Level, distribution and sources of Np, Pu and Am isotopes in Peter the Great Bay of Japan sea.

Transuranium elements such as Np, Pu and Am, are considered to be the most important radioactive elements in view of their biological toxicity and environmental impact. Concentrations of 237Np, Pu isotopes and 241Am in two sediment cores collected from Peter the Great Bay of Japan Sea were determined using radiochemical separation combined with inductively coupled plasma mass spectrometry (ICP-MS) measurement. The 239,240Pu and 241Am concentrations in all sediment samples range from 0.01 Bq/kg to 2.02 Bq/kg and from 0.01 Bq/kg to 1.11 Bq/kg, respectively, which are comparable to reported values in the investigated area. The average atomic ratios of 240Pu/239Pu (0.20 ± 0.02 and 0.21 ± 0.01) and 241Am/239+240Pu activity ratios (3.32 ± 2.76 and 0.45 ± 0.17) in the two sediment cores indicated that the sources of Pu and Am in this area are global fallout and the Pacific Proving Grounds through the movement of prevailing ocean currents, and no measurable release of Np, Pu and Am from the local K-431 nuclear submarine incident was observed. The extremely low 237Np/239Pu atomic ratios ((2.0-2.5) × 10-4) in this area are mainly attributed to the discrepancy of their different chemical behaviors in the ocean due to the relatively higher solubility of 237Np compared to particle active plutonium isotopes. It was estimated using two end members model that 23% ± 6% of transuranium radionuclides originated from the Pacific Proving Grounds tests, and the rest (ca. 77%) from global fallout.

Pyridine Diphosphonate Ligand for Stabilization of Tetravalent Uranium and Neptunium in Aqueous Medium under Aerobic Conditions.

Though uranium is usually present in its +6 oxidation state (as uranyl ion) in aqueous solutions, its conversion to oxidation states such as +4 or +5 is a challenging task. Electrochemical reduction and axial oxo activation are the preferred methods to get stable unusual oxidation states of uranium in an aqueous medium. In previous studies, dicarboxylic acid has been used to stabilize UO2+ in aqueous alkaline solutions. In the present work, a diphosphonate ligand was chosen due to its higher complexing ability compared to that of the carboxylate ligands. Neptunium complexation studies with 2,6-pyridinediphosphonic acid (PyPOH) indicated the formation of different species at different pH values and the complexation facilitates disproportionation of NpO2+ to Np4+ and NpO22+ at pH 2. Hexavalent actinides form insoluble complexes in aqueous media at pH = 2, as confirmed by UO22+ complexation studies. The in situ complexation-driven precipitation resulted in conversion to pure Np4+ in aqueous media as the Np4+-PyPOH complex. A strong complexing ability of the PyPOH ligand toward the Np4+ ion is also seen for the stabilization of the electrochemically generated U4+ in aqueous medium under aerobic conditions. The U4+-PyPOH complex was found to be stable for 3 months. Raman, UV-vis, fluorescence, and cyclic voltametric studies along with density functional theory (DFT) calculations were done to get structural insights into the PyPOH complexes of actinides in different oxidation states.

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2'-bipyridine.

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.

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.

Laboratory-based X-ray spectrometer for actinide science.

X-ray absorption and emission spectroscopies nowadays are advanced characterization methods for fundamental and applied actinide research. One of the advantages of these methods is to reveal slight changes in the structural and electronic properties of radionuclides. The experiments are generally carried out at synchrotrons. However, considerable progress has been made to construct laboratory-based X-ray spectrometers for X-ray absorption and emission spectroscopies. Laboratory spectrometers are reliable, effective and accessible alternatives to synchrotrons, especially for actinide research, which allow dispensing with high costs of the radioactive sample transport and synchrotron time. Moreover, data from laboratory spectrometers, obtained within a reasonable time, are comparable with synchrotron results. Thereby, laboratory spectrometers can complement synchrotrons or can be used for preliminary experiments to find perspective samples for synchrotron experiments with better resolution. Here, the construction and implementation of an X-ray spectrometer (LomonosovXAS) in Johann-geometry at a radiochemistry laboratory is reported. Examples are given of the application of LomonosovXAS to actinide systems relevant to the chemistry of f-elements, the physical chemistry of nuclear power engineering and the long-term disposal of spent nuclear fuel.

