High-energy synchrotron radiation (SR) X-rays will be a decoder to interpret the provenance information of materials in the nondestructive manner. In this paper, the author introduces two studies as actual examples of application of SR-X-ray analytical techniques for environmental samples and cultural heritages: radioactive aerosol particles emitted from Fukushima Daiichi nuclear power plant accident, and two pieces of ancient glass vessels excavated from a tumulus at Nara prefecture, Japan. Applying the advanced SR-X-ray analytical techniques to these specimens with public concerns would be an example in point to demonstrate the importance and availability of the techniques to the society.

This study aimed at developing a rapid and highly sensitive analytical method to detect uranium in small amount of water found at the decommissioning site of TEPCO's Fukushima Daiichi Nuclear Power Plant (FDNPP). The target for the method developed in this study is to achieve the detection limit of less than 1/1000 of 20 mBq/cm³, which is the effluent standard value of uranium concentration in drainage water. Uranium in a small amount of liquid is difficult to detect by radiation measuring devices because of its extremely low specific radioactivity. Therefore, in the conventional analysis of uranium in wastewater, several liters of sample are dried, followed by α-particle counting. However, small volumes of contaminated water are found at the decommissioning site of FDNPP. The rapid analysis of uranium in a small amount of sample solution is difficult by the conventional method; thus, the development of a new method is required. In this study, we developed a method to analyze uranium contained in water that may be found in buildings using total reflection X-ray fluorescence analysis. It is considered that such solution contains components derived from the surrounding rubble. As simulated contaminated water, a mixture of the immersion liquid of demolition debris and diluted uranium standard solution was prepared. From this mixture, uranium was extracted with the chromatography resin and analyzed with a desktop total reflection X-ray fluorescence spectrometer. The detection limit of uranium was less than 1/100 of the effluent standard value, but the target value was not achieved. Moreover, this solution was concentrated 10 times and analyzed. Nevertheless, the detection limit of uranium was approximately 1/450 of the effluent standard value, which also failed to achieve the target value. Graphene oxide (GO) is attracting attention as a material that can efficiently adsorb actinides; by extracting and concentrating uranium using GO, we achieved the target of 1/1000 of the effluent standard value. Thus, extraction and concentration of uranium by GO and total reflection X-ray fluorescence analysis facilitated the rapid detection of uranium in a small amount of sample solution.

Mössbauer spectroscopy is widely used for measuring the electronic state of solids, particularly for measuring the state of iron atoms. There are three main parameters obtained from the Mössbauer spectra: isomer shift reflecting the valence of the atoms, internal magnetic field reflecting the magnetic moments, and quadrupole splitting reflecting the symmetry around the atoms. Mössbauer spectroscopy generally uses a radioactive isotope (RI) source as a γ-ray source, but several Mössbauer spectroscopy methods have been developed that use synchrotron radiation instead of the RI source. As a result, the advantage of synchrotron radiation such as high brightness and high directivity can be used in Mössbauer spectroscopy. Among these methods, two methods that can obtain spectra almost similar to ordinary Mössbauer spectroscopy are introduced.

The high-brightness X-ray source and high-focus X-ray mirror lens are developed for the X-ray analyzed instruments. By manufacturing the targets of the X-ray source a fine structure, it becomes possible to generate X-rays with high brightness and selectable X-ray energy. The high-focus X-ray mirror lens for laboratory equipment that reflect X-rays twice with an axisymmetric paraboloid are developed. The X-ray fluorescence analysis, X-ray absorption spectroscopy, and X-ray CT measurements using these technologies are reported.

We have developed a new soft X-ray absorption spectroscopic equipment that can easily and inexpensively measure volatile substances and liquids under atmospheric pressure. This apparatus uses a thin SiN free-standing membrane with a thickness of 100 nm as a pressure partition wall, and puts the sample in a container filled with He gas. Using this apparatus, it is possible to measure soft X-ray absorption spectra of free surface of samples by total electron yield (TEY) and total fluorescence yield (TFY) methods. We measured soft X-ray absorption spectra at the O-K, C-K, and Ti-L-edge under atmospheric pressure for standard solid samples, highly volatile solid sample, and several types of liquid samples such as water.

Full field type X-ray fluorescence analysis is useful technique for obtaining element distribution images by using 2D camera. This method is expected to be applied to various fields, however it is required to improve the resolution of elemental images. Therefore, we aimed to obtain high-quality elemental distribution images by applying a compressed sensing technique to full-field X-ray fluorescence imaging. In this paper, usefulness of the analytical method was demonstrated by showing the elemental images of a metal sample composed of copper and titanium plates.

