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Reductive precipitation of the radiotoxic nuclide Np-237 from nuclear waste on the surface of iron canister material at simulated deep repository conditions was investigated. Pristine polished as well as pre corroded iron specimens were interacted in a deoxygenated solution containing 10-100 mu M Np(V), with 10 mM NaCl and 2 mM NaHCO3 as background electrolytes. The reactivity of each of the two different systems was investigated by analyzing the temporal evolution of the Np concentration in the reservoir. It was observed that pre-oxidized iron specimen with a 40 tm Fe3O4 corrosion layer are considerably more reactive regarding the reduction and immobilization of aqueous Np(V) as compared to pristine polished FeM surfaces. Np-237 immobilized by the reactive iron surfaces was characterized by scanning electron microscopy as well as synchrotron-based micro-X-ray fluorescence and X-ray absorption spectroscopy. At the end of experiments, a 5-8 tm thick Np-rich layer was observed to be formed ontop of the Fe3O4 corrosion layer on the iron specimen. The findings from this work are significant in the context of performance assessments of deep geologic repositories using iron as high level radioactive waste (HLW) canister material and are of relevance regarding removing pollutants from contaminated soil or groundwater aquifer systems.

We characterized, for the first time, submicro- and nanosized fission product-alloy particles that were extracted nondestructively from spent nuclear fuel, in terms of noble metal (Mo-Ru-Tc-Rh-Pd-Te) composition, atomic level homogeneity and lattice parameters. The evidences obtained in this work contribute to an improved understanding of the redox chemistry of radionuclides in nuclear waste repository environments and, in particular, of the catalytic properties of these unique metal alloy particles., 7

For the first time, hydrogen catalytic effects of fission product alloy particles nondestructively extracted from spent nuclear fuel were demonstrated. The redox sensitive radionuclides at oxidized forms Se(IV), Tc(VII), U(VI), Np(V) and Pu(VI) were found to be stable in a solution saturated with a gas mixture (Ar + 10% H-2 + 0.03% CO2) but rapidly immobilized in the same solution when contacted with the particles. In comparison, a synthetic alloy sample with similar elemental composition as the alloy particles generated in nuclear fuel displayed a smaller, but unequivocal catalytic effect. The smaller catalytic effect of synthetic alloy was apparently enhanced by a P-radiation source. The information obtained in this work contributes to improved understanding of the redox chemistry of radionuclides in nuclear waste geologic repository environments and, in particular, of the catalytic properties of these unique alloy particles., authorCount :4

This work is a continuation of a long-term spent fuel leaching and radionuclides immobilization (by iron canister) experiment under simulated near-field conditions, in deoxygenated 2 mM NaHCO3 solution with 1 Gy/h γ irradiation. The corrosion of iron canister material was investigated by electrochemical and microanalytical methods. Significant amounts of radionuclides (U, Np, Tc, Sr) were found to be immobilized on the corrosion layer of iron canister material by using SEM-WDS and SIMS methods. The observation is useful for bettering our understanding of near-field chemical processes at earlier canister failure conditions., QC 20141010

This paper reports on the results of a long term experiment on spent fuel leaching, canister corrosion and radionuclide immobilization under repository conditions corresponding to early canister failure. A γ-dose of 850 mGy per hour, and Ar-flushed synthetic groundwater were used. During the first 287 days, the fractions of inventory in aqueous phase per day (f/d) increased nearly constantly for each radionuclide (except for 100Mo), with higher fractions for fission products than for actinides. After this initial stage, iron, cast iron and copper coupons (of̃30 mm2 size) were inserted into the leaching vessel: the concentrations of 238U, 237Np and 99Tc decreased by 80%, 97% and 88% to relatively stable levels (500ppb, 0.2ppb and 0.6ppb respectively). 239Pu concentrations slightly increased to the level of PuO2 solubility (0.5ppb). The leaching process for Cs, Mo and 90Sr was not influenced by the added metals. The pH and Eh values and corrosion potential were measured. The polarization resistance (Rp) was obtained from fitting of electrochemical impedance spectra, and then corrected by the surface area of the sample. The corrosion current density Icorr was calculated according to the Stern-Gary relationship, and using the same Tafel constants (26 mV)for all samples, i.e., Icorr = 0.026/Rp. The momentary corrosion rates of iron, cast iron and copper (Cu/Cu+) calculated based on the Faraday's law are in reasonable agreement with the values estimated from observation of thickness of corrosion layers using SEM microscope. The copper coupon appeared much more stable against corrosion than the other coupons. The corrosion layer and radionuclides deposited on corrosion products on iron coupons were analyzed by SEM-EDS and SIMS. Si was found to be coordinated with all iron corrosion products; however, redox sensitive elements U and Pu were mainly coordinated with the inner layer of iron corrosion products even though some 1-2 μm sized uranium-silica rich particles were foun, QC 20141208