Search Results (14)

This work continues the review and illustrative application to energy systems of the “Fourth-Order Best-Estimate Results with Reduced Uncertainties Predictive Modeling” (4th-BERRU-PM) methodology. The 4th-BERRU-PM methodology uses the Maximum Entropy (MaxEnt) principle to incorporate fourth-order experimental and computational information, including fourth (and higher) order sensitivities of computed model responses with respect to model parameters. The 4th-BERRU-PM methodology yields the fourth-order MaxEnt posterior distribution of experimentally measured and computed model responses and parameters in the combined phase space of model responses and parameters. The 4th-BERRU-PM methodology encompasses fourth-order sensitivity analysis (SA) and uncertainty quantification (UQ), which were reviewed in the accompanying work (Part 1), as well as fourth-order data assimilation (DA) and model calibration (MC) capabilities, which will be reviewed and illustrated in this work (Part 2). The applicability of the 4th-BERRU-PM methodology to energy systems is illustrated by using the Polyethylene-Reflected Plutonium (acronym: PERP) OECD/NEA reactor physics benchmark, which is modeled using the linear neutron transport Boltzmann equation, involving 21,976 imprecisely known parameters. This benchmark is representative of “large-scale computations” such as those involved in the modeling of energy systems. The result (“response”) of interest for the PERP benchmark is the leakage of neutrons through the outer surface of this spherical benchmark, which can be computed numerically and measured experimentally. The impact of the high-order sensitivities of the response with respect to the PERP model parameters is quantified for “high-precision” parameters (2% standard deviations) and “typical-precision” parameters (5% standard deviations). Analyzing the best-estimate results with reduced uncertainties for the 1st—through 4th-order moments (mean values, covariance, skewness, and kurtosis) produced by the 4th-BERRU-PM methodology for the PERP benchmark indicates that, even for systems modeled by linear equations (e.g., the PERP benchmark), retaining only first-order sensitivities is insufficient for reliable predictive modeling (including SA, UQ, DA, and MC). At least second-order sensitivities should be retained in order to obtain reliable predictions. Full article

This work (in two parts) will review the recently developed predictive modeling methodology called “4th-BERRU-PM” and its applicability to nuclear energy systems as exemplified by an illustrative application to the Polyethylene-Reflected Plutonium (acronym: PERP) OECD/NEA reactor physics benchmark. The acronym 4th-BERRU-PM designates the “Fourth-Order Best-Estimate Results with Reduced Uncertainties Predictive Modeling” methodology, which uses the Maximum Entropy (MaxEnt) principle to incorporate fourth-order experimental and computational information, including fourth (and higher) order sensitivities of computed model responses to model parameters, while yielding best-estimate results with reduced uncertainties for the first fourth-order moments (mean values, covariance, skewness, and kurtosis) of the optimally predicted posterior distribution of model results and calibrated model parameters. The 4th-BERRU-PM methodology encompasses the scopes of high-order sensitivity analysis (SA), uncertainty quantification (UQ), data assimilation (DA) and model calibration (MC), as will be illustrated in this work by means of the above-mentioned OECD/NEA reactor physics benchmark. This benchmark is modeled using the neutron transport Boltzmann equation involving 21,976 imprecisely known parameters, the solution of which is representative of “large-scale computations”. The model result (“response”) of interest is the leakage of neutrons through the outer surface of this spherical benchmark, which can be computed numerically and measured experimentally. Part 1 of this work illustrates the impact of high-order sensitivities, in conjunction with parameter standard deviations of various magnitudes, on the determination of the expected value and variance of the computed response in terms of the first four moments of the distribution of the uncertain model parameters. Part 2 of this work will illustrate the capabilities of the 4th-BERRU-PM methodology for combining computational and experimental information, up to and including forth-order sensitivities and distributional moments, for producing best-estimate values for the predicted responses and model parameters while reducing their accompanying uncertainties. Full article

Based on density functional theory, a first-principles study of the adsorption behavior of hydrogen atoms on the PuO₂(111) surface is carried out in this work. Models for three different surface morphologies of PuO₂(111) are established. It is found that the surface with the outermost oxygen atom (sub outer Pu atom) morphology has the best stability. Based on this model, the adsorption energy, bader charge, and electronic density of the states of a hydrogen atom at different adsorption sites are calculated. Finally, we analyzed the process of hydrogen dissociation into hydrogen atoms on the surface using the cNEB method. The results indicate that the top position of the outermost oxygen atom and the bridge position of the second outermost plutonium atom are relatively stable adsorption configurations, where hydrogen atoms lose electrons and release heat, forming O-H bonds with oxygen atoms. The density of states of O-p orbital electrons will undergo significant changes, reflecting the hybridization of O-p and H-s orbital electrons, forming a stable bonding effect. The dissociation of hydrogen molecules into two hydrogen atoms adsorbed on the top of oxygen atoms requires crossing an energy barrier of 1.06 eV. The decrease in total energy indicates that hydrogen tends to exist on the PuO₂(111) surface in a hydrogen atom state. The research results lay the foundation for theoretically exploring the hydrogenation corrosion mechanism of the PuO₂(111) surface, providing theoretical support for exploring the corrosion aging of plutonium oxide, predicting the material properties of plutonium oxide under extreme and special environments. Full article

