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Uranium oxide microparticles ingestion is one of the potential sources of internal radiation doses to the humans at accidental or undesirable releases of radioactive materials. It is important to predict the obtained dose and possible biological effect of these microparticles by studying uranium oxides transformations in case of their ingestion or inhalation. Using a combination of methods, a complex examination of structural changes of uranium oxides in the range from UO 2 to U 4 O 9 , U 3 O 8 and UO 3 as well as before and after exposure of uranium oxides in simulated biological fluids: gastro-intestinal and lung-was carried out. Oxides were thoroughly characterized by Raman and XAFS spectroscopy. It was determined that the duration of expose has more influence on all oxides transformations. The greatest changes occurred in U 4 O 9 , that transformed into U 4 O 9-y. UO 2.05 and U 3 O 8 structures became more ordered and UO 3 did not undergo significant transformation., (© 2023. The Author(s).)

A Citrobacter sp. accumulates heavy deposits of metal phosphate, derived from an enzymically liberated phosphate ligand. The cells are not subject to saturation constraints and can accumulate several times their own weight of precipitated metal. This high capacity is attributable to biomineralization; uranyl phosphate accumulates as polycrystalline HUO2PO4 at the cell surface. The precipitated metal is indistinguishable from crystalline HUO2PO4.4H2O grown by chemical methods.

Antigen-specific T cell activation depends on T cell receptor-ligand interaction and costimulatory signals generated when accessory molecules bind to their ligands, such as CD28 to the B7 (also called BB1) molecule. A soluble fusion protein of human CTLA-4 (a protein homologous to CD28) and the immunoglobulin (lg) G1 Fc region (CTLA4lg) binds to human and murine B7 with high avidity and blocks T cell activation in vitro. CTLA4lg therapy blocked human pancreatic islet rejection in mice by directly affecting T cell recognition of B7+ antigen-presenting cells. In addition, CTLA4lg induced long-term, donor-specific tolerance, which may have applications to human organ transplantation.

Twenty-four Fischer 344 rats were exposed to enriched uranium dioxide (UO2) aerosols to give a mean initial lung burden of 291 +/- 89 (SD) micrograms. Groups of rats were killed at 1, 7, 180, 360, 540, and 720 days post-inhalation (PI). Their lungs were fixed and inflated. Sections cut from all five lung lobes were used to prepare CR-39 neutron-induced 235U fission fragment autoradiographs. A single traverse across a CR-39 autoradiograph of a tissue section, from the left lung of all the rats, was made using a motorized microscopic stage. The traverse was divided into 10 fields. The track counts per field were used to test for homogeneity of track distribution and to assess if there was any tendency for tracks to be related to the peripheral region of the lung. Full raster scans across the entire tissue image were made on left lung autoradiographs from two animals killed at each time point to assess the homogeneity of fission fragment track distribution throughout the entire section. There was no evidence of any temporal change in the proportion of tracks associated with the lung periphery. At all time points PI, the track distribution was significantly nonhomogeneous, suggesting a nonuniform pattern of tissue irradiation from the 234U alpha particles. At time points from 180 to 720 days PI, large clusters of macrophages were observed in some of the sections taken from all five lung lobes. The total number of macrophage clusters increased with time PI. These macrophage clusters produced many 235U fission fragment tracks within the CR-39 autoradiographs.(ABSTRACT TRUNCATED AT 250 WORDS)

A simple and rapid in vitro chemical solubility test applicable to industrial uranium trioxide (UO3) was developed together with two in vitro cellular tests using rat alveolar macrophages maintained either in gas phase or in alginate beads at 37 degrees C. Industrial UO3 was characterized by particle size, X-ray, and IR spectra, and chemical transformation (e.g., aging and hydration of the dust) was also studied. Solvents used for the in vitro chemical solubility study included carbonates, citrates, phosphates, water, Eagle's basal medium, and Gamble's solution (simulated lung fluid), alone, with oxygen, or with superoxide ions. Results, expressed in terms of the half-time of dissolution, according to International Commission on Radiological Protection (ICRP) classification (D,W,Y), varied for different hydration states of UO3, showing a lower solubility of hydrated UO3 in solvents compared to basic UO3 or UO3 heated at 450 degrees C. Two in vitro cellular tests on cultured rat alveolar macrophages (cells maintained in gas phase and cells immobilized in alginate beads) were used on the same UO3 samples and generally showed a lower solution transfer rate in the presence of macrophages than in the culture medium alone. The results of in vitro chemical and cellular tests were compared, with four main conclusions: a good reproducibility of the three tests in Eagle's basal medium the effect of hydration state on solubility, the classification of UO3 in terms of ICRP solubility criteria, and the ability of macrophages to decrease uranium solubility in medium.

In vitro cellular dissolution tests for insoluble forms of uranium oxide are technically difficult with conventional methodology using adherent alveolar macrophages. The limited number of cells per flask and the slow dissolution rate in a large volume of nutritive medium are obvious restricting factors. Macrophages in suspension cannot be substituted because they represent different and poorly reproducible functional subtypes with regard to activation and enzyme secretion. Preliminary results on the dissolution of uranium oxide using immobilized alveolar macrophages are promising because large numbers of highly functional macrophages can be cultured in a limited volume. Cells were obtained by bronchoalveolar lavages performed on baboons (Papio papio) and then immobilized after the phagocytosis of uranium octoxide (U3O8) particles in alginate beads linked with Ca2+. The dissolution rate expressed as percentage of initial uranium content in cells was 0.039 +/- 0.016%/day for particles with a count median geometric diameter of 3.84 microns(sigma g = 1.84). A 2-fold increase in the dissolution rate was observed when the same number of particles was immobilized without macrophages. These results, obtained in vitro, suggest that the U3O8 preparation investigated should be assigned to inhalation class Y as recommended by the International Commission on Radiological Protection. Future experiments are intended to clarify this preliminary work and to examine the dissolution characteristics of other particles such as uranium dioxide. It is recommended that the dissolution rate should be measured over an interval of 3 weeks, which is compatible with the survival time of immobilized cells in culture and may reveal transformation states occurring with aging of the particles.

