The present paper is a summary of documents submitted to Wakayama District Court related to Wakayama Arsenic Curry Murder Incident in 1998. Problems of prosecutor's document against the Kawai's forensic reports are pointed out: Data fabrications in the prosecutor's forensic reports written by Profs. Nakai and Yamauchi, as well as their false testimonies in the trial. The injustice in the document of prosecutor, Mr. Yamaguchi, has been revealed out.

The formation of precipitation bands in gels, such as Liesegang bands, is regarded as a self-assembling phenomenon. Although X-ray spectroscopic methods, including X-ray fluorescence and XANES spectroscopy, have not been employed for such band formation phenomena until recently, the situation changed from 2011. This paper surveys basic properties of Liesegang bands, theoretical aspects of periodic precipitation, and several effects to change the band morphology, comments points to note for applications of X-ray spectroscopies to the periodic precipitation systems, refers some previous studies by using related X-ray methods, and reviews recent X-ray spectroscopic studies on periodic and non-periodic precipitation bands of Prussian blue analogs (PBAs) in water-glass gels, after outlining the interesting properties of PBAs.

In order to assess the applicability of a 3D printer to spectroscopic analysis, 3D printed spectrometers with various type of optics were assembled. The input data used in the 3D printer have the same format as those used in machining, i.e., the 3D printer can be directly replaced the conventional way. The 3D printer enables to easily make resin holders of X-ray tubes and detectors, which can reduce interference peaks generated from parts made of alloys. Combined with the conventional machining, 3D printer should facilitate making lightweight portable spectrometers, keeping with high accuracy and sensitivity.

Two types of spectrometers developed in Seidler's Laboratory at University of Washington, Seattle, are explained. These two types are now commercially available. The X-ray tube power is from 20 to 50 watts, forced air cooled. The author of the present paper (Jun Kawai) visited Seidler's laboratory in August 2017. Seidler's XRF spectrometer is high resolution in energy and can measure one sulfur spectrum within 15 minutes, which is a similar energy resolution and sensitivity to a double-crystal spectrometer made by Gohshi 40 years ago with kW water cooled X-ray tube. The key elements are focusing analyzing crystal and cheap 2D CMOS X-ray detector with 200 eV energy resolution. Seidler's XAFS spectrometer is high resolution and again an XANES-EXAFS spectrum can be measured within 30 minutes. This XAFS spectrometer can also measure XRF spectra. An important technique of developing these spectrometers is the 3D printer.

In the latest practical X-ray fluorescence analysis, reference-free determination without the use of calibration curve is frequently employed. Supplying and distributing certified reference materials widely are crucial to maintain high reliability of analysis, in spite of wide variety of instruments, operators and conditions for measurements. Based on some experiences of the round robin test for developing the certified reference material NMIJ CRM 5208-a, the present paper describes some recommendations and remarks for end users.

For many years, X-ray fluorescence movie has been believed as a kind of special technology requiring highly sophisticated expensive hardware. The method needs to have sufficient energy resolution to distinguish elements, spatial resolution to identify the positions in the sample, and time resolution to know the change. As this appears technically difficult, X-ray fluorescence movie has not been used in the ordinary industries, hospitals and other workplaces. Summarizing the authors' series of work done since late 1990s, the present paper describes how simultaneous multi-element movie is realized at any places where X-ray fluorescence analysis is currently used.

An in-situ time-resolved quick scanning X-ray absorption fine structure (quick XAFS) technique is a powerful tool for investigating the local structure and chemical state of target elements during transient chemical reaction processes. Recently, we developed new beamline at SPring-8 optimized for quick XAFS and realized high quality time-resolved XAFS measurements with millisecond order. In this review, we describe the outline of the measurement systems and beamlines and recent results of electrochemical reaction processes in electrode catalysts in fuel cells.

Phase-contrast X-ray imaging, which uses phase-shift information of a passing sample, has been actively developed using synchrotron radiation. The sensitivity for electron density is about 1000 times higher than that of conventional X-ray CT for light elements, and enables to perform fine observations of biomedical and organic material samples. In this article, the principal of the imaging method, outline of various phase-shift detecting methods, and its applications for lithium-ion battery, biomedical samples, and complex materials are described.

We have conducted the analysis of chemical species of water-insoluble sulfur compounds in rime ice and snow and used the analysis to propose a long-range transport mechanism for coal-burning emissions in East Asia under winter monsoon conditions. Thin films of insoluble substances included in rime ice and snow on a 0.45 μm pore size membrane filter were analyzed by wavelength-dispersive X-ray fluorescence spectrometry with single dispersive crystal. Using this approach, we could analyze the sulfur-containing chemical species by examining the chemical shift of the S-Kα line. The chemical species containing sulfur were analyzed exclusively from the Ca and S concentrations in the residues of rime ice and snow. Single-particle analysis of the thin film on the membrane filter was performed for particles with size below 3 μm using a tabletop low-vacuum scanning electron microscopy with energy dispersive X-ray spectroscopy instrument. Particles were classified into six categories according to their compositions. Five major categories of spider chart distribution patterns were identified, and we proposed that they depended on the 24-hour back trajectory, such as Huabei, China, Northeast China, Korea Peninsula, Heilongjiang-Russia, and Japan types. We could assign the generating area of the air pollutants using the mole ratios of water-soluble Cd, Pb, and nss-SO₄^2-species. These categories corresponded with the areas in China based on the isotope ratio of sulfur in Chinese coal and the isotope ratio of Pb collected in Japan.

Silver metal corrosion is observed at the Huajiachi, which is a research barge of Zhejiang University at Zhoushan area in China using an SEM-EDX. Corrosion experiments on Ag specimens using 2.7 wt% artificial seawater for comparison are observed.

The flux synthesis of YAG:Ce crystals was investigated using a non-lead flux. By B₂O₃-KF flux the single crystals of YAG:Ce with a diameter of several 10 μm were obtained, and the yellow photoluminescence was observed. The X-ray fluorescence analysis of the obtained samples, however, showed that the Pb contamination from the furnace should be possible, which is to be considered in the experiment. And many small crystals in the bulky mass were obtained, urging our reconsideration to the crystal growth process.

We studied the ultrafast structural dynamics of 1T'-MoTe₂ by the time-resolved hard X-ray diffraction at SACLA. The bulk single crystals were cut into the thin flakes with thickness of 50 nm and used to observe the Bragg spots in a transmission geometry. The 200 and 020 Bragg peaks showed different evolution in thier intensity after the photoexcitation. The unusual lattice dynamics over 10 ps for 200 peak suggests the photoinduced modification of the one-dimensional structural chains. The present results might indicate the presence of the metastable state in 1T'-MoTe₂ which is not achieved in the thermal equirilibrium state.

4f electron compounds like Yb systems are often called heavy electron systems, and show various anomalous quantum properties such as Kondo effects and superconductivity. However, compared to more common d electron systems, little has been studied about photoinduced phase transitions in f electron compounds. Here, we first describe the construction of soft X-ray time-resolved measurement instruments. We recently succeeded in time-resolved X-ray magnetic circular dichroism (XMCD) measurements in soft X-ray beamline BL07LSU in SPring-8. By using Fe L edge (soft X-ray), we observed demagnetization dynamics of FePt thin films with perpendicular magnetic anisotropy. As for dynamics study of Yb systems, we used both soft X-ray time-resolved and hard X-ray Yb L₃ edge absorption measurements. Here, we describe our static temperature-dependent measurements in SPring-8 and our challenges for time-resolved measurements in SACLA. We would like to continue systematic studies of 4f electron dynamics.

We assemble a compact three dimensional-polarized X-ray fluorescence (XRF) spectrometer with a low wattage power X-ray tube (four watts, tungsten target) and measure stainless steels. We use acrylic resin as a polarizer and the incident X-rays are polarized by the Compton scattering. We find that the intensity of nickel Kα of the 3D-XRF spectra is less than that of 2D-XRF spectra because of the shift of tungsten Lα line to the lower energy side of the nickel absorption K-edge by the Compton scattering.

Bottled water named “Purifie” produced by Organo Corporation, Japan, is examined for portable-type total reflection X-ray fluorescence (TXRF) spectrometer. “Purifie” is a 500 mL bottled water. “Purifie” is used for a light-weight (7 kg) portable TXRF spectrometer with an X-ray tube (625 mW) and a Si-PIN detector. This spectrometer is designed for field analysis. Ultrapure water for LC/MS analysis is compared as a reference. The concentrations of K and Ca in the two water samples are determined at ppb level by an internal standard method. The results show that the “Purifie” bottled water is satisfactorily usable for portable TXRF spectrometer in the field.

The de Broglie wavelength and a scattering angle of a recoil electron in a polarizer were calculated based on the wave picture of Compton scattering. The de Broglie wave of the recoil electron changes its wavelength so as to move to the direction of 45 degrees to the incident X-rays. The recoil electron in the polarizer satisfies 45-degrees Bragg diffraction condition with respect to any wavelength of the incident X-rays. Therefore, The de Broglie wave of the recoil electron can be regarded as a “Bragg crystal” with a variable lattice spacing, which can generate highly polarized continuous white X-rays without changing the optics.

In the energy dispersive X-ray (EDX) analysis, electric pulses are transferred through the concentric electric cables. Effects associated with signal disturbances due to the electric cables are measured. When a long cable is used, the pulse height is reduced, which causes a spectral shift to the lower energy side. When impedance matching is not achieved, pulses are reflected, which causes artificial peaks in the spectra. Spectral shifts depend on the pulse height analyzers (PHA) used.