In this study, a column experiment was employed to evaluate the nuclide migration behavior in the surrounding rock medium of a near-surface disposal site in China and to investigate the advection–dispersion behavior of tritium (H-3) and plutonium-238 (Pu-238) in highly weathered argillaceous shale. A reasonable numerical model was selected to fit the experimental breakthrough curves (BTCs) and to obtain the relevant migration parameters. The results show the following: (1) the internal structure of the highly weathered argillaceous shale exhibited heterogeneity, and the nuclide migration BTC showed characteristics of a “curve peak moving forward” and a “tail curve trailing”; (2) compared with other models, the stream tube mode could better fit the BTCs and obtain the average dispersion coefficient <D>, average distribution coefficient <K_d>, and other parameters; (3) compared to the results of the batch experiment, the distribution coefficient K_d obtained from the column experiment was smaller than that obtained from the batch experiment, which is speculated to be due to the influence of contact time and the contact area between the nuclide and the medium. Full article

Three doping models with different aluminum atomic contents on the δ-Pu surface are established. The surface energy of the doping model and the electronic structure at the Fermi level is calculated. After finding out the stable structure, the adsorption behavior of the H atoms at three different positions is simulated. It is concluded that the surface energy of the doping model obtained by substituting two Al for plutonium (100) is the lowest (0.041 eV), and the structure is the most stable. In the H adsorption, the heart site has the largest adsorption energy (4.659 eV), which is the most stable adsorption. In the work function analysis, the Pu-Al system, after adsorbing an H atom, less likely to lose electrons, thus slowing down further chemical corrosion. In the doping model, the 5f and 6d electrons of the plutonium and the 3d electrons of the aluminum have strong interactions to form a stable structure. Full article

The distributions of artificial radionuclides, radiocesium (¹³⁴Cs and ¹³⁷Cs) and plutonium isotopes (²³⁸Pu and ^239+240Pu), in the surface water around the Korean seas (East/Japan Sea and Yellow Sea) in 2011–2012 and in three sections in the North Pacific between 2011 and 2014 were examined. The ¹³⁷Cs activities in the surface water in the Korean seas in 2011 (immediately after the Fukushima nuclear power plant (NPP) accident on 17 March 2011) were comparable or not significantly different relative to those in 2010 and 2012. However, ¹³⁴Cs, which had been not detected in the study area before the Fukushima accident (under the detection limit of 0.1 mBq kg⁻¹ level), were detected rapidly in 2011 after the accident (in about 60% of the 72 samples) and gradually disappeared due to their short half-life (t_1/2 = 2.06 years) in 2012 (detected in about 16% of the 24 samples). In addition, the highest activities of radiocesium and Pu isotopes appeared locally in some stations of the Korean Strait region (located between Korea and Japan) within 1–2 months immediately after the accident. This suggests that the radioactive nuclides released immediately after the Fukushima accident were significantly introduced through the atmosphere, based on recent studies conducted in neighboring areas. We also showed that the spatial distribution of radiocesium in the North Pacific moved eastward from 2012 to 2014, and we attempted to quantify the residence time of radiocesium (¹³⁷Cs) in the Korean seas based on the long-term (tens of years scale) temporal trends of ¹³⁷Cs activity data, which have been collected since the 1960s and 1970s. The estimated retention time of ¹³⁷Cs in the East/Japan Sea and Yellow Sea were 25 ± 0.6 and 8.0 ± 0.1 years, respectively. These results are expected to be used as a preliminary study for a potential future event of a marine radioactive accident (which, of course, cannot be predicted) and as basic data for predicting the influences of radionuclide releases in the ocean. Full article

