Selective adsorption of Pd(II) over Ag(I) in nitric acid solutions using nitrogen-donor-type adsorbents

Suzuki, Tomoya*; Otsubo, Ukyo*; Ogata, Takeshi*; Shiwaku, Hideaki; Kobayashi, Toru; Yaita, Tsuyoshi; Matsuoka, Mitsuaki*; Murayama, Norihiro*; Narita, Hirokazu*

Separation and Purification Technology, 308, p.122943_1 - 122943_7, 2023/03

https://doi.org/10.1016/j.seppur.2022.122943

HNO leaching is used in recycling Pd metal from spent products that primarily contain Ag, and most Pd residues are separated from solutions containing Ag(I). However, a small amount of Pd(II) often remains in these Ag(I) solutions. Therefore, the separation of Pd(II) and Ag(I) in HNO solutions is essential to promote efficient Pd recycling. In this study, the separation of Pd(II) and Ag(I) in HNO solutions was investigated using four N-donor-type adsorbents functionalized with amine (R-Amine), iminodiacetic acid (R-IDA), pyridine (R-Py), or bis-picolylamine (R-BPA). R-Amine, R-IDA, and R-Py selectively adsorbed Pd(II) over Ag(I), Cu(II), Ni(II), and Fe(III) from HNO solutions (0.3-7 M), but R-Amine exhibited a lower Pd adsorption efficiency. In contrast, 90% of Pd(II), Ag(I), and Cu(II) were adsorbed by R-BPA over the entire range of HNO concentrations. Structural analyses of the adsorbed metal ions using Fourier transform infrared spectroscopy and extended X-ray absorption fine structure spectroscopy revealed the separation mechanisms of the N-donor-type adsorbents. Pd(II) adsorption on R-IDA, R-Py, and R-BPA occurred via Pd(II) coordination of the functional groups (iminodiacetic acid, pyridine, and bis-picolylamine, respectively), whereas that on R-Amine occurred via anion exchange of NO with [Pd(NO)]. The coordinative adsorption mechanisms resulted in the higher Pd(II) adsorption behaviors of R-IDA, R-Py, and R-BPA. HCl (5.0 M) and thiourea (0.1 M) eluents desorbed 83% of Pd(II) from R-IDA and 95% from R-Py, respectively. R-Py was the most effective Pd(II) adsorbent based on adsorption selectivity and desorption efficiency.

Transfer and operation of WSPEEDI-II automatic calculation system for responses to nuclear tests by North Korea

Nemoto, Miho*; Ebine, Noriya; Okamoto, Akiko; Hosaka, Yasuhisa*; Tsuzuki, Katsunori; Terada, Hiroaki; Hayakawa, Tsuyoshi; Togawa, Orihiko

JAEA-Technology 2021-013, 41 Pages, 2021/08

JAEA-Technology-2021-013.pdf:2.52MB

When North Korea has carried out nuclear tests, Nuclear Emergency Assistance and Training Center (NEAT) predicts atmospheric dispersion of radionuclides by using the WSPEEDI-II upon requests from Nuclear Regulation Authority (NRA) and submits the predicted results to NRA in cooperation with Nuclear Science and Engineering Center (NSEC). This is a part of the activity of NEAT supporting the Japanese Government in emergency responses. The WSPEEDI-II automatic calculation system specialized for responses to nuclear tests by North Korea was developed by NSEC and was used for responses to three nuclear tests from February 2013 to September 2017. This report describes the transfer and installation of the calculation system to NEAT, and the subsequent maintenance and operation. Future issues for responses to nuclear tests are also described in this report.

Lanthanide intra-series separation by a 1,10-phenanthroline derivative; Counterion effect

Simonnet, M.; Suzuki, Shinichi; Miyazaki, Yuji*; Kobayashi, Toru; Yokoyama, Keiichi; Yaita, Tsuyoshi

Solvent Extraction and Ion Exchange, 38(4), p.430 - 440, 2020/00

https://doi.org/10.1080/07366299.2020.1744806

Intercomparison of numerical atmospheric dispersion prediction models for emergency response to emissions of radionuclides with limited source information in the Fukushima Dai-ichi Nuclear Power Plant accident

Iwasaki, Toshiki*; Sekiyama, Tsuyoshi*; Nakajima, Teruyuki*; Watanabe, Akira*; Suzuki, Yasushi*; Kondo, Hiroaki*; Morino, Yu*; Terada, Hiroaki; Nagai, Haruyasu; Takigawa, Masayuki*; et al.

