Date of this Version
Geochimica et Cosmochimica Acta 71 (2007) 2137–2157
The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6–8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 · 10-9 atm O2). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 µmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)(aq) = 0.05–0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe–X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. 57Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O2•nH2O(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O2•nH2O(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or ground waters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99Tc remobilization upon the return of oxidizing conditions.