We have developed the portable X-ray fluorescence spectrometer by which sensitive analysis is possible. We have developed double curved crystal monochromator. We have developed a portable X-ray fluorescence spectrometer using two kinds of monochroma tor for K line and L line. Recently, development of the portable X-ray fluorescence spectrometer equipped with polymer window detector and a vacuum chamber. In this report, development of the technology is described.

Fundamental parameter method (FP method) in X-ray fluorescence analysis is a method which utilizes theoretical intensity calculation of fluorescent X-rays and the typical application is semi-quantitative analysis often used for the cases such as screening analysis. However, the utilization of the other functios of the FP method seems to be rather limited depending on the fields. This paper describes theoretical intenisty calculation which is a basic element of FP method and the outlines of three major applications and typical analyzed results of FP method. The first application is a method that sensitivitiy calibrations, which is relationship between measured and theoretically calculated intensities are set up and uknown sample concentrations are determined by obtaining composition where measured and calculated intensities are matched. The second application is an emprical calibration method using theoretical matrix correction coefficints obtained by using theoretcal intensities of FP method and this method gives comparable correction with FP quantification method in regular limited composition ranges within each type of samples and is adopted in several standard analysis methods such as JIS and ISO. The third application is semi-quantitative analysis in which standard samples matched to unkown samples are not required and the analysis can be done with minimum sample information such as metal or oxide. The intensities of detected elements using qualtitative analysis are quantified using FP method in the semiquantitative analysis.

When charged particles collide with atoms, atomic inner shell electrons are ionized and then characteristic X-rays are emitted. This phenomenon is called Particle Induced X-ray Emission: PIXE. Since the production cross-sections of characteristic X-rays in PIXE is very large, PIXE can be applied to trace element analysis and uranium from sodium can be simultaneously analyzed with the sensitivity of ppb. Two dimensional distributions for each element can be obtained by scanning ion beams on the surface of sample. The use of micro beams enables to investigate elements inside a cell: Micro-PIXE analysis. A micron size point source of monochromatic X-ray is made by irradiating a metal target with micro-beams and can be used to an X-ray CT with the spatial resolution of 1 μm: Micron X-ray CT. Three dimensional distributions of elements in the inside of sample with 100 μm size can be non-destructively obtained using absorption edges for each element. The PIXE analysis is now applied to medicine, biology, fisheries science, agriculture, geology, petrology, environmental problems, archeology, resource search, material science, chemistry, astrophysics, earth science, criminal investigation, food inspection etc. To investigate the radioactive cesium contamination of foods and soil by the Fukushima Daiichi Nuclear power plants accidents, Micro-PIXE and Micron X-ray CT were useful especially in rice grain and in clay, respectively.

The authors have investigated the correction methods of the self-absorption effect for soft X-ray absorption spectra taken with the fluorescence yield mode. In this paper, we studied the ability in chemical state analysis of iron oxides and hydroxides after self-absorption corrections. One of the correction methods is (1) inverse partial fluorescence yield (IPFY), which spectrum is the reciprocal of O K yield, PFY(O), in the range of metal element absorption energy region. Another is (2) partial fluorescence yield ratio (PFYR), which spectrum is the ratio of PFY to PFY(O). After both self-absorption corrections, the Fe L-edge XAFS peak shapes showed the chemical shift corresponding to the valence number. Therefore, these methods can be employed to identify chemical states. The intensity of IPFY spectra varied from sample morphology, such as thickness, powder or pellet. On the other hand, the intensity of PFYR spectra showed almost similar among samples. It is easier to discriminate chemical state with PFYR correction than IPFY. Compared the Fe L-edge spectrum of Fe (III) oxide with Fe (III) hydroxide, the chemical shift was not observable. But there was a small difference in the O K-edge features between Fe (III) oxide and Fe (III) hydroxide.

