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 raffinates1 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.