Glancing incidence x-ray fluorescence spectrometry based on a single-bounce parabolic capillary

Glancing incidence x-ray fluorescence spectrometry using a single-bounce parabolic capillary is proposed for the analysis of layered samples.The divergence of the x-ray beam was 0.33 mrad.In this paper,we used this instrumental setup to analyze a Si single crystal and a 50 nm HfO_(2) single-layer film deposited on a Si substrate.

Geochemical analysis of marine sediments using fused glass disc by X-ray fluorescence spectrometry

A method was developed for content determination of Na, Mg, A1, Si, P,S, C1, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Nb, Zr, Y, Sr, Rb, Ba, La and Ce etc. covering 26 major, minor, and trace elements in marine sediment samples using fused glass disc by X-ray Fluorescence spectrometry. Calibration was made using marine sediment certified reference materials and the synthetic standard samples prepared by mixing several marine sediments with stream sediment and carbonate standard samples in different proportions. The matrix effect was corrected using theoretical alpha coefficients, experience coefficients and the scattered radiation as the internal standard （for the trace elements）. The accuracy of the method was evaluated by analysis of certified reference materials GBW07314, GBW07334 and GSMS6. The results are in good agreement with the certified values of the standards with RSD less than 2.60%, except for Y, Cr, Ga, Ce, La, Nb, Rb, and V with RSD less than 9.0% （n=12）.

L-shell x-ray fluorescence relative intensities for elements with 62≤Z≤83 at 18 keV and 23 keV by synchrotron radiation

The relative intensities of L-subshell x-ray fluorescence(XRF)for elements with atomic numbers 62≤Z≤83 were measured at two excitation energies,18 keV and 23 keV,using a synchrotron radiation source at a beamline of the Synchrotron Light Center for Experimental Science and Applications in the Middle East(SESAME),Jordan.The experimentally measured results of the relative intensities were compared with the calculated results using the subshell fluorescence yield and the Coster-Kronig transition probabilities recommended by Campbell and the values based on the Dirac-Hartree-Slater model by Puri.The experimental and theoretical results are in agreement.In this work,L XRF relative intensities for the elements Sm,Gd,Tb,Er,Ta,W,Re,Hg,Pb and Bi at energies of 18 keV and 23 keV were measured.

Elemental composition x-ray fluorescence analysis with a TES-based high-resolution x-ray spectrometer

The accurate analysis of the elemental composition plays a crucial role in the research of functional materials.The emitting characteristic x-ray fluorescence(XRF)photons can be used for precisely discriminating the specified element.The detection accuracy of conventional XRF methodology using semiconductor detector is limited by the energy resolution,thus posing a challenge in accurately scaling the actual energy of each XRF photon.We adopt a novel high-resolution x-ray spectrometer based on the superconducting transition-edge sensor(TES)for the XRF spectroscopy measurement of different elements.Properties including high energy resolution,high detection efficiency and precise linearity of the new spectrometer will bring significant benefits in analyzing elemental composition via XRF.In this paper,we study the Ledge emission line profiles of three adjacent rare earth elements with the evenly mixed sample of their oxide components:terbium,dysprosium and holmium.Two orders of magnitude better energy resolution are obtained compared to a commercial silicon drift detector.With this TES-based spectrometer,the spectral lines overlapped or interfered by background can be clearly distinguished,thus making the chemical component analysis more accurate and quantitative.A database of coefficient values for the line strength of the spectrum can then be constructed thereafter.Equipped with the novel XRF spectrometer and an established coefficient database,a direct analysis of the composition proportion of a certain element in an unknown sample can be achieved with high accuracy.

Accuracy analysis of iron content of galvanized coating using an X-ray fluorescence spectrometer with an L-spectrum

The accuracy(repeatability and reproducibility) of the iron content analysis of galvanized coating using an X-ray fluorescence spectrometer with an L-spectrum is not better than that of flame atomic absorption spectrometry, sometimes it exceeds the quality control limit.Influences, such as current, voltage, equipment(internal circulating water, 10%CH4+90%Ar, and vacuum) checking, instrument monitoring, sample cleaning, and oper-ators, were investigated by means of 6-sigma and lean operations to improve accuracy.

