Energy dispersive X-ray fluorescence determination of cadmium in uranium matrix using Cd Kα line excited by continuum

An energy dispersive X-ray fluorescence method for determination of cadmium (Cd) in uranium (U) matrix using continuum source of excitation was developed. Calibration and sample solutions of cadmium, with and without uranium were prepared by mixing different volumes of standard solutions of cadmium and uranyl nitrate, both prepared in suprapure nitric acid. The concentration of Cd in calibration solutions and samples was in the range of 6 to 90 µg/mL whereas the concentration of Cd with respect to U ranged from 90 to 700 µg/g of U. From the calibration solutions and samples containing uranium, the major matrix uranium was selectively extracted using 30% tri-n-butyl phosphate in dodecane. Fixed volumes (1.5 mL) of aqueous phases thus obtained were taken directly in specially designed in-house fabricated leak proof Perspex sample cells for the energy dispersive X-ray fluorescence measurements and calibration plots were made by plotting Cd Kα intensity against respective Cd concentration. For the calibration solutions not having uranium, the energy dispersive X-ray fluorescence spectra were measured without any extraction and Cd calibration plots were made accordingly. The results obtained showed a precision of 2% (1σ) and the results deviated from the expected values by < 4% on average.     

Uranium determination in phosphoric acid solutions

In order to determine uranium from raw phosphoric acid solutions, resulted by the sulphuric acid attack of phosphate rocks and the strip solutions of the solvent extraction process for uranium recovery, two classes of analytical methods were established: one for low uranium content in phosphoric acid, and the other for higher uranium concentration in the same medium. The study was based on specific methods, therefore interference probability with other impurities in phosphoric acid medium is low. In the first class, X-ray fluorescence and spectrophotocolorimetric methods were used. X-ray fluorescence was applied on direct raw phosphoric acid solution and raffinate. The last one was associated with solvent extraction [di-(2-ethylhexyl) phosphate + triocylphosphine oxide] on the U(IV)-Arsenazo III complex in strip. The methods of the second class, were used for strip uranium concentrated solutions: X-ray fluorescence isotopic dilution and mass spectrometry, spectrophotocolorimetry and activation analysis associated with gamma-spectrometry. Here spectrophotocolorimetry involves two methods. The first one is based on the U(IV)-Arsenazo III complex and the other on direct U(IV)—phosphoric acid solutions measurements. A good agreement was obtained in each case for all comparative measurements involving various methods.     

Direct chlorine determination in crude oils by energy dispersive X-ray fluorescence spectrometry: An improved method based on a proper strategy for sample homogenization and calibration with inorganic standards

Official guidelines to perform chlorine determination in crude oil are (i) American Society for Testing and Materials (ASTM) D6470, which is based on the extraction of water from the oil and subsequent determination of the chloride by potentiometry, (ii) ASTM D3230, that measures the conductivity of a solution of crude oil in a mixture of organic solvents and (iii) US Environmental Protection Agency (EPA) 9075 that uses energy dispersive X-ray fluorescence spectrometry to quantify chlorine and it is applicable for the range from 200 μg g^− 1 to percent levels of the analyte. The goal of this work is to propose method to quantify lower amounts of chlorine in crude oil using energy dispersive X-ray fluorescence spectrometry using a simple calibration strategy. Sample homogenization procedure was carefully studied in order to enable accurate results. The calibration curve was made with standards prepared by diluting aqueous NaCl standard in glycerin. The method presented a linear response that covers the range from 8 to at least 100 μg g^− 1 of chlorine. Chlorine in crude oil samples from Campos Basin - Brazil were quantified by the proposed method and by potentiometry after extraction of chlorine from the oil. Results achieved using both methods were statistically the same at 95% confidence level.     

Direct Determination of Uranium in the D2EHPA-TOPO Organic Phase Using EDXRF Spectrometry

The determination of uranium in liquid samples using energy dispersive X-ray fluorescence was investigated. The organic phase di-(2-ethyl hexyl) phosphoric acid and trioctyl phosphine oxide (D2EHPA-TOPO)/kerosene, which resulted from first and second cycles of uranium extraction from commercial phosphoric acid, was directly analyzed using ¹⁰⁹Cd as a primary excitation source. Copper was used as an internal standard, which led to a linear relation between relative intensity of uranium and its concentration. Three calibration curves, 0–100, 100–1000 and 1000–6500 g· ml^–1, according to uranium concentration in the studied samples, were constructed. The effect of different molarities of D2EHPA and TOPO was considered. The detection limit, precision and accuracy were 1.1 g · ml^–1, 3% and 1.4%, respectively. The obtained results were compared with other techniques such as -ray spectroscopy, UV spectrometry and volumetry.     

