Treatment of radioactive wastes: an X-ray absorption spectroscopy study of the reaction of technetium with green rust.

Technetium is a long-lived product of nuclear fission that readily forms the soluble pertechnetate anion TcO(4). Green rusts (layered hydrous oxides containing both Fe(II) and Fe(III) and with interlayer sulfate or carbonate anions) concentrate >99.8% of 99Tc, present as TcO(4), from aqueous solution, even in the presence of high concentrations of NaNO(3), a common constituent of radioactive waste streams. The mechanism of removal from solution is apparently reduction and formation of strong Tc(IV) surface complexes. X-ray absorption spectroscopy shows that TcO(4) is indeed reduced by reaction with both sulfate- and carbonate-form green rusts and is found in a TcO(2)-like environment. On contact with air, the green rusts oxidize to poorly crystalline goethite but the Tc environment is unchanged. There is no increase in Tc solubility associated with oxidation of the host green rust. This behavior suggests that green rusts may be useful in the treatment of Tc-containing waste streams, in groundwater cleanup, and in restricting Tc migration from repositories.