Atmospheric Environment, 214, p.116830_1 - 116830_11, 2019/10

https://doi.org/10.1016/j.atmosenv.2019.116830

The utilization of numerical atmospheric dispersion prediction (NDP) models for accidental discharge of radioactive substances was recommended by a working group of the Meteorological Society of Japan. This paper is to validate the recommendation through NDP model intercomparison in the accidental release from the Fukushima Dai-ichi Nuclear Power Plant in 2011. Emission intensity is assumed to be constant during the whole forecast period for the worst-case scenario unless time sequence of emission is available. We expect to utilize forecasts of surface air contaminations for preventions of inhalations of radioactive substances, and column-integrated amounts for mitigation of radiation exposure associated with wet deposition. Although NDP forecasts have ensemble spread, they commonly figure out relative risk in space and time. They are of great benefit to disseminating effective warnings to public without failure. The multi-model ensemble technique may be effective to improve the reliability.

Evaluation of electronic state of Cs-adsorbed clay minerals by NEXAFS analysis using DFT calculations

Suzuki, Chikashi; Yaita, Tsuyoshi; Suzuki, Shinichi; Pacold, J.*; Altman, A. B.*; Minasian, S. G.*; Tyliszczak, T.*; Shuk, D. K.*; Yoshida, Hiroyuki; Osaka, Masahiko

Journal of Physics and Chemistry of Solids, 127, p.169 - 177, 2019/04

https://doi.org/10.1016/j.jpcs.2018.11.011

A combined method of NEXAFS measurement and DFT-calculation was employed for Cs evaluation in clay minerals. The Cs M NEXAFS spectra of Cs halides were analyzed using the DFT-calculations, and were well reproduced by incorporating the core-hole strength. The Cs M NEXAFS spectrum of clay minerals was well-reproduced by the DFT-calculations including the major transitions and tail structures with the established method. The further evaluation of this spectrum by charge density suggests that these major transitions and the tail structures likely reflect bonding states and local environments around the Cs atoms. Comparison of electronic states of Cs in the clay mineral with those in the Cs halides by DFT-calculations has shown that the interaction between Cs and the nearest-neighbor atom is largest in the clay mineral, because the energy level of Cs-5s and 5p is closer to that of O-2s and 2p than the s and p orbitals of other alkali metal and alkali earth metal elements.

Crack expansion and fracturing mode of hydraulic refracturing from Acoustic Emission monitoring in a small-scale field experiment

Ishida, Tsuyoshi*; Fujito, Wataru*; Yamashita, Hiroto*; Naoi, Makoto*; Fujii, Hirokazu*; Suzuki, Kenichiro*; Matsui, Hiroya

Rock Mechanics and Rock Engineering, 52(2), p.543 - 553, 2019/02

AA2017-0694.pdf:2.54MB

https://doi.org/10.1007/s00603-018-1697-5

We pressurized and injected water in a hole drilled downward from a floor of the 500 m level gallery in MIU, central Japan. Acoustic emissions (AEs) monitored with 16 sensors in four boreholes located 1 m away from the HF hole exhibited two-dimensional distributions, which likely delineate a crack induced by the fracturing. Expansions of the regions in which AEs occurred were observed only immediately after the first and second BDs. Many AE events in other periods were distributed within the regions where AE events had already occurred. The initial motion polarities of P-waves indicate that tensile-dominant AE events occurred when the regions expanded and they were distributed primarily on the frontiers of the regions where AE events had already occurred. The experimental results suggest that increasing the injection flow rate is effective for generating new cracks in the refracturing, with the new crack expansions being induced by tensile fracturing.

