Reduction of Tc(VII) by Fe(II) Sorbed on Al (hydr)oxides

Under oxic conditions, Tc exists as the soluble, weakly sorbing pertechnetate [TcO4−] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2·nH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) adsorbed on Al (hydr)oxides [diaspore (α-AlOOH) and corundum (α-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (Mössbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11 (diaspore suspension) and 4 days (corundum suspension). Mössbauer measurements revealed that the Fe(II) signal became less intense with Tc(VII) reduction and was accompanied by an increase in the intensity of the Fe(III) doublet and magnetically ordered Fe(III) sextet signals. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2·nH2O.