Advances in X-Ray Chemical Analysis, Japan
Online ISSN : 2758-3651
Print ISSN : 0911-7806
Current issue
Displaying 1-23 of 23 articles from this issue
Review Articles
  • Atsushi OHBUCHI
    2022 Volume 53 Pages 7-18
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    The benchtop X-ray diffractometer equipped with a one dimensional detector was developed to achieve higher sensitivity analysis. Developed variable knife edge was used as a countermeasure for unwanted scattering. High sensitivity analysis was achieved by equipping a 600 W X-ray tube and a one dimensional detector. Also, a multifaceted X-ray analysis using various X-ray analysis techniques was applied for environmental materials. Crystalline phases of minor elements in a municipal solid waste incineration fly ash classified into each particle size were estimated by confirming correlations between concentrations of major and minor elements. Chemical forms of soluble as chloride and insoluble as amorphous content, free, and oxide phase content forms of radioactive cesium in a municipal solid waste incineration fly ash were analyzed.

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  • Hisanobu WAKITA
    2022 Volume 53 Pages 19-28
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Today is the age of the instrumental analysis. Some of instumental analysis methods employ the ionising radiation represented by X-ray as a tool of looking into the microscopic world. In this time, understanding the history of analytical chemisty is helpful to evaluate the results (numeric values) of the instrumental analysis based on the discussion of analytical chemistry. This review is composed Justus von Liebig (1803-1873) who tought analytical chemistry emphasizing the student laboratory in late 19th century) at the center of the story, and is devided into three parts: before Liebig, Liebig age, and after Liebig. This review also includes partly the history of Japan analytical chemistry. From the late of 17th century British Industrial Revolution brought the construction of factories, ships, and trains powered by the steam engine, and accelerated the progress of those tequniques and theories. Especially the story of the contribution of the thermodynamic theory for the steam engine and that of the phase equiribrium and phase rule theories for the iron manufaturing give big hints to the progress of recent technology.

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  • Masashi OKUBO
    2022 Volume 53 Pages 29-34
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Reversibility of an electrode reaction is important for energy-efficient rechargeable batteries with a long battery life. Additional oxygen-redox reactions have become an intensive area of research to achieve a large specific capacity of the positive electrode materials. However, most oxygen-redox electrodes exhibit a large voltage hysteresis >0.5 V upon charge/discharge, and hence possess unacceptably poor energy efficiency. Here, we demonstrate how reversible oxygen-redox reactions can be achieved based on the state-of-the-art understandings of oxygen-redox chemistry.

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  • Toshiaki OHTA
    2022 Volume 53 Pages 35-44
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Li K-edge X-ray absorption spectra of Li metal and Li compounds have been published in many papers. These spectra were taken not only by using soft X-ray synchrotron radiation, but also by using hard X-ray synchrotron radiation and high energy electrons as energy loss spectra. In the SR center, Ritsumeikan University, we have also measured the spectra of Li compounds, although most of which have not been published yet. By digitizing the published spectra, we can compare these spectra with each other in the same scale. It was found that these spectra are not always same. This is mainly due to high reactivity, easiness of decomposition, radiation damage of Li compounds. In this report, the spectral similarity and dissimilarity are discussed for several representative Li compounds.

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Instrumentation & Experimental Technique
  • Shoji KUWABARA
    2022 Volume 53 Pages 45-68
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Since the quantitative element distribution can be obtained without scanning the sample by real-time XRF microscopy(R-XRFM), it is described that R-XRFM is particularly useful in the field of biochemistry and material development where in-situ observation is required. Spatial resolution and X-ray intensity distribution of R-XRFM are evaluated by ray-tracing simulation calculation considering the excitation X-ray intensity on the sample surface assuming a point-focus X-ray tube and the diffraction X-ray intensity by the monochromator. The derivation of the formula based on the dynamical theory used for the calculation and the geometrical relationship between the physical quantities and parameters used for the calculation in the reciprocal lattice space are reviewed. In addition, the normalizing coefficient Ns when the analyzed element is dotted on the sample surface and the normalizing coefficient Np when the analytical element is distributed in a wider range than the pixel size of the detector, are obtained from the simulation calculation.

