Yomogida, Takumi; Akiyama, Daisuke*; Ouchi, Kazuki; Kumagai, Yuta; Higashi, Kotaro*; Kitatsuji, Yoshihiro; Kirishima, Akira*; Kawamura, Naomi*; Takahashi, Yoshio*
Inorganic Chemistry, 61(50), p.20206 - 20210, 2022/12
FeUO was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of HERFD-XANES spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near edge structure (HERFD-XANES) spectroscopy at the U L-edge, which is a novel technique in the U(V) compounds. Theoretical calculations revealed that the peak splitting was caused by splitting the 6d orbital of U(V). 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.
Yomogida, Takumi; Kitatsuji, Yoshihiro; Miyamoto, Yutaka
KEK Proceedings 2022-2, p.148 - 153, 2022/11
The Research Group for Safeguards Analytical Chemistry is currently developing a method to analyze the chemical state of uranium particles in environmental samples collected at nuclear facilities using micro-Raman spectroscopy. The chemical state of uranium particles in environmental samples can be partially oxidized by long-term exposure to air. It is necessary to develop a method to analyze the chemical state of the entire particle. In this study, uranium dioxide stored under atmospheric conditions was analyzed by micro-Raman mapping. The Raman spectra showed that uranium peroxide was locally present in the UO particle. The Raman peaks originating from the structure of UO around 570 cm and 1150 cm could not be observed in the point analysis of the particle center. On the other hand, in mapping analysis, Raman peaks originating from the structure of UO can be observed from the same particle, demonstrating that Raman mapping analysis is an effective method for analyzing the chemical state of the entire particle.
Maeda, Shigetaka; Kitatsuji, Yoshihiro
Enerugi Rebyu, 42(10), p.19 - 22, 2022/09
Ac-225 is attracting attention as an alpha-emitting medical radioisotope. Since its demand is expected to increase, domestic production of Ac-225 is required from the viewpoint of Japan's medical research and economic security. To establish the technical bases for the Ac-225 production, JAEA has evaluated the radioactivity that can be produced in the experimental fast reactor Joyo and designed the concept that upgrades the existing facilities for transporting the irradiated target from Joyo to a neighboring PIE facility rapidly. Efficient Actinium-225 Separation from Ra-226 irradiated in a fast reactor was studied. Ba and La were used as alternatives to Ra and Ac, respectively. By using DGA resin as an adsorbent, it can be expected that Ra and impurities generated by irradiation will be removed and Ac will be isolated. This study has revealed that Joyo can sufficiently produce Ac-225 as a raw material for pharmaceuticals.
Yomogida, Takumi; Ouchi, Kazuki; Oka, Toshitaka; Kitatsuji, Yoshihiro; Koma, Yoshikazu; Konno, Katsuhiro*
Scientific Reports (Internet), 12(1), p.7191_1 - 7191_10, 2022/05
Particles containing alpha () nuclides were identified from sediment in stagnant water at the torus room of the Fukushima Dai-ichi Nuclear Power Station (FDiNPS)'s Unit 2 reactor. Several uranium-bearing particles were identified by SEM observation. These particles contained Zr and other elements which constituted fuel cladding and structural materials. The U/U isotope ratio in the solid fractions that included U particles was consistent with the nuclear fuel in the Unit 2 reactor, which indicated that the U particles had been derived from nuclear fuel. The particles with alpha-emitters detected by alpha track analysis were several tens to several hundred m in size. The EDX spectra showed that these particles mainly comprised iron, which indicated Pu, Am, and Cm were adsorbed on the Fe-baring particles. This study clarifies that the major morphologies of U and other -nuclides were differed in the sediment of stagnant water in the torus room of FDiNPS's Unit 2 reactor.
Sato, Nobuaki*; Kirishima, Akira*; Watanabe, Masayuki; Sasaki, Takayuki*; Uehara, Akihiro*; Takeda, Shino*; Kitatsuji, Yoshihiro; Otobe, Haruyoshi; Kobayashi, Taishi*
The Chemistry of Thorium, Plutonium and MA, 254 Pages, 2022/03
The chemistry of nuclear materials such as Thorium (Part 1) and Plutonium (Part 2) was described in relation from the fundamentals on solid chemistry and solution chemistry to the practicals on the experiment and evaluation method in detail. Minor actinides such as Neptunium, Americium, Curium and Protoactinium, was introduced the basics on the solid and solution chemistry.
