Prediction of thermodynamic data for radium suitable for thermodynamic database for radioactive waste management using an electrostatic model and correlation with ionic radii among alkaline earth metals

Kitamura, Akira; Yoshida, Yasushi*

Journal of Radioanalytical and Nuclear Chemistry, 327(2), p.839 - 845, 2021/02

https://doi.org/10.1007/s10967-020-07527-5

Thermodynamic data for radium for radioactive waste management have been predicted using an electrostatic model and correlation with the ionic radii of the alkaline earth metals. Estimation of the standard Gibbs free energy of formation and standard molar entropy of aqueous radium species and compounds has been based on such approaches as extrapolation of the thermodynamic properties of strontium and barium, and use of a model of ion pair formation. The predicted thermodynamic data for radium have been compared with previously reported values.

Development methodology on determination of instant release fractions for generic safety assessment for direct disposal of spent nuclear fuel

Kitamura, Akira; Akahori, Kuniaki; Nagata, Masanobu*

Genshiryoku Bakkuendo Kenkyu (CD-ROM), 27(2), p.83 - 93, 2020/12

https://doi.org/10.3327/jnuce.27.2_83

Direct disposal of spent nuclear fuel (SNF) in deep underground repositories (hereafter "direct disposal") is a concept that disposal canisters stored fuel assemblies dispose without reprocessing. Behavior of radionuclide release from SNF must be different from that from vitrified glass. The present study established a methodology on determination of instant release fraction (IRF) of radionuclides from SNF, which is the one of the parameters on radionuclide release based on the latest safety assessment reports in other countries, especially for IRF values proportional to a fission gas release ratio (FGR). Recommended and maximum values of FGR have been estimated using the fuel performance code FEMAXI-7 after collecting FGR values on Japanese SNFs. Furthermore, recommended and maximum values of IRF for Japanese SNFs used in a pressurized water reactor (PWR) have been estimated using the presently obtained FGR values and experimentally obtained IRF values on foreign SNFs. The recommended and maximum IRF values obtained in the present study have been compared with those of the latest safety assessment reports in other countries.

Thermodynamic interpretation of uranium(IV/VI) solubility in the presence of -isosaccharinic acid

Kobayashi, Taishi*; Sasaki, Takayuki*; Kitamura, Akira

Journal of Chemical Thermodynamics, 138, p.151 - 158, 2019/11

https://doi.org/10.1016/j.jct.2019.06.006

The effect of -isosaccharinic acid (ISA) on the solubility and redox of tetravalent and hexavalent uranium (U(IV), U(VI)) was investigated in the hydrogen ion concentration (pH) range of 613 and at total ISA concentration ([ISA]) = 1010 mol/dm. The dependence of U(IV) solubility on pH and [ISA] suggested the existence of U(OH)(ISA) as a dominant species within the investigated pH range of 612. For the U(VI)-ISA system, UO(OH)(ISA) was suggested as a dominant species at pH 713. The formation constants of the U(IV)-ISA and U(VI)-ISA complexes were determined by least-squares fitting of the solubility data. The solubility of U(IV) and U(VI) in the presence of ISA and its effect on the redox behavior were thermodynamically interpreted based on the obtained constants.

Thermodynamic data development; Solubility method and future research needs (PLENARY)

Rai, D.*; Yui, Mikazu; Kitamura, Akira

Progress in Nuclear Science and Technology (Internet), 5, p.19 - 26, 2018/11

https://doi.org/10.15669/pnst.5.19

The objectives of this presentation are (1) to describe the solubility method, (2) to list desirable criteria of the solubility method so that the reader can recognize which studies have been done in a way that yields quality information, (3) to present an example of how to use the evaluation criteria, and (4) to provide a few examples of future research needs where the solubility method is ideally suited and the other methods are unsuitable for these investigations.

Thermodynamic equilibrium constants for important isosaccharinate reactions; A Review

Rai, D.*; Kitamura, Akira

Journal of Chemical Thermodynamics, 114, p.135 - 143, 2017/11

https://doi.org/10.1016/j.jct.2017.02.012

Isosaccharinic acid is a cellulose degradation product that can form in low-level nuclear waste repositories and is known to form strong complexes with many elements, including actinides, disposed of in these repositories. We (1) reviewed the available data for deprotonation and lactonisation constants of isosaccharinic acid, and the isosaccharinate binding constants for Ca, Fe(III), Th, U(IV), U(VI), Np(IV), Pu(IV), and Am(III), (2) summarized complexation constant values for predicting actinide behavior in geologic repositories in the presence of isosaccharinate, and (3) outlined additional studies to acquire reliable thermodynamic data where the available data are inadequate.

A Thermodynamic model for the solubility of HfO(am) in the aqueous K - HCO - CO - OH - HO system

Rai, D.*; Kitamura, Akira; Rosso, K.*

Radiochimica Acta, 105(8), p.637 - 647, 2017/08

https://doi.org/10.1515/ract-2016-2623

Solubility of HfO(am) was determined as a function of KHCO concentrations ranging from 0.001 mol.kg to 0.1 mol.kg. The solubility of HfO(am) increased dramatically with the increase in KHCO concentrations, indicating that Hf(IV) makes strong complexes with carbonate. Thermodynamic equilibrium constants for the formation of Hf-carbonate complexes were determined using both the Pitzer and SIT models. The dramatic increase in Hf concentrations with the increase in KHCO concentrations can best be described by the formation of Hf(OH-)(CO) and Hf(CO). The log K values for the reactions [Hf + 2 CO +2 OH Hf(OH)(CO)] and [Hf + 5 CO Hf(CO)], based on the SIT model, were determined to be 44.53 0.46 and 41.53 0.46, respectively.

Issues concerning the determination of solubility products of sparingly soluble crystalline solids; Solubility of HfO(cr)

Rai, D.*; Kitamura, Akira; Rosso, K. M.*; Sasaki, Takayuki*; Kobayashi, Taishi*

Radiochimica Acta, 104(8), p.583 - 592, 2016/08

https://doi.org/10.1515/ract-2015-2540

Solubility studies were conducted with HfO(cr) solid as a function of acid concentrations. These studies involved (1) using two different amounts of the solid phase, (2) acid washing the bulk solid phase, (3) preheating the solid phase to 1400 C, and (4) heating amorphous HfO(am) suspensions to 90 C to ascertain whether the HfO(am) converts to HfO(cr) and to determine the solubility from the oversaturation direction. Based on the results of these treatments it is concluded that the HfO(cr) contains a small fraction of less crystalline, but not amorphous, material [HfO(lcr)] and this, rather than the HfO(cr), is the solubility-controlling phase in the range of experimental variables investigated in this study. The solubility data are interpreted using both the Pitzer and SIT models. The log of the solubility product of HfO(cr) is estimated. The observation of a small fraction of less crystalline higher solubility material is consistent with the general picture that mineral surfaces are often structurally and/or imperfect leading to a higher solubility than the bulk crystalline solid. This study stresses the urgent need, during interpretation of solubility data, of taking precautions to make certain that the observed solubility behavior for sparingly-soluble solids is assigned to the proper solid phase.

Evaluation of source term parameters for spent fuel disposal in foreign countries, 1; Instant release fraction from spent fuel matrices and composition materials for fuel assemblies

Nagata, Masanobu; Chikazawa, Takahiro*; Akahori, Kuniaki*; Kitamura, Akira; Tachi, Yukio

Genshiryoku Bakkuendo Kenkyu (CD-ROM), 23(1), p.31 - 54, 2016/06

https://doi.org/10.3327/jnuce.23.1_31

Although spent nuclear fuel is planned to be disposed after reprocessing and vitrification of high-level radioactive waste (HLW), feasibility study on direct disposal of spent nuclear fuel (SF) has been started as an alternative option to flexibly apply change of future energy situation in Japan. Radionuclide inventories and their release behavior after breaching spent fuel container should be assessed to confirm safety of the SF disposal. However, these detailed studies have not been performed in Japan. Therefore, we investigated some foreign safety assessment reports on direct disposal of spent nuclear fuel by focusing on the source term of the fast release of radionuclides (i.e. instant release fraction; IRF) for the purpose of contributing to the safety assessment of Japanese SF disposal system. As a result of comparison between the safety assessment reports in foreign countries, although some fundamental data have been referred to the reports in common, the final source term dataset (IRF) was seen differences between countries in the result of taking into account the national circumstances (Reactor type and burnup, etc.). We also found the difference of assignment of uncertainties among the investigated reports; a report selected pessimistic values and another report selected mean values and their deviations. It is expected that these findings are useful as fundamental information for determination of the release rates for the safety assessment of Japanese SF disposal system.

Impact assessment of the forest fires on Oarai Research and Development Center Waste Treatment Facility

Shimomura, Yusuke; Hanari, Akira*; Sato, Isamu*; Kitamura, Ryoichi

JAEA-Technology 2015-062, 47 Pages, 2016/03

JAEA-Technology-2015-062.pdf:1.85MB

In response to new standards for regulating waste management facilities, it was carried out impact assessment of forest fires on the waste management facilities existed in Oarai Research and Development Center of Japan Atomic Energy Agency. At first, a fire spread scenario of forest fires was assumed. The intensity of forest fires was evaluated from field surveys, forest fire evaluation models and so on. As models of forest fire intensity evaluation, Rothermel Model and Canadian Forest Fire Behavior Prediction (FBP) System were used. Impact assessment of radiant heat to the facilities was carried out, and temperature change of outer walls for the assumed forest fires was estimated. The outer wall temperature of facilities was estimated around 160C at the maximum, it was revealed that it doesn't reach allowable temperature limit. Consequently, it doesn't influence the strength of concrete. In addition, a probability of fire breach was estimated to be about 20%. This report illustrates an example of evaluation of forest fires for the new regulatory standards through impact assessment of the forest fires on the waste management facilities.

Effects of -radiation on a direct disposal system for spent nuclear fuel, 2; Review of research into safety assessments of direct disposal of spent nuclear fuel in Europe and North America

Kitamura, Akira; Takase, Hiroyasu*; Metcalfe, R.*; Penfold, J.*

Journal of Nuclear Science and Technology, 53(1), p.19 - 33, 2016/01

https://doi.org/10.1080/00223131.2015.1014874

Not only geological disposal of vitrified waste generated by spent fuel (SF) reprocessing, but also the possibility of disposing of SF itself in deep geological strata (hereinafter "direct disposal of SF") may be considered in the Japanese geological disposal program. In the case of direct disposal of SF, the radioactivity of the waste is higher and the potential effects of the radiation are greater. Specific examples of the possible effects of radiation include: increased amounts of canister corrosion; generation of oxidizing chemical species in conjunction with radiation degradation of groundwater and accompanying oxidation of reducing groundwater; and increase in the dissolution rate and the solubility of SF. Therefore, the influences of radiation, which are not expected to be significant in the case of geological disposal of vitrified waste, must be considered in safety assessments for direct disposal of SF. Focusing especially on the effects of -radiation in safety assessment, this study has reviewed safety assessments in countries other than Japan that are planning direct disposal of SF. The review has identified issues relevant to safety assessment for the direct disposal of SF in Japan.