The behavior of neutron-irradiated, simulated Chernobyl UO2 particles containing 141Ce, 144Ce, 95Zr, 95Nb, and 103Ru in the gastrointestinal tract was investigated to obtain basic information for dosimetric and risk analyses of nuclear accidents. After the UO2 particles were administered to rats intragastrically, the distribution and retention of specific radionuclides were studied by using whole-body autoradiography and gamma-spectrometric analysis of tissues. None of the radionuclides were detected in liver, kidney, muscle, bone, brain, blood, and urine. Approximately 98% of the total administered radioactivity was excreted in feces within 3 days. A two times greater intestinal retention (about 6%) of 95Nb than for the other radionuclides was observed 1 day after administration. The results indicate that this kind of relatively insoluble particulate material is not absorbed or retained significantly in the epithelial cells of the intestinal wall. Fallout particles containing high-energy beta sources, 106Ru and 144Ce, result in a very high radiation dose (up to several Gy/day) in the vicinity of a hot particle. Niobium-95 with low average beta energy (0.043 MeV (100%)) does not increase the total dose to the GI tract significantly despite its longer retention in the intestine. Evaluation of the biological effects of these particles in the GI tract by using a dosimetric model based on uniform distribution of activity may be misleading.

In this experiment the relative masses of UO2 particles per unit mass of tissue are determined between intrapulmonary airways and pulmonary tissue in rat lungs. A mean value of 0.57 +/- 0.06 (SE) was determined in tissue sections taken at 3-mm or 5-mm intervals throughout the lobes of animals killed from 2 to 35 days after inhalation. The experimental results are compared with data derived from the ICRP Lung Model for man and indicate that in the rate approximately 4% of the lung burden as opposed to about 0.02% derived for man is associated with the intrapulmonary airways. The 4% figure, if also applicable to man, would have extremely important implications in radiological protection, since the basal cells of the bronchial epithelium are thought to be sensitive to the induction of bronchogenic carcinoma.

For a large smooth particle with charges at the surface, the electrophoretic mobility is proportional to the zeta potential, which is related to the charge density by the Gouy-Chapman theory of the diffuse double layer. This classical model adequately describes the dependence of the electrophoretic mobility of phospholipid vesicles on charge density and salt concentration, but it is not applicable to most biological cells, for which new theoretical models have been developed. We tested these new models experimentally by measuring the effect of UO2++ on the electrophoretic mobility of model membranes and human erythrocytes in 0.15 M NaCl at pH 5. We used UO2++ for these studies because it should adsorb specifically to the bilayer surface of the erythrocyte and should not change the density of fixed charges in the glycocalyx. Our experiments demonstrate that it forms high-affinity complexes with the phosphate groups of several phospholipids in a bilayer but does not bind significantly to sialic acid residues. As observed previously, UO2++ adsorbs strongly to egg phosphatidylcholine (PC) vesicles: 0.1 mM UO2++ changes the zeta potential of PC vesicles from 0 to +40 mV. It also has a large effect on the electrophoretic mobility of vesicles formed from mixtures of PC and the negative phospholipid phosphatidylserine (PS): 0.1 mM UO2++ changes the zeta potential of PC/PS vesicles (10 mol % PS) from -13 to +37 mV. In contrast, UO2++ has only a small effect on the electrophoretic mobility of either vesicles formed from mixtures of PC and the negative ganglioside GM1 or erythrocytes: 0.1 mM UO2++ changes the apparent zeta potential of PC/GM1 vesicles (17 mol % GM1) from -11 to +5 mV and the apparent zeta potential of erythrocytes from -12 to -4 mV. The new theoretical models suggest why UO2++ has a small effect on PC/GM1 vesicles and erythrocytes. First, large groups (e.g., sugar moieties) protruding from the surface of the PC/GM1 vesicles and erythrocytes exert hydrodynamic drag. Second, charges at the surface of a particle (e.g., adsorbed UO2++) exert a smaller effect on the mobility than charges located some distance from the surface (e.g., sialic acid residues).

Alveolar macrophages obtained by bronchial lavage were used to assess the response of these cells to cultivation in media containing increasing concentrations of particulate UO2. The characteristic time course of uranium effects on alveolar macrophages was determined by analyzing cell viability and incorporation of uranium particles. This study reveals the ability of alveolar macrophages to phagocytize uranium particles despite the high toxicity the metal exerts on cell membranes. However, lethal effects soon become evident. Ultrastructural analysis showed uranium particles confined within membrane bound vacuoles or free in the cytoplasm. Marked ultrastructural alterations consistent with cell death were frequently observed. The elimination of the first biological barrier hinders the scavenging of particulate contaminants in alveolar spaces, thus favoring the translocation to target organs.

An analysis is described of the mass distribution of inhaled UO2 particles in the pulmonary tissue of rats by random sampling of fields in autoradiographs of histological sections. The degree of nonrandomness is compared between fields, between sections, and between lobes and interpreted in terms of the physical distribution of UO2. The error in the estimate of the mean number of charged-particle tracks from UO2 per field in the pulmonary tissue by selective tissue sampling is related to the degree of nonrandomness of the UO2 distribution. Estimates of this error in the lungs from nine animals range from 5.2 to 8.4%. When estimating this error, it is concluded that, in the case of the rat, sections should be taken at intervals of 3 mm or less throughout the lobes.

The features of uranium mining on Kazakhstan's enterprises have been examined, and uranium deposits located in the Syrdarya and Shu-Sarysu depressions have been described. Actual and projected data on the development of technological blocks in areas with complex geological structures have been analyzed and compared. Core samples were collected and, using X-ray diffraction analysis, quantitative and qualitative characteristics as well as mineral compositions of ores from various productive horizons of uranium deposits in the Syrdarya and Shu-Sarysu depressions were comparatively analyzed. It was determined that the ores in the Syrdarya depression are relatively homogeneous compared to those in the Shu-Sarysu depression, although in some places, clay minerals and gypsum are present, which hinder the uranium leaching processes. In the ores of the Shu-Sarysu depression, clay minerals that impede the uranium leaching processes are present in certain areas. Microscopic analysis of core material samples using a LEICA DM 2500 P microscope revealed particle sizes and shapes, as well as their distribution within the structure of host rocks in the productive horizon. Using X-ray diffraction analysis, mineral compositions of sediment-forming components during uranium well mining in the considered productive horizons were determined and comparatively analyzed. It was established that in the geotechnological wells of the Syrdarya depression, sediments of predominantly chemical origin, such as gypsum, are formed. However, in the geotechnological wells of the Shu-Sarysu depression, sediments of mechanical origin, consisting predominantly of quartz particles and clay minerals, are formed. Based on the obtained data, a method for intensifying underground uranium leaching in complex geological conditions has been developed, which involves dissolving sediment formations and increasing the oxidative–reductive potential of the leaching solution. The proposed and experimentally substantiated universal methodology for enhancing uranium well production involves the dissolution and prevention of precipitation using hydrofluoric acid solutions, as well as the oxidation of uranium dioxide with hydrogen peroxide. [ABSTRACT FROM AUTHOR]

