Thermodynamic properties and revised Helgeson-Kirkham-Flowers equations of state parameters of the hydrated and dehydrated monomeric silica species at = 0.01-600C, = 1-3000 bars, = 0.35-1.1 g cm, and = 0

Walker, C. S.*; Arthur, R. C.*; Anraku, Sohtaro; Sasamoto, Hiroshi; Mihara, Morihiro

Applied Geochemistry, 175, p.106086_1 - 106086_17, 2024/11

https://doi.org/10.1016/j.apgeochem.2024.106086

The thermodynamic properties and revised Helgeson-Kirkham-Flowers equation of state (r-H-K-F EoS) parameters of the hydrated (Si(OH)(aq), SiO(OH) and SiO(OH)) and fictive dehydrated (SiO(aq), HSiO and SiO) monomeric silicon species are used extensively to describe the pH, composition, temperature, and pressure dependence of formation/breakdown reactions of all silicon-bearing compounds globally. Experimental log10 equilbrium constant, K values describing the formation reactions of the hydrated and dehydrated monomeric silicon species were therefore compiled from the literature, extrapolated to zero ionic strength by specific ion interaction theory as required and used to derive their thermodynamic properties and r-H-K-F EoS parameters. Consideration of all formation reactions in the same study provides a collective, internally consistent update to the thermodynamic properties and r-H-K-F EoS parameters of the monomeric silicon species that can provide a satisfactory match to the experimental log10 K values at = 0.01-600C, = 1-3000 bars, = 0.35-1.1 g cm, and zero ionic strength. These temperature and pressure limits comfortably bracket t=0.01-100C and P =1-270 bars relecant to the geological disposal of radioactive wastes at depths of up to 1 km.

Consideration of the dielectric response for radiation chemistry simulations

Toigawa, Tomohiro; Kai, Takeshi; Kumagai, Yuta; Yokoya, Akinari*

Journal of Chemical Physics, 160(21), p.214119_1 - 214119_9, 2024/06

https://doi.org/10.1063/5.0211089

The spur reaction is crucial for determining radiolysis or photolysis in liquid, but the spur expansion process has yet to be elucidated. One reason is the need to understand the role of the dielectric response of the solvating molecules surrounding the charged species generated by ionization. The dielectric response corresponds to the time evolution of the permittivity and might affect the chemical reaction-diffusion of the species in a spur expansion process. This study examined the competitive relationship between reaction-diffusion kinetics and the dielectric response by solving the Debye-Smoluchowski equation while considering the dielectric response. The Coulomb force between the charged species gradually decreases with the dielectric response. Our calculation results found a condition where fast recombination occurs before the dielectric response is complete. Although it has been reported that the primary G-values of free electrons depend on the static dielectric constant under low-linear-energy transfer radiation-induced ionization, we propose that considering the dielectric response can provide a deeper insight into fast recombination reactions under high-linear-energy transfer radiation- or photo-induced ionization. Our simulation method enables the understanding of fast radiation-induced phenomena in liquids.

An Analytical model to decompose mass transfer and chemical process contributions to molecular iodine release from aqueous phase under severe accident conditions

Zablackaite, G.; Shiotsu, Hiroyuki; Kido, Kentaro; Sugiyama, Tomoyuki

Nuclear Engineering and Technology, 56(2), p.536 - 545, 2024/02

https://doi.org/10.1016/j.net.2023.10.030

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 …

Development of tailor-made adsorbents for uranium recovery from seawater on the basis of uranyl coordination chemistry (Contract research); FY2020 Nuclear Energy Science & Technology and Human Resource Development Project

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

JAEA-Review 2021-041, 42 Pages, 2022/01

JAEA-Review-2021-041.pdf:2.03MB

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 FY2020. 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 in FY2020. 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.

Toward evaluation of cesium chemistry during transportation in a boiling water reactor; Effects of boron on cesium chemistry

Miwa, Shuhei; Miyahara, Naoya*; Nakajima, Kunihisa; Imoto, Jumpei; Suzuki, Eriko

Nihon Genshiryoku Gakkai-Shi ATOMO, 63(12), p.825 - 829, 2021/12

https://doi.org/10.3327/jaesjb.63.12_825

In the BWR severe accident, it was indicated that the control material boron significantly influences chemical behavior and transition behavior of cesium, which is important from the viewpoint of exposure, and it causes great uncertainty in the prediction of environmental release and distribution in the reactor. Therefore, in order to elucidate the important chemistry to be considered in severe accident analysis, we have developed the experimental setup that enables the evaluation of chemistry during transportation in the reactor, and evaluated cesium chemistry. Based on the results, we developed the chemistry database named ECUME composed of datasets and models that are the basis of chemical reaction analysis so that chemical behavior could be evaluated by severe accident analysis code.