An improvement of spatial resolution of micro-XRF by a “shifted confocal micro-XRF configuration” was investigated. In the shifted confocal configuration, the focus points on the incident side and the detection side are intentionally shifted from the conventional confocal setup, and the area where both the focal points coincide with each other is narrowed to improve the spatial resolution. Although the obtained XRF intensities were reduced, the spatial (depth and in-plane) resolutions were improved by more than 10%.

X-ray fluorescence analysis (XRF) is a non-destructive analysis used in a wide range of fields such as forensic science and archaeology. In general, powdered samples are prepared by loose-powder technique, however, it has remained challenging molding trace powdered materials. In this study, we designed a sample holder for trace powered samples and applied into a couple of specimen using X-ray Microscope. The results were calculated by fundamental parameter method (FPM) with calibration of one standard sample, which corrects sensitivity coefficients. Here, we describe the results showed high accuracy for major elements whose certified values are more than 1.0 mass% in the case the samples were as small as 1 mg.

There is a strong need for fundamental knowledge on the internal exposure of nuclear fuel elements such as uranium with regard to the decommissioning work following the Fukushima Daiichi Nuclear Power Plant accident. In this study we investigated methods of preparing urine drop samples to quickly and easily quantify uranium in urine by using micro-PIXE (Particle Induced X-ray Emission) analysis. Yttrium was employed to simulate uranium because it has similar characteristic X-ray energy to uranium. Urine drops diluted five or ten-fold with nitric acid were placed on polypropylene film coated with perfluoroalkoxy alkanes and dried at room temperature. Micro-PIXE imaging analysis revealed uniform dispersal of yttrium in the sample droplets and yttrium concentrations between 1 and 50 μg/g could be quantified based on the count of yttrium Kα-line.

Understanding of elemental distribution corresponding to tissue structure is critical for studies of biometal function. Combination of bio-imaging with untreated or unstained tissue samples with non-destructive elemental analyses, such as SR-XRF and micro-PIXE would be a powerful technique for dynamics of biometal distribution. In the present study, extraction of tissue structure and localized elements using autofluorescence was examined for rat renal specimens.

Clear histological images that can distinguish glomeruli and renal tubules were obtained by fluorescent filters (excitation, 520-550 nm; emission, 580 nm< or excitation, 470-490 nm; emission, 515-550 nm). In the case of uranium-treated rats, PIXE imaging revealed that phosphorus concentrated areas appeared in the outer stripe of the outer medulla (OSOM, located in the area between the cortex and the mudulla). The fluorescence images of this area agreed well with phosphorus localization.

In order to perform on-site X-ray fluorescence analysis of minute part of ink character written on paper, developed a small portable X-ray fluorescence system with a measurement room that satisfies the criteria for setting the X-ray control area. The measurement room is a box-shaped (width 500×depth 500×height 600 mm) container in which the top plate and front door are made of a transparent acrylic plate containing 0.3 mm equivalent of lead, and the other plates are covered with an iron plate to prevent leakage of X-rays. The X-ray fluorescence system combined a small X-ray generator from Amptek, a Si-PIN detector, and a digital pulse height analyzer. Using this device, the fluorescent X-ray spectra of characters written on paper with three types of inks manufactured from 1955 to 1965 were measured. As a result, it was confirmed that the metals contained (Cr, Mn, Fe) differ depending on the type of ink, and that the old ink contained unique elements.

Quantitativity of Rietveld refinement has been evaluated using montmorillonite without the existence a pure material. For Rietveld refinement, the JCSS-3101 clay reference material with the known concentration of montmorillonite and the corundum powder as an internal standard material were added to the waste earthenware and akadama soil as matrix mixed by the V-type mixing machine for 60 min. Quantification values of montmorillonite in the two samples were shown in good agreement with the preparation values. Existence of montmorillonite in the bentonite has been confirmed by preparing the orientated specimens using the ethylene glycol. The fraction of montmorillonite quantified by Rietveld refinement was compared with the result estimated by the calibration curve which was prepared from the integrated intensity of montmorillonite (001) divided by the integrated intensity of corundum (104). The relative error of quantification values between Rietveld refinement and calibration curve method was 1.2 %, and their values were shown in good agreement. Quantitativity of Rietveld refinement can be evaluated by using the JCSS-3101 clay reference material with the known concentration of montmorillonite.

Problems of synchrotron radiation X-ray fluorescence (SR-XRF) analysis is studied based on the forensic analysis of the Wakayama Arsenic Curry Murder Incident. In this case, 25 cans of As₂O₃ produced by Sumitomo Metal Mining Co. Ltd. were measured by Prof. Nakai at SPring-8 BL08W in order to prove that the concentration of impurity element Sb was changed as the change of cans. Nakai concluded in his forensic report that the relative intensity of Sb was different when the can was different. However Sb concentration of 9 of 25 cans were 120 ppm, which were analyzed by ICP-AES, and some of them were testified different by Nakai. On the other hand, some were tesfified as same concentration in spite that the concentrations were different. Based on Nakai's forensic report as well as on the testimony, the judge concluded that the arsenic poisoned the curry was identical to that of the arrested houswife and sentensed death penalty. The precision of SR-XRF is also checked for another forensic report, and again the precision was not enough for identification.