Paper presents short characteristic of the waveguide-resonance mechanism of quasimonochromatic X-ray fluxes featured for planar extended slit clearances with nanosize width. There is discussed properties of planar X-ray waveguide-resonator with simplest design and composite waveguide-resonance structure. The phenomenological model of its functioning is presented in details.

We experimentally determined the X-ray absorption edge in the C K region of graphite using selectively-excited X-ray emission spectroscopy. The selectively-excited X-ray emission measurements of normal X-ray fluorescence, resonant inelastic X-ray scattering (RIXS), and X-ray Raman scattering (XRS) using synchrotron radiation were performed at the Advanced Light Source. The spectral border between RIXS and XRS can be evaluated from the relationship between the energy positions of the main emission peaks and their excitation energies. Thus, the X-ray absorption edge in the C K region at the lower limit of RIXS is 284.1 eV for graphite.

Wood is useful as construction material; however, wood is not strong for decay and insect damages. Generally, injecting copper-based preservative treatment is effective for these damages. However, in some cases, the amount of injection treatment is not enough and homogenous in wood. In previous studies, wood samples had been cut to confirm Cu distribution in the samples. Analytical method for investigating the injection amount of Cu is required in non-destructively and non-contact way. In this study, we attempted to acquire elemental distribution in wood by using micro XRF method. European red pine (Pinus sylvestris) wood was measured by micro XRF instrument manufactured in the laboratory. XRF images of Cu, Ca, and K were measured on the surface and cross section of the wood sample. It was found that the injection depth of copper depended on the structure of wood. In addition, the detection efficiency of Cu fluorescent X-rays was evaluated according to Lambert-Beer's law and compared with the experimental result.

We measured Kα intensities of Al, Si, Ca, Ti, Mn, Fe, and Zn, and Lβ intensities of Pb, for 25 geological standard powder samples (igneous rocks, sedimentary rocks, and river sediments) using a handheld fluorescent X-ray analyzer (PXRF) to produce calibration curves for these elements. The calibration curves of Al, Si, Ca, Ti, Zn, and Pb were characterized by high correlation coefficients exceeding 0.95. The correlation coefficients of Mn and Fe were 0.87 and 0.93, respectively.

To obtain better calibration coefficients, we measured X-ray intensities of Compton and Rayleigh scattering of Rh Kα (C/R ratio correction) of these standards. The C/R ratio correction significantly improved the correlation coefficients of Mn and Fe to 0.93 and 0.98, respectively. The X-ray intensities of Compton scattering increased with decreasing Fe concentrations of the standards.

We calculated Al, Si, Ca, Ti, M, Fe, Zn, and Pb concentrations of the 25 geological standard powder samples, using the fundamental parameter (FP) program. Comparison of the calculated Al, Si, Ca, Ti, M, Fe, Zn, and Pb concentrations with the certificated values showed that correlation coefficients exceeded 0.99 for Si, Ca, Ti, Mn, Fe, Zn, and Pb, and 0.98 for Al. This suggests that the FP program is a very powerful tool for PXRF screening surveys of mining fields and sites with contaminated soil.

On-site chemical analysis of topsoils was performed using a handheld X-ray analyzer (PXRF) in six parks in Toyama city, where rice fields were contaminated by wastewater from a zinc and lead mine over 50 years ago. The Zn and Pb concentrations of these soils were determined using the FP grogram. The highest Zn concentrations for on-site analysis were 287 mg/kg at Nakashima North Park, 213 mg/kg at Nunose Park, 287 mg/kg at Nunose South Park, 237 mg/kg at Jinzu River South Green Park, 145 mg/kg at Osawano Sports Park, and 384 mg/kg at Toyama Prefecture General Sports Park. The topsoils with Zn exceeding 100 mg/kg were sampled for detailed XRF laboratory analysis.