Ouchi, Kazuki; Tsukahara, Takehiko*; Brandt, A.*; Muto, Yuki*; Nabatame, Nozomi*; Kitatsuji, Yoshihiro
Analytical Sciences, 37(12), p.1789 - 1794, 2021/12
We attempted to scale down a separation process of uranium (U) using the microchip column loaded with anion exchange resin to develop safety and waste-reducing separation technique. The ideal separation performance of U was obtained by the properly design of a microchannel. The concentration of U in seawater as a real-world sample could be quantified with the prepared microchip column. It indicates that the microchip column is sufficiently practical. Compared to separation of U with a general column, the column size was successfully scaled down to 1/5000.
Yomogida, Takumi; Saeki, Morihisa*; Morii, Shiori; Oba, Hironori*; Kitatsuji, Yoshihiro
Analytical Sciences, 37(12), p.1843 - 1846, 2021/12
In this study, we developed a simple and one-step Pd separation technique based on photoreduction with Xe lamp irradiation for the determination of Pd in highly radioactive samples. A simulated high-level radioactive liquid wastes (HLLW) solution, which consists of 14 major elements (Rb, Sr, Zr, Mo, Ru, Rh, Pd, Cs, Ba, La, Ce, Pr, Nd, Sm) in a 3 mol L HNO solution, was used to evaluate the separation performance. The Pd precipitate were formed by Xe lamp irradiation and recovered by centrifugation. The results showed that the recovery of Pd from a simulated HLLW solution depend on the irradiation time and concentration of ethanol. By optimizing the conditions at photo irradiation, the Pd recovery from the simulated HLLW solution reached up to 50 %, while 99.5 % of the other 13 elements were separated. The Pd precipitate could be separated from the elements that are the main source of radioactivity (Sr, Cs, and Ba) and the source of spectral interference for the determination of Pd (Zr, and Ru). These results indicate that selective separation of Pd is achieved with the proposed method, showing the applicability of the proposed separation technique to HLLW samples.
Inagawa, Jun; Kitatsuji, Yoshihiro; Otobe, Haruyoshi; Nakada, Masami; Takano, Masahide; Akie, Hiroshi; Shimizu, Osamu; Komuro, Michiyasu; Oura, Hirofumi*; Nagai, Isao*; et al.
JAEA-Technology 2021-001, 144 Pages, 2021/08
Plutonium Research Building No.1 (Pu1) was qualified as a facility to decommission, and preparatory operations for decommission were worked by the research groups users and the facility managers of Pu1. The operation of transportation of whole nuclear materials in Pu1 to Back-end Cycle Key Element Research Facility (BECKY) completed at Dec. 2020. In the operation included evaluation of criticality safety for changing permission of the license for use nuclear fuel materials in BECKY, cask of the transportation, the registration request of the cask at the institute, the test transportation, formulation of plan for whole nuclear materials transportation, and the main transportation. This report circumstantially shows all of those process to help prospective decommission.
Ouchi, Kazuki; Komatsu, Atsushi; Takao, Koichiro*; Kitatsuji, Yoshihiro; Watanabe, Masayuki
Chemistry Letters, 50(6), p.1169 - 1172, 2021/06
The electrochemical behavior of uranium (IV) tetrachloride in ionic liquid-DMF mixture was studied for first time in order to build a redox flow battery (RFB) using U as an electrode active material. We found a quasi-reversible U/U couple that could be applied to the anode reaction of the RFB.
Sasaki, Yuji; Morita, Keisuke; Kitatsuji, Yoshihiro; Ito, Keisuke*; Yoshizuka, Kazuharu*
Solvent Extraction Research and Development, Japan, 28(2), p.121 - 131, 2021/00
High concentration of Cs is present in high-level radioactive waste. It is well-known that Cs is an alkali element and difficult to extract completely into an organic phase. Crown ether compounds are widely available for Cs extractants; DtBuDB18C6 (di--butyl-dibenzo-18crown6), was used in this study. Organic solvents used for the industrial applications, such as -dodecane and 1-octanol, have low solubility concerning the compound; other solvents were employed and tested. In this study, ketone-, ether-, and ester-type solvents showed high solubility for DtBuDB18C6 and DtBuDB18C6, when dissolved in ketones and alcohols, exhibited relatively high Cs distribution ratios ((Cs)), closely to 10.
