Determination of rare-earth elements in rock samples by neutron activation analysis with a lithium-drifted germanium detector after chemical group-separation

A lithium-drifted germanium detector combined with chemical group-separation has been utilized for the determination of rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb and Lu) in rock samples by neutron activation. This procedure has the advantage of a low background level which cannot be attained in the non-destructive method. The combination of the Ge(Li) detector and chemical group-separation also offers a distinct simplification in the correction of contributions from other nuclides. For optimum utility of a Ge(Li) detector in neutron activation analysis, chemical group-separations are recommended.     

Separation of transplutonium and rare-earth elements by extraction with HDEHP from DTPA solutions

The extraction behaviour of Am, Cm, Bk, Cf, Es, La, Ce, Pr, Pm, Sm, Eu, Gd, Ho, Yb and Lu in the system HDEHP—DTPA in lactic acid has been studied from the point of view of group separation of the transplutonium and rare-earth elements. Optimum separation conditions have been found on the basis of the results obtained. Some test separations of transplutonium elements from rare-earth fission products have been carried out in real solutions by extraction chromatography. It has been shown that this method can be used successfully for the analytical determination of transplutonium elements as well as for recovery of the latter from irradiated samples.     

Determination of rare earths and other trace elements in samples of Antarctica by neutron activation analysis

The concentrations of REE and other trace elements have been determined in samples of Antarctica by Instrumental Neutron Activation Analysis (INAA). The samples were collected from the West Lake area near Great Wall Station. The samples include sediment, residual plants, rock and soil taken from the bottom of the lake to 3.4 m deep. The amounts of samples were very rare. In order to get more information, reactor NAA using both short and long irradiations with K₀ standardization has been adopted. Nine rare-earth elements (REE) namely La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, and Lu as well as other trace elements (As, Au, Ba, Br, Co, Cr, Hf, Sc, Se, Th, V, Zn) have been determined. The concentrations and distribution patterns of REE in the samples have been given.     

Rare earth analysis of usgs rocks SCo-1 and STM-1

Twelve of the rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu) were determined by radiochemical neutron activation analysis on two samples per bottle from two bottles each of SCo-1 (Cody shale) and STM-1 (nepheline syenite). The data provide no evidence for differences in REE concentrations between bottles of the same rock. Values of the concentrations for most of the REE in SCo-1 and STM-1, based on the samples analyzed, have been established to better than ±10% overall uncertainty, with a 95% confidence limit.     

Color-Changing Sparks from Rare Earth Metal Powders

Commonly, sparks emit light according to the well-known black (gray) body radiation. Recently, we reported on color-changing sparks based on erbium powder, which switch their light emission between black body emission (surface combustion) and element-specific emission (vapor phase combustion). Herein, we investigated the spark formation from the adjacent rare-earth elements. The corresponding boiling points are significantly below (Yb, Sm, Tm) or above (Y, Lu) the boiling point of Er. While Yb and Sm evaporate too fast to form longer sparks, Y, Lu and Tm form color-changing sparks with varying length of the element-specific emission phase. The sparks were investigated by time-resolved emission spectroscopy, long-time exposures, and NIR/MIR imaging. The same basic pyrotechnic formulation containing one of these metal powders reveals a strongly differing burning behavior depending on the boiling point of the metal. The burning characteristics change from a green strobe (Yb) to intense colorful crackling (Tm) and finally a sparkling fountain with long-flying sparks (Lu, Y, Er).     

Determination of rare-earth eleemnts in rock samples by neutron activation analysis

A Ge(Li) detector combined with cation exchange separation has been used for the determination of 12 rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu) in rock samples by neutron activation analysis. After purification by the conventional hydroxide-fluoride precipitation, the rare-earth elements are separated into two fractions, light (La-Tb) and heavy (Ho-Lu), by EDTA cation exchange, and the γ-activities of the two fractions are measured by a Ge(Li) detector. The heavy rare-earths, such as Ho, Er, and Tm, can be easily γ-counted without serious interference from the intense Compton background and photopeaks due to the light rare-earths such as¹⁴⁰La,¹⁵³Sm,¹⁵²Eu, and¹⁶⁰Tb. The chemical yields (60%) for the individual rare-earths are determined by a reactivation technique. The results obtained for the U.S. Geological Survey standard rocks G-1 and W-1 are compared with the previously reported data.     