Detailed XRF analyses were performed for dried and crushed soil samples using calibration lines determined by 25 geological standard samples and PXRF. The Zn concentrations of the dried and crushed soil samples significantly differed from the on-site analytical data, suggesting that Zn occurred as Zn-rich particles non-homogeneously distributed in soils. There were small differences between Pb concentrations of dried and crushed soil samples and the on-site analytical data, suggesting that Pb was homogeneous in soils. The Pb may occur mainly on the surface of soil particles as an adsorbed phase.

The Zn/Pb weight ratios of some soils were about 3. These ratios are very similar to those of soils in rice fields contaminated by wastewater from a Zn and Pb mine. The contaminated rice fields contained Zn up to 288 mg/kg. The park soils with Zn/Pb significantly higher than 3 may contain Zn-bearing wear fragments originating from car tires, because these soils were mainly near roads and parking spots. These high Zn/Pb soils contain high Zn levels of up to 380 mg/kg.

A nondestruction and noncontact analytical method has been required for measurement of arts and paintings, in order not to hurt the samples. X-ray fluorescence analysis (XRF) is one of suitable techniques for this purpose. To obtain elemental images, a micro-XRF spectrometer was developed using an X-ray micro beam. In order to measure paintings safely, we developed an X-ray mono-capillary focusing device with a long working distance. z In this paper, we report obtained for Vincent van Gogh's painting arts at POLA museum collection by using the X-ray analytical microscope.

Crystal structure of a molecular assembly is related to the molecular conformation. FT-IR spectroscopy is a powerful tool for investigating molecular conformations. We have developed an energy-dispersive X-ray diffractometer to combine a commercial-use FT-IR spectrometer. The energy-dispersive X-ray diffractometer is equipped with a 3 kW tungsten sealed tube and a Cadmium Telluride diode X-ray detector. The incident X-ray beam is irradiated onto the sample stage of ATR-FTIR spectrometer. It has been applied to study the structural changes in the melting process of cocoa butter. We found that the crystalline cocoa butter melts associated with the trans-gauche conformational transition in the molecular chain.

X-ray fluorescence analysis (XRF) is a non-destructive method. There is a lot of applications like analysis of industrial material. A confocal micro XRF instrument enables elemental analysis of point-limited region. The confocal micro XRF instrument was applied to in situ analysis of microbiologically influenced corrosion process. Finally, it was realized to visualized Fe distribution corroded from steel sample in the solution.

Minerals play a great role in the human body. Therefore, it is important to know the excess or deficiency of minerals for health examination. However, the mineral concentrations in the blood are kept constant due to homeostasis, therefore blood tests cannot give us the abnormality. On the other hand, since hair takes in and holds mineral information, it is possible to examine the mineral concentrations in the body by measuring the hair itself. Therefore, we decided to study element determination method in hair more easily and quickly than ICP-AES/MS analysis. In this study, we considered a scattered X-ray internal standard method using a tabletop X-ray fluorescence analyzer. As a result, S, Ca, Zn in the hair could be quantified. However, for elements with small content such as Ca and Zn, the dispersion in quantitative value became larger. Also, since it depends on the sample form, it was found that preparation method of hair sample is important.

In the decommissioning field of the Fukushima Daiichi Nuclear Power Plant, several kinds of radionuclide-contaminated demolition debris are discharged. Although demolition debris contaminated with uranium at high concentrations has not yet been detected, it may be encountered in the near future. Since uranium radioisotopes rarely emit easily detectable α- and γ-rays, quantification of uranium in the demolition debris by radiation measurement is difficult. The most suitable method for this purpose is mass analysis of an acid elution solution of the demolition debris by inductively coupled plasma mass spectrometry (ICP-MS). Total reflection X-ray fluorescence (TXRF) analysis is another potential technique to estimate uranium in an acid elution solution of demolition debris. Although ICP-MS has higher detection sensitivity than TXRF analysis, it requires a time-consuming ashing process for decomposition of the organic matter which is not required for TXRF analysis. In this paper, we demonstrate that the viability of using TXRF analysis as a screening method for uranium-contaminated concrete. Uranium was extracted from a model acid elution solution of uranium-contaminated concrete by using chromatography resin separation. The uranium content in the model solution obtained by TXRF measurement was similar to that obtained by ICP-MS measurement. Although the obtained minimum detection limit of uranium for TXR measurement, 1.4 ng/mL, is higher than that for ICP-MS, 0.002 ng/mL (U-238), the total analysis time for TXRF measurement, about 6 hours, is one third of that for ICP-MS.

