Separation and inductively coupled plasma optical emission spectrometric (ICP-OES) determination of trace impurities in nuclear grade uranium oxide

A simple and rapid inductively coupled plasma optical emission spectrometric method for the determination of trace level impurities like REEs, Y, Cd, Co, V, Mg, B, Ca, Cr, Mn, Ni, Cu, Zn and Al in uranium oxide samples is described. The method involves solvent extraction separation of uranium from 6 M HNO₃ acid medium using di (2-ethyl hexyl) phosphoric acid in toluene, which selectively separates uranium leaving behind the trace impurities in the aqueous media, for quantification by ICP-OES. The method has been applied to few synthetic samples and five certified reference U₃O₈ standards. The results are compared with other methods such as TBP-TOPO-CCl₄ and 1,2 diaminocyclohexane N,N,N′,N′-tetra acetic acid (CyDTA)–ammonium hydroxide (NH₄OH) separation techniques. Different experimental parameters like contact time, acidity, aqueous to organic ratio etc., are optimized for better and accurate results. The method is simple, rapid, accurate and precise for all the studied elements, showing a relative standard deviation of 1.5–12.0% at trace levels studied (5.5–12% at 0.2 μg/mL and 1.5–6.0% at 0.5 μg/mL), on the synthetic samples prepared from high purity oxides.     

微型柱在线分离-ICP-MS法测定高纯氧化铕中的14个稀土杂质

研究了微型柱在线分离-电感耦合等离子质谱法（ICP-MS）测定高纯Eu2O3中痕量Tm的方法，研制了Cyanex272负载树脂微型分离柱，优化了分离Eu2O3基体的实验条件，在线分离测定时间为25min。建立了在线柱分离测定Tm，内标补偿法直接测定其余稀土杂质的高纯Eu2O3中14个稀土杂质的ICP-MS分析方法。方法检出限为0.01μg/g-0.15μg/g，加标回收率为91.5%-110%,相对标准偏差为1.7%-4.9%。可满足快速测定99.999%Eu2O3中14个稀土杂质的要求。     

Selective ion exchange separation of uranium from concomitant impurities in uranium materials and subsequent determination of the impurities by ICP-OES

An ion exchange method has been developed for the separation of uranium from trace level metallic impurities prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES) in uranium materials. Selective separation of uranium from trace level metallic impurities consisting Cr, Co, Cu, Fe, Mn, Cd, Gd, Dy, Ni, and Ca was achieved on anion exchange resin Dowex 1 × 8 in sulphate medium. The resin (100–200 mesh, in chloride form) was packed in a small Teflon column (7.8 cm × 0.8 cm I.D.) and brought into sulphate form by passing 0.2 N ammonium sulphate solution. Optimum experimental conditions including pH and concentration of sulphate in the liquid phase were investigated for the effective uptake of uranium by the column. Uranium was selectively retained on the column as anionic complex with sulphate, while impurities were passed through the column. Post column solution was collected and analyzed by ICP-OES for the determination of metallic impurities. Up to 2,500 μg/mL of uranium was retained with >99% efficiency after passing 25 mL sample through the column at pH 3. Percentage recoveries obtained for most of the metallic impurities were >95% with relative standard deviations <5%. The method established was applied for the determination of gadolinium in urania–gadolinia (UO₂–Gd₂O₃) ceramic nuclear fuel and excellent results were achieved. Solvent extraction method using tributylphosphate (TBP) as extractant was also applied for the separation of uranium in urania–gadolinia nuclear fuel samples prior to the determination of gadolinium by ICP-OES. The results obtained with the present method were found very comparable with those of the solvent extraction method.     

Determination of rare earth elements impurities in high purity uranium

A sensitive radiochemical procedure has been developed for the separation and determination of Dy, Sm, Gd, Eu, La and Lu in high purity uranium. The method is based on quantitative extraction of uranium using NPy/benzene as an extractant from 7M HCl solution. Rare earth elements (REE) remaining in the aqueous phase were subsequently determined by INAA.     

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.     