X-ray fluorescence spectrometry determination of open-hearth furnace slag by pressed powder briquetting

A rapid analysis method of determining content of eight compounds of open-hearth furnace slag was developed using X-ray fluorescence spectrometry and pressed powder briquettes. Matrix effect was corrected using theoretical alpha coefficient. Grains-size effect was eliminated by optimized sample preparation technique parameters. Mineral effect was corrected with standard curve of specially made standard samples. The analysis results of TiO2, TFe, SiO2, MgO, Al2O3, CaO, MnO and P2O5 in slag samples showed that both precision and accuracy are comparable with that of chemical method.

Determination of Content of Eight Elements in Metal Coating Smeared on Waste Plastics by X-ray Fluorescence Spectrometry

X-ray fluorescence spectrometry was used to detect the content of eight elements in metal coating smeared on waste plastics,and effects of sample cups,elements in plastic substrate,and interaction of elements in metal coating on detection results were analyzed. The results show that the RSD of the method used to detect element content in the metal coating smeared on the waste plastics ranged from 0.008% to 0.044%; the determination range of the eight elements was 0.002%-52.0%,and their detection limit ranged from 0.0002% to 0.0008%. The determination results of X-ray fluorescence spectrometry were consistent with that of ICP-AES. The method can provide technical support for the determination of damage and pollution caused by metal coating smeared on waste plastics.

Quantitative Analysis of FeMo Alloys by X-Ray Fluorescence Spectrometry

A quantitative analysis method of molybdenum in FeMo alloys by X-ray spectrometry using borate fusion technique was compared with that with pressed pellet. The complete pre-oxidation of FeMo alloys for the preparation of homogeneous fused discs was achieved by employing an automated fusion machine equipped with specially designed O2-blowing nozzles, which used lithium tetra-borate as flux with the addition of lithium nitrate (LiNO3) as oxidizer. The calibration curves of Mo and Fe were used in the quantitative analysis of standard materials and unknown plant samples with satisfactory accuracy and precision, utilizing the corrections of the matrix effects and line overlap. It was confirmed that the newly proposed method of preparing fused glass discs of FeMo alloys can replace the conventional wet chemical analyses requiring the labor intensive and time consuming procedure.

SMONTE CARLO CALCULATION FOR CALIBRATION FUNCTIONS IN TOTAL REFLECTION X-RAY FLUORESCENCE SPECTROMETRY

Simulation approach includes such processes as photon emissions from X-ray tube with a spectral distribution, total reflection on the sample support, photoelectric effect in thin layer sample, as well as characteristic line absorption and detection. The calculation results are in agreement with experimental ones.

Determination of Arsenic and Mercury in Soil by Microwave Digestion and Hidride GenerationAtomic Fluorescence Spectrometry

[Objective] The aim was to develop a rapid, simple method for determina- tion of arsenic and mercury in soil samples by atomic fluorescence spectrometry. [Method] The method for determination of As and Hg in soil by combined atomic fluorescence spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-80.0μg/L of As and 0-8.0 μg/L of Hg, and the detection limits of As and Hg was 0.036 μg/L and 0.015 μg/L, respectively. The precision for elevenfold determination of As at 40.0 ug/L level and Hg at 4.0μg/L level were 1.1% and 2.2%（RSD）, respectively. Recoveries of 103.0%-106.6% for As and 90.0%-95.0% for Hg were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of As and Hg in soil samples.

Elemental and proximate analysis of coal by x-ray fluorescence assisted laser-induced breakdown spectroscopy

Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.

Quantitative energy-dispersive X-ray fluorescence analysis for unknown samples using full-spectrum least-squares regression

The full-spectrum least-squares(FSLS) method is introduced to perform quantitative energy-dispersive X-ray fluorescence analysis for unknown solid samples.Based on the conventional least-squares principle, this spectrum evaluation method is able to obtain the background-corrected and interference-free net peaks, which is significant for quantization analyses. A variety of analytical parameters and functions to describe the features of the fluorescence spectra of pure elements are used and established, such as the mass absorption coefficient, the Gi factor, and fundamental fluorescence formulas. The FSLS iterative program was compiled in the C language. The content of each component should reach the convergence criterion at the end of the calculations. After a basic theory analysis and experimental preparation, 13 national standard soil samples were detected using a spectrometer to test the feasibility of using the algorithm. The results show that the calculated contents of Ti, Fe, Ni, Cu, and Zn have the same changing tendency as the corresponding standard content in the 13 reference samples. Accuracies of 0.35% and 14.03% are obtained, respectively, for Fe and Ti, whose standard concentrations are 8.82% and 0.578%, respectively. However, the calculated results of trace elements (only tens of lg/g) deviate from the standard values. This may be because of measurement accuracy and mutual effects between the elements.

