Plasma Atomic Emission Spectrometric Analysis Research Articles

Separation of fission products from spent pressurized water reactor fuels by anion exchange and extraction chromatography for inductively coupled plasma atomic emission spectrometric analysis

A study has been carried out on the separation of fission products from spent pressurized water reactor (PWR) fuels and their quantitative determination using inductively coupled plasma atomic emission spectrometry (ICP-AES). Plutonium and uranium were separated from fission products using anion exchange and tri- n-butylphosphate (TBP) extraction chromatography, respectively. Americium was separated and fission products such as Sr, Ba, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd and Y were quantitatively recovered using di(2-ethylhexyl)phosphoric acid (HDEHP) extraction chromatography. An ICP-AES/shielding system, which was specially designed and built for the analysis of radioactive materials, was employed and the analytical precision for all metal elements studied was found to be <5%. Three spent PWR fuels whose burnup rates were between 15,000 and 35,000 MWd/MTU were analysed and then the relation between the burnup and the quantity of the fission products was compared to that calculated by burnup code, ORIGEN 2.

Comparison of slurry preparation and microwave digestion of freshwater algae for multi-element analysis by total reflection X-ray fluorescence spectrometry

The purpose of this study was to investigate the usefulness of slurry sampling for total reflection X-ray fluorescence (TXRF) analysis of freshwater algae. Slurry samples were prepared from freeze-dried algae by sonication. Solution samples were prepared by vapour-phase microwave digestion. TXRF analyses of 20-200 µg of specimens made from freeze-dried algal samples are reported. The concentrations of P, K, Ca, Mn, Fe, Cu, Zn and Pb were determined in the range 5-40 000 µg g –1 ; similar values have been published by other investigations for marine and freshwater algae samples. Good agreement was found between the results of the TXRF analysis of the slurries and the digested samples, and also the results of an additional inductively coupled plasma atomic emission spectrometric analysis of the digested samples. Student's t-test was used to demonstrate the applicability of slurry sampling. It is concluded that the slurry preparation simplifies the sample treatment and is suitable for TXRF measurement.

Inductively Coupled Plasma–Atomic Emission Spectrometric Analysis of Aqueous Slurries of Solids

The direct injection of solids–water slurries into the torch of an inductively coupled plasma–atomic emission spectrometer offers a quick and easy method for the analysis of major and minor elements in various solids. In this project aqueous slurries of solids were prepared by wet milling with a stirred-ball slurry attritor mill and analyzed. Slurries of standard reference materials, prepared in the same way, were used as calibration standards. The best results were obtained with solids having a small particle size (2–5 μm) and a close distribution of particle sizes. The average percent relative error for slurry–ICP analysis of most major and minor elements was generally less than 5% for the solids studied.

Determination of Elements in Biological and Botanical Materials by Inductively Coupled Plasma Atomic Emission and Mass Spectrometry After Extraction With a Tertiary Amine Reagent

A simple inductively coupled plasma atomic emission and mass spectrometric (ICP-AES and ICP-MS) analysis procedure for biological and botanical materials was developed based on an extraction with a commercial, water-soluble tertiary amine solution. Standard reference materials were dispersed in a 10% v/v amine mixture at pH 8 and the resulting dispersion was agitated for 30 min at room temperature. After centrifugation, Al, Ca, Cu, Fe, Mg, Mn, Na, K and Zn were determined by ICP-AES and As, Ba, Ca, Cu, Pb, Mn, Mo, Rb, Se, Cr and Zn were determined by ICP-MS in the supernatant. Recoveries of nearly all elements in most samples were close to 100%, and no significant difference at a 95% confidence level was found between determined and certified values. Low recoveries were observed for Al and Fe in all materials and for Ca in spinach and apple leaves. The simple procedure is useful for screening purposes in the analysis of biological and botanical materials.

