Photocatalytic Reduction of Perrhenate and Pertechnetate in a Strongly Acidic Aqueous Solution.

Pertechnetate (99TcO4-), a physiologically toxic radioactive anion, is of great concern due to its high mobility in environmental contamination remediation. Although the soluble oxyanion can be photoreduced to sparingly soluble TcO2·nH2O, its effective removal from a strongly acidic aqueous solution remains a challenge. Here, we found that low-crystalline nitrogen-doped titanium oxide (N-TiO2, 0.6 g L-1) could effectively uptake perrhenate (ReO4-, 10 mg L-1, a nonradioactive surrogate for TcO4-) with 50.8% during 360 min under simulated sunlight irradiation at pH 1.0, but P25 and anatase could not. The nitrogen active center formed by trace nitrogen doping in N-TiO2 can promote the separation and transfer of photogenerated carriers. The positive valence band value of N-TiO2 is slightly higher than those of P25 and anatase, which means that the photogenerated holes have a stronger oxidizability. These holes are involved in the formation of strong reducing •CO2- radicals from formic acid oxidation. The active radicals convert ReO4- to Re(VI), which is subsequently disproportionated to Re(IV) and Re(VII). Effective photocatalytic reduction/removal of Re(VII)/Tc(VII) is performed on the material, which may be considered a potential and convenient strategy for technetium decontamination and extraction in a strongly acidic aqueous solution.

Leaching behaviour of 226Ra from uranium tailings and adsorption behaviour in geotechnical medias.

The leaching process of uranium tailings is a typical water-rock interaction. The release of 226Ra from uranium tailings depends on the nuclides outside the intrinsic properties of uranium tailings on the one hand, and is influenced by the water medium on the other. In this paper, a uranium tailings repository in southern China was used as a research object, and uranium tailings at different depths were collected by drilling samples and mixed to analyze the 226Ra occurrence states. Static dissolution leaching experiments of 226Ra under different pH conditions, solid-liquid ratio conditions, and ionic strength conditions were carried out, and the adsorption and desorption behaviours of 226Ra in five representative stratigraphic media were investigated. The results show that 226Ra has a strong adsorption capacity in representative strata, with adsorption distribution coefficient Kd values ranging from 1.07E+02 to 1.29E+03 (mL/g) and desorption distribution coefficients ranging from 4.97E+02 to 2.71E+03 (mL/g), but the adsorption is reversible. The 226Ra in uranium tailings exists mainly in the residual and water-soluble states, and the release of 226Ra from uranium tailings under different conditions is mainly from the water-soluble and exchangeable state fractions. Low pH conditions, low solid-liquid ratio conditions and high ionic strength conditions are favourable to the release of 226Ra from uranium tailings, so the release of 226Ra from uranium tailings can be reduced by means of adjusting the pH in the tailings and setting up a water barrier. The results of this research have important guiding significance for the management of existing uranium tailings ponds and the control of 226Ra migration in groundwater, which is conducive to guaranteeing the long-term safety, stability and sustainability of uranium mining sites.

Research on leaching behavior of uranium from a uranium tailing and its adsorption behavior in geotechnical media.

The release of uranium from uranium tailings into the aqueous environment is a complex process controlled by a series of interacting geochemical reactions. In this paper, uranium tailings from a uranium tailings pond in southern China were collected at different depths by means of borehole sampling and mixed to analyze the fugacity state of U. Static leaching experiments of U at different pH, oxidant concentration and solid-to-liquid ratios and dynamic leaching experiments of U at different pH were carried out, and the adsorption and desorption behaviour of U in five representative stratigraphic media were investigated. The results show that U is mainly present in the residue state in uranium tailings, that U release is strong in the lower pH range, that the leached U is mainly in the form of U(VI), mainly from the water-soluble, Fe/Mn oxides and exchangeable fraction of uranium tailings, and that the reduction in U leaching at higher pH is mainly due to the combined effect of precipitation formation and larger particle size of platelets in uranium tailings. Experiments with different oxidant concentrations and solid-liquid ratios showed that the oxygen-enriched state and low solid-liquid ratios were favorable for the leaching of U from uranium tailings. Adsorption and desorption experiments show that U is weakly adsorbed in representative strata, reversibly adsorbed, and that U is highly migratory in groundwater. The present research results have important guiding significance for the management of existing uranium tailings ponds and the control of U migration in groundwater, which is conducive to ensuring the long-term safety, stability and sustainability of uranium mining sites.