Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate ( 99 TcO 4 − ) and other ions. This study investigates the potential for incorporation of perrhenate (ReO 4 − ), a chemical surrogate for 99 TcO 4 − , into mixed perrhenate/nitrate (ReO 4 − /NO 3 − ) sodalite.Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90°C for 24 h. The resulting solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products' chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O 4 − . The nonlinear increase of the unit cell parameter with ReO 4 − /NO 3 − ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO 3 − over ReO 4 − . Calculated enthalpy and Gibbs free energy of formation at 298 K for NO 3 -and ReO 4 -sodalite suggest that NO 3 − incorporation into the cage is favored over the incorporation of the larger ReO 4 − , due to the smaller ionic radius of NO 3 − . Based on these results, it is expected that NO 3 − , which is present at significantly higher concentrations in alkaline waste solutions than 99 TcO 4 − , will be strongly preferred for incorporation into the sodalite cage.
■ INTRODUCTIONTechnetium-99 presents a major environmental concern due to its long half-life (211 000 years) and high mobility of pertechnetate (TcO 4 − ), the dominant ionic species in oxidized subsurface systems. 1 At the U.S. Department of Energy's Hanford site, approximately 1900 kg of 99 Tc was generated and stored underground in 177 tanks, which contain an estimated 65 million gallons of nuclear waste from the production of plutonium during the Cold War era. 2 Seventy-seven of these tanks have leaked high-level radioactive waste (HLW) into the vadose zone (the unsaturated region between the ground surface and the top of the water table), which extends 50−70 m below the storage tanks. 2 In addition 99 Tc was also released to the subsurface via cribs and trenches, which received in excess of 50 million gallons of reprocessed tank waste. Due to weak adsorption of TcO 4 − to the predominantly negatively charged, oxic sediments prevalent at the Hanford site, 99 Tc migration into the vadose zone pore water and groundwater is expected to be largely unimpeded. 3 The Hanford tank waste solutions are alkaline (free OH − is from 0.1 to 5.3 M, Na + from 2.9 to 19.6 M, and NO 3 − from 0.5 to 5.5 M), high in ionic strength (I = 2−14 M), and supersaturated with an Al(OH) 3 phase....