Determination of rare earth elements in recent and fossil shells by radiochemical neutron activation analysis

Seven rare earth elements (La, Ce, Sm, Eu, Tb, Yb and Lu) in marine shell samples were determined by neutron activation analysis. In order to measure γ-ray using a Ge(Li) detector without serious interference from the intense Compton background from²⁴Na, a simple radiochemical separation was performed by a co-precipitation method with hydrated iron(III) oxide. The chemical yields for shell samples (91–99%) were determined by a re-activation technique for Gd and Yb. The interference from the²³⁵U(n, fission) reaction was corrected for determination of La and Ce. The data obtained in this study showed the behavior of rare earth elements in shells during the process of fossilization.     

Effect of rare-earth component of the RE/Ni catalyst on the formation and nanostructure of single-walled carbon nanotubes

A systematic experimental study has been carried out on the efficiency of bimetallic catalysts based on Ni and the rare-earth elements Y, La, Ce, Nd, Gd, Tb, Dy, Ho, Er, and Lu (group A) and Eu, Sm, Yb, and Tm (group B) in the synthesis of single-walled carbon nanotubes (SWNTs). The two groups give quite different results when analyzed by a combination of SEM/TEM and Raman and UV-NIR spectroscopies. The elements in group A have an obvious catalytic effect and increase the yield of SWNTs dramatically, whereas those in group B are not efficient catalysts. The diameter distribution of the synthesized SWNTs was also affected by the rare-earth element used. For group A metals, there is a tendency that the fraction of small-diameter tubes decreases with decreasing ionic radius of the rare-earth element used. EDX and X-ray analyses indicate that group A metals deposit on the cathode deposits and form rare-earth carbides, whereas no group B metals are found in cathode deposits, except for a small amount of Tm present in the form of thulium carbide. Further analysis indicates that there is a very strong correlation between the ability to form rare-earth carbides and the catalytic efficiency for the formation of SWNTs.     

Determination of rare earths and thorium in apatites by thermal and epithermal neutron-activation analysis

A procedure is described for the non-destructive determination of Na, Mn, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu and Th in apatites by thermal and epithermal neutron-activation of independent portions of the material. The method was applied to three apatites with different contents. The precision obtained was better than +/-5% for La, Ce, Sm, Eu, Gd, Tb and Dy and +/-20% for Yb, Nd, Ho, Er and Lu for an apatite with a total rare-earth oxide content of the order of 1%. Determination of Ce, Tb and Yb could only be carried out with thermal neutron-activation analysis, while Gd, Ho and Er could only be determined after irradiation with epithermal neutrons.     

Determination of rare earth elements in international geochemical reference materials

Instrumental neutron activation analysis of eight geochemical standard materials has been carried-out and the concentration values of nine rare-earth elements (REE) (La, Ce, Nd, Sm, Eu, Gd, Tb, Yb and Lu) have been determined. Discussion of some problems in the determination of those elements is presented and the results obtained are compared with literature values. In general, good agreement with available data was obtained but discrepancies with concentration values for a number of elements in some of these standards are discussed.     

Determination of rare earth impurities in high purity europium oxide by inductively coupled plasma-mass spectrometry and evaluation of concentration values for europium oxide standard material

Direct determinations of 13 rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Lu and Y) in high purity europium oxide by inductively coupled plasma mass spectrometry (ICP-MS) have been reported. The operating parameters of the instrument were optimized and the spectral interferences and the matrix effects were investigated. Using Ga or Rh as the internal standard can eliminate most of the matrix effects. The detection limits (3 sigma, n=10, integral time=1s) are 0.013-0.085 ng mL(-1) and the reproducibility (n=11) is 0.9-3%. The recoveries of spiking samples are 80-108%. Europium oxide standard material was made and its concentration values were evaluated by various techniques from 10 collaborating laboratories. By comparison of the results of ICP-MS with the results of other techniques, we have validated that ICP-MS is an accurate and reliable technique for analysis of ultratrace impurities in high purity rare earth matrix.     