For purpose of suppressing particles generation from the yttrium-based coated film on inner wall in a plasma etcher, we investigated a residual stress and an average crystallite size of the coated film which formed under several conditions using XRD. Results were as follows. When discharged with fluorine gas plasma, compressive residual stress on the surface increased, cracks occurred in the crystals, and crystallite size decreased. The crystallite size was decreased to about 40 to 50 nm. It was found that the yttrium-based coated films with less generation of particles had a smaller crystallite size. We proposed a particle generation model in which the surface of the yttrium-based coated film on the inner wall is fluorinated and expanded by plasma discharge, cracks occur in the Y₂O₃ crystal, and yttrium-based particles are scattered at the time. In order to reduce the generation of particles from the yttrium-based coated film on the inner wall, it is effective to reduce the crystallite size of the inner wall material.

Since the chemical composition of glass reflects raw materials and production site we have studied, the origin of the glass by using X-ray fluorescence analysis focusing on ancient and medieval glass beads. In Honshu of the Middle Ages, the circulation of glass had declined, but in Hokkaido of the same period a unique culture called the Ainu Culture Period was emerging, and the circulation of glass was thriving. We focused on glass beads excavated from sites in Hokkaido during Ainu culture period. The analytical results showed that these glass beads can be classified into two types-lead potash silicate glass (K₂O-PbO-SiO₂) and potash lime silicate glass (K₂O-CaO-SiO₂). Analysis of the earliest glass of the Ainu culture period also revealed that the glass type that circulated changes significantly when it comes to the Ainu culture period. In addition, we analyzed the glass beads of Hokkaido throughout, suggesting that there is a high possibility that potassium lime glass was probably made in China in terms of chemical composition, and we were able to clarify the compositional type of glass beads circulated in Hokkaido during the Ainu culture period.

Montmorillonite in the clay reference material was determined by the Rietveld refinement with transmission method using laboratorial X-ray diffractometer. Quantitative analysis of clay minerals using X-ray diffractometry was difficult due to a characteristic of preferred orientation toward to [00l] direction. The preferred orientation of montmorillonite was suppressed using the transmission method by preparing the measurement specimen using a glass capillary without pressurization filling. In the Rietveld refinement, an amorphous phase is determined using an internal standard material with high crystallinity. Therefore, corundum was added to the clay reference material as an internal standard material for determination of amorphous phase. The quantitative values of montmorillonite, quartz, and amorphous phase in the clay reference material were 28.1±0.4, 1.1±0.6, and 70.8±1.4 mass% respectively. The quantitative value of quartz showed good agreement with result of standard addition method (1.09±0.02 mass%)．

Trace elements of Brassica rapa var. perviridis (Komatsuna) were analyzed by an XRF spectrometer with three-dimensional polarization optics. Thirteen elements (P, S, Cl, K, Ca, Mn, Fe, Cu, Zn, Br, Rb, Sr, Ba) were detected in all samples (95 samples from Japan and 2 samples from China). Under the optimal measurement conditions, the lower limit of detection (LLD) for Ba was 1.6 ppm and those for other elements were in sub ppm ranges. Quantitative analyses for 8 elements (Mn, Fe, Cu, Zn, Br, Rb, Sr, Ba) were carried out by using the calibration curves obtained from the certified reference materials of plants. The elemental concentration calculated by XRF was validated by ICP-OES. As a result of cross-checking, the XRF data agreed with the ICP-OES data, and it was indicated that this XRF analytical method was enough reliable as a simple and quick evaluation for trace elements in leafy greens. Furthermore, the multivariate analysis using elemental concentration data was demonstrated to determine the vegetable production area in Japan.