Effects of several metals on spore, biomass, and geosmin production byStreptomyces tendae andPenicillium expansum

Cultures ofStreptomyces tendae andPenicillium expansum grown on Actinomyces and Czapek's media, respectively, were exposed to 5 mg L−1 of manganese, magnesium, iron, cobalt, nickel, copper and zinc, supplied as sulfate salts. Only copper markedly increased geosmin (1α, 10β-dimethyl-9α-decalol), biomass, and spore production. inductively coupled plasma-atomic emission spectrometric analysis ofS. tendae andP. expansum cells did not indicate an accumulation of copper. Both 1 and 5 mg L−1 copper, as copper sulfate, increased total geosmin production in cultures ofS. tendae on several media, but decreased production on others, suggesting that substrate composition affects responses to copper.

Inductively coupled plasma atomic emission spectrometric analysis of low levels of selenium in natural waters

Selenium is an environmentally important element that is difficult to determine in natural waters owing to its low concentrations. Research has shown that selenium levels are typically <0.5 µg l–1 in most waters sampled. The increased environmental interest in selenium has promoted the modification of analytical methods with the aim to improve analysis at the sub-µg l–1 level. The determination of selenium by hydride generation has been widely documented by a number of authors. Selenium may be reduced to a gaseous hydride by reaction with sodium tetrahydroborate and introduced directly into the base of the ICP torch. This allows almost 100% efficiency of sample injection compared with only 2–5% by standard nebulization, hence improving sensitivity. Hydride generation represents a greatly improved method of selenium analysis and detection limits of 1 µg l–1 or lower may be obtained. However, when measuring selenium in most natural waters, samples must be preconcentrated to further lower detection limits into the usual range of occurrence. Coprecipitation with lanthanum hydroxide is a rapid and efficient method of concentrating selenium. In natural groundwaters and similar environments, selenium occurs mostly as SeVI(selenate) although small amounts of SeIV(selenite) may also be present. This research has shown that the dominant form of selenium (selenate) is not effectively precipitated with lanthanum hydroxide. Previously documented methods have therefore been modified here by reducing all Se to selenite prior to preconcentration and analysis. A method is described that allows selenium levels as low as 0.06 µg l–1 to be analysed rapidly and accurately. The selenium in each sample is reduced to selenite by heating with HCl and KBr. Selenite is then coprecipitated with lanthanum hydroxide and separated by centrifugation. The resulting precipitate is dissolved in an acid solution and introduced into the ICP in the form of gaseous hydride. Standard solutions show very good linear calibration across the range 0–10 µg l–1.

Analysis of zirconium alloys by inductively coupled plasma atomic emission spectrometry

In the inductively coupled plasma atomic emission spectrometric analysis of real samples, influences of the matrix on the analyte spectral lines could be expected, especially when the ratio of the concentration of the matrix to that of the analyte is extremely high. In addition to the elimination of stray-light effects by background correction, there are also spectral interferences which must be investigated. It is of great importance to obtain information concerning the spectral line overlaps before setting up an analytical programme. The experiments performed dealt with the interferences to be expected in a Zr matrix. In general, because of the nature of Zr the chemistry and technology associated with this element are very complicated, therefore the methods applied in its analysis have specific requirements. Where possible, for all the analytes of interest (Al, B, Cd, Co, Cr, Cu, Fe, Hf, Mg, Mn, Mo, Nb, Ni, Sn, Ta, V, U and W) spectral lines were selected that were free from interferences caused by the matrix element. Where no interference-free analyte line could be found, it was necessary to perform line interference corrections. The analytical programme developed in this way was tested with Standard Reference Materials (National Institute of Standards and Technology). The data compare well with the certified values. The confidence intervals for 95% probability were in the range of 2–12%, depending on the element and the concentration.

Vapour-phase acid digestion of micro samples of biological material in a high-temperature, high-pressure asher for inductively coupled plasma atomic emission spectrometry.

This vapour-phase acid decomposition of small biological samples (50-165 mg) and concurrent purification of the reagent acid were achieved in a mini-quartz sample holder inserted in a commercial high-pressure digestion vessel. A 3.1 ml volume sample contained was developed to hold the sample and to maximize the successful decomposition of a variety of biological samples. When biological standard reference materials were digested at 230 degrees C and 122 bar (1770 psi), the residual carbon content in the digested samples was less than 1.8 +/- 0.1%. Inductively coupled plasma atomic emission spectrometric analysis of the digested materials for C, Ca, Cu, Cd, Fe, Mg, Mn and Zn provided good recoveries and low reagent blank values and demonstrated complete matrix decomposition.