Horita, Takuma; Asai, Shiho*; Konda, Miki; Matsueda, Makoto; Hanzawa, Yukiko; Kitatsuji, Yoshihiro
Bunseki Kagaku, 69(10/11), p.619 - 626, 2020/10
We have developed a Sr adsorption fiber for rapid analysis of Sr. The prepared Sr adsorption fiber has a Sr-extraction layer that densely retains a Sr-selective extractant, an 18-crown-6 ether derivative, on the fiber surface. Hydrophobic group-containing polymer chains embedded onto the surface of the fiber allow to form a hydrophobic phase, incorporating Sr-selective extractants. This unique surface structure provides high adsorption capacity, leading to rapid and highly efficient adsorption of Sr. The adsorption capacity of the Sr adsorption fiber was 3 times higher than commercially available 18-crown-6 ether derivative-impregnated resin (Sr Resin). The equilibrium adsorption capacity of the Sr adsorption fiber was comparable to the Sr Resin. The retained Sr was finally determined by a GM counter. The total analysis time including the Sr adsorption and measurement was about 1 hour.
Asai, Shiho*; Ohata, Masaki*; Hanzawa, Yukiko; Horita, Takuma; Yomogida, Takumi; Kitatsuji, Yoshihiro
Analytical Chemistry, 92(4), p.3276 - 3284, 2020/02
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 Cs content prior to final disposal. Cs 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 Cs. To address this challenge, we herein employed laser ablation ICP-MS for direct quantitation of Cs 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. The use of the Cs/Cs ratio and Cs radioactivity obtained by gamma spectrometry achieved simple and precise quantitation of Cs and the resulting Cs activity of 0.36 Bq agreed well with that in the original radiocesium-containing liquid waste.
Kaneko, Masashi; Kato, Akane*; Nakashima, Satoru*; Kitatsuji, Yoshihiro
Inorganic Chemistry, 58(20), p.14024 - 14033, 2019/10
We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste, to give a theoretical correlation between Ru Mssbauer spectroscopic parameters ( and ) and ligand field strength () for the first time. The structures of the series of complexes, [Ru(NO)L] (L = Br, Cl, NH, 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)L] complexes were the most stable. The calculated results of both the and values reproduced the experimental results by reported previously and increased in the order of L = Br, Cl, NH, CN. Finally, we estimated the ligand field strength () based on molecular orbitals, assuming C symmetry and showed the increase of values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of -donor and -acceptor of the L-ligands to the Ru atom, resulting in the increase of the values.
Kimuro, Shingo; Kirishima, Akira*; Kitatsuji, Yoshihiro; Miyakawa, Kazuya; Akiyama, Daisuke*; Sato, Nobuaki*
Journal of Chemical Thermodynamics, 132, p.352 - 362, 2019/05
A combination of potentiometry and calorimetry was used for the determination of the thermodynamic quantities of complexation of generic and groundwater humic acid (HA), which was isolated from deep groundwater at Horonobe, Hokkaido, Japan, with copper (II) ions and uranyl (VI) ions. The apparent complexation constant of Horonobe HA was independent of the pH, whereas that of generic HA was dependent on the pH. This observation indicates that the polyelectrolyte effect of Horonobe HA is negligible because of its small molecular size. In addition, the effect of the heterogeneity of Horonobe HA was not significant. Moreover, the complexation enthalpy of Horonobe HA was consistent with that of homogeneous poly(acrylic acid), which means the complexation of Horonobe HA was not affected by the functional group heterogeneity. Consequently, the characteristic complexation mechanism of Horonobe HA was revealed based on the determined thermodynamic quantities.
Asai, Shiho; Ohata, Masaki*; Yomogida, Takumi; Saeki, Morihisa*; Oba, Hironori*; Hanzawa, Yukiko; Horita, Takuma; Kitatsuji, Yoshihiro
Analytical and Bioanalytical Chemistry, 411(5), p.973 - 983, 2019/02
Determination of radiopalladium Pd is required for ensuring the radiation safety of Pd extracted from spent nuclear fuel for recycling or disposal. We employed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to simplify an analytical procedure of Pd. Pd was separated through selective Pd precipitation reaction from spent nuclear fuel. Laser ablation allows direct measurement of the Pd precipitates, skipping the dissolution and dilution procedure. In this study, Pd in natural Pd standard solution was used as an internal standard, taking advantage of its absence in spent nuclear fuel. The Pd precipitate was uniformly embedded on the surface of the centrifugal filter, forming a microscopically thin flat surface of Pd. The resulting homogeneous Pd layer is suitable for obtaining a stable signal ratio of Pd/Pd. The amount of Pd obtained by LA-ICP-MS corresponds to the values obtained by conventional solution nebulization measurement.
Radioisotopes, 67(10), p.483 - 493, 2018/10
Electrochemical reactions and redox properties of actinides such as uranium and neptunium are outlined. The flow electrolysis enables rapid and high-efficient treatment. It was demonstrated to measure slow processes of actinide redox. Experimental results of electrolysis of actinide ions and the preparation method of oxidation state of the ions based on the fundamental data are described. Mediator reaction and catalysis observed in the process of electrolysis of actinide ions are also explained.
