Capacity Retention for (De)lithiation of Silver Containing α-MnO2: Impact of Structural Distortion and Transition Metal Dissolution
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Engineered surface barriers (or covers) are used to isolate underlying contaminants from water, plants, animals, and humans. To understand the flow processes within a barrier and the barrier's ability to store and release water, the field hydraulic properties of the barrier need to be known. A multiyear test of the evapotranspiration (ET) barrier at the US Department of Energy's Hanford Site in the southeast of the state of Washington has yielded in situ soil water content and pressure data from multiple locations for a 9‐yr period, offering the opportunity to estimate soil water retention properties at different locations and times. The upper 2‐m layer of the ET barrier is a silt loam, and the top 1 m also contains 15% (w/w) pea gravel. Within this layer, valid monitoring data from 1995 to 2003 for four depths at 12 monitoring stations were used to determine the field water retention of the silt loam, with and without gravel. The data covered a wide range of wetness, from near saturation to the permanent wilting point, and each retention curve contained 51 to 96 data points. The data were described well with the commonly used van Genuchten water retention model. It was found that the spatial variation of the saturated and residual water content and the pore size distribution parameter was relatively small, while that of the van Genuchten α was relatively large. The effects of spatial variability of the retention properties appeared to be larger than the combined effects of added pea gravel and plant roots on the properties. Neither the primary wetting process in the winter season nor the drying process in the summer season nor time had a detectable effect on the water retention of the silt loam barrier.
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One of the main advantages of using tungsten (W) as a plasma facing material (PFM) is its low uptake and retention of tritium. However, in high purity (ITER grade) W, hydrogenic retention increases significantly with neutron-induced displacement damage in the W lattice. This experiment examines an alternative W grade PFM, ultra-fine grain (UFG) W, to compare its retention properties with ITER grade W after 12 MeV Si ion displacement damage up to 0.6 dpa (displacements per atom.) Following exposure to plasma in the DIII-D divertor, D retention was then assessed with Nuclear Reaction Analysis (NRA) depth profiling up to 3.5 µm and thermal desorption spectrometry (TDS). Undamaged specimens were also included in our test matrix for comparison. For all samples, D release peaks were observed during TDS at approximately 200 °C and 750 °C. For the ITER-grade W specimens, the intensity of the 750 °C release peak was more pronounced for specimens that had been pre-damaged. Conversely, UFG samples that had been damaged by 12 MeV Si showed enhancement of the lower temperature release peak (200 °C). NRA profiles also reveal a higher D concentration for UFG W samples up to the peak in the damage profile at a depth of 2 m. Overall, we observed that the total trapped inventory in UFG W was 20% higher than ITER grade W in the undamaged case and 10% higher in the damaged case. A comparison of NRA and TDS data indicates that a larger fraction of the total retained D is trapped near the surface (86–100%) in UFG W pre-damaged to 0.6 dpa compared with ITER grade W (39–61%). Further examination of the UFG material with microscopy is recommended for a definitive determination of the types of defects responsible for D trapping. Our results highlight some potential trade-offs associated UFG W regarding its performance from a tritium retention standpoint. That said, our TDS results indicate that this enhanced inventory can be released by baking at relatively low temperatures (<500 °C), providing an avenue for minimizing tritium retention in this material that would be practical for implementation in a tokamak.
Native cargo proteins exit the endoplasmic reticulum (ER) in COPII-coated vesicles, whereas resident and misfolded proteins are substantially excluded from vesicles by a retention mechanism that remains unresolved. We probed the ER retention process using the proteostasis regulator 4-phenylbutyrate (4-PBA), which we show targets COPII protein to reduce the stringency of retention. 4-PBA competes with p24 proteins to bind COPII. When p24 protein uptake is blocked, COPII vesicles package resident proteins and an ER-trapped mutant LDL receptor. We further show that 4-PBA triggers the secretion of a KDEL-tagged luminal resident, implying that a compromised retention mechanism causes saturation of the KDEL retrieval system. The results indicate that stringent ER retention requires the COPII coat machinery to actively sort biosynthetic cargo from diffusible misfolded and resident ER proteins.
Technetium (99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals. Two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 – 1,000 oC. After being cooled, the solid glass specimens prepared at different temperatures were analyzed for Tc oxidation state using Tc K-edge XANES. In most samples, Tc was partially oxidized from Tc(IV) to Tc(VII) as the melt temperature increased. However, Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were moderately higher than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.
Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samples exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.
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Small-scale crucible melting tests on simulated waste glass were performed with technetium-99 (Tc-99) introduced as different species in a representative low activity waste simulant. The glass saw an increase in Tc-99 retention when TcO2∙2H2O and various Tc-minerals containing reduced tetravalent Tc were used compared to tests in which pertechnetate with hexavalent Tc was used. We postulate that the increase of Tc retention is likely caused by different reaction paths for Tc incorporation into glass during early stages of melting, rather than the low volatility of reduced tetravalent Tc compounds, which has been a generally accepted idea. Additional studies are needed to clarify the exact mechanisms relevant to the effect of reduced Tc compounds on Tc incorporation into or volatilization from glass melt.
Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition-metal fission products. In this study, three Ga-doped titanate hollandite-type phases, Ba 1.33 Ga 2.67 Ti 5.33 O 16 , Ba 0.667 Cs 0.667 Ga 2 Ti 6 O 16 , and Cs 1.33 Ga 1.33 Ti 6.67 O 16 , were synthesized using a solid-state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X-ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs 1.33 Ga 1.33 Ti 6.67 O 16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high-temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.
This paper examines the mechanisms of desorption within cement pastes for superabsorbent polymers (SAP) with different sorption kinetics: retentive and non-retentive (self-releasing). Despite the different behavior in solution, both SAP types mitigated the autogenous shrinkage of cement pastes. {sup 1}H NMR and X-ray tomography showed that the cavities formed by both SAP types were saturated until 9–11 h after mixing, while the entrained water in the cavities redistributed to the cement matrix afterwards. In particular, the non-retentive SAP might have rapidly released the absorbed water, but the released water stayed in the original cavities. Therefore, the behavior of the SAP in the pore solution may not completely determine their internal curing performance in cement pastes. In particular, the initial absorption that forms the solution-filled cavities might be more important than whether the SAP are able to retain the solution for extended periods of time or not.
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Difficulty incorporating radioactive Tc-99 into glass during vitrification of low-activity waste (LAW) at the Hanford Site is a technical challenge. Previous studies suggested that the presence of sulfate salts in the melt hinder the incorporation of Re, a non-radioactive surrogate for Tc-99, into nuclear waste glass. In this study, we assessed the capability of a Ba-Sn composite to sequester sulfate during vitrification of AN-102 LAW feed and the resulting effects on Re retention in the glass. We also investigated a feed where the initial soluble sulfate source in the simulated LAW (Na2SO4) was replaced with insoluble BaSO4. The Ba-Sn composite-treated feed and BaSO4-substitute feed were compared to a control, AN-102 baseline. The feeds were prepared and then heated to temperatures from 400-1000 °C at 5 °C/min and air-quenched to room temperature. The heated samples and dried feeds were leached in deionized water. The solutions from the leach test were analyzed by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) to determine the amount of soluble sulfate as a function of temperature and the resulting solids were analyzed for Re retention. Although the Ba-Sn composite material successfully sequestered sulfate in the as-prepared LAW feed, heating to 400 °C resulted in most of the sulfate partitioning to a soluble salt phase. By 700°C, sulfate partitioning in the composite-treated feed was identical to the baseline feed. Throughout the entire temperature range the BaSO4-substitute feed behaved similarly to the composite-treated feed. The results of the study show that sequestering sulfate into a BaSO4 phase is ineffective for rhenium retention as the sulfate salt behavior was identical in the three feeds at =700 °C. The fraction of rhenium retained in the glass at 1000°C varied from 39.4-46.6% for the three feeds, which is shown to be an insignificant difference.
This study reports on the quantification of deuterium in ion-irradiated gamma-LiAlO2 pellets as a function of dose and temperature. The gamma-LiAlO2 pellets were sequentially irradiated with He+ and D2+ ions to the same fluences of 5E16, 1E17 and 2E17 He++D+/cm2 at 188 K. Additional irradiation was performed to 1E17, 2E17 and 4E17 He++D+/cm2 at 573 K. A set of the pellets irradiated at 188 K was shipped and stored at low temperatures from 80 to 132 K and characterized using time-of-flight secondary ion mass spectrometry at ~173 K. The deuterium depth profiles show a Gaussian-like distribution in the low-temperature pellets. The total deuterium retention is found to be directly proportional to the ion fluence. About 27 at.% of the implanted deuterium atoms were released from the pellet irradiated to 2E17 He++D+/cm2 at 188 K during storage at room temperature for ~1 month. Retention of the trapped or bound deuterium during ion irradiation at 573 K increases initially with ion fluence and tends to saturate at a high fluence. The amount of the released deuterium is observed to be quantitatively consistent with that of the released tritium from similar standard pellets during neutron irradiation at 573 K.
This work explores the effect of co-mingled dopants, Co(II) and Cr(III), on Tc(IV) incorporation and retention in magnetite when heat treated to 625 or 700 °C. Key trends in Tc retention in the high temperature regime were identified using a combination of density-functional-theory based ab initio molecular dynamics (AIMD) simulations, and batch experiments including solid phase characterization techniques, e.g. X-ray absorption spectroscopy. A stabilizing effect on Tc(IV) was observed when the number of Tc and Cr atoms are equal or when the magnetite surface is oversaturated with Tc and Cr inclusions. Here, oversaturation is hypothesized to force Cr from the magnetite surface to form a Cr2O3 phase, which may act as a protective layer that prevents Tc release. With the addition of Co, Tc(IV) is stabilized via redox processes. The presence of Cr in low concentrations interferes with this redox stabilization and Cr is preferentially stabilized as opposed to Tc. As a result, using Co as a stabilizing dopant for Tc may be compromised in the presence of Cr. When the relative concentration of Tc, Cr and Co is the same, or more Co atoms are added to high Cr incorporated systems, the formation of the Cr2O3 phase may be suppressed. Although waste streams with co-mingled Tc and Cr potentially may benefit from a Co dopant, since the formation of a Cr2O3 passivation layer may protect incorporated Tc from being released, the relative concentration of the three elements will be a critical parameter for maximizing effectiveness of this strategy.
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