Multielement standards in routine reactor neutron activation analysis

The application of multielement standards (MES) in routine neutron activation analysis brings a whole range of advantages. This paper deals with the experience obtained during many years of application of these MES. Nine of these MES contain a total of 50 elements in suitable combinations and concentrations; thus, the determination of most of the common elements by NAA can be carried out simultaneously. This refers to the following elements: Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, W, Re, Au, Hg, Th and U. For the determination of the remaining elements such as Zr, Ta, Ir etc., single element standards (SES) are used.     

Use of INAA and ICP-MS for the assessment of trace element mass fractions in adult and geriatric prostate

The variation with age of the mass fraction of 54 trace elements (Ag, Al, As, Au, B, Be, Bi, Br, Cd, Ce, Co, Cr, Cs, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, Ir, La, Li, Lu, Mn, Mo, Nb, Nd, Ni, Pb, Pd, Pr, Pt, Rb, Re, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, Y, Yb, Zn, and Zr) in intact nonhyperplastic prostate of 65 healthy 21–87 year old males was investigated by instrumental neutron activation analysis with high resolution spectrometry of long-lived radionuclides and inductively coupled plasma mass spectrometry. This work revealed that there is a significant tendency for an increase in Bi, Cd, Co, Fe, Hg, Sc, Sn, Th, U, and Zn (p < 0.0014) mass fraction in normal prostate from age 21 years to the sixth decade. In the sixth to ninth decades the mass fractions of almost all chemical elements investigated in nonhyperplastic prostates were maintained at approximately stable levels. Our finding of correlation between pairs of prostatic chemical element mass fractions indicates that there is a great disturbance of prostatic chemical element relationships with increasing age.     

Elemental content in ground and soluble/instant coffee

The concentration of thirty-four elements in twelve coffee brands has been measured using instrumental neutron activation analysis. The samples investigated included four brands of commercially available ground coffee and eight brands of soluble/instant coffee. The elements measured were Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Gd, Hf, K, La, Lu, Mg, Mn, Na, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, Tm, U, V, Yb and Zn. Twenty four elements were found to be below the detection limit in one or more samples. These elements were Ce, Cr, Fe, V, As, Eu, Ba, Dy, Gd, Hf, La, Lu, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, Yb, Tm, and U.     

Multitracer study on transport and distribution of metal ions in plants

Transport and distribution of metal ions in rice and soybean plants were studied using multitracers produced by irradiating an Au target by 135 MeV/nucleon¹²C,¹⁴N, or¹⁶O ions accelerated by RIKEN Ring Cyclotron. The multitracer consisted of radioisotopes of the following elements: Be, Na, Sc, Mn, Fe, Co, Zn, Se, Rb, Sr, Y, Zr, Nb, Ag, Te, Ba, Ce, Pm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ir, and Pt. Rice and soybean plants were grown in a nutrient solution and also on soil containing a multitracer. -ray spectroscopy of different parts of the plants showed that all the elements were more or less taken up by roots, while appreciable transport to leaves and seeds was observed only for Mn, Zn, Se, Rb, Sr, and Ba.     

Silicide und Germanide mit Gd6Cu8Ge8-Struktur

Zusammenfassung Die Verbindungen {Sc,Y,Tb,Dy,Ho,Er,Tm,Yb,Lu}₆Cu₈Si₈ sowie {Y,Yb}₆Cu₈Ge₈ werden hergestellt. Diese sind isotyp mit der Gd₆Cu₈Ge₈-Struktur. Die Gitterparameter werden ermittelt.

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Silicides and germanides with Gd₆Cu₈Ge₈-structure type

The compounds {Sc,Y,Tb,Dy,Ho,Er,Tm,Yb,Lu}₆Cu₈Si₈ and {Y,Yb}₆Cu₈Ge₈ have been prepared. They were found to be analogous with the Gd₆Cu₈Ge₈-structure type. The lattice parameters have been determined.

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NAA and ICP analysis of obsidian from Central Europe and the Aegean: Source characterisation and provenance determination

INAA and ICPES are compared for their discriminative power in obsidian source characterisation. Geological samples from the Aegean and Carpathian sources were analysed for Na, Sc, Fe, Co, Rb, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, Ta, Th, U by INAA and for B, Na, Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Zn, Y, Yr, Cs, Ba, La, Ce, Sm, Eu, Gd, Tb, Yb, Lu, Hf by two ICPES procedures. It is shown that all techniques work successfully, however, INAA is more efficient in the chemical discrimination of neighbouring sources.     

