Development of a novel X-ray fluorescence instrument equipped with a noble gas filter.

In X-ray fluorescence (XRF) analysis, which has been used to analyze elements in various samples, it is important to decrease the background (BG) intensity. Generally, BG signals are reduced by inserting metal foils of various types and thicknesses between the X-ray tube and sample as primary X-ray filters. In this study, we developed a unique gas filter-XRF (GF-XRF) instrument to easily reduce the BG effect by changing the pressure of the gas to ensure that the absorption edge of the gas element is slightly lower than the energy of the XRF peak of the target element. The advantage of using a gas is that the gas pressure can be altered easily. To evaluate the performance of this instrument, Ti and Zr were selected as target elements, and Ar and Kr were selected as the filtering gases. When the XRF spectra of the Ti sample were recorded using the Ar gas filter, as the Ar gas pressure increased, the background signal in the energy region of the Ti Kα peak decreased, resulting in an increase in the signal-to-noise ratio (SNR) of that peak. When the Kr gas filter was used, both the SNR and the minimum detection limit of Zr improved. These results demonstrate that the unique GF-XRF instrument is useful for high-sensitivity analyses.

Correction: Development of a novel X-ray fluorescence instrument equipped with a noble gas filter.

Correction for 'Development of a novel X-ray fluorescence instrument equipped with a noble gas filter' by Tsugufumi Matsuyama et al., Analyst, 2024, https://doi.org/10.1039/d4an00122b.

High-accuracy determination of trace elements by total reflection X-ray fluorescence spectrometry using freeze-dried specimens.

Total reflection X-ray fluorescence (TXRF) analysis is conducted to determine trace elements in a sample solution, which is dropped onto a substrate and dried. Therefore, the form of the residue affects the quantitative results. The absorption of X-ray fluorescence (XRF) follows the Lambert-Beer law; the absorption effect of XRF in a thick residue (dotted-type residue) is stronger than that in a thin residue (film-type residue). The absorption effect is particularly remarkable during the determination of low-Z elements in a high-elemental concentration solution. In this study, we propose a new film-like-residue preparation process based on the freeze-drying method to obtain accurate TXRF results. The sample solution is dropped onto the substrate and inserted into a chamber. The chamber is cooled using liquid nitrogen; resultantly, an aliquot of the sample is frozen. The chamber is depressurized using a vacuum pump, and the freeze-dried residue is prepared by maintaining the chamber at room temperature. To evaluate the efficiency of the freeze-drying-based method for sample preparation for TXRF analysis, we prepare a multi-element solution containing high-elemental concentration components. For the residue prepared using the freeze-drying method, the relative standard deviations of the quantitative values and the minimum detection limits are improved because the absorption effect is weakened. The sample preparation process based on the freeze-drying method facilitates accurate TXRF analysis of high-elemental concentration solutions and can be applied for the analysis of trace elements in different types of solutions such as environmental water and wastewater.

Multi-Modal Compositional Analysis of Layered Paint Chips of Automobiles by the Combined Application of ATR-FTIR Imaging, Raman Microspectrometry, and SEM/EDX.

For the forensic analysis of multi-layered paint chips of hit-and-run cars, detailed compositional analysis, including minor/trace chemical components in the multi-layered paint chips, is crucial for the potential credentials of the run-away car as the number of layers, painting process, and used paints are quite specific to the types of cars, color of cars, and their surface protection depending on the car manufacturer and the year of manufacture, and yet overall characteristics of some paints used by car manufacturers might be quite similar. In the present study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) imaging, Raman microspectrometry (RMS), and scanning electron microscopy/energy-dispersive X-ray spectrometric (SEM/EDX) techniques were performed in combination for the detailed characterization of three car paint chip samples, which provided complementary and comprehensive information on the multi-layered paint chips. That is, optical microscopy, SEM, and ATR-FTIR imaging techniques provided information on the number of layers, physical heterogeneity of the layers, and layer thicknesses; EDX on the elemental chemical profiles and compositions; ATR-FTIR imaging on the molecular species of polymer resins, such as alkyd, alkyd-melamine, acrylic, epoxy, and butadiene resins, and some inorganics; and RMS on the molecular species of inorganic pigments (TiO2, ZnO, Fe3O4), mineral fillers (kaolinite, talc, pyrophyllite), and inorganic fillers (BaSO4, Al2(SO4)3, Zn3(PO4)2, CaCO3). This study demonstrates that the new multi-modal approach has powerful potential to elucidate chemical and physical characteristics of multi-layered car paint chips, which could be useful for determining the potential credentials of run-away cars.

