NMR study of C-A-S-H structures

Hanamachi, Yuji*; Walker, C.*; Sasamoto, Hiroshi; Mihara, Morihiro

NIMS Bisai Kozo Kaiseki Purattofuomu Riyo Hokokusho (Internet), 2 Pages, 2023/12

A High-volume Fly ash Silica fume Cement (HFSC) has been considered as the use of concrete support of drift in deep disposal of radioactive wastes. JAEA has been carried out experiments and modeling studies to evaluate chemical stability of C-A-S-H gel synthesized which would be believed as the dominant component of the HFSC. For the modeling purpose, it is necessary to evaluate the chemical composition both of C-A-S-H gel synthesized and accompanied minerals in the experiment. In the year of 2020, Al and Si NMR measurement were performed to identify Al and Si distribution in the sample and chemical composition of C-A-S-H gel was derived. However, it was impossible to derive the C-A-S-H gel composition having the expected Al/Si molar ratio since there were several accompanied minerals produced in the experiment due to the short term of immersion. This time similar approach to derive C-A-S-H gel composition is adopted using NMR measurement for the sample of longer time (6 months).

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.

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.

Synthesis report on the R&D for the Horonobe Underground Research Laboratory; Project carried out during fiscal years 2015-2019

Nakayama, Masashi; Saiga, Atsushi; Kimura, Shun; Mochizuki, Akihito; Aoyagi, Kazuhei; Ono, Hirokazu; Miyakawa, Kazuya; Takeda, Masaki; Hayano, Akira; Matsuoka, Toshiyuki; et al.

JAEA-Research 2019-013, 276 Pages, 2020/03

JAEA-Research-2019-013.pdf:18.72MB

The Horonobe Underground Research Laboratory (URL) Project is being pursued by the Japan Atomic Energy Agency (JAEA) to enhance the reliability of relevant disposal technologies for geological disposal of High-level Radioactive Waste through investigations of the deep geological environment within the host sedimentary rock at Horonobe Town in Hokkaido, north Japan. The investigations will be conducted in three phases, namely "Phase 1: Surface based investigations", "Phase 2: Construction phase" (investigations during construction of the underground facilities) and "Phase 3: Operation phase" (research in the underground facilities). According to the research plan described in the 3rd Mid- and Long- term Plan of JAEA, "Near-field performance study", "Demonstration of repository design option", and "Verification of crustal-movement buffering capacity of sedimentary rocks" are important issues of the Horonobe URL Project, and schedule of future research and backfill plans of the project will be decided by the end of 2019 Fiscal Year. The present report summarizes the research and development activities of these 3 important issues carried out during 3rd Medium to Long-term Research Phase.

Mudstone redox conditions at the Horonobe Underground Research Laboratory, Hokkaido, Japan; Effects of drift excavation

Mochizuki, Akihito; Ishii, Eiichi; Miyakawa, Kazuya; Sasamoto, Hiroshi

Engineering Geology, 267, p.105496_1 - 105496_11, 2020/03

https://doi.org/10.1016/j.enggeo.2020.105496

The mechanical and hydraulic properties of rocks around mine drifts change significantly during the construction and operation of a radioactive-waste repository, with air intrusion causing the oxidation of rock and groundwater in excavation-damaged zones (EDZ). Redox conditions in such zones associated with niches excavated in mudstone at the Horonobe Underground Research Laboratory (URL), which is believed to be generally representative of conditions that could exist in the EDZ of a repository, were studied with the aim of improving our understanding of factors that control redox conditions in such rock-groundwater systems. Groundwater Eh values around the niches have reducing values of less than -150 mV. The SO concentration, regarded as an oxidation indicator, is consistently as low as 1 mol L. Gas occupies more than 50% of zone volumes, including CH and CO with traces of N and O. Cores drilled from host rock around a URL gallery were analyzed, with no pyrite dissolution or precipitation of calcium sulfates being found. It is concluded that oxidizing conditions do not exist in the excavation-damaged zones, which is attributed to the suppression of air intrusion by the release of CH and CO from groundwater as pressures decreased and their accumulation in fractures. The modeling of oxygen diffusion into host rock further indicates that a reducing environment is maintained around the URL drifts.