Elemental analysis of soils from Toshki by using instrumental neutron activation analysis techniques

Instrumental neutron activation analysis has allowed performing a complete characterization of the chemical composition of thirty soil samples soil samples from ten locations collected from the Toshki area in Upper Egypt. The samples were irradiated with thermal neutrons at the Mainz TRIGA research reactor. Gamma-ray spectra were recorded using a high efficiency HPGe detector to determine the contents of major, minor and trace elements in these samples. As a result of the analysis, altogether 32 elements were identified qualitatively and quantitatively. These elements are: Al, As, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Ga, Hf, K, La, Lu, Mg, Mn, Na, Nb, Nd, Rb, Sc, Sm, Sn, Ta, Ti, Th, U, V, Yb, Zn and Zr. In several cases, X-ray fluorescence analysis was used for comparison. The results obtained for U and Th were compared with data reported in literature.     

Syntheses of rare-earth metal oxide nanotubes by the sol-gel method assisted with porous anodic aluminum oxide templates

In this paper, we report a versatile synthetic method of ordered rare-earth metal (RE) oxide nanotubes. RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction (XRD) have been employed to characterize the morphology and composition of the as-prepared nanotubes. It is found that as-prepared RE oxides evolve into bamboo-like nanotubes and entirely hollow nanotubes. A new possible formation mechanism of RE oxide nanotubes in the AAO channels is proposed. These high-quantity RE oxide nanotubes are expected to have promising applications in many areas such as luminescent materials, catalysts, magnets, etc.     

Interplay between Cu and Fe Valences in BaR(Cu0.5Fe0.5)2O5+δ Double Perovskites with R=Lu, Yb, Y, Eu, Sm, Nd, and Pr

We have conducted a systematic ⁵⁷Fe Mössbauer study on BaR(Cu_0.5Fe_0.5)₂O_5+δ double perovskites with various oxygen contents and rare-earth elements (R=Lu, Yb, Y, Eu, Sm, Nd, and Pr). In samples based on R=Lu, Yb, Y, Eu, Sm the oxygen content remained at δ≈0, upon reductive or oxidative heat treatments under normal pressure. The larger rare-earth elements, i.e. Nd or Pr, readily allowed for continuous oxygen content tuning up to δ≈0.3. By employing high-pressure heat treatments higher oxygen contents were achieved for all samples. The Néel temperature of the samples was found to decrease with increasing amounts of oxygen entering the lattice. In high-pressure oxygenated samples the decrease was less severe indicating that despite the incorporation of oxygen a large amount of Fe still remains in the high-spin trivalent state. By using charge-neutrality arguments together with the relative intensities of the Mössbauer spectral components the average valences of Fe and Cu were obtained. Oxygenation under normal pressure led to a corresponding increase of the valence of Fe, while Cu remained divalent. Upon high-pressure heat treatment equal amounts of Fe³⁺ and Cu²⁺ were found to be oxidized to Fe⁵⁺ and Cu³⁺, respectively.     

Studies on extracting solutions of endohedral rare-earth metallofullerenes by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Thirteen extracting solutions of rare-earth metallofullerenes containing La,Ce,Pr,Nd Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm and Yb respectively have been investigated by means of matrix-assisted laser desorpuon/ ionization time-of-flight mass spectrometry.The influences of the positive-ion/negative-ion mode,laser intensity,ma trix and mass discrimination to the analytical results are studied,based on which the optimal analytical conditions have been determined.The results show that the extracting solutions contain large quantities of rare-earth metallofullerenes besides empty fullerenes.On the basis of comparing their relative intensities,the different structure stabilities and solubilities of metallofullerenes with different rare-earth metals encapsulated into the fullerene cages,as well as some possible reasons to those differences,are discussed.     

