Inductively coupled plasma-atomic emission spectrometric determination of rare earth elements in geological materials

Inductively coupled plasma-atomic emission spectrometry (ICP-AES) has been applied to the determination of the rare earth elements (REE) lanthanum to lutetium (except terbium) in a range of geological materials. Group separation of the REE is carried out by sintering the sample with sodium peroxide to remove the bulk of the matrix, followed by fluoride precipitation with an yttrium carrier. This minimizes spectral interferences and provides sensitivities that are adequate for concentration levels around crustal abundances. The precision (2σ) is 3–5% for most of the elements and about 10% for some of the less abundant elements with concentrations that approach the limit of determination. Comparison of results obtained on a range of reference samples with literature values demonstrates the suitability of the procedures to provide rare earth abundance data for geochemical investigations.     

A one-pot process based on P44414Cl-HCl aqueous biphasic system for recovering rare earth elements from NdFeB permanent magnet

Recovering critical metals from secondary resources have attracted great interest recently.In this work,a green one-pot leaching-extraction process based on tributyl（tetradecyl）phosphonium chloride (P₄₄₄₁₄Cl)aqueous biphasic system （ABS） was developed to efficiently recover rare earth elements （REEs） from Nd Fe B permanent magnet.The reaction process,phase separation mechanism,and operation conditions were thoroughly investigated.It is found that the P₄₄₄₁₄Cl-HCl ABS showed...     

Determination of rare earth elements by radioisotope induced X-ray emission spectroscopy

A ring-shaped, 10⁹ Bq²⁴¹Am radioisotope source was used for the excitation of K-shell X-rays from rare earth elements (56<Z<64), present in powdered geological material. In order to improve the efficiency of the measurement of these elements in the concentration range down to 10 ppm, the optimum geometry of the system was found. The results obtained are presented and discussed.     

True detection limit of rare earth elements in atomic emission analysis with an arc two-jet plasmatron

The “true detection limit” C_L,true was measured by a method proposed by Boumans et al. for 10 prominent lines of La, Ce, Pr, Nd and Sm, the most abundant rare earth elements (REEs) in geological samples. It is demonstrated how spectral interferences can increase of C_L,true. The spectra were excited in an argon arc plasma jet with evaporation powders of five complex natural samples. The data show that there is a significant increase of C_L,true in real samples containing large concentrations of such elements as Ti, Zr, Cr, Nb, Ta and REEs emitting complex spectra. Received: 17 June 1997 / Revised: 20 October 1997 / Accepted: 26 October 1997     

True detection limit of rare earth elements in atomic emission analysis with an arc two-jet plasmatron

The “true detection limit” C_L,true was measured by a method proposed by Boumans et al. for 10 prominent lines of La, Ce, Pr, Nd and Sm, the most abundant rare earth elements (REEs) in geological samples. It is demonstrated how spectral interferences can increase of C_L,true. The spectra were excited in an argon arc plasma jet with evaporation powders of five complex natural samples. The data show that there is a significant increase of C_L,true in real samples containing large concentrations of such elements as Ti, Zr, Cr, Nb, Ta and REEs emitting complex spectra.     

X-ray fluorescence spectrometric analysis of erbium oxide for rare earth impurities

An X-ray fluorescence spectrometric method has been developed for the analysis of high purity erbium oxide for the determination of yttrium, terbium, dysprosium, holmium, thulium, ytterbium and lutetium oxide impurities in the concentration range 0.005–0.1%. The sample is taken in oxalate form, mixed with a binder (boric acid) in the weight ratio 31 and made into a double layer pellet. The analysis is done on a Philips PW 1220 X-ray fluorescence spectrometer using a LiF (200) analyzing crystal. The precision at each concentration of the standards and theoretical minimum detection limit for each element has been calculated.     

辉光放电质谱法测定稀土矿中的15种稀土元素

利用高纯铜粉与稀土矿石粉末均匀混合压片制样.混合15种高纯稀土氧化物制样建立标准工作曲线,校正15种稀土元素相对灵敏度因子,再进行定量分析.结果 表明,稀土元素工作曲线的线性方程相关系数R2均大于0.996,相对标准偏差(RSD)小于5％,满足定量分析要求.测定结果与电感耦合等离子体质谱法(ICP-MS)和电感耦合等离...     