The Effect of dissolved gas on rock desaturation in artificial openings in geological formations

Miyakawa, Kazuya; Aoyagi, Kazuhei; Sasamoto, Hiroshi; Akaki, Toshifumi*; Yamamoto, Hajime*

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

The construction and operation of geological repositories require excavation and ventilation of galleries, with significant groundwater drainage. Desaturation of rock around galleries is unavoidable and may affect hydraulic properties and redox conditions. This study used numerical modeling to assess the influence of dissolved gas on the degree of saturation of rock surrounding excavated galleries, focusing on siliceous mudstone rock in the 140 m, 250 m, and 350-m-deep galleries of the Horonobe Underground Research Laboratory, Japan. Based on previous electrical survey, the degree of saturation in the 250 m gallery was higher than that in the 140 m and 350 m galleries. In the Horonobe area, deep groundwater contains high concentrations of dissolved methane, and exsolution of this methane from pore water can affect desaturation. Simple numerical modeling, including simulation of multiphase flows, was undertaken for each gallery to confirm the effect of dissolved gas and rock permeability on desaturation. A sensitivity analysis was performed by varying dissolved gas contents and permeability. Results indicate that the dissolved gas content affects both the degree of saturation and its spatial extent, whereas rock permeability affects only the latter. Higher dissolved gas concentrations result in lower degrees of saturation with a greater spatial extent of desaturation, and higher permeability leads to greater extents of desaturation. It is therefore likely that gas content, rather than rock permeability, caused the observed variations in the saturation degree.

Evaluation of uncertainty of redox potential in deep groundwater; A Case study in the Horonobe area, Hokkaido

Mochizuki, Akihito; Sasamoto, Hiroshi; Mezawa, Tetsuya*; Miyakawa, Kazuya

Chikasui Gakkai-Shi, 61(1), p.3 - 20, 2019/02

https://doi.org/10.5917/jagh.61.3

Redox potential of deep groundwater in the Horonobe area, Hokkaido, was measured, and uncertainty of the measurement and thermodynamic interpretation was evaluated. The redox potential of groundwater obtained using monitoring units in the Underground Research Laboratory ranged between -250 and -100 mV, and the effect of the excavation of drifts on the redox potential is considered to be small in spite of its temporal variation. The redox potential is controlled by the reaction of chemical pairs of SO/FeS, SO/HS and CO(aq)/CH(aq). The comparison between the equilibrium potential for these reactions and the measured redox potentials suggests that 50 mV of uncertainty for the measurement of the redox potential is appropriate.

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.

An Evaluation of the long-term stagnancy of porewater in the neogene sedimentary rocks in northern Japan

Nakata, Kotaro*; Hasegawa, Takuma*; Oyama, Takahiro*; Ishii, Eiichi; Miyakawa, Kazuya; Sasamoto, Hiroshi

Geofluids, 2018, p.7823195_1 - 7823195_21, 2018/01

https://doi.org/10.1155/2018/7823195

A groundwater scenario is one of the scenario for safety assessment of geological disposal of high-level radioactive waste. In the safety assessment for groundwater scenario, the slow groundwater flow for a long-term should be an important factor. In the present study, study on stability of groundwater in the Koetoi and Wakkanai formations of Neogene marine based sedimentary rock at the Horonobe area, Hokkaido was performed by investigating the isotopes of chlorine and helium, and the stable isotopes of water. As the results, the stability of groundwater in deeper part of the Wakkanai formation was suggested due to no direct evidence of meteoric water intrusion during the uplift since ca. 1 Ma. Contrary, the groundwater both in the Koetoi formation and the upper Wakkanai formation would be unstable because the meteoric water intrusion was suggested by paleohydrogeological condition and the results of groundwater dating. Likely the Horonobe area, the accurate dating of groundwater would be difficult due to the complex effects of upward and mixing water derived from diagenesis in the thick sediment formation. However, a comparative procedure using both the results of groundwater dating and paleohydrogeological information would be useful for general evaluation of groundwater flow conditions for the long-term (i.e., check the possibility for long-term stability of groundwater).

Groundwater pressure records by geochemical monitoring system in the Horonobe Underground Research Laboratory

Mezawa, Tetsuya; Mochizuki, Akihito; Miyakawa, Kazuya; Sasamoto, Hiroshi

JAEA-Data/Code 2017-010, 63 Pages, 2017/06

JAEA-Data-Code-2017-010.pdf:9.66MB
JAEA-Data-Code-2017-010-appendix(CD-ROM).zip:5.08MB

Japan Atomic Energy Agency (JAEA) has been conducting "geoscientific study" and "research and development on geological disposal" in the Horonobe Underground Research Laboratory (URL) for safe geological disposal of high-level radioactive waste. Geochemical parameters of groundwater pressure, pH, and oxidation-reduction potential in the deep groundwater has been continuously monitored by the monitoring system which was developed in the Horonobe URL Project. This report presents the data of groundwater pressure which have been obtained by the monitoring system installed at the 140 m and 350 m gallery. The data obtained until March 31, 2016 was summarized along with related information such as the specifications of boreholes and the excavation of the URL.