Multitracer study on permeation of rare earth elements through a supported liquid membrane

Separation by means of supported liquid membranes is a useful method for the preparation and preconcentration of radioactive nuclides. The permeation of rare earth elements through a bis(2-ethylhexyl) hydrogen phosphate-decalin membrane supported on a microporous polytetrafluoroethylene sheet was studied using a multitracer containing radioactive nuclides of Sc, Zr, Nb, Hf, Ce, Pm, Gd, Yb, and Lu. Permeation rates of these elements from feed solutions of various acidity to receiving solutions of 0.5 mol·dm⁻³ HCl were determined simultaneously. The feed solution at pH 1.4 gave the highest permeation rate for Ce, Pm, and Gd, amounting to about 95% of permeation for Ce and Pm, 80% for Gd, and 10% for Yb in 21 h. Scandium, Zr, Nb, Hf, and Lu were not transported at all from the feed solution. Permeation rates of Yb and Lu from the feed solution at pH 1.4 to receiving solutions of 0.75, 1.0, 2.3, and 4.0 mol·dm⁻³ HCl increased with the concentration. The results obtained indicate that the light rare earth elements can be separated from the heavy ones by this method.     

Neutron activation analysis of aluminium with radiochemical separation of 24Na

Summary In the irradiation of aluminium with fission neutrons, dominant radioactivity of ²⁴Na (t _1/2=15.03 h) is produced from the matrix element by fast neutrons via the ²⁷Al(n,) reaction. The high Compton underground resulting from this matrix radionuclide is a serious limiting factor of the determination of low contents of elemental impurities in aluminium by direct gamma ray spectrometry via indicator radionuclides with t _1/23 d. A specific removal of this matrix activity was achieved by adsorption of sodium (> 99%) on hydrated antimony pentoxide from a HCl/HF-medium, while 48 other elements remain in the eluate with yields > 99% and the elements Br, Cs, K, Rb, and Se with yields between 93–98.5%. Applying this radiochemical separation to the analysis of high purity aluminium, the limits of detection could be improved by a factor up to 200. The attainable limits of detection are at the 0.01 ng/g level for Au, Eu and Sc, at the 0.1 ng/g level for

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Neutronenaktivierungsanalyse von Aluminium mit radiochemischer Abtrennung von ²⁴Na

Zusammenfassung Bei der Bestrahlung von Aluminium mit Spaltneutronen wird durch die ²⁷Al(n,)-Reaktion aus dem Matrixelement eine dominierende Aktivität von ²⁴Na (t _1/2=15,03 h) gebildet. Der aus dieser Matrixaktivität resultierende hohe Comptonuntergrund stellt eine wesentliche Beeinträchtigung der direkten gammaspektrometrischen Bestimmung von sehr kleinen Spurenelementgehalten in Aluminium über Indicatorradionuklide mit t _1/23d dar. Eine spezifische Abtrennung dieser Matrixaktivität wurde durch Adsorption des Natriums (< 99%) an hydratisiertem Antimonpentoxid aus HCl/HF-Medium erreicht, während 48 andere Elemente mit Ausbeuten > 99% und die Elemente Br, Cs, K, Rb und Se mit Ausbeuten zwischen 93–98,5% im Eluat verbleiben. Bei Anwendung dieser radiochemischen Trennung für die Analyse von hochreinem Aluminium können die Nachweisgrenzen der INAA um einen Faktor bis 200 verbessert werden. Die erreichbaren Nachweisgrenzen liegen in der Größenordnung von 0,01 ng/g für die Elemente Au, Eu und Sc, von 0,1 ng/g für Co, Cs, Dy, Hf, Ir Lu, Mn, Re, Sb, Sm, Ta, Tb, Th, U und Yb, von 1 ng/g für Ag, As, Cd, Ce, Cr, Cu, Er, Ga, Hg, Ho, In, La, Mo, Pt, Rb, Ru, Se, Te, Tm und W und zwischen 10 ng/g und 7 g/g für die Elemente Ba, Ca, Fe, Gd, K, Nd, Ni, Os, Pd, Pr, Sn, Zn und Zr.

