls on aluminum and magnesium in uranium mill tailings: Key Lake, Saskatchewan, Canada.

The mineralogy and evolution of Al and Mg in U mill tailings are poorly understood. Elemental analyses (ICP-MS) of both solid and aqueous phases show that precipitation of large masses of secondary Al and Mg mineral phases occurs throughout the raffinate neutralization process (pH 1-11) at the Key Lake U mill, Saskatchewan, Canada. Data from a suite of analytical methods (ICP-MS, EMPA, laboratory- and synchrotron-based XRD, ATR-IR, Raman, TEM, EDX, ED) and equilibrium thermodynamic modeling showed that nanoparticle-sized, spongy, porous, Mg-Al hydrotalcite is the dominant mineralogical control on Al and Mg in the neutralized raffinate (pH ≥ 6.7). The presence of this secondary Mg-Al hydrotalcite in mineral samples of both fresh and 15-year-old tailings indicates that the Mg-Al hydrotalcite is geochemically stable, even after >16 years in the oxic tailings body. Data shows an association between the Mg-Al hydrotalcite and both As and Ni and point to this Mg-Al hydrotalcite exerting a mineralogical control on the solubility of these contaminants.

Reservoirs of Selenium in Coal Waste Rock: Elk Valley, British Columbia, Canada.

Selenium (Se) reservoirs in coal waste rock from the Elk Valley, southeastern British Columbia, the location of Canadas major steelmaking coal mines, were characterized and quantified by analyzing samples collected from the parent rock, freshly blasted waste rock (less than 10 days old), and aged waste rock (deposited between 1982 and 2012). Se is present throughout the waste rock dumps at a mean digestible (SeD) concentration of 3.12 mg/kg. Microprobe analyses show that Se is associated with the primary minerals sphalerite, pyrite, barite, and chalcopyrite and secondary Fe oxyhydroxides. Selenium K-edge X-ray absorption near-edge spectroscopy analyses indicate that, on average, 21% of Se is present as selenide (Se(2-)) in pyrite and sphalerite, 19% of Se is present as selenite (Se(4+)) in barite, 21% of Se is present as exchangeable Fe oxyhydroxide and clay-adsorbed Se(4+), and 39% of Se is present as organoselenium associated with coaly matter. The dominant source minerals for aqueous-phase Se are pyrite and sphalerite. Secondary Fe oxyhydroxide sequesters, on average, 37% of Se released by pyrite oxidation. Measured long-term Se fluxes from a rock drain at the base of a waste dump suggest that at least 20% of Se(2-)-bearing sulfides were oxidized and released from that dump over the past 30 year period; however, the Se mass lost was not evident in SeD analyses.

Arsenate partitioning from ferrihydrite to hematite: Spectroscopic evidence

Abstract Despite the number of detailed studies on arsenate adsorption onto synthetic 2-line ferrihydrite carried out during the past few decades, questions remain regarding the fate of adsorbed arsenate during phase transformation of this poorly crystalline iron oxy-hydroxide. We assessed arsenate partitioning during this transformation by aging synthetic 2-line ferrihydrite with adsorbed arsenate (at an As/Fe molar ratio of ~0.017) for 7 days at 75 °C under highly alkaline conditions (pH ~10). X-ray diffraction patterns show that ~55% of the ferrihydrite converted almost entirely to hematite (with traces of goethite) after aging 7 days, accompanied by a ~54% loss of reactive surface area (BET). ICP-MS analyses indicate that despite this conversion and significant loss of surface area, the aqueous arsenate concentration decreased from ~1.48 to ~0.51 mg/L during the course of the experiment. XAS analyses suggest that the concentration of arsenate and its speciation are controlled by its incorporation into the hematite.

Geochemistry of arsenic in low sulfide-high carbonate coal waste rock, Elk Valley, British Columbia, Canada.

This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO42- in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91μg/L) and rock-drain effluent (median: 0.31μg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley.