We assess the quantitative accuracy of energy dispersive X-ray fluorescence (EDXRF) analysis by measuring spectra of stainless steel using an EDXRF spectrometer combined with a modified FP method whose integral variable is transformed from wavelength, λ, to energy, E. In the present paper, E² term is included in the conventional FP method, which leads to the improvement of quantitative accuracy of EDXRF.

Confocal micro X-ray fluorescence is an effective method for obtaining information about elemental distribution inside the sample. A hair has trace elements such as Ca and Zn, so it is possible to examine deficiency of these elements and whether we take harmful metal by scanning one's hair. Then, we tried obtaining elemental map at any position and revealing information about elemental distribution from the hair root to top by applying confocal micro XRF. We also investigated the possibility about invasion of element from outside by analyzing fluorescent X-ray intensity of hair on surface and at center in specific cross section. In the hair applied a permanent wave, it became clear that it receives strong contamination from the outside.

X-ray absorption spectra (XAS) of insulating materials such as papers, clothes, and tapes which are put on conductive carbon tape have been measured using a total-electron-yield (TEY) method. TEY-XAS measurements were performed in BL-6.3.2 at the Advanced Light Source and in BL10 at the NewSUBARU. Although thickness of the insulating samples is several tens μm, sample currents of more than several pA can be detected and TEY-XAS were successfully obtained in C K, O K, and F K regions.

To clarify the oxidation reaction of mechanically ground (MG) hexagonal boron nitride (h-BN), X-ray absorption near-edge structure (XANES) in the B K, N K, and O K regions of MG-h-BN were measured in BL-6.3.2 at the Advanced Light Source (ALS) and in BL10 at the NewSUBARU. From the XANES measurements and theoretical analysis using the discrete variational (DV) -Xα method, it can be confirmed that nitrogen atoms in hexagonal BN layers are substituted with oxygen atoms by exposure to atmospheric air after MG process.

Mapping analysis of cross section of pasta was carried using table type X-ray analytical microscope (Micro-XRF) and visualization of salt concentration distribution was displayed. Table type Micro-XRF has advantages that low tube voltage and current of the X-ray tube greatly minimize surface discoloration of samples including organic ones caused by X-ray irradiation, and can be easily handled in a laboratory.

Calibration curve of salt was created using boiled pasta which salt concentration was known. Pasta samples which salt concentratons were unknown were analysed and it was confirmed that the salt was permeating from the outside to the inside of the pasta. It was also possible to confirm the salt concentration distribution by performing quantification using a calibration curve. It also showed a positive correrarion with salt concentration obtained by the coulometric titration method. By using Micro-XRF, it was shown that the quantitative map image of elements in food can be confirmed nondestructively.

X-ray elemental mapping of two species of vascular plants (Aristolochia debilis and Athyrium yokoscense) was performed using an X-ray analysis microscope XGT (HORIBA, Ltd.). We could obtain distribution patterns of different kinds of element in the living plant body. The pattern is gauged with fluorescence evoked by X-ray that narrowed down to the material from a capillary of the XGT.

The observation was designed to avoid dehydration of plant samples in the detection chamber during the X-ray exposure. We report here some results as an example of XGT use for fresh plant material.

We have developed a portable X-ray powder diffractometer suitable for analysis of paintings. The diffractometer is composed of θ-θ type goniometer, light weight MAGPRO^TM X-ray tube and SDD. We can change X-ray tube from Cu to Cr, easily. 60 kV X-ray tube is suitable for XRF analysis utilizing white X-rays from high energy exciting source. Thus, we can obtain diffraction data and XRF data from the same sample point. We obtained a chance to analyze painting of Katsushika Hokusai (1760-1849) using this diffractometer and demonstrated the performance of the new diffractometer.

We brought a set of portable analytical instruments necessary for analysis of paintings to Hokusaikan in Obuse, Nagano: i.e. X-ray powder diffractometer, X-ray fluorescence spectrometer, Raman spectrometer, infrared camera, and conducted nondestructive onsite analysis of the paintings. The analyzed samples include the ceiling painting “Onami” and “Menami” (1845) drawn by Hokusai in his eighties and the pair of hanging scroll “Kiku-zu” (1840-1849). First, focusing on blue pigments, we succeeded in identifying multiple blue pigments, including Prussian blue. Analysis of the yellow pigment used in “Kiku-zu” revealed the use of As-S glass, an artificial new yellow pigment, just developed in Europe at that time, was identified and offering a new knowledge from the art historical point of view. Furthermore, we have revealed use of multiple red colors showing attractive coloration. It was proved scientifically that Hokusai was drawing vivid colors by using various colorants.