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Dedicated to Prof. Dr. K. H. Lieser on the occasion of his 65th birthday     

Application of atomic absorption spectrophotometry for the determination of lanthanides in ores and rare earth concentrates

Summary Concentrations of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Y were determined in rare earth ores and concentrates by the flame atomic absorption method, those of Eu, Gd, Dy, Ho, Er, Tm, Yb and Y also by the flameless method with a graphite cell. Accuracy was checked by using a standard lanthanides mixture. The results of the determinations in concentrates (by flame and by furnace AAS, both direct measurement and standard addition method) were compared with those obtained by spectrophotometry. Detection limits were defined in a HGA-70 graphite cell with application of a standard graphite tube. The results of the examinations revealed that both the AAS methods are suitable for lanthanide determinations in the above materials. Heavy lanthanides can be determined in lower concentrations than by spectrophotometry.

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Anwendung der Atomabsorptions-Spektralphotometrie zur Bestimmung von Lanthaniden in Erzen und Seltenerd-Konzentraten

Zusammenfassung La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb und Y wurden in Erzen und Konzentraten mit Hilfe der Flammen-Atomabsorptionsspektrometrie bestimmt, Eu, Gd, Dy, Ho, Er, Tm, Yb und Y auch nach der flammenlosen Methode unter Anwendung der Graphitküvette. Die Genauigkeit wurde mit Hilfe einer Standardmischung von Lanthaniden geprüft. Die Ergebnisse der Bestimmungen in Konzentraten (Flammen- und flammenlose AAS, Direktmessung und Methode der Standardzugaben) wurden mit spektralphotometrischen Resultaten verglichen. Die Nachweisgrenzen wurden für die Graphitküvette HGA-70 mit Standardgraphitröhre bestimmt. Es ergab sich, daß beide AAS-Methoden für den genannten Zweck verwendbar sind. Die schweren Lanthanide können in niedrigeren Konzentrationen bestimmt werden als mit Hilfe der Spektralphotometrie.

     

Thermal behaviour of hydrated lanthanide complexes with heptanedioic acid

The multi-step dehydration and decomposition of trivalent lanthanum and lanthanide heptanediate polyhydrates were investigated by means of thermal analysis completed with infrared study. Further more, X-ray diffraction data for investigated heptanediate complexes of general stoichiometry Ln₂(C₇H₁₀O₄)₃.nH₂O (wheren=16 in the case of La, Ce, Pr, Nd and Sm pimelates,n=8 for Eu, Gd, Tb, Dy, Er and Tm pimelates,n=12 for Ho, Yb and Lu pimelates) were also reported.

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Zusammenfassung Mittels TG, DTG, DTA wurde in Verbindung mit IR-Methoden der mehrstufige Dehydratations- und der Zersetzungsvorgang der Polyhydrate der PimelinsÄuresalze von dreiwertigem Lanthan und dreiwertigen Lanthanoiden untersucht. Röntgendiffraktionsdaten der untersuchten Heptandiat-Komplexe mit der allgemeinen Formel Ln₂(C₇H₁₀O₄)₃ nH₂O (mitn=16 für Ln=La, Ce, Pr, Nd und Sm,n=8 für Ln=Eu, Gd, Tb, Dy, Er und Tm sowien=12 für Ln=Ho, Yb und Lu) werden ebenfalls gegeben.

     

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.

     

Multielement analysis of Northwestern Nigerian rocks by instrumental neutron activation analysis

Rock samples from seven different locations in northwestern Nigeria were analyzed by reactor instrumental neutron activation analysis and Ge(Li) gamma-ray spectrometry. Concentration values were obtained for 18 elements (As, Ce, Co, Cr, Cs, Eu, Fe, Hf, La, Lu, Sc, Sm, Sr, Ta, Tb, Th, U, Yb). The geochemical implications of the results are discussed.     

Mikrobestimmung des Chlorids durch radioaktiven Fällungsaustausch

Zusammenfassung Es wurde eine radiochemische Methode zur Chloridbestimmung ausgearbeitet. Man schüttelt die Chloridlösung mit markierter Hg^*(JO₃)₂-Suspension und mißt die Aktivität der Hg^*Cl₂-haltigen Lösung. Auf die gleiche Art kann auch Bromid bestimmt werden.

