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.

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.

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.

Preliminary determination of calcium,phosphorus,and the calcium/phosphorus ratio in cortical bone of Chinstrap penguin using synchrotron X-ray fluorescence analysis

Synchrotron radiation X-ray fluorescence （SR-XRF） approach was applied to analyzing of Chinstrap penguin （ Pygoscelis Antarctica） cortical bone. The method enabled the in situ determination of Ca and P concentrations and the Ca/P ratio in cortical bone. The preliminary results show that ： （ 1 ） there is the bone site-related difference for Ca and P concentrations. The mean values for the investigated parameters （ on a dry-weight basis） are： 30.7% （Ca） and 14.9% （P） for the femoral cortical bone, 21.4% （Ca） and 11.5% （P） for wing cortical bone. （2） The variation for the Ca/P ratio in cortical bone is lower than those for Ca and P separately. This is in agreement with the previous report that the specificity of the Ca/P ratio is better than that of Ca and P concentrations and is more reliable for the diagnosis of bone disorders. The authors suggest that further studies be conducted to establish norreal values of Ca, P and Ca/P ratio for polar animals and provide a basis for the diagnosis of bone disorders.

Synchrotron radiation X-ray fluorescence analysis of Fe, Zn and Cu in mice brain associated with Parkinson's disease

The contents and distributions of metal elements in the brain are closely related to neurodegenerative diseases.In this study, we examined Fe, Cu and Zn contents in the brain section associated with Parkinson‘s disease(PD)using synchrotron radiation X-ray fluorescence(SRXRF). PD mouse model induced by 1-methyl-4-phenyl-1,2,3,6-terahydropyridine(MPTP) was used for the elemental analysis(e.g., Fe, Cu and Zn) in the substantia nigra pars compacta(SNpc) region of mice brain tissue samples. We found that mice in the MPTP group had higher contents of Fe, Cu and Zn in the SNpc than the control group. After treating the PD mice with rapamycin, the contents of Fe, Cu and Zn were reduced, the dopamine neurons and motor function were rescued correspondingly. The results prompted that the SRXRF provided an ideal method for tracing and analyzing the metal elements in the brain section to assess the pathological changes of PD model and the therapeutic effect of drugs.

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.

Determination of Optimum Conditions for X-Ray Fluorescence Analysis Using Coupling Equations

Coupling equations used to calculate the chemical composition of substances by X-ray fluorescence analysis can be classified as empirical, theoretical or semi-empirical based on the method for determining the coefficients of the calibration function. The advantages and disadvantages of each class of equations are discussed. Recommendations for the selecting the optimum conditions for determining empirical correction coefficients and their control during analysis are provided.

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）.

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.

Chemical Analysis of Hydroxyapatite Artificial Bone Powders by Energy Dispersive X-Ray Fluorescence Spectrometry(EDXRF)

Stoichiometric hydroxyapatite(HA)nanoparticles were synthesized by a wet chemical method.Calcium nitrate tetra hydrate used as calcium source and dibasic ammonium phosphate used as phosphorous source.Calcium nitrate tetra hydrate and dibasic ammonium phosphate solutions were prepared by dissolving the salts in distilled water.Stoichiometric hydroxyapatite nanoparticles used by artificial bone powders and synthesized by a wet chemical method were analyzed using EDXRF method.The concentrations of K,Ca,Ti,V,Cr,Fe,Ni,Cu,Sr and Pb for artificial bone powders have been determined.Besides,Calcium contents were evaluated according to the agitation time and temperature in the production process.

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.

Analysis of Heavy Metals in Human Scalp Hair Using Energy Dispersive X-Ray Fluorescence Technique

Analysis of six heavy metals (Cr, Mn, Ni, Cu, Zn and Mo) in human scalp hair was carried out among various occupational distributions to ascertain their heavy metal burden, using energy dispersive x-ray fluorescence technique (ED-XRF). The result of the analysis shows that mean concentrations (mg/kg) of heavy metals obtained were as follows: Cr = 17.1 ± 12.7;Mn = 3.11 ± 0.50;Ni = 11.3 ± 9.3;Zn = 451 ± 128;Cu = 83.3 ± 35.8 and Mo is 9.16 ± 9.1.While the mean concentrations of Cr, Cu, and Mo were higher in the females, that of Mn, Ni and Zn were more in the males. Statistical analysis of the results for both genders at 0.05 probably shows significant difference for Ni, Zn and Mo while Cr, Mn and Cu showed no significant difference. The relationships between age, body mass, height, and heavy metal concentrations were also investigated. Statistical analysis of the results indicates that there was no correlation between the body mass (R2 ≤ 0.048), height (R2 ≤ 0.002) and heavy metal concentration in hair. Zn showed the highest deviation among other elements in the individual samples for both genders which reflect the individual variation in the concentration of Zn.

X-RAY FLUORESCENCE SPECTRA ANALYSIS ON THE STRUCTURE AROUND Ti^(4+) OF BaO-SiO_2-B_2O_3-TiO_2 SYSTEM GLASSES

The structure around Ti^(4+) in Bao-SiO_2 -B_2O_3-TiO_2 had been studied by X-ray fluorescence spectra. The results show that the Ti^(4+) mainly exists in the [TiO_4] and enters the network of [SiO_4]. [TiO_4] has the tendency to change to [TiO_6] with the increase of TiO_2 con-tent. When the TiO_2 content increases to about 20mol% the tendency reaches its maximum.