Neutron activation analysis of rare earth impurities in europium oxide

A neutron activation analysis method for determining Yb, Dy, Ho, Sm and La impurities in europium oxide with sensitivities of 10^?5 to 10^?7% is described. The method is based on a preliminary concentration of the rare earth elements by reducing europium(III) with zinc to europium(II), and separating the trivalent rare earth elements by extraction chromatography. After neutron irradiation, the individual radioisotopes of the rare earth elements are separated by using KU-2 cation exchange resin and ammonium α-hydroxyisobutyrate solution as the eluant.     

Identification and determination of natural radioactive impurities in rare earth chlorides

²²⁷Ac,²²⁸Th,²²⁶Ra,²¹⁰Po and²¹⁰Pb can be present at rare earth chlorides. A radiochemical procedure is presented for the identification and determination of natural radioactive impurities in rare earth chlorides. The determination limits for these radionuclides were 1.5·10^–4 to 3·10^–1 Bq/g. The relative standard deviations for determining 10^–2 Bq/g radionuclides were usually less than ±7%.     

An XRF method for the determination of common rare earth impurities in high purity yttrium oxide

Summary An XRF method for the determination of Eu, Gd, Tb, Dy, Ho, Er and Yb in yttrium oxide has been developed. The samples are converted to yttrium oxalate and presented to the spectrometer in the form of pressed pellets. Philips PW-1220, semiautomatic X-ray spectrometer is used for analysis. Analysis lines have been chosen after careful study of line interferences. The lower estimation limit for Yb is 0.01% and for other elements it is 0.005%. The method has been tested for its accuracy by analysing synthetic samples with known composition.

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Bestimmung von häufig vorkommenden Verunreinigungen an Seltenen Erden in Yttriumoxid hoher Reinheit mit Hilfe der Röntgenfluorescenzanalyse

Zusammenfassung Ein Verfahren zur röntgenfluorescenzanalytischen Bestimmung von Eu, Gd, Tb, Dy, Ho, Er und Yb in Yttriumoxid wurde ausgearbeitet. Die Probe wird zu Yttriumoxalat umgesetzt und in Form von Preßtabletten der RFA unterworfen. Das halbautomatische Röntgenfluorescenz-Spektrometer Philips PW-1220 wurde verwendet. Eine sorgfältige Untersuchung der Interferenzen führte zur Wahl der Analysenlinien. Die untere Bestimmungsgrenze liegt für Yb bei 0,01%, für die anderen Elemente bei 0,005%. Die Zuverlässigkeit des Verfahrens wurde anhand von synthetischen Proben bekannter Zusammensetzung geprüft.

     

X-Ray fluorescence analysis of thulium oxide for rare earth impurities

A wavelength dispersive X-ray fluorescence spectrometric method has been developed for the analysis of thulium oxide to determine the neighbouring rare earth impurities. The sample is taken in oxalate form and the analysis is done on a Philips PW 1220 spectrometer with a LiF (200) crystal. The detection limit for holmium, lutetium and yttrium is 0.002%, for dysprosium and erbium 0.005% and for, ytterbium it is 0.01%. The precision at each concentration of the standards and the theoretical detection limits have been calculated. Intensity correction factors for the line overlaps have been determined.     

Determination of rare earth impurities in high purity uranium by isotope dilution analysis

Summary An isotope dilution method for the determination of rare earth impurities in uranium has been developed and Ce, Nd, Sm, Eu and Gd have been determined in uranium oxide samples. The method involves isotopic dilution with enriched isotopes of the rare earths being measured, followed by the separation of rare earths from uranium. A mass spectrometer with thermionic source was used to determine the relative isotopic abundances in each of these rare earths. All these five elements were analysed selectively by preferential evaporation technique. Trace concentrations down to parts per billion range can be measured with good sensitivity and accuracy.

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Bestimmung von Verunreinigungen an Seltenen Erden in hochreinem Uran durch Isotopenverdünnungsanalyse

Zusammenfassung Eine Isotopenverdünnungsmethode wurde ausgearbeitet zur Bestimmung von Ce, Nd, Sm, Eu und Gd in Uranoxidproben. Das Verfahren umfaßt isotopische Verdünnung mit angereicherten Isotopen der zu bestimmenden Elemente und nachfolgende Abtrennung der Seltenen Erden von Uran. Die relativen Isotopenhäufigkeiten wurden mit Hilfe eines Massenspektrometers mit thermischer Ionenquelle bestimmt. Alle fünf Elemente wurden durch selektive Verdampfung analysiert. Spurenkonzentrationen bis herab zum ppb-Bereich konnten mit guter Empfindlichkeit und Genauigkeit erfaßt werden.