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Summary A radiochemical method has been developed for the determination of chloride. The chloride solution is shaken with tagged Hg^*(IO₃)₂-suspension and the activity of the solution containing Hg^*Cl₂ is measured. Bromide can be determined in the same way.

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Résumé On a élaboré une méthode radiochimique pour le dosage des chlorures. On agite la solution de chlorure avec une suspension de Hg^*(IO₃)₂ marquée et l'on mesure l'activité de la solution contenant Hg^*Cl₂. On peut doser de la même manière les bromures.

     

Room temperature acid sonication ICP-MS multielemental analysis of milk

Room temperature acid sonication of milk samples is proposed as a fast alternative methodology for the determination of the total content of 45 elements (Li, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Y, Mo, Ag, Cd, In, Sn, U, Sb, Te, Cs, Ba, Hg, Pb, Bi, Th, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Hf and Ta) in milk by inductively coupled plasma mass spectrometry (ICP-MS). The aforementioned procedure involves a 10 min sample pre-treatment. Measurements were made in quantitative and semiquantitative (Totalquant^®) modes of analysis using Rh as internal standard and Be, Ge, Tb and Re for internal calibration of the equipment in the semiquantitative mode. The selected isotopes were in general the most abundant ones of each element, except in cases where polyatomic or isobaric interferences were detected. Results of total concentrations in 10 liquid and 11 powdered commercially available milk samples were presented. Method validation was performed by measuring a SRM NIST-1549 non-fat milk powder and through the use of recovery experiments. Additionally, the proposed methodology was compared with a method based on a previous microwave-assisted digestion of samples and a direct analysis of 1:4 diluted samples.     

Radioanalytical methods for the non-destructive analysis of lunar samples

The elemental compositions of Apollo 11 and Apollo 12 lunar soil samples 10084,141 and 12070,83 and Apollo 12 rock fragment 12063,73 were determined by non-destructive radioanalytical methods. Main mineral fractions and glasses separated from these samples were analyzed as well. Instrumental neutron activation analysis (INAA) was used to determine Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Cs, Ba La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Hf, Ta, W, Ir, Au, Th and U. A method of delayed neutron counting was used for the determination of uranium, and non-dispersive radioisotopic X-ray fluorescence analysis was applied to the determination of Ti, Fe, Sr, Y and Zr.     

Über Salze und Doppelsalze der Seltenen Erden, 3. Mitt.

Complexes of the type Cs[Ln(SO₄)₂(H₂O)₃]H₂O, (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were prepared from aqueous solution. The compounds are all isomorphous and crystallise monoclinic, space group P2₁/c,Z=4. Unit cell parameters were determined by the single crystal technique and correlated to the ionic radii of Ln³⁺.IR spectra were recorded in the range 4000-250 cm^–1 and tentatively assigned. The number of observed bands exceeds the predicted number by site symmetry selection rules, indicating coupling in the layer structure.

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2. Mitt.     

Synthesis and characterization of some lanthanide(III) chelates of some schaffer acid azo dyes

Summary A series of trivalent lanthanide chelates of the type [Ln(PHNSA) (H₂O) _n ] (2 Cl) (whereLn ³⁺=Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb or Lu;PHNSA=2-(X)-phenylazo-2-hydroxynaphthalene-6-sulphonic acid;X=H, Cl, OCH₃, CH₃ and SO₃H) have been synthesized and characterized by elemental and thermal analysis, molar conductance, IR,¹H NMR (for diamagnetic complexes), electronic spectra and magnetic susceptibility measurements. IR data along with those of the¹H NMR unequivocally proved that the coordination of the ligands to the metal ions took place in a bidentate fashion through the oxygen of the hydroxyl group and the nitrogen of the azo group. The magnetic moment values showed little deviation from Van Vleck values.