This study synthesized (3-aminopropyl)triethoxysilane-functionalized porous silica (AP@MPS) to adsorb aqueous uranium (U(VI)). To comprehensively analyze the surface properties of the AP@MPS materials, a combination of SEM, BET, XPS, NMR, and zeta potential tests were conducted. The adsorption experiments for U(VI) revealed the rapid and efficient adsorption capacity of AP@MPS, with the solution condition of a constant solution pH = 6.5, an initial U(VI) concentration of 600 mg × L−1, a maximum U(VI) capacity of AP@MPS reaching 381.44 mg-U per gram of adsorbent, and a removal rate = 63.6%. Among the four types of AP@MPS with different average pore sizes tested, the one with an average pore size of 2.7 nm exhibited the highest U(VI) capacity, particularly at a pH of 6.5. The adsorption data exhibited a strong fit with the Langmuir model, and the calculated adsorption energy aligned closely with the findings from the Potential of Mean Force (PMF) analysis. The outcomes obtained using the Surface Complex Formation Model (SCFM) highlight the dominance of the coulombic force ΔG0coul as the principal component of the adsorption energy (ΔG0ads). This work garnered insights into the adsorption mechanism by meticulously examining the ΔG0ads across a pH ranging from 4 to 8. In essence, this study's findings furnish crucial insights for the future design of analogous adsorbents, thereby advancing the realm of uranium(VI) removal methodologies. [ABSTRACT FROM AUTHOR]

As UO2 is easily oxidized during the nuclear fuel cycle it is important to have a detailed understanding of the structures and properties of the oxidation products. Experimental work over the years has revealed many stable uranium oxides including UO2, U4O9 (UO2.25), U3O7 (UO2.33), U2O5 (UO2.5), U3O8 (UO2.67), and UO3, all with a number of different polymorphs. These oxides are broadly split into two categories, fluorite-based structures with stoichiometries in the range of UO2 to UO2.5 and less dense layered-type structures with stoichiometries in the range of UO2.5 to UO3. While UO2 is well characterized, both experimentally and computationally, there is a paucity of data concerning higher stoichiometry oxides in the literature. In this work we determine the ambient melting points of all the six stoichiometric uranium oxides listed above and compare them to the available experimental and/or theoretical data. We demonstrate that a family of the six ambient melting points map out a solid-liquid transition boundary consistent with the high-temperature portion of the phase diagram of uranium-oxygen system suggested by Babelot et al. [ABSTRACT FROM AUTHOR]

A promising way to recover spent nuclear fuel (SNF) is the method of extracting transuranium compounds from molten salt, which makes it possible to obtain a partial separation between transuranium compounds and lanthanides. This work is devoted to the quantum mechanical study of changes in the structure, energy and electronic properties of the main SNF component, uranium dioxide, upon the removal of oxygen from the system. The influence of the considered properties on the substitution of uranium by plutonium is also studied at a ratio, of the number of plutonium atoms to uranium atoms, of 1:7 and 1:3. The removal of oxygen leads to a narrowing of the band gap up to the transition to a conductive state at a ratio of uranium to oxygen of 2:3. The band gap narrows and metallization sets in even when uranium is replaced by plutonium. A two-stage UO2 metallization scheme based on lithium reduction and direct (electronic) reduction is proposed. [ABSTRACT FROM AUTHOR]

2-(((2,7-Dihydroxynaphthalen-1-yl)methylene)amino)-3′,6′-bis(ethylamino)-2′,7′-dimethylspiro[isoindoline-1,9′-xanthen]-3-one was synthesized using Rhodamine 6G hydrazide (prepared using literature methods) and commercially available 2,7-dihydroxynaphthalene-1-carbaldehyde via imine condensation. Structural characterization was performed using FT-IR, 1H-NMR, 13C-NMR, X-ray, and HRMS. This Schiff base shows promise as a ligand for the colorimetric analysis of uranium in water. [ABSTRACT FROM AUTHOR]

The authors synthesized a series of functionalized diatomite-based materials and assessed their U(VI) removal performance. Phosphor-derivative-modified diatomite adsorbents were synthesized by the three-route procedures: polymerisation (DIT-Vin-PAin), covalent (DIT-Vin-PAcov), and non-covalent (DIT-PA) immobilization of the functional groups. The effects of the diatomite modification have been studied using powder XRD, solid state NMR, FTIR spectroscopy, electronic microscopy, EDX, acid–base titrations, etc. The maximum adsorption capacities of DIT-Vin-PAcov, DIT-PA, and DIT-Vin-PAin samples were 294.3 mg/g, 253.8 mg/g, and 315.9 mg/g, respectively, at pH0 = 9.0. The adsorption amount of U(VI) ions using the prepared DIT-Vin-PAin was 95.63%, which is higher compared with that of the natural diatomite at the same concentration. The adsorption studies demonstrated that the phosphonic and hydroxyl groups on the surface of the diatomite played pivotal roles in the U(VI) adsorption. The U(VI) ions as a "hard" Lewis acid could easily form bonds with the "hard" donor P-containing ligands, so that the as-prepared DIT-Vin-PAin sample had excellent adsorption properties. The monolayer adsorption of the analyte on the surface of the raw diatomite and DIT-PA was observed. It was found from the thermodynamic parameters that the uptake of the U(VI) ions by the obtained adsorbents was a spontaneous process with an endothermic effect. Findings of the present work highlight the potential for using modified diatomite as effective and reusable adsorbents for the extraction of U(VI) in the waste, river, and tap waters with satisfactory results. [ABSTRACT FROM AUTHOR]

