Saeki, Morihisa*; Yomogida, Takumi; Matsumura, Daiju; Saito, Takumi*; Nakanishi, Ryuzo*; Tsuji, Takuya; Oba, Hironori*
Analytical Sciences, 36(11), p.1371 - 1378, 2020/11
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.
Rizaal, M.; Nakajima, Kunihisa; Saito, Takumi*; Osaka, Masahiko; Okamoto, Koji*
Journal of Nuclear Science and Technology, 57(9), p.1062 - 1073, 2020/09
The interaction of cesium hydroxide and a calcium silicate insulation material was experimentally investigated at high temperature conditions. A thermogravimetry equipped with differential thermal analysis was used to analyze thermal events in the samples of mixed calcium silicate and cesium hydroxide under Ar-5%H and Ar-4%H-20%H0 with maximum temperature of 1100C. Prior being mixed with cesium hydroxide, a part of calcium silicate was pretreated at high temperature to evaluate the effect of possible structural changes of this material due to a preceding thermal history and also the sake of thermodynamic evaluation to those available ones. Based upon the initial condition (preliminary heat treatment) of calcium silicate, it was found that if the original material consisted of xonotlite (CaSi0(0H)), the endothermic reaction with cesium hydroxide occurred over the temperature range 575-730C meanwhile if the crystal phase of original material was changed to wollastonite (CaSi0), the interaction occurred over temperature range 700-1100C. Furthermore, the X-ray diffraction analyses have indicated on both type of pretreated calsils that regardless of Ar-5%H and Ar-4%H-20%H0 atmosphere, cesium aluminum silicate, CsAlSi0 was formed with aluminum in the samples as an impurity or adduct.
Rizaal, M.; Saito, Takumi*; Okamoto, Koji*; Erkan, N.*; Nakajima, Kunihisa; Osaka, Masahiko
Mechanical Engineering Journal (Internet), 7(3), p.19-00563_1 - 19-00563_10, 2020/06
The adsorption of cesium (Cs) on calcium silicate insulation of primary piping system is postulated to contribute in high dose rate of surrounding pedestal area in Fukushima Daiichi NPP unit 2. In this study, room-temperature experiment of Cs adsorption on calcium silicate has been studied as an initial approach of Cs adsorption behavior toward higher temperature condition. As the result of analyzing of Cs adsorption kinetics, it was expected that the underlying adsorption mechanism is chemisorption. Furthermore, analysis of adsorption isotherm suggested unrestricted monolayer formation followed by multilayer formation.
Marumo, Kazuki*; Matsumoto, Atsumasa*; Nakano, Sumika*; Shibukawa, Masami*; Saito, Takumi*; Haraga, Tomoko; Saito, Shingo*
Environmental Science & Technology, 53(24), p.14507 - 14515, 2019/12
Humic acids (HA) are responsible for the fate of metal ions in the environment. We developed a polyacrylamide gel electrophoresis (PAGE) technique to investigate the MW distributions of metal ion (copper ion). Combining contaminant-metal-free and high-resolution PAGE systems for HA provided accurate MW distributions for the metal ions. Coupling this system with UV-Vis spectrometry and the excitation-emission matrix (EEM) spectrometry-parallel factor analysis (PARAFAC) method revealed new insights into metal-HA complex. Interestingly, the MW distributions of the three metal ions were entirely different, indicating that the presence of specific binding environments in HA for the metal ions depending its MW. The MW distributions of five fluorescent components were associated with the metal ion distributions. Our PAGE-based methodology suggests that metal binding sites and fluorescent components in HA exhibit heterogeneity in terms of metal binding affinity and MW.
Kato, Tomoaki*; Yu, Q.*; Tanaka, Kazuya; Kozai, Naofumi; Saito, Takumi*; Onuki, Toshihiko
Journal of Environmental Sciences, 86, p.78 - 86, 2019/12
This paper investigated the fate of the dissolved permanganate in aqueous solution after contact with bacterial cells and metal accumulation during precipitation of Mn oxides. When Mn(VII) was contacted with bacterial cells, cells were damaged and Mn(VII) was reduced by cells to lower valence and precipitated as Mn oxides (biomass Mn oxides). When Co ions were present, Co was incorporated into Mn oxides as Co. These results suggest that Mn(VII) can be used to remove metal ions when introduced to wastewater as disinfectant.
Kobayashi, Taishi*; Nakajima, Shogo*; Motokawa, Ryuhei; Matsumura, Daiju; Saito, Takumi*; Sasaki, Takayuki*
Langmuir, 35(24), p.7995 - 8006, 2019/06
Saeki, Morihisa*; Matsumura, Daiju; Yomogida, Takumi; Taguchi, Tomitsugu*; Tsuji, Takuya; Saito, Hiroyuki*; Oba, Hironori*
Journal of Physical Chemistry C, 123(1), p.817 - 824, 2019/01
Reaction kinetics of laser-induced particle formation in an aqueous solution of PdCl was investigated by transmission electron microscope (TEM) and dispersive X-ray absorption fine structure (DXAFS). The Pd particle was generated by irradiation of nanosecond pulsed 266-nm laser. The TEM observation showed dependence of the particle size on the laser fluence and promotion of the particle growth by irradiation of high-fluence laser. The DXAFS data give us the Pd concentration. Temporal changes of the Pd concentration analyzed based on Finke-Watzky two step mechanism. The analysis elucidates that the laser photon contributes to the reduction of the PdCl ion by the one-photon process and to the autocatalytic growth of the Pd particles by the multi-photon process.
