Efficient separation of americium by a mixed solvent of two extractants, a diamideamine and a nitrilotriacetamide

Suzuki, Hideya*; Ban, Yasutoshi

Analytical Sciences, 39(8), p.1341 - 1348, 2023/08

https://doi.org/10.1007/s44211-023-00344-2

The Japan Atomic Energy Agency (JAEA) has proposed the Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation (SELECT) process by solvent extraction as a new separation technology to recover minor actinides (MA) from high-level liquid waste (HLLW) produced by spent fuel reprocessing. The MA separation in the SELECT process comprises the batch recovery of MA and rare earths (RE) from HLLW, MA/RE separation, and Am/Cm separation. Three highly practical extractants are used in the MA separation. Furthermore, this flow configuration facilitates the preparation of nitric acid concentrations in the aqueous phase. However, the separation factor between Cm and Nd in the MA/RE separation is small ( = 2.5), requiring many extraction stages for continuous extraction in a mixer-settler. Therefore, this study investigated the separation of only Am from an aqueous nitric acid solution containing MA (Am and Cm) and RE using an organic phase mixed with two extractants alkyl diamideamine with 2-ethylhexyl alkyl chains (ADAAM(EH)) and hexa-n-octylnitrilotriacetamide (HONTA) used in the SELECT process. Under high-concentration nitric acid conditions, Am and La, Ce, Pr, Nd (light lanthanides) were extracted in the ADAAM(EH) + HONTA mixed solvent, whereas Cm, medium, and heavy lanthanides, and Y were partitioned in the aqueous phase. Subsequently, only light lanthanides could be back extracted from the ADAAM(EH) + HONTA mixture solvent containing Am and light lanthanides in low nitric acid concentrations. Furthermore, Am could be easily stripped with 0.2 M or 5 M nitric acid. This method does not require the mutual separation of Cm and Nd, which have low separation factors. Am can be efficiently separated by one extraction and two back-extractions, reducing the number of steps in the SELECT process.

Mass-spectrometric determination of iodine-129 using O-CO mixed-gas reaction in inductively coupled plasma tandem quadrupole mass spectrometry

Matsueda, Makoto; Aoki, Jo; Koarai, Kazuma; Terashima, Motoki; Takagai, Yoshitaka*

Analytical Sciences, 38(11), p.1371 - 1376, 2022/11

https://doi.org/10.1007/s44211-022-00180-w

The I analysis using ICP-MS is challenging caused by xenon-129 (Xe) and IH generated from excess stable isotope I. In this study, mass discrimination between iodine-129 (I) and interfering substances was achieved by inductively coupled plasma-tandem quadrupole mass spectrometry (ICP-MS/MS) with a dynamic reaction cell introduced a mixture gas of O and CO. As a result, the ratio of (background noise intensity at m/z 129)/I was 3.8 10 and 10 mBq/L of I was analyzed without chemical separation in the presence of 100 mg/L stable I. Spiked tests with actual rainwater were performed, and obtained values were agreed with the spiked amounts.

Lanthanide extraction using a thiodiglycolamic acid extractant; Effect of S-donor on lanthanide separation

Shimojo, Kojiro; Fujiwara, Iori*; Oshima, Tatsuya*; Yokoyama, Keiichi; Yaita, Tsuyoshi

Analytical Sciences, 38(7), p.1003 - 1006, 2022/07

https://doi.org/10.1007/s44211-022-00123-5

Liquid-liquid extraction of lanthanide (Ln) ions was investigated using -dioctylthiodiglycolamic acid (DOTDGAA), which is a sulfur donor ligand with an amide group and a carboxyl group connected by a thioether chain. The extraction performance and selectivity of DOTDGAA for Ln ions were compared with those of -dioctyldiglycolamic acid (DODGAA), which is also an oxygen donor ligand with a similar chemical structure, to assess the effect of the soft/hard donor atom on Ln separation. DOTDGAA quantitatively extracted all Ln ions while being selective toward light and middle Ln ions, in contrast to the selectivity of DODGAA for heavier Ln ions. Slope analysis demonstrated that the Ln transfer using DOTDGAA proceeded through a proton-exchange reaction, forming a 1:3 complex, Ln(DOTDGAA). The back-extraction of Ln ions from the extracting phase was successfully achieved under acidic conditions.

Design of microchannel suitable for packing with anion exchange resins; Uranium separation from seawater containing a large amount of cesium

Ouchi, Kazuki; Tsukahara, Takehiko*; Brandt, A.*; Muto, Yuki*; Nabatame, Nozomi*; Kitatsuji, Yoshihiro

Analytical Sciences, 37(12), p.1789 - 1794, 2021/12

https://doi.org/10.2116/analsci.21P110

We attempted to scale down a separation process of uranium (U) using the microchip column loaded with anion exchange resin to develop safety and waste-reducing separation technique. The ideal separation performance of U was obtained by the properly design of a microchannel. The concentration of U in seawater as a real-world sample could be quantified with the prepared microchip column. It indicates that the microchip column is sufficiently practical. Compared to separation of U with a general column, the column size was successfully scaled down to 1/5000.

Separation of light and middle lanthanides using multistage extraction with diglycolamide extractant

Matsutani, Takafumi; Sasaki, Yuji; Katsuta, Shoichi*

Analytical Sciences, 37(11), p.1603 - 1609, 2021/11

https://doi.org/10.2116/analsci.21P120

We investigated the chemical behavior of lanthanides (Ln) using diglycolamide extractant with multistage extraction. We obtained the breakthrough curves for light and middle Ln. Our study reveals that the metal extraction limit depends on their values and metal concentrations used in the experiments. From the multistage extractions of 15 aqueous phases and 15 organic phases, three curves (extraction curves, back-extraction curves, and separation curves) were obtained by changing the nitric acid concentration. As an example, under a condition of the separation curve experiment (aqueous phase: 0.5 M HNO, organic phase: 0.1 M TDDGA (-tetradecyl-diglycolamide) in -dodecane), a recovery of more than 99% of Sm in the organic phase with less than 1% Nd can be obtained.