Contamination of underground water by uranium (U) and other heavy metals is a growing concern. Mesoporous silica nanoparticles (MSNs) have shown great potential as an adsorbent material for heavy metal removal. This study synthesized a novel MSN using surface-initiated atom transfer radical polymerization (SI-ATRP) and evaluated its effectiveness for removing uranium from aqueous solutions under different conditions. The particle size was reduced to 150–240 nm to enhance adsorption. Fourier transform infrared characterization and thermogravimetric analysis confirmed successful synthesis and modification. Results showed that the MSN adsorbent was highly effective in removing U, with a removal rate of 85.35% at 120 min. Temperature had a significant impact, with the highest removal rate of 96.7% achieved at 25 °C and a U concentration of 10 ppm. The highest removal rate of 91.89% was achieved at a pH of 6 and a U concentration of 50 ppm. The highest removal rate of 95.16% was achieved at 25 mg and a U concentration of 50 ppm at room temperature for 60 min. The MSNs also showed a 58.27% removal rate in a mixture solution at room temperature for 60 min. This study demonstrates the effectiveness of the MSN adsorbent for removing U under different conditions. [ABSTRACT FROM AUTHOR]

The type of reactions and the availability of monomers for the synthesis of sp2-c linked covalent organic frameworks (COFs) are considerably limited by the irreversibility of the C=C bond. Herein, inspired by the Claisen-Schmidt condensation reaction, two propenone-linked (C=C–C=O) COFs (named Py-DAB and PyN-DAB) are developed based on the base-catalyzed nucleophilic addition reaction of ketone-activated α-H with aromatic aldehydes. The introduction of propenone structure endows COFs with high crystallinity, excellent physicochemical stability, and intriguing optoelectronic properties. Benefitting from the rational design on the COFs skeleton, Py-DAB and PyN-DAB are applied to the extraction of radionuclide uranium. In particular, PyN-DAB shows excellent removal rates (>98%) in four uranium mine wastewater samples. We highlight that such a general strategy can provide a valuable avenue toward various functional porous crystalline materials. The synthesis of sp2 carbon-conjugated covalent organic frameworks is limited to a few reactions and monomers due to the poor irreversibility of carbon double bonds. Here the authors synthesize propenone-linked covalent organic frameworks for the removal of radionuclide uranium from mine wastewater samples. [ABSTRACT FROM AUTHOR]

The efficient removal of radionuclide uranium is crucial for sustainable nuclear energy and achieving a zero-carbon loop. In this study, we synthesized MXene/MnO2 nanocomposites and evaluated their ability to adsorb and reduce uranium. The results showed that the nanocomposites achieved a uranium removal rate of 99% and an adsorption capacity of 696 mg/g. Adsorption experiments were conducted under different conditions, including pH, cation, anion, and humic acid, and the uranium removal rate by the composite remained high at 91%, 70%, and 60% under the influence of pH = 4.97, 1.0 mM CaCl2, and 20 mg/L humic acid, respectively. The XRD and SEM analyses revealed that the uranium element was removed by the reduction and fixation of the composite material. These findings indicate that the MXene/MnO2 composite is an effective adsorption cleaning agent for the purification of radioactive nuclear wastewater, which has significant implications for pollution control. [ABSTRACT FROM AUTHOR]

During nuclear fuel processing, workers can potentially be exposed to repeated inhalations of uranium compounds. Uranium nephrotoxicity is well documented after acute uranium intake, but it is controversial after long-term or protracted exposure. This study aims to analyze the nephrotoxicity threshold after repeated uranium exposure through upper airways and to investigate the resulting uranium biokinetics in comparison to reference models. Mice (C57BL/6J) were exposed to uranyl nitrate (0.03–3 mg/kg/day) via intranasal instillation four times a week for two weeks. Concentrations of uranium in urines and tissues were measured at regular time points (from day 1 to 91 post-exposure). At each exposure level, the amount of uranium retained in organs/tissues (kidney, lung, bone, nasal compartment, carcass) and excreta (urine, feces) reflected the two consecutive weeks of instillation except for renal uranium retention for the highest uranium dose. Nephrotoxicity biomarkers, KIM-1, clusterin and osteopontin, are induced from day 4 to day 21 and associated with changes in renal function (arterial fluxes) measured using non-invasive functional imaging (Doppler-ultrasonography) and confirmed by renal histopathological analysis. These results suggest that specific biokinetic models should be developed to consider altered uranium excretion and retention in kidney due to nephrotoxicity. The threshold is between 0.25 and 1 mg/kg/day after repeated exposure to uranium via upper airways. [ABSTRACT FROM AUTHOR]

This work presents the results of studies of extraction properties in relation to the uranium of bis(2,2,2-trifluoroethyl)diallylamido phosphite, bis(2,2,2-trifluoroethyl)dimethylamido phosphite, and bis(N, Ndialamido) isopropyl phosphite synthesized by us earlier. Tests were carried out in a factory laboratory, as the initial solutions used nitrate solution prepared from uranium oxide (CU = 10.30 g/dm3, CHNO3 = 56.40 g/dm3) and uranium sulfate solution prepared from the chemical concentrate of natural uranium and deoxidized with sulfuric acid (CU = 10.60 g/dm3, CH2SO4 = 25.10 g/dm3). It was proved that the synthesized acyclic amido phosphites can effectively extract uranium from these technological solutions with a proper selection of technological parameters, and the degree of uranium extraction may vary from 34.43 to 95.94%. [ABSTRACT FROM AUTHOR]

There is no safe level of exposure to inorganic arsenic or uranium, yet recent studies identified sociodemographic and regional inequalities in concentrations of these frequently detected contaminants in public water systems across the US. We analyze the county-level association between racial/ethnic composition and public water arsenic and uranium concentrations from 2000–2011 using geospatial models. We find that higher proportions of Hispanic/Latino and American Indian/Alaskan Native residents are associated with significantly higher arsenic and uranium concentrations. These associations differ in magnitude and direction across regions; higher proportions of non-Hispanic Black residents are associated with higher arsenic and uranium in regions where concentrations of these contaminants are high. The findings from this nationwide geospatial analysis identifying racial/ethnic inequalities in arsenic and uranium concentrations in public drinking water across the US can advance environmental justice initiatives by informing regulatory action and financial and technical support to protect communities of color. Environmental justice and drinking water in the US: Higher proportions of Hispanic/Latino, American Indian/Alaskan Native, and non-Hispanic Black residents were associated with higher public water arsenic and uranium at the county-level, findings differed by region. [ABSTRACT FROM AUTHOR]