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Synthese und Charakterisierung einiger Lanthaniden(III)-Chelate von Schaffersäure-Azofarbstoffen

Zusammenfassung Es wurde eine Reihe von dreiwertigen Lanthanidenchelaten des Types [Ln(PHNSA) (H₂O) _n ] (2 Cl) (mitLn ³⁺=Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb oder Lu undPHNSA=2-(X)-Phenylazo-2-hydroxynaphthalin-6-sulphonsäure,X=H, Cl, OCH₃, CH₃ und SO₃H) synthetisiert und mittels Elementar- und thermischer Analyse, molarer Leitfähgigkeit, IR,¹H-NMR (für diamagnetische Komplexe), Elektronenspektren und Messungen der magnetischen Suszeptibilität charakterisiert. Die IR-Daten zusammen mit¹H-NMR-Befunden zeigten eindeutig, daß die Koordinierung der Liganden zum Metallion zweizähnig durch den Sauerstoff der Hydroxylgruppe und den Stickstoff der Azo-Gruppe erfolgt. Die magnetischen Momente zeigten nur eine geringe Abweichung von den Van Vleck-Werten.

     

A Revised Periodic Table: With the Lanthanides Repositioned

The lanthanide elements from lanthanum to lutetium inclusive are incorporated into the body of the periodic table. They are subdivided into three sub-groups according to their important oxidation states: La to Sm, Eu to Tm, Yb and Lu, so that Eu and Yb fall directly below Ba; La, Gd, Lu form a column directly below Y; Ce and Tb fall in a vertical line between Zr and Hf. Pm falls below Tc; both are radioactive, and not naturally occurring. The elements with easily attained 2⁺ and 4⁺ oxidation states are grouped and clearly differentiated. Gadolinium has an important position as the centre of four triads in the block of elements that surround it– La, Gd, Lu; Ba, Gd, Hf; Eu, Gd, Tb; Yb, Gd, Ce. This new arrangement has the advantages of compactness, simplicity and clarity – there are no tie lines; and important oxidation states of these metals are emphasized. The actinides are also accommodated within this system, and element 114 falls naturally below lead in Group 14.     

Extraktion der Seltenen Erden mit Tributylphosphat

Zusammenfassung Es wurde die Extraktion von Gd(NO₃)₃ und Yb(NO₃)₃ mitTBP in Abhängigkeit von der Nitrationenkonzentration untersucht. Nach der Methode vonFomin wurden die Stabilitätskonstanten für die Komplexe zwischen Metall und Nitration in der wäßr. Phase bestimmt. Auf Grund der Infrarotspektren von Ce(NO₃)₃·3TBP, Pr(NO₃)₃·3TBP, Gd(NO₃)₃·3TBP, Yb(NO₃)₃·3TBP und Lu(NO₃)₃·3TBP wurde gefunden, daß die Festigkeit der Bindung zwischen Metall und Phosphorylsauerstoff sich mit Erhöhung der Ordnungszahl vermindert. Durch Gegenüberstellen der Ergebnisse über die Komplexbildung in der wäßr. Phase einerseits und die Beständigkeit der Komplexe in der org. Phase andererseits kann man das Maximum der Kurve Verteilungskoeffizient/Ordnungszahl, welches bei niedriger Acidität auftritt, erklären.

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The extraction of Gd(NO₃)₃ and Yb(NO₃)₃ with tributyl phosphate (TBP) has been studied in dependence on the nitrate ion concentration. The metalnitrate ion complex stability constants in aqueous solution have been determined according to a method proposed byFomin. From the IR spectra of Ce(NO₃)₃·3TBP, Pr(NO₃)₃·3TBP, Gd(NO₃)₃·3TBP, Yb(NO₃)₃·3TBP and Lu(NO₃)₃·3TBP a decrease of the strength of the metal-phosphoryl oxygen bond with increasing atomic number was deduced. Comparison of the results of complex formation in aqueous solution with those of complex stability in organic solution provides a possibility to explain the maximum in the distribution coefficient/atomic number curve found at low acidities.

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Verbindungen der Seltenerdelemente mit α-Benzoinoxim, 1. Mitt.

Zusammenfassung Substanzen der ZusammensetzungLnCl₃·3H₂ Box ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) und LaBr₃·3 H₂ Box wurden isoliert und durch Thermoanalyse, IR-Absorptionsspektren und Röntgenstreuung charakterisiert.

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Compounds of the rare earth elements with -benzoin oxime

Compounds of compositionLnCl₃·3 H₂ Box ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) and LaBr₃·3H₂ Box were isolated and characterized by thermoanalysis, IR spectroscopy and X-ray diffraction.