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 gold in germanium by neutron-activation analysis

Gold was determined in gold-doped germanium by neutron-activation analysis. The irradiated samples were dissolved in aqua regia, in the presence of gold carrier. The matrix activity was eliminated by distillation, and gold precipitated in the residue with hydroquinone. The gold fraction was essentially radiochemically pure. For a neutron dose of 5 x 10(15)n/ cm(2), a sensitivity of 1 ppM Au can be obtained, with a 2.4-g sample. The samples investigated contained from 24 to 36 ppM Au.     

Determination of cadmium in soils by neutron-activation analysis

A radiochemical neutron-activation method for the determination of cadmium in soils is presented. The irradiation is carried out in a neutron flux with a high epithermal component, taking advantage of the high ratio of the resonance-activation integral to the thermal-neutron cross-section for (114)Cd to obtain an increased sensitivity. The irradiated samples are decomposed with hydrofluoric acid-nitric acid and cadmium is separated by anion-exchange. Zinc may also be determined. There is good agreement with results obtained by atomic-absorption spectrophotometry based on solvent extraction separation of cadmium.     

Determination of noble metals by neutron-activation analysis

The scope and limitations of neutron-activation analysis in the field of the platinum metals are discussed. Special attention is given to interferences that occur in determination of noble metals in platinum metals and in natural samples. The problem of standards, carriers and chemical yield determination is emphasised. A recommendation is given of modern techniques for counting radionuclides formed by neutron activation of the platinum metals.     

Determination of rhenium in molybdenite by neutron-activation analysis

A neutron-activation method is described for the determination of rhenium in molybdenite. Radiochemical separation by a carrier technique was carried out very rapidly by means of successive liquid-liquid extraction processes. The recovery of rhenium, which was determined by a spectrophotometric method, was about 93%. About 10 samples could be analysed within 6 hr in parallel runs.     

Determination of Samarium in rocks by epithermal neutron-activation analysis

Summary A non-destructive neutron-activation method for the determination of samarium in rocks, based on activation with epithermal neutrons, is described. By this means the formation of¹⁵³Sm, as compared to most interfering radionuclides, is considerably higher than by thermal neutron activation. The precision of the method is 2–3% in the range of 3–25 ppm, and the sensivity is about 0,1 ppm. Results are presented for some standard rocks. The influence of other rare earth nuclides on the measurement of the 41 KeV X-ray of¹⁵³Sm has been investigated.

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Zerstörungsfreie Bestimmung von Samarium in Gesteinen durch Aktivierungsanalyse mit epithermischen Neutronen

Zusammenfassung Die Bildung von¹⁵³Sm ist hierbei im Vergleich zu den meisten störenden Radionukliden beträchtlich größer als bei der Aktivierung mit thermischen Neutronen. Die Präzision des Verfahrens beträgt 2–3% im Bereich von 3–25 ppm, die Empfindlichkeit etwa 0,1 ppm. Für einige Standardgesteine werden die Ergebnisse angeführt. Der Einfluß anderer Nuklide Seltener Erden auf die Messung der 41 keV Röntgenstrahlung von¹⁵³Sm wurde untersucht.

     

Determination of palladium in biological samples by neutron-activation analysis

Summary A neutron-activation method for determination of nanogram levels of palladium in biological samples is described. It is based on radiochemical separation of 13.5-hr¹⁰⁹Pd by solvent extraction of its dimethylglyoximate complex into chloroform from the acid solution obtained by wet ashing of the irradiated sample. The effect of the acidity of the aqueous phase on the extraction coefficient was also investigated by radiotracer experiments. Results are reported for biological standard reference materials and a few environmental samples.

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Bestimmung von Palladium in biologischen Proben durch Neutronen-Aktivierung

Zusammenfassung Eine Neutronen-Aktivierungsmethode zur Bestimmung von Nano-grammengen Palladium in biologischen Proben wurde beschrieben. Sie beruht auf der radiochemischen Trennung des¹⁰⁹Pd durch Extraktion seines Dimethylglyoxim-Komplexes mit Chloroform aus der sauren, durch nasse Veraschung gewonnenen Lösung der bestrahlten Probe. Der Einfluß der Acidität der wäßrigen Phase auf den Extraktionskoeffizienten wurde ebenfalls durch Radiotracer-Versuche geprüft. Untersuchungsergebnisse für biologische Standardproben und einige Milieuproben wurden mitgeteilt.

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Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.     

Determination of rhenium in geological materials by radiochemical neutron-activation analysis

A neutron-activation method for the determination of rhenium in geological materials is described. Radiochemical separation, using Re-carrier and liquid-liquid extractions, yields (186)Re in a state of radiochemical purity. The gamma-ray activity of the radionuclide is counted with an NaI(Tl) crystal scintillation detector, and the chemical yield is determined spectrophotometrically. Results for the contents of rhenium in the standard rock W-1 and in nickeliferous lateritic profiles are reported. Particular problems arising in neutron-activation analysis for rhenium in lunar surface materials are discussed.     