Preconcentration method for the determination of thorium in natural water by wavelength dispersive X-ray fluorescence spectrometry

The preconcentration of thorium from natural water and its determination directly by wavelength dispersive X-ray fluorescence spectrometry (WDXRF) were attempted. The first step consists of thorium preconcentration from slightly acid solutions on polyurethane foam (PUF) loaded with 2-etilhexylphosphonic acid (EHPA) reagent as solid phase. PUF held up to 50% (w/w) of the reagent and the preconcentration was maximum at the acidity of 0.25 mol^.l^-1 hydrochloric solution. Sorption on PUF had fast kinetics and 4.0 and 10 mg^.l^-1 detection and quantitation limits of thorium were achieved, respectively, as well as a R.S.D. of 4.2% at 21.7 mg^.l^-1. This method was successfully applied to natural water analyses. The results were in good agreement with reference values of water samples at 95% confidence level.     

X-Ray fluorescence analysis using the filter paper method for the determination of La,Pr and Nd in solution

The use of radioisotope-induced energy dispersive X-ray fluorescence technique for elemental analysis in solutions by the filter paper method has been investigated. The calibration has been found to be linear over the range studied. Non-uniformity of specimen, the precision and accuracy of the method have been examined. The minimum detectable amounts have also been determined.     

A method for prompt in situ uranium assay and free acidity determination in uranyl nitrate solutions by density and Raman measurements

A precise and accurate compositional characterization methodology using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry for mixed oxide nuclear fuels is reported. The methodology involves pelletization of standards and samples. The calibration plots were made by plotting the percent intensity of analyte X-ray lines against their amount percent. The relative standard deviation were 0.4% and 0.25%, respectively for uranium and thorium, having U ranging from 2.85 to 4.2 (wt%). The analytical results were compared with chemical analysis method and were in good agreement. The developed WDXRF method is non-destructive, fast and better in comparison to chemical analysis methods.

     

Field study on thorium uptake by plants within and around of a thorium ore deposit

Thorium concentration was determined in natural forage materials, thyme and barley (stern and kemel) in underlying substrate soil within, and around the thorium mine in Kizilcaoren-Eskisehir. Plant/soil concentration ratios (CR) for thorium were estimated in details for sixteen places including ore pits, mine tailings and cultivation area. The experiments were carried out by using energy dispersive X-ray fluorescence spectrometry. As a result, no demonstrable differences in thorium concentrations between washed plant groups except thyme, and collection time were found. However, thorium amount and CR values for unwashed plant samples were higher than those for washed ones at all sites due to dust contamination. No thorium was observed in the kemels     

Direct determination of uranium in sintered deeply depleted uranium oxide pellets by wavelength dispersive X-ray fluorescence spectrometry

This paper presents studies on direct non-destructive determination of uranium in sintered deeply depleted (DD) uranium oxide (UO₂) pellets by wavelength dispersive X-ray fluorescence (WDXRF) spectrometry. A special collet was designed and fabricated for holding the sintered DDUO₂ pellets for direct analysis, thus avoiding the sample preparation steps. The samples were analyzed using a calibration plot obtained from WDXRF spectra of matrix matched calibration standards. The WDXRF determined uranium values were found to be in very close agreement with titrimetric values and has reproducibility better than 0.05% (RSD, 1 s, n = 10) for the sintered DDUO₂ pellets having U: 86.81–88.04 wt%.

     

Development of off-line layer chromatographic and total reflection X-ray fluorescence spectrometric methods for arsenic speciation

Rapid and low cost off-line thin layer chromatography–total reflection X-ray fluorescence spectrometry and overpressured thin layer chromatography–total reflection X-ray fluorescence spectrometry methods have been developed for separation of 25 ng of each As(III), As(V), monomethyl arsonic acid and dimethylarsinic acid applying a PEI cellulose stationary phase on plastic sheets and a mixture of acetone/acetic acid/water = 2:1:1 (v/v/v) as eluent system. The type of eluent systems, the amounts (25–1000 ng) of As species applied to PEI cellulose plates, injection volume, development distance, and flow rate (in case of overpressured thin layer chromatography) were taken into consideration for the development of the chromatographic separation. Moreover, a microdigestion method employing nitric acid for the As spots containing PEI cellulose scratched from the developed plates divided into segments was developed for the subsequent total reflection X-ray fluorescence spectrometry analysis. The method was applied for analysis of root extracts of cucumber plants grown in As(III) containing modified Hoagland nutrient solution. Both As(III) and As(V) were detected by applying the proposed thin layer chromatography/overpressured thin layer chromatography–total reflection X-ray fluorescence spectrometry methods.     