Kimuro, Shingo*; Kirishima, Akira*; Nagao, Seiya*; Saito, Takumi*; Amano, Yuki; Miyakawa, Kazuya; Akiyama, Daisuke*; Sato, Nobuaki*
Journal of Nuclear Science and Technology, 55(5), p.503 - 515, 2018/05
no abstracts in English
Saito, Takumi*; Aoyagi, Noboru; Terashima, Motoki
Journal of Nuclear Science and Technology, 54(4), p.444 - 451, 2017/04
Humic substances (HSs) are ubiquitous in various environments including deep underground and play an important role in the speciation and mobility of radionuclides. The binding of Eu, a chemical homologue of trivalent actinide ions, to HSs isolated from sedimentary groundwater at -250 m below the surface was studied by time-resolved laser fluorescence spectroscopy combined with parallel factor analysis (PARAFAC) as a function of pH and salt concentration. PARAFAC modeling reveals the presence of multiple factors that corresponds to different Eu species. These factors resemble those observed for Eu binding to HSs from surface environments; however, detailed comparison shows that there are some particularities in Eu binding to the deep groundwater HSs. The distribution coefficients () of Eu binding to the HSs calculated from the PARAFAC modeling exhibits a rather strong salt effect. At 0.01 M NaClO the values are relatively large and comparable to those to the surface HSs; they are decreaed at 0.1 M NaClO by more than an order of the magnitude. The values are larger for humic acid fraction of the deep underground HSs than fulvic acid over the entire range of pH and salt concentration investigated in this study.
Sasaki, Takayuki*; Ueda, Kenyo*; Saito, Takumi; Aoyagi, Noboru; Kobayashi, Taishi*; Takagi, Ikuji*; Kimura, Takaumi; Tachi, Yukio
Journal of Nuclear Science and Technology, 53(4), p.592 - 601, 2016/04
The influences of pH and the concentrations of Eu and NaNO on the sorption of Eu to Na-montmorillonite were investigated through batch sorption measurements and time-resolved laser fluorescence spectroscopy (TRLFS). The pH had a little effect on the distribution coefficients (Kd) in 0.01 M NaNO, whereas the Kd strongly depended on pH at 1 M NaNO. A cation exchange model combined with a one-site non-electrostatic surface complexation model was successfully applied to the measured Kd. The TRLFS spectra of Eu sorbed were processed by parallel factor analysis (PARAFAC), which corresponded to one outer-sphere (factor A) and two inner-sphere (factor B and C) complexes. It turned out that factors A and B correspond to Eu sorbed by ion exchange sites and inner-sphere complexation with hydroxyl groups of the edge faces, respectively. Factor C became dominant at relatively high pH and ionic strength and likely correspond to the precipitation of Eu(OH) on the surface.
Nagasaki, Shinya*; Saito, Takumi; Yang, T.*
Journal of Radioanalytical and Nuclear Chemistry, 308(1), p.143 - 153, 2016/04
Sorption of Np(V) on illite, shale and MX-80 under oxidizing conditions were first studied in two types of high ionic strength solutions: (1) a reference brine solution (SR-270-PW) with an ionic strength (I) of 6.0 M, and (2) Na-Ca-Cl solutions (with different Na/Ca molar ratios and different ionic strengths, up to a maximum of 4.6 M). The effects of pHc, Na/Ca ratio, and ionic strength on sorption in Na-Ca-Cl solutions were investigated. The Kd values increased with increasing pHc and Na/Ca ratio for all sorbents studied. The Kd values on illite and shale were independent of the ionic strength over the range 0.10-4.6 M, and the Kd value on MX-80 was independent of ionic strength greater than 1.0 M. The Kd values and the sorption isotherms in both SR-270-PW and Na-Ca-Cl solutions were also studied.
Takahashi, Naoki; Yoshinaka, Kazuyuki; Harada, Akio; Yamanaka, Atsushi; Ueno, Takashi; Kurihara, Ryoichi; Suzuki, Soju; Takamatsu, Misao; Maeda, Shigetaka; Iseki, Atsushi; et al.