Potential Applications of X-ray Fluorescence Core Scanner in Elemental Analyses of the Muddy Sediments on the Coastal Shelves of China and in Ecological Study

Large areas of muddy sediments on the coastal shelves of China provide important samples for studying climate and ecological changes. Analysis of a large number of such samples, which is essential for systematic study on environmental information recorded in mud areas because of complicated sedimentary environment and variable sedimentary rate, requires a fast and economical method. In this study, we investigated the potential of X-ray fluorescence core scanner （XRFS）, a fast analytical instrument for measuring the elemental concentrations of muddy sediments, and observed a significant correlation between the element concentrations of muddy sediments determined by regular X-ray fluorescence spectrometer （XRF） and XRFS, respectively. The correlations are mainly determined by excitation energy of elements, but also influenced by solubility of element ions. Furthermore, we found a striking link between A1 concentrations and marine-originated organic carbon （MOC）, a proxy of marine primary productivity. This indicates that MOC is partly controlled by sedimentary characteristics. Therefore, XRFS method has a good potential in fast analysis of a large number of muddy sediment samples, and it can also be used to calibrate MOC in ecological study of coastal seas.

Speciation Analysis of Arsenic Compounds in Seafood by Ion Chromatography-Atomic Fluorescence Spectrometry

Ion chromatography-ultra violet-hydride generation-Atomic Florescence Spectrometry was applied to detect 5 arsenic species in seafoods. The arsenic species studied include arsenobetaine(As B), arsenite(As(III)), dimethylarsinic acid(DMA), monomethylarsonic acid(MMA), and arsenate(As(V)), which were extracted from samples using 2% formic acid. Gradient elution using 33 mmol L^(-1) CH_3COONH_4 and 15 mmol L^(-1) Na_2CO_3 with 10 mL CH_3CH_2OH at pH 8.4 allowed the chromatographic separation of all the species on a Hamilton PRP-X100 anion-exchange column in less than 8 min. In this study, an ultrasound extraction method was used to extract arsenic species from seafood. The extraction efficiency was good and the recoveries from spiked samples were in the range of 72.6%–109%; the precision between sample replicates was higher than 3.6% for all determinations. The detection limits were 3.543 μg L^(-1) for As B, 0.4261 μg L^(-1) for As(III), 0.216 μg L^(-1) for DMA, 0.211 μg L^(-1) for MMA, and 0.709 μg L^(-1) for As(V), and the linear coefficients were greater than 0.999. We also developed an application of this method for the determination of arsenic species in bonito, Euphausia superba, and Enteromorpha with satisfactory results. Therefore, it was confirmed that this method was appropriate for the detection of arsenic species in seafood.

Determination of Trace Germanium in Marine Sediments by Hydride Generation-Atomic Fluorescence Spectrometry (HG-AFS)

A method for the analysis of trace germanium in marine sediments by HG-AFS has been investigated. The experimental conditions such as the acidity of reduction reaction, the amount of sodium boro-hydride, the carrier gas flow rate, etc., were tested and optimized by using a kind of orthogonal design. The detection limit of the presented method is 0.95 μg L -1 for germanium. The calibration curve shows a satisfactory line in the concentration range 0-320 μg L -1 Ge with a variation coefficient of ±2.1%.