Radiation-induced effects on the extraction properties of hexa--octylnitrilo-triacetamide (HONTA) complexes of americium and europium

Toigawa, Tomohiro; Peterman, D. R.*; Meeker, D. S.*; Grimes, T. S.*; Zalupski, P. R.*; Mezyk, S. P.*; Cook, A. R.*; Yamashita, Shinichi*; Kumagai, Yuta; Matsumura, Tatsuro; et al.

Physical Chemistry Chemical Physics, 23(2), p.1343 - 1351, 2021/01

https://doi.org/10.1039/D0CP05720G

The candidate An(III)/Ln(III) separation ligand hexa--octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions using a solvent test loop in conjunction with cobalt-60 gamma irradiation. We demonstrate that HONTA undergoes exponential decay with increasing gamma dose to produce a range of degradation products which have been identified and quantified by HPLC-ESI-MS/MS techniques. The combination of HONTA destruction and degradation product ingrowth, particularly dioctylamine, negatively impacts the extraction and back-extraction of both americium and europium ions. The loss of HONTA was attributed to its reaction with the solvent (-dodecane) radical cation of (HONTA + R) = (7.61 0.82) 10 M s obtained by pulse radiolysis techniques. However, when this ligand is bound to either americium or europium ions, the observed -dodecane radical cation kinetics increase by over an order of magnitude. This large reactivity increase to additional reaction pathways occurring upon metal-ion binding. Lastly nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (100 ns) HONTA radical cation as well as a longer-lived (s) HONTA triplet excited state. These HONTA species are important precursors to the suite of HONTA degradation products observed.

Computational approach to the evaluation of fission product behaviors

Miwa, Shuhei; Nakajima, Kunihisa; Suzuki, Chikashi; Rizaal, M.; Suzuki, Eriko; Horiguchi, Naoki; Osaka, Masahiko

Proceedings of Joint International Conference on Supercomputing in Nuclear Applications + Monte Carlo 2020 (SNA + MC 2020), p.253 - 260, 2020/12

We have proceeded the fundamental study for the improvement of the evaluation of fission product (FP) chemistry and the treatment of fine space resolution which are main issues for the evaluation of FP behaviors in a severe accident (SA). We have been developing FP chemistry database named ECUME for the improvement of SA analysis codes. We prepared thermodynamic data for Cs compounds which is no experimental data available by computational approach. Regarding the space resolution issue, we have been developing analysis tool named CHASER based on 3D-CFD code with the model for FP chemistry. More accurate evaluation of FP behavior can be achieved by incorporating ECUME to the CHASER.

Development of fission product chemistry database ECUME for the LWR severe accident

Miwa, Shuhei; Nakajima, Kunihisa; Miyahara, Naoya; Nishioka, Shunichiro; Suzuki, Eriko; Horiguchi, Naoki; Liu, J.; Miradji, F.; Imoto, Jumpei; Afiqa, B. M.; et al.

Mechanical Engineering Journal (Internet), 7(3), p.19-00537_1 - 19-00537_11, 2020/06

https://doi.org/10.1299/mej.19-00537

We constructed the fission product (FP) chemistry database named ECUME for LWR severe accident. This version of ECUME is equipped with dataset of the chemical reactions and their kinetics constants for the reactions of cesium(Cs)-iodine(I)-boron(B)-molybdenum(Mo)-oxygen(O)-hydrogen(H) system in gas phase, the elemental model for the high temperature chemical reaction of Cs with stainless steel applied as the structural material in a reactor, and thermodynamic data for CsBO vapor species and solids of CsSiO and CsFeSiO for these chemical reactions. The ECUME will provide estimation of Cs distribution due to the evaluation of effects of interaction with BWR control material B and stainless steel on Cs behavior in the Fukushima Daiichi Nuclear Power Station.

Fission product chemistry database ECUME version 1.1

Development Group for LWR Advanced Technology

JAEA-Data/Code 2019-017, 59 Pages, 2020/03

JAEA-Data-Code-2019-017.pdf:3.26MB
JAEA-Data-Code-2019-017-appendix(CD-ROM).zip:0.09MB

ECUME (ffective hemistry database of fission products nder ultiphase raction) is the database for the analyses of FP chemistry which strongly affects all the FP behaviors in a severe accident (SA) of nuclear facility like LWR. ECUME consists of three kinds of datasets: CRK (dataset for hemical eaction inetics), EM (lemental odel set) and TD (hermoynamic dataset). The present version of ECUME is prepared especially for the more accurate evaluation of cesium and iodine distribution in a reactor and release amount into an environment which should be of crucial importance towards the decommissioning of Fukushima Daiichi Nuclear Power Station of Tokyo Electric Power Company Holdings (1F) and the enhancement of LWR safety after the 1F SA.