Application of on-line HPLC-ICP-MS for the determination of the nuclide abundances of lanthanides produced via spallation reactions in an irradiated tantalum target of a spallation neutron source

An analytical procedure has been developed for the determination of spallation nuclides in an irradiated tantalum target using HPLC coupled on-line to ICP-MS after dissolution and separation of the tantalum matrix. Pieces of tantalum were taken from different locations of the irradiated tantalum target which had been used as the target material in a spallation neutron source. Tantalum was dissolved in a HNO₃/HF mixture and the tantalum matrix was separated by liquid-liquid extraction so that only the spallation nuclides were left in the sample solutions. The major fraction of the spallation nuclides in the tantalum target are lanthanide metals in the μg g^–1 concentration range determined in the present study. Additional reaction products are formed by the irradiation of trace impurities in the original tantalum target. The nuclide abundances of the lanthanide metals measured in the tantalum target differ significantly from the natural isotopic composition so that a lot of isobaric interferences of long-lived radionuclides and stable isotopes in the mass spectrum are to be expected. Therefore, all the lanthanide metals had to be separated chemically prior to their mass spectrometric determination. The separation of all rare earth elements was performed by ion chromatography on-line to ICP-MS. The nuclide abundances of each lanthanide were determined using a sensitive double-focusing sector field inductively coupled plasma mass spectrometer. The nuclide abundances of the lanthanides in the irradiated tantalum target calculated theoretically and the experimental results obtained by on-line HPLC-ICP-MS proved to be in good agreement.     

Nuclide analysis of a tantalum target irradiated with high-energy protons

First results of γ-spectrometric measurements of radionuclides produced in a tantalum target irradiated for 500 days with 800 MeV protons are presented. The activities of the γ-ray-emitting nuclides measured after a cooling period of 2–4 years differ by more than four orders of magnitude. Within this cooling period about 95% of the activity of the target is determined by¹⁷²Lu,¹⁷³Lu,¹⁷⁴Lu,¹⁷²Hf (daughter nuclide of¹⁷²Lu) and¹⁸²Ta nuclides. These highly active nuclides, together with some other medium-active nuclides, were measured with good precision by γ-ray spectrometry directly in the sample solution. Weakly active nuclides could not be measured in this way because of the high Compton background in the γ-ray spectrum. For the sensitive measurement of many other nuclides present in weaker activities a simple chemical separation procedure was developed to separate Lu, Hf and Ta. With the separation of these elements and simultaneously of the high-active nuclides, the Compton background in the γ-ray spectra could be drastically reduced and many weakly active nuclides additionally measured.     

Preparation of carrier-free group tracers from a gold target irradiated by high-energy heavy ions

A rapid radiochemical separation procedure has been finished by using of radiochemical separation and -spectrum measurement methods. In this isolation procedure, tantalum nuclides produced by the irradiation of natural tungsten targets with 14 MeV neutrons were extracted by methyl isobutyl ketone (MIBK) in the system of HF-HNO₃ mixed solutions. It has been found that tantalum was rapidly and efficiently separated in the isolation procedure and the decontamination factors of tungsten were more than 10⁴. The procedure is simultaneously used to separate tantalum from tungsten bombarded with intermediate energy (47 MeV/u)¹⁸O beams. The measured -spectra showed that tantalum can be separated from most elements produced in the nuclear reactions except for a few elements.     

Experimental Simulation on Separation of Alpha-Particle Induced Rhenium Isotopes from Bulk Tantalum

Trace level tantalum and rhenium, ¹⁸²Ta and ^186,188Re, have been separated with liquid anion exchanger, TOA from HNO₃ medium. The feasibility of the separation process has also been verified for the separation of trace level rhenium from bulk or macro quantity of tantalum. The developed radiochemical scheme will be useful for the separation of carrier-free rhenium radionuclides produced in -particle activated matrix target.     

Determination of radioisotopes of Ce,Eu, Pu,Am and Cm in low-level-wastes from power reactors

Long-lived isotopes of lanthanides and actinides are very important for the disposal of low-level radioactive wastes. These nuclides serve for risk calculations of accidents. Their determination requires radiochemical separation from high activity main nuclides. Supervision of waste vessels is done by direct non-destructive -spectrometry of the key nuclides:⁶⁰Co for corrosion products and¹³⁷Cs as for fission products as for transuranic elements. The activity ratios of the long-lived nuclides to the key nuclides are called scaling factors. They have to be determined radiochemically in the laboratory in representative samples of each waste type. They are used for activity calculations of long-lived nuclides in the waste vessels. The scaling factors determined are of the order of magnitude of 10^–6 and due to the fact that we have used low-level measurement techniques, we could performe the necessary chemical separations in a laboratory not exceeding the 10-fold free-level limit.     

