The First observation of hydrated radium at the molecular level

Yamaguchi, Akiko; Okumura, Masahiko; Takahashi, Yoshio*

Isotope News, (789), p.20 - 23, 2023/10

https://www.jrias.or.jp/pdf/2310_TRACER_YAMAGUCHI_HOKA.pdf

Radium is a radioactive element produced from uranium and thorium and is important for environmental contamination issues around uranium mines and for geological disposal. In addition, radium is used in radiometric dating and cancer therapy, making it important not only in environmental chemistry but also in many other fields, including geochemistry and nuclear medicine. However, because radium is a radioactive element with no stable isotopes, spectroscopic measurement of radium is difficult, and little information at the molecular level has been obtained so far. In this study, we have clarified the molecular-level information of hydrated radium for the first time in the world by combining extended X-ray absorption fine structure (EXAFS) measurements and first-principles molecular dynamics simulations.

Improvement of the stability of IO-, SeO-, and SeO-coprecipitated barite after treatment with phosphate

Tokunaga, Kohei; Tanaka, Kazuya; Takahashi, Yoshio*; Kozai, Naofumi

Environmental Science & Technology, 57(8), p.3166 - 3175, 2023/02

https://doi.org/10.1021/acs.est.2c08939

Coprecipitation of radionuclides with barite has been studied to remove radionuclides from radioactive liquid waste because of its excellent removal efficiency; however, little information exists concerning the stability of the ions coprecipitated with barite. This study systematically investigated the stability of iodate, selenite, and selenate coprecipitated with barite via leaching tests. These oxyanions were gradually leached from the oxyanion-bearing barite into ultrapure water over time. Leaching of the oxyanions significantly increased in leaching solutions containing NaCl (pH5.3), NaNO (pH5.9), and NaSO (pH5.7). Conversely, leaching of the oxyanions was suppressed in KHPO solution (pH8.5), indicating that phosphate stabilized the oxyanion-bearing barite. The effect of phosphate treatment on oxyanion-bearing barite was further investigated. The results showed that the barite surface was modified with phosphate, and a thin surface layer of a barium phosphate-like structure was formed. The amount of oxyanions leached from the phosphate-treated samples into leaching solutions containing NaCl or NaNO was much lower than the amounts leached from the untreated barite samples into ultrapure water. The barite coprecipitation combined with subsequent phosphate treatment may be a promising method to efficiently remove iodate, selenite, and selenate from wastewater and stabilize them as barite coprecipitates.

Application of high-energy-resolution X-ray absorption spectroscopy at the U L-edge to assess the U(V) electronic structure in FeUO

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

https://doi.org/10.1021/acs.inorgchem.2c03208

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.

Microbial influences on manganese deposit formation at Yunotaki Fall, Japan

Shiraishi, Fumito*; Chihara, Ryoji*; Tanimoto, Risa*; Tanaka, Kazuya; Takahashi, Yoshio*

Island Arc, 31(1), p.e12448_1 - e12448_9, 2022/05

https://doi.org/10.1111/iar.12448

At Yunotaki Fall in north Japan, manganese-oxidizing bacteria were previously assumed to have oxidized manganese to precipitate birnessite, which relied on oxygen released from algae. However, it remained unclear whether larger-scale manganese oxide precipitation was actually occurring under light conditions. This study evaluated the contribution of indirect oxidation using microelectrodes to analyze local water chemistry, in addition to bulk water chemistry and DNA analyses. The results of this study demonstrate that low bulk pH values in the hot spring water hindered indirect oxidation despite the occurrence of active oxygenic photosynthesis and that direct oxidation by manganese-oxidizing bacteria is considered to dominate in the investigated sample.

Investigation of hydration and adsorption structures on clay minerals of radium by EXAFS

Yamaguchi, Akiko; Nagata, Kojiro*; Tanaka, Kazuya; Kobayashi, Keita; Kobayashi, Toru; Shimojo, Kojiro; Tanida, Hajime; Sekiguchi, Tetsuhiro; Kaneta, Yui; Matsuda, Shohei; et al.