X-ray absorption spectroscopy, especially XANES, is one of powerful tool for environmental analysis in various environmental materials such as soil, water, aerosol, and so on. In this paper, it was demonstrated the valence analysis using a laboratory X-ray absorption spectrometer to chromium in the environmental materials as an example. A dried up droplet of aqueous solution of Cr(VI) salt and two urban particulate material standard samples were used as model samples including small amount of Cr. The XANES measurements at Cr K absorption edge was performed by the laboratory apparatus Rigaku R-XAS Looper in fluorescence-yield mode using Ge-SSD or SDD as detector for the Cr K fluorescent X-ray emitted from the measurement samples. The measurement conditions were as follows; 11 kV and 70 mA of tube voltage and current, Ge(220) Johansson-type monochromator, anode and cathode of W, Ne gas sealed proportional counter as incident X-ray beam monitor. As a result, the XANES spectra with enough quality to discriminate chromium with different valence were obtained by using SDD with high energy resolution of 135 eV@5.9 keV although small detection area of 50 mm².

Rietveld texture analysis with the use of neutron diffraction is a promising analytical method to observe microstructural evolution of steels in high-temperature processes. Phase fraction and texture evolution can be analyzed from diffraction intensities in the Rietveld texture analysis. However, since the diffraction intensities can vary with the isotropic temperature factor, B_iso, which is a parameter of the atomic thermal vibration, the analytical accuracy of B_iso would affect the texture and phase fraction analyses. We examined the influence of the divergence of B_iso on the analytical accuracy of phase fraction and texture in Rietveld texture analysis by using neutron diffraction data of steels. It was confirmed that the decrease in diffraction intensities at high reflection indices became significant with an increase in temperatures, as a result of the increase in the atomic thermal vibration. By observing the clear attenuation of diffraction intensities from low to high reflection indices, the B_iso equivalent to the literature value was successfully estimated, and appropriate phase fraction of ferrite and cementite phases were obtained. When the B_iso was intentionally changed in Rietveld texture analysis, the estimated phase fraction deviated from the actural value while the texture results was affected little. We also examined the number of diffraction peaks necessary for obtaining appropriate B_iso. It was confirmed that 11 or more diffraction peaks are required for estimating an appropriate B_iso value, so that phase fraction of ferrite and cementite phases is to be analyzed correctly.

Na(1s, 2s, 2p) X-ray photoelectron (XPS) spectra of sodium L-tartrate, which is used as an asymmetric modifier of a catalyst that efficiently produces only one of the enantiomers during the asymmetric reduction synthesis of prochiral methyl acetoacetate (MAA), were measured. In addition, those of various sodium compounds were measured as the related compounds, and the electronic states of sodium ions in these compounds were clarified. The Na KLL Auger electron (AES) spectra were also measured to determine the Auger parameters of the sodium compounds. The value of Auger parameter of sodium L-tartrate was the largest among the measured sodium compounds. On the other hand, when MAA was added to sodium L-tartrate, its value of Auger parameter greatly decreased, and became nearly the same as those of other sodium compounds. Furthermore, C and O K-edge X-ray absorption (XANES) spectra were measured for L-tartaric acid and its alkali metal salts (Li, Na), and the L-tartrate-complexes with MAA. Though the energy resolution of the XANES spectra is much higher than that of the XPS spectra, C and O K-edge XANE spectra of the L-tartrate-complexes with MAA were very similar to the corresponding L-tartrates, respectively. There are no big changes not only in the XPS, but also XANES spectra between L-tartrates and L-tartrates-complexes with MAA, regarding the peak positions and peak shapes. On the other hand, in Ni (2p) XPS and Na KL₂₃L₂₃ AES spectra, the shifts of 0.6 and 2.1 eV were observed, respectively. These results suggest that the addition of MAA slightly changes the electronic state of the outermost shell of sodium ion, which could be confirmed from the Na (2p) XPS and Na KL₂₃L₂₃ AES spectral peaks.

The decommissioning of TEPCO's Fukushima Daiichi Nuclear Power Plant is expected to result in demolition debris, which has the potential to be contaminated with uranium, in the near future. Consequently, rapid analysis of the uranium surface contamination density will be required. Since uranium has a long half-life, it is difficult to be quantified by radiation measurements. Hence, inductively coupled plasma-mass spectrometry (ICP-MS) is generally used for analysis. However, in this method, it is necessary to perform an ashing treatment to remove organic substances, and the analysis is time-consuming. In this study, a method for quantifying the uranium surface contamination of demolition debris is developed, which includes the following sequence of steps: preparation of a sample simulating the surface of rubble contaminated with uranium; acid elution of the components from the sample, extraction of uranium by solid-phase extraction, and total reflection X-ray fluorescence (TXRF) analysis. Furthermore, the improvement of the detection limit by physically concentrating the uranium extract was investigated.