Scaling factors for activated corrosion products in low-level-wastes from power reactors

Long-lived isotopes of corrosion products are very important for the disposal of low-level radioactive wastes. These nuclides serve for risk calculations of accidents. Their determination needs the radiochemical separation from high active main nuclides. Supervision of waste vessels is done by direct non-destructive -spectrometry of the key nuclide⁶⁰Co for corrosion products. The activity ratios of the long-lived nuclides to the key nuclides are called scaling factors. We have determined such factors radiochemically in evaporation residues of power water and cooling water. They are used for activity calculations of long-lived nuclides in the waste vessels. In case of⁵⁹Ni the obtained scaling factor was compared with a literature value and values calculated on the basis of nuclear data. Our value was in a good agreement with the calculated one. Due to the fact, that we have used low-level measurement techniques, we could perform the necessary chemical separations in a laboratory not exceeding the 10-fold free-level limit.     

Laboratory standard for radionuclides in nuclear waste

A laboratory standard for the determination of long-lived radionuclides in nuclear waste has been prepared using concrete as matrix. It will be used to check sample preparation procedures, chemical separations and methods for the determination of nuclides, e.g., nuclear counting techniques or mass spectrometry. The material chosen was a fine-grained ready-to-use cement mixture, to which the following radionuclides were added:⁶⁰Co and¹³⁷Cs as -ray-emitting nuclides,⁹⁹Tc,⁹⁰Sr and⁵⁵Fe as radionuclides emitting pure -radiation or low-energy electrons, and²³³U,²³⁷Np,²³⁸Pu and²⁴¹Am as -emitters. Care was taken to attain a homogeneous distribution of the nuclides in the standard material. Pieces of about 1 g were formed as suitable and representative samples. Repeated analyses were carried out with the standard to check its homogeneity. The analytical procedures are described in brief. The pieces of the standard material have the same content of nuclides within ±5% at a 95% level of confidence.     

Tracer scale solvent extraction separation of tantalum from niobium using di-(2-ethylhexyl)-phosphoric acid as extractant

A simple solvent extraction procedure for the efficient separation of the radioactive tracers⁹⁵Nb and¹⁸²Ta from each other in a mixture using di-(2-ethylhexyl)phosphoric acid (HDEHP) as extractant is described. Tantalum was found to be quantitatively extracted from an aqueous madium, which is 1.6N in HCl and 10^?2 M in oxalic acid, with a HDEHP solution of 0.1 M concentration. Extractabilities of both niobium and tantalum in mineral acids like HCl, H₂SO₄ and HNO₃ and in some organic acids like oxalic, citric, etc., in HDEHP under the experimental conditions were also studied. The reliability of the separation procedure was verified further by γ-ray spectrometry.     

Neutron activation analysis of lithium niobate

A radiochemical neutron activation analysis procedure for the determination of Ta, W, Ir, Pt, Au, Cu, Cr, Co and Zn in lithium niobate has been developed. The method involves a one-step removal of radioactive nuclides of Nb, Ta and W representing the dominating radioactivity of the irradiated sample. After irradiation, the sample is fused with inactive carriers and Na₂O₂ in a nickel crucible. The fused cake is dissolved in HCl–H₂O₂ and Nb, Ta and W are homogeneously precipitated. The impurities are separated by combinations of precipitation and ion-exchange separations for precise -ray measurements with an overall chemical yield of 70% to 90%. The results are discussed.     

Analysis of tantalum by ICP-AES involving trace-matrix separation

Summary A trace-matrix separation technique for the analysis of high-purity tantalum by ICP-AES has been developed to overcome the difficulties caused by the line-richness of this matrix. The procedure is based on the extraction of tantalum with diantipyrylmethane from 12 mol/l HF in dichloroethane. The extraction behaviour of 35 elements has been investigated from which 25 can quantitatively be separated with a residual matrix concentration <0.01% at 1 g sample portion. The achievable limits of detection for ICP-AES are between 0.02 g/g and 10 g/g. The method was applied to the analysis of a high-purity tantalum sample. For a number of elements, the results of this technique are compared with those of other techniques whereby, in general, a good agreement was achieved.     

Determination of trace impurities in tantalum powder and its compounds by inductively coupled plasma optical emission spectrometry using solvent extraction

A procedure was developed for the analysis of 18 trace impurity elements in capacitor-grade tantalum powder (Ta), potassium tantalum fluoride (K₂TaF₇), and tantalum pentoxide (Ta₂O₅) using inductively coupled plasma optical emission spectrometry (ICP-OES). The detection limits achieved were in the ppb levels. The samples were dissolved in hydrofluoric acid (HF) in a microwave digestion system and the Ta matrix was extracted using cyclo hexanone. The impurity traces remained almost completely in the aqueous phase. The text was submitted by the authors in English.     