In this study, the possibility of sintering industrial pressed uranium dioxide pellets using microwave radiation for the production of nuclear fuel is shown. As a result, the conditions for sintering pellets in an experimental microwave oven (power 2.9 kW, frequency 2.45 GHz) were chosen to ensure that the characteristics of the resulting fuel pellets meet the regulatory requirements for ceramic nuclear fuel, including the following: a density of about 10.44 g/cm3; a volume fraction of open pores of tablets of about 0.1%; an oxygen coefficient of no more than 2.002; hydrogen content of about 0.30 ppm; and the change in density after re-sintering on average no more than 1.16%. [ABSTRACT FROM AUTHOR]

We report a comprehensive study on lanthanide monouranate–based glass–ceramic (GC) composites as potential waste forms for the immobilization of the lanthanide actinide fraction waste arising from the reprocessing of spent nuclear fuel (SNF). Although the crystalline LnUO4 precursor prepared via a nitrate route can be well stabilized in a sodium aluminoborosilicate glass, the in situ crystallization of EuUO4 in glass from oxide precursors (Eu2O3 and U3O8) is rather robust with regards to various processing conditions such as waste loadings, ceramic‐to‐glass ratios, and cooling rates. Scanning electron microscopy and transmission electron microscopy investigations revealed the detailed microstructures, where ∼1–5‐μm spheres for NdUO4 and EuUO4, and ∼1–5‐μm rectangular crystals for DyUO4 and HoUO4 were observed in residual glasses. As designed, the pentavalent uranium has been confirmed by diffuse reflectance spectroscopy. Overall, LnUO4‐based GC composite waste forms are chemically durable, offering flexible processing options with wide operating windows for SNF and process waste stream management. [ABSTRACT FROM AUTHOR]

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2. It is found that UO2+x thin films are hypostoichiometric (x<0) with in‐plane tensile strain, while they are hyperstoichiometric (x>0) with in‐plane compressive strain. Different from strain engineering in non‐actinide oxide thin films, the epitaxial strain in UO2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO2+x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films. [ABSTRACT FROM AUTHOR]

Quantifying fission product yield uncertainty contribution to reactor burnup calculation is an important aspect of pebble-bed High Temperature Gas-cooled Reactor (pebble-bed HTGR) uncertainty analysis. In this work, uncertainty propagation of fission product yield to pebble-bed HTGR burnup calculation is conducted. Uncertainty of fission product yields from four fissile isotopes, namely 233U, 235U, 239Pu and 241Pu, are considered. The stochastic sampling-based uncertainty analysis method is adopted and fission product yield covariance matrices are estimated from ENDF/B-VII.1. The covariance matrix for each fissile actinide is estimated based on the Bayesian method and fission product yields are assigned with log-normal distribution in the sampling process with the Latin Hypercube Sampling (LHS) method. Since the fission fraction from 239Pu plays an important role in fissions of fuels with high burnup value in pebble-bed HTGR, the fission product yield uncertainty contribution from 239Pu is highlighted in this work. The result shows that, in the burnup equilibrium state of pebble-bed HTGR, fission product yield uncertainty contributions from 235U and 239Pu to relative uncertainty of keff are 0.027% and 0.026%, respectively. The overall uncertainty contribution from four fissile isotopes (233U, 235U, 239Pu and 241Pu) to relative uncertainty of equilibrium core keff is 0.038%. Furthermore, fission product yield uncertainty has an important contribution to the nuclide density uncertainty of fission products. The most relative uncertainty, 10.82%, is observed in 109Ag contributed from the fission product yield uncertainty of 239Pu at the burnup equilibrium state. This indicates the uncertainty contribution from the fission product yield of 239Pu cannot be neglected in pebble-bed HTGR burnup uncertainty analysis. [ABSTRACT FROM AUTHOR]

Unconsolidated sandstone uranium deposits exploited by the in situ leaching (ISL) method, contain complex tetravalent and hexavalent uranium compounds, mostly as UO2 and UO3 oxides that have different dissolution rates in sulfuric acid solutions. This work investigates a reactive transport model that takes into account the dissolution of both UO2 and UO3 in sulfuric acid solution together with possible interactions with rock minerals during the ISL uranium extraction. Several empirical reaction rate constants were determined during lab experiments on uranium extraction assays, including dissolution rates of tetravalent and hexavalent uranium oxides, and the dissolution rate of rock components by sulfuric acid solution. Effects on the recovery of solution flow rates and ratios between tetravalent and hexavalent uranium compounds are also investigated. The experimental dissolution constants were then used in the proposed reactive transport model to be applied to a real case study in Kazakhstan for comparing the 16 months history matching of an exploitation block consisting of 18 well injectors and 4 producers. The obtained numerical results show good agreement with empirical data gathered during exploitation. [ABSTRACT FROM AUTHOR]

Production of phosphate fertilizers (PF), without uranium recovery, amounts to dispersing uranium compounds on agricultural fields. These compounds are naturally hidden in phosphate rock deposits prior to processing. Such a dispersion is a cumulative environmental damage, that may become rather catastrophic in few hundred years, under the current rates & impurities of phosphate fertilization of agricultural lands. It is also an avoidable irreversible waste of one of the world's major energy resources. This study demonstrates quantitatively the low impact of U costs on the nuclear power generation costs, which happens, so far, to be a main reason for nonrecovery of uranium from the present PF industry. It reports on novel procedures for (i) estimating the required U feed to nuclear power plants (NPPs), (ii) pricing U as a function of its cumulative world production, and (iii) for quantifying U accumulation in phosphate fertilized lands. We also demonstrate that countries of the eastern Mediterranean can, in the long run, become collectively U partially self-sufficient, by recovering U from their phosphate resources, to power 13.2% of their entire electric energy generation contemporary needs. [ABSTRACT FROM AUTHOR]