To non-destructively detect contents of commercially drinks, X-ray absorption spectra (XAS) of the contents adsorbed on insulating wiping clothes 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 (ALS) and in BL10 at the NewSUBARU. Low-concentration contents or hydrocarbon contents as same as wiping clothes cannot be easily detected in C K- and O K-XANES. However, protein and lipid contents in the drinks can be detected in XANES. It is therefore concluded that contents (protein, lipid) in drinks adsorbed on wiping clothes can be non-destructively detected by using the TEY method.

Nondestructive analysis of the chemical states of the interface in Ru/B₄C multilayers was achieved using soft X-ray emission spectroscopy in the B K and C K regions of the multilayer measured under X-ray standing-wave conditions. The Ru/B₄C multilayer samples were selectively excited by monochromatized undulator radiation under X-ray standing-wave conditions at an excitation energy of 386 eV with an incident angle of 16°. Symmetrical differences in spectral features were observed between the on-standing-wave-conditions and the off-conditions at 386 eV (the Bragg condition). This symmetrical spectral feature change demonstrates that the chemical state differences in boron and carbon atoms between the interface and internal B₄C layers are observable by soft X-ray emission measurements under the X-ray standing-wave conditions.

Bromine (Br) and Zinc (Zn) in hard tissues of some crustacean were measured by X-ray analytical microscope. It was confirmed that Br can be accumulated around mouth in crustaceans. Accumulations of Zn have been observed some species living in the river or land. It is suggested that Br should be an element derived from seawater, and some crustaceans tend to accumulate not only Br but also Zn depending on living places.

To improve the O K-XANES database for chemical analysis of oxygenated carbon materials, O K-XANES of various liquid aliphatic compounds having oxygenated functional groups were measured and were analyzed by using the first-principles calculations. O K-XANES of the measured alcohol, ether, ketone, aldehyde, carboxylic acid, and ester were in agreement with other aliphatic and aromatic compounds having oxygenated functional groups. However, in carbonyl functional groups bonding to the sp²-carbon atoms, the π^* peak of carbonyl-oxygen splits into several peaks. Hence, unsaturated bonding should be taken care for analysis of oxygenated carbon materials using O K-XANES.

In-situ neutron diffraction measurements during tensile-deformation test for magnesium were carried out to investigate the correction method of line-profile analysis for hexagonal metals. Anisotropy of elastic constants and crystallite refinement with respect to crystal orientation were corrected in Williamson-Hall method. Elastic constant for each crystal orientation was obtained from the Kröner model, and the breadth of the diffraction peak due to the elastic anisotropy was corrected. Because of the small elastic anisotropy of magnesium, the effect of correction for the elastic anisotropy was small. A spheroid model was used for refined crystallite. It was confirmed that the crystallite diameter was large in the {0001} plane, which is the slip plane of magnesium, and small in the normal direction of the {0001} plane. This anisotropy relaxed with an increase in the tensile deformation. Generally, only the elastic anisotropy has been corrected in line profile analysis for metallic materials, it was demonstrated that the correction of the anisotropy of crystallite refinement is indispensable for hexagonal metals in the line-profile analysis.

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 analyzed by using the first-principles calculations. In the calculations, BBL polymer unit takes an orthorhombic structure. The measured XANES profiles were reproduced by the calculated XANES, which suggested the intermolecular effects between the BBL layers. However, peak intensity of the measured characteristic peaks in C K- and O K-XANES cannot be reproduced by the calculations. It is therefore confirmed that BBL polymers may take more complicated layer structure.

X-ray fluorescence analysis (XRF) is one of the ideal quantitative analytical methods for slightly soluble materials such as fine ceramics. In this study, non-distructive quantitative analyses of C, N, and O in silicon nitride were investigated by XRF especially regarding sample preparations and measurement conditions. Standard silicon nitride powders were made into briquettes and measured with a wavelength dispersive X-ray fluorescence spectrometer. In this measurement system, main error sources were decreasing vacuum level of the sample chamber and the adsorption of contaminations on the surface of briquettes. However, results indicated that quantitative analysis of C, N and O are possible by setting up calibrations.

Adenosine tri-phosphate (ATP), one of ribonucleic acids, acts as an intra-cellular energy transfer. ATP is also used as a substrate to synthesize messenger RNA and as a ligand of up-regulation of these biological function. In this study, we examined the relation between molecular activity, genetic information transfer, and inter-cellular signaling activity. The obtained results showed that the altered ATP molecule might contribute the induction of changing of a radiation sensitivity of cancer cells.