Separation of trivalent rare earths plus sc(iii) from al,ga,in,tl, fe,ti, u and other elements by cation-exchange chromatography

A method is presented for the quantitative separation of the trivalent rare earths plus Sc(III) as a group from Al(III), Ga(III), In(III), Tl(III), Fc(III). Ti(IV), U(VI), Be(II). Mn(II), Co(II), Cu(II), Ni(II). Zn(II). and Cd(II). These elements can be eluted from a cation-exchange column with 1.75 N HCl, while the rare earth group elements are retained. Numerous other elements not investigated have low distribution coefficients in 1.75 N HCl and therefore should be separated by the same procedure; Th(IV) is retained by the column when the rare earths are elutcd with 3.0 N HCl. The only elements which partially accompany the rare earths plus Sc(III) are Zr(IV), Hf(IV), Sr(II), and Ba(II) ; these have to be separated by special procedures. The method is suitable for accurate reference analysis over a wide range of concentrations.     

Electrodeposition studies of rare earths

The combination of neutron activation analysis (NAA) and electrochemistry has been used to study the deposition behavior of rare earth elements, as it is reported that excepting La, no other rare earths are electrodeposited. The radiotracers of rare earth elements were electrolyzed in an aqueous medium on a graphite electrode by varying the voltage and time of electrodeposition, thereby optimizing the final experimental conditions for quantitative deposition of rare earth elements. The observations are reported in this work.     

Activation analysis of rare earths : The determination of rare earths in minerals by the single comparator technique

The determination of rare earths in minerals by activation analysis is described. The rare earths are separated as a group from the bulk of the material before irradiation. After irradiation the rare earths are separated from each other by gradient elution with ammonium α-hydroxyisobutyrate on a cation-exchange column. The elements are determined by the single comparator technique. This method permits a practical application of activation analysis to the routine determination of rare earths in complex matrices,     

In-situ micro-analysis of platinum and rare earths in ferromanganese crusts by laser ablation-ICP-MS (LAICPMS)

A 500 mJ Nd: YAG laser coupled to an inductively coupled plasma mass spectrometer (ICPMS) has been used for the direct determination of platinum (Pt) and the rare earth elements (REE) in concentration micro-profiles through ferromanganese crusts from the South Pacific. The instrument has been calibrated with briquetted powder pellets of U.S.G.S. reference materials NOD-A-1 and NOD-P-1. Linear calibration curves including the origin have been obtained for all elements of interest. An external calibration strategy has been developed which also accounted for variations in instrument response. The precision of the LA-ICP-MS measurements in this matrix has been 4–5% for platinum and <4% for the rare earths. Platinum concentrations have varied from 150 ng g^–1 to 500 ng g^–1 through the analysed microprofile. Two major peak areas in the platinum concentration profile have correlated roughly with cerium values and with changes in the normalised REE pattern: an enrichment of Pt coincides with a pronounced positive cerium anomaly and with an enrichment of the heavy REE relative to the light REE.     

Activation analysis of rare earths : Separation of rare earths from accompanying elements

A scheme for the separation of rare-earth elements from gadolinite and tantalocolumbite minerals is discussed. The possibility of interference from traces of nonseparated elements in the subsequent separation of rare-earth elements from each other by cation exchange with α-hydroxyisobutyrate as the eluting agent is investigated.     

Comparative methods for determination of rare earths in geological and mineral samples

Particle induced X-ray emission (PIXE) has been used for the quantitative analysis of rare earth elements (REE) in thick targets prepared from geological and mineral samples. Measurements were made with 1 and 3 MeV proton beams. For comparison, determination of the same elements was made by X-ray fluorescence (XRF) using a²⁴¹Am annular source. Minimal detectable limits (MDL) have been estimated for the two situations. Neutron activation analysis (NAA) has also been used for the determination of REE at the ppm level.     

