[en] The long-range objective of this project is to provide a scientific basis for safely processing high-level nuclear tanks wastes for disposal. Our goals are to identify a means to prepare realistic simulant formulations for complexant-containing Hanford tank wastes, and then use those simulants to determine the relative importance of various organic complexants and their breakdown products on the partitioning of important radionuclides. The harsh chemical and radiolytic environment in high-level waste tanks alters both the organic complexants and the metal species, producing radionuclide-chelator complexes that resist standard separation methods. A detailed understanding of the complexation reactions of the key radionuclides in tank wastes would allow for reliable, science-based solutions for high-level waste processing, but a key problem is that tank waste samples are exceedingly difficult to obtain, transport and handle in the laboratory. In contrast, freshly-prepared simulated wastes are safe and readily obtained, but they do not reproduce the partitioning behavior of actual tank waste samples. For this project, we will first artificially age complexant-containing tank waste simulants using microwave, ultrasound, and photolysis techniques that can be applied in any standard laboratory. The aged samples will be compared to samples of actual Hanford tank wastes to determine the most realistic aging method, on the basis of the organic fragments present, and the oxidation states and partitioning behavior of important radionuclides such as 90Sr, 99Tc, and 239Pu. Our successful completion of this goal will make it possible for scientists in academic and industrial laboratories to address tank waste remediation problems without the enormous costs and hazards associated with handling actual tank waste samples. Later, we will use our simulant aging process to investigate the relative effects of chelator degradation products on the partitioning of important radionuclides from the waste. Using NMR-active labels in the chelators, we will use a combinatorial approach of generating multiple chelator fragments in a single experiment and then determining which, if any, of the fragments have a negative effect on the separations chemistry. Our successful completion of this goal will specifically identify the most problematic organic fragments in complexant-containing waste and provide the basis for developing successful treatment strategies for these wastes

[en] The aging of the US nuclear stockpile presents a number of challenges, including the increasing radioactivity of plutonium residues due to the ingrowth of ²⁴¹Am from the β-decay of ²⁴¹Pu. We investigated parameters that affect the sorption of Am onto anion-exchange resins from concentrated effluents derived from nitric acid processing of plutonium residues. These postevaporator wastes are nearly saturated solutions of acidic nitrate salts, and americium removal is complicated by physical factors, such as solution viscosity and particulates, as well as by the presence of large quantities of competing metals and acid. Single- and double-contact batch distribution coefficients for americium and neodymium from simple and complex surrogate solutions are presented. Varied parameters include the nitrate salt concentration and composition and the nitric acid concentration. We find that under these extremely concentrated conditions, Am(III) removal efficiencies can surpass 50% per contact. Distribution coefficients for both neodymium and americium are insensitive to solution acidity and appear to be driven primarily by low water activities of the solutions

[en] Americium (III) exhibits an unexpectedly high affinity for anion-exchange material from the high-salt evaporator bottoms solutions--an effect which has not been duplicated using simple salt solutions. Similar behavior is observed for its lanthanide homologue, Nd(III), in complex evaporator bottoms surrogate solutions. There appears to be no single controlling factor--acid concentration, total nitrate concentration or solution ionic strength--which accounts for the approximately 2-fold increase in retention of the trivalent ions from complex solutions relative to simple solutions. Calculation of species activities (i.e., water, proton and nitrate) in such concentrated mixed salt solutions is difficult and of questionable accuracy, but it is likely that the answer to forcing formation of anionic nitrate complexes of americium lies in the relative activities of water and nitrate. From a practical viewpoint, the modest americium removal needs (ca. 50--75%) from nitric acid evaporator bottoms allow sufficient latitude for the use of non-optimized conditions such as running existing columns filled with older, well-used Reillex HPQ. Newer materials, such as HPQ-100 and the experimental bifunctional resins, which exhibit higher distribution coefficients, would allow for either increased Am removal or the use of smaller columns. It is also of interest that one of the experimental neutral-donor solid-support extractants, DHDECMP, exhibits a similarly high level of americium (total alpha) removal from EV bottoms and is much less sensitive to total acid content than commercially-available material