Comparison of multiple X-ray fluorescence techniques for elemental analysis of particulate matter collected on air filters.

This work reports on qualitative and semi-quantitative elemental analysis of particulate matter (PM) collected on PTFE membrane filters, for a source apportionment study conducted in Brescia (Italy). Sampling was undertaken in a residential area where an increase in Mn emissions has been highlighted by previous studies. Filters are measured by means of X-ray Fluorescence (XRF) based techniques such as micro-XRF and grazing incidence XRF using synchrotron radiation, Mo or W excitation sources, after applying an automatized sample preparation method. A heterogeneous distribution in PM shape, size and composition was observed, with features typical of anthropogenic sources. XRF measurements performed at various incidence angle, on large areas and different experimental setup were reproducible. The results demonstrate a successful comparison of the various XRF instrumentation, and the decrease in Mn content with the distance away from the identified emission source. This work highlights the potentialities of the presented approach to provide a full quantitative analysis, and ascertain its suitability for providing a direct, fast, simple and sensitive elemental analysis of filters in source apportionment studies and screening purposes.

Depth-selective x-ray diffraction using energy-dispersive x-ray detector and straight capillary optics.

Depth-selective x-ray diffraction (XRD) technique was developed. In this technique, XRD spectra were measured using an energy dispersive (ED) x-ray detector at fixed angles. A straight capillary optic was used to define the incident x-ray beam, and a second straight capillary defined the beam path from the sample to detector. Thereby, only the XRD spectrum at the small intersection of two capillary optics could be obtained. A depth-selective XRD is possible by changing the sample position in depth. Many XRD peaks appear in a high-energy range more than 10 keV in the ED spectrum. The detection of these peaks will be advantageous for depth analysis because of low absorption in the sample. Depth-selective measurement would be advantageous over general XRD. In this study, depth-selective and ED-XRD spectra are demonstrated for the layered sample, which consisted of film-like Si powder and a muscovite film.

Confocal micro-X-ray fluorescence analysis for difference identification of ceramic samples.

A nondestructive analytical method for difference identification is required in the research fields such as forensic science or archeology. An X-ray fluorescence (XRF) analysis is one of feasible techniques for this purpose. Micro-XRF using an X-ray micro-beam gives elemental distributions by scanning the samples. A confocal micro-XRF (CM-XRF) technique is a unique analytical technique to analyze limited volume. CM-XRF enables elemental depth imaging and elemental profiling in depth nondestructively. Therefore, CM-XRF has been applied for various samples such as industrial samples, paintings, forensic samples, food materials, and human hairs. CM-XRF technique would be a suitable method for difference identification because the CM-XRF gives detailed information on elemental distribution not only on the surface of the sample but also in depth. We developed CM-XRF instrument in the laboratory and applied to two very similar ceramics samples. It showed differences in the intensity profiles of Fe and Mn for blue paintings on the ceramics. In addition, depth elemental analysis revealed different depth profiles especially of Co and Zn for both samples. These results suggest that CM-XRF provides useful information for the identification of ceramic samples.

Elemental analysis of hourly collected air filters with X-ray fluorescence under grazing incidence.