Separation of tervalent rare earths and scandium from aluminium, iron(iii), titanium(iv), and other elements by cation-exchange chromatography in hydrochloric acid-ethanol

Tervalent rare earths and Sc are separated from the silicate-forming elements Al, Fe(III), Mg and Ti(IV), and also from Mn(II), U(VI), Be, Ga, In(III), Tl(III), Bi(III), Ni, Zn, Cu(II), Cd and Pb by cation-exchange chromatography. The other elements are eluted with 3.0 M HC1 containing 50% ethanol from a column of 60 ml of AG50W-X8 resin (200-400 mesh) while the rare earths are retained. Separation factors are larger than in aqueous hydrochloric acid. Th, Zr, Hf, Ba, Sr, Ca, K, and Rb are the only elements which accompany the rare earths group, but these can easily be separated by other methods which are described. Relevant distribution coefficients, elution curves and accurate results of quantitative separations of synthetic mixtures are presented.     

Determination of yttrium in rare earths by photon activation analysis

The determination of yttrium in the presence of large amounts of the rare earths by the thermal neutron reaction (89)Y(n, gamma)(90)Y is complicated because of frequent problems of sample self-shielding from major constituents of the sample, and the difficulty of separating (90)Y, a pure beta-emitter, from other elements which are very similar chemically. A non-destructive photon activation analysis method has been developed for this determination. Bremsstrahlung from a 35-muA beam of 35-MeV electrons induces the photonuclear reaction (89)Y(gamma, n)(88)Y. Optimum sensitivity is obtained by coincidence counting of the 0.90 and 1.84 MeV gamma-rays associated with the decay of (88)Y. The detection limit is less than 1 mug of yttrium.     

Neutron activation analysis of heavy rare earths

A method of nondestructive activation analysis of heavy rare earth elements (Sm−Lu) is described. Intensities of γ-ray peaks are compared to that of an internal reference after irradiations by both thermal and fission spectrum neutrons. Results are obtained from computer comparisons of peak areas. Work was performed at the Ames Laboratory of the U.S. Atomic Energy Commission. Contribution No. 2895.     

Analysis of low levels of rare earths by radiochemical neutron activation analysis

A procedure for the radiochemical neutron-activation analysis for the rare earth elements (REE) involves the separation of the REE as a group by rapid ion-exchange methods and determination of yields by reactivation or by energy dispersive X-ray fluorescence (EDXRF) spectrometry. The U. S. Geological Survey (USGS) standard rocks, BCR-1 and AGV-1, were analyzed to determine the precision and accuracy of the method. We found that the precision was ±5–10% on the basis of replicate analysis and that, in general the accuracy was within ±5% of accepted values for most REE. Data for USGS standard rocks BIR-1 (Icelandic basalt) and DNC-1 (North Carolina diabase) are also presented.     

Trace elements in land plants: Concentration ranges and accumulators of rare earths,Ba, Ra,Mn, Fe,Co and heavy halogens

More than 2000 samales of land plant leaves, mostly of tree, have been analyzed by neutron activation analysis in order to find out macroscopic relations between distributions of chemical elements in plants and soil characteristics. The distributions of the elements in plants were also examined from the view point of botanical taxonomy or phylogeny. New species which accumulate Co, rare earths, Ba, Ra, heavy halogens and some other elements have been found. Capability or potentiality for accumulating elements could be related to higher ranks of taxonomy, that is, genus or family. The nature of soil is also found to have profound effects on the extent of accumulation of elements in plants.     

Determination of trace elements in manganese metal and compounds by ion-exchange chromatography and atomic absorption spectrometry : part 2. Determination of Bi,Cd, In,Zn, Pb,Fe(III), Ga,Cu(II), Co and U(VI)

Traces of the specified elements are separated from 1 g of manganese (II), using a 30- g column of AG50W-X8 cation-exchange resin and mixtures of hydrochloric acid and acetone as eluents. The trace elements are separated into three groups and are determined by atomic absorption spectrometry, except uranium for which spectrophotometry is used. Recoveries for 10 μg amounts (20 μg for gallium) vary between 94% (for gallium) and 103% (for uranium). A combined elution curve, results for the analysis of synthetic mixtures and for the determination of ten trace elements in samples of manganese metal, chloride and dioxide are presented.     