Redox stability of As(III) on schwertmannite surfaces

As(III)-enriched mine discharge often drains through Fe(III)-mineral abundant land covers which makes the understanding of its fate and redox behaviour extremely important. We therefore conducted batch kinetic and equilibrium studies at pH 3.0±0.05 in anoxic media coupled with spectroscopic and microscopic examinations at variable conditions to understand possible As(III) binding mechanisms and the redox stability of As(III) on schwertmannite, a prominent ferric mineral in acid mine drainage environments. Schwertmannite acted as an efficient scavenger for As(III) compared to goethite at identical sorbent:solute ratios. As K-edge X-ray absorption near-edge structure (XANES) demonstrated partial oxidation of sorbed As(III) to As(V) on both the minerals depending on the Fe(III)/As(III) ratios (goethite acted as a better oxidant than schwertmannite). Sorbed As(III) and As(V) coordinated in a bidentate binuclear binding mechanism with As(III)/As(V)-O and As(III)/As(V)-Fe interatomic distances as 1.78/1.69 and 3.37/3.31Å, respectively. Scanning (SEM-EDX) and transmission (TEM) electron microscopic, and IR spectroscopic measurements revealed the formation of As-containing surface coatings by sorbed As on schwertmannite.

Geochemical and mineralogical characterization of sulfur and iron in coal waste rock, Elk Valley, British Columbia, Canada

Exposure of coal waste rock to atmospheric oxygen can result in the oxidation of sulfide minerals and the release of sulfate (SO42-) and associated trace elements (e.g., Se, As, Cd, and Zn) to groundwaters and surface waters. Similarly, reduced iron minerals such as siderite, ankerite, and the sulfide, pyrite, present in the waste rock can also undergo oxidation, resulting in the formation of iron oxyhydroxides that can adsorb trace elements released from the oxidation of the sulfide minerals. Characterization and quantification of the distribution of sulfide and iron minerals, their oxidation products, as well as leaching rates are critical to assessing present-day and future impacts of SO42- and associated trace elements on receiving waters. Synchrotron-based X-ray absorption near edge spectroscopic analysis of coal waste rock samples from the Elk Valley, British Columbia showed Fe present as pyrite (mean 6.0%), siderite (mean 44.3%), goethite (mean 35.4%), and lepidocrocite (mean 14.3%) with S present as sulfide (mean 26.9%), organic S (mean 58.7%), and SO42- (mean 14.4%). Squeezed porewater samples from dump solids yielded mean concentrations of 0.28mg/L Fe and 1246mg/L SO42-. Geochemical modeling showed the porewaters in the dumps to be supersaturated with respect to Fe oxyhydroxides and undersaturated with respect to gypsum, consistent with solids analyses. Coupling Fe and S mineralogical data with long-term water quality and quantity measurements from the base of one dump suggest about 10% of the sulfides (which represent 2% of total S) in the dump were oxidized over the past 30years. The S from these oxidized sulfides was released to the receiving surface water as SO42- and the majority of the Fe precipitated as secondary Fe oxyhydroxides (only 3.0×10-5% of the Fe was released to the receiving waters over the past 30years). Although the data suggest that the leaching of SO42- from the waste rock dump could continue for about 300years, assuming no change in the rate of oxidation of sulfides, SO42- is currently not a concern in receiving surface waters as the concentration levels are below regulatory limits.

Dissolved Selenium(VI) Removal by Zero-Valent Iron under Oxic Conditions: Influence of Sulfate and Nitrate

Dissolved Se(VI) removal by three commercially available zero-valent irons (ZVIs) was examined in oxic batch experiments under circumneutral pH conditions in the presence and absence of NO3– and SO42–. Environmentally relevant Se(VI) (1 mg L–1), NO3– ([NO3—N] = 15 mg L–1), and SO42– (1800 mg L–1) were employed to simulate mining-impacted waters. Ninety percent of Se(VI) removal was achieved within 4–8 h in the absence of SO42– and NO3–. A similar Se(VI) removal rate was observed after 10–32 h in the presence of NO3–. Dissolved Se(VI) removal rates exhibited the highest decrease in the presence of SO42–; 90% of Se(VI) removal was measured after 50–191 h for SO42– and after 150–194 h for SO42– plus NO3– depending on the ZVI tested. Despite differences in removal rates among batches and ZVI materials, Se(VI) removal consistently followed first-order reaction kinetics. Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction analyses of reacted solids showed that Fe(0) present in ZVI undergoes oxidation to magnetite [Fe3O4], wüstite [FeO], lepidocrocite [γ-FeOOH], and goethite [α-FeOOH] over time. X-ray absorption near-edge structure spectroscopy indicated that Se(VI) was reduced to Se(IV) and Se(0) during removal. These results demonstrate that ZVI can be effectively used to control Se(VI) concentrations in mining-impacted waters.