X-ray fluorescence spectrometry (XRF) is used for routine analysis of ancient pottery. Nevertheless, the pottery samples are often difficult to apply sample preparation appropriate to reliability XRF determination due to the limited sampling amount. Then, new specimens for XRF determination were developed to accurately assay the small amount of ancient pottery for the provenance study in archaeology. In this paper, first, importance of specimen preparation for XRF was demonstrated by comparison among the precisions of fluorescent X-ray intensities from three pottery specimens (unprepared pottery, powder pellet and glass bead) made from one pottery shard and estimation of escape depth of the X-ray assuming direct measurement of Japanese pottery. Next, synthetic calibration standards were reviewed. The standards were produced in imitation of the chemical compositions of Japanese pottery. Finally, the following preparation techniques were devised as a means to measure precious and limited ancient pottery sample: (1) molded-loose-powder technique using 100 mg of powered sample; (2) micro-sized glass bead specimen using 1.1 mg of powdered sample; and (3) a low dilution, undersized (12.5 mm diameter) glass bead specimen using 200 mg of powdered sample.

X-ray absorption fine structure (XAFS) analysis is an important technique that realize to discuss the local structure around a specific element in a sample in atomic scale and to discuss the chemical states of the specific element. Recently, as a developed XAFS measurement, 3d-XAFS (CT-XAFS) measurements are reported, while longer measurement time and increased data volume are problem disturbing the CT-XAFS measurement to be a popular technique. We had reported modified linear-combination-fitting (MLCF) technique is useful to reduce the measurement points and hence to decrease the measurement time and data volume. In this report, the MLCF technique is shortly introduced with a simple example which shows the MLCF technique works well. Then, it is demonstrated that the MLCF technique is successfully applied to obtain the 3d chemical state map of Cu in a tablet from CT data sets obtained at several selected energy points.

This review focuses on the recent significant progress on the development of Muon-Induced X-ray Emission Analysis. The principle of the analysis is similar to the X-ray fluorescence analysis except for its X-ray energy. The characteristic X-ray energy of muons is about 200 times higher than that of electrons. This feature enables us to analyze light elements, isotope ratios, and chemical states, non-destructively. There are many successful applications of the analysis in the field of archeology, cultural property science, and earth and planetary science and so on.

“Kingaisen” is an old term for ultraviolet rays in Japanese. Its period of use, the terminological properties, and the causes of the disuse have been examined. Comprehensive documentary analysis over wide range of studies provided the following conclusions. In 1910-1950, “Kingaisen” was registered in the then dictionaries and encyclopedias, and was used as an academic synonym of “Shigaisen” by many Japanese, including Bin Ueda (a Japanese author), Kenji Miyazawa (a Japanese novelist and poet of children's literature), and Hantaro Nagaoka (a pioneer of Japanese physics). After World War II, this term came to hardly be used under strong influence of the language policy of GHQ/SCAP.

In order to investigate the degree of polarization of Compton scattered X-rays, we made a small device, and measured it with acryl and lead polarizers. The polarization degree of acryl polarizer was 0.63 and higher than that of lead. Acryl is composed of light elements so that Compton scattering occurs with high probability. That affected the differences of acryl and lead's degree of polarization.

X-ray fluorescence (XRF) analysis offers the great advantage of providing nondestructive elemental analysis at an ambient pressure. However, it is not possible to obtain the 3D elemental image because primary X-rays penetrate deep into the sample. To obtain the 3D elemental image, polycapillary lens are placed in front of an X-ray tube and a detector in confocal micro XRF method. The foci of primary X-ray and XRF are adjusted to be at the same point, which is called the confocal point and confocal micro XRF method obtains XRF spectra in the confocal point. When this method is applied to a sample with layer structure, it is not necessary to obtain the 2D plane imaging. To reduce the measurement time for obtaining the 2D depth profile, we proposed confocal line XRF method. Developed instrument was equipped with an X-ray tube, a detector and limited slits. Limited slits that were placed in front of an X-ray tube and a detector were used to prepare the thin X-ray beams. The focus line between primary X-ray and XRF is adjusted to be at the same line. We called this line “confocal line” and confocal line XRF method obtains XRF spectra in the region.

In this study, we evaluated the performances such as a beam size, a spatial resolution and a lower limit of detection in confocal line XRF instrument. Usefulness of the analytical method was shown by measuring a sample with layer structure.

