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.

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）.

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.

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.

Scanning electron microscopy coupled with energydispersive X-ray spectrometry for quick detection of sulfuroxidizing bacteria in environmental water samples

Detection of sulfur-oxidizing bacteria has largely been dependent on targeted gene sequencing technology or traditional cell cultivation, which usually takes from days to months to carry out. This clearly does not meet the requirements of analysis for time-sensitive samples and/or complicated environmental samples. Since energy-dispersive X-ray spectrometry(EDS) can be used to simultaneously detect multiple elements in a sample, including sulfur, with minimal sample treatment, this technology was applied to detect sulfur-oxidizing bacteria using their high sulfur content within the cell. This article describes the application of scanning electron microscopy imaging coupled with EDS mapping for quick detection of sulfur oxidizers in contaminated environmental water samples, with minimal sample handling. Scanning electron microscopy imaging revealed the existence of dense granules within the bacterial cells, while EDS identified large amounts of sulfur within them. EDS mapping localized the sulfur to these granules. Subsequent 16S rRNA gene sequencing showed that the bacteria detected in our samples belonged to the genus Chromatium, which are sulfur oxidizers. Thus, EDS mapping made it possible to identify sulfur oxidizers in environmental samples based on localized sulfur within their cells, within a short time(within 24 h of sampling). This technique has wide ranging applications for detection of sulfur bacteria in environmental water samples.

Review of the diagnosis of gastrointestinal lanthanum deposition

Lanthanum carbonate is used for treatment of hyperphosphatemia mostly in patients with chronic renal failure.Although lanthanum carbonate is safe,recently,lanthanum deposition in the gastrointestinal mucosa of patients has been reported in the literature.This review provides an overview of gastroduodenal lanthanum deposition and focuses on disease's endoscopic,radiological,and histological features,prevalence,and outcome,by reviewing relevant clinical studies,case reports,and basic research findings,to better understand the endoscopic manifestation of gastrointestinal lanthanum deposition.The possible relationship between gastric lanthanum deposition pattern and gastric mucosal atrophy is also illustrated;in patients without gastric mucosal atrophy,gastric lanthanum deposition appears as diffuse white lesions in the posterior wall and lesser curvature of the gastric body.In the gastric mucosa with atrophy,lanthanum-related lesions likely appear as annular or granular whitish lesions.Moreover,these white lesions are probably more frequently observed in the lower part of the stomach,where intestinal metaplasia begins.

Chemical Characterization of Auriferous Ores from the Brazilian State of Paraiba

One of the most important problems facing the gold industry is that the placer and free milling gold ores are almost terminating. Hence, the use of refractory ores has been increased during the recent years. In general, gold refractory ores occurs in various types of deposits associated with a range of minerals. Among the refractory ores, the sulfide type is the most common. The methodology employed in the mining process depends on the mode of occurrence of the ore and on the particle size, shape and degree of purity of the auriferous species. We have undertaken a mineralogical investigation of a representative sample of a complex gold mining ore collected in the municipality of Princesa Isabel, Paraiba, Brazil, using X-ray fluorescence spectrometry, X-ray diffractometry, infrared spectroscopy, inductively coupled plasma-atomic emission spectrometry and the Fire Assay. The results showed that the arsenic content of the ore was closely related to the gold content, and that the occurrence of “invisible gold” was associated primarily with pyrite and secondarily with arsenopyrite. The sulfur content of the ore was directly related to its refractoriness. It is concluded that gold mineralization in the study area is mainly of the gold-quartz-sulfide veins (lode gold), while the gold found in the mini-fractures of the deposits is probably associated with the hydrothermal processes that occurred in the region.