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  • Masato KOIKE, Takanori MURANO, Shogo KOSHIYA, Tadashi HATANO, Alexande ...
    2022 Volume 53 Pages 69-76
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    In the design of the diffraction grating mounted on the diffraction grating spectrometers for general-purpose soft X-ray emission spectroscopy, it has been the common practice to design to enhance basic performance such as resolution and diffraction efficiency (DE) in the widest possible wavelength range. We have recently conceived a new evaluation index named “spectral flux (SF)” which defined by the product of the numerical aperture and the diffraction efficiency and correlates with the analytical sensitivity of the spectrometer. In this study, we performed the grating design to increase DE and SF, focusing on Li-K emission (54.3 eV, 22.83 nm) by optimizing the parameters of the incidence angle and coating structure on the surface of the grating by numerical calculation. As a result, it was found that the newly designed grating which employs a coating of a carbon system layer having a certain thickness on a metal layer on the grating surface indicates a high diffraction efficiency at a smaller incident angle than a traditional incident angle increasing the numerical aperture and reveals about 8 times higher SF at Li-K emission comparing with conventional spectrometer design and cover a wide wavelength range maintaining a high SF.

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  • Tomoki FUCHITA, Taisei URATA, Tsugufumi MATSUYAMA, Masashi MURAKAMI, Y ...
    2022 Volume 53 Pages 77-87
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    X-ray fluorescence (XRF) analysis is an analytical method to obtain elemental information by detecting fluorescence X-rays emitted from a sample irradiated with X-rays. It is possible to obtain two-dimensional elemental distribution images by scanning a sample with micro X-ray beam. In this study, we developed an XRF analytical instrument to rapidly obtain the elemental distributions for moving samples on a belt conveyor by applying the micro XRF technique. X-rays were widely irradiated to the belt conveyor. The elemental distributions were measured by scanning an X-ray detector, crossing above the belt conveyor. A collimator was attached to the top of the detector to limit the analyzing area. Both detection limit and spatial resolutions for moving directions of the detector and the belt conveyor were evaluated. Finally, it was demonstrated that the multi-elemental imaging was possible with the developed XRF instrument.

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  • Hiroshi YOSHII, Yumi TAKATA, Kodai TAKAMURA, Tetsuaki UWATOKO, Yasuhir ...
    2022 Volume 53 Pages 89-96
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    In the dismantling of nuclear facilities or the decommissioning of TEPCO's Fukushima Daiichi Nuclear Power Station, it is necessary to evaluate the material contamination levels by nuclear fuels and fission products. In this study, we propose a method for screening the uranium contamination level of concrete surfaces in such a scenario. Using this method, the concrete surface is scraped, and its components are acid-eluted. Uranium is extracted by the solid-phase extraction method, and total reflection X-ray fluorescence analysis is performed. We concluded that it is appropriate to use 0.5 g of concrete for analysis because the solid phase extraction recovery decreases owing to the matrix effect when using larger concrete samples. The relationship between the added uranium content and that determined in the eluate showed a straight line with a slope of almost 1; whereas uncontaminated concrete also contains uranium, the vertical intercept has a significant value. The lower limit of detection was 37 ng, which indicates that the uranium contamination can be detected when an increase in uranium content exceeding 37 ng is observed in the acid eluate for concrete suspected of contamination compared to that for uncontaminated concrete.

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  • Masahito UCHIKOSHI, Kozo SHINODA, Takatoshi MATSUMOTO
    2022 Volume 53 Pages 97-117
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Fitting thermodynamic models to ultraviolet-visible absorption spectra yielded the distribution of the cobaltous aqua and chloro complexes and their molar attenuation coefficients. The X-ray absorption near edge structures and the extended X-ray absorption fine structures spectra of the individual species were assessed dividing a series of spectra by the distribution obtained through the fitting analysis. Then, the structure analysis was conducted using the decomposed EXAFS spectra of the individual species. However, the most possible complex structure for each species could not be fixed. The most possible structures were determined by comparing the single point energies between the observed structures and the optimum structures calculated using ab-initio technique. It was confirmed that there were three complexes of [CoII(H2O)6]2+, [CoIICl2(H2O)4]0, and [CoIICl4]2- and their stability constants were determined. The analysis procedure conducted in the present work consisted of ultraviolet-visible/X-ray absorption spectra, fitting analysis of thermodynamic models, and ab-initio calculation. The distribution and the structures of the cobaltous aqua and chloro complexes were determined with the benefit of the mutual compensation for the disadvantages of the other analyses.