The X-ray fluorescence under grazing incidence condition (XRF-UGI) was applied for the direct analysis of aerosol filters. Particulate matter less than 2.5 microns (PM2.5) was collected hourly on polytetrafluoroethylene filters using a continuous PM monitor with a virtual impactor method. Although the sampling mass is in trace amounts of 5-30 µg, the metallic contents, such as V, Cr, Mn, Fe, Zn, and Pb, can be measured at sub-ng m-3 detection limits. The effects of the non-uniformity and poor flatness of the PM filters were discussed with regard to the measurement repeatability. The relationship between the XRF-UGI intensities and the mass concentrations obtained via conventional X-ray fluorescence (XRF) analysis was confirmed using the fundamental parameter method. Finally, quantification was successfully demonstrated using the XRF-UGI results with the relative sensitivity factors.

High-accuracy total reflection X-ray fluorescence analysis for determining trace elements using substrate cleaned by ammonia-hydrogen peroxide mixture.

Total reflection X-ray fluorescence (TXRF) analysis is one of the useful techniques for determining trace elements. Owing to the high detection sensitivity of X-ray fluorescence in small residues, the hydrophobic substrates are generally used to form dot-type residue. However, when measuring low-Z elements in sample solutions with high concentrations of matrix elements, obtaining sufficient measurement sensitivity can be difficult. X-ray fluorescence is absorbed by the matrix elements, which means that the absorption effect increases in the thicker dried residue compared to the thinner dried residue. To avoid this absorption effect, we have proposed a thin film-type residue. In this study, the glass substrate was treated with an ammonia-hydrogen peroxide mixture (APM). The hydrogen peroxide decomposes organic components, and ammonia slightly etches glass materials. The APM-treated region was limited to a diameter of 6 mm by using a polytetrafluoroethylene mask placed on the glass substrate. As a result, the surface is refreshed to expose the hydroxyl group to make it superhydrophilic. The measured contact angle was 5°. By using the APM-treated superhydrophilic substrate to prepare dried residue, the net intensities in low Z elements were improved. The ratio of Al Kα intensity, calculated as net intensity in the APM-treated substrate divided by it in the hydrophobic substrate, was 2.29. The recovery of each element in the APM-treated substrate was almost 100%; however, recoveries of elements (Al, P, K, and Ca) in the hydrophobic substrate showed significant deviations from 100% (the recovery of Al was approximately 32%). In summary, we successfully improved both analytical sensitivity and accuracy in TXRF analysis by using the APM treated substrate.

Direct digestion of human scalp hair on the substrate used for total reflection X-ray fluorescence analysis.

It is important to determine the elemental content of scalp hair to evaluate human health and environmental contamination. Here, a new sample preparation method for total reflection X-ray fluorescence analysis was developed by directly digesting the human hair on the sample holder. A human hair sample was subjected to thermal nitric acid treatment for sample digestion and homogenization. The Zn concentration was estimated to be ~ 1.89 × 102 µg/g. We can evaluate other elements of human hair by using this method.

Wavelength dispersive X-ray fluorescence imaging.

A new wavelength-dispersive X-ray fluorescence (WD-XRF) imaging spectrometer equipped with a two-dimensional X-ray detector was developed in the laboratory. Straight polycapillary optics was applied instead of a soller slit, which is used in conventional WD-XRF spectrometers. X-rays were guided through the straight polycapillary to the exit of the optics by X-ray external total reflections. X-ray fluorescence was dispersed by an analyzing crystal (LiF(200)), keeping the information of elemental distribution on the surface of the sample. The energy resolution of the developed spectrometer was 130-152 eV at the Zn Kα peak. X-ray elemental images of Cu Kα and Ni Kα were successfully obtained by an X-ray CCD detector at the corresponding diffraction angles. The analytical performance of this technique, and further improvements are discussed.

Depth elemental imaging of forensic samples by confocal micro-XRF method.

