Precise trace rare earth analysis by radiochemical neutron activation

A rare earth group separation scheme followed by normal Ge(Li), low energy photon detector (LEPD), and Ge(Li)−NaI(Tl) coincidence-noncoincidence spectrometry significantly enhances the detection sensitivity of individual rare earth elements (REE) at or below the ppb level. Based on the selected γ-ray energies, normal Ge(Li) counting is favored for¹⁴⁰La,¹⁷⁰Tb and¹⁶⁹Yb; LEPD is favored for low γ-ray energies of¹⁴⁷Nd,¹⁵³Sm,¹⁶⁶Ho and¹⁶⁹Yb; and noncoincidence counting is favored for¹⁴¹Ce,¹⁴³Ce,¹⁴²Pr,¹⁵³Sm,¹⁷¹Er and¹⁷⁵Yb. The detection of radionuclides^152mEu,¹⁵⁹Gd and¹⁷⁷Lu is equally sensitive by normal Ge(Li) and noncoincidence counting;¹⁵²Eu is equally sensitive by LEPD and normal Ge(Li); and¹⁵³Gd and¹⁷⁰Tm is equally favored by all the counting modes. Overall, noncoincidence counting is favored for most of the REE. Precise measurements of the REE were made in geological and biological standards. Prepared for the U.S. Department of Energy under Contract DE-AC06-76RLO 1830.     

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.     

Determination of dysprosium,europium, samarium and gadolinium in yttrium oxide of high purity by means of neutron activation analysis

Radioactivation analysis is the only method which allows the determination of individual rare earth element impurities in rare earth elements of high purity. The determination of dysprosium, europium, samarium and gadolinium in yttrium oxide is complicated by the short half-life of¹⁶⁵Dy (138 min.) and by the difficulty of separating traces of these elements from the matrix. A chromatographic method has been developed, for the separation of traces of Dy, Eu, Sm and Gd from ytrium, on a column packed with anion exchangerAV-17, by means of elution with 0.1N and 0.3M solutions of EDTA-sodium salt, followed by the separation of the mixture of the rare earth impurities on a microcolumn of cation exchangerKU-2, using a 0.17M solution of ammonium α-hydroxyisobutyrate as the eluent. The sensitivity of the determination of Dy, in the case of irradiating 10 mg of Y₂O₃ with a flux of 1.2·10¹³ n·cm⁻²·sec⁻¹ for 5 min. was 1·10⁻⁷%; the corresponding values for Sm, Eu and Gd, when irradiating a 100 mg sample of Y₂O₃ for 20 hours with the same flux, were 2·10⁻⁷%, 1·10⁻⁸% and 5·10⁻⁶%, respectively.     

Neutron activation analysis of rare earth impurities in metallic uranium

A method with a sensitivity of 2·10⁻⁷ to 1·10⁻¹⁰% has been developed for determining Yb, Ho, Dy, Gd, Eu, Sm and La impurities in metallic uranium by means of neutron activation. The method is based on a preliminary chromatographic separation of the total amount of rare earth elements from uranium by passing the solution in sulphuric acid through KU-2 cation exchange resin and eluting the traces of uranium retained by the resin with a solution of ascorbic acid. The rare earth impurities are then eluted from the resin with 4–5N HCl, evaporated, and irradiated for 20 hours with a neutron flux of 1.2·10¹³ n·cm⁻²·sec⁻¹. Subsequently the traces of the rare earth elements are co-precipitated with Fe(OH)₃, dissolved in concentrated HCl and separated from the iron and other impurities by passing the solution through Dowex 1X8 anion exchange resin in the chloride form. The individual rare earth elements are then separated from each other using KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutyrate as the eluant.     

Evaluation of the radioactivity in concrete from accelerator facilities

For evaluation of radioactivity induced in the concrete samples from accelerator facilities, the residual radioactivity in concrete sample, collected from seven accelerator facilities, was determined by γ-ray spectrometry. The tritium was extracted by the heating method using an IR furnace, and measured with a liquid scintillation counter. It was found that the major radioisotopes activated mainly by neutrons in the concrete samples were ¹⁵²Eu, ⁶⁰Co, ¹³⁴Cs and ³H. The concentrations of radioactivities induced by thermal neutron capture are the highest at a depth of 10 cm in the concrete wall. The correlation between tritium, ⁶⁰Co and ¹⁵²Eu activity was investigated by measuring many concrete samples for seven accelerator facilities. The results indicate that their activities are strongly correlated with each other. So it would also be concluded that the total activity in shielding concrete could be estimated on the basis of the activities of ⁶⁰Co and ¹⁵²Eu.     

