Pu(Ⅴ) and Pu(Ⅳ) Sorption to Montmorillonite

摘要

Plutonium (Pu) adsorption to and desorption from mineral phases plays a key role in controlling the environmental mobility of Pu. Here we assess whether the adsorption behavior of Pu at concentrations used in typical laboratory studies (≥10~(-10) [Pu] ≤ 10~(-6) M) are representative of adsorption behavior at concentrations measured in natural subsurface waters (generally ＜10~(-12) M). Pu(Ⅴ) sorption to Na-montmorillonite was examined over a wide range of initial Pu concentrations (10~(-6)-10~(-16) M). Pu(Ⅴ) adsorption after 30 days was linear over the wide range of concentrations studied, indicating that Pu sorption behavior from laboratory studies at higher concentrations can be extrapolated to sorption behavior at low, environmentally relevant concentrations. Pu(Ⅳ) sorption to montmorillonite was studied at initial concentrations of 10~(-6)-10~_(-11) M and was much faster than Pu(Ⅴ) sorption over the 30 day equilibration period. However, after one year of equilibration, the extent of Pu(Ⅴ) adsorption was similar to that observed for Pu(Ⅳ) after 30 days. The continued uptake of Pu(Ⅴ) is attributed to a slow, surface-mediated reduction of Pu(Ⅴ) to Pu(Ⅳ). Comparison between rates of adsorption of Pu(Ⅴ) to montmorillonite and a range of other minerals (hematite, goethite, magnetite, groutite, corundum, diaspore, and quartz) found that minerals containing significant Fe and Mn (hematite, goethite, magnetite, and groutite) adsorbed Pu(Ⅴ) faster than those which did not, highlighting the potential importance of minerals with redox couples in increasing the rate of Pu(Ⅴ) removal from solution.