Chemical state of Fe and Cr in CaO-SiO₂ based oxide glasses prepared assuming actual steel making slags with different composition under different melting conditions was investigated using the measurements of X-ray absorption spectroscopy (XAS) with X-ray absorption near-edge structure (XANES) method, and the valence proportion was calcurated. It varied depending on oxygen partial pressure, basicity(wt%CaO/wt%SiO₂) and coexisting of Fe and Cr. Espacially, the effect of coexisting was complicated by the chemical state of Fe and Cr. The chemical state of metal in actual steel making slag is expected to vary intricately, and can be investgated by XAS.

Synchrotron X-ray absorption edge imaging of painting was tested to know the applicability of the method for identification of elements in the pigment of the painting. Two absorption images were acquired, each at two different energies, 100 eV above and below the absorption edges of the target element. By subtracting the two images, a distribution image of the element was obtained.

The experiments were performed at a Synchrotron Radiation Facility (SPring-8) in Hyogo. The X-ray absorption edge imagings were carried out at BL20B2 (215-m-long, bending magnet beamline) utilizing monochromatic beam with wide size (12×1 cm²). The experimental system composed of θ-Z stage and a flat panel detector (12×12 cm²). In the case of self-made test samples, the arrangement of applied paints and the distribution of elements are in good agreement, demonstrating that it is possible to quickly perform elemental imaging of paintings by this method. Analysis of a modern oil painting demonstrated that this technique is useful for elemental imaging of elements with absorption edge energies above 12 keV. Furthermore, from the imaging of Pb and Cd, it is possible to observe in detail the traces of the brush at the time of drawing, and it is found that the two paints are mixed to express the yellow color of the fruit.

It is reported there are some species of terrestrial arthropods that clearly have Zn accumulation inside their mandibles (fang) while others do not. In some insects (insecta) that belong to the arthropods, there are some species that clearly have an accumulation of Zn inside their mandibles while others do not.

21 species in two suborders of beetles (coleoptera) and in insects (insecta) were measured for accumulation of metal elements inside their mandibles by using an X-ray analytical microscope. As a result, distinct accumulation of Mn was discovered in beetles' (coleoptera) mandibles, but no species were found which had obvious accumulation of Zn instead. Until the present day, the definite accumulation of Mn expected for beetles (coleoptera) has not been confirmed. Using the jewel beetle (Chrysochroa fulgidissima) as a test subject, Mn was detected in adult mandibles.

To identify the three- or four-coordinate boron (B) atoms in sodium borate silicate glasses (Na₂O-B₂O₃-SiO₂ glass system), B K-XANES of borate silicate glass was measured by using synchrotron radiation. By comparing to B₂O₃ in which B atoms take three-coordination, σ^* peak of borate silicate glass exhibits the lower-energy shift for 3.1 eV. From the unoccupied B 2p density of state (DOS) in borate glass clusters, which were calculated using the discrete variational (DV) -Xα method, the energy-shift can be well reproduced by the four-coordinate B atoms. It is therefore confirmed that the σ^* peak profile in B K-XANES enables to identify the coordination of B atoms in borate silicate glasses.

Three types of stacked LiTaO₃ single crystal units were assembled to investigate effects of shape of the single crystal and degree of ambient pressure on X-ray emission and discharge behavior based on the pyro electricity. Every instantaneous emission of visible light due to discharge occurred at the side of stacked crystals during heating and cooling cycle between room temperature and 400 K under atmospheric pressure. Discharge frequency on a stacked unit made of equal-sized four pieces (type-A) was five times more than that on a unit made of irregularly-sized pieces (type-C). Discharge occurred possibly at narrow gap between two pieces of plate-like single crystal. During heating process up to ca. 400 K under 1 or 10^-4 Pa, spike-like X-ray emission for a few seconds through one minute occurred repeatedly on both type-A and -C units. The maximum energy of emitted X-ray was independent on both degree of vacuum and shape of stacked plate-like LiTaO₃ single crystal. Discharge on type-A unit was suppressed by coating of stacked crystals with dielectric grease whereas high voltage generated on the coated unit. Origin of spike-like X-ray emission and discharge on stacked LiTaO₃ units was discussed.