Simultaneous Determination of Major Constituents and Impurities in High-Purity Mullite Using Pressure Acid Decomposition

A simple, precise and sensitive method is described for the simultaneous determination of major constituents (Al2O3 and Si02) and impurities (Ca, Cr, Fe, K, Li, Mg, Mn, Na, Sr, Ti, V, Y, Zn and Zr) in high-purity mullite (3Al2O3·2SiO2). A 0.5 g amount of the powder sample was decomposed with 5 ml of H2SO4 (1+2) at 230°C for 16 h in a polytetrafluoroethylene pressure vessel. The decomposed mixture was separated to a solution and a precipitate by filtration. After the solution was diluted to a constant volume with water, inductively coupled plasma atomic emission spectrometric analysis for the impurity elements and conventional volumetric analysis for Al2O3 were carried out. The precipitate was ashed in a platinum crucible and gravimetric analysis for SiO2 was carried out. The proposed method was successfully applied to the simultaneous determination of Al2O3, SiO2 and the impurities in commercial mullite samples. The analytical results were in good agreement with those obtained by other methods. This method has advantages in simplicity, good precision and high sensitivity for the comprehensive analysis of high-purity mullite.

Calculation of method evaluation functions for inductively coupled plasma atomic emission spectrometric analysis for iron, manganese and titanium from metal-spiked filter samples

The method evaluating function (MEF) is defined as the expected value of the analysis as a function of the ‘true’ content of the analyte in the samples. The MEF describes the complete analytical range and contains most of the relevant information on a chemical analytical method. The calculation of the MEF provides an easy way to obtain stringent documentation on an analytical method. MEFs for the multi-element inductively coupled plasma atomic emission spectrometric (ICP-AES) determination of Fe, Mn and Ti have been established. Parameter estimators, based on the method of weighted least-squares regression, including confidence intervals for the zero-point error α and the slope of β of the regression curve, were determined. The overall analytical error, i.e., the day-to-day variation and the variation within a single run of the analysis were calculated. Certification limits were set, for use of the ICP-AES analysis in the development of interlaboratory control filters, based on the square root of the relative mean square error.

Use of the Hildebrand grid nebulizer for inductively coupled plasma atomic emission spectrometric analysis of foodware leach solutions and rodent soft tissues and femurs.

The Hildebrand grid nebulizer (HGN) was used for the inductively coupled plasma atomic emission spectrometric determination of major, minor and trace elements in perchloric acid digests of rodent femurs, sulphuric acid digests of rodent soft tissues and in solutions leached from foodware using acetic acid. The HGN performed well when the signal-to-background ratio was optimized for each acid solution by adjusting the injector gas flow, solution uptake rate and observation height. Three problems were overcome while using the HGN: (i) nebulizer wash-out time was reduced by rinsing at high uptake rate with the solution to be analysed; (ii) clogging of the injector tip of the torch during femur analysis was minimized by extensive rinsing; and (iii) errors due to the suppression of the Cu, Fe, Mn and Zn signal intensities by matrix elements Ca and P in femur digests were eliminated by calibrating the spectrometer with matched matrix standard solutions. Overall, the precision of analysis for the leach and tissue solutions analysed in this study ranged from 0.5 to 2.9% relative standard deviation.

Rapid procedure for the dissolution of a wide variety of ore and smelter samples prior to analysis by inductively coupled plasma atomic emission spectrometry

A standard methodology for the dissolution of a wide range of metallurgical analytical samples is described. The procedure involves peroxide fusion in a zirconium crucible, followed by dissolution of the cooled melt in an acid solution prior to inductively coupled plasma atomic emission spectrometric analysis. The method is rapid and cost-effective. The recovery of sulphur is almost total and separate combustion analysis is unnecessary.