     

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.     

X-ray-fluorescence analysis of high-purity holmium oxide for common rare earth impurities

Summary An X-ray fluorescence analysis method for determination of Gd, Tb, Dy, Er, Tm and Yb in Holmium oxide is described. Samples are converted to oxalate form and mixed with boric acid in the ratio 31. A double layer pellet is obtained by pressing about 800 mg of this mixture on a boric acid pellet. Selection of experimental parameters and analysis lines are discussed. The estimation limit ranges from 0.005% to 0.5%.

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Röntgenfluorescenzspektrometrische Analyse von hochreinem Holmiumoxid auf Verunreinigung von Seltenen Erden

Zusammenfassung Die Proben werden in die Oxalatform übergeführt, mit Borsäure vermischt (31) und in Mengen von 800 mg als zweite Schicht auf eine Borsäuretablette gepreßt. Die Auswahl der experimentellen Parameter und der Analysenlinien wird diskutiert. Die Erfassungsgrenzen für Gd, Tb, Dy, Er, Tm und Yo liegen im Bereich von 0,005–0,5%.

     

ICP-MS同时测定植物性食品中稀土元素的方法研究

建立了植物性食品中16种稀土杂质(Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu)元素的电感耦合等离子体质谱(ICP-MS)的分析方法.考察了基体效应及质谱干扰,应用In内标,有效地补偿基体效应所引起的测量偏差,建立修正公式校正质谱干扰.对照分析了参考标准物质.对所测定元素,校正曲线的相关系数为＞0.9990,方法的检出限低于2.2 pg/g(Sc为95pg/g),回收率为92%～106%,RSD优于3.2%(n=7).     

Determination of rare earth impurities in ytterbium oxide by X-ray fluorescence spectrometry

Summary Determination of Kare Earth Impurities in Ytterbium Oxide by X-ray Fluorescence Spectrometry An X-ray fluorescence spectrometric method for the determination of traces of Ho, Er, Tm, Lu and Y oxides in the concentration range of 0.005–1% in ytterbium oxide is developed. The precision at various concentrations of the standards is given. Intensity corrections for line overlaps have been determined.     

X-ray fluorescence analysis of terbium oxide and oxalate for rare earth impurities

Summary A method for the determination of samarium, europium, gadolinium, dysprosium, holmium and yttrium oxides in terbium oxide is described. The sample is converted to terbium oxalate, mixed with boric acid binder in the ratio 21, pelleted at a pressure of 20 tons over a boric acid backing pellet and irradiated with X-rays from a tungsten tube operated by Philips PW 1140 generator. The secondary X-rays thus generated are analysed by a LiF(200) crystal in Philips PW 1220 X-ray fluorescence spectrometer. The minimum determination limit is 0.01% for all rare earth oxides determined except for yttrium oxide for which it is 0.005%.

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Zusammenfassung Eine Methode zur Bestimmung der Oxide von Samarium, Europium, Gadolinium, Dysprosium, Holmium und Yttrium in Terbiumoxid wurde beschrieben. Die Probe wird zu Terbiumoxalat umgesetzt, mit Borsäure im Verhältnis 2 1 gemischt, mit 20 Tonnen Druck auf eine Borsäuretablette aufgepreßt und mit Röntgenstrahlen aus einer Wolframröhre bestrahlt, die mit einem Philips-Generator PW 1140 gespeist wurde. Die dabei entstehenden Sekundärstrahlen wurden mit Hilfe eines LiF-Kristalls (200) in einem Philips PW 1220 Röntgenfluoreszenz-Spektrometer analysiert. Die untere Grenze der Bestimmbarkeit liegt bei 0,01% für alle bestimmten Seltenerden-Oxide mit Ausnahme von Yttriumoxid mit 0,005%.