Preconcentration and atomic spectrometric determination of rare earth elements (REEs) in natural water samples by inductively coupled plasma atomic emission spectrometry

The usage of a variety of sorbents has been shown as promising matrix removal/preconcentration strategies for the determination of rare earth elements (REEs) in various natural water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES). The sorption efficiency of various zeolites (clinoptilolite, mordenite, zeolite Y, zeolite Beta), ion-exchangers (Amberlite CG-120, Amberlite IR-120, Rexyn 101, Dowex 50W X18) and chelating resins (Muromac, Chelex 100, Amberlite IRC-718) towards REEs was investigated in terms of solution pH, shaking time and sorbent amount. The results have shown that most of the materials can take up REEs at a wide pH range. The experiments were continued with clinoptilolite, zeolite Y and Chelex 100 and it was demonstrated that all three materials displayed very fast kinetics for REE sorption (higher than 96% in 1 min). Desorption from the sorbents was realized with 2.0 M HNO₃ for clinoptilolite and 0.1 M HNO₃ for zeolite Y and Chelex 100. Only the lower concentration range (0.01-2.0 mg l⁻¹) of matrix-matched standards were used in quantitation although the calibration graphs were linear at least up to 10.0 mg l⁻¹ for all REEs studied. The limit of detection (3 s) without preconcentration was 0.1, 1.0, and 0.2 μg l⁻¹ for Eu, La, and Yb, respectively. The validity of the method with the selected sorbents was checked through spike recovery experiments.     

Determination of rare earth elements in mineral raw materials and rare earth industry products by neutron activation analysis

To determine REE in mineral raw materials, high purity RE metals and their compounds, neutron activation analysis with extraction chromatographic REE separation has been developed. Combination of the developed RE extraction and separation procedures with subsequent -spectrometric analysis of the RE radionuclides allows to determine their content with the lower detection limit –10^–5–10^–8%. The relative standard deviation is 0.2–0.3.     

Determination of aluminium, scandium and rare earth elements by emission flame spectrometry

Summary Emission spectrometry in nitrous oxide-acetylene flames in combination with a highly resolving double monochromator and sensitive detecting system enables simple, sensitive and selective determinations of aluminium, scandium and all rare earth elements with exception of cerium in complicated matrices. Calibration plots are linear for a large concentration interval ( 100 g·ml^–1), detection limits are in ng · ml^–1 level and RSD does not exceed 3% on the optimal concentration level of the particular element. The determination of Al, Sc, Eu and Yb showed particular advantages as to methods using ICP-spectrometry.

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Bestimmung von Aluminium, Scandium und Seltenen Erden durch Emissions-Flammenspektrometrie

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Determination of rare earth elements in phosphorites by neutron activation analysis

Fourty three phosphorite rocks from Western Iraq were analyzed for eleven REE as well as uranium by NAA using IRT Reactor with a neutron flux of 2.3·10¹³ n·cm^–2·s^–1. The gamma activity from each sample was counted with a Ge(Li) and well-type HPGe, each detector connected to an on-line computer. Uranium fission products and different reaction interferences were assessed and allowed for. The results were also checked against international reference materials.     

Radiochemical neutron activation analysis of rare earth elements in peridotitic rocks

The understanding of the geochemistry of basalt petrogenesis and the nature of the upper mantle requires the examination of such rocks as peridotites which in many cases are thought to represent upper mantle material. The mineralogical composition of peridotitic rocks in such that they accommodate large proportions of such trace elements as the transition elements but very small amounts of the rare earths and hygromagmaphile elements. The last two groups are often able to provide a large amount of information leading to petrogenetic models. Owing to the extremely low concentrations of the REE in peridotitic rocks it is necessary to separate them from other elements which will interfere with their precise determination. We have used a radiochemical neutron activation analytical method which is adapted from various published methods. It involves a post-irradiation sample fusion, two separate ion-exchange chromatographic stages and finally a fluoride precipitation. The RNAA procedure is capable of providing very precise REE data for perioditic samples and we have used it for the analysis of such rocks from several geodynamic environments.     