Elemental analysis of welding fumes by X-ray fluorescence spectrometry

A method is described for the simultaneous multi-element determination of arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel, titanium, vanadium and zinc in welding fumes by wavelength dispersive X-ray fluorescence (XRF) spectrometry. Instrumental calibration is achieved by a thin-film dibenzyldithiocarbamate precipitation procedure based on standard metal solutions. The results obtained for the rapid and simple X-ray methodology described are found to be favourable in comparison with inductively coupled plasma atomic emission spectrometric analysis of synthetic and real samples. Details are given of the instrumental optimisation conditions and the interference characteristics for both the XRF and inductively coupled plasma atomic emission spectrometry (ICP-AES) techniques. The sampling strategy for welding fumes is considered with particular reference to the particle size distribution. The XRF analysis described compares favourably with ICP-AES analysis giving a sufficiently accurate method of analysis for the elements of interest without the need for lengthy sample preparation or calibration procedures.

Communications. Serial single particle analysis by atomic spectrometry after remote laser ablation

The inductively coupled plasma atomic emission spectrometric analysis of single particles in the mass range 10–100 pg is discussed and the analysis of laser ablation ejecta, one particle at a time, is demonstrated.

Inductively coupled plasma atomic emission spectrometric analysis of cobalt-base superalloys

This paper describes the procedure developed for the accurate analysis by ICP-AES of Co-base superalloys, using yttrium as an internal standard. The chemical composition of these materials makes the development of spectroscopic analytical methods difficult due to the presence of major elements that exhibit intense and complex ICP emission spectra. A quantitative sample dissolution procedure and careful selection of the analytical lines used was carried out. The elements investigated were Co, Cr, Ni, W, Fe, Ta, Nb, Al, Mo and Mn. Synthetic solutions were used for calibration, and standard samples were analysed to demonstrate the precision and accuracy of the developed method.

Determination of trace elements of some Egyptian crops by instrumental neutron activation, inductively coupled plasma-atomic emission spectrometric and flameless atomic absorption spectrophotometric analysis

Instrumental neutron activation analysis was used for the determination of Al, Br, Ca, Ce, Cl, Co, Cr, Cs, Eu, Fe, K, La, Mg, Mn, Na, Rb, Sb, Sc, Se, Ti, Th, V and Zn, ICP-AES for the determination Al, Ag, Ba, Be, Ca, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Na, Ni, P, Sc, Sr, Ti, V and Zn and flameless AAS for the determination of Cd, Hg and Pb in egg plant, potatoes, green pepper (Leguminosae), vegetable marrow (Cucurbitaceae), pears, apple (Rosaceae), castor oil plant (Euphorbiaceae), lettuce (compositae), dill, parsley, coriander (Umbelliferae), and in some soil samples collected from Aswan province.

Determination of trace elements in Egyptian cane sugar (Deshna Factories) by neutron activation, atomic absorption spectrophotometric and inductively coupled plasma-atomic emission spectrometric analysis

Multielemental instrumental neutron activation (INAA), inductively coupled plasmaatomic emission spectrometric (ICP-AES) and atomic absorption spectrophotometric (AAS) analyses are utilized for the determination of Ag, Al, As, Au, Ba, Be, Br, Ca, Cd, Ce, Cl, Co, Cr, Cu, Eu, Fe, Ga, Hf, K, La, Li, Lu, Mg, Mn, Na, Nb, Ni, P. Pb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Th, Ti, U, V, W and Zn in sugar cane plant, raw juice, juice in different stages, syrup, deposits, molasses, A, B and C sugar, refinery 1 and 2 sugar, and in soil samples picked up from the immediate vicinity of the cane plant roots at surface, 30 and 60 cm depth.

Simultaneous determination of major and trace elements in urinary calculi by microwave-assisted digestion and inductively coupled plasma atomic emission spectrometric analysis.

A procedure that permits the simultaneous determination of major, minor and trace elements in urinary calculi by inductively coupled plasma atomic emission spectrometry is described. The dissolution of samples is achieved with a commercial microwave oven using a mixture of nitric and perchloric acids. Ca, Mg, P, Al, Cu, Fe, K, Li, Mn, Mo, Na, Pb, S, Sr and Zn were determined in more than 100 South African stones.