Quantitative analysis of Cs extraction by some dialkoxycalix[4]arene-crown-6 extractants

Simonnet, M.; Miyazaki, Yuji*; Suzuki, Shinichi; Yaita, Tsuyoshi

Solvent Extraction and Ion Exchange, 37(1), p.81 - 95, 2019/00

https://doi.org/10.1080/07366299.2019.1575002

Absorbent property of fullerene for cesium isotope separation investigated using X-ray photoelectron spectroscopy

Sekiguchi, Tetsuhiro; Yokoyama, Keiichi; Uozumi, Yuki*; Yano, Masahiro; Asaoka, Hidehito; Suzuki, Shinichi; Yaita, Tsuyoshi

Progress in Nuclear Science and Technology (Internet), 5, p.161 - 164, 2018/11

https://doi.org/10.15669/pnst.5.161

For nuclear transmutation of cesium-135 (Cs), which is long-lived fission product, we are developing selective absorbent which takes only Cs atom in, but does not CsI. In this study, absorbing property of Cs atom onto the surface of fullerene (C) film has been investigated using synchrotron-based angle-dependent X-ray photoelectron spectroscopy (XPS). The results were compared with those of CsI. It was found that Cs penetrates into C deep bulk. In contrast, CsI deposits on shallow surface. Furthermore, XPS spectra were measured as a function of Ar-sputtering time in order to know Cs concentration profiles in deep region. Results showed that Cs penetrates into deep region of several hundreds .

Lanthanides complexation properties of O, N-hetero donor ligand PTA

Kobayashi, Toru; Suzuki, Shinichi; Shiwaku, Hideaki; Yaita, Tsuyoshi

Progress in Nuclear Science and Technology (Internet), 5, p.74 - 77, 2018/11

https://doi.org/10.15669/pnst.5.74

Development of extractant, which can efficiently separate actinides, is of increasing importance because it concerns establishment and simplification of separation techniques in nuclear fuel cycle and decontamination of radioactive wastes. In this study, the complexation properties of N-alkyl-N-phenyl-1,10-phenanthroline-2-carboxamide (PTA) with trivalent lanthanides (Ln) were investigated based on structural analysis by using X-ray crystallography and extended X-ray absorption fine structure (EXAFS) methods. As a result, it is revealed that two PTA molecules coordinate with Ln as tridentate ligand via two nitrogen in phenanthroline moiety and one oxygen in amide moiety in both crystal and solution states. The slight difference in coordination bond distances are observed between Eu and Nd complexes, this difference corresponds to the difference in ionic radius between Nd and Eu. This result indicates slight difference in ionic radii of Ln hardly affects coordination properties of PTA.

Speciation of ruthenium(III) chloro complexes in hydrochloric acid solutions and their extraction characteristics with an amide-containing amine compound

Suzuki, Tomoya*; Ogata, Takeshi*; Tanaka, Mikiya*; Kobayashi, Toru; Shiwaku, Hideaki; Yaita, Tsuyoshi; Narita, Hirokazu*

Metals, 8(7), p.558_1 - 558_10, 2018/07

AA2018-0670.pdf:2.11MB

https://doi.org/10.3390/met8070558

The refining of platinum group metals is based mainly on solvent extraction methods, whereas Ru is selectively recovered by distillation as RuO. Replacement of distillation byextraction is expected to simplify the purification process. To develop an effective extraction system for Ru, we analyzed the Ru species in HCl with UV-Vis and EXAFS spectroscopies, and we examined the properties of Ru extracted with N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide) amine (EHBAA). EXAFS and UV-Vis spectra of Ru in HCl solutions revealed that the predominant Ru species in 0.5-10 M HCl solutions changed from [RuCl(HO)] to [RuCl] with the HCl concentration. The extraction percentages of Ru in the EHBAA system increased with increasing HCl concentration, reached 80% at [HCl] = 5 M, and decreased athigher HCl concentrations. EXAFS analysis of the extracted complex indicated that the Ru had 5 Cl and 1 HO in its inner coordination sphere. The similarity of the dependence on HCl concentrations of the extraction in the EHBAA system and the distribution profile of [RuCl(HO)] on [RuCl(HO)] suggested that the EHBAA extracted the pentachlorido species.