Sensing and extraction of hazardous metals by di-phosphonates of heterocycles: a combined experimental and theoretical study.

In this study, pyridine and phenanthroline diphosphonate ligands were investigated for the first time from the context of solvent extraction and potentiometric sensing of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) cations. The extraction efficiency under the same conditions for phenanthroline-diphosphonates is considerably higher than that for pyridine ligands. At the same time, the pyridine-diphosphonates show pronounced selectivity towards lead in this metal series. The extraction systems with phenanthroline diphosphonates provided the most efficient extraction of Cd(II) and Pb(II) cations (D > 90). The newly developed pyridine and phenanthroline diphosphonate ligands have proven to be highly effective components in plasticized polymeric membranes. These ligands can be utilized to construct potentiometric ion sensors that exhibit a notable response specifically towards Pb(II) cations. Among the previously reported tetradentate ligands, the phenanthroline diphosphonate ligand, when incorporated into plasticized polymeric membranes, demonstrated the highest sensitivity towards d-metals and Pb(II). The structure of the single crystal complex of Pb(II) and Cd(II) with pyridine-diphosphonates was studied by X-ray diffraction analysis (XRD). The geometry of Cu(II), Zn(II), Cd(II) and Pb(II) complexes and the energy effect of the complex formation, including pseudo-oligomerization reactions, were determined by DFT calculations. The high sensing and extraction efficiency of diphosphonates with respect to Pb(II) is consistent with the minimum values of complex formation energies. The variation in sensory and extraction properties observed among the studied diphosphonate ligands is influenced by the ability to form polynuclear complexes with Pb(II) cations, whereas such properties are absent in the case of Cd(II) cations.

Insights into Actinium Complexes with Tetraacetates─AcBATA versus AcDOTA: Thermodynamic, Structural, and Labeling Properties.

In the current research, we conducted a comparative study of the Ac3+ complex with H4DOTA and H4BATA. The stability constants of the [AcBATA]- and [AcDOTA]- complexes were studied directly by extraction methods. We discovered that the thermodynamic properties of the [AcBATA]- complex are superior to those of [AcDOTA]-. Moreover, the fast kinetics of H4BATA complexation with Ac3+ during the radiolabeling experiment was observed already at room temperature. Ac3+ was placed inside the macrocyclic cavity of the [AcBATA]- complex, preventing the release of the cation. According to DFT studies, two possible conformations were found, where two pendant arms coordinate with the metal cation on one side of the azacrown cavity and two on the other side, or three pendant arms are located on one side and one on the other. Finally, high inertness in vitro and in vivo of [AcBATA]- was discovered, making the H4BATA ligand highly preferable for application as a component of actinium-based radiopharmaceuticals.

The features of Cs sorption onto peaty-podzolic-gleyic soil.

This article studies sorption regularities and estimates the strength of 137Cs fixation by various soil horizons in peaty-podzolic-gleyic soils under a model experiment. The interaction time varied from 1 week to 3 months while Cs concentration varied from trace to micromolar concentrations. To understand the interaction mechanisms of cesium with individual soil components, we used the method of sequential removal of organic matter and non-silicate iron compounds from the soil before the sorption experiment. Illite and vermiculite were found to be the main soil components for radiocesium sorption in the mineral soil horizons. The highly selective positions (FES - frayed edge sites) of the abovementioned minerals fixed radiocesium so strongly that even strong acid solutions could not extract it from soil. Organic matter significantly contributed to the fixation of radiocesium in the soil only in the ELih horizon which contained 4.71% Corg. In the ELg horizon, a small amount of organic matter was able to inhibit sorption by blocking highly selective to radiocesium FES. The Tessier sequential extraction method of radiocesium revealed that all the studied soil samples could strongly fix the radionuclide. Increasing the interaction period up to three months under periodic wetting and drying contributed to the increased proportion of strongly bound 137Cs. The results of sorption experiments carried out before and after the removal of non-silicate iron compounds from the soil indicate that 137Cs has little or no sorption on the surface of iron hydroxides.

