Sorption structure of cesium in various clay minerals by Cs -edge XAFS measurement

Tsuji, Takuya; Matsumura, Daiju; Kobayashi, Toru

SPring-8/SACLA Riyo Kenkyu Seikashu (Internet), 11(4), p.214 - 217, 2023/08

https://doi.org/10.18957/rr.11.4.214

no abstracts in English

New approach to understanding the experimental Cs NMR chemical shift of clay minerals via machine learning and DFT-GIPAW calculations

Okubo, Takahiro*; Takei, Akihiro*; Tachi, Yukio; Fukatsu, Yuta; Deguchi, Kenzo*; Oki, Shinobu*; Shimizu, Tadashi*

Journal of Physical Chemistry A, 127(4), p.973 - 986, 2023/02

https://doi.org/10.1021/acs.jpca.2c08880

The identification of adsorption sites of Cs on clay minerals has been studied in the fields of environmental chemistry. The nuclear magnetic resonance (NMR) experiments allow direct observations of the local structures of adsorbed Cs. The NMR parameters of Cs, derived from solid-state NMR experiments, are sensitive to the local neighboring structures of adsorbed Cs. However, determining the Cs positions from NMR data alone is difficult. This paper describes an approach for identifying the expected atomic positions of Cs adsorbed on clay minerals by combining machine learning (ML) with experimentally observed chemical shifts. A linear ridge regression model for ML is constructed from the smooth overlap of atomic positions descriptor and gauge-including projector augmented wave (GIPAW) ab initio data. The Cs chemical shifts can be instantaneously calculated from the Cs positions on any clay layers using ML. The inverse analysis from the ML model can derive the atomic positions from experimentally observed chemical shifts.

Key factors controlling radiocesium sorption and fixation in river sediments around the Fukushima Daiichi Nuclear Power Plant, 1; Insights from sediment properties and radiocesium distributions

Tachi, Yukio; Sato, Tomofumi*; Akagi, Yosuke*; Kawamura, Makoto*; Nakane, Hideji*; Terashima, Motoki; Fujiwara, Kenso; Iijima, Kazuki

Science of the Total Environment, 724, p.138098_1 - 138098_11, 2020/07

https://doi.org/10.1016/j.scitotenv.2020.138098

To understand and predict radiocesium transport behaviors in the environment, highly contaminated sediments from Ukedo and Odaka rivers around the Fukushima Daiichi Nuclear Power Plant were investigated systematically focusing on key factors controlling radiocesium sorption and fixation, including particle size, clay mineralogy and organic matter.

Selective removal of radiocesium from micaceous clay for post-accident soil decontamination by temperature-controlled Mg-leaching in a column

Yin, X.; Zhang, L.*; Meng, C.*; Inaba, Yusuke*; Wang, X.*; Nitta, Ayako; Koma, Yoshikazu; Takeshita, Kenji*

Journal of Hazardous Materials, 387, p.121677_1 - 121677_10, 2020/04

https://doi.org/10.1016/j.jhazmat.2019.121677

Development of gel filler that facilitates fuel debris retrieval (Contract research); FY2018 Center of World Intelligence Project for Nuclear Science/Technology and Human Resource Development

Collaborative Laboratories for Advanced Decommissioning Science; Osaka University*

JAEA-Review 2019-029, 36 Pages, 2020/02

JAEA-Review-2019-029.pdf:2.33MB

JAEA/CLADS, had been conducting the Center of World Intelligence Project for Nuclear Science/Technology and Human Resource Development (hereafter referred to "the Project") in FY2018. The Project aims to contribute to solving problems in nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station, Tokyo Electric Power Company Holdings, Inc. 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 FY2018, this report summarizes the research results of the "Development of Gel Filler that Facilitates Fuel Debris Retrieval". When gel materials such as polymer, silicate and clay minerals with adjusted viscosity are used in the process of debris retrieval, the gel would not leak down from the damaged parts, resulting in the reduction of surrounding air dose rate. In addition, gel materials can reduce the diffusion and scattering of dust that is produced by cutting. For these reasons, we propose a method where inside of a containment vessel is filled by gel materials in order to simplify the debris retrieval.

Enhancement of permeability activated by supercritical fluid flow through granite

Nohara, Tsuyoshi; Uno, Masaoki*; Tsuchiya, Noriyoshi*

Geofluids, 2019, p.6053815_1 - 6053815_16, 2019/08

https://doi.org/10.1155/2019/6053815

Amphibole-plagioclase thermometry was applied to estimate the temperature of a glassy vein as approximately 700. The results of observations of the rock core revealed that of supercritical fluid flow was microfracture filling with hornblende and plagioclase. The current high permeability was recognized to be microfracture network. A high-angle fracture of chlorite filling in combination with an open fracture was recognized as characteristics of a high-permeability type.