The use of tetra-alkylcarbamides as novel ligands: N,N-butyl-N',N'-hexylurea (L1: ABHU), and N,N-butyl-N',N'-pentylurea (L2: ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO3 and NO3− concentrations in the aqueous phase on the distribution ratio of U(VI) were examined. Under 5 mol/L HNO3 concentration, DU reached 5.02 and 4.94 respectively without third-phase formation. During the extraction, slope measurements and IR spectral analysis revealed that the U(VI) complexes are a form of UO2(NO3)2·2L for both ligands. In addition, thermodynamic studies showed that the uranium extraction reaction was a spontaneous exothermic reaction. The deep structural analysis of the complexes was realized with DFT calculation. The bond length, bond properties, and topology of the complexes were discussed in detail to analyze the extraction behavior. This study enriches the coordination chemistry of U(VI) by tetra-alkylcarbamides, which may offer new clues for the design and synthesis of novel ligands for the separation, enrichment, and recovery of uranium in the nuclear fuel cycle. [ABSTRACT FROM AUTHOR]

A series of solid-phase uranium extractants were prepared by post-synthesis impregnation of a mesoporous silica support previously functionalized with octyl chains by direct silanization. Five materials were synthesized with 0, 0.2, 0.3, 0.4 and 0.5 mmol of the amidophosphonate ligand DEHCEBP per gram of functionalized solid, and the effect of the ligand concentration on the uranium extraction efficiency and selectivity of the materials was investigated. Nitrogen adsorption–desorption data show that with increasing ligand loadings, the specific surface area and average pore volume decrease as the amidophosphonate ligand fills first the micropores and then the mesopores of the support. Acidic uranium solutions with a high sulfate content were used to replicate the conditions in ore treatment leaching solutions. Considering the extraction kinetics, the equilibration time was found to increase with the ligand concentration, which can be explained by the clogging of micropores and the multilayer arrangement of the DEHCEBP molecules in the materials with their highest ligand contents. The fact that the equilibrium ligand/uranium ratio is about 2 mol/mol regardless of the ligand concentration in the material suggests that all the ligand molecules remain accessible for extraction. The maximum uranium extraction capacities ranged from 30 mg∙g−1 at 0.2 mmol∙g−1 DEHCEBP to 54 mg∙g−1 in the material with 0.5 mmol∙g−1 DEHCEBP. These materials could therefore potentially be used as solid-phase uranium extractants in acidic solutions with high sulfate concentrations. [ABSTRACT FROM AUTHOR]

This review summarizes the recent developments regarding the use of uranium as nuclear fuel, including recycling and health aspects, elucidated from a chemical point of view, i.e., emphasizing the rich uranium coordination chemistry, which has also raised interest in using uranium compounds in synthesis and catalysis. A number of novel uranium coordination features are addressed, such the emerging number of U(II) complexes and uranium nitride complexes as a promising class of materials for more efficient and safer nuclear fuels. The current discussion about uranium triple bonds is addressed by quantum chemical investigations using local vibrational mode force constants as quantitative bond strength descriptors based on vibrational spectroscopy. The local mode analysis of selected uranium nitrides, N≡U≡N, U≡N, N≡U=NH and N≡U=O, could confirm and quantify, for the first time, that these molecules exhibit a UN triple bond as hypothesized in the literature. We hope that this review will inspire the community interested in uranium chemistry and will serve as an incubator for fruitful collaborations between theory and experimentation in exploring the wealth of uranium chemistry. [ABSTRACT FROM AUTHOR]

Unavoidable organics in uranium wastewater or contaminated waters derive great challenges to traditional uranium removal techniques. Here, a drivingpower enhanced photocatalytic fuel cell (DEPFC) is designed by using a carbon felt (CF)-based UiO-66-NH 2 derived zirconia (ZrO 2)/N-doped porous carbon (ZrON-C/CF) cathode and a monolithic photoanode, composing of a front FTO glass-based BiVO 4 film and a rearmounted Si photovoltaic cell, for effectively oxidizing organics and simultaneously reducing UO 2 2+ from complex wastewater under sunlight illumination. The water contact angle measurements demonstrate that ZrO 2 can improve the hydrophilia of cathode thus increases the contact between UO 2 2+ and cathode. The density functional theory indicates that N-doping can enhance the electronegativity of cathode and increases UO 2 2+ adsorption. Meanwhile, the enhanced UO 2 2+ reduction facilitates the charge separation in BiVO 4 film, therefore enhancing the organic oxidation. Consequently, under AM 1.5 illumination, the designed DEPFC can remove almost 100% of UO 2 2+ and simultaneous degrade 99% organics within 40 min [Display omitted] • A novel drivingpowers enhanced photocatalytic fuel cell system was fabricated. • The introduction of photovoltaic cell provides greater drivingpowers than conventional PFC. • The incorporation of ZrO 2 can improve the hydrophilia of cathode. • N-doping can enhance the electronegativity and enrich nitrogen-containing functional group of cathode. • The DEPFC can remove almost 100% of U(VI) and simultaneous degrade more than 99% TC under 40 min illumination. [ABSTRACT FROM AUTHOR]

Residues generated from the uranium purification process, characterized by a high uranium content, pose a significant challenge for recovery through leaching and present a considerable environmental threat. After using XRD and SEM-mapping characterization analysis combined with the BCR continuous graded extraction test to analyze the content of different states of uranium, it was found that the main reason why the uranium in the residue was difficult to leach because it was encapsulated by SiO 2 crystals. Using NH 4 HF 2 as a leaching agent, a leaching study of uranium in the residue was carried out, and the results showed that the H+ and F− produced by NH 4 HF 2 could react with SiO 2 , destroying the crystal lattice of SiO 2 and causing the encapsulated uranium to come into contact with the leaching agent, facilitating the leaching of uranium in the residue. The optimum conditions for uranium leaching were 10% mass fraction of NH 4 HF 2 , a liquid-solid ratio of 30:1, a reaction temperature of 30 °C and a reaction time of 120 min, and the leaching efficiency of uranium from the residue was as high as 98.95%. The leaching kinetics of uranium by NH 4 HF 2 were consistent with the mixed controlled model in the shrinking core models, indicating that the surface chemical reaction and mass diffusion dominated both uranium leaching processes. This may provide a viable method for resource recovery and the treatment of uranium purification residues. • Up to 98.95 % leaching of uranium from extremely difficult-to-leach uranium-containing residue. • BCR continuous graded extraction experiments were carried out to explore the morphology of difficult-to-leach uranium. • Ammonium hydrogen fluoride disrupts the silica lattice structure and promotes leaching of encapsulated uranium. [ABSTRACT FROM AUTHOR]