Geochemical Characterization and Mineralogy of Babouri-Figuil Oil Shale,North-Cameroon

Organic geochemistry methods such as high temperature combustion, Rock-Eval pyrolysis and gas analysis were used to analyze oil shale from Babouri-Figuil Basin. Results show that the average content of organic matter is 36.25 %wt, while that of mineral matter is 63.75 %wt. The total organic carbon (TOC) is between 15.93 %wt and 26.82 %wt. The HI vs. Tmax diagram indicates an immature Type I kerogen. The average value of the oil potential (S2b) is 149.95 mg HC/g rock. The gases obtained by retort process are H2, CO2, CO and CnH2n, CnH2n+2. Finally, it emerges that, the organic matter of Babouri-Figuil shales was immature or has just reached the beginning of the oil window. The mineralogical study of Babouri-Figuil oil shale has been carried out by means of XRD (X-Ray Diffractometry) and XRF (X-Ray Fluorescence spectrometry). The results show that mineral matrix contains silica, carbonates, sulphates, oxides and clay minerals. Besides, compounds contain metals and metalloids like Fe, In, Ca. The main oxides are SiO2 (majority), CaO, Fe2O3, Al2O3, SO3, and K2O.

Neutron Activation Analysis and Scanning Electron Microscopy of Phytoplankton in the Coastal Zone of Crimea (The Black Sea)

The physiology and ecology of planktonic organisms are influenced by the concentration, chemical speciation and resulting bioavailability of some trace metals. The determination of the elemental structure of phytoplankton is important for interpretation of physiological and functional states of coastal ecosystems. The present study is focused on the structure and elemental composition of the phytoplankton assemblages from the different coastal zones by instrumental neutron activation analysis (INAA), scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDS). For the first time these complementary techniques were simultaneously applied to study the Black Sea phytoplankton. The concentrations of 45 elements in the coastal phytoplankton communities used as bioindicator of inorganic contamination of the Black Sea coastal area near Sevastopol, Ukraine, were determined. Phytoplankton samples were collected by total tows of the plankton net with 35 μm pore size at 3 stations situated in polluted and relatively pristine water areas of the Sevastopol coastal zone during autumn period of the phytoplankton growth. The concentration of Mg, Al, Sc, Ti, V, Mn, As, Rb, Ba, Th and Fe, Cr increases exponentially from relatively pristine station to more polluted station and 10-times and 3-times greater, respectively, in the phytoplankton of the Sevastopol Bay. The rare-earth elements have relatively the same concentration values less than 1 μg/g and tend to accumulate in the phytoplankton from the polluted station in the Sevastopol Bay. The obtained results are in a good agreement with the elemental concentration data in the oceanic plankton, plankton communities from the White Sea and the Black Sea. Using energy-dispersive X-ray spectrometry the mineral particles of unknown origin and impurities of copper (0.42% by weight) in the phytoplankton at the polluted station and zinc (0.57% by weight) at the relatively pristine station were determined.

Using Prostatic Fluid Levels of Some Trace Elements and Their Combinations in Non-Invasive and Highly Accurate Screening for Prostate Cancer

Objective: Prostate specific antigen (PSA) does not provide the high reliability and precision that is required for an accurate screening for prostate cancer?(PCa). The aim of our study was to search for a simple, rapid, direct, preferably non-invasive, and highly accurate biomarker and procedure for the screening for PCa. Method: The levels of trace elements (TE) Br, Fe, Rb, Sr,?and Zn were prospectively evaluated in expressed prostatic fluid (EPF). Also?Zn/Br, Zn/Fe, Zn/Rb, Zn/Sr concentration ratios as well as ZnRb and (ZnRb)/Fe concentration combinations were calculated for EPF samples, obtained from 38 apparently healthy males and from 33, 51, and 24 patients with chronic prostatitis, benign prostatic hyperplasia, and PCa, respectively. Measurements were performed using an energy dispersive X-ray fluorescent (EDXRF) microanalysis. Results: It was found that in the EPF of cancerous prostates the levels of Rb, Zn, Zn/Br, Zn/Fe, Zn/Sr, ZnRb, and (ZnRb)/Fe were significantly lower in comparison with those in the EPF of normal, inflamed, and hyperplastic prostates. For example, in comparison hyperplastic?with cancerous prostates p values obtained using Student’s t-test and?Wilcoxon-Mann-Whitney U-test were Conclusions: The levels of TE and their combinations in EPF, obtained by EDXRF, is a fast, reliable, andnon-invasive diagnostic tool that can be successfully used by local, non- urologist physicians at the point-of-care to provide a highly effective PCa screening and as an additional confirmatory test before a prostate gland biopsy.