Retention studies following (n, γ) activation of rare earth bromates

The initial retentions (at ∼20°C) of (n, γ) activated rare earth bromates were studied using a²⁵²Cf fission neutron source with respect to⁸⁰Br,^80mBr and⁸²Br. They lay over the ranges 19–23, 21–23 and 28–32%, respectively. On heating, retention progressively increases and closes on ∼100% for Sm-bromate while for other systems the optimum values reach <85%. Thus, cation effect becomes more pronounced during thermal annealing. The isothermal data show that the weight-loss is due to dehydration. The cation effect on retention is discussed in the light of various parameters like lanthanide contraction, crystal structure, lattice energy, crystal water, properties of anion and mode of thermal decomposition.     

Determination of trace amounts of gold in the presence of rare earth elements in rock samples from Makhtesh Ramon (Southern Israel), by instrumental epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA), followed by high resolution gamma-ray spectrometry, was applied to determine trace amounts of Au in the presence of rare earth elements (REE) from vein samples in the basaltic rocks of Makhtesh Ramon, located in southern Israel. The contribution of¹⁵²Eu (411.1 KeV) to the 411.8 keV peak of¹⁹⁸Au was determined using multiple gamma-peak, ratios derived from Eu standards and mixtures of Au and Eu. The concentration of Au was found to be in the range of 10–80 ppb. A group of rare earth elements: La, Eu, Ce, Tb, Sm, Lu, Yb was identified; the concentration of Eu was found to be 0.5 ppm.     

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.     

Rapid determination of tungsten in rocks using183mW

A rapid method has been developed for the determination of tungsten, especially in rocks. The reaction¹⁸²W(n, γ)^183mW (T=5.3 sec), with a thermal neutron capture cross-section of 0.5 b was used. The samples were irradiated in the fast pneumatic system of the FRM, which is described briefly. The low-energy γ-rays of the isomer^183mW were measured by a high-resolving Ge(Li) detector. The sensitivity of the method is 0.1 mg tungsten with an accuracy of about 5%; the minimum concentration is 0.1–0.2% W in geological samples. The analysis time is 2 min per sample.     

Interference by neutron induced second order nuclear reaction in activation analysis of rare earths

In determining the trace impurities existing in high-purity rare earth samples by the neutron activation analysis, there are much interference due to nuclides induced from neutron induced second order nuclear reaction. This paper presents the degree of interference calculated over the ranges of irradiation time from 10⁵ to 10⁷ sec and of thermal-neutron flux from 1·10¹² to 1·10¹⁵ n·cm⁻²·sec⁻¹. According to the results of these calculations, degree of interference under the neutron irradiation condition for 288 hrs in the thermal-neutron flux of 3·10¹³n·cm⁻²·sec⁻¹ is concluded to be 6.4·10⁶ ppm Gd in Eu, 2.2·10⁴ ppm Sm in Eu, 1.9·10⁴ ppm Ho in Dy, 1.1·10³ ppm Eu in Sm, 1.1·10² ppm Ce in La and 1.1·10 ppm Tb in Gd, respectively. Especially, the Gd determination in the Eu target is extremely affected by¹⁵³Gd formed from the¹⁵¹Eu (n, γ) reaction. On the contrary, this reaction is effective in producing¹⁵³Gd activity.     

ICP-AES and D.C.arc-AES determination of Sc, Y and lanthanides in nuclear grade graphite

Summary Inductively Coupled Plasma-Atomic Emission Spectrometric and Direct Current Arc-Emission Spectrometric methods have been developed for the determination of rare earths in nuclear grade graphite. The graphite matrix was selectively removed from the analytes by controlled heating in air at 900°C in a muffle furnace. The residual ash containing analytes was dissolved and analysed by ICP-AES for rare earths specially required for assessing the nuclear purity, viz. Dy, Eu, Gd and Sm and for all rare earths, Sc and Y by D.C.arc-AES by photographing their spectra in III order on an 3.4 M Ebert Spectrograph. The recovery of rare earths after ashing was confirmed using -activities of¹⁴¹Ce,^152–154Eu,¹⁵³Gd,¹⁷⁰Tm and¹⁶⁹Yb which was found to be quantitative within experimental error.