F K-edge X-ray absorption spectra (XAS) of insulators such as AlF₃ a nd L iF w ere obtained at BL-11 in the SR Center of Ritsumeikan University. To obtain the spectra, two kinds of electron yield methods were used simultaneously. One is total electron yield (TEY) method measuring sample current, and the other is partial electron yield (PEY) method detecting high energy electrons emitted from the sample. As is expected, the TEY method produced distorted spectra for the insulators. The electron emission from the sample surface after the X-ray absorption causes positive potential (charge-up) on the surface. Since the charge-up potential varies during the XAS measurements depending upon the variation in X-ray absorbance and the rate of discharge, the variation in absorbance results in the TEY data distortion. However, it was found that such distortion almost disappeared in the PEY spectra. The PEY method collects only the high energy electrons, thus the number of electrons detected by the PEY detector depends less on the charge-up potential and it can be a very convenient experimental mode for insulator samples.

In the imaging XAFS method using an X-ray CCD detector, a transmission method has been applied to heavy elements with absorption edges at relatively high energies. Although the transmission method requires the sample to be an optimal thickness, the high-energy X-rays have high transmission capability, and can be applied to relatively thick samples. In this study, we attempted to develop a fluorescence method for fast screening of transition metal elements with the low energy X-ray absorption edges and their valence distribution in the samples such as glass materials, which are difficult to make thin. In order to obtain XAFS spectra with high sensitivity and positional resolution, a direct imaging detector without a scintillator and a pinhole were used. The results were demonstrated with a highly brilliant synchrotron radiation undulator X-ray with variable incident energy.

X-ray scattering spectroscopy is a powerful tool for investigations on rough surface and interface structures of multilayered thin film materials ^1-33), and X-ray reflectometry is used for such investigations of various materials in many fields. In many previous studies in X-ray reflectometry, the X-ray reflectivity was calculated based on the Parratt formalism ¹⁾, coupled with the use of the theory of Nevot and Croce to include roughness ²⁾. However, the calculated results of the X-ray reflectivity done in this way often showed strange results where the amplitude of the oscillation due to the interference effects would increase for a rougher surface.

Because the X-ray scattering vector in a specular reflectivity measurement is normal to the surface, it provides the density profile solely in the direction perpendicular to surface. On the other hand, diffuse scattering can provide information about the lateral extent of the roughness. In contrast to previous calculations of the X-ray reflectivity, in the present analysis we consider the effect of a decrease in the intensity of penetrated X-rays due to diffuse scattering at a rough surface and rough interface. We show that the strange result has its origin in the limitation of the currently used equation in the value of the reflection coefficient because of a lack of consideration of diffuse scattering.

The analyzed results of XRR showed that the effective roughness measured by XRR might depend on the angle of incidence. Then we introduced the effective roughness with depending on the incidence angle of X-ray. The new improved XRR formalism derived more accurate surface and interface roughness with depending on the size of coherent X-rays probing area, and derived the roughness correlation function and the lateral correlation length. In this review, an improved XRR formalism, considering the diffuse scattering and the effective roughness, is presented. The calculated reflectivity obtained by the use of this accurate reflectivity equation gives a physically reasonable result, and should enable the structure of buried interfaces to be analyzed more accurately.

Round-robin experiments on soft X-ray absorption spectroscopy have been performed at the 5 synchrotron radiation facilities in Japan. One of the aims of the experiments is that synchrotron radiation users can get compatible spectrum data of their same samples at different facilities, while it became clear through the experiments that we need more brush ups on experiment condition settings, including energy calibration. In this report, experimental results at AichiSR are shown with some discussion. Posting of the obtained spectra on several standard oxide samples is going on at each facility's web site.

Mixing ratio of the 2nd order X-rays in C K region of BL-6.3.2/ALS was evaluated from the X-ray transmission measurements in the C K∼O K region of a self-standing 230-nm-thick polyacrylic acid (PAA) film. Comparing the peak intensity of characteristic peak in the O K region to the second-order peak in C K region, mixing ratio of the 2nd order X-rays in C K region can be obtained as approximately 18.5%. It can also be confirmed that the Ti filter equipped in BL-6.3.2 can reduce the mixing ratio to be approximately 1.7%. The proposed method from the X-ray transmission measurements will be useful to estimate the mixing ratio of higher order X-rays in C K region.