Determination of trace contaminants in hydrogenation catalysts by neutron-activation analysis

A neutron-activation method has been developed for the determination of the active constituents and contaminants in hydrogenation catalysts. The active constituents of palladium and nickel catalysts (Pd and Ni) and Zn and Co contaminants present in small amount were determined by a direct instrumental method. A NaI(Tl) scintillator and a Ge(Li) semiconductor connected to a multichannel analyser were used for the measurements. A computer was used to evaluate the γ-spectra. Contaminants present in small amount were also determined by means of a radiochemical separation method based on heterogeneous isotopic exchange on mercury(II) sulphide and zinc sulphide precipitates.     

Determination of thorium with DBF-arsenaz by flow-injection analysis

A sensitive,selective,rapid,simple,and convenient method for the determination of thoriumwas developed.The method was based on the color reaction of thorium with DBF-arsenazo in astrong acidic medium (4 mol/L HCI).The flow-injection technique was used with an automated flow-injection analyzer.Beer's law was obeyed in the range of 0—1.4 μg/mL.The relative standarddeviations were less than 1%.     

Determination of rare earth element distribution patterns in rocks and minerals by neutron-activation analysis

Summary A routine procedure for determining eleven of the fourteen naturally occurring rare earth elements (REE) in rocks and minerals is described. Following thermal neutron activation the samples are decomposed, in the presence of REE carriers, by fusion with Na₂O₂. The REE are separated as a group using a gel removal technique for silica and a conventional hydroxide-fluoride cycle. The REE concentrates are then counted with a high resolution Ge(Li) spectrometer system. Chemical yields are determined by reirradiation and counting of the carrier.The high precision and accuracy of the technique have been proven through replicate analyses and through analyses of the U.S. Geological Survey standard rock, W-1. The technique, with slight modifications, has been tested to date on more than a hundred rock and mineral samples. Experience has shown that the eleven REE determined by this technique more than adequately describe the total distribution patterns for the REE in naturally occurring samples.

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Neutronenaktivierungsanalytische Bestimmung der Verteilung der Seltenen Erden in Gesteinen und Mineralien

Zusammenfassung Ein Routineverfahren für die Bestimmung von 11 Elementen der Seltenen Erden in natürlich vorkommenden Mineralien und Gesteinen wird beschrieben. Die Proben werden mit thermischen Neutronen bestrahlt und anschließend die Substanzen nach Zusatz von Trägerelementen (Seltene Erden) mit, Na₂O₂ aufgeschlossen. Die Seltenen Erden werden dann als Gruppe mittels eines Hydroxid-Fluorid-Trennverfahrens isoliert. Silicium wird als Gel abgetrennt. Die Messung der Aktivitäten in den Lanthanidenkonzentraten erfolgt mit einer Ge(Li) Gamma-Spektrometer-Meßanordnung hoher Auflösung. Die bei der chemischen Abtrennung der Seltenen Erden erzielte Ausbeute wird anschließend durch Bestrahlung der Anreicherungsprodukte und Messung der Aktivitäten der Trägerelemente bestimmt.Die Reproduzierbarkeit und Genauigkeit der Methode wurde durch die mehrfache Analysierung bestimmter Proben und von Standardgesteinen (z.B. W-1) geprüft. Mit leichten Änderungen wurde das Verfahren an über 100 Gesteins- und Mineralproben erprobt. Es hat sich gezeigt, daß mit den 11 durch Neutronenaktivierung quantitativ bestimmten Seltenen Erden die Verteilung dieser Elementgruppe in natürlich vorkommenden Mineralien und Gesteinen hinreichend gut beschrieben werden kann.

Presented at 3. Seminar Aktivierungsanalyse, Kernforschungszentrum Karlsruhe, May 30/31, 1972.     

Determination of trace elements in iron by neutron-activation techniques

A systematic analytical procedure for the determination of some trace impurities in iron matrices was developed by employing both direct and destructive neutron-activation techniques. Irradiations in fast neutron fluxes, selective activation by epithermal neutrons and coincidence γ-spectrometry measurements were used in some cases, in order to improve the sensitivity for non-destructive analysis; for destructive methods, radiochemical separations based on ion exchange and solvent extraction were applied. Procedures are described, and some results of the determination of low concentrations of Al, Mn, Ti, V (non-destructive), P, S, Zn (destructive) and As, Co, Cr, Cu, Mo, Ni, Sc, W (both methods) in iron are reported and discussed.     