Characterization of mineralogical controls on ammonium concentrations in deep groundwaters of the Horonobe area, Hokkaido

Sasamoto, Hiroshi; Sato, Hisao*; Arthur, R. C.*

Journal of Geochemical Exploration, 188, p.318 - 325, 2018/05

https://doi.org/10.1016/j.gexplo.2018.01.013

Ammonium is potentially an important constituent of deep groundwater under reducing condition. The retention of cesium by sorption in geological formations may have an important role ensuring the long-term safety of high-level radioactive waste. Cesium sorption will be affected by competing effects due to dissolve cation likely ammonium in groundwater, however. In the present study, a possible reaction to control of ammonium in deep groundwater was evaluated based on the data selected in the Horonobe as a test case in Japan. Results of investigation of mineralogy, thermodynamic evaluation of groundwaters and the Electron Probe Micro Analysis (EPMA) to identify nitrogen distribution on minerals suggest that the clay minerals bearing potassium, particularly smectite, illite and interstratified illite/smectite, appear to control the ammonium concentration in groundwaters by ion exchange reactions. Additionally, the selected groundwaters in the Horonobe seem to resemble to the gas and oil fields groundwater in the screened dataset in Japan in terms of ammonium distribution.

Desorption behavior of Cs from clay minerals by thermal heating in a vacuum; Analyses by thermal desorption spectroscopy and synchrotron radiation X-ray photoelectron spectroscopy

Hirao, Norie; Shimoyama, Iwao; Baba, Yuji; Izumi, Toshinori; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi

Bunseki Kagaku, 65(5), p.259 - 266, 2016/05

https://doi.org/10.2116/bunsekikagaku.65.259

After the Fukushima nuclear plant accident, radiocesium was strongly fixed to clay minerals in the soil. Some dry methods with heating are being developed to remove radiocesium from the soil. In this work, we propose a new dry method that combines heat treatment in vacuum and molten salts to reduce the processing temperature in dry methods. Vermiculite saturated with non-radioactive Cs was heated in vacuum, and Cs contents in the vermiculite were compared before and after heating using X-ray photoelectron spectroscopy. Approximately 40% of cesium were removed by heating at 800C for three minutes when only vermiculite was heated. Approximately 70% of cesium were removed by heating at 450C for three minutes when vermiculite was heated with NaCl/CaCl mixed salts. Based on these results, this method is expected to reduce temperature and increase efficiency on dry methods for cesium removal from clay minerals.

Characterization of adsorbed alkali metal ions in 2:1 type clay minerals from first-principles metadynamics

Ikeda, Takashi; Suzuki, Shinichi; Yaita, Tsuyoshi

Journal of Physical Chemistry A, 119(30), p.8369 - 8375, 2015/07

https://doi.org/10.1021/acs.jpca.5b05934

Adsorption states of alkali metal ions in three kinds of 2:1 type clay minerals are systematically investigated via first-principles-based metadynamics. Our reconstructed free energy surfaces in a two dimensional space of coordination numbers specifically employed as collective variables for describing the interlayer cations show that an inner-sphere (IS) complex is preferentially formed for Cs in the 2:1 type trioctahedral clay minerals with saponitelike compositions, where lighter alkali ions show a tendency to form an outer-sphere one instead. The strong preference for an IS complex observed for Cs is found to result partially from the capability of recognizing selectively Cs ions at basal O atoms with the Lewis basicity significantly enhanced by the isomorphic substitution in tetrahedral sheets.

Enhanced electrochemical oxidation of spent organic solvent under ultrasonic agitation

Sugikawa, Susumu; Umeda, Miki; Kobayashi, Fuyumi; Nagata, Masanobu*; Dojiri, Shigeru; Amano, Masae*

Proceedings of International Conference on Nuclear Energy System for Future Generation and Global Sustainability (GLOBAL 2005) (CD-ROM), 4 Pages, 2005/10

The mineralization of radioactive contaminated organic wastes by mediated electrochemical oxidation process has some attractive features as alternative to incineration process: The process operates safely at low temperatures and ambient pressures. JAERI has been investigated the process since 1996 and confirmed complete mineralization of this organic solvent. In order to greatly improve current efficiency for the oxidation reaction, further experiments were performed under condition of strong mixing of organic solvent and anolyte with an aide of ultrasonic wave. The current efficiencies for the oxidation reaction by ultrasonic agitation between organic solvent and anolyte were twice to that by mechanical agitation. On the basis of these results, two processes, one for destruction of a small amount of TBP/dodecane and the other for destruction of intermediate compounds following alkaline hydrolysis of a large amount of TBP/dodecane, were proposed.