Solvent extraction of technetium(VII) and rhenium(VII) using a hexaoctylnitrilotriacetamide extractant

Shimojo, Kojiro; Suzuki, Hideya; Yokoyama, Keiichi; Yaita, Tsuyoshi; Ikeda, Atsushi

Analytical Sciences, 36(12), p.1435 - 1437, 2020/12

https://doi.org/10.2116/analsci.20C014

Liquid-liquid extraction for the removal of pertechnetate (TcO) and perrhenate (ReO) is reported using tripodal extractant -hexa--octylnitrilotriacetamide (HONTA) composed of three amide groups and a tertiary amine. The extraction behavior was compared with those using alkyldiamideamines (ADAAM(Oct) and ADAAM(EH)), and the commercial amine-type extractant, trioctylamine (TOA). HONTA quantitatively extracted TcO and ReO in the pH range from 1.0 to 2.5 by co-extraction of protons. Extraction performance of extractants was improved in the order of HONTA ADAAM(Oct) ADAAM(EH) TOA. TcO and ReO in the extracting phase were successfully stripped using neutral aqueous solutions as the receiving phase, and the extraction ability of HONTA was maintained after five repeated uses.

Application of an augmentation method to MCR-ALS analysis for XAFS and Raman data matrices in the structural change of isopolymolybdates

Saeki, Morihisa*; Yomogida, Takumi; Matsumura, Daiju; Saito, Takumi*; Nakanishi, Ryuzo*; Tsuji, Takuya; Oba, Hironori*

Analytical Sciences, 36(11), p.1371 - 1378, 2020/11

https://doi.org/10.2116/analsci.20P147

We measured X-ray absorption fine structure (XAFS) and Raman spectra of isopolymolybdates(VI) in HNO solution (0.15- 4.0 M), which change their geometries depending on acid concentration, and performed simultaneous resolution of the XAFS and Raman data using a multivariate curve resolution by alternating least-squares (MCR-ALS) analysis. In iterative ALS optimization, initial data matrices were prepared by two different methods. The MCR-ALS result of single XAFS data matrix shows large dependence on the preparation method of the initial data matrices. The MCR-ALS result of an augmented matrix of Raman and XAFS data has little dependence on the initial data matrices. It indicates that the augmentation method effectively improves the rotation ambiguities in the MCR-ALS analysis of the XAFS data. Based on the model fitting of the pure EXAFS oscillations, we revealed the change of [MoO(HO)] [MoO(HO)] [HMoO(HO)] in the highly concentrated HNO solution.

Effects of diluents on the separation of minor actinides from lanthanides with tetradodecyl-1,10-phenanthroline-2,9-diamide from nitric acid medium

Tsutsui, Nao; Ban, Yasutoshi; Suzuki, Hideya*; Nakase, Masahiko*; Ito, Sayumi*; Inaba, Yusuke*; Matsumura, Tatsuro; Takeshita, Kenji*

Analytical Sciences, 36(2), p.241 - 246, 2020/02

https://doi.org/10.2116/analsci.19P275

To investigate the effective separation of actinides (Ans) from lanthanides (Lns), single-stage batch extraction experiments were performed with a novel extractant, tetradodecyl-1,10-phenanthroline-2,9-diamide (TDdPTDA) with various diluents such as 3-nitrobenzotrifluoride (F-3), nitrobenzene, and -dodecane for Am, Cm, and Lns. The extraction kinetics with TDdPTDA was rapid enough to perform the actual extraction flow sheet. The slopes of the distribution ratio versus TDdPTDA concentration and the distribution ratio versus nitric acid concentration were similar for F-3 and nitrobenzene systems but different from -dodecane system. These differences were attributed to the characteristics of the diluents. This study reveals high distribution ratios of Am ( ) and Cm ( ) for TDdPTDA, with the high separation factors (s) of Am from Lns enough for their separation.

Extraction mechanism of lanthanide ions into silica-based microparticles studied by single microparticle manipulation and microspectroscopy

Otaka, Toshiki*; Sato, Tatsumi*; Ono, Shimpei; Nagoshi, Kohei; Abe, Ryoji*; Arai, Tsuyoshi*; Watanabe, So; Sano, Yuichi; Takeuchi, Masayuki; Nakatani, Kiyoharu*

Analytical Sciences, 35(10), p.1129 - 1133, 2019/10

https://doi.org/10.2116/analsci.19P155

Evaluation of photocatalytic abilities by variation of conductivity and dimethyl sulfoxide; Photocatalytically active TiO-coated wire mesh prepared via a double-layer coating method

Mori, Masanobu*; Sugita, Tsuyoshi; Fujii, Kengo*; Yamazaki, Taiki*; Isaka, Mayu*; Kobayashi, Kentaro*; Iwamoto, Shinji*; Itabashi, Hideyuki*

Analytical Sciences, 34(12), p.1449 - 1453, 2018/12

https://doi.org/10.2116/analsci.18N012

The photocatalyst coating stainless-steel wire mesh (TiO-WM) was prepared by double-layer coating method. The TiO-WM was evaluated using flow analytical system, which included the reactor and conductimetric detector (FAS-CD). The DMSO decomposition test through the FAS-CD reveal that photocatalytst was stable coating on the stainless-steel wire mesh.