Acid dissolution treatment of aged plutonium oxide

Emori, Tatsuya; Kitatsuji, Yoshihiro; Ban, Yasutoshi

JAEA-Technology 2026-013, 12 Pages, 2026/08

JAEA-Technology-2026-013.pdf:1.49MB

The use of Radioisotope Thermoelectric Generator (RTGs) using the decay heat of Pu-238 is being considered as a power source for permanently shadow regions on the lunar surface, where solar power is impractical, as well as for deep-planet missions far from Jupiter. However, Japan does not have the capability to produce Pu-238 or the operational performance of its usage. Additionally, it is difficult to employ nuclear fuel materials for space probes in Japan due to regulatory constraints. Consequently, development related to the utilization of Am-241 has been carried out. We performed dissolution experiments using aged PuO powder that has been stored for research purposes, aiming at the mutual separation of Pu and Am. Two experiments were conducted: one using a nitric acid solution and the other using a mixture solution of nitric acid and hydrogen peroxide. The dissolution time with the latter solution was less than half that required for the former. Furthermore, unlike other commonly used oxidants, the use of hydrogen peroxide prevented contamination by salts and metals and minimized potential detrimental effects on the subsequent Pu/Am separation experiments.

Temperature effect on radiolytically generated hydrogen yield from a plutonium nitric acid aqueous solution

Toigawa, Tomohiro; Hotoku, Shinobu; Kumagai, Yuta; Abe, Yuma*; Oyama, Kanichi*; Fukaya, Hiroyuki; Ban, Yasutoshi; Kida, Takashi; Hasegawa, Satoshi*; Nakano, Masanao*; et al.

Journal of Nuclear Science and Technology, 63(3), p.322 - 327, 2026/03

https://doi.org/10.1080/00223131.2025.2541067

The effect of temperature on hydrogen production generated from radiolysis was investigated to determine the associated implications for nuclear fuel reprocessing safety. The hydrogen yield from radiolysis of plutonium nitric acid solution was measured at temperatures up to the boiling temperature of the solution. The results showed no notable temperature dependence even under boiling conditions. The impact of solution agitation on hydrogen production was also assessed, which revealed minor differences in the hydrogen yield between static and agitated conditions at room temperature. These findings suggest that high temperatures or boiling the solution do not considerably enhance hydrogen generation, and provide crucial information for accurately modeling hydrogen risks under severe accidents.

Role of Alkyl Chain Branching in the Self-Assembly of Nitrilotriacetamide-Based Lanthanide Extractants

Ueda, Yuki; Kobayashi, Toru; Nakamura, Satoshi; Ban, Yasutoshi; Kaneta, Yui; Nabatame, Nozomi; Micheau, C.; Tokunaga, Kohei; Nakabe, Rintaro; Kaneko, Masashi*; et al.

Langmuir, 42(1), p.1613 - 1626, 2026/01

https://doi.org/10.1021/acs.langmuir.5c05651

Understanding the structural factors governing the metal ions selectivity of solvent extraction systems is crucial for developing advanced processes for partitioning and transmutation of high-level radioactive waste. Here, we systematically investigated the effect of alkyl side-chain branching in nitrilotriacetamide (NTAamide) extractants on the extraction of lanthanum (La) and neodymium (Nd), chosen as representative lanthanides. Four extractants having each eight carbon atoms as one of the amide chains with identical molecular weights but different degrees of alkyl branching were examined. Distribution ratios were measured as a function of HNO concentration, and the local coordination structures of La and Nd were analyzed by extended X-ray absorption fine structure (EXAFS), while supramolecular aggregation in the organic phase was characterized by small-angle neutron scattering (SANS). EXAFS analysis revealed that the inner-sphere coordination environment of La and Nd was essentially unaffected by the degree of alkyl branching. In contrast, SANS results showed that extractants with fewer branched alkyl groups formed larger aggregates at low HNO concentrations, particularly in the case of Nd, where aggregation was found to facilitate extraction and prevent precipitation of poorly soluble complexes. These findings demonstrate that alkyl branching strongly influences supramolecular aggregation, which in turn governs extraction behavior. This work highlights the potential of nanoscale structural control as a new design concept for improving selectivity in lanthanide and actinide solvent extraction systems.

Separation test of heat generating nuclides from high-level liquid waste

Hotoku, Shinobu; Ban, Yasutoshi; Konda, Miki; Kitatsuji, Yoshihiro

JAEA-Technology 2025-009, 33 Pages, 2025/11

JAEA-Technology-2025-009.pdf:1.9MB

High-level liquid waste (HLLW) produced from reprocessing of spent nuclear fuels contains heat generating nuclides such as Sr-90, Y-90, Cs-137, Ba-137m, and Am-241. Separation and recovery of these nuclides lead to reduce the volume and toxicity of high-level waste. Furthermore, the recovered nuclides and elements could be utilized as resources after purification. In this test, Sr separation by extraction chromatography using Sr resin and Pb resin, Cs separation by co-precipitation using ammonium phosphomolybdate (AMP), and Am separation by solvent extraction using alkyl diamideamine (ADAAM) were carried out, cold tests were performed for the separation of Cs and Sr in a nitric acid solution. Based on the results, hot tests were performed using dissolution solutions of spent fuel at the Nuclear Fuel Cycle Safety Engineering Research Facility (NUCEF), and each component contained in the separated solution was analyzed. In the Sr separation by extraction chromatography, most of Sr was separated from other elements using 8 mol/L nitric acid for absorption and 0.02 mol/L nitric acid for elution. In the separation of Cs, more than 99.9% of Cs was selectively co-precipitated by adding AMP to the HLLW, in which nitric acid concentration was adjusted to 3.1 mol/L. In solvent extraction of Am by ADAAM, 81.4% of Am-241 was recovered by a single stage batch experiment. Since Sr, Cs, and Am were properly separated and recovered from HLLW, the effectiveness of the present separation method was successfully demonstrated.

Extraction properties of glycine-based amic-acid-type extractants for minor actinides and rare-earth elements

Nakamura, Satoshi; Suzuki, Hideya*; Ban, Yasutoshi; Ohashi, Akira*

Progress in Nuclear Science and Technology (Internet), 8, p.228 - 232, 2025/09

https://doi.org/10.15669/pnst.8.228

To reduce volume and radiotoxicity of high-level radioactive waste, JAEA has been developing a separation process recovering minor actinides (MA) from high-level radioactive liquid-waste. In the separation process, separating trivalent MA such as Am and Cm, from RE is challenging due to their similar chemical properties. In this study, extraction properties of three different glycine-based amic-acid-type extractants for MA(III) and RE(III) were studied by a single-stage batch method. The results revealed that the distribution ratios of all metal ions increased with an increase of equilibrium pH, and all extractants showed higher distribution ratios for Am than for RE.

Extraction, separation and isolation of MA from Ln using two extractants (TODGA and ADAAM) and a masking agent (DTBA)

Sasaki, Yuji; Kaneko, Masashi; Kumagai, Yuta; Ban, Yasutoshi

Progress in Nuclear Science and Technology (Internet), 8, p.202 - 204, 2025/09

https://doi.org/10.15669/pnst.8.202

Two extractants and a masking agent of TODGA (TetraOctyl-DiGlycolAmide), ADAAM (AlkylDiAmideAMine), and DTBA (DiethyleneTriamine-triacetic-BisAmide) were developed in JAEA. TODGA can extract both trivalent actinides (An) and lanthanides (Ln), DTBA may separate An from Ln, and ADAAM has high separation factor (SF: 6) for Am/Cm. The suitable conditions for the extraction, separation and isolations of An from Ln are investigated using these reagents. In this work, we show the basic information on extraction behavior of An and Ln using TODGA, DTBA and ADAAM and propose the suitable aqueous and the organic conditions for An+Ln extraction, An/Ln separation and Am/Cm separation.

Development of technology for separating Am-241 in aged plutonium

Emori, Tatsuya; Kitatsuji, Yoshihiro; Ban, Yasutoshi

JAEA-Technology 2024-025, 20 Pages, 2025/03

JAEA-Technology-2024-025.pdf:1.65MB

Radioisotope Thermoelectric Generators (RTGs) using the decay heat of Pu-238 has been applied for outer planet missions far from Jupiter, where solar power is limited. However, no facilities are available to produce Pu-238 for space probes in Japan. Moreover, the use of nuclear materials for the space exploration is difficult in term of the regulation. Thus, we focused on Am-241 whose half-life is around 432 years as an alternative heat source for RTGs. This report describes the procedure of separating Am-241 decayed from Pu-241 in aged plutonium oxide. Two experiments were performed: one using solid-liquid extraction and the other combining liquid-liquid extraction and solid-liquid extraction. Packed columns were used in the experiments, with their number reduced by less than one-fifth in the latter experiment compared to the former. Furthermore, the time required for separation in the latter experiment was less than half that of the former. We performed the separation experiments six times, collecting a total of approximately 0.43 g of Am-241 as an oxalate salt.

Development of a dissolution method for analyzing the elemental composition of fuel debris using sodium peroxide fusion technique

Nakamura, Satoshi; Ishii, Sho*; Kato, Hitoshi*; Ban, Yasutoshi; Hiruta, Kenta; Yoshida, Takuya; Uehara, Hiroyuki; Obata, Hiroki; Kimura, Yasuhiko; Takano, Masahide

Journal of Nuclear Science and Technology, 62(1), p.56 - 64, 2025/01

https://doi.org/10.1080/00223131.2024.2381553

A dissolution method for analyzing the elemental composition of fuel debris using the sodium peroxide (NaO) fusion technique has been developed. Herein, two different types of simulated debris materials (such as solid solution of (Zr,RE)O and molten core-concrete interaction products (MCCI)) were taken. At various temperatures, these debris materials were subsequently fused with NaO in crucibles, which are made of different materials, such as Ni, AlO, Fe, and Zr. Then, the fused samples are dissolved in nitric acid. Furthermore, the effects of the experimental conditions on the elemental composition analysis were evaluated using inductively coupled plasma-atomic emission spectroscopy (ICP-AES), which suggested the use of a Ni crucible at 923 K as an optimum testing condition. The optimum testing condition was then applied to the demonstration tests with Three Mile Island unit-2 (TMI-2) debris in a shielded concrete cell, thereby achieving complete dissolution of the debris. The elemental composition of TMI-2 debris revealed by the proposed dissolution method has good reproducibility and has an insignificant contradiction in the mass balance of the sample. Therefore, this newly developed reproducible dissolution method can be effectively utilized in practical applications by dissolving fuel debris and estimating its elemental composition.

Using X-ray absorption near edge structure to evaluate adsorption properties of rare earths and nitrogen by difference of their interactions

Minowa, Kazuki*; Watanabe, So; Nakase, Masahiko*; Takahatake, Yoko; Miyazaki, Yasunori; Ban, Yasutoshi; Matsuura, Haruaki*

Nuclear Instruments and Methods in Physics Research B, 556, p.165496_1 - 165496_6, 2024/11

https://doi.org/10.1016/j.nimb.2024.165496

In this study, X-ray absorption near edge structure (XANES) spectral analysis and column experiments were used to verify the selectivity of rare earth (RE) ions by alkyl diamide amine (ADAAM) adsorbent. In addition, the interactions between the N atoms of ADAAM and RE ions were evaluated to determine whether any of the RE ions are a valid simulant for developing a mutual separation process for minor actinides (MAs) in highly radioactive liquid waste. It was confirmed that La and Ce interacted with the amine N atom of ADAAM and they showed a peak shift of the N-K edge XANES spectrum; this finding suggested that a soft interaction is an essential factor influencing ion selectivity. Therefore, the selection factor of RE ions by ADAAM adsorbent was similar to that of MAs. It was concluded that RE ions are reasonable species to simulate MAs.

Mutual separation of Am and Cm using ADAAM (alkyl DiAmide AMine) and reduction of volumes for liquid waste generated via batch-wise multistage extractions

Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Suzuki, Hideya*

Journal of Nuclear Science and Technology, 61(7), p.883 - 893, 2024/07

https://doi.org/10.1080/00223131.2023.2283214

The mutual separation of Am and Cm is conducted using an alkyl-diamide amine (ADAAM) extractant. ADAAM exhibits extremely high separation factor with respect to Am and Cm separation (5.9) in a nitric acid--dodecane system. The batch-wise multistage extractions are performed using a system containing 0.2 M ADAAM and 1.5 M nitric acid. In this multistage extraction, an organic solvent give 96.5% and 1.06% yields of Am and Cm. After the mutual separation of Am and Cm, an additional extraction step is included to reduce the volumes of these aqueous and organic phases. Taking these steps, Am and Cm can be recovered in just two or three stages in the aqueous phases.