Unusually kinetically inert monocationic neptunyl complex with a fluorescein-modified 1,10-phenanthroline-2,9-dicarboxylate ligand; Specific separation and detection in gel electrophoresis

Yamagata, Kazuhito*; Ouchi, Kazuki; Marumo, Kazuki*; Tasaki-Handa, Yuiko*; Haraga, Tomoko; Saito, Shingo*

Inorganic Chemistry, 62(2), p.730 - 738, 2023/01

https://doi.org/10.1021/acs.inorgchem.2c02908

The inert NpO complex with a fluorescein-modified phenanthroline-2,9-dicarboxylic acid was found by kinetic selection using polyacrylamide gel electrophoresis (PAGE) from a small chemical library. The small spontaneous dissociation rate constant of 810 s (the half-life of 23 hours) was determined. This is the singly-charged NpO complex exhibiting unusual kinetic inertness in aqueous solution, one million times slower than widely accepted fast kinetics of neptunyl complexes. Selective fluorescence detection of NpO was achieved in PAGE with a detection limit of 68 pmol dm(17 fg). This system was successfully applied to simulated spent nuclear fuel and high-level radioactive waste samples.

Development of tailor-made adsorbents for uranium recovery from seawater on the basis of uranyl coordination chemistry (Contract research); FY2021 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; Tokyo Institute of Technology*

JAEA-Review 2022-028, 54 Pages, 2022/11

JAEA-Review-2022-028.pdf:2.97MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2021. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station, Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2019, this report summarizes the research results of the "Development of Tailor-made Adsorbents for Uranium Recovery from Seawater on the Basis of Uranyl Coordination Chemistry" conducted from FY2019 to FY2021. Since the final year of this proposal was FY2021, the results for three fiscal years were summarized. The present study aims to develop a new ligand class for efficient and selective capture of uranium from seawater. On the basis of deep understanding on uranyl coordination chemistry, we design molecular structures of pentadentate ligands as functional moieties for uranium adsorption from seawater and study fundamental coordination chemistry of uranyl ion with those ligands in order to resolve current problems in uranium recovery technology …

Rotation of complex ions with ninefold hydrogen coordination studied by quasielastic neutron scattering and first-principles molecular dynamics calculations

Omasa, Yoshinori*; Takagi, Shigeyuki*; Toshima, Kento*; Yokoyama, Kaito*; Endo, Wataru*; Orimo, Shinichi*; Saito, Hiroyuki*; Yamada, Takeshi*; Kawakita, Yukinobu; Ikeda, Kazutaka*; et al.

Physical Review Research (Internet), 4(3), p.033215_1 - 033215_9, 2022/09

https://doi.org/10.1103/PhysRevResearch.4.033215

Sorption of Cs and Eu ions onto sedimentary rock in the presence of gamma-irradiated humic acid

Zhao, Q.*; Saito, Takeshi*; Miyakawa, Kazuya; Sasamoto, Hiroshi; Kobayashi, Taishi*; Sasaki, Takayuki*

Journal of Hazardous Materials, 428, p.128211_1 - 128211_10, 2022/04

https://doi.org/10.1016/j.jhazmat.2021.128211

The influence of humic acid and its radiological degradation on the sorption of Cs and Eu by sedimentary rock was investigated to understand the sorption process of metal ions and humic substances. Aldrich humic acid (HA) solution was irradiated with different doses of gamma irradiation using a Co-60 gamma-ray source prior to the contact between the metal ions and the solid sorbent. The HA molecule decomposed to smaller molecules with a lower complexation affinity. Batch sorption experiments were performed to evaluate the effect of gamma-irradiated HA on the sorption of Cs and Eu ions. The addition of non-irradiated HA weakened the sorption of Eu because of the lower sorption of the neutral or negatively charged Eu-HA complexes compared with free Eu ions. The sorption of monovalent Cs ions was barely affected by the presence of HA and its gamma irradiation. The concentration ratio of HA complexed species and non-complexed species in the solid and liquid phases was evaluated by sequential filtration and chemical equilibrium calculations. The ratios supported the minimal contribution of HA to Cs sorption. However, the concentration ratio for Eu in the liquid phase was high, indicating that the complexing ability of HA to Eu was higher than that of HA to Cs ions. Therefore, the sorption of free Eu would predominate with the gamma irradiation dose applied to the HA solution under a radiation field near the HLW package.