The determination of tantalum and tungsten in rocks and meteorites by neutron activation analysis

A method for the determination of Sub-microgram amounts of tantalum and tungsten in rocks and meteorites by neutron activation analysis is described Radiochemical suparation from the components of the irradiated sample was employed to provide sources for measuring ¹⁸²Ta and ¹⁸⁷W by beta and gamma counting and by gamma spectrometry. Determinations of tantalum at the lower limit of 8.10^-10 g and tungsten at 2.10^-9 g have been made Amongst the materials examined using the method were the intercomparison rocks G₁ and W₁, rock samples from the Skaergaard Intrusion of East Greenland and a number of iron and stony meteorites In addition a number of standard steel samples of known tungsten content and one of known tantalum content were examined and good agreement was observed between the published results and those determined by activation analysis     

Direct determination of trace elements in niobium,tantalum and their oxides by inductively coupled plasma atomic emission spectrometry after microwave dissolution

Analytical schemes for the determination of trace elements in high-purity niobium, tantalum and their oxides are proposed. The schemes are based on microwave dissolution of the metals and oxides followed by inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of impurities in the solutions. The possibilities of interelement and off-peak background corrections in ICP-AES analysis are discussed. The accuracy of the results obtained is confirmed by the determination of trace elements after a matrix sorption separation procedure. For a number of elements, a comparison of the results obtained by ICP-AES without and with the matrix separation procedure and by electrothermal atomic absorption spectrometry (ETAAS) shows good agreement. The limits of detection for direct ICP-AES determination are in the range 0.4*1.0 μg g⁻¹ for Ba, Ca, Fe, Mg, Mn, Y and La; between 2.0 and 10.0 μ g⁻¹ for B, Cd, Co, Cr, Cu, Hf, Mo, Na, Nb, Ni, Pb, Sr, Ti, Zr and Ta; and for K, Sb and W a detection limit of 20 μ g⁻¹ is achieved. The schemes proposed are intended for rapid routine analysis.     

Determination of traces of uranium in tungsten and molybdenum by radiochemical neutron activation analysis via the fission product140Ba

A radiochemical separation procedure has been developed to determine traces of uranium in tungsten and molybdenum. In this procedure the fission product¹⁴⁰Ba, as indicator nuclide for uranium, is selectively separated from the matrix activities and from all other long-lived activation and fission products and obtained at high purity. The radionuclide in the final fraction is sufficiently pure so that it can be measured with high counting efficiency by -counting. The separation procedure consists of two steps: a cation-exchange separation to separate barium from the anionic matrix tungste or molybdate, and many other elements. In the second step the Ba-fraction is further purified by precipitation of barium as barium chloride in 8M hydrochloric acid. The precipitate is then dissolved in water for -counting via the Cerenkov effect. The chemical yield for barium is 94.6±2.6%. When samples of 0.1 g, a thermal neutron flux of 2·10¹³ n·cm^–2·s^–1, an irradiation time of 10 hours and a measuring time of 2 hours were applied, then the detection limit of uranium was 4 ng/g.Presented at the 3rd Intern. Conf. on Nuclear and Radiochemistry, Vienna, September 7–11, 1992.     

Separation of182Ta from biological material by precipitating it as tantalum phosphate

The method of the separation of¹⁸²Ta from urine and stool by precipitating as tantalum phosphate was elaborated. The conditions of Ta phosphate precipitation as well as coprecipitation of⁴⁵Ca,¹⁰⁶Ru,¹⁴⁴Ce,¹⁴⁷Pm,¹⁵²Eu,⁶⁰Co,⁹⁰Sr,⁹⁰Y,⁹⁵ Zr,⁹⁵Nb and U were studied. The results show that tantalum can be separated from all macrocomponents of the mineralized biological material and from the great number of radionuclides which can be present in the sample.     

The use of universal comparator method in large-scale NAA

For simplicity and unification of the comparator methods it is proposed to obtain a calibrating function of changing relative efficiency of registrating -radiation for any geometry of measurement (for any detector) from -spectrum comparator isotopes directly. In determining elements by their short- and medium-lived radionuclides the comparators⁵²V and²⁴Na were used. Biisotope comparator (⁶⁵Zn,¹²²Eu or¹⁸²Ta) was used for long-lived radionuclides. The developed universal comparator method significantly simplifies the procedures for determining relative registration efficiencies of analytical lines of interesting radionuclides, thus reducