X-Ray Raman scattering (XRS) provides a means for obtaining the information content of soft X-ray absorption spectra while maintaining the experimental benefits of hard X-ray techniques. In the XRS process, an incident photon is inelastically scattered and part of its energy is transferred to excite an inner shell electron into an unoccupied state. Under the dipole approximation, the resulting features are identical to the corresponding XAS spectrum. In the past, the extremely low cross-section of XRS has made this technique impractical, but intense new X-ray sources and improvements in crystal spectrometers have helped to put XRS on the brink of becoming a routine spectroscopic tool. In this review, we describe the history, theoretical background, instrumental techniques, and recent examples on XRS, comparing other related techniques such as EELS. We also discuss the problems and prospects for the future of XRS method.

This article introduces applications of focused ion beams (∼1μm) with glass capillaries systems. A first report on the interaction between ion beams and glass capillaries was published in 1996. The guiding capabilites of glass capillaries were discovered due to ion reflection from inner wall of glass surfaces. Meanwhile, the similar optics have been already realized in focusing X-rays using glass capillaries. The basic technology of X-rays optics using glass capillaries had been developed in the 1980's and 1900's. Also, low energy atom scattering spectroscopy for insulator material analysis will be mentioned

Several obsolete words in X-ray analysis and its related fields, including old terms, old units, and person's names previously used in Japanese translation, have been overviewed. Many of such words can be found in the literature before/during World War II (∼1940s), but not after 1970s.

The author's invited talk in the special session "Challenge of Analytical Chemistry: Question of Life and the Universe" at the 73th The Japan Society for Analytical Chemistry Workshop (May 18 - 19, 2013, Hakodate Campus, Hokkaido University), is summarized. Synchrotron-based Scanning Transmission soft X-ray Microscope (STXM) with high spatial resolution (< 30 nm) enables non-destructive quantitation of the chemical structures of submicron-sized organic polymers and biological samples. In this review paper, applications of STXM in the fields of cosmochemistry (organic matter in meteorites and cometary dusts), geochemistry (hydrothermal plume particles, ancient graphite in 3.85 Ga old rock), and life science (quantitative component maps, 3D-spectro-tomography, microbe-mineral interaction) are introduced, which could lead to a further application of STXM in the future sample return space explorations for understanding planetary environments and habitability.

A lot of metal materials are used in outdoor telecommunication equipment, and corrosion is basic and important for determining the lifetime of the equipment. The present condition and degree of corrosion of such equipment are checked visually, so it is therefore possible that something could be overlooked since the inspection is based on human eyesight. Moreover, there are very few ways of confirming the degree of deterioration of a piece of equipment that is not directly observed. The degree of deterioration of equipment is predicted by calculating on computer the amount of airborne sea-salt particles, which can accelerate corrosion, and the corrosion rate using the climate and geographical conditions at the location of the equipment. However, to increase the accuracy of prediction, it is necessary to measure the amount of sea-salt adhering to equipment and the corroded condition of actual equipment and/or a specimen placed near the equipment.

Portable X-ray sources and handheld X-ray fluorescence analysis (XRF) systems have been developed recently and can potentially provide effective on-site diagnosis and analysis methods. The radioparency of portable X-ray sources and the analytical capability of a handheld XRF system were examined in order to evaluate their applicability in diagnosing the degree of deterioration of structural material and measuring the amount of sea-salt adhesion at the site. The results indicated that the portable pulsed X-ray source was capable of capturing transmission images of a deteriorated galvanized steel wire strand through a plastic box covering it in a short time. It was also shown that the handheld XRF system was effective for evaluating the thickness of the electroplated zinc coating and for measuring the amount of sea-salt adhesion with sufficient sensitivity.

The Wakayama poisoning case was that curry served at summer festival on July 25th, 1998, was poisoned by arsenic with a paper cup. It has not been widely known but desk-top type X-ray fluorescence analysis was performed for the forensic analysis, and Si and Ca was found to be related to the Ba detected arsenic. The present paper concludes that the desk-top X-ray fluorescence analysis was more informative than SPring-8 analysis.

It was believed that the SPring-8 X-ray fluorescence analysis was the key scientific evidence for the forensic analysis in the Wakayama arsenic curry case in 1998. The infrared absorption spectra were measured for most of the arsenic samples but were never used in the court. Those infrared spectra were compared and the meaning of the infrared spectra was discussed. It was said that only the SPring-8 X-ray fluorescence analysis was enough for the identification of arsenic in the sample specimens. Consequently, the infrared spectra were not completely measured. If the infrared spectra were thoroughly measured at that time, the decision of the court would be different.

X-ray photoelectron spectroscopy (XPS) valence band spectra reflect the chemical bonding states. To take this advantage, we tried to interpret experimental spectra by the occupied density of states (DOS) based on first principles calculation. In this work, we discussed XPS and X-ray Absorption Near Edge Structure (XANES) spectra of 6, 13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pen), which is well known as an organic semiconductor. We studied chemical structure change of TIPS-Pen caused by heat-treatment at 300°C under nitrogen and under the air. It has been suggested that the structural change of pentacene skeleton by Diels-Alder type reaction occurs in both cases. In addition, the sample heat-treated under the air showed desorption of the isopropyl group and increase of oxygen concentration.

Tobermorite (5CaO·6SiO₂·5H₂O) is one of the most important crystalline almino-silicate for construction industry, because it is known as a main component of autoclaved aerated concrete. We have investigated crystallization mechanism of tobermorite under autoclave conditions using an originally developed in-situ XRD cell. In order to simplify the reaction we used the model system with high purity CaO and silica as starting materials. In this paper, we report the effect of silica source on the structure of C-S-H gel (precursor of tobermorite) and on the formation reaction of tobermorite using in-situ XRD and small angle X-ray scattering. It has been revealed that silicate aggregated structure of the C-S-H-gel is an important parameter for the tobermorite formation

The author is doing the conceptual design of the Real-time X-ray Fluorescence Microscope (R-XRFM) which can perform elemental mapping by X-ray fluorescence without scanning the sample. Doubly curved crystal of a Johansson type monochromator or a Johann type monochromator will be used as a point-to-point focus monochromator in R-XRFM and the performances in each case were evaluated by simulation calculation using ray-tracing method.

From the result of the calculation in conditions of a 60 mm diameter α-quartz crystal monochromator, a 300 mm radius Rowland circle, and an X-ray fluorescence wavelength of Al Kα₁, in both cases of the Johansson type and in case of the Johann type 40 mm in width, it was found that the angular resolution is 0.010°, and there is a possibility that R-XRFM can perform elemental mapping identifying the differences in the fluorescent X-ray wavelength of the aluminum due to the difference in the coordination number.

In the case of Johansson type, it was found that the X-rays converge on the detector surface with the spatial resolution < 0.001-1.3 μm from the analyzing area of 0-50 μm square, and with the spatial resolution 1.3-2.5 μm from the analyzing area of 50-100 μm square.

In the case of Johann type 40 mm in width, it was found that the X-rays converge on a detector surface with the spatial resolution 1.5-3.7 μm from the analyzing area of 0-100 μm square.

XRF imaging is analytical method to obtain 2D elemental distribution by using XRF. One of the typical methods of XRF imaging is scanning XRF imaging using micro X-ray beam. For this method, energy dispersive detector is used. However, in energy dispersive scanning XRF imaging, since the sample is scanned with a fixed micro X-ray beam, this method needs long measurement time to obtain elemental images of a wide area. The alternative method for performing XRF imaging in a shorter time is a projection XRF imaging. For this method, incident X-ray is irradiated to a sample in a wide area and fluorescence X-ray is detected by 2D detector. However, since 2D detector has no energy resolution, there is a problem that the identification of the elements can not be performed. Therefore, we proposed the projection XRF imaging combined with wavelength dispersive spectroscopy (WDS). In this paper, we discuss WD-XRF imaging using straight polycapillary and X-ray CCD camera.

L-series emissions of manganese, iron and zinc oxides were studied using electron beam excitation and brilliant synchrotron radiation excitation. We showed that manganese and iron oxides show different Lβ/Lα intensity ratio due to their oxidized states, and excitation electron voltages, as were previously reported. On the other hand, we could not get any L-series emissions from those bulk samples when excited by normal incident high energy monochromatic X-rays, while samples of thin films and samples excited by glancing incident monochromatic X-rays showed clear emissions. It is suggested that the difference of Lβ/Lα intensity ratio due to the oxidized states mainly concerns with the Coster-Kronig transition ratio of the samples, while self-absorption effects should also deeply contribute the ratio, considering the experimental results.

Japanese roof tiles weathered for 50 years on Himeji Castle have been evaluated by soft X-ray absorption spectroscopy using synchrotron radiation. Carbon oxides, iron oxides and calcium oxides were observed on the surface carbon films of the roof tiles. Ion oxides came from the sintered clay substrates, and the calcium oxides from mortar. The carbon films were oxidized with various oxygenated functional groups, and sp³ carbons with alkyl groups were formed on the graphitic sp² carbon films. This caused the disorder of the orientation of the graphitic carbon films. These oxidation and degradation of the carbon films were apparently accelerated by the exposure to the weather. However, carbon films have sufficiently remained on the roof tiles. This suggests that the weathered roof tiles can be surely reused as "Ibushi Kawara" coated with carbon films in the restoration of Himeji Castle.

Japanese roof tiles weathered for 50 years on Himeji Castle, which has been restored in 2009 - 2015, have been evaluated by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Although surface carbon films have been partially exfoliated by the weathering, they have been sufficiently held on 90% of roof tiles. The carbon films have kept the thickness of 2-3 μm. This suggests that the weathered roof tiles can be surely reused as "Ibushi Kawara" coated with carbon films in the restoration of Himeji Castle.

Time dependent X-ray emission due to the change of temperature of a pyroelectric crystal in vacuum and optical luminescence during the X-ray emission were measured. Two types of instable X-ray emission were observed at the beginning of cooling of the pyroelectric crystal; a sudden increase and decrease of X-ray emission with energies over 14 keV and a sudden stop of X-ray emission with all energies were observed. The former was derived from glow discharge on the -z surface of the pyroelectric crystal, and the latter was caused by a creeping discharge on the side of the pyroelectric crystal. The creeping discharge occurred only on a specific side of the pyroelectric crystal.

Characteristic X-rays of Si (Si Kα Line) was detected in samples which did not contain Si with a portable electron probe microanalyzer we previously reported. We prevented the emission of Si Kα line by replacing polyimide tape used as the X-ray window with polyimide film which did not contain Si and by placing polyimide films and paper on vacuum grease. Al, Ca, Mn and Fe were detected in a steelmaking slag with the improved portable EPMA without discharging agent and S and Ni were detected in nickel sulphide with the improved portable EPMA. X-rays with low energies were attenuated by a polyimide film and the air because the X-ray detector was placed in the air.

We conducted analysis of sulfur in gasoline using a portable total reflection X-ray fluorescence spectrometer. Analysis of sulfur in gasoline has been difficult before, because gasoline drip spread widely when dropped on an optical flat.

In this article, we performed fluoride coating on the optical flat. As a result, the size of drip mark got smaller and analytical sensitivity of sulfur was greatly improved.

A portable total reflection X-ray fluorescence spectrometer (TXRF) was used to analyze leaching solutions of hijiki seaweeds. S, Cl, K, Ca, Ti, Fe, Ni, As and Br were detected in the solutions. Arsenic quantification results were compared to those from ICP-AES. The TXRF quantification results of arsenic were not significantly different from those of ICP-AES, as two-way analysis of variance (ANOVA) method was applied to the significance test. This kind of small and high sensitive TXRF spectrometer can be used in food quality and environmental pollution investigation.

We developed a portable X-ray reflectometer which measures energy dispersive X-ray reflectivity using a polychromatic X-rays from a low power (a few watts) X-ray tube and a silicon drift detector. A thin Cu film on silicon substrate using the portable reflectometer was measured. A fringe pattern was shifted due to the change of the X-ray incident angle. The measured peak position of the fringe pattern was satisfactorily agreed with the calculation.

A new scattering X-ray correction method which can correct for the influence of immeasurable base elements in oil has been developed. This method can simultaneously correct for the influence of varying carbon to hydrogen ratio (C/H ratio) and oxygen content, as well as for the absorption by measurable inorganic elements in oil.

It was confirmed by theoretical calculations and experimental results that the influence of C/H ratio and oxygen content can be both accurately corrected for simultaneously by selecting a scattering X-ray with an appropriate wavelength as an internal standard line. It was also found that this method can prevent the appearance of the geometry effect, and the influence of sample thickness and density can be disregarded.

