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.

The Impact of cement on argillaceous rocks in radioactive waste disposal systems; A Review focusing on key processes and remaining issues

Wilson, J.*; Bateman, K.; Tachi, Yukio

Applied Geochemistry, 130, p.104979_1 - 104979_19, 2021/07

https://doi.org/10.1016/j.apgeochem.2021.104979

The concept of deep geological disposal will include the multiple use of cement-based materials. In the case of argillaceous host rocks, the presence of hyperalkaline cement porefluid results in the destabilization of primary minerals in the argillite, resulting in the development of a zone of alteration at cement-rock interfaces. The process understanding gained from experimental, analogue, and modelling studies has been reviewed, and remaining areas of uncertainty identified. Although there is a reasonably good understanding of the mineral assemblages that are likely to occur due to cement-rock interactions, there are still some areas where a degree of uncertainty remains, in particular: the evolution of cement-argillite interfaces at T 25C; the rates at which secondary minerals form; the extent of pore clogging due to secondary mineral precipitation; the implications of alteration for radionuclide transport.

Using natural systems evidence to test models of transformation of montmorillonite

Savage, D.*; Wilson, J.*; Benbow, S.*; Sasamoto, Hiroshi; Oda, Chie; Walker, C.*; Kawama, Daisuke*; Tachi, Yukio

Applied Clay Science, 195, p.105741_1 - 105741_11, 2020/09

https://doi.org/10.1016/j.clay.2020.105741

Safety functions for the clay buffer in a repository for high-level radioactive waste (HLW) are fulfilled if the presence of montmorillonite with high swelling capacity and low permeability is maintained in the long-term. The transformation of montmorillonite to the non-swelling mineral likely illite is addressed in most safety assessments by using simple semi-empirical kinetic models, but this approach contrasts with more complex reactive-transport simulations. In the present study, reactive-transport simulations are compared with simple semi-empirical kinetic models. Results suggest that reactive-transport simulations err on the side of conservatism, but may produce unrealistic estimates of illitization. This comparison demonstrates that reactive-transport models may be carefully applied to simulate the long-term evolution of near field environment for HLW disposal.

Key factors controlling radiocesium sorption and fixation in river sediments around the Fukushima Daiichi Nuclear Power Plant, 2; Sorption and fixation behaviors and their relationship to sediment properties

Tachi, Yukio; Sato, Tomofumi*; Takeda, Chizuko*; Ishidera, Takamitsu; Fujiwara, Kenso; Iijima, Kazuki

Science of the Total Environment, 724, p.138097_1 - 138097_10, 2020/07

https://doi.org/10.1016/j.scitotenv.2020.138097

To understand and predict radiocesium transport behaviors in the environment, sorption and fixation behaviors of radiocesium on river sediments from Ukedo and Odaka rivers around the Fukushima Daiichi Nuclear Power Plant were investigated systematically focusing on Cs sorption and fixation mechanisms and their relationship with Cs concentrations and sediment properties including clay mineralogy and organic matter.

Development of JAEA sorption database (JAEA-SDB); Update of sorption/QA data in FY2019

Sugiura, Yuki; Suyama, Tadahiro*; Tachi, Yukio

JAEA-Data/Code 2019-022, 40 Pages, 2020/03

JAEA-Data-Code-2019-022.pdf:2.22MB

Sorption behavior of radionuclides (RNs) in buffer materials, rocks and cementitious materials is one of the key processes in a safe geological disposal. This report focuses on updating of JAEA sorption database (JAEA-SDB) as a basis of integrated approach for the performance assessment (PA)-related distribution coefficient (K) setting and development of mechanistic sorption models. K data and their quality assurance (QA) results were updated by focusing on the following systems as potential needs extracted from our recent activities on the K setting and development of mechanistic models, i.e., clay minerals, sedimentary rocks and cementitious materials. As a result, 6,702 K data from 60 references were added and the total number of K values in JAEA-SDB reached 69,679. The QA/classified K data reached about 72% for all K data in JAEA-SDB.

Permeability measurement for macro-fractured granite using water including clay

Nara, Yoshitaka*; Kato, Masaji*; Sato, Tsutomu*; Kono, Masanori*; Sato, Toshinori

Proceedings of 5th ISRM Young Scholars' Symposium on Rock Mechanics and International Symposium on Rock Engineering for Innovative Future (YSRM 2019 and REIF 2019) (USB Flash Drive), 6 Pages, 2019/12

It is important to understand the long-term migration of radionuclides considering carious rock engineering projects such as the geological disposal of radioactive wastes. The network of fractures and pores in a rock mass can play important roles as the pathway of the fluid flow of rock. Usually groundwater contains fine-grained minerals such as clays. It is probable that the accumulation of the fine-grained minerals occurs in a fracture if the groundwater flows in a fracture in a rock. In this study, we have conducted the permeability measurement using water including clays. Specifically, we used a macro-fractured granite as a rock sample, and investigated the change of the permeability under the flow of the water including clays. It was shown that the hydraulic conductivity decreased with elapsed time.

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.

Challenges for management of radioactively contaminated wastes and volume reduction and reuse/recycling of removed soil derived from the activities for environmental remediation after the Fukushima Daiichi Nuclear Power Station accident, 2; Cs adsorption and desorption mechanism on clay minerals for aiming reuse

Yaita, Tsuyoshi

Nihon Genshiryoku Gakkai-Shi ATOMO, 59(8), p.441 - 443, 2017/08

no abstracts in English

Clay-based modeling approach to diffusion and sorption in the argillaceous rock from the Horonobe URL; Application to Ni(II), Am(III), and Se(IV)

Tachi, Yukio; Suyama, Tadahiro; Yotsuji, Kenji; Ishii, Yasuo; Takahashi, Hiroaki*

CMS Workshop Lectures, Vol.21, p.241 - 250, 2016/00

https://www.clays.org/other-cms-publications-wrksh21/

Sorption and diffusion of radionuclides in argillaceous rocks are key processes in the safe geological disposal. The diffusion and sorption behavior of Ni(II), Am(III) and Se(IV) in mudstone from the Horonobe URL were investigated by experimental and modeling approaches. Effective diffusivities obtained by the through-diffusion experiments were in the sequence of Cs, Ni, HTO, I, Se(SeO), Am(Am(CO)) by comparison with the previous study. The distribution coefficient values were consistent with those obtained by batch sorption tests. These results were interpreted by the clay-based modeling approach coupling the thermodynamic sorption model assuming key contributions of clays (smectite and illite) and the diffusion model assuming the electrical double layer theory and the simplified pore model with size distribution. This clay-based model could provide reasonable account of observed trends and could be basically applicable for various radionuclides.