Comparison of analytical methods for the determination of trace amounts of strontium and yttrium by photon induced X-ray fluorescence techniques in lateritic materials

Three different analytical methods for the determination of strontium and yttrium in Venezuelan latterites by radioisotope induced X-ray fluorescence are compared, also with results from conventional wavelength dispersive X-ray fluorescence. The samples analyzed were from Cerro Impacto, Venezuela. The photon-induced energy dispersive X-ray fluorescence system consisted of a¹⁰⁹Cd (7 mCi) source for excitation of the characteristic K X-rays for strontium and yttrium. The detection system employed a high resolution Si(Li) detector and was completely controlled by a PDP-11/05 processor. Of the three analytical methods described, the internal standard-thin film technique was shown to be slightly superior to the conventional standard calibration curve method and the standard additon/dilution procedure. This can be explained by considering the effectiveness of the compensation of the sources of errors by these methods. It should also be noted that in the case of wavelength dispersive X-ray fluorescence, an about 5–10 times greater sample is needed, which is a limitation compared to energy dispersive X-ray fluorescence in some cases. Finally, typical relative standard deviations of the energy dispersive X-ray fluorescence methods were about 10–15% for the range of about 100–100 ppm of strontium and yttrium; these values are acceptable considering the large degree of heterogeneity in this type of geological material. This project was funded by Consejo Nacional de Investigaciones Científicas y Technológicas (CONICIT) and performed as part of UNESCO's IGCP-129 “Lateritization Processes” project.     

Synthesis of polyamidoamine dendrimer (PAMAM/CuS/AA) nanocomposite and its application in the removal of Isma acid fast yellow G Dye

The adsorption of Isma acid fast yellow G dye was studied using polyamidoamine (PAMAM)/Copper sulfide (CuS)/AA nanocomposite containing different amounts of CuS by batch technique. PAMAM dendrimer/CuS/AA nanocomposites were synthesized via gamma irradiation cross‐linking method with the aid of sonication. The nanocomposites were characterized by Fourier‐transform infrared, X‐ray diffraction, transmission electron microscope, energy dispersive spectroscopy X‐ray, thermal gravimetric analysis, ultraviolet‐visible, and fluorescence spectroscopy. The size of the CuS nanoparticles was formed in the range of 12–19 nm. The adsorption capacity of the nanocomposites was evaluated as a function of initial dye concentration, pH, adsorbent dosage, and time. It was verified that the adsorption rate fits a pseudo‐second‐order kinetics for initial Isma acid fast yellow G dye concentrations. Results indicated that the adsorption of Isma acid fast yellow G dye fitted well to the Langmuir model. Our results demonstrate that the PAMAM dendrimer/CuS/AA nanocomposite is very promising for removing organic dyes from wastewater. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of antimony in sediments and soils by slurry sampling graphite furnace atomic absorption spectrometry using a permanent chemical modifier

For comparison of action of mixed permanent modifiers Ir/Nb and Ir/W, the influence of the amounts of modifier components was studied and the atomic absorption pyrolysis and atomization curves were determined with different modifiers. The optimum amounts of modifier components were 30 μg Ir and 40 μg of Nb that were deposited onto the L'vov platform in advance to analytical measurements. The long-term performance of the Ir and Nb permanent modifiers was derived from the investigations by scanning electron microscopy and energy dispersive X-ray spectrometry. The soil and sediment slurries were prepared in 4% hydrofluoric acid and 6% suspension of polytetrafluoroethylene in order to remove the high concentration of silica during the pyrolysis step of 900 °C. The calibration was made by using aqueous standards. The analysis of certified reference materials confirmed the accuracy and reliability of the proposed analytical approach. The precision of Sb determination was characterized with less than 6% RSD.     

Fluorimetric estimation of U(VI) in the presence of a large excess of Th(IV)

A fluorescence based method has been developed for the determination of trace amounts of uranium in thorium matrix using a mixture of phosphoric acid (H₃PO₄) and sulfuric acid (H₂SO₄), as fluorescence enhancing reagent for uranyl (UO₂ ²⁺) ion fluorescence. Synthetic samples mimicking the composition of ThO₂ fuel were prepared and the concentration of U(VI) was estimated. Satisfactory results are obtained when uranium is present at a concentration of 10 ppm in solid thorium samples with good precision.     

X-射线荧光光谱分析技术的发展

归纳了X-射线荧光光谱分析技术发展的进程。从现代控制技术的改善、仪器检测性能的提高、元素检测范围的扩大等8方面阐述了波长色散X-射线荧光光谱技术的进展,还就能量色散X-射线荧光光谱仪的X射线管和探测器技术的快速发展及近10年来我国在X-射线荧光光谱分析方法方面的论文发表情况进行了总结,对近年来X-射线荧光光谱仪的发展趋势———手持式、偏振、微束分析等进行了评述,并对其技术的发展方向进行了展望。     

Continuous flow extraction of indium with bis(2-ethylhexyl)phosphoric acid in 4-methylpentane-2-one coupled on-line with flame atomic absorption spectrometry

Extraction in liquid-liquid segmented flow is used for preconcentration of indium from dilute nitric acid solutions into bis(2-ethylhexyl)phosphoric acid dissolved in 4-methylpentane-2-one. The extraction setup is coupled on-line with flame spectrometry to give a fully mechanized system. The detection limit of the method is 0.03 mg l^?1, the calibration plot is linear up to 1.75 mg l^?1. Repeatability is 1.5% RSD measured at 1 mg l^?1. Sample throughput is 60 h^?1.     