Use of portable X-ray fluorescence in the analysis of surficial sediments in the exploration of hydrothermal vents on the Southwest Indian Ridge

Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sediment samples from the Southwest Indian Ridge（SWIR） were analyzed by a portable X-ray fluorescence（PXRF） analyzer on board to find a favorable method fast and efficient enough for sea floor sulfide sediment geochemical exploration. These sediments were sampled near, at a moderate distance from, or far away from hydrothermal vents. The results demonstrate that the PXRF is effective in determining the enrichment characteristics of the oreforming elements in the calcareous sediments from the mid-ocean ridge. Sediment samples（〉40 mesh） have high levels of elemental copper, zinc, iron, and manganese, and levels of these elements in sediments finer than 40 mesh are lower and relatively stable. This may be due to relatively high levels of basalt debris/glass in the coarse sediments, which are consistent with the results obtained by microscopic observation. The results also show clear zoning of elements copper, zinc, arsenic, iron, and manganese in the surficial sediments around the hydrothermal vent. Sediments near the vent show relatively high content of the ore-forming elements and either high ratios of copper to iron content and zinc to iron content or high ratios of copper to manganese content and zinc to manganese content. These findings show that the content of the ore-forming elements in the sediments around hydrothermal vents are mainly influenced by the distance of sediments to the vent, rather than grain size. In this way, the PXRF analysis of surface sediment geochemistry is found to satisfy the requirements of recognition geochemical anomaly in mid-ocean ridge sediments. Sediments with diameters finer than 40 mesh should be used as analytical samples in the geochemical exploration for hydrothermal vents on mid-oceanic ridges. The results concerning copper, zinc, arsenic, iron, and manganese and their ratio features can be used as indicators in sediment geochemical exploration of seafloor sulfides.

Spatial resolution and image processing for pinhole camera-based X-ray fluorescence imaging: a simulation study

Spatial resolution and image-processing methods for full-field X-ray fluorescence(FF-XRF)imaging using X-ray pinhole cameras were studied using Geant4simulations with different geometries and algorithms for image reconstruction.The main objectives were:(1)calculating the quantum efficiency curves of specific cameras,(2)studying the relationships between the spatial resolution and the pinhole diameter,magnification,and camera binning value,and(3)comparing image-processing methods for pinhole camera systems.Several results were obtained using a point and plane source as the X-ray fluorescence emitter and an array of 100×100 silicon pixel detectors as the X-ray camera.The quantum efficiency of a back-illuminated deep depletion(BI-DD)structure was above 30%for the XRF energies in the 0.8–9 keV range,with the maximum of 93.7%at 4 keV.The best spatial resolution of the pinhole camera was 24.7μm and 31.3 lp/mm when measured using the profile function of the point source,with the diameter of 20μm,magnification of 3.16,and camera bin of 1.A blind deconvolution algorithm with Gaussian filtering performed better than the Wiener filter and Richardson iterative methods on FF-XRF images,with the signal-to-noise ratio of 7.81 dB and improved signalto-noise ratio of 7.24 dB at the diameter of 120μm,magnification of 1.0,and camera bin of 1.

Simulation Study of Quantitative X-Ray Fluorescence Analysis of Ore Slurry Using Partial Least-Squares Regression

X-ray fluorescence （XRF） in combination with partial least-squares （PLS） regression was employed to analyze the ore slurry grade. Using the Monte Carlo simulation code PENELOPE, X-ray fluorescence spectra of ore samples were obtained. Good accuracy was achieved when this method was used to analyze elements with concentrations of several percent or above. It was demonstrated that the more the number of X-ray fluorescence spectra used to calibrate, the better the obtained accuracy. In this method detector resolution was found to have little or no effect on the results of quantitative analysis. The effect of the concentration of water was investigated as well, and it was found to have little influence on the results.

Impact of Different Grinding Aids on Standard Deviation in X-Ray Fluorescence Analysis of Cement Raw Meal

X-ray fluorescence (XRF) analysis utilizes particle size which is resulted from milling of a material. The milling ensures uniform and fine grained powder. The finer and more uniform the particle size is, the better the result and easier it is for material quality control. To ensure uniformity in particle size and finer powder, a comparative analysis was conducted with different grinding aids and pressed pellet method was used in obtaining analysis results. Pressed pellets of cement raw meal sample milled with different grinding aids (graphite, aspirin and lithium borate) were subjected to XRF. Graphite produced better particle size uniformity with a corresponding standard deviation that made quality control of raw meal easier and better than aspirin and lithium borate.