Long-term immobilization of technetium via bioremediation with slow-release substrates

Radionuclides are present in groundwater at contaminated nuclear facilities with technetium-99, one of the most mobile radionuclides encountered. In situ bioremediation via the generation of microbially reducing conditions has the potential to remove aqueous and mobile Tc(VII) from groundwater as insoluble Tc(IV). However, questions remain regarding the optimal methods of biostimulation and the stability of reduced Tc(IV) phases under oxic conditions. Here, we selected a range of slow-release electron donor/chemical reduction based substrates available for contaminated land treatment, and assessed their potential to stimulate the formation of recalcitrant Tc(IV) biominerals under conditions relevant to radioactively contaminated land. These included a slow-release polylactate substrate (HRC), a similar substrate with an additional organosulfur ester (MRC) and a substrate containing zerovalent iron and plant matter (EHC). Results showed that Tc was removed from solution in the form of poorly soluble hydrous Tc(IV)-oxides or Tc(IV)-sulfides during the development of reducing conditions. Reoxidation experiments showed that these phases were largely resistant to oxidative remobilization and were more resistant than Tc(IV) produced via biostimulation with an acetate/lactate electron donor mix in the sediments tested. The implications of the targeted formation of recalcitrant Tc(IV) phases using these proprietorial substrates in situ is discussed in the context of the long-term management of technetium at legacy nuclear sites.