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  • Yuji KURIMOTO, Jun KAWAI
    2022 Volume 53 Pages 119-126
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    We tried to detect X-rays by a webcam as a low price detector. We wrote computer programs to measure with the webcam and to integrate data from it. White dots were appeared on frames while a CMOS sensor on the webcam was exposed to X-rays. By making shadow on the sensor with a steel wire, we estimated source-sensor distance and source size. We also estimated spatial resolution of the webcam at 5×5 pixels per photon by counting events by number of affected pixels by photons.

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  • Daisuke OHSAWA, Akihiro UEHARA, Teruaki KONISHI, Yasuko TERADA, Masato ...
    2022 Volume 53 Pages 127-138
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Specific internally exposed radionuclides such as uranium are known to migrate into bone and accumulate over a long period of time. However, there is a lack of fundamental data on how uranium migrates into bone and how it affects bone development, particularly during juvenile period when bones are actively developing. Aiming at establishing a method to evaluate uranium migration into bone, as a first step, the possibility of visualizing and quantifying uranium migrated into rat femurs was investigated using a synchrotron radiation (SR)-μCT-based absorption-edge subtraction method. Two sets of radiographic images were taken at X-ray energies just below and above the L3-absorption edge (17.17 keV) of uranium (16.9 and 17.5 keV, energy gap of 600 eV) at the BL20B2 beamline of SPring-8, Japan, and reconstructed into microtomographic images by a convolution back-projection algorithm, followed by their subtraction, to leave a set of the differential images (voxel size of 2.73 μm). In addition to 1- and 10-week-old juvenile rat femurs treated with or without uranyl acetate, uranium calibration standards of solution and hydroxyapatite (HAP) were prepared and subjected to the μCT imaging.

    For the standards, non-uniform distribution of uranium was observed both in solution and HAP, especially at higher concentrations of uranium, which was possibly caused by the cryo-condition for the solution and by the grain diameter larger than the pixel size for the HAP, respectively. This suggests that the μCT imaging for the standards should be performed at room temperature by using HAP with a grain diameter much smaller than the pixel size.

    For the rat femurs, the histograms of the pixel values in the bone area of the differential images showed no significant difference between the uranium-treated group and the control group, confirming that uranium was not detectable in the present experimental setup. This was mainly due to the large standard deviation of the histograms for the control group. The detection limit of uranium under the present experimental condition was estimated to be several tens of thousands of ppm. On the other hand, the histograms of the pixel values in the bone area of the reconstructed images confirmed that the bone density of 10-week-old rat femurs increased by 20% compared with that of 1-week-old rat femurs. They also demonstrated that the three-dimensional microstructure of the bone was clearly visualized with a high spatial resolution of a few micrometers.

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  • Mayu MORITA, Tomoki AOYAMA, Hitomi NAKANO, Shintaro KOMATANI
    2022 Volume 53 Pages 139-149
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    X-ray Analytical Microscope (micro-EDXRF) visualizes distribution of elements contained in a sample by overlaying the elemental images onto the optical image of the sample, the key feature of which is called elemental imaging. Being Taken advantage of this, micro-XRF is widely used for failure analysis, and elemental analysis of foreign objects. In general, it is impossible to detect light elements by EDXRF, including carbon, oxygen, and fluorine. This is because these elements are subject to attenuation by beryllium in transmission window. In contrast, thin polymer window is used for SEM-EDX, but the transmission of visible light causes to generate undesired signals since the X-ray detector element responds to the visible light. In this study, we have installed a new detector with graphenic carbon window instead of Be into our instrument. Here, we will describe improvements in X-ray intensity for light elements contained in several industrial materials.

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Analytical Application
  • Yuma KASAMA, Shintaro ICHIKAWA, Ayuko KITAJOU, Tsutomu KURISAKI
    2022 Volume 53 Pages 151-163
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    To clarify a surface state of ionic liquid and its lithium salt solution, X-ray photoelectron spectroscopy (XPS) was applied to a neat ionic liquid N, N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI) with and without a lithium salt of Li TFSI. Core level peaks were recorded for Li 1s, C 1s, N 1s, O 1s, F 1s and S 2p. Valence band XPS spectra (0-40 eV bond energy) were also studied. The structure of ionic liquids under X-ray irradiation was investigated by time-dependence measurements of Li 1s, F 1s and N 1s spectra.