Clustering analysis of ancient celadon based on SOM neural network

In the study, chemical compositions of 48 fragments of ancient ceramics excavated in 4 archaeological kiln sites which were located in 3 cities (Hangzhou, Cixi and Longquan in Zhejiang Province, China) have been examined by energy-dispersive X-ray fluorescence (EDXRF) technique. Then the method of SOM was introduced into the clustering analysis based on the major and minor element compositions of the bodies, the results manifested that 48 samples could be perfectly distributed into 3 locations, Hangzhou, Cixi and Longquan. Because the major and minor element compositions of two Royal Kilns were similar to each other, the classification accuracy over them was merely 76.92%. In view of this, the authors have made a SOM clustering analysis again based on the trace element compositions of the bodies, the classification accuracy rose to 84.61%. These results indicated that discrepancies in the trace element compositions of the bodies of the ancient ceramics excavated in two Royal Kiln sites were more distinct than those in the major and minor element compositions, which was in accordance with the fact. We argued that SOM could be employed in the clustering analysis of ancient ceramics.

Field-scale spatial variability of soil calcium in a semi-arid region:Implications for soil erosion and site-specific management

Excess calcium(Ca)in soils of semi-arid and arid regions has negative effects on soil structure and chemical properties,which limits the crop root growth as well as the availability of soil water and nutrients.Quantifying the spatial variability of soil Ca contents may reveal factors influencing soil erosion and provide a basis for site-specific soil and crop management in semi-arid regions.This study sought to assess the spatial variability of soil Ca in relation to topography,hydraulic attributes,and soil types for precision soil and crop management in a 194-ha production field in the Southern High Plains of Texas,USA.Soils at four depth increments(0-2,0-15,15-30,and 30-60 cm)were sampled at 232 points in the spring of 2017.The Ca content of each sample was determined with a DP-6000 Delta Premium portable X-ray fluorescence(PXRF)spectrometer.Elevation data was obtained using a real-time kinematic GPS receiver with centimeter-level accuracy.A digital elevation model(DEM)was derived from the elevation data,and topographic and hydraulic attributes were generated from this DEM.A generalized least-squares model was then developed to assess the relationship between soil Ca contents of the four layers and the topographic and hydraulic attributes.Results showed that topographic attributes,especially slope and elevation,had a significant effect on soil Ca content at different depths(P<0.01).In addition,hydraulic attributes,especially flow length and sediment transport index(STI),had a significant effect on the spatial distribution of soil Ca.Spatial variability of soil Ca and its relationships with topographic and hydraulic attributes and soil types indicated that surface soil loss may occur due to water or wind erosion,especially on susceptible soils with high slopes.Therefore,this study suggests that the application of PXRF in assessing soil Ca content can potentially facilitate a new method for soil erosion evaluation in semi-arid lands.The results of this study provide valuable information for site-specific soil conservation and crop management.