Stoichiometry between humate unit molecules and metal ions in supramolecular assembly induced by Cu and Tb measured by gel electrophoresis techniques

Nakano, Sumika*; Marumo, Kazuki*; Kazami, Rintaro*; Saito, Takumi*; Haraga, Tomoko; Tasaki-Handa, Yuiko*; Saito, Shingo*

Environmental Science & Technology, 55(22), p.15172 - 15180, 2021/11

https://doi.org/10.1021/acs.est.1c03993

Humic acid (HA) can strongly complex with metal ions to form a supramolecular assembly via coordination binding. However, determining the supramolecular size distribution and stoichiometry between small HA unit molecules constituting HA supramolecule and metal ions has proven to be challenging. Here, we investigated the changes in the size distributions of HAs induced by Cu and Tb ions using a unique polyacrylamide gel electrophoresis (PAGE) for the separation and quantification of HA complexes and metal ions bound, followed by UV-Vis spectroscopy and EEM-PARAFAC. It was found that the supramolecular behaviors of Cu and Tb complexes with HA collected from peat and deep groundwater (HHA) differed. Our results suggest that this supramolecular stoichiometry is related to the abundance of sulfur atoms in the elemental composition of HHA. Our results provide new insights into HA supramolecules formed via metal complexation.

Development of tailor-made adsorbents for uranium recovery from seawater on the basis of uranyl coordination chemistry (Contract research); FY2019 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; Tokyo Institute of Technology*

JAEA-Review 2020-026, 41 Pages, 2020/12

JAEA-Review-2020-026.pdf:3.25MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2019. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station, Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2019, this report summarizes the research results of the "Development of Tailor-Made Adsorbents for Uranium Recovery from Seawater on the Basis of Uranyl Coordination Chemistry". On the basis of deep understanding on uranyl coordination chemistry, we design molecular structures of pentadentate ligands as functional moieties for uranium adsorption from seawater and study coordination chemistry of uranyl ion with those ligands in order to resolve current problems in uranium recovery technology from seawater and to develop novel selective and efficient adsorbents for this purpose.

Consideration on modeling of Nb sorption onto clay minerals

Yamaguchi, Tetsuji; Ohira, Saki; Hemmi, Ko; Barr, L.; Shimada, Asako; Maeda, Toshikatsu; Iida, Yoshihisa

Radiochimica Acta, 108(11), p.873 - 877, 2020/11

https://doi.org/10.1515/ract-2020-0006

Extraction mechanism of lanthanide ions into silica-based microparticles studied by single microparticle manipulation and microspectroscopy

Otaka, Toshiki*; Sato, Tatsumi*; Ono, Shimpei; Nagoshi, Kohei; Abe, Ryoji*; Arai, Tsuyoshi*; Watanabe, So; Sano, Yuichi; Takeuchi, Masayuki; Nakatani, Kiyoharu*

Analytical Sciences, 35(10), p.1129 - 1133, 2019/10

https://doi.org/10.2116/analsci.19P155

A Thermodynamic model for the solubility of HfO(am) in the aqueous K - HCO - CO - OH - HO system

Rai, D.*; Kitamura, Akira; Rosso, K.*

Radiochimica Acta, 105(8), p.637 - 647, 2017/08

https://doi.org/10.1515/ract-2016-2623

Solubility of HfO(am) was determined as a function of KHCO concentrations ranging from 0.001 mol.kg to 0.1 mol.kg. The solubility of HfO(am) increased dramatically with the increase in KHCO concentrations, indicating that Hf(IV) makes strong complexes with carbonate. Thermodynamic equilibrium constants for the formation of Hf-carbonate complexes were determined using both the Pitzer and SIT models. The dramatic increase in Hf concentrations with the increase in KHCO concentrations can best be described by the formation of Hf(OH-)(CO) and Hf(CO). The log K values for the reactions [Hf + 2 CO +2 OH Hf(OH)(CO)] and [Hf + 5 CO Hf(CO)], based on the SIT model, were determined to be 44.53 0.46 and 41.53 0.46, respectively.

Sorption behavior of thorium onto granite and its constituent minerals

Iida, Yoshihisa; Yamaguchi, Tetsuji; Tanaka, Tadao; Hemmi, Ko

Journal of Nuclear Science and Technology, 53(10), p.1573 - 1584, 2016/10

https://doi.org/10.1080/00223131.2016.1138901

The sorption behavior of thorium (Th) onto granitic rock and its major constituent were investigated by batch sorption experiments. Experiments were carried out under variable pH and carbonate concentrations. Distribution coefficients decreased with increased carbonate concentrations and showed the minimal value at pH 9-10. This sorption tendency was likely due to forming the hydroxide-carbonate complexes of Th in the solutions. The order of sorbability for Th was mica feldspar quartz = granite. The sorption behaviors of Th onto these minerals were analyzed by the triple-layer surface complexation model with the Visual Minteq computer program. The model calculations assuming the inner-sphere surface complexation of Th were able to explain the experimental results reasonably well. It was shown that the sorption behavior of Th onto granite can be explained primarily by the complexation with the surface sites of feldspar.