To evaluate electric conductivity of titanium oxide (TiO₂) in dye-sensitized solar cell, total-electron-yield (TEY) soft X-ray absorption spectra of TiO₂ films and carbon-containing TiO₂ films were measured. Photocurrent spectra in the C K, Ti L, and O K regions of the TiO₂ samples were measured, and the following findings were obtained; (1) Electric conductivity in the excitation at C K, Ti L, O K edges are identical in rutile and anatase structures. (2) In carboncontaining TiO₂, electron capture by carbon is suggested at the Ti L excitation. (3) Electric conductivity at the C K excitation of graphene-containing TiO₂ is higher than that of conductivecarbon- containing TiO₂. Hence, X-ray absorption spectroscopy using the TEY method is useful for evaluate the electric conductivity of TiO₂.

To evaluate the corrosion behavior of steel sheet in a CO₂ gas corrosive environment, the total ref lection X-ray f luorescence (TXRF) analysis was performed focusing on the solution eluted by corrosion. The solution was continuously collected from near the surface of the corroded steel to generate micro volume droplets that were used for TXRF analysis. The immersion time and temperature dependence of the X-ray fluorescence (XRF) signal derived from Fe ions suggested that a protective film was formed on the surface of the steel sheet. It was also found that it is important to reduce the sampling amount of the solution so as not to affect the reaction environment of corrosion and film formation. From the above, it is considered that the spatial resolution of solution analysis has improved and the diffusion process of Fe ions, which are elution elements, has been observed. This method is useful for detail analysis near the solidliquid interface, and is expected to be applied to the analysis of solid-liquid interface reactions.

In this study, we performed operando XAFS (X-ray absorption fine structure) measurements under voltage application on thin films of a perovskite-type vanadium oxide La_1−xSr_xVO₃ grown on a silicon substrate. These materials are not band insulators but Mott insulators due to the Coulomb repulsion between electrons. We measured the V K-edge XAFS spectra and the current-voltage characteristics at the same time. By using the energy barrier at the interface between a vanadium oxide and silicon, we expected that the vanadium valence would change with voltage application. However, almost no change in the V K-edge XAFS spectrum was observed under the application of 0-60 V. This result indicates that the region of vanadium valence change may be smaller than the size of the electrode or the carrier number change is limited to about 2 nm at the lower interface and may not be large enough to change the overall V valence.

Tobermorite is an important crystal phase of autoclaved aerated light-weight concrete (ALC) and amorphous calcium silicate hydrate (C-S-H) is a main hydration production in concrete. These microstructures were investigated by XAFS (X-ray Absorption Fine Structure), particularly XANES (X-ray Absorption Near Edge Structure) spectra.

It was found that the absorption energy of main peak for the XANES spectra of α-quartz and phyllosilicate minerals changes with SiO₄ binding mode and that it is nearly linearly related to the Si 1s binding energy in XPSs.

In the XANES spectra of α-quartz and natural tobermorite, the main absorbance energy decreased in the order of α-quartz, 1.1 nm tobermorite, and 1.4 nm tobermorite, corresponding to changes in the binding mode of SiO₄ tetrahedron with Q₄, mixed Q₃-Q₂, and Q₂. Moreover, the width of the main peak was increased in the above order, which was considered to correspond to the structural regularity (crystallinity).

In the XANES spectra of C-S-H as a low crystalline calcium silicate hydrate, it was found that the absorbed energy of the main peak decreased, and the peak width increased with increase of Ca/Si molar ratio. It is attributed to the decrease in the degree of polymerization of SiO₄ tetrahedron with increase of Ca/Si molar ratios.

In this study, Jomon pottery excavated in Saitama Prefecture was analyzed by synchrotron radiation X-ray powder diffraction (SR-XRD) and high-energy synchrotron radiation X-ray fluorescence analyses (HE-SR-XRF) to reveal the production sites. The compositional data of pottery excavated from each site was compared with the data of Japanese River Sediment Database (JRS-DB) of the surrounding area to examine whether the JRS-DB is effective in the provenance analysis. First, heavy minerals in the pottery were semi-quantified using SR-XRD, and heavy elements were quantified using HE-SR-XRF. Next, we attempted to classify the artifacts excavated from eight sites in Saitama Prefecture by conducting principal component analysis based on the obtained compositional data of heavy minerals and heavy elements. Next, the heavy mineral and heavy element compositions of the pottery excavated from each site were compared with those of the surrounding JRS-DB samples to estimate the local or imported products. As a result, we were able to demonstrate that synchrotron radiation X-ray analysis and JRS-DB are useful for provenance analysis of Jomon pottery .

It is expected that various types of waste will be produced at the decommissioning of the Fukushima Daiichi Nuclear Power Station of TEPCO. Their disposal method is determined according to the contamination level. Among the various radioactive materials and nuclear fuel materials, uranium has a very long half-life and may be difficult to detect by radiation measurement. Therefore, in this study, we propose X-ray fluorescence (XRF) analysis as a method for rapidly screening the level of uranium contamination on the waste surface. As a model of contaminated area, a filter paper, at which a uranyl nitrate solution was dropped, was sealed with a polypropylene one-sided adhesive tape and Mylar film. They were layered on the top of a concrete compression molded plate, polyethylene block, or glass plate, as a model wherein the surface of these substances is contaminated with uranium. XRF analysis results showed that the relationship between the signal intensity of the U Lα peak and concentration of uranium in the uranyl nitrate solution dropped on the filter paper showed a straight line. Since the concrete contains uranium, the vertical intercept had a significant value in the sample by the concrete compression molded plate.

The northern region of Kyushu abounds with iron manufacturing sites estimated to have originated from the late sixth century to the early seventh century. These may be the oldest among Japanese iron manufacturing sites. The area around Mt. Aburayama (Fukuoka, Japan), located to the south of Fukuoka University, also has some iron manufacturing sites that probably have originated from the same period as the above-mentioned sites have. However, archeological iron artifacts found in this area are seldom researched. Thus, the origin of the raw material is unclear. Mt. Aburayama is mainly composed of granite that contains abundant iron sand. Therefore, it is possible that iron sand collected from Mt. Aburayama was used as a raw material for iron products in ancient times. In this study, the iron sands collected from river sands around Mt. Aburayama were characterized by X-ray fluorescence spectrometry (XRF) and X-ray diffractometry (XRD). In addition, the geology of the sampling spots was estimated using XRF and XRD results of the river sands.

Quantitative analysis of geological samples is of particular importance because it allows to identify the presence of specific elements within samples. These represent: types of minerals, soil, and sediments. Furthermore, it enables to determine the origin, age, and possible geological events that may have contributed to the formation of samples. At the same time, quantitative analysis of geological samples presents challenges. Analysis of samples contains organic matter that includes hydrogen, carbon and oxygen, including water produced by a process of fermentation of plants, insects and the metabolism of micro-organisms. Energy Dispersive X-ray Fluorescence Analysis (EDXRF) cannot detect these light elements easily. In this study, we experimented with a new application that combined Raman Spectroscopy and XRF. Raman spectroscopy makes it possible to discover organic components and identify the matrix of each sample without destroying samples. Being able to specify different types of chemical components in the sample using Raman spectroscopy during the calculation of Fundamental Parameter Method (FPM), we were able to determine the sample composition with minor fluctuations that occur due to the presence of organic matter.

On March 29, 2017, Wakayama Local Court denied the request of retrial by the death row prisoner and the lawyers with respect to the Wakayama Curry Arsenic Murder Case. Kawai pointed out the faults of the denial document by the three Judges of the Wakayama Local Court. The present review paper is a summary of the Kawai's documents #21-32 which were submitted to the Osaka Court of Appeal during April and December 2017.

Trace elemental analysis of chocolate ingredient (cacao nibs and cacao mass) was performed using X-ray fluorescence (XRF) analysis in order to characterize the geographical origins of the cacao beans. By using an energy-dispersive XRF spectrometer equipped with three-dimensional polarization optics and employing three secondary targets (Ti, Ge, and Mo), determination of trace elements at the sub-ppm level in cacao bean samples was accomplished. For example, the Lower Limit of Detection (LLD) of bromine was calculated to 0.40 mg/kg and 12 elements (P, S, K, Ca, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr) were detected for cacao samples. Cacao nibs and cacao mass samples from 10 different geographical area covering Africa, Asia Pacific, Central and South America were analyzed. Results showed that there were some difference between the trace element contents, reflecting a difference in their geographical origins. A statistical analysis showed that the concentration of seven elements (Mn, Fe, Ni, Cu, Zn, Rb, Sr) are good parameters for constructing a discriminant function of geographical origin. The present work demonstrates that XRF is useful as a rapid and simple tool for provenance analyses of agricultural products.