Understanding the speciation of technogenic uranium in natural systems is crucial for estimating U migration and bioavailability and for developing remediation strategies for contaminated territories. Reference EXAFS data of model laboratory‐prepared uranium compounds ('standards') are necessary to analyze U‐contaminated samples from nuclear legacy sites. To minimize errors associated with measurements on different synchrotrons, it is important not only to compare data obtained on environmentally contaminated samples with the literature but also with 'standards' collected at the same beamline. Before recording the EXAFS spectra, all reference compounds were thoroughly characterized by Raman spectroscopy and powder X‐ray diffraction. The U(VI) local molecular environments in the reference compounds, i.e. uranyl oxyhydroxides, phosphates, carbonates and uranates, were examined using XAFS. Based on the EXAFS fitting results obtained, including the nature of the bonding, interatomic distances and coordination numbers, parameters that are typical for a particular U compound were differentiated. Using data for 'standards', U speciation in the sample of radioactively contaminated soil was determined to be a mixture of U oxyhydroxide and carbonate phases. [ABSTRACT FROM AUTHOR]

Hydrated titanium dioxide was modified with K2Co[Fe(CN)6] nanoparticles with size up to 10 nm. The nanoparticles are unaggregated, since they are stabilized by the inorganic matrix. The optimal modifier content, which allows us to obtain large granules of the composite, was found. The modifier nanoparticles loose titanium dioxide increasing its micro- and mesoporosity. Sorption of both cationic and anionic forms of U(VI) under batch conditions was investigated. The modifier improves sorption from one- and multicomponent solutions, especially in weakly acidic and neutral media: the removal degree of U(VI) reaches 80–100%. When the concentration of U(VI) is 0.02–0.04 mmol dm−3, the modifier increases the degree of U(VI) removal from river water by 50%. Sorption rate is described by the model of pseudo-second-order. The modifier slows down sorption of cations, while no effect on the rate of anion sorption has been found. Sorption isotherms are described with Freundlich model. The K2Co[Fe(CN)6] nanoparticles decrease energetic heterogeneity of sorption centers. [ABSTRACT FROM AUTHOR]

The title compound, [UO2(acac)2(H2O)] consists of a uranyl(VI) unit ([O=U=O]2+) coordinated to two monoanionic acetylacetonate (acac, C5H7O2) ligands and one water molecule. The asymmetric unit includes a one-half of a uranium atom, one oxido ion, one-half of a water molecule and one acac ligand. The coordination about the uranium atom is distorted pentagonal-bipyramidal. The acac ligands and Ow atom comprise the equatorial plane, while the uranyl O atoms occupy the axial positions. Intermolecular hydrogen bonding between complexes results in the formation of two-dimensional hexagonal void channels along the c-axis direction with a diameter of 6.7 Å. The monoclinic (P21/c space group) polymorph was reported by Alcock & Flanders [(1987). Acta Cryst. C43, 1480-1483]. [ABSTRACT FROM AUTHOR]

Oil production (1942-1966) and uranium extraction (1953-1961) from the Alum Shale Formation in Kvarntorp, Sweden has had a great environmental impact on the area. Other industrial activities have also contributed to pollution. This study combines archive research with monitoring data and new sampling in order to assess the extent of the impact. During the production period, process water containing oil, phenols, sulfur compounds and high concentrations of iron reached the stream resulting in low water quality downstream. Also the landscape was reshaped, resulting in water filled pit lakes and a 100-meter-high shale waste deposit. Today, past alum shale activities still have an impact on the environment. Sulfate concentrations in the pit lakes are significantly higher than background values and downstream water also shows higher concentrations of elements such as nickel and uranium. The waste deposit still has a hot interior and an important question is the cooling rate and possible future leaching scenarios. Remaining hydrocarbons show today only a local impact while trace elements are transported downstream and affect a larger area. [ABSTRACT FROM AUTHOR]

Disproportionation, where a chemical element converts its oxidation state to two different ones, one higher and one lower, underpins the fundamental chemistry of metal ions. The overwhelming majority of uranium disproportionations involve uranium(III) and (V), with a singular example of uranium(IV) to uranium(V/III) disproportionation known, involving a nitride to imido/triflate transformation. Here, we report a conceptually opposite disproportionation of uranium(IV)-imido complexes to uranium(V)-nitride/uranium(III)-amide mixtures. This is facilitated by benzene, but not toluene, since benzene engages in a redox reaction with the uranium(III)-amide product to give uranium(IV)-amide and reduced arene. These disproportionations occur with potassium, rubidium, and cesium counter cations, but not lithium or sodium, reflecting the stability of the corresponding alkali metal-arene by-products. This reveals an exceptional level of ligand- and solvent-control over a key thermodynamic property of uranium, and is complementary to isolobal uranium(V)-oxo disproportionations, suggesting a potentially wider prevalence possibly with broad implications for the chemistry of uranium. Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium [ABSTRACT FROM AUTHOR]

New syntheses have been developed for the synthesis of (borohydrido-κ³H)tris[η5-(trimethylsilyl)cyclopentadienyl]uranium(IV), [U(BH4)(C8H13Si)3] or Cp'3U(BH4) (Cp' = C5H4SiMe3) and its structure has been determined by single-crystal X-ray crystallography. This compound crystallized in the space group P... and the structure features three η5-coordinated Cp' rings and a κ³-coordinated (BH4)- ligand. [ABSTRACT FROM AUTHOR]

New syntheses have been developed for the synthesis of (borohydrido-κ³H)tris[η5-(trimethylsilyl)cyclopentadienyl]uranium(IV), [U(BH4)(C8H13Si)3] or Cp'3U(BH4) (Cp' = C5H4SiMe3) and its structure has been determined by single-crystal X-ray crystallography. This compound crystallized in the space group P... and the structure features three η5-coordinated Cp' rings and a κ³-coordinated (BH4)- ligand. [ABSTRACT FROM AUTHOR]