Proton induced X-ray emission (PIXE) analysis on thick samples exemplified on the rare earth elements

Summary A semiempirical procedure is developed for the calculation of the signal intensity for thick sample PIXE experiments. The calculated X-ray intensity emerged out of a thick sample is factorized into the overall produced intensity within a thick sample and an effective transmission factor for the X-ray self-absorption.The accuracy of this procedure is limited by the reliability of the experimental input parameters to about ±25%.We find as an important result of this study: The signal intensity is calculated as a function of the various experimental parameters, i.e. proton energy and sample composition including interelement- and matrix effects. This function is presented as a closed equation, which can be applied very easily, i.e. without large scale computers, to calculate the sample elemental concentration. The mass absorption coefficient of the sample most strongly influences the effective transmission term.Enhancement corrections are calculated for additional interfering rare earth elements j. No significant interelement-effects appear at concentrations c _j 2 weight%, where analysis by PIXE may be interesting. The calculated results agree well with experimental data for the rare earth elements in different matrices.Dedicated to Karl Gleu on the occasion of his 80th birthday     

Proton induced X-ray emission (PIXE) analysis on thick samples exemplified on the rare earth elements

Summary Proton Induced X-ray Emission (PIXE) analysis calibration curves (i.e. intensity of analytical signal as a function of concentration c _i ) are determined on thick solid samples with rare earth element concentrations c _i 0.3g/g. The calibration curves are linear at low concentrations c _i 0.3 weight% at proton energies 1.7E _PO 2.5MeV. The precision of the quantitative analysis amounts to ±4 %. The shape of the curves at higher concentrations may be understood by simple qualitative considerations.Distortions by interelement-effects caused by additional other rare earth elements j in concentrations c _j 2 weight% are not detectable. The agreement between the experimental and the calculated intensities for different matrices is very good at low concentrations c _i 1 weight% of analyte.

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Protoneninduzierte Röntgenspektralanalyse (PIXE) dicker Proben am Beispiel der Seltenen ErdelementeI. Experimentelle Bestimmung von Eichkurven, Genauigkeit und Matrixeffekten

Zusammenfassung Es werden Eichkurven (d. h. Intensität des Analysensignals in Abhängigkeit von der Analytkonzentration c _i ) für die protoneninduzierte Röntgenspektralanalyse (PIXE) dicker Festkörperproben mit Seltenen Erdelementen im Konzentrationsbereich c _i 0,3g/g aufgenommen. Diese Eichkurven verlaufen bei niedrigen Konzentrationen c _i 0,3 Gewichts-% und Protonenenergien 1,7E_PO2,5MeV linear. Die Genauigkeit der quantitativen Analyse beträgt ±4 %. Der Verlauf der Eichkurven bei höheren Konzentrationen kann durch einfache qualitative Überlegungen verstanden werden.Es werden keine Störungen durch Interelementeffekte beobachtet, die durch zusätzliche andere Seltene Erdelemente j in Konzentrationen c _j 2 Gewichts-% hervorgerufen werden. Die Übereinstimmung der experimentellen und berechneten Intensitäten für verschiedene Matrices ist bei niedrigen Analytkonzentrationen c _i 1 Gewichts-% sehr gut.

Dedicated to Karl Gleu at the occasion of his 80th birthday     

Polyphenylcyclopentadienyl complexes of rare earth elements

Reaction of LnCl₃(thf) _x (Ln = Y, La, Yb, Lu) with NaCp^Phn (Cp^Phn = 1,3-Ph₂C₅H₃, 1,2,4-Ph₃C₅H₂, Ph₄C₅H) leads to formation of monocyclopentadienyl dichloride complexes Yb(Ph₂C₅H₃)Cl₂(thf)₃ (1), Ln(Ph₃C₅H₂)Cl₂(thf)₃ (Ln = Y (2), Lu (3)), La(Ph₄C₅H)Cl₂(thf)₃ (4). Molecular structures of 1, 2 and the polynuclear complex [(Ph₃C₅H₂)₃Lu₄(Cl)₇(O)(thf)₃] (5), which is a partial hydrolysis product of 3, have been established by the X-ray method.     

Determination of boron in steel by an ICP emission spectrometric technique

Summary A method was developed for the emission spectrometric determination of boron in steel using ICP excitation. Interfering effects of the matrix are avoided by pyrohydrolytic separation of boron. It is possible to determine boron from 1 mg/kg upwards.