Nippon Genshiryoku Gakkai Homu Peji (Internet), 64 Pages, 2016/00
no abstracts in English
Mori, Daisuke*; Tanaka, Kie*; Saito, Hiroyuki; Kikegawa, Takumi*; Inaguma, Yoshiyuki*
Inorganic Chemistry, 54(23), p.11405 - 11410, 2015/12
Yamashita, Yuji*; Saito, Takumi
Journal of Environmental Chemical Engineering, 3(4), p.3024 - 3029, 2015/12
Humic substances are natural organic matters with heterogeneity in the size distribution and composition of there functional groups. In this study, the effects of organic acid, which are often used as pH buffering agents, on the size of a humic substance and size-dependent binding of metal ions on the humic substance were investigated by flow-field flow fractionation (Fl-FFF). Comparing the three organic acids, Tris, MES, and MOPS, the size of purified Aldrich humic acid (PAHA) changed in the presence of Tris and MES, suggesting that the interaction with these organic acid modulated the molecular structure of PAHA; on the other hand, MOPS hardly affect the size of PAHA. Size-dependent binding of europium (Eu) and uranium (UO) were also studied by Fl-FFF in the presence of MOPS. The binding of these metal ions were not homogeneous with respect to the size of PAHA; they exhibited high affinity to PAHA fractions with 5 nm hydrodynamic diameter.
Saito, Takumi; Terashima, Motoki; Aoyagi, Noboru; Nagao, Seiya*; Fujitake, Nobuhide*; Onuki, Toshihiko
Environmental Science; Processes & Impacts, 17(8), p.1386 - 1395, 2015/08
The deep groundwater HSs were different from surface HSs, having high aliphaticities, sulfur contents, and small molecular sizes. The amounts of their acidic functional groups were comparable to or slightly larger than those of surface HSs; however, the magnitude of Cu binding to the deep groundwater HSs was smaller. The NICA-Donnan model attributed this to the binding of Cu to chemically homogeneous carboxylic-type sites via mono-dentate coordination at relatively low pH. The binding mode tended to shift to multi-dentate coordination with carboxylic-type and probably more heterogeneous alcoholic hydroxide-type groups at higher pH. This study shows the particularity of the deep groundwater HSs in terms of their physicochemical and ion-binding properties, compared with surface HSs.
Kitayama, Takumi*; Nakajima, Kaoru*; Suzuki, Motofumi*; Narumi, Kazumasa; Saito, Yuichi; Matsuda, Makoto; Sataka, Masao*; Tsujimoto, Masahiko*; Isoda, Shoji*; Kimura, Kenji*
Nuclear Instruments and Methods in Physics Research B, 354, p.183 - 186, 2015/07
Saito, Takumi; Hamamoto, Takafumi*; Mizuno, Takashi; Iwatsuki, Teruki; Tanaka, Satoru*
Journal of Analytical Atomic Spectrometry, 30(6), p.1229 - 1236, 2015/06
Size distribution and elemental compositions of colloids in granitic and sedimentary deep groundwater was determined by flow field flow fractionation (Fl-FFF) combined with ICP-MS. In the granitic groundwater organic colloids and various inorganic elements were found in limited size ranges (10 nm and 140 nm). The presence of different types of organic colloids was suggested in this groundwater. Most of the inorganic elements exhibited similar size distributions at 10 nm, which were largely overlapped with organic colloids rich in fluorophores. In the sedimentary groundwater small organic and probably inorganic colloids were found at 5 nm together with relatively large inorganic colloids. Organic colloids in this groundwater were homogeneous in terms of their sizes and the compositions of chromohores and fluorophores. The size distribution of inorganic elements depended on their types, indicating the presence of different host colloidal phases for them.
Saito, Takumi; Aoyagi, Noboru; Kimura, Takaumi
Journal of Radioanalytical and Nuclear Chemistry, 303(2), p.1129 - 1132, 2015/02
Time-resolved laser-induced fluorescence spectroscopy (TRLFS) is a powerful speciation technique for fluorescent metal ions and can be further improved by combining with multi-mode factor analysis such as parallel factor analysis (PARAFAC). This study demonstrates the applicability of TRLFS combined with PARAFAC for the speciation of uranyl (UO) in the presence of silicic acid (Si(OH)). A series of TRLFS data with varied Si(OH) concentration was processed by PARAFAC, resulting in three factors corresponding to free UO, UOSiO(OH), and UOOH. The stability constant of UOSiO(OH) was further optimized, based on the intensity profiles of the factors.
Saito, Takumi; Makino, Hisashi*; Tanaka, Satoru*
Journal of Environmental Radioactivity, 138, p.11 - 18, 2014/12
Radioactive cesium was predominantly found in the extract obtained by strong-acid dissolution and the extraction residue and was more concentrated in silt and clay grains. X-ray diffraction analyses revealed that micaceous minerals as well as kaolin minerals were predominantly dissolved by the strong-acid treatment. Correlation between the fraction of Cs and the content of micaceous minerals in different grain-size fractions of soil minerals suggests that micaceous minerals are responsible for the fixation of Cs in the soils. The isotopic ratio of Cs and Cs in the extract by strong-acid dissolution was more than three times smaller than those in the extracts by water, ion exchange, and reductive dissolution. This indicates that the distribution of Cs was not in the steady state in 2 y after the accident due to relatively slow fixation by the soil clay minerals.
Nakajima, Kaoru*; Morita, Yosuke*; Kitayama, Takumi*; Suzuki, Motofumi*; Narumi, Kazumasa; Saito, Yuichi; Tsujimoto, Masahiko*; Isoda, Shoji*; Fujii, Yoshikazu*; Kimura, Kenji*
Nuclear Instruments and Methods in Physics Research B, 332, p.117 - 121, 2014/08