Postmetallocene lanthanide-hydrido chemistry: A new family of complexes [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) supported by guanidinate ligands-synthesis, structure, and catalytic activity in olefin polymerization

The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single-crystal X-ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal-atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol(-1) atm(-1) h(-1), respectively).     

稀土元素R4OCl6四面体嵌合物的化学键研究

以SCC-DV-X,方法对Sm_4OCl_6、Eu_4OCl_6、Yb_4OCl_6和Gd_6N_2Cl_(12)等4个体系作了量化计算。结果表明,嵌入原子在四面体簇的合成中起决定性作用。体系6个骨架轨道中,3个是嵌入原子与稀土原子的成键轨道,另3个是稀土原子通过嵌入原子形成的弱键轨道。用Sm、Eu等元素能合成四面体嵌合物,与其价态较低有关,低价态使稀土元素d、f轨道收缩较少、成键能力增大。而富含f电子的Yb体系,4f为主要价轨道。     

Enrichment of rare-earth elements (REE) and Gd-DTPA in surface water samples by means of countercurrent chromatography (CCC)

An analytical scheme was developed for the determination of rare-earth elements and gadolinium diethylenetriaminepentaacetate (Gd-DTPA) in river water by ICP-MS. Since the concentration of Gd-DTPA and the rare-earth elements in river water is often lower than the limits of detection in quadrupole ICP-MS applying pneumatic nebulization, a preconcentration procedure is essential.In this work, the capabilities of countercurrent chromatography (CCC) for preconcentration of REE were investigated. For preconcentration ethylhexylphosphates as stationary phase had been used. Acidified aqueous samples (pH 2) and river water spiked with REE and Gd-DTPA were under study. The procedure was compared with solid phase extraction (SPE) using the same samples and ethylhexylphosphates as stationary phase. The recovery of the light and middle REE was found to be at about 100%, which was found to be more efficient than applying SPE. In contrast, the recovery rates for Yb and Lu were low (and poorly reproducible) using CCC (57% and 73%, respectively) while significant better results were obtained with SPE (89% and 84%, respectively).The recoveries of Gd applying Gd-DTPA were 80 ± 4% in the investigation of river water samples.     

57Fe Mössbauer spectroscopy of banded iron formations from eastern India

Samples of the mosses Hylocomium splendens and Pleurozium schreberi, collected in the summer of 1998, were used to study the atmospheric deposition of heavy metals and other toxic elements in the Chelyabinsk Region situated in the South Urals, one of the most heavily polluted industrial areas of the Russian Federation. Samples of natural soils were collected simultaneously with moss at the same 30 sites in order to investigate surface accumulation of heavy metals and to examine the correlation of elements in moss and soil samples in order to separate contributions from atmospheric deposition and from soil minerals. A total of 38 elements (Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Rb, Sr, Zr, Mo, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Hf, Ta, W, Au, Th, U) in soil and 33 elements Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Tb, Yb, Hf, Ta, W, Au, Th, U) were determined by epithermal neutron activation analysis. The elements Cu, Cd and Pb (in moss samples only) were obtained by atomic absorption spectrometry. VARIMAX rotated principal component analysis was used to identify and characterize different pollution sources and to point out the most polluted areas.     

Instrumentelle Aktivierungsanalyse an Lunarem Material

Lunar soil samples of the Luna 16 Luna 20 missions were analysed by neutron activation in a neutron generator and a nuclear reactor, respectively, and following gammaspectrometry by NaI(T1) and Ge(Li) detectors. By 14 MeV neutron activation there were determined the abundances of 5 major elements (O, Mg, Al, Si, Fe) and by reactor activation the abundances of 18 major and trace elements (Na, K, Sc, Cr, Mn, Fe, Co, Mo, La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, W, Th) and the detection limits of 4 additional elements (As, Rb, Sb, Cs). The standard rocks BM and GM of the ZGI were used as standards in the reactor activation analysis.