The feasibility of uranium recovery from lean uranium solutions (like seawater) having extremely low concentrations has been explored using an iminodiacetic acid (ImDAc) modified mesoporous silica (MPS) adsorbent (MPS-ImDAc). Foremost, synthesis of the MPS, its chemical modification using ImDAc and characterization were emphasized. The MPS was prepared by a template assisted preparative route, and the incorporation of ImDAc moiety to the MPS was accomplished through chemical functionalization. Subsequently, the adsorption efficacy of the MPS-ImDAc has been investigated as a function of the pH of the aqueous medium, kinetics of adsorption, uranium loading to the adsorbent, and the effect of interfering elements. Zeta potential analyses were also conducted to investigate the role of ImDAc functional groups and charges at different pH values, and the study suggested that the negatively charged acetate moiety is likely responsible for adsorption above pH.The adsorption has been modeled using pseudo-first and second order kinetic and the Langmuir adsorption isotherm models. Superior adsorption of uranium above pH 4, based on cation exchange mechanism that leads to an adsorption capacity of approximately 110 mg/g was observed. Adsorption characteristics have been investigated from a synthetic seawater composition with all possible interfering elements, and the study confirmed that though sodium is significantly present in sea water, it has negligible adsorption to ImDAc and thus pose no competition to uranium adsorption. Small pore size and massive surface area of MPS in combination with uranium selective ImDAc functional group offer excellent uranium adsorption. [Display omitted] [ABSTRACT FROM AUTHOR]

The use of permeable reactive bio-barriers (Bio-PRBs) is a developing method for remediation of uranium groundwater pollution. However, some remediation effects are difficult to estimate when because of the subsurface environment. Advanced knowledge of uranium migration and reactions in Bio-PRBs is crucial for successful practical application. In this study, a bidirectional kinetic reaction model was developed for predicting uranium reduction in a Bio-PRB system. The research demonstrates that the model is able to predict the uranium migration and rapidly evaluate the Bio-PRBs performance. The results show that contact period and microbial growth are the key factors that affect the remediation performance of Bio-PRBs. Microbial growth could lead to a decrease in hydraulic conductivity (K). The hydraulic conductivity loss in the free microorganisms (FM) group was 0.8–2.3 m/d, which was significantly smaller than the immobilized microorganism (IM) group (0.8–5.2 m/d). Compared to the IM group, the simulation results reveal that longer contact reaction period improves the remediation performance of SO 4 2− and uranium by 32.6% and 21.7%, respectively. The bidirectional reaction between microorganisms and pollutants leads to a decrease in the remediation efficiency. In addition, the model can be used to design standard Bio-PRBs for real field of uranium contanminated groundwater. To meet the remediation goal of groundwater, the width of IM group needs to be increased to 250 cm while 500 cm for FM group. Therefore, IM-PRBs save costs significantly. The model has successfully optimized Bio-PRBs and predicted uranium contaminant-plume evolution and microbial growth inhibition in different Bio-PRBs. [Display omitted] • The reaction model could quickly evaluate the performance of different Bio-PRBs. • Sulfate affected the uranium remediation by controlling microbial growth. • The reaction contact time was the key point to improve Bio-PRBs performance. • Bidirectional reaction model could be as a tool to develop Bio-PRBs for real field. [ABSTRACT FROM AUTHOR]

This paper reports a study of leaching of uranium and P2O5 from Syrian phosphate using commercial nitric and hydrochloric acids. The effect of different parameters such as the liquid:solid ratio, the acid concentration, the leaching time and the reaction temperature is studied aiming optimization of various process parameters and hence maximization of uranium and P2O5 recovery. The optimal dissolution efficiency of uranium and P2O5 in hydrochloric acid referring to 88.46 % and 91.37 %, respectively, is obtained under the following conditions: a liquid:solid ratio of 5:1 mL:g, an acid concentration of 29.6 %, contact time of 25 min and a reaction temperature of 40°C. The optimal dissolution efficiency of uranium and P2O5 in nitric acid referring to 94.16 % and 93.07 %, respectively, is obtained under the following conditions: a liquid:solid ratio of 6:1 mL:g, an acid concentration of 40.9 %, contact time of 20 min and a reaction temperature of 50°C. [ABSTRACT FROM AUTHOR]

This work reports the architecture of a novel class of membrane-supported 1D MOF hollow superstructures, by using the bio-inspired polydopamine (PDA) mediated contra-diffusion synthetic strategy, for facile and efficient separation of uranium in a flow-through mode. PDA chemistry was firstly employed to modify the inner surfaces of the cylindrical pore channels of polycarbonate track-etched membrane (PCTM), thereby regulating the heterogeneous nucleation and interfacial growth of ZIF-8 crystals. ZIF-8 hollow superstructures embedded in membrane matrix with well-defined 1D channels were obtained. These membrane-supported MOF hollow superstructures then, for the first time, served as integrated chromatographic micro-column arrays for effective entrapment of uranium from aqueous solutions. It is highlighted that the PCTM supported ZIF-8 superstructures exhibited outstanding uranium entrapment ability in both traditional batch mode (capacity 62.3 mg/g) and fast flow-through mode (removal rate over 90% for 3 level). Moreover, new insights into the interaction between ZIF-8 and uranyl ions were obtained, suggesting that an ion-exchange mechanism involved synergistic effect was responsible for uranium binding, especially in a long-term exposure. The membrane-supported 1D MOF hollow superstructures developed in this work represent a new category of organic-inorganic composite membrane. And, it is envisioned that the methodology established in this work would be versatile for preparing more MOF superstructures with deployable form for separation applications. In summary, a novel class of membrane-supported ZIF-8 hollow superstructure was fabricated for effective separation of uranyl ions. A novel class of membrane-supported ZIF-8 hollow superstructure, fabricated by polydopamine-mediated contra-diffusion synthesis, serves as integrated chromatographic micro-column arrays for effective separation of uranyl ions. Image 1 • New membrane-supported 1D MOF hollow superstructures for facile uranium separation. • Novel strategy using bio-inspired polydopamine mediated contra-diffusion synthesis. • Efficient uranium entrapment and good reusability. • New insights into the interaction between MOFs and uranyl ions. [ABSTRACT FROM AUTHOR]