Super-oxidized "activated graphene" as 3D analogue of defect graphene oxide: Oxidation degree vs U(VI) sorption.

Porous carbons are not favorable for sorption of heavy metals and radionuclides due to absence of suitable binding sites. In this study we explored the limits for surface oxidation of "activated graphene" (AG), porous carbon material with the specific surface area of ∼2700 m2/g produced by activation of reduced graphene oxide (GO). Set of "Super-Oxidized Activated Graphene" (SOAG) materials with high abundance of carboxylic groups on the surface were produced using "soft" oxidation. High degree of oxidation comparable to standard GO (C/O=2.3) was achieved while keeping 3D porous structure with specific surface area of ∼700-800 m2/. The decrease in surface area is related to the oxidation-driven collapse of mesopores while micropores showed higher stability. The increase in the oxidation degree of SOAG is found to result in progressively higher sorption of U(VI), mostly related to the increase in abundance of carboxylic groups. The SOAG demonstrated extraordinarily high sorption of U(VI) with the maximal capacity up to 5400 µmol/g, that is 8.4 - fold increase compared to non-oxidized precursor AG, ∼50 -fold increase compared to standard graphene oxide and twice higher than extremely defect-rich graphene oxide. The trends revealed here show a way to further increase sorption if similar oxidation degree is achieved with smaller sacrifice of surface area.

Oxidation and Nanoparticle Formation during Ce(III) Sorption onto Minerals.

The sorption of Ce(III) on three abundant environmental minerals (goethite, anatase, and birnessite) was investigated. Batch sorption experiments using a radioactive 139Ce tracer were performed to investigate the key features of the sorption process. Differences in sorption kinetics and changes in oxidation states were found in the case of the sorption of Ce(III) on birnessite compared to that on other minerals. Speciation of cerium onto all of the studied minerals was investigated using spectral and microscopic methods: high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and X-ray absorption spectroscopy (XAS) in conjunction with theoretical calculations. It was found that during the sorption process onto birnessite, Ce(III) was oxidized to Ce(IV), while the Ce(III) on goethite and anatase surfaces remained unchanged. Oxidation of Ce(III) by sorption on birnessite was also accompanied by the formation of CeO2 nanoparticles on the mineral surface, which depended on the initial cerium concentration and pH value.

Uranium oxides structural transformation in human body liquids.

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 UO2 to U4O9, U3O8 and UO3 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 U4O9, that transformed into U4O9-y. UO2.05 and U3O8 structures became more ordered and UO3 did not undergo significant transformation.

Novel candidate theranostic radiopharmaceutical based on strontium hexaferrite nanoparticles conjugated with azacrown ligand.

In this article, we report to the best of our knowledge the first modification of NPs with ligands for combined radiopharmaceuticals. Nanoparticles with suitable magnetic properties can be used both for diagnostics as a contrast for MRI and for therapy, including the insufficiently studied magneto-mechanical therapy. Strontium hexaferrite is one of the few hard-magnetic materials for which stable biocompatible colloidal solutions can be obtained. Strontium hexaferrite nanoparticles coated with silicon dioxide (SHF@SiO2) were modified with an amino silane coupling agent (3-aminopropyl)triethoxysilane and azacrown ether derivatives with six heteroatoms in rings were covalently linked to the amine group through the carboxyl group. The hard magnetic nanoparticles were then radiolabeled with 207Bi with a labelling yield of up to 99.8%. In vitro experiments showed that the complex SHF@SiO2-APTES-L2-207Bi is stable enough to be a potential theranostic radiopharmaceutical.

Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands.