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  • Hinano TANAKA, Shintaro ICHIKAWA, Tsutomu KURISAKI
    2022 Volume 53 Pages 165-173
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Atamadai-type potteries, a kind of Jomon pottery, from Hinoki site (Tochigi, Japan) are said that might be purposely mixed biotite as a temper into the raw clay. In practice, 59 Atamadai-type potteries and 18 other types Jomon potteries from Hinoki site were analyzed qualitatively by XRD. As the result, it was indicated that biotite (K(Mg,Fe)3AlSi3O10(OH,F)2) which is solid-solution mineral, was mixed as a temper in Atamadai-type potteries. The lattice spacing d may be useful for estimation of the minerals' origin because the solid-solution ratio probably depends on the origin. In this study, we examined origin dependency of biotite's lattice spacing using the 14 biotite-containing rock samples by X-ray diffractometry (XRD) to estimate the origin of temper that is contained in Atamadai-type potteries. The lattice spacing values of biotite 001 was classified into five groups. Some of them were not significantly different although they were collected from the different origins. Furthermore, others were significantly different although the sampling points are close to each other. The clarification of the causes is required for provenance estimation of the temper in Atamadai-type potteries using the lattice spacing of biotite.

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  • Kana BABA, Yusuke ONUKI, Yuma NAGAOKA, Masato ITO, Shigeru SUZUKI, Shi ...
    2022 Volume 53 Pages 175-182
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    In order to understand the mechanism of temperature dependence of flow stress in high-temperature deformation of pure copper, dislocation behaviors during deformation were investigated by using in-situ time-of-flight neutron diffraction. The dislocation density was determined by line-profile analysis of the neutron diffraction data. Based on the dislocation density, the flow stress was estimated using the Bailey-Hirsch equation, and the relationship between the mechanical properties and the dislocation density was discussed. The increase in the dislocation density during the deformation was suppressed with increasing temperature. It can be deduced that dislocation recovery with annihilation was more likely to occur at higher temperatures. Estimation of the flow stress using the measured dislocation density reproduced well the temperature dependence of the flow stress. It was also confirmed that the oscillation of flow stress was caused above a certain temperature by the alternating increase and decrease of dislocations in the range of 1012-1013 m-2. The decrease in ductility as the temperature increases to about 400°C corresponds to the decrease in dislocation strengthening per unit length along with the decrease in dislocation density.

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  • Izumi OKUBO, Shintaro ICHIKAWA, Hisanobu WAKITA, Chiya NUMAKO, Kotaro ...
    2022 Volume 53 Pages 183-194
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    In this study, the relationship between the chemical compositions of iron sands from Okuizumo (Shimane) and the outcrops which are sources of the iron sands, was examined in order to estimate the origin of the raw material for Tatara iron manufacture. The soil samples were collected from eight outcrops in this area. The iron sand samples were taken out of the soil samples. The concentrations of major and trace elements in the soil and iron sand samples were quantified by X-ray fluorescence spectrometry (XRF). In general, As/Sb and Ti/V ratios are constant regardless of the iron making process. Thus, these ratios were focused to classify the iron sand samples in this area. As a result of XRF, Ti and V were detected in the iron sand samples, on the other hand, As and Sb could not be detected in the samples. The scatter diagram using Ti and V concentration values distinguished four outcrops which had been probably used for Tatara iron manufacture in this area, from other samples. Therefore, the concentration values of Ti and V may be useful for identification of the outcrops which were the sources of iron sand for Tatara iron manufacture.

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  • Haruko YAKUMARU, Izumi TANAKA, Mika TANAKA, Kazuko YOKOCHI, Kyoko AYAM ...
    2022 Volume 53 Pages 195-202
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    The intestine plays an important role to absorb nutrients. The Fukushima Daiichi Nuclear Power Plant accident renewed public concerns about the internal exposure of radionuclides posed by food intake. In order to understand the dynamics of elemental distribution in the intestine, elemental images for intestinal tissue specimens were obtained with micro-PIXE system, QST. Cryo-sections of mouse intestine (10 μm thickness) placed on a polypropylene film (6 μm thickness) were prepared for the analysis. Histological observation was performed with serial-sections stained with hematoxylin and eosin. Micro-PIXE measurements were performed for the areas (1000 μm×1000 μm) covering from the base of the intestinal tract to the lumen in intestinal cross-sections from 5 regions (the upper, middle, and lower part of the jejunum, the ileum, and the colon). Clear images of phosphorus, sulfur, chloride, and potassium were obtained. Further measurements with higher resolution revealed that potassium localized areas were found in the villi and the bottom area of the mucosal layer of the middle and lower jejunum. The present method would be valuable for the studies on elemental distribution in the intestine corresponding to the fine tissue structure.

