The subsurface behaviour of 99 Tc, 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 À9 atm O 2 ). 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 lmol/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. 57 Fe-Mö ssbauer, 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)O 2 AEnH 2 O (s) . The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O 2 AEnH 2 O (s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99 Tc remobilization upon the return of oxidizing conditions.

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Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of Fe 2þ ðaqÞ adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added Fe 2þ ðaqÞ that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) $ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ( structural Fe(II) in phyllosilicates ( Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO 2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mö ssbauer spectroscopy applied to an experiment with 56 Fe-goethite with adsorbed 57 Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxideadsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.

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Abiotic reduction of 0.1 mM U(VI) by Fe(II) in the presence of synthetic iron oxides (biogenic magnetite, goethite, and hematite) and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids. U(VI) was rapidly and extensively (> or = 80%) reduced in the presence of synthetic Fe(III) oxides and highly Fe(II) oxide-enriched (18-35 wt % Fe) Atlantic coastal plain sediments. In contrast, long-term (20-60 d) U(VI) reduction was less than 30% in suspensions of six other natural solids with relatively low Fe(III) oxide content (1-5 wt % Fe). Fe(II) sorption site density was severalfold lower on these natural solids (0.2-1.1 Fe(II) nm(-2)) compared tothe synthetic Fe(lII) oxides (1.6-3.2 Fe(II) nm(-2)), which may explain the poor U(VI) reduction in the natural solid-containing systems. Addition of the reduced form of the electron shuttling compound anthrahydroquinone-2,6-disulfonate (AH2DS; final concentration 2.5 mM) to the natural solid suspensions enhanced the rate and extent of U(VI) reduction, suggesting that AH2DS reduced U(VI) at surface sites where reaction of U(VI) with sorbed Fe(II) was limited. This study demonstrates that abiotic, Fe(II)-driven U(VI) reduction is likely to be less efficient in natural soils and sediments than would be inferred from studies with synthetic Fe(III) oxides.

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The effects of natural organic matter (NOM), ferrozine, and AQDS (anthraquinone-2,6-disulfonate) on the reduction of hematite (alpha-Fe2O3) by Shewanella putrefaciens CN32 were studied. It has been proposed that NOM enhances the reduction of Fe(III) by means of electron shuttling or by Fe(II) complexation. Previously both mechanisms were studied separately using "functional analogues" (AQDS for electron shuttling and ferrozine for complexation) and are presently compared with seven different NOMs. AQDS enhanced hematite reduction within the first 24 h of incubation, and this had been ascribed to electron shuttling. Most of the NOMs enhanced hematite reduction after 1 day of incubation indicating that these materials could also serve as electron shuttles. The effect of ferrozine was linear with concentration, and all of the NOMs exhibited this behavior. Fe(II) complexation only enhanced hematite reduction after sufficient Fe(II) had accumulated in the system. Fe(II) complexation appeared to alleviate a suppression of the hematite reduction rate caused by accumulation of Fe(II) in the system. Addition of Fe(II) to the hematite suspension, prior to inoculation with CN32, significantly inhibited hematite reduction and greatly diminished the effects of all of the organic materials, although some enhancement was observed due to addition of anthroquinone-2,6-disulfonate. These results demonstrate that NOM can enhance iron reduction by electron shuttling and by complexation mechanisms.

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