Phenanthroline diamides (L) demonstrated a unique ability to extract uranium from nitric acid solutions into a polar organic solvent forming complexes of 1:2 stoichiometry as tight ion pairs {[UO2LNO3]+[UO2(NO3)3]-} by a novel extraction mechanism, which is a combination of two already well-known mechanisms: solvation and ion-pair anion exchange. A UV-vis study was used to confirm the formation of such complexes directly in the organic phase. Moreover, chemical synthesis and single crystal growth were performed to confirm unambiguously the structure of the complexes in the solid state.

CeO2-Azacrown Conjugate as a Nanoplatform for Combined Radiopharmaceuticals.

This study is one of the first attempts to assess CeO2 nanoparticles as a nanoplatform for radiopharmaceuticals with radionuclides. The process of functionalization using a bifunctional azacrown ligand is described, and the resulting conjugates are characterized by IR and Raman spectroscopy. Their complexes with 207Bi show a high stability in medically relevant media, thus encouraging the further study of these conjugates in vivo as potential combined radiopharmaceuticals.

Pyridine-di-phosphonates as chelators for trivalent f-elements: kinetics, thermodynamic and interfacial study of Am(III)/Eu(III) solvent extraction.

The fractionation of high-level radioactive waste from nuclear power plants simplifies the handling of its components, and facilitates the reduction of radiotoxic effects on the environment. The search and study of new ligands for solvent extraction, as one of the methods in fractionation, remains a complex and important research task. In this work, four pyridine diphosphonate ligands were synthesized. These ligands are part of the class of the N,O-donor extractants, which are selective towards Am(III). The separation factor SF(Am/Eu) for the best extractant reached values up to 10. The influence of the substituents on the efficiency of extraction and complexation of trivalent f-elements, the kinetics of extraction, and the behavior of the ligand at the interface were described. The effect of nitric acid concentration on the extraction was shown. The stoichiometry of the complexes was determined by slope analysis in solvent extraction experiment and verified by spectrophotometric titration in acetonitrile. Liquid tension experiments with a pendant drop method revealed the interfacial properties of the ligands in "F-3 solvent/H2O" and "F-3 solvent/HNO3" systems. The relationship between the surface activity and the ligand structure was shown. Studies of the extraction kinetics were performed in a modified Lewis cell. The effect of the ligand structure on the extraction rate was shown. The DFT calculation with the B3LYP density functional was used to explain the extraction properties of the ligands, including selectivity. The calculation of the pre-organization energy of the ligands explained the kinetics and extraction patterns for the studied series.

First Trifluoromethylated Phenanthrolinediamides: Synthesis, Structure, Stereodynamics and Complexation with Ln(III).

The first examples of 1,10-phenanthroline-2,9-diamides bearing CF3-groups on the side amide substituents were synthesized. Due to stereoisomerism and amide rotation, such complexes have complicated behavior in solutions. Using advanced NMR techniques and X-ray analysis, their structures were completely elucidated. The possibility of the formation of complex compounds with lanthanoids nitrates was shown, and the constants of their stability are quantified. The results obtained are explained in terms of quantum-chemical calculations.

Novel Hybrid Benzoazacrown Ligand as a Chelator for Copper and Lead Cations: What Difference Does Pyridine Make.

A synthetic procedure for the synthesis of azacrown ethers with a combination of pendant arms has been developed and the synthesized ligand, characterized by various techniques, was studied. The prepared benzoazacrown ether with hybrid pendant arms and its complexes with copper and lead cations were studied in terms of biomedical applications. Similarly to a fully acetate analog, the new one binds both cations with close stability constants, despite the decrease in both constants. The calculated geometry of the complexes correlate with the data from X-ray absorption and NMR spectroscopy. Coordination of both cations differs due to the difference between the ionic radii. However, these chelation modes provide effective shielding of cations in both cases, that was shown by the stability of their complexes in the biologically relevant media towards transchelation and transmetallation.

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.

From EXAFS of reference compounds to U(VI) speciation in contaminated environments.

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.