Spatial distribution of heavy metals in the middle nile delta of Egypt

Heavy metal contamination in the El-Gharbia Governorate(District)of Egypt was identified by using remote sensing,Geographical Information Systems(GIS),and X-ray fluorescence(XRF)spectrometry as the main research tools.Digital Elevation Model(DEM),Landsat 8 and contour map images were used to map the landforms.Different physiographic units in the study area are represented by nine soil profiles.X-ray fluorescence spectrometry(XRF)was used for geochemical analysis of 33 soil samples.Vanadium(V),nickel(Ni),chromium(Cr),copper(Cu)and zinc(Zn)concentrations were measured and they all exceeded the average global concentrations identified by Wedepohl(1995).Ni and Cr concentrations exceeded recommended values in all soil profile horizons(Canadian Soil Quality Guidelines,2007),while Cu had a variable distribution.Zn concentrations are under recommended concentration limits in most soil samples.Contamination Factor,Pollution Load Index and Degree of Contamination indices were used to assess the environmental risks of heavy metal contamination from the soils.All analysed metals pose some potential hazard and pollution levels were particularly high near industrial and urban areas.

A statistic comparison of multi-element analysis of low atmospheric fine particles(PM_(2.5)) using different spectroscopy techniques

Over the past few decades,the metal elements(MEs)in atmospheric particles have aroused great attention.Some well-established techniques have been used to measure particlebound MEs.However,each method has its own advantages and disadvantages in terms of complexity,accuracy,and specific elements of interest.In this study,the performances of inductively coupled plasma-optical emission spectrometry(ICP-OES)and total reflection X-ray fluorescence spectroscopy(TXRF)were evaluated for quality control to analyze data accuracy and precision.The statistic methods(Deming regression and significance testing)were applied for intercomparison between ICP-OES and TXRF measurements for same lowloading PM_(2.5)samples in Weizhou Island.The results from the replicate analysis of standard filters(SRM 2783)and field filters samples indicated that 10 MEs(K,Ca,V,Cr,Mn,Fe,Ni,Cu,Zn,and Pb)showed good accuracies and precision for both techniques.The higher accuracy tended to the higher precision in the MEs analysis process.In addition,the interlab comparisons illustrated that V and Mn all had good agreements between ICP-OES and TXRF.The measurements of K,Cu and Zn were more reliable by TXRF analysis for low-loading PM_(2.5).ICP-OES was more accurate for the determinations for Ca,Cr,Ni and Pb,owing to the overlapping spectral lines and low sensitivity during TXRF analysis.The measurements of Fe,influenced by low-loading PM_(2.5),were not able to determine which instrument could obtain more reliable results.These conclusions could provide reference information to choose suitable instrument for the determination of MEs in low-loading PM_(2.5)samples.

Significance of trace element quantities in the prostatic secretion of patients with benign prostatic hyperplasia and prostate cancer

Aim:Benign prostatic hyperplasia and prostate cancer is an internationally important health problem of the man,particularly in developed countries.The aim of this exploratory study was to evaluate whether significant difference in the levels of Zn and some other trace elements of prostatic fluid exist between the inflamed and malignantly transformed prostate.Methods:Prostatic fluid levels of Br,Fe,Rb,Sr,and Zn were prospectively evaluated in 52 patients with benign prostatic hyperplasia and 24 patients with prostate cancer.Measurements were performed using 109Cd radionuclide-induced energy dispersive X-ray fluorescent microanalysis.Prostatic fluid samples were divided into two portions.One was used for cytological study to exclude prostatitis,while the other was intended for trace element analysis.Results:Mean values±standard error of means for concentration(mg/L)of trace element in the prostatic fluid of hyperplastic prostate were:Br 2.32±0.30,Fe 11.5±1.8,Rb 1.70±0.23,Sr 1.41±0.26,and Zn 488±42.The contents of Rb and Zn were significantly lower(approximately 3.2 and 7.7 times,respectively)in fluid of cancerous prostate compared with those in fluid of hyperplastic prostate.Conclusion:There are significant differences in trace element contents in the fluid of hyperplastic and malignantly transformed prostate.The great decrease in levels of Rb and Zn in the fluid of cancerous prostate might demonstrate ;an involvement of these trace elements in etiology and pathogenesis of malignant prostate tumors.It was supposed that the differences in Rb and Zn levels in prostatic fluid can be used as tumor markers.