Micro-XRF is a significant tool for the analysis of small regions. A micro-X-ray beam can be created in the laboratory by various focusing X-ray optics. Previously, nondestructive 3D-XRF analysis had not been easy because of the high penetration of fluorescent X-rays emitted into the sample. A recently developed confocal micro-XRF technique combined with polycapillary X-ray lenses enables depth-selective analysis. In this paper, we applied a new tabletop confocal micro-XRF system to analyze several forensic samples, that is, multilayered automotive paint fragments and leather samples, for use in the criminaliztics. Elemental depth profiles and mapping images of forensic samples were successfully obtained by the confocal micro-XRF technique. Multilayered structures can be distinguished in forensic samples by their elemental depth profiles. However, it was found that some leather sheets exhibited heterogeneous distribution. To confirm the validity, the result of a conventional micro-XRF of the cross section was compared with that of the confocal micro-XRF. The results obtained by the confocal micro-XRF system were in approximate agreement with those obtained by the conventional micro-XRF. Elemental depth imaging was performed on the paint fragments and leather sheets to confirm the homogeneity of the respective layers of the sample. The depth images of the paint fragment showed homogeneous distribution in each layer expect for Fe and Zn. In contrast, several components in the leather sheets were predominantly localized.

Improvement of Detection Limits for Particle Contamination by Confocal Configuration in X-Ray Fluorescence Microscope.

Micro X-ray fluorescence (XRF) enables the non-destructive analysis of particle contamination. In this study, we compared the detection sensitivities and the LLD (lower limit of detection) values of micro-metallic particle contaminations on the plastic detected by micro-XRF and confocal micro-XRF. First, to verify the effectiveness of the confocal micro-XRF, we compared the intensities of different shaping copper samples (plate, thin film and particle). The results demonstrated that confocal micro-XRF is more effective than micro-XRF for the detection of micro particles. Second, to compare the SN ratios of different X-ray energies, several micro-metallic particles (Si, Fe, and Cu) set on an acrylic plate were measured by micro-XRF and confocal micro-XRF. It was found that the SN ratios of the confocal micro-XRF when measuring the Si, Fe, and Cu particles were improved to be approximately 14.6, 21.9, and 43.5-times those of the micro-XRF, respectively. It was determined that confocal micro-XRF is more effective for micro-metallic particles in the higher energy region.

Depth Elemental Imaging during Corrosion of Hot-Dip Galvanized Steel Sheet by Confocal Micro XRF Analysis.

The elucidation of the mechanism for steel corrosion under a coating layer has been attracting research attention. Herein, we utilized a confocal micro-X-ray fluorescence (XRF) analytical instrument to conduct non-destructive elemental analysis near the surface of a steel sheet. Using this method, elemental map images of steel sheet cross sections were obtained without sample destruction. To confirm corrosion suppression in the presence of Mg ions, we observed the corrosion behavior of hot-dip galvanized steel sheets immersed in an aqueous NaCl solution to which Mg ions were added. By using the confocal micro XRF system, the elution of the coating components and the precipitation process of the corrosion products were confirmed.

Grazing exit micro X-ray fluorescence analysis of a hazardous metal attached to a plant leaf surface using an X-ray absorber method.