---

Bestimmung von Sc, Y und Lanthaniden in nuklear-reinem Graphit mit Hilfe der ICP-AES und der Gleichstrombogen-Spektrometrie

     

Extraction of americium(III) and europium(III) using a gamma pre-irradiated solution of N,N′-dimethyl-N,N′-dibutyltetradecyl malonamide in n-dodecane modified with N,N′-dihexyloctanamide

The extraction of Am(III) and Eu(III) using a γ-pre-irradiated N,N′-dimethyl-N,N′-dibutyltetradecyl malonamide (DMDBTDMA) modified with N,N′-dihexyloctanamide (DHOA) in n-dodecane (NDD) at 4.5M HNO₃ has been studied as a function of the absorbed dose up to 2×10⁶ Gray. The distribution ratios of Am(III) and Eu(III) were almost constant until a dose of 1×10⁵ Gray and then they decreased gradually up to a dose of 2×10⁶ Gray. The decrease of the distribution ratios of Am(III) and Eu(III) are due to the decreasing concentration of the DMDBTDMA by a γ-pre-irradiation and these results were supported by a determination of the DMDBTDMA concentration with a gas chromatography method. The distribution ratios of Am(III), Eu(III), Ce, Nd and Y with γ-pre-irradiated (DMDBTDMA-DHOA)/NDD have also been studied as a function of the nitric acid concentration and the extraction temperature.     

Mg–Al layered double hydroxide intercalated with sodium lauryl sulfate as a sorbent for <Superscript>152+154</Superscript>Eu from aqueous solutions

In the present study, Mg–Al layered double hydroxide intercalated with nitrate anions (LDH-NO₃) was synthesized, modified with the anionic surfactant, sodium lauryl sulfate, and applied for the removal of ^152+154Eu from aqueous solutions. Modification of the as-synthesized Mg–Al layered double hydroxide was carried out at surfactant concentration of 0.01 M (the organo-LDH produced denoted LDH-NaLS). The as-synthesized and surfactant-intercalated LDHs were characterized by FT-IR and energy-dispersive X-ray spectroscopy techniques. The effect of some variables such as solution pH, contact time and sorbate concentration on removal of ^152+154Eu was investigated. The kinetic data obtained were well fitted by the pseudo-second-order kinetic model rather than the pseudo-first-order model. Intraparticle diffusion model showed that sorption of ^152+154Eu proceed by intraparticle diffusion together with boundary layer diffusion. Experimental isotherm data were well described by Langmuir model. Organo-LDH was found to have higher capacity (156.45 mg g⁻¹) for europium than the as-synthesized LDH-NO₃ (119.56 mg g⁻¹). Comparing LDHs capacities obtained for Eu(III) in the present work with other sorbents reported in literature indicated that LDHs have the highest capacities. Application of the developed process for removal of ^152+154Eu(III) from radioactive process wastewaters was also studied and the obtained results revealed that these LDHs are promising materials for treatment of radioactive wastewaters.     

Adsorptive Voltammetric Studies on the Cerium(III)–Alizarin Complexon Complex at a Carbon Paste Electrode

A novel procedure was developed for the determination of trace cerium on the basis of anodic adsorption voltammetry of the Ce(III)–alizarin complexon (ALC) complex at a carbon paste electrode (CPE). The procedure is convenient to determine cerium individually in the presence of other rare earths because there is a 100 mV difference between the peak potentials of Ce(III)–ALC and other rare earth(III)–ALC complexes in a supporting electrolyte of 0.08 M HAc–NaAc and 0.012 M potassium biphthalate (pH 4.7) when performing linear-scanning from −0.2 to 0.8 V (vs. SCE) at 100 mV/s. The second-order derivative peak currents are directly proportional to the Ce(III) concentration over a range of 6.0 × 10⁻⁹–3.0 × 10⁻⁷ M. The detection limit is as low as 2.0 × 10⁻⁹ M (S/N = 3) for a 120 s preconcentration. An RSD of 3.5% was obtained for 15 determinations of Ce(III) at a concentration of 4.0 × 10⁻⁸ M on the same CPE surface. The method was applied successfully to the determination of cerium in samples of rare earth nodular graphite cast iron.     

Neutron activation determination of uranium by coprecipitation of neptunium-239 on zirconium phosphate

A method is proposed for neutron activation determination of U via²³⁹Np. This is separated by coprecipitation of ZrO(H₂PO₄)₂ and its 106 keV γ-peak measured. The sensitivity of the determination is 10⁻⁹ g. The method is based on the well-known ability of Np(IV) to coprecipitate with zirconium phosphate, while Np(VI) does not form insoluble phosphates or fluorides. This permits elimination of elements interfering, with the determination of²³⁹Np via the 106 keV γ-peak: Sm, Nd, Yb, Lu, Pa (from Th) and Ta. The rare earths are eliminated by coprecipitation on LaF₃, and Pa and Ta as insoluble phosphates in an oxidizing medium. The method is suitable for phosphorus-containing samples: phosphorites, apatites and their industrial treatment products. The results obtained for the uranium content with the proposed method are in good agreement with the results of other methods and authors.     