Influence of crystal materials on the synchrotron X-ray fluorescence analysis:a study of crystal and amorphous clinopyroxene

Synchrotron X-ray fluorescence analyses of crystal and amorphous clinopyroxene were compared. The results showed that using the synchrotron X-ray as a source of energy, the diffraction X-ray of crystal materials will seriously affect the X-ray fluorescence analysis. In order to avoid the influence of diffraction, the best way to solve it is to use the monochromatic source, or to have a collimating slit between sample and Si(Li) detector.

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.

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.

FLUORESCENCE SPECTRUM ANALYSIS OF ETHER-WATER SOLUTION BASED ON GAUSSIAN DECOMPOSITION METHOD

The fluorescence spectrum of the ether-water solution excited by the ultraviolet light with the wavelength of 245 nm is experimentally detected. Based on the second derivative analysis, the fluorescence spectrum of the ether-water solution is used as Gaussian decomposition and seven Gaussian spectral lines are obtained. The center wavelength, the peak intensity and the half peak bandwidth of each Gaussian spectral line are measured, and the multi-peak fitting is made by using Gaussian primitive parameters. The highest and the lowest oscillation energy level differences in the ground state of each Gaussian spectrum are calculated. It is found that there are seven types of luminescent association molecules formed by ether and water molecules in different configurations existed in the solution. The location of each optimum absorption wavelength and the half peak bandwidth of the Gaussian spectral line is different. The energy level difference with the central wavelength of 304 nm attains the maximum value The result can contribute to the study of the molecular association in ether-water solution.

Simultaneous fluorescence and Compton scattering computed tomography based on linear polarization X-ray

Purpose To propose a method for simultaneous fluorescence and Compton scattering computed tomography by using linearly polarized X-rays.Methods Monte Carlo simulations were adopted to demonstrate the feasibility of the proposed method.In the simulations,the phantom is a polytetrafluoroethylene cylinder inside which are cylindrical columns containing aluminum,water,and gold(Au)-loaded water solutions with Au concentrations ranging between 0.5 and 4.0 wt%,and a parallel-hole collimator imaging geometry was adopted.The light source was modeled based on a Thomson scattering X-ray source.The phantom images for both imaging modalities were reconstructed using a maximumlikelihood expectation maximization algorithm.Results Both the X-ray fluorescence computed tomography(XFCT)and Compton scattering computed tomography(CSCT)images of the phantom were accurately reconstructed.A similar attenuation contrast problem for the different cylindrical columns in the phantom can be resolved in the XFCT and CSCT images.The interplay between XFCT and CSCT was analyzed,and the contrast-to-noise ratio(CNR)of the reconstruction was improved by correcting for the mutual influence between the two imaging modalities.Compared with K-edge subtraction imaging,XFCT exhibits a CNR advantage for the phantom.Conclusion Simultaneous XFCT and CSCT can be realized by using linearly polarized X-rays.The synergy between the two imaging modalities would have an important application in cancer radiation therapy.

Fluorescence Microscopic Image Analysis of Nucleic Acids Based on The Capillary Flow Directed Assembly Ring of Neutral Red-nucleic Acid Supramolecular Complexes

It is critical to establish a direct and precise method with a high sensitivity and selectivity in analytical chemistry. In this research, making use of a well known phenomenon of capillary flow, we have proposed an image analysis method of nucleic acids at the price of a small amount of sample. When a droplet of the supramolecular complex solution, formed by neutral red and nucleic acids(NA) under an approximate neutral condition, was placed on the hydrophobic surface of dimethyl dichlorosilane pretreated glass slides, and it was evaporated, the supramolecular complex exhibited the periphery of the droplet due to the capillary effect, and accumulated there to form a red capillary flow directed assembly ring(CFDAR). A typical CFDAR has an outer diameter of (2 r ) about 1.18 mm and a ring width(2 δ ) of about 41 μm. Depending on the experimental conditions, a variety of CFDAR can be assembled. The experimental results are in agreement with our former theoretical discussion. It was found that when a droplet volume is 0.1 μL, the fluorescence intensity of the CFDAR formed by the NR NA is in proportion to the content of calf thymus DNA in the range of 0-0.28 ng, fish sperm DNA of 0-0.24 ng and yeast RNA of 0-0.16 ng with the limit of detection(3 σ ) of 1 7, 1.4 and 0.9 pg, respectively for the three nucleic acids.

Characterization of metal element distributions in the rat brain following ischemic stroke by synchrotron radiation microfluorescence analysis

Ischemic stroke is one of the leading causes of death worldwide,and effective treatment strategies in the chronic phase of this disease remain insufficient.Homeostasis of metals in the brain plays an important role in maintaining normal brain function.However,the dynamic spatial distributions of iron,zinc,calcium,potassium,and copper in a rat brain following ischemic stroke and the association between structural distribution and function remain to be elucidated.In this study,we used a synchrotron radiation-based micro-X-ray fluorescence technique to image element mapping changes in special rat brain regions after ischemic stroke,showing the distribution characteristics of iron,zinc,calcium,potassium,and copper.We demonstrated,for the first time,the consistent dynamic spatial distributions of metal elements at a series of time points(3 h,4.5 h,6 h,12 h,1 d,3 d,5 d,7 d,10 d,14 d,28 d)after brain ischemia,which revealed that the homeostasis of iron,zinc,calcium,potassium,and copper in the brain was disturbed with distinctive change trends,providing clear insights in understanding the underlying pathogenesis of stroke from a novel perspective,thus laying the foundation of further developing new drug targets for stroke treatment.