Determination of platinum and palladium in geological materials by neutron-activation analysis after fire-assay preconcentration

Fire-asay preconcentration followed by neutron-activation analysis permits the determination of as little as 0.5 ppM of platinum and 0.5 ppM of palladium on a 20-g sample. Platinum and palladium are separated with carriers and beta-counted. Results for the platinum and palladium content of seven U.S.G.S. standard rocks are presented.     

Substoichiometric determination of manganese by neutron-activation analysis

A simple and rapid method for the substoichiometric determination of traces of manganese in various materials by neutron-activation analysis has been developed. After dissolution of the irradiated test sample, manganese(II) carrier is added and subsequently oxidised by peroxodisulphate to the heptavalent state. The permanganate thus formed is finally extracted into chloroform as tetraphenylarsonium permanganate using a substoichiometric amount of tetraphenylarsonium chloride. This single separation step isolates radiochemically pure manganese-56 in the analysis of a relatively simple material in which interfering elements (gold, rhenium, etc.) are absent. When this is not true, a preliminary separation of manganese from the irradiated sample, based on the extraction of manganese diethyldithio-carbamate into chloroform and followed by stripping of the manganese with dilute sulphuric acid, must be used. A simultaneously irradiated standard containing manganese must be treated in exactly the same way as a test sample. In the materials analysed by the new method 10(-5) to 10(-3)% of manganese has been determined.     

Determination of uranium in thorium matrixes by epithermal neutron activation analysis

Uranium in thorium matrixes or in minerals and ores containing thorium is determined by epithermal neutron activation analysis (ENAA). In some minerals and ores, such as monazite sands, the analysis can be carried out by purely instrumental means with no chemical separation of uranium or thorium from the irradiated matrix. For thorium compound matrixes with very low uranium contents, a rapid radiochemical separation method, based on the retention of uranyl ion on anion-exchange resins, is first carried out, before counting the gamma-ray peaks for²³⁹U in multichannel analysers coupled to NaI(Tl) scintillators or to Ge(Li) detectors.     

Determination of oxygen and silicon in rocks by 14-MeV neutron-activation analysis and its precision

Oxygen and silicon have been determined in the six new U.S. Geological Survey standard rocks and two standard refractory materials by 14-MeV neutron-activation analysis, followed by both single and multichannel analyser counting of the induced (16)N (4.5-8 MeV gamma radiation) and (28)Al activities (1.78 MeV photopeak). Owing to the long analysing time per pulse, dead-time corrections are necessary in multichannel analyser counting. Four methods were investigated in this work: counting in the live-time mode without additional correction, short counting corrected by an external live-time scaler, the method of Bartoseck, and the method of Schonfeld. Each measurement was controlled by a simultaneous measurement with a single-channel analyser. Silica ignited at 1000 degrees was used as a reference. Correction was made for the interfering elements, F, P, Al, Fe and Mg, using literature data. Attention was paid to neutron, gamma and beta attenuation. For oxygen the mean coefficient of variation for a single determination with a single-channel analyser was 1.7 % for silicon 1.1 %. The mean results for single-channel counting were compared with literature values.     

Substoichiometric determination of copper by neutron-activation analysis

A rapid and selective method has been developed for the determination of Cu in complex matrices by thermal neutron-activation analysis employing substoichiometric extraction with 1,2,3-benzotriazole /1,2,3-BT/ into chloroform. The time required for radiochemical purification and counting of two samples was 2 h. 1.015 g Cu can be determined with an accuracy of 6.40% and a purification of 5.26%.     

Determination of uranium at trace levels by radiochemical neutron-activation analysis employing radioisotopic yield evaluation

Nanogram and picogram quantities of uranium were determined in biological materials by radiochemical neutron-activation analysis. Two different approaches using either (239)U or (239)Np were employed for cross-checking, and the question of negative errors due to incomplete acid dissolution of any possible inorganic (siliceous) fraction was studied. In the first and main approach, radiochemical separation of the short-lived (239)U (23.5 min) nuclide was based on TBP extraction following rapid conventional wet-ashing. Addition of large amounts of uranium carrier (ca. 50 mg) allowed the chemical yield to be evaluated from the gamma spectrum of the isolated fraction by means of the 186 keV peak of (235)U. In the second approach, the longer-lived (239)Np (56.5 hr) daughter was separated by anion-exchange; this nuclide allowed use of lengthier dissolution procedures employing total decomposition with hydrofluoric acid. Nanogram quantities of (237)Np were irradiated simultaneously with the sample and an aliquot of the resulting solution containing (237)Np and (238)Np (51 hr) was added prior to sample destruction, these isotopes serving as carrier and yield tracer, respectively. Results are presented for a series of reference materials. The methodologies and results from the two approaches are discussed and evaluated.