Determination of trace amounts of rare earth and other elements in rice samples by ICP-AES with sample introduction by tungsten-coil electrothermal vaporization

Summary A device with tungsten-coil electrothermal vaporization for sample introduction into ICP has been proposed. It was applied to the determination of trace amounts of rare earth and other elements in rice samples. Several influencing factors were investigated in detail, such as drying and vaporization parameters, carrier gas flow rate, volume of vaporization chamber and matrix effects. Under optimal experimental conditions, the detection limits for Mg, Cu, Mn, Cr, Fe, Co, Ni and eight rare earth elements are of the order of 10⁻⁹−10⁻¹¹ g. The detection limits for the rare earth elements tested by the present method are comparable to and, in most instances, exceed those for the GFAAS and conventional pneumatic nebulisation-ICP-AES. A precision with RSD<6% was obtained.     

Neutron activation determination of lanthanum in praseodymium oxide near the detection limit. Comparison of various procedures

Trace amounts of lanthanum in spectrally pure praseodymium oxide have been determined by four independent methods: (1) non-destructive Ge(Li) spectrometry, (2) spectrometry of slow γ-γ coincidences, (3) radiochemical separation of¹⁴⁰La from macro amounts of¹⁴²Pr and other interfering activities (mainly^192,194Ir and^152,154Eu) with∼100% yield, by several ion-exchange steps followed by NaI(Tl) spectrometry, (4) method of standard additions using the same procedure as in method (3). Near the detection limit only the two last methods gave accurate results.     

Simultaneous determination of 152Eu and 241Am in liquid solution by liquid scintillation counting

¹⁵²Eu and ²⁴¹Am are the most frequently used radiotracers in the separation studies on trivalent minor actinides and lanthanides. In almost all those studies, the determination of ¹⁵²Eu and ²⁴¹Am has been based on measuring their γ radiation by using a NaI(Tl) scintillation detector and/or a germanium detector. In this study, based on measuring the β particles and mono-energy electrons from ¹⁵²Eu and the α particles from ²⁴¹Am, we provide a new option to simultaneously determine the radioactivities of ¹⁵²Eu and ²⁴¹Am by liquid scintillation counting (LSC) with the aid of α/β discrimination. If the count rate ratio of ²⁴¹Am to ¹⁵²Eu is within the range of 100:1–1:100, the radioactivities of ¹⁵²Eu and ²⁴¹Am in mixed samples can be simultaneously determined by LSC with the errors less than 5 %. In addition, the interferences of ²⁴¹Am on Eu are divided into two parts: inside and outside the ²⁴¹Am region of interest. Only if the count rate ratio of ²⁴¹Am to Eu is more than 10:1, should the latter interference be in consideration.     

Distribution of samarium and ytterbium in rats measured by enriched stable isotope tracer technique and INAA

In the present study a method using enriched stable isotope tracer and instrumental neutron activation analysis (INAA) was developed to study the dynamic distribution of rare earth elements (REEs) in a variety of organs and tissues of Wistar rats. Stable isotopes ¹⁵²Sm and ¹⁶⁸Yb were selected as tracers for the experiment. Intravenously injected ¹⁵²Sm and ¹⁶⁸Yb in chloride form could be quickly absorbed and distributed in almost all the organs and tissues of interest, including liver, skeleton, kidney, spleen, heart, lung, testicle, and blood serum. Liver and skeleton had high ability to take up ¹⁵²Sm and ¹⁶⁸Yb under the experimental conditions, whereas the contents of the elements in other organs were generally lower than 2% of the given dose during the whole experimental period. The difference in distribution of ¹⁵²Sm and ¹⁶⁸Yb in the body was also discussed.     

Integral invariants for high-symmetry open-shell molecules

A method for calculating the energies of electronic states arising from a degenerate open shellγ ^N in terms of integral invariants H^k(γ,γ) is presented. The calculation proceeds from expansions for the electron repulsion integrals 〈mm/nn〉 on degenerate orbitals ofγ symmetry in terms of H^k(γ,γ). The energies of states for theγ ^N electronic configurations with dimγ≤3 (e^N and t^N configurations) are tabulated. Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 2, pp. 183–195, March–April, 1998. This work was supported by RFFR grants No. 96-03-01167 and 96-03-34035.