In order to perform hard X-ray XAFS measurements of all-solid-state batteries during charge/discharge operation, a novel spectro-electrochemical cell was developed. The developed cell is a compact vacuum chamber made of aluminum, and it is possible to set battery samples in a general glove box. Using the cell, the partial fluorescence yield (PFY) mode as a bulk sensitive detection and the total-electron yield (TEY) mode as a surface sensitive detection are possible to obtain different probing depth information of all-solid-state batteries. XAFS measurement of a surface contaminated copper foil using the developed cell was carried out. Hence XAFS spectra with different probing depths between the TEY and PFY modes were obtained. In addition, from operando XAFS measurements of the LiCoO₂ (LCO) positive electrode of the all-solid-state battery, the reaction behavior of the LCO electrode during charging/ discharging could be observed. These results indicate the developed cell is an efficient and useful tool for charge/discharge reactive mechanism analysis of all-solid-state batteries.

Three adhesive films, Kawamoto film used for histopathological sections of hard tissues, Kapton film, and polypropylene film were examined for preparation of thin section specimens and compared by microscopic observation and PIXE analysis of contained elements. Cryo-sections could be obtained for these films by appressing each films strongly to the surfaces of the frozen samples. By microscopic observation, cryo-sections on Kapton film suited for two-dimensional elemental analyses, while fine cracks were slightly occurred in the soft tissues than those on Kawamoto film. In contrast, a small part of the soft tissues on polypropylene film was missed. Kawamoto and polypropylene films contained biological essential elements, such as Ca, Fe and Zn slightly. These results suggested that the adhesive Kapton film was most suitable for two-dimensional elemental analyses.

To analyze correlation between the condensed structure and C K-XANES of polycyclic aromatic hydrocarbon (PAH), C K-XANES of various PAHs were measured and analyzed by using the first principle calculations. It was clarified that there is correlation between the local condensed structures and C K-XANES in PAH. Such correlation between will be useful for predicting the condensed structure in carbon black from C K-XANES.

To characterize benzimidazobenzophenanthroline (BBL) polymer films which are materials for graphite ultrathin films, X-ray absorption near edge structure (XANES) spectra in the C K, N K and O K regions of the BBL polymer films were measured by using soft X-ray synchrotron radiation. It can be clarified that orientation of the BBL polymer films is approximately corresponding to that of graphite ultrathin films. From XANES analyses by using the first principle calculations of the C K, N K, and O K edges, most of all the BBL polymer films can be understood with the simple BBL polymer structure. However, it was suggested that some BBL polymers take intermolecular interaction.

In the field of forensic science, non-destructive discrimination of minute and trace amount sample is important. A benchtop total reflection X-ray fluorescence (TXRF) spectrometer was evaluated for trace elemental analysis of polyester fiber comparison. Black single polyester fibers from the trunk mats of different manufacturers and model types were measured. In the TXRF spectra, the peaks of Ca, Ti, Mn, Fe, Cu, Zn, Ge, and Br were observed and the spectral profiles were similar to those of synchrotron radiation micro X-ray fluorescence (SR-μXRF). Scattered radiation internal standard with scattered Mo-Kα intensities from X-ray tube was effective to correct the variation of TXRF intensities due to sample shape and sample position. The sample fibers were classified by principal component analysis (PCA) with corrected TXRF intensities. The intensity plot of Ti-Kα and Ge-Kα could discriminate the sample fibers.