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  • Akira WATANABE, Yaeko SUZUKI, Akiko HOKURA
    2022 Volume 53 Pages 203-222
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Trace elemental analysis of polished rice was performed using an X-ray fluorescence spectrometer equipped with 3D polarized optics system in order to characterize the geographical origins. Using the XRF spectrometer, trace elements in polished rice were determined in a total of 10 countries: eight Asian countries (Japan, China, Malaysia, Bangladesh, Myanmar, Cambodia, Sri Lanka, and Thailand), plus the United States and Australia. By using Ti, Ge, and Zr as secondary targets, 11 elements (P, S, Cl, K, Ca, Mn, Fe, Cu, Zn, Br and Rb) were detected in a 15-minute measurement, and 7 of these elements (P, K, Mn, Fe, Cu, Zn, and Rb) were quantified by the calibration curve method. Multivariate analysis of the compositions of these seven elements in combination with the stable isotope ratios δ13C, δ15N, and δ18O revealed more geographical characteristics of Asian rice than when the elemental compositions or the isotope ratios was used for multivariate analysis. In particular, P concentration and δ15N values were effective in discriminating between geographically close Japan and China. Furthermore, a comparison between Japanese conventional rice and organically grown rice with a clear cultivation history showed that Rb concentration and δ15N value were greatly affected by the cultivation method.

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  • Akihiro UEHARA, Xian SHUHUI, Ryotaro SATO, Daiju MATSUMURA, Takuya TSU ...
    2022 Volume 53 Pages 223-229
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Internal contamination of plutonium in nuclear accidents is of critical concern. In the present study, chemical forms of zirconium (Zr), a simulated plutonium, coordinated with the organic/inorganic ligands as well as decorporation chelating agents were estimated based on X-ray absorption spectroscopy. Chelating agents used were 1-hydroxyethane-1,1-diphosphonic acid (EHBP) and diethylenetriaminepentaacetic acid (DTPA). First coordination sphere of the Zr-EHBP complex, which was octahedral structure, was significantly different from other ligands such as carbonate, phosphate and DTPA. Furthermore, it was found that the Zr-EHBP complex was more stable than Zr-DTPA complex. These findings would be useful for the effective excretion of internal contamination of plutonium.

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  • Kazuki UMEMURA, Yusuke ONUKI, Akinori HOSHIKAWA, Toshiro TOMIDA, Yasua ...
    2022 Volume 53 Pages 231-241
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    Time-of-Flight neutron diffraction measurements were performed to investigate microstructural evolution during bainitic transformation of a low-alloyed transformation induced plasticity steel. Phase fractions of austenite and ferrite phases during the transformation are determined by analyzing diffraction intensities by the Rietveld method. March-Dollase (MD) and Extended Williams-Imhof-Matthies-Vihel (E-WIMV) methods were also employed in the Rietveld analysis to correct effects of crystallographic textures on the diffraction intensities. It was confirmed that the E-WIMV method could correct the influence of textures on the diffraction intensity with higher accuracy than the MD method. The analysis revealed the presence of low-carbon and high-carbon austenite phases during the bainitic transformation. Ex-situ measurements on quenched samples using electron microscopy and X-ray diffraction confirmed that the low-carbon and high-carbon austenite phases observed by neutron diffraction were those transformed to a martensite phase and retained as an austenite phase at room temperature, respectively.

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  • Runa MARUYAMA, Yasuji MURAMATSU
    2022 Volume 53 Pages 243-256
    Published: March 31, 2022
    Released on J-STAGE: October 05, 2024
    JOURNAL FREE ACCESS

    To develop the non-destructive analytical method for oils adsorbed on insulating wipers using soft X-ray absorption spectroscopy with a total-electron-yield (TEY) method, TEY-XANES spectra of various liquid unsaturated fatty acids adsorbed on the insulating wipers of Kimwipe® (denoted by KW) were measured in BL10 at NewSUBARU. Fraction of the fatty acid and KW were >75% and <25%, respectively, in the TEY-C K-XANES of fatty acid adsorbed on KW. In the TEY-O K-XANES, fraction of fatty acid and KW was approximately 50% each. Such the difference of fraction between C K and O K regions can be explained by the difference of detection depth of TEY in C K and O K regions. Considering the detection depth, XANES of oil compounds can be extracted from TEY-XANES of the oil compounds adsorbed on insulating wipers.

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