Dispersive XAFS Study on the Laser-Induced Reduction of a Rh ion complex; Presence of a Rh Intermediate in Direct Photoreduction

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

Journal of Physical Chemistry C, 126(12), p.5607 - 5616, 2022/03

https://doi.org/10.1021/acs.jpcc.1c10160

The reaction mechanism of the direct photoreduction of a Rh ion complex to a Rh species induced by pulsed ultraviolet laser irradiation was studied using dispersive X-ray absorption fine structure (DXAFS) spectroscopy. The time-resolved X-ray absorption near edge structure (XANES) showed the absence of isosbestic points and suggested that more than two Rh species contribute toward the direct photoreduction of Rh. Analysis of the time-resolved XANES data by singular value deposition showed that the direct photoreduction involves three Rh species. Multivariate curve resolution by alternating least-squares analysis (MCR-ALS) of the time-resolved XANES data gave pure spectra and concentration profiles of the three Rh species. The Rh species were assigned to Rh, Rh, and Rh species based on the features of the pure XANES spectra. The concentration profiles suggested that the direct photoreduction proceeds in the order of Rh Rh Rh. A reaction mechanism, which was proposed involving photoreductions of Rh and Rh, photoinduced autocatalytic reductions of Rh and Rh, and photooxidation of Rh, well reproduced the concentration profiles of three Rh species.

Highly sensitive detection of sodium in aqueous solutions using laser-induced breakdown spectroscopy with liquid sheet jets

Nakanishi, Ryuzo; Oba, Hironori; Saeki, Morihisa; Wakaida, Ikuo; Tanabe, Rie*; Ito, Yoshiro*

Optics Express (Internet), 29(4), p.5205 - 5212, 2021/02

https://doi.org/10.1364/OE.415308

Laser-induced breakdown spectroscopy (LIBS) combined with liquid jets was applied to the detection of trace sodium (Na) in aqueous solutions. The sensitivities of two types of liquid jets were compared: a liquid cylindrical jet with a diameter of 500 m and a liquid sheet jet with a thickness of 20 m. Compared with the cylindrical jet, the liquid sheet jet effectively reduced the splash from the laser-irradiated surface and produced long-lived luminous plasma. The limit of detection (LOD) of Na was determined to be 0.57 g/L for the sheet jet and 10.5 g/L for the cylindrical jet. The LOD obtained for the sheet jet was comparable to those obtained for commercially available inductively coupled plasma emission spectrometers.

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.

Status of study of long-term assessment of transport of radioactive contaminants in the environment of Fukushima (FY2018)

Nagao, Fumiya; Niizato, Tadafumi; Sasaki, Yoshito; Ito, Satomi; Watanabe, Takayoshi; Dohi, Terumi; Nakanishi, Takahiro; Sakuma, Kazuyuki; Hagiwara, Hiroki; Funaki, Hironori; et al.

JAEA-Research 2019-002, 235 Pages, 2019/08

JAEA-Research-2019-002.pdf:21.04MB

The accident of the Fukushima Daiichi Nuclear Power Station (hereinafter referred to 1F), Tokyo Electric Power Company Holdings, Inc. occurred due to the Great East Japan Earthquake, Sanriku offshore earthquake, of 9.0 magnitude and the accompanying tsunami. As a result, large amount of radioactive materials was released into the environment. Under these circumstances, JAEA has been conducting Long-term Environmental Dynamics Research concerning radioactive materials released in environment, especially migration behavior of radioactive cesium since November 2012. This report is a summary of the research results that have been obtained in environmental dynamics research conducted by JAEA in Fukushima Prefecture.

Estimation of mitigation effects of sodium nanofluid for SGTR accidents in SFR

Ichikawa, Kenta*; Kanda, Hironori; Yoshioka, Naoki*; Ara, Kuniaki; Saito, Junichi; Nagai, Keiichi

Proceedings of 26th International Conference on Nuclear Engineering (ICONE-26) (Internet), 6 Pages, 2018/07

Studies on the suppression of the reactivity of sodium itself have been performed on the basis of the concept of suspended nanoparticles in liquid sodium (sodium nanofluid). According to the experimental and theoretical results of studies for sodium nanofluid, velocity and heat of sodium nanofluid-water reaction are lower than those of the pure sodium-water reaction. The analytical model for the peak temperature of a sodium nanofluid-water reaction jet has been developed in consideration of these suppression effects by the authors. In this paper, the prediction method for mitigation effects for a damage of adjacent tubes in a steam generator tube rupture (SGTR) accidents is arranged by applying this analytical model for the peak temperature of the reaction jet. On the assumption that the sodium nanofluid is used for the secondary coolant of sodium-cooled fast reactor (SFR), mitigation effects under the design-base accident (DBA) condition and the design-extension condition (DEC) of SGTR are estimated by using this method. As a result, there is a possibility to reduce the number of damaged tubes and to suppress the pressure generated by SGTR accidents by using sodium nanofluid in the secondary coolant.

Synthesized research report in the second mid-term research phase, Mizunami Underground Research Laboratory Project, Horonobe Underground Research Laboratory Project and Geo-stability Project (Translated document)

Hama, Katsuhiro; Sasao, Eiji; Iwatsuki, Teruki; Onoe, Hironori; Sato, Toshinori; Fujita, Tomoo; Sasamoto, Hiroshi; Matsuoka, Toshiyuki; Takeda, Masaki; Aoyagi, Kazuhei; et al.

JAEA-Review 2016-014, 274 Pages, 2016/08

JAEA-Review-2016-014.pdf:44.45MB

We synthesized the research results from the Mizunami/Horonobe Underground Research Laboratories (URLs) and geo-stability projects in the second midterm research phase. This report can be used as a technical basis for the Nuclear Waste Management Organization of Japan/Regulator at each decision point from siting to beginning of disposal (Principal Investigation to Detailed Investigation Phase).

Development of a fiber-coupled laser-induced breakdown spectroscopy instrument for analysis of underwater debris in a nuclear reactor core

Saeki, Morihisa; Iwanade, Akio; Ito, Chikara; Wakaida, Ikuo; Thornton, B.*; Sakka, Tetsuo*; Oba, Hironori

Journal of Nuclear Science and Technology, 51(7-8), p.930 - 938, 2014/07

https://doi.org/10.1080/00223131.2014.917996

To inspect post-accident nuclear core reactor of the TEPCO Fukushima Daiichi Nuclear Power Plant, a transportable fiber-coupled LIBS instrument was developed. The developed LIBS instrument was designed to analyze the underwater sample in high-radiation field by single-pulse breakdown with gas flow or double-pulse breakdown. To check the feasibility of the assembled fiber-coupled LIBS instrument to the inspection inside Fukushima Daiichi Nuclear Power Plant, we investigated (1) influence of radiation dose on optical transmittance of the laser delivery fiber, (2) survey of the LIBS techniques to analyze the underwater sample and (3) candidates of emission lines for analysis of the debris. By employing the selected emission lines, we demonstrated that the developed LIBS instrument can analyze the simulated debris underwater by the single-pulse breakdown with the gas flow with high signal to noise ratio.

In-vessel inspection probing technique using optical fibers under high radiation dose

Ito, Chikara; Naito, Hiroyuki; Oba, Hironori; Saeki, Morihisa; Ito, Keisuke; Ishikawa, Takashi; Nishimura, Akihiko; Wakaida, Ikuo; Sekine, Takashi

Proceedings of 22nd International Conference on Nuclear Engineering (ICONE-22) (DVD-ROM), 7 Pages, 2014/07

https://doi.org/10.1115/ICONE22-31110

A high-radiation resistant optical fiber has been developed in order to investigate the interiors of the reactor pressure vessels and the primary containment vessels of the Fukushima Daiichi Nuclear Power Station. The radiation resistance of an optical fiber was improved by increasing the amount of hydroxyl up to 1000 ppm in pure silica fiber. The improved image fiber consists of common cladding and a large number of fiber cores made from pure silica that contains 1000 ppm hydroxyl. The transmissive rate of an infrared image was not affected after the irradiation of 1 MGy. We have developed the fiber-coupled LIBS system to detect plasma emission efficiently in near-infrared region. In addition, we have performed a ray dose rate measurement using an optical fiber of which scintillator is attached to the tip. As a result, the concept of applicability of a probing system using the high-radiation resistant optical fibers has been confirmed.

Mizunami Underground Research Laboratory Project, Annual report for fiscal year 2012

Hama, Katsuhiro; Mikake, Shinichiro; Nishio, Kazuhisa; Matsuoka, Toshiyuki; Ishibashi, Masayuki; Sasao, Eiji; Hikima, Ryoichi*; Tanno, Takeo*; Sanada, Hiroyuki; Onoe, Hironori; et al.

JAEA-Review 2013-050, 114 Pages, 2014/02

JAEA-Review-2013-050.pdf:19.95MB

Japan Atomic Energy Agency (JAEA) at Tono Geoscience Center (TGC) is pursuing a geoscientific research and development project namely the Mizunami Underground Research Laboratory (MIU) Project in crystalline rock environment in order to construct scientific and technological basis for geological disposal of High-level Radioactive Waste (HLW). The MIU Project has three overlapping phases: Surface-based Investigation phase (Phase I), Construction phase (Phase II), and Operation phase (Phase III). The MIU Project has been ongoing the Phase II and the Phase III in fiscal year 2012. This report presents the results of the investigations, construction and collaboration studies in fiscal year 2012, as a part of the Phase II and Phase III based on the MIU Master Plan updated in 2010.

Indirect contribution of transition metal towards oxygen reduction reaction activity in iron phthalocyanine-based carbon catalysts for polymer electrolyte fuel cells

Kobayashi, Masaki*; Niwa, Hideharu*; Saito, Makoto*; Harada, Yoshihisa*; Oshima, Masaharu*; Ofuchi, Hironori*; Terakura, Kiyoyuki*; Ikeda, Takashi; Koshigoe, Yuka*; Ozaki, Junichi*; et al.

Electrochimica Acta, 74, p.254 - 259, 2012/07

https://doi.org/10.1016/j.electacta.2012.04.075

The electronic structure of the residual metal atoms in FePc-based carbon catalysts, prepared by pyrolyzing a mixture of FePc and phenolic resin polymer at 800C, before and after acid washing have been investigated using XAFS spectroscopy to clarify the role of Fe in the ORR activity. The decomposition analyses for the XAFS spectra reveal that the composition ratio of each Fe component is unaltered by the acid washing, indicating that the residual Fe components were removed by the acid washing irrespective of their chemical states. Because the oxygen reduction potential was approximately unchanged by the acid washing, the residual Fe itself does not seem to contribute directly to the ORR activity. The residual Fe can act as a catalyst to accelerate the growth of the sp carbon network during pyrolysis. The results imply that light elements are components of the ORR active sites in the FePc-based carbon catalysts.