If human beings or animals repeatedly ingest plant leaves contaminated with minute quantities of hazardous metals (Pb, As, Hg, Cd, etc.), the metals will gradually accumulate in their bodies. When the quantities of the metals in the bodies reach toxic levels, they may cause serious symptoms of poisoning. Therefore, it is significant to detect and analyze the minute quantities of hazardous metals that attach to plant leaves in terms of epidemiology and disease prevention. We developed grazing exit micro X-ray fluorescence analysis (GE-micro-XRF), which was expected to analyze the localized surface of an aqueous plant leaf with a much faster and simpler sample treatment than with conventional analytical methods, to detect Pb attached to a surface of a leaf of Camellia hiemalis. A micro X-ray beam was produced by using a polycapillary X-ray lens. GE-v-XRF is a grazing exit X-ray analysis (GE-XA) method in which X-rays emitted from only the near-surface region of a specimen are selectively detected under a grazing exit angle condition (extremely low exit angle near 0 degrees). In any GE-XA method, X-rays emitted from inside the specimen must be absorbed inside the specimen and attenuated when X-rays pass through the specimen. However, we deduced that X-rays emitted from inside aqueous organic material such as a plant leaf are scarcely absorbed because X-ray absorption in any aqueous organic material is much smaller than that in most metallic and semiconductor materials, which was analyzed with GE-XA methods. Therefore, we have developed a novel GE-micro-XRF method in which a chip of a silicon wafer is placed between the analyzed leaf and an X-ray detector as an absorber of the X-rays emitted from inside the leaf. As a result of GE-XRF analysis of a leaf dipped in Pb standard solution using the X-ray absorber, we have for the first time selectively detected X-rays emitted from the near-surface region of an aqueous plant leaf. Therefore, we have detected X-rays emitted from Pb with much higher peak/background ratios (P/B ratios) as compared to those of conventional XRF analysis. In the analysis, we also found a difference in element distributions between the leaf surface and its interior. Therefore, we observed and analyzed a cross section of the leaf with a SEM-EDX to confirm the validity of this result. The result of the analysis of the cross section has been in excellent agreement with that of the XRF analysis.

Application of confocal 3D micro-XRF for solid/liquid interface analysis.

Solid/liquid interfaces are important locations for various chemical reactions, such as electrode chemical reactions and metal corrosions. Conventional surface analytical methods, such as XPS and SEM-EDS, have been applied to solid materials after being removed from the liquid phase. These methods do not involve direct observation, although useful information is available. It is important to directly observe surface reactions on solid materials in the liquid phase in order to understand the details of these reactions. One feasible method of doing this is 3D micro-XRF analysis. The confocal 3D micro XRF method enables nondestructive x-ray elemental analysis of localized microspace. We have applied a confocal 3D micro-XRF instrument for solid/liquid interface analysis. This technique was applied for direct observation of the chemical deposition of Cu on an Fe plate and the dissolution of Fe in a CuSO4 solution.

X-ray energy dependence of the properties of the focused beams produced by polycapillary X-ray lens.

We investigated X-ray energy distribution in an X-ray microbeam produced by a polycapillary X-ray lens in combination with a sealed-type X-ray tube. This polycapillary X-ray lens has an output focal distance (OFD) of approximately 15 mm. The size of the X-ray microbeam and its OFD were estimated by using a wire scanning method. In our case, the sizes of the X-ray microbeams at the output focal distance were 49 microm for Mo L(alpha), 36 microm for W L(alpha), and 28 microm for Mo K(alpha). The spot sizes depend on the energy of the X-ray fluorescence. The reason for the energy dependence is that X-ray capillary optics is based on the principle of propagation through glass capillaries by means of X-ray total external reflection. The evaluated OFD values of Mo L(alpha) and Mo K(alpha) were slightly changed in 17 microm. However, a deviation of 100 microm from the OFD caused only a 3% increase of the focal spot size. Therefore, we concluded that the OFD showed no significant dependence on X-ray energy.

Grazing-exit and micro X-ray fluorescence analyses for chemical microchips.

Grazing-exit x-ray fluorescence (GE-XRF) and micro x-ray fluorescence (micro-XRF) methods were applied to chemical microchips as a detection method. Since an energy-dispersive x-ray detector was used, the simultaneous detection of multiple elements was possible. An analyzing region was especially designed on the microchip so that a sample solution could be dried and concentrated in a suitable area corresponding to the size of the primary x-ray beam. Finally, it was confirmed that both analytical methods could be combined well for use with a microchip. In GE-XRF, the background intensity in the XRF spectrum was reduced at grazing-exit angles. In addition, a good relationship between the x-ray fluorescence intensities and the concentrations of standard solutions that were introduced into the microchip was obtained. This indicates that the GE-XRF method is feasible for trace elemental analysis in chemical microchip systems. In micro-XRF, an attempt was made to concentrate and dry the analyte within a small analyzing region. The preliminary results indicated that the micro-XRF method could be applied for the analysis of microchips.