     

Relative sensitivity factors for the determination of rare earth elements in uranium oxide by Spark Source Mass Spectrometry

Summary Relative Sensitivity Factors (RSFs) for the rare earth elements Ce, Nd, Sm, Eu, Gd, Dy, Er and Lu in U₃O₈ have been determined by Spark Source Mass Spectrometry (SSMS) using the electrical detection system in peak switching mode. Earlier RSFs for these elements were determined in uranyl nitrate and it was expected that though the absolute value of the RSFs may be different, the trend would be the same. However, the present work shows that apart from the magnitude, the trend in RSF values is also different. The data from the present work are in agreement with the theoretical calculations based on the decomposition energies of the rare earth oxides and support the work carried out by others in the case of Y₂O₃ matrix.

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Relative Empfindlichkeitsfaktoren für die Bestimmung Seltener Erden in Uranoxid mit Hilfe der Funken-Massenspektrometrie

Zusammenfassung Die relativen Empfindlichkeitsfaktoren für die Elemente Ce, Nd, Sm, Eu, Gd, Dy, Er und Lu in U₃O₈ wurden mit der Funken-Massenspektrometrie mit elektrischem Nachweis (peak switching) bestimmt. Früher sind diese Faktoren in Uranylnitrat bestimmt worden und es wurde erwartet, daß trotz unterschiedlicher absoluter Werte der Trend derselbe wäre. Es zeigte sich jedoch, daß auch der Trend verschieden ist. Die Werte der vorliegenden Untersuchung stimmen mit theoretischen Berechnungen aus den Zersetzungsenergien der Seltenerdoxide überein und bestätigen die Ergebnisse anderer Autoren für die Y₂O₃-Matrix.

     

Emission-spectrometric determination of trace rare earth elements in europium oxide

Summary A dc arc excitation method in a controlled atmosphere was applied in the presence of CsCl-graphite (19) buffer for the quantitative determination of traces of rare earth elements in europium oxide. The intensities of the cyanogen band spectra and the background could be reduced by the use of argon-oxygen (41) mixed gas atmosphere and it was possible to obtain higher sensitivity than in the excitation in air. Addition of CsCl-graphite buffer causes an increase of the evaporation rate of the sample and of the number of atoms in the arc plasma, and the atoms and ions of rare earths distribute uniformly along the axis of the discharge gap. The buffer enhances the sensitivity and reproducibility and permits the determination of microquantities of 10 impurity elements within limits of detection from 3 to 11 ppm in high-purity europium oxide. The coefficients of variation are less than 13%.

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Emissionsspektrometrische Bestimmung von Spuren Seltener Erden in Europiumoxid

Zusammenfassung Die Anregung erfolgt im Gleichstrombogen in kontrollierter AtmosphÄre (Argon/Sauerstoff, 41) in Gegenwart eines CsCl-Graphit (19)-Puffers. Durch die Verwendung von Argon/Sauerstoff konnte die IntensitÄt des Untergrundes und der Cyanbanden erheblich reduziert und eine grö\ere Empfindlichkeit erreicht werden als bei der Anregung in Luft. Durch den Puffer wird die Verdampfungsgeschwindigkeit erhöht, die Anzahl der Atome im Bogenplasma vergrö\ert und eine gleichmÄ\ige Verteilung der Atome und Ionen lÄngs der Bogenachse erzielt. Empfindlichkeit und Reproduzierbarkeit werden verbessert. Spurenverunreinigungen von 10 Elementen können in hochreinem Europiumoxid bestimmt werden. Die Nachweisgrenzen liegen zwischen 3 und 11 ppm; der Variationskoeffizient ist < 13%.

     

Anion exchange separation and determination of yttrium in uranium oxide — Yttrium oxide mixture

A procedure has been developed for quantitative separation of yttrium from uranium by anion exchange from nearly saturated NH₄Cl solution in 0–2N HCl medium. Apparently no organic matter is leached out during the separation as yttrium could be determined by EDTA titration without resorting to fuming with perchloric acid before titration. The precision obtained in the analysis of yttrium in a mixture containing about 12 mg of yttrium and about 300 mg of uranium was ±0.3% (27 determinations).