For samples such as lubricating and heavy oils which can contain high concentration levels of inorganic elements, absorption caused by the inorganic elements can be significant. Analysis errors caused by this effect can be corrected using correction coefficient alphas calculated by the fundamental parameter method.

Applying this new correction method has the advantage that the calibration curve can be easily generated using readily available standard oil samples. Regardless of sample type such as crude, shale or lubricating oils which can differ in C/H ratio and oxygen content, accurate quantitative analysis can be performed with a single universal calibration curve.

We investigated whether X-rays are generated or not using charging by fracturing crystal sugar, NaCl crystal, and LiCl crystal. X-rays with energy of about 4-6 keV were generated by fracturing crystal sugar, but not generated by fracturing NaCl crystal and LiCl crystal. In addition, we took photos of visible light emitted by fracturing these three materials in the air and helium. Colors of visible light emitted by fracturing these three materials were different in the air and helium. The green visible light emitted by fracturing LiCl crystal in the air were also seen in helium. Therefore, it seems that LiCl crystal is charged at fracture. And, it seems that the green visible light emitted by fracturing LiCl crystal is not due to charging.

X-ray irradiation can produce color centers in alkali halide. Each compound irradiated with X-rays exhibits its own characteristic color. The color of crystals of NaCl changed to orange after X-ray irradiation at room temperature. It was still orange in a dark room, but the color changed to black after exposure to white fluorescent lamp. In addition, the color of NaCl changes to pale purple when irradiated with 405 nm laser after X-ray irradiation and to light brown when irradiated with 532 nm laser after X-ray irradiation. The color of the powder NaCl of 75 μm particle size became whiter after exposure to X-rays than that of 700 μm particle size. The single crystal NaCl turned orange after X-ray irradiation, but the color was returned to transparent after exposure to white fluorescent lamp. The NaCl of low purity (cooking salt) left under white fluorescent light after X-ray irradiation exhibited bluish color and violet.

X-ray fluorescence analysis (XRF) is a non-destructive method. Using polycapillary X-ray lens (PCXL), the micro-area analysis has been possible. In confocal setup, foci of both X-ray focusing PCXL and collecting PCXL are adjusted to the identical point, therefore depth elemental profiling and three dimensional elemental analysis are possible by scanning sample in three dimensions. In our laboratory, confocal 3D micro-XRF instrument which provides a vacuum chamber was developed. Under vacuum condition, it becomes possible to detect soft X-rays from light elements because of the absence of atmosphere which absorb soft X-rays. The depth resolution of the confocal 3D-XRF instrument which had been developed in our laboratory is about 11 μm at the confocal point at Mo-Kα (17.4 keV). The confocal 3D-XRF instruments were applied to analysis the electrode materials of Li-ion secondary battery under atmospheric and vacuum conditions. Depth-dependent elemental mapping was performed for a positive-electrode material, which consists of LiMn_1.5Ni_0.5O₄, after charge-discharge processes. On the negative electrode material (graphite), Ni and Mn were observed.

High-energy synchrotron radiation X-ray fluorescence spectrometry (HE-SR-XRF) utilizing 116 keV X-ray was applied to ancient glass artefacts for nondestructive-analysis of trace heavy elements including rare earth elements (REEs) that were useful for provenance identification. Prior to actual applications to ancient glass artefacts, we examined an effect of a sample thickness on spectrum obtained nondestructively and confirmed that an intensity-normalization using Compton scattering peak was effective within the range of 30∼60 keV in energy. Lower limits of detection and quantification were calculated for 19 elements (Cs. Ba, REEs, Hf, Ta, W) respectively and compared to literature data of trace heavy element concentration ranges determined by LA-ICP-MS of Late Bronze Age (LBA) glasses from Egypt and Mesopotamia. It was suggested that nondestructive HE-SR-XRF analysis has enough sensitivity to distinguish between LBA glasses from Egypt and Mesopotamia based on REEs compositions. In fact a significant difference between LBA glass from Egypt and Mesopotamia was found in the peak intensities of REEs in the spectra. A glass piece from LBA (Mycenaean) Greece which may be imported from Egypt or Mesopotamia was analyzed as an example of the provenance identification of ancient glass. A quantification of trace heavy elements using sensitive factors was carried out for the Mycenaean glass piece. It is found that quantified values are close to the literature data of the similar examples. The result suggests that the Mycenaean glass piece would be imported from LBA Egypt. It was therefore considered that HE-SR-XRF could be a powerful technique for the nondestructive analytical study of ancient glass artefacts.