Determination of metallic impurities in U3O8 using energy dispersive X-ray fluorescence spectrometry

In order to examine the capability of energy dispersive X-ray fluorescence spectrometry for the determination of some common metallic impurities in nuclear grade U₃O₈ matrix, a series of synthetic U₃O₈ standards, containing impurities such as Ca, Co, Cr, Cu, Fe, Mn, Mo, Ni ,V, W and Zn in the concentration range, 100–1000 μg/g, were prepared. Using these standards, calibration curves were set up for different elements after optimizing the spectrometer parameters. Two synthetic samples and five reference standards obtained through an inter-laboratory comparison exercise within analytical laboratories of Department of Atomic Energy, India were analyzed to evaluate the performance of the newly developed analytical methods. The estimates for most of the analytes were in good agreement with the added amounts. The method is fast, since it requires no chemical treatment. The method has good precision for the analytes determined.     

Analysis of low Z elements in various environmental samples with total reflection X-ray fluorescence (TXRF) spectrometry

Recently there is a growing interest in low Z elements such as carbon, oxygen up to sulphur and phosphorus in biological specimen. Total reflection X-ray fluorescence (TXRF) spectrometry is a suitable technique demanding only very small amounts of sample. On the other side, the detection of low Z elements is a critical point of this analytical technique. Besides other effects, self absorption may occur in the samples, because of the low energy of the fluorescence radiation. The calibration curves might be not linear any longer. To investigate this issue water samples and samples from human cerebrospinal fluid were used to examine absorption effects. The linearity of calibration curves in dependence of sample mass was investigated to verify the validity of the thin film approximation. The special requirements to the experimental setup for low Z energy dispersive fluorescence analysis were met by using the Atominstitute's TXRF vacuum chamber. This spectrometer is equipped with a Cr-anode X-ray tube, a multilayer monochromator and a SiLi detector with 30 mm² active area and with an ultrathin entrance window. Other object on this study are biofilms, living on all subaqueous surfaces, consisting of bacteria, algae and fungi embedded in their extracellular polymeric substances (EPS). Many trace elements from the water are bound in the biofilm. Thus, the biofilm is a useful indicator for polluting elements. For biomonitoring purposes not only the polluting elements but also the formation and growth rate of the biofilm are important. Biofilms were directly grown on TXRF reflectors. Their major elements and C-masses correlated to the cultivation time were investigated. These measured masses were related to the area seen by the detector, which was experimentally determined. Homogeneity of the biofilms was checked by measuring various sample positions on the reflectors.     

Effect of alkali metals,alkaline earth metals and lanthanides on the adsorption of uranium on activated charcoal from aqueous solutions

Effects of alkali metals, alkaline earth metals and some lanthanides on the adsorption of uranium on activated charcoal from aqueous solutions have been studied. These effects are correlated with the ionic radii of metal ions present in the solutions. Adsorption capacity, X_m and binding energy contant, K for uranium adsorption were calculated from the Langmuir equätion. The mean energy of adsorption, E_s was calculated from adsorption energy constant, K, values determined from the Dubinin-Radushkevich isotherm equation. Wavelength dispersive X-ray fluorescence spectrometry was used for measuring the uranium concentration.     

Determination of sulphur in liquids obtained by thermal cracking of waste polymers and commercial fuels with different analytical methods

Low sulphur concentration in hydrocarbon products as fuels or lubricants is an important requirement for the high quality standards of refineries. A non-polarised energy dispersive X-ray fluorescence spectroscopy (EDXRFS) and sample combustion technique (ASTM D6428-99) was compared. A new application of energy dispersive X-ray spectrometry as analytical method for the determination of sulphur in fuels and fuel-like fractions was investigated. Low sulphur containing fuels and hydrocarbon mixtures obtained by thermal cracking of waste polymers were measured and the influence of C/H ratio on accuracy was studied. The concentration of sulphur in samples was measured with calibration graphs of different hydrocarbon matrices (commercial gasoline, diesel oil and white oil were used). Good correlation was observed between the different methods, but the correlation was depending on the characteristics of the matrices. Detection limits of 1.0 ppm, 1.1 ppm and 0.9 ppm were obtained for S in gasoline, diesel oil and white oil, respectively.