John Rowson

Predicting arsenic concentrations in the porewaters of buried uranium mill tailings

Abstract The proposed JEB Tailings Management Facility (TMF) to be emplaced below the groundwater table in northern Saskatchewan, Canada, will contain uranium mill tailings from McClean Lake, Midwest and Cigar Lake ore bodies, which are high in arsenic (up to 10%) and nickel (up to 5%). A serious concern is the possibility that high arsenic and nickel concentrations may be released from the buried tailings, contaminating adjacent groundwaters and a nearby lake. Laboratory tests and geochemical modeling were performed to examine ways to reduce the arsenic and nickel concentrations in TMF porewaters so as to minimize such contamination from tailings buried for 50 years and longer. The tests were designed to mimic conditions in the mill neutralization circuit (3 hr tests at 25°C), and in the TMF after burial (5–49 day aging tests). The aging tests were run at, 50, 25 and 4°C (the temperature in the TMF). In order to optimize the removal of arsenic by adsorption and precipitation, ferric sulfate was added to tailings raffinates 1 having Fe/As ratios of less that 3–5. The acid raffinates were then neutralized by addition of slaked lime to nominal pH values of 7, 8, or 9. Analysis and modeling of the test results showed that with slaked lime addition to acid tailings raffinates, relatively amorphous scorodite (ferric arsenate) precipitates near pH 1, and is the dominant form of arsenate in slake limed tailings solids except those high in Ni and As and low in Fe, in which cabrerite-annabergite (Ni, Mg, Fe(II) arsenate) may also precipitate near pH 5–6. In addition to the arsenate precipitates, smaller amounts of arsenate are also adsorbed onto tailings solids. The aging tests showed that after burial of the tailings, arsenic concentrations may increase with time from the breakdown of the arsenate phases (chiefly scorodite). However, the tests indicate that the rate of change decreases and approaches zero after 72 hrs at 25°C, and may equal zero at all times in the TMF at 4°C. Consistent with a kinetic model that describes the rate of breakdown of scorodite to form hydrous ferric oxide, the rate of release of dissolved arsenate to tailings porewaters from slake limed tailings: (1) is proportional to pH above pH 6–7; (2) decreases exponentially as the total molar Fe/As ratio of tailings raffinates is increased from 1/1 to greater than 5/1; and (3) is proportional to temperature with an average Arrhenius activation energy of 13.4 ± 4.2 kcal/mol. Study results suggest that if ferric sulfate and slaked lime are added in the tailings neutralization circuit to give a raffinate Fe/As molar ratio of at least 3–5 and a nominal (initial) pH of 8 (final pH of 7–8), arsenic and nickel concentrations of 2 mg/L or less, are probable in porewaters of individual tailings in the TMF for 50 to 10,000 yrs after tailings disposal. However, the tailings will be mixed in the TMF, which will contain about 35% tailings with Fe/As = 3.0, and 65% tailings with Fe/As = 5.0–7.7. Thus, it seems likely that average arsenic pore water concentrations in the TMF may not exceed 1 mg/L.

Analysis of the Mo speciation in the JEB tailings management facility at McClean Lake, Saskatchewan.

The JEB Tailings Management Facility (TMF) is central to reducing the environmental impact of the uranium ore processing operation located at the McClean Lake facility and operated by AREVA Resources Canada (AREVA). The geochemical controls of this facility are largely designed around the idea that elements of concern, such as Mo, will be controlled in the very long term through equilibrium with supporting minerals. However, these systems are far from equilibrium when the tailings are first placed in the TMF, and it can take years, decades, or centuries to reach equilibrium. Therefore, it is necessary to understand how these reactions evolve toward an equilibrium state to understand the very long-term behavior of the TMF and to ensure that the elements of concern will be adequately contained. To this end, the Mo speciation in a series of samples taken from the JEB TMF during the 2008 sampling campaign has been analyzed. This analysis was performed using powder X-ray diffraction (XRD), X-ray fluorescence mapping (μ-XRF), and X-ray absorption near-edge spectroscopy (XANES). These results show that only XANES was effective in speciating Mo in the tailings samples, because it was both element-specific and sensitive enough to detect the low concentrations of Mo present. These results show that the predominant Mo-bearing phases present in the TMF are powellite, ferrimolybdite, and molybdate adsorbed on ferrihydrite.

Investigating the Geochemical Model for Molybdenum Mineralization in the JEB Tailings Management Facility at McClean Lake, Saskatchewan: An X-ray Absorption Spectroscopy Study

The geochemical model for Mo mineralization in the JEB Tailings Management Facility (JEB TMF), operated by AREVA Resources Canada at McClean Lake, Saskatchewan, was investigated using X-ray Absorption Near-Edge Spectroscopy (XANES), an elemental-specific technique that is sensitive to low elemental concentrations. Twenty five samples collected during the 2013 sampling campaign from various locations and depths in the TMF were analyzed by XANES. Mo K-edge XANES analysis indicated that the tailings consisted primarily of Mo(6+) species: powellite (CaMoO4), ferrimolybdite (Fe2(MoO4)3·8H2O), and molybdate adsorbed on ferrihydrite (Fe(OH)3 - MoO4). A minor concentration of a Mo(4+) species in the form of molybdenite (MoS2) was also present. Changes in the Mo mineralization over time were inferred by comparing the relative amounts of the Mo species in the tailings to the independently measured aqueous Mo pore water concentration. It was found that ferrimolybdite and molybdate adsorbed on ferrihydrite initially dissolves in the TMF and precipitates as powellite.

Raffinate Neutralization Experiments at the McClean Lake Mill — Removal of Arsenic and Nickel

Uranium ores at the McClean Lake Operation in the Athabasca Basin of Northern Saskatchewan can produce elevated levels of arsenic (up to 700 mg/L) and nickel (up to 500 mg/L) in acidic (pH<1.5) spent leaching solutions (raffinates). Prior to neutralization, if necessary, ferric sulfate is added to tailings slurries to increase their Fe/As (molar) ratio to greater than 3. The slurries are then neutralized with lime to pH 4, and subsequently to pH 7–8. After neutralization, As and Ni concentrations average less than 1 mg/L. Solids from bench scale experiments demonstrate that As is associated primarily with scorodite and annabergite, with small amounts adsorbed onto or co-precipitated with ferrihydrite.

A method to measure arsenic readily released to pore waters from uranium mill tailings

A method to quantify the amount of readily released arsenic in uranium mill tailings was developed using a technique known as Equilibrium Partitioning In Closed Systems (EPICS). The method employs a gentle leaching solution that, except for its arsenic (As) concentration, is identical to the neutralized raffinate that contacts the tailings. Prior to implementation, the experimental design and mathematical approach were verified in geochemical models using PHREEQC. Laboratory experiments using tailings from the Athabasca Basin of Northern Saskatchewan demonstrated that As that could be readily released to pore waters is about 0.2 % of the total As in the tailings.