A new type of high-level waste (HLW) is generated during pyrochemical reprocessing of mixed nitride spent uranium–plutonium nuclear fuel. Such waste is a spent electrolyte, which is a mixture of chloride salts containing approximately 25.7 wt.% LiCl + 31.6 wt.% KCl + 4.1 wt.% CsCl + 5.1 wt.% BaCl₂ + 3.8 wt.% SrCl₂ + 29.7 wt.% LaCl₃, and its immobilization in reliable matrices is an actual radiochemical problem. The structure and hydrolytic stability of sodium aluminoironphosphate (NAFP) glass and a low-temperature mineral-like magnesium potassium phosphate (MPP) matrix, which are promising for spent electrolyte immobilization in the presence of hydrogen peroxide solutions simulating natural water radiolysis products, were studied in this work. The structure of the samples was studied using the SEM-EDS method. It was shown that the initial samples of NAFP glass after leaching in hydrogen peroxide solutions are prone to precipitation of crystalline phases on the surface, which are mainly represented by a mixture of sodium–iron–aluminum pyrophosphates. It was established that the leaching rate of structure-forming components of NAFP and MPP matrices generally increase, but remain at a low level, meeting modern requirements for HLW immobilization. This confirms the effectiveness of the studied matrices for the industrial use of the spent electrolyte. Full article

To deeply understand the adsorption process of oxygen on the surface of a plutonium gallium system and to reveal the chemical reaction mechanism at the initial stage of oxidative corrosion on the surface of plutonium gallium alloy at a theoretical level, the adsorption behavior of oxygen molecules on the surface of a plutonium gallium system was investigated by a first-principles approach based on density flooding theory. The results show that the molecular bond length increases and finally breaks when the surface oxygen molecule is adsorbed on the surface of plutonium gallium system and dissociates into two atomic states. The most likely adsorption position of oxygen molecules on the surface of plutonium gallium system is hole-site vertical adsorption with the adsorption energy size of 10.7 eV. The bonding between oxygen atom and surface is mainly due to the overlapping hybridization of Pu-6s, Pu-7s, Pu-6d, Ga-3d and O-2p orbitals. Oxygen molecules mainly interact with the atoms of the first layer on the surface of the plutonium gallium system. The oxygen atoms after stable adsorption are able to diffuse to the subsurface of the plutonium gallium system after overcoming the energy barrier of 16.7 eV and form a stable structure. The research results reveal the initial reaction process and adsorption law of oxygen on the surface of plutonium gallium system from microscopic level, which is helpful to further explore the surface corrosion prevention technology of plutonium gallium system and improve the reliability and safety of plutonium gallium alloy components. Full article

In order to understand the mechanism of hydrogen interaction on the surface of a plutonium–gallium system, the adsorption and dissociation behaviors of hydrogen molecules on the surface of a plutonium–gallium system were studied using the first-principles approach. The results show that the physical adsorption of hydrogen molecules occurs on the surface with a small degree of interaction; the most stable adsorption configuration is hollow-site parallel adsorption (H-b-hor1). During adsorption, charge transfer occurs mainly in the first atomic layer, and the density of states and surface function does not change significantly before and after adsorption. When the hydrogen molecule overcomes the energy barrier of 4.96 eV, it dissociates into two hydrogen atoms chemisorbed on the surface, which reduces the energy of the whole system by 1.95 eV. The essence of the hydrogen atom–surface interaction is that the 1s orbital of the hydrogen atom hybridizes with the 4s and 4p orbitals of the gallium atom and the 6s, 7s, and 6d orbitals of the plutonium atom to form a chemical bond. Full article

This contribution describes the fabrication of plutonium-adsorptive membranes by non-solvent induced phase separation. The dope solution comprised poly(vinylidene fluoride) (PVDF) and a Pu-extractive copolymer additive of PVDF-g-poly(ethylene glycol methacrylate phosphate) (EGMP) in dimethylformamide (DMF). The effects of casting conditions on membrane permeability were determined for PVDF membranes prepared with 10 wt% PVDF-g-EGMP. Direct-flow filtration and alpha spectrometry showed that membranes containing the graft copolymer could recover Pu up to 59.9 ± 3.0% from deionized water and 19.3 ± 3.5% from synthetic seawater after filtering 10 mL of 0.5 Bq/mL ²³⁸Pu. SEM-EDS analysis indicated that the graft copolymer was distributed evenly throughout the entire depth of the copolymer membranes, likely attributing to the tailing observed in the alpha spectra for ²³⁸Pu. Despite the reduction in resolution, the membranes exhibited high Pu uptake at the conditions tested, and new membrane designs that promote copolymer surface migration are expected to improve alpha spectrometry peak energy resolutions. Findings from this study also can be used to guide the development of extractive membranes for chromatographic separation of actinides from contaminated groundwater sources. Full article

