Edgar C. Buck

Ten-year results from unsaturated drip tests with UO2 at 90°C: implications for the corrosion of spent nuclear fuel

Alteration phases may influence both the dissolution of nuclear waste forms and release of radionuclides from the waste package environment. In the present study, UO2 pellets serve as surrogates for commercial spent nuclear fuel, with the pellets being exposed to periodic drops of simulated groundwater at 90°C. Uranium release was very rapid between one and two years, resulting from grain boundary corrosion and spallation of micrometer-sized UO2+x particles from the sample surface. The development of a dense mat of alteration phases after two years apparently trapped loose particles, resulting in reduced rates of uranium release. The paragenetic sequence of alteration phases is similar to that observed in surficial weathering zones of natural uraninite deposits, with alkali and alkaline earth uranyl silicates being the long-term solubility-limiting phases for uranium. Results from this study and comparisons with natural analogue deposits suggest that the migration of fission products from altered spent fuel may be retarded by their incorporation in secondary uranium phases.

Imaging Hydrated Microbial Extracellular Polymers: Comparative Analysis by Electron Microscopy

ABSTRACT Microbe-mineral and -metal interactions represent a major intersection between the biosphere and geosphere but require high-resolution imaging and analytical tools for investigation of microscale associations. Electron microscopy has been used extensively for geomicrobial investigations, and although used bona fide, the traditional methods of sample preparation do not preserve the native morphology of microbiological components, especially extracellular polymers. Herein, we present a direct comparative analysis of microbial interactions by conventional electron microscopy approaches with imaging at room temperature and a suite of cryogenic electron microscopy methods providing imaging in the close-to-natural hydrated state. In situ, we observed an irreversible transformation of the hydrated bacterial extracellular polymers during the traditional dehydration-based sample preparation that resulted in their collapse into filamentous structures. Dehydration-induced polymer collapse can lead to inaccurate spatial relationships and hence could subsequently affect conclusions regarding the nature of interactions between microbial extracellular polymers and their environment.

Influence of Dynamical Conditions on the Reduction of UVI at the Magnetite—Solution Interface

The heterogeneous reduction of U(VI) to U(IV) by ferrous iron is believed to be a key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural Fe(II) has been studied for numerous substrates, including magnetite. Published results from U(VI)-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of U(IV). In this contribution, we used XAS and high resolution (+/-cryogenic) XPS to study the interaction of U(VI) with nanoparticulate magnetite. The results indicated that U(VI) was partially reduced to U(V) with no evidence of U(IV). However, thermodynamic calculations indicated that U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation and stabilization of U(V) and U(VI) into secondary phases is invoked to explain the observations. The results suggest an important and previously unappreciated role of U(V) in the fate and transport of uranium in the environment.

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 μg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

A new uranyl oxide hydrate phase derived from spent fuel alteration

An alteration phase that formed during the corrosion of commercial oxide spent nuclear fuel has been characterized with analytical transmission electron microscopy (AEM). The phase is a CsBa uranyl molybdate oxide hydrate that has an orthorhombic structure related to the alkaline earth uranyl oxide hydrates of the protasite-group minerals. On the basis of the compositional analysis and a proposed model of the structure, the ideal structural formula is (Cs0.8Ba0.6)(UO2)5(MoO2)O4(OH)6·nH2O (where n is around 6). Low levels of strontium are also present in the phase. The estimated unit cell parameters are a = 0.754 nm, b = 0.654 nm, and c = 3.008 nm. Although many of the phases formed during corrosion of spent oxide fuel are similar to those observed in natural uraninite deposits, such as Pena Blanca in Mexico, there are important differences owing to the presence of fission products in the spent fuel. Thus, accurate determination of corrosion processes in actual radioactive waste forms is important. This study suggests that the natural UMo deposits at Shelby, WY, and Bates Mountain Tuff, NV, may be good analogues for the long-term behavior of UMo phases formed due to spent fuel corrosion.

Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite

Summary The contact of commercial spent nuclear fuel (CSNF) with water over a 2-year period led to an unexpected corrosion phase and morphology. At short hydration times, crystallites of metaschoepite [(UO2)8O2(OH)12](H2O)10 were observed on the hydrated CSNF particles. Over the 2-year contact period, all evidence of metaschoepite disappeared, and the fuel particles were coated by a new alteration phase. Additionally, films of the reacted fuel were observed at the sample air-water interface of each sample. The corrosion phases on fuel powders and on the suspended films were examined by scanning electron microscopy, energy-dispersive X-ray fluorescence, and X-ray diffraction and were identified as studtite [(UO2)(O2)(H2O)2](H2O)2 and metastudtite (UO4·2H2O), respectively. The reason for the partitioning of the latter phase to the sample air-water interface is unclear at this time but may be due to structural differences between the two phases. Scanning electron micrographs of the CSNF powders indicated surface corrosion along grain boundaries and fragmentation of the primary solid. The occurrence of studtite and metastudtite on CSNF could have implications for the potential attenuation of released radionuclides during oxidative corrosion of CSNF in a geologic repository.

Microanalysis of colloids and suspended particles from nuclear waste glass alteration

Fully radioactive and non-radioactive Savannah River Laboratory (SRL) borosilicate glasses were reacted with water under static conditions at glass surface area to leachant volume (S/V) ratios of 340 m−1, 2000 m−1, and 20 000 m−1 for times varying from several days to several years at 90°C. A radioactive SRL 200 glass was also reacted under intermittent flow conditions at 90°C. Colloidal and suspended glass alteration particles present in the leachates of these tests were examined with analytical transmission electron microscopy (AEM). The major colloidal phase identified in all tests was partially crystalline dioctahedral smectite clay. At 20 000 m−1, the clay colloids flocculate and sediment, becoming attached to available surfaces when the ionic strength reached a value of about 0.3–0.5 mol·kg−1. Clay colloids remained stable in the solution for the duration of the experiment in tests conducted at S/V values of 2000 m−1 and 340 m−1. Calcite, dolomite, and transition metal oxide particles were more common in the intermittent flow tests but were also found in the static tests. Layered, Mn-bearing minerals, birnessite and asbolane, were found exclusively in the intermittent flow tests. Weeksite and a U-Ti phase were found exclusively in the static tests. Partially crystalline rare earth-bearing calcium phosphate colloids, structurally related to rhabdophane, were found in both types of tests. These particles exhibited a negative Ce anomaly. The affinity of phosphate for Pu was investigated through geochemical modeling. The results from this study and others were used to form a picture of colloidal development in the leachate from waste glass testing.

EELS analysis of redox in glasses for plutonium immobilization

Abstract The chemical and structural environments of f-electron elements in glasses are the origin of many of the important optical, electronic, and magnetic properties of materials incorporating these elements. Thus, the oxidation state and chemical coordination of lanthanides and actinides in host materials constitute an important design consideration in optically active glasses, magnetic materials, perovskite superconductors, and nuclear waste materials. We have made use of the characteristic line shapes of cerium to determine its oxidation state in alkali borosilicate glasses that are being developed for immobilization of plutonium. Cerium, it should be noted, is often used as a “surrogate” element for plutonium in materials design because of its similar ionic size (for Pu in the + 3 and + 4 states) and preferred chemical coordination. The solubility of the plutonium (or cerium) in a waste glass will likely be determined by its redox state in the glass. By examining several compositions of prototype immobilization glass using electron energy loss spectroscopy (EELS), we found that the redox state of cerium doped to 7 wt% could be varied by a suitable choice of alkali elements in the glass formula. Preliminary results on plutonium-doped glasses confirm the design strategy employed, leading to 5 wt% (or more) plutonium being truly dissolved in the glass.

Retention of Neptunium in Uranyl Alteration Phases Formed During Spent Fuel Corrosion

Uranyl oxide hydrate phases are known to form during contact of oxide spent nuclear fuel with water under oxidizing conditions; however, less is known about the fate of fission and neutron capture products during this alteration. We describe, the first time, evidence that neptunium can become incorporated into the uranyl secondary phase, dehydrated schoepite (UO{sub 3}{lg_bullet}0.8H{sub 2}O). Based on the long-term durability of natural schoepite, the retention of neptunium in this alteration phase may be significant during spent fuel corrosion in an unsaturated geologic repository.

Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product

Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).