Spectrographic determination of the rare earths in high-purity graphite

A spectrographic method has been developed for determination of the rare-earth elements in graphite. The rare earths are concentrated from ignited graphite on a calcium base. The impurities (Fe, V, Mn, Al, Ti) associated with the rare earths are separated by precipitation of the rare earths as hydroxides in the presence of Fe as a carrier, followed by precipitation of the rare earths as oxalates in the presence of Ca carrier. The mixture of calcium and rare-earth oxides obtained after ignition of the corresponding oxalates is mixed with graphite in 1:1 ratio and excited in a 15-A d.c. arc, with Nd as internal standard. The concentration ranges of determination are as follows: 0.006-0.125 ppm for Eu, 0.006-0.25 ppm for Gd, 0.006-0.06 ppm for Dy, 0.06-0.5 ppm for Sm. This sensitivity is achieved with 35-g samples of graphite. Higher enrichment factors are needed in order to enhance the sensitivity of the method.     

Chemical characterization of ancient potteries from Himera and Pestavecchia necropolis (Sicily, Italy) by Inductively Coupled Plasma–Optical Emission Spectrometry (ICP–OES)

Thirty-eight samples of pottery were analyzed for determining chemical composition in order to establish their provenance. The potteries tested in the present research come from Himera and Pestavecchia archaeological sites. After digestion in microwave oven, the samples have been analyzed for fourteen minor elements (Ba, Cd, Co, Cr, Cu, Ga, Li, Mn, Ni, Pb, Sr, Ti, Tl, and Zn) and six major elements (Al, Ca, Fe, K, Mg, and Na). Chemical analysis was carried out by Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP–OES). The most abundant minor elements are Cr, Ba and Ni. Cr concentration ranged from 66 to 3635 mg kg^{− 1}, Ba concentration ranged from 388 to 2677 mg kg^{− 1} and Ni concentration ranged from 35 to 1758 mg kg^{− 1}. The relative standard deviation (RSD) of the replicates on the concentrations of analyzed metals ranged from 0.07% to 14%.The aim of this study is to assign the local or non-local provenance of the examined potteries, in particular validating and clarifying archaeological hypothesis based on the simple visual examination and stylistic characterization of ceramic objects. Principal component analysis performed on the dataset, together with the application of cluster technique and non statistical analysis, allowed the identification of three main groups of samples and a lonely one (R 97). In particular, sample R 97 shows high Cr concentration (3635 mg kg^{− 1}) and high Ni concentration (1758 mg kg^{− 1}), typical of Corinthian pottery. The results of chemical analysis show that the stylistic features are not always sufficient to correctly identify the origin of a ceramic object.     

The determination of rare earths in yttrium oxide by means of a preconcentration technique and Ge(Li) gamma-spectrometry

Before preconcentration the yttrium matrix is separated from the lanthanides by means of cation- and/or anion-exchange. The rare earth elements are then concentrated by coprecipitation with 5.0 mg of iron as Fe(OH) in quartz centrifuge tubes. The dehydrated Fe-REE mixture is then irradiated and counted, without any further major manipulations, by means of Ge(Li) gamma-spectrometry, the⁵⁹Fe activity acting as a f' x monitor and as an internal standard.     

Prompt gamma-ray yields from proton bombardment of transition elements (Ti to Zn)

Gamma-ray yields from bombardment with protons of thick targets of Ti, V, Mn, Cr, Fe, Co, Ni, Cu and Zn are tabulated for proton energies ranging between 0.6 and 3.2 MeV. The applications of these reactions for quantitative analysis of these chemical elements are discussed. The sensitivity of this technique of analysis is poorer than the PIXE method for these transition elements, but is sufficient for rapid and accurate quantitative analysis of alloys when elements are present in concentrations down to 1%. The knowledge of the γ-ray energies and intensities produced by the bombardment of these elements with protons is also necessary for solving interferences with several γ-rays induced in light elements, for which the proton induced γ-ray technique is sensitive, without any correction for photon attenuation.     