Soft X-ray absorption spectra of liquid unsaturated aliphatic compounds and engine oil samples were measured at a multi-purpose beamline BL10 in NewSUBARU. Liquid samples were casted on clean gold substrates and their X-ray absorption near-edge structure (XANES) were successfully measured with a total electron yield (TEY) method under the vacuum of 10^-5 Pa. In the unsaturated aliphatic compounds, π* and σ* peaks which depend on the length of alkyl substituents can be clearly observed. In the deteriorated engine oil samples, anti-oxidizing agents disappeared and alkyl chains were formed by opening the C=C double bonds. It is therefore confirmed that liquid organic samples can be analyzed by soft X-ray absorption spectroscopy in BL10/NS.

Ancient glass beads from the Yayoi to Kofun period excavated from 24 archaeological sites in Miyazaki and Kagoshima prefectures (the Southern Kyushu area) were nondestructively analyzed by using a portable XRF spectrometer. The origin and distribution of glass beads were discussed based on their chemical compositions. The chemical compositions of glass beads from these regions can be classified into three types from their major components: i.e., high alumina soda lime glass type (Na₂O-Al₂O₃-CaO-SiO₂), soda lime glass type (Na₂O-CaO-SiO₂), and potash silica glass type (K₂O-SiO₂). The trace heavy element compositions of glass beads excavated from Miyazaki and Kagoshima prefectures were basically similar to those excavated from Kumamoto, Saga and Ibaraki reported in our previous studies. These results suggest that these regions in Japan imported the glass beads or cullet from the same origins.

After the tragedy in Fukushima, soil and food pollution by radionuclides has become a serious problem. Cs can be uptaken by many plants due to its chemical similarities with K. So, removal of radioactive Cs from the soils can be carried out using the phytoremediation technology. However, the development of phytoremediation techniques require the knowledge on the interactions between the plants and soils. Although the competitive relation between K and Cs to enter the plant is known, few works were dedicated to the visual localization of Cs in the plant and its relation to potassium. In this study, we have used synchrotron radiation X-ray fluorescence (SR-XRF) imaging in order to reveal accumulation of Cs with a cellular spatial resolution. The Cs Lβ intensity measured in the XRF imaging were transformed into the Cs concentration based on the calibration curves prepared using in house standard samples of known Cs concentrations.

It is remarkable that after exposure to 10 ppm Cs solution for 4 weeks Camellia sinensis accumulated Cs up to 300 ppm (expressed in dry weight) in the body. XRF imaging of the root show that Cs was located mainly at the epidermis. On the other hand, K was located mainly at endodermis and the cell wall. A correlation coefficient(R) between XRF intensity of K and that of Cs in the root was about R=0.5. This suggest that Cs is hardly absorbed from roots of Camellia sinensis compared with K, due to its large ionic radius. In the case of stem, distribution of Cs was similar to that of K. They were located at the exodermis, epidermis and the cell wall. Their correlation coefficient was about R=0.8. These results suggest that Cs was transported through the same pathway as that of K in the stem.

A special collimator was designed and developed to improve sensitivity for light elements in X-ray fluorescence analysis under atmospheric condition. The air path between the sample and the detector could be greatly reduced by evacuating interior volume of the collimator, and the observed gain of Al Kα line was 76 with the use of the vacuum collimator. The expected gain of Mg Kα was approximately 1000, and the clear Mg peak was observed under atmospheric condition. Trace impurities of Mg and MgO were investigated by using 8 keV X-rays from SPring-8, and the weight fraction of Fe was derived from the comparison between the observed and calculated intensity ratio of Mg and Fe.

A high temperature-type compact device for pyroelectric high electric field generation was assembled with 8 pieces of thin-type LiTaO₃ or LiNbO₃ single crystals (10 × 10 × 0.5 mm) stacked and a ceramic heater. Pyroelectricity-induced X-ray emission behavior from the crystals was investigated as a function of ambient temperature in the range 300 through 650 K. End-point energy of continuous X-ray was 28 keV upon heating of stacked thin LiTaO₃ crystals from 473 to 650 K. Discharge behaviors at the side of stacked pyroelectric crystals accompanied with X-ray emission were also discussed.