Yomogida, Takumi; Asai, Shiho; Saeki, Morihisa*; Hanzawa, Yukiko; Horita, Takuma; Esaka, Fumitaka; Oba, Hironori*; Kitatsuji, Yoshihiro
Bunseki Kagaku, 66(9), p.647 - 652, 2017/09
Palladium-107 is a long-lived fission product, which can be found in high-level radioactive liquid wastes (HLLW). Determination of the Pd contents in HLLW is essential to evaluate the long-term safety of HLLW repositories. However, the Pd content in HLLW has not been reported because of difficulties in pretreatment for the measurement. In this study, we investigated applicability of laser-induced photoreduction to HLLW solution: it enables a simple and non-contact separation of Pd. The results showed the recovery of 60% was achieved at the conditions: 40% ethanol, 20 min irradiation, 100 mJ of pulse energy. Additionally, major radionuclides and potentially interfering components in ICP-MS were removed from the simulated HLLW over a wide concentration range of Pd from 0.24 to 24 mg L, showing the applicability of the proposed separation technique to HLLW samples.
Segawa, Yukari; Horita, Takuma; Kitatsuji, Yoshihiro; Kumagai, Yuta; Aoyagi, Noboru; Nakada, Masami; Otobe, Haruyoshi; Tamura, Yukito*; Okamoto, Hisato; Otomo, Takashi; et al.
JAEA-Technology 2016-039, 64 Pages, 2017/03
The laboratory building No.1 for the plutonium research program (Bldg. Pu1) was chosen as one of the facilities to decommission by Japan Atomic Energy Agency Reform in September, 2013. The research groups, users of Bldg. Pu1, were driven by necessity to remove used equipment and transport nuclear fuel to other facilities from Bldg. Pu1. Research Group for Radiochemistry proactively established the Used Equipment Removal Team for the smooth operation of the removal in April, 2015. The team classified six types of work into the nature of the operation, removal of used equipment, disposal of chemicals, stabilization of mercury, stabilization of nuclear fuel, transportation of nuclear fuel and radioisotope, and survey of contamination status inside the glove boxes. These works were completed in December, 2015. This report circumstantially shows six works process, with the exception of the approval of the changes on the usage of nuclear fuel in Bldg. Pu1 to help prospective decommission.
Horita, Takuma; Asai, Shiho; Konda, Miki; Hanzawa, Yukiko; Saito, Kyoichi*; Fujiwara, Kunio*; Sugo, Takanobu*; Kitatsuji, Yoshihiro
Bunseki Kagaku, 66(3), p.189 - 193, 2017/03
A Sr-selective adsorption fiber was prepared for rapid analysis of Sr content by using radiation-induced emulsion graft polymerization and subsequent chemical modification. A polyethylene fiber with a diameter of 13 m was first immersed in a methanol solution of an epoxy-group-containing vinyl monomer, glycidyl methacrylate (GMA), and polyoxyethylene sorbitol ester (Tween20) as a surfactant for graft-polymerization of GMA. Octadecylamine was then bound to a polymer chain extending from the fiber surface providing hydrophobicity to the polymer chain. Dicyclohexano-18-crown-6 (DCH18C6) was finally impregnated onto the polymer chain via a hydrophobic interaction between the octadecyl moiety of the polymer chain and the cyclohexyl moiety of DCH18C6. The fiber surface structure, characterized by DCH18C6 molecules loosely entangled with polymer chains, afforded realizes the rapid and selective adsorption of Sr ions with an adsorption rate approximately 100 times higher than that of a commercially available Sr-selective resin (Sr Resin).
Ouchi, Kazuki; Otobe, Haruyoshi; Kitatsuji, Yoshihiro; Yamamoto, Masahiro
ECS Transactions, 75(27), p.51 - 57, 2017/01
We investigated the deposition of U(IV) following a valence change of U as electrodeposition using an electrochemical quartz crystal microbalance (EQCM). When measurements of the reduction of U(VI) in a weak acid solution were performed, deposits of U(IV) were observed on the electrode surface. From deposition rates, pH dependence of them, and oxidation potentials of deposits, we proposed the following deposition mechanism. The deposition is divided into the three phases; First, in the induction phase, U(IV) produced by the disproportionation forms U(IV) hydroxide nucleus. Next, in the growth phase, U(IV) deposits begin to grow. In this phase, the deposits catalyze the reduction of U(V) to U(IV), resulting an increase of the reduction current. Finally, in the transformation phase, U(IV) hydroxide species transform into U dioxide having more stable state.