The surface corrosion of plutonium in air is mainly the result of the interaction with O₂ and H₂O in air. In this paper, the co-adsorption behavior of O₂ and H₂O on a δ-Pu (100) surface is studied by the first-principle method. Two different cases of preferential adsorption of H₂O and O₂ are considered, respectively. Bader charge analysis and adsorption energy analysis are carried out on all stable adsorption configurations, and the most stable adsorption configurations are found under the two conditions. The results of differential charge density analysis, the density of states analysis and Crystal Orbital Hamilton Populations (COHP) analysis show that the two molecules can promote each other’s adsorption behavior, which leads to the strength and stability of co-adsorption being far greater than that of single adsorption. In the co-adsorption configuration, O atoms preferentially interact with Pu atoms in the surface layer, and the essence is that the 2s and 2p orbitals of O overlap and hybridize with the 6p and 6d orbitals of Pu. H atoms mainly form O–H bonds with O atoms and hardly interact with Pu atoms on the surface layer. Full article

Radioactive strontium-90 (⁹⁰Sr²⁺) is a fission byproduct of uranium and plutonium production, and therefore understanding its environmental fate is of particular importance for predicting the evolution of long-term risk from historical releases. The nonradioactive strontium cation, Sr²⁺, is a chemical analog for ⁹⁰Sr²⁺ that is often used in studies designed to understand the environmental behaviors of ⁹⁰Sr²⁺. The focus of this work was on understanding the dynamics of remobilization of strontium following evaporation to dryness in porous media. Evaporation is ubiquitous in the unsaturated zone, and has the potential to significantly impact the dynamics of transport by driving adsorption or precipitation on solid surfaces. For this work, a series of transport experiments were conducted examining the behavior of strontium over a range of pH values, ionic strengths, and concentrations. Saturated transport experiments were conducted, followed by experiments designed to examine the release and transport following evaporation to dryness. Results show increasing saturated retardation with increasing pH, decreasing ionic strength, and decreasing concentration, with the concentration exhibiting the strongest effect. Breakthrough curves at low concentrations were also found to be consistent with significant rate-limited desorption. Remobilization elution curves measured following evaporation to dryness exhibited the high initial effluent concentrations, exceeding the influent strontium concentration, most likely caused by the initial dissolution and accumulation of strontium by the advancing solution. Concentrations at later times were found to be largely consistent with the dynamics of saturated transport for the systems studied. Full article

Plutonium mononitride is one of the main fuels for Generation IV reactors and can be prepared from nitrogenation of plutonium hydride. We investigated the adsorption and dissociation of nitrogen on PuH₂ (111) surface to elaborate the initial stage of nitrogenation. The adsorption energies varied greatly with respect to the adsorption sites and orientations of the adsorbed molecule. The nitrogen exhibited preferential adsorption above the ccp site, where the molecular nitrogen was nearly parallel to the PuH₂ surface and pointed to the nearest Pu atom. The orbital hybridization and the electrostatic attraction between the Pu and N weakened the N-N bond in the adsorbed molecule. The mechanism of the dissociation process was investigated within transition state theory, and the analysis of the activation barrier indicated that dissociation of nitrogen is not the rate-determining step of nitrogenation. These findings can contribute to a better understanding of the nuclear fuel cycle. Full article

In this study, synthetic zirconolite samples with a target composition Ca_0.75Ce_0.25ZrTi₂O₇, prepared using two different methods, were used to study the stability of zirconolite for nuclear waste immobilisation. Particular focus was on plutonium, with cerium used as a substitute. The testing of destabilisation was conducted under conditions previously applied to other highly refractory uranium minerals that have been considered for safe storage of nuclear waste, brannerite and betafite. Acid (HCl, H₂SO₄) leaching for up to 5 h and alkaline (NaHCO₃, Na₂CO₃) leaching for up to 24 h was done to enable comparison with brannerite leached under the same conditions. Ferric ion was added as an oxidant. Under these conditions, the synthetic zirconolite dissolved much slower than brannerite and betafite. While the most intense conditions were observed previously to result in near complete dissolution of brannerite in under 5 h, zirconolite was not observed to undergo significant attack over this timescale. Fine zirconolite dissolved faster than the coarse material, indicating that dissolution rate is related to surface area. This data and the long term stability of zirconolite indicate that it is a good material for long-term sequestration of radioisotopes. Besides its long term durability in the disposal environment, a wasteform for fissile material immobilisation must demonstrate proliferation resistance such that the fissile elements cannot be retrieved by leaching of the wasteform. This study, in conjunction with the previous studies on brannerite and betafite leaching, strongly indicates that the addition of depleted uranium to the wasteform, to avert long term criticality events, is detrimental to proliferation resistance. Given the demonstrated durability of zirconolite, long term criticality risks in the disposal environment seem a remote possibility, which supports its selection, above brannerite or betafite, as the optimal wasteform for the disposition of nuclear waste, including of surplus plutonium. Full article