Technetium reduction and reoxidation behaviour in Dounreay soils

Technetium is a radioactive contaminant found in groundwaters at sites where nuclear wastes have been processed or stored. The redox chemistry of technetium is a major control on its environmental mobility. Under oxic conditions, technetium exists as the pertechnetate ion, Tc(VII)O-4(-), which is poorly sorbed by minerals across a wide range of environmentally relevant pH values. Under reducing conditions pertechnetate is converted to lower valency species, of which Tc(IV) tends to predominate. Typically, the Tc(IV) oxidation state readily precipitates as insoluble hydrous Tc(IV) oxides or, at low concentrations, is removed from solution by association with mineral surfaces. Here, we present novel X-ray absorption spectroscopy (XAS) data examining Tc associations with reduced Dounreay soils. In reduced unamended microcosms and in microcosms where we added the co-contaminants ethylenediaminetetraacetic acid (EDTA) or bicarbonate to investigate their effect on Tc biogeochemistry, Tc was removed from solution on exposure to the reduced sediments and was present on solids as hydrous Tc(IV)O-2-like phases. Furthermore, to investigate the long term stability and remobilization of solid phase associated Tc in reduced soils, we reoxidized reduced, Tc(IV)-labeled soils, in the presence of air and nitrate. The extent of remobilization of Tc to solution was dependent on the oxidant used. After reoxidation with air for 60d, 42 +/- 6% of the initial soil bound Tc was resolubilized. In the presence of 25 or 100 mmol L-1 nitrate as an oxidant, negligible microcosm reoxidation or remobilization of Tc to solution occurred. XAS analysis of soils treated with the two oxidants showed that in both systems, the remaining soil associated Tc was present as hydrous TCO2-like phases. The recalcitrance of Tc remobilization under reoxidizing conditions has implications for the fate of Tc in contaminated environments.