Oxidation, characterization, and separation of non-pertechnetate species in Hanford wastes

Under DOE's privatization initiative, Lockheed Martin and British Nuclear Fuels Limited are preparing to stabilize the caustic tank waste generated from plutonium production at the Hanford Site. Pretreatment of Hanford tank waste will separate it into low-level waste (LLW) and high-level waste (HLW) fractions. The scope of the technetium problem is indicated by its inventory in the waste: ∼2000 kg. Technetium would normally exist as the pertechnetate anion, TcO4-, in aqueous solution. However, evidence obtained at Los Alamos National Laboratory (LANL) indicates that the combination of radiolysis, heat, organic complexants, and time may have reduced and complexed a significant fraction of the technetium in the tank waste. These species are in a form that is not amenable to current separation techniques based on pertechnetate removal. Thus, it is crucial that methods be developed to set technetium to pertechnetate so these technologies can meet the required technetium decontamination factor. If this is not possible, then alternative separation processes will need to be developed to remove these non-pertechnetate species from the waste. The simplest, most cost-effective approach to this problem is to convert the non-pertechnetate species to pertechnetate. Chemical, electrochemical, and photochemical oxidation methods, as well as hydrothermal treatment, are being applied to Hanford waste samples to ensure that the method works on the unknown technetium species in the waste. The degree of oxidation will be measured by determining the technetium distribution coefficient, TcKd, between the waste and Reillex trademark-HPQ resin, and comparing it to the true pertechnetate Kd value for the waste matrix. Other species in the waste, including all the organic material, could be oxidized by these methods, thus selective oxidation is desirable to minimize the cost, time, and secondary waste generation