Formation of Neptunium(V) Carbonates: Examining the Forceful Influence of Alkali and Alkaline Earth Cations.

Herein, neptunium(V) carbonates containing sodium or potassium cations were synthesized via chemical precipitation. Various techniques such as scanning electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetry combined with differential scanning calorimetry, X-ray diffraction, and X-ray absorption spectroscopy were used to analyze the microstructures and elemental compositions of these samples. The crystal structures of hydrated NaNpO2CO3·3H2O (P1, a = 4.3420(2) Å, b = 4.8962(2) Å, c = 10.0933(11) Å, α = 91.014(7)°, ß = 77.834(11)°, and γ = 90.004(10)°) and KNpO2CO3 (P63/mmc, a = b = 5.0994(2) Å, c = 10.2210(15) Å) were determined for the first time using the Rietveld method. The synthesized carbonates exhibited distinct structural features and decomposition behaviors, as demonstrated through thermogravimetry analysis, which revealed the presence of crystalline hydrate water in sodium neptunium(V) carbonate. Furthermore, calcium-containing neptunium(V) carbonates were synthesized and characterized. Samples with the general composition Ca0.5NpO2CO3 were obtained using the ion exchange method and chemical precipitation from solutions containing competing cations (Ca2+, Na+, K+, and Mg2+). The synthesis conditions notably affected the diffraction patterns of the obtained calcium neptunium(V) carbonates. This investigation enhances our understanding of the structural properties and thermodynamic stability of neptunium(V) carbonates in the presence of diverse cations commonly found under radioactive waste disposal conditions.

To form or not to form: PuO2 nanoparticles at acidic pH.

The aim of this study is to synthesize PuO2 nanoparticles (NPs) at low pH values and characterize the materials using laboratory and synchrotron-based methods. Properties of the PuO2 NPs formed under acidic conditions (pH 1-4) are explored here at the atomic scale. High-resolution transmission electron microscopy (HRTEM) is applied to characterize the crystallinity, morphology and size of the particles. It is found that 2 nm crystalline NPs are formed with a PuO2 crystal structure. High energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy at the Pu M4 edge has been used to identify the Pu oxidation states and recorded data are analysed using the theory based on the Anderson impurity model (AIM). The experimental data obtained on NPs show that the Pu(iv) oxidation state dominates in all NPs formed at pH 1-4. However, the suspension at pH 1 demonstrates the presence of Pu(iii) and Pu(vi) in addition to the Pu(iv), which is associated with redox dissolution of PuO2 NPs under acidic conditions. We discuss in detail the mechanism that affects the PuO2 NPs synthesis under acidic conditions and compare it with one in neutral and alkaline conditions. Hence, the results shown here, together with the first Pu M4 HERFD data on PuF3 and PuF4 compounds, are significant for the colloid facilitated transport governing the migration of plutonium in a subsurface environment.

Effective coordination numbers from EXAFS: general approaches for lanthanide and actinide dioxides.

Extended X-ray absorption fine structure (EXAFS) is a comprehensive and usable method for characterizing the structures of various materials, including radioactive and nuclear materials. Unceasing discussions about the interpretation of EXAFS results for actinide nanoparticles (NPs) or colloids were still present during the last decade. In this study, new experimental data for PuO2 and CeO2 NPs with different average sizes were compared with published data on AnO2 NPs that highlight the best fit and interpretation of the structural data. In terms of the structure, PuO2, CeO2, ThO2, and UO2 NPs exhibit similar behaviors. Only ThO2 NPs have a more disordered and even partly amorphous structure, which results in EXAFS characteristics. The proposed new core-shell model for NPs with calculated effective coordination number perfectly fits the results of the variations in a metal-metal shell with a decrease in NP size.

Enhanced Sorption of Radionuclides by Defect-Rich Graphene Oxide.

Extremely defect graphene oxide (dGO) is proposed as an advanced sorbent for treatment of radioactive waste and contaminated natural waters. dGO prepared using a modified Hummers oxidation procedure, starting from reduced graphene oxide (rGO) as a precursor, shows significantly higher sorption of U(VI), Am(III), and Eu(III) than standard graphene oxides (GOs). Earlier studies revealed the mechanism of radionuclide sorption related to defects in GO sheets. Therefore, explosive thermal exfoliation of graphite oxide was used to prepare rGO with a large number of defects and holes. Defects and holes are additionally introduced by Hummers oxidation of rGO, thus providing an extremely defect-rich material. Analysis of characterization by XPS, TGA, and FTIR shows that dGO oxygen functionalization is predominantly related to defects, such as flake edges and edge atoms of holes, whereas standard GO exhibits oxygen functional groups mostly on the planar surface. The high abundance of defects in dGO results in a 15-fold increase in sorption capacity of U(VI) compared to that in standard Hummers GO. The improved sorption capacity of dGO is related to abundant carboxylic group attached hole edge atoms of GO flakes as revealed by synchrotron-based extended X-ray absorption fine structure (EXAFS) and high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy.