Application of transition-edge sensors for micro-X-ray fluorescence measurements and micro-X-ray absorption near edge structure spectroscopy: a case study of uranium speciation in biotite obtained from a uranium mine.

In this study, we successfully applied a transition-edge sensor (TES) spectrometer as a detector for microbeam X-ray measurements from a synchrotron X-ray light source in the hard X-ray region to determine uranium (U) distribution at the micro-scale and its chemical species in biotite obtained from a U mine. It is difficult to separate the fluorescent X-ray of the U Lα1 line at 13.615 keV from that of the Rb Kα line at 13.395 keV in the X-ray fluorescence spectrum with an energy resolution of approximately 220 eV using a conventional silicon drift detector (SDD). Meanwhile, the fluorescent X-rays of U Lα1 and Rb Kα were fully separated by a TES with 50 eV energy resolution at an energy of around 13 keV. The successful peak separation by the TES led to an accurate mapping analysis of trace U in micro-X-ray fluorescence measurements and a decrease in the signal-to-background ratio in micro-X-ray absorption near edge structure spectroscopy. Thus, it could be a powerful tool for studying the U distribution and speciation in various environmental samples.

UO2 dissolution in bicarbonate solution with H2O2: the effect of temperature.

Upon nuclear waste canister failure and contact of spent nuclear fuel with groundwater, the UO2 matrix of spent fuel will interact with oxidants in the groundwater generated by water radiolysis. Bicarbonate (HCO3-) is often found in groundwater, and the H2O2 induced oxidative dissolution of UO2 in bicarbonate solution has previously been studied under various conditions. Temperatures in the repository at the time of canister failure will differ depending on the location, yet the effect of temperature on oxidative dissolution is unknown. To investigate, the decomposition rate of H2O2 at the UO2 surface and dissolution of UVI in bicarbonate solution (0.1, 1, 10 and 50 mM) was analysed at various temperatures (10, 25, 45 and 60 °C). At [HCO3-] ≥ 1 mM, the concentration of dissolved UVI decreased with increasing temperature. This was attributed to the formation of UVI-bicarbonate species at the surface and a change in the mechanism of H2O2 decomposition from oxidative to catalytic. At 0.1 mM, no obvious correlation between temperature and U dissolution was observed, and thermodynamic calculations indicated this was due to a change in the surface species. A pathway to explain the observed dissolution behaviour of UO2 in bicarbonate solution as a function of temperature was proposed.

Uranium hydroxide/oxide deposits on uranyl reduction.

We clarified the chemical reaction of deposits following the reduction of uranyl ions (UVIO22+) from the results of electrochemical quartz crystal microbalance, impedance spectra, and X-ray absorption fine structure measurements. We propose the following deposition mechanism: (1) UIV is formed by the disproportionation of UV, (2) UIV forms UIV hydroxide deposits, and (3) finally, the hydroxide deposits change to UIV oxide, which generally have a larger electrical resistance than the hydroxide form.

Application of High-Energy-Resolution X-ray Absorption Spectroscopy at the U L3-Edge to Assess the U(V) Electronic Structure in FeUO4.

FeUO4 was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near-edge structure (HERFD-XANES) spectroscopy at the U L3-edge, which is a novel technique in uranium(V) monouranate compounds. Theoretical calculations revealed that the peak splitting was caused by splitting of the 6d orbital of U(V) in FeUO4, which would be used to detect minor U(V) species. Such distinctive electronic states are of major interest to researchers and engineers working in various fields, from fundamental physics to the nuclear industry and environmental sciences for actinide elements.

Analysis of particles containing alpha-emitters in stagnant water at torus room of Fukushima Dai-ichi Nuclear Power Station's Unit 2 reactor.

Particles containing alpha (α) nuclides were identified from sediment in stagnant water in the torus room of the Fukushima Dai-ichi Nuclear Power Station(FDiNPS)'s Unit 2 reactor. We analyzed uranium (U), which is the main component of nuclear fuel, using scanning electron microscopy (SEM). Other α-nuclides (plutonium [Pu], americium [Am], and curium [Cm]) were detected by alpha track detection and the morphology of particles with α-nuclides were analyzed by SEM-energy dispersive X-Ray (EDX) analysis. Several uranium-bearing particles ranging from sub-µm to several µm in size were identified by SEM observation. These particles contained zirconium (Zr) and other elements which constituted fuel cladding and structural materials. The 235U/238U isotope ratio in the solid fractions that included U particles was consistent with what was found for the nuclear fuel in the Unit 2 reactor. This indicated that the U of similar fuel composition had made finer. The α-nuclide-containing particles identified by alpha track analysis were several tens to several hundred µm in size. The EDX spectra showed that these particles mainly comprised iron (Fe). Since the amount of α-nuclide material was very small, Pu, Am, and Cm were adsorbed on the Fe particles. This study clarifies that the major morphologies of U and other α-nuclides in the sediment of stagnant water in the torus room of FDiNPS's Unit 2 reactor differed.

Design of Microchannel Suitable for Packing with Anion Exchange Resins: Uranium Separation from Seawater Containing a Large Amount of Cesium.

We present a resin-packed microchannel that can reduce the radiation exposure risk and secondary radioactive wastes during uranium (U) separation by downscaling the separation using a microchip. Two types of microchips were designed to densely pack the microchannels with resins. The microchannels had almost the same cross-sectional area, but different outer circumferences. A satisfactory separation performance could be obtained by arranging more than ca. 10 resins along the depth and width of the microchannels. A resin-packed microchannel is an effective separation technique for determining the U concentration via inductively coupled plasma mass spectrometry owing to its ability to avoid the contamination of equipment by cesium, and to reduce the matrix effect. The size of the separation site was scaled down to <1/5000 compared to commonly used counterparts. The radiation exposure risk and secondary radioactive wastes can be reduced by 10- and 800-fold, respectively, using a resin-packed microchannel.

Selective Pd Separation from Simulated Radioactive Liquid Waste by Precipitation Using Xenon Lamp Irradiation for a Simplified Procedure.

In this study, we developed a simple and one-step Pd separation technique based on photoreduction with Xe lamp irradiation for the determination of 107Pd in highly radioactive samples. A simulated high-level radioactive liquid wastes (HLLW) solution, consisting of 14 major elements in a 3 mol L-1 HNO3 solution, was used to evaluate the separation performance. The Pd precipitate was formed by Xe lamp irradiation, and recovered by centrifugation. The Pd recovery from the simulated HLLW solution reached up to 50%, while 99.5% of the other 13 elements was separated. These results indicate that the applicability of the proposed separation technique to HLLW samples.

Direct Quantitation of 135Cs in Spent Cs Adsorbent Used for the Decontamination of Radiocesium-Containing Water by Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

The long-term safety assessment of spent Cs adsorbents produced during the decontamination of radiocesium-containing water at the Fukushima Daiichi nuclear power plant requires one to estimate their 135Cs content prior to final disposal. 135Cs is usually quantified by inductively coupled plasma mass spectrometry (ICP-MS), which necessitates the elution of Cs from Cs adsorbents. However, this approach suffers from the high radiation dose from 137Cs that is present in the contaminated water and Cs adsorption irreversibility. To address these challenges, we herein employed laser ablation ICP-MS for direct quantitation of 135Cs in Cs adsorbents and used a model Cs adsorbent prepared by immersion of a commercially available Cs adsorbent into radiocesium-containing liquid waste to verify the developed technique. Crushing and subsequent coating with a nitrocellulose-based curing agent provided a thin flat surface and thus allowed for stable solid sampling during laser ablation. The use of the 135Cs/137Cs ratio and 137Cs radioactivity obtained by gamma spectrometry achieved simple and precise quantitation of 135Cs. The obtained 135Cs/137Cs ratio of 0.41 ± 0.02 well agreed with that obtained for the original liquid waste sample by solution nebulization measurements, and the proposed method was concluded to be suitable for large-scale 135Cs quantitation, requiring only very small (<10 mg) samples with total 137Cs radioactivity.

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with 99Ru Mössbauer Parameters of Ruthenium-Nitrosyl Complexes.

We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste generating during reprocessing of spent nuclear fuel, to give a theoretical correlation between 99Ru Mössbauer spectroscopic parameters and ligand field strength for the first time. The structures of the series of complexes, [Ru(NO)L5] (L = Br-, Cl-, NH3, CN-), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO+)L5] complexes were the most stable. This result was supported by the benchmark calculations of the 99Ru Mössbauer isomer shift (δ) and quadrupole splitting (ΔEQ) values. The calculated results of both the δ and ΔEQ values reproduced the experimental results by reported previously and increased in the order of L = Br-, Cl-, NH3, CN-. Finally, we estimated the ligand field strength (Δo) based on molecular orbitals, assuming C4v symmetry and showed the increase of Δo values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of σ-donor and π-acceptor of the L-ligands to the Ru atom, resulting in the increase of the δ values. Furthermore, the increase of the σ-type donation into Ru dx2-y2 orbital and the π-type back-donation from Ru dxz, dyz orbitals in that order caused the decrease of the electron density along the Ru-NO axis, resulting in the increase of the ΔEQ values. This study is expected to contribute to the ligand design for the ruthenium-nitrosyl complexes, leading to the drug design for NO carrier and the decontamination of radioactive ruthenium from the ecological system, as well as the recovery of platinum-group metals from high-level radioactive waste.

Determination of 107Pd in Pd purified by selective precipitation from spent nuclear fuel by laser ablation ICP-MS.

Determination of radiopalladium 107Pd is required to ensure radiation safety of the Pd extracted from spent nuclear fuel for recycling or disposal. We employed nanosecond laser ablation inductively coupled plasma quadrupole mass spectrometry (ns-LA-ICP-QMS) to simplify the analytical procedure of 107Pd. Pd was separated through a selective Pd precipitation reaction induced by pulsed laser irradiation that reduces Pd(II) ions to metal Pd(0). Laser ablation facilitates direct measurement of the Pd precipitates, skipping the dissolution and dilution procedure with aqua regia and HCl, which causes serious corrosion damage to the introduction system of the ICP. In the present study, 102Pd in natural Pd standard solution was used as an internal standard owing to its absence in spent nuclear fuel. Pd precipitates with diameters ranging from 0.2 to 0.5 µm, obtained by pulsed laser irradiation, were embedded uniformly on the surface of the centrifugal filter to form a microscopically thin and flat Pd surface. The resulting homogeneous Pd layer is suitable for obtaining a stable signal ratio of 107Pd/102Pd (< 4%, 2RSD). The mass bias-corrected ratio of 107Pd/102Pd and the amount of 107Pd were 0.163 ± 0.004 and 17.8 ± 0.6 ng, respectively, which correspond to the values obtained by solution nebulization measurement after the dissolution of identical Pd precipitates. Graphical abstract ᅟ.

Determination of 107Pd in Pd Recovered by Laser-Induced Photoreduction with Inductively Coupled Plasma Mass Spectrometry.

Safety evaluation of a radioactive waste repository requires credible activity estimates confirmed by actual measurements. A long-lived radionuclide, 107Pd, which can be found in radioactive wastes, is one of the difficult-to-measure nuclides and results in a deficit in experimentally determined contents. In this study, a precipitation-based separation method has been developed for the determination of 107Pd with inductively coupled plasma mass spectrometry. The photoreduction induced by pulsed laser irradiation at 355 nm provides short-time and one-step recovery of Pd. The proposed method was verified by applying it to a spent nuclear fuel sample. To recover Pd efficiently, a natural Pd standard was employed as the Pd carrier. Taking advantage of the absence of 102Pd in spent nuclear fuel, 102Pd in the Pd carrier was utilized as the internal standard. The chemical yield of Pd was about 90% with virtually no impurities, allowing accurate quantification of 107Pd. The amount of 107Pd in the Pd precipitate was 17.3 ± 0.7 ng, equivalent to 239 ± 9 ng per mg of 238U in the sample.

Measurement of the Md3+/Md2+ reduction potential studied with flow electrolytic chromatography.

The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By application of the appropriate potentials on the chromatography column, the more stable Md(3+) is reduced to Md(2+). The reduction potential of the Md(3+) + e(-) → Md(2+) couple was determined to be -0.16 ± 0.05 V versus a normal hydrogen electrode.

Flavin mononucleotide mediated electron pathway for microbial U(VI) reduction.

Microbial reduction of U(VI) is an important phenomenon affecting uranium mobility in the subsurface environments. Elucidation of its mechanism is necessary for predicting uranium migration and for applying environmental remediation. In this study, we have examined the electron pathway for the U(VI) reduction mediated by flavin mononucleotide (FMN), which is secreted by Shewanella species. The cyclic voltammetry (CV) and photo-electrochemical methods with an optically transparent thin-layer electrode (OTTLE) cell were utilized in investigating in vitro the electron transfer reactions that take place between FMN and U(VI). The CV measurements of U(VI) were carried out in a citrate and Tris-HCl buffer both with and without FMN. A scarce U(VI) reduction current was observed in the absence of the FMN. To the contrary, a catalytic U(VI) reduction current was observed in the presence of FMN at the redox potential of the FMN. The reduction current increased with an increase in the concentration of the U(VI). The reduced form of the U was confirmed to be U(VI) by the photo-electrochemical analysis using the OTTLE cell. The results demonstrated that FMN acts as a mediator in the electro-reduction of U(VI) to U(iv). In addition, in vivo bio-reduction experiments on U(VI) with Shewanella putrefaciens revealed that the addition of FMN accelerated the reduction rate of U(VI). These results indicate that the bio-reduction of U(VI) by the Shewanella species can be catalyzed by FMN secreted from the cells.

Oxidation of element 102, nobelium, with flow electrolytic column chromatography on an atom-at-a-time scale.

We report here on the successful oxidation of element 102, nobelium (No), on an atom-at-a-time scale in 0.1 M alpha-hydroxyisobutyric acid (alpha-HIB) solution using a newly developed technique, flow electrolytic column chromatography. It is found that the most stable ion, No(2+), is oxidized to No(3+) within 3 min and that the oxidized No complex with alpha-HIB holds the trivalent state in the column above an applied potential of 1.0 V.

Complexation and back extraction of various metals by water-soluble diglycolamide.

Water-soluble ligands, N,N,N',N'-tetramethyldiglycolamide (TMDGA), N,N,N',N'-tetraethyldiglycolamide (TEDGA), N,N,N',N'-tetrapropyldiglycolamide (TPDGA) and N,N-dipropyldiglycolamic acid (DPDGAc) were prepared and their abilities to complex with and to back-extract the metal cations were investigated. These results indicate that the DGA series and DPDGAc have a stronger complexing ability with Am(III) and Pu(IV) than comparable carboxylic and aminopolycarboxylic acids. Among these ligands, the trend of the strength of their complexing ability is TPDGA approximately TEDGA > TMDGA approximately DPDGAc. TPDGA has significant loss to the extraction solvent due to its high hydrophobicity. It is evident from the present work that TEDGA is the best reagent for the reverse-extraction of not only An(III), (IV) but also Ca(II), Sc(III), Y(III), Zr(IV), La(III), Hf(IV), and Bi(III).

Plutonium(VI) accumulation and reduction by lichen biomass: correlation with U(VI).

The uptake of plutonium(VI) and uranium(VI) by lichen biomass was studied in the foliose lichen Parmotrema tinctorum to elucidate the migration behavior of Pu and U in the terrestrial environment. Pu and U uptake by P. tinctorum averaged 0.040+/-0.010 and 0.055+/-0.015 g gdry (-1), respectively, after 96 h incubation with 4.0 x 10(14) mol 1(-1) Pu solutions of pH 3, 4 and 5. SEM observations showed that the accumulated Pu is evenly distributed on the upper and lower surfaces of P. tinctorum, in contrast to U(VI), which accumulated in both cortical and medullary layers. UV/VIS absorption spectroscopy demonstrates that a fraction of Pu(VI) in the solution is reduced to Pu(V) by the organic substances released from P. tinctorum, and the accumulated Pu on the surface is reduced to Pu(IV), while U(VI) keeps the oxidation state of VI. Since the solubility of Pu(IV) hydroxides is very low, reduced Pu(VI) does not penetrate to the medullary layers, but is probably precipitated as Pu(IV) hydroxides on the cortical lichen surface. It is concluded that the uptake and reduction of Pu(VI) by lichens is important to determine the mobilization and oxidation states of Pu in the terrestrial environment.