Characteristic x-rays from (n, γ) products and their utilization in activation analysis

The possibility of using characteristic X-rays from radioactive elements in activation analysis was investigated during this work with particular emphasis on (n, γ) products. At least 27 of 56 elements investigated during this work were found to yield themselves to activation analysis employing characteristic X-rays from electron capture or internal conversion processes during isomeric transition. In presenting the results, a survey made of several elements and the limits of detection of 21 elements have been reported. Specific applications of this method were studied for the analysis of copper in a variety of samples (ores, minerals, steels, spent lubricants and human blood). The results of this investigation show that the use of characteristic X-rays in activation analysis has several advantages because the energies of these radiations are closely related to the periodicity of the elements themselves. Presented at the First IMR International Symposium, Trace Characterization—Chemical and Physical, National Bureau of Standards, USA (October, 1966).     

Quantitative separation of gallium from zinc, copper, indium, iron(III) and other elements by cation-exchange chromatography in hydrobromic acid-acetone medium

Gallium can be separated from Zn, Cu(II), In, Cd, Pb(II), Bi(III), Au(III), Pt(IV), Pd(II), Tl(III), Sn(IV) and Fe(III) by elution of these elements with 0.50M hydrobromic acid in 80% acetone medium, from a column of AG50W-X4 cation-exchange resin. Gallium is retained and can be eluted with 3M hydrochloric acid. Separations are sharp and quantitative except for iron(III) which shows extensive tailing. With 0.20M hydrobromic acid in 80% acetone as eluting agent, all the species above except iron(III) and copper(II) can be separated from gallium with very large separation factors. Only a 1-g resin column and small elution volumes are required to separate trace amounts and up to 0.5 mmole of gallium from more than 1 g of zinc or the other elements. Hg(II), Rh(III), Ir(IV), Se(IV), Ge(IV), As(III) and Sb(III) have not been investigated, but should be separated together with zinc according to their known distribution coefficients. Relevant elution curves, results for the analysis of synthetic mixtures and for amounts of some elements remaining in the gallium fraction are presented.     

Preconcentration of rare earths in geological materials with ascorbic acid for their neutron activation analysis

The potential use of ascorbic acid as a complexing reagent in the separation and preconcentration of rare earth elements (REE) in geological materials in a suitable solid matrix has been demonstrated. Traces of REE from some USGS standard rock samples, viz., GSP-1, G-2, AGV-1 and PCC-1, have been separated after acid dissolution in two ways: (1) by ion exchange chromatography on Dowex 50×8 column and Na-ascorbate as eluent and (2) by direct complexation with ascorbic acid under specific experimental conditions. The separated REE were coprecipitated with the non isotopic diluent, calcium fluoride, before neutron activation analysis. Radiometric determinations showed that the overall recovery of REE in both cases was practically quantitative.     

Complexation of aluminium, yttrium, lanthanum and lanthanides with 4-(2-pyridylazo)resorcinol (par)

The sensitive reactions between 4-(2-pyridylazo)resorcinol (PAR) and yttrium, lanthanum and the lanthanides can be used for the spectrophotometric determination of these elements. The method has no advantage over other methods for the determination of aluminium and lanthanum. Only M(PAR)H and M(PAR) complexes are formed in solutions where the molarity of the metal ion is greater than or nearly equal to the molarity of the ligand at pH < 7-5. If there is molar excess of PAR, 1:2 complexes may be formed but this is certain only for the yttrium-PAR system. Errors in analysis may result from the simultaneous occurrence of optically different complexes; close control of pH and reagent concentration is essential. Optical and equilibrium data are given for the systems investigated.