Hosha Kagaku, (45), p.28 - 30, 2022/03

no abstracts in English

Hydration structures of barium ions; molecular dynamics simulations using the SCAN meta-GGA density functional and EXAFS spectroscopy studies

Yamaguchi, Akiko; Kobayashi, Keita; Takahashi, Yoshio*; Machida, Masahiko; Okumura, Masahiko

Chemical Physics Letters, 780, p.138945_1 - 138945_5, 2021/10

https://doi.org/10.1016/j.cplett.2021.138945

no abstracts in English

Effective removal of iodate by coprecipitation with barite; Behavior and mechanism

Tokunaga, Kohei; Takahashi, Yoshio*; Tanaka, Kazuya; Kozai, Naofumi

Chemosphere, 266, p.129104_1 - 129104_10, 2021/03

https://doi.org/10.1016/j.chemosphere.2020.129104

Radioactive iodine (I) is of great concern owing to its high mobility in the environment and long-term radiotoxicity, but there is a lack of effective techniques for removing iodate (IO) from aqueous solution. The aim of this study is to develop a new technique for removing radioactive iodate from contaminated solution by using barite (BaSO). In the present study, we examined the coprecipitation mechanism of iodate by barite at the molecular level for determining optimum conditions for iodate removal. The results showed that iodate was effectively removed from aqueous solution by coprecipitation, even in the presence of competitive anions in solution. Comparing our method with previous studies, iodate removal efficiency by barite was determined to be about two orders of magnitude greater than that by hydrotalcite-like layered double hydroxide at Cl concentration of 10 mmol L. Extended X-ray absorption fine structure (EXAFS) analysis indicated that incorporated iodate was strongly bound in the crystal lattice of barite by substituting the sulfate site in the structure when the iodine concentration was low. The charge compensation problem from the IO substitution in SO site is achieved by the substitution of Na-IO pairs at the nearest Ba site. Therefore, considering high removal efficiency and strong binding of iodate in barite, coprecipitation with barite is a promising material for removing radioactive iodate from various aqueous solutions contaminated with iodate.

First isolation and analysis of caesium-bearing microparticles from marine samples in the Pacific coastal area near Fukushima Prefecture

Miura, Hikaru*; Ishimaru, Takashi*; Ito, Yukari*; Kuribara, Yuichi; Otosaka, Shigeyoshi*; Sakaguchi, Aya*; Misumi, Kazuhiro*; Tsumune, Daisuke*; Kubo, Atsushi*; Higaki, Shogo*; et al.

Scientific Reports (Internet), 11, p.5664_1 - 5664_11, 2021/03

https://doi.org/10.1038/s41598-021-85085-w

For the first time, we isolated and investigated seven CsMPs (radioactive caesium-bearing microparticles) from marine particulate matter and sediment. From the elemental composition, the Cs/Cs activity ratio, and the Cs activity per unit volume results, we inferred that the five CsMPs collected from particulate matter were emitted from Unit 2 of the FDNPP, whereas the two CsMPs collected from marine sediment were possibly emitted from Unit 3. The presence of CsMPs can cause overestimation of the solid-water distribution coefficient of Cs in marine sediments and particulate matter and a high apparent radiocaesium concentration factor for marine biota. CsMPs emitted from Unit 2, which were collected from the estuary of a river that flowed through a highly contaminated area, may have been deposited on land and then transported by the river. By contrast, CsMPs emitted from Unit 3 were possibly transported eastward by the wind and deposited directly onto the ocean surface.

Local structure of rare earth elements (REE) in marine ferromanganese oxides by extended X-ray absorption fine structure and its comparison with REE in ion-adsorption type deposits

Nagasawa, Makoto*; Qin, H.-B.*; Yamaguchi, Akiko; Takahashi, Yoshio*

Chemistry Letters, 49(8), p.909 - 911, 2020/08

https://doi.org/10.1246/cl.200257

Sorption behavior of selenide on montmorillonite

Sugiura, Yuki; Tomura, Tsutomu*; Ishidera, Takamitsu; Doi, Reisuke; Francisco, P. C. M.; Shiwaku, Hideaki; Kobayashi, Toru; Matsumura, Daiju; Takahashi, Yoshio*; Tachi, Yukio

Journal of Radioanalytical and Nuclear Chemistry, 324(2), p.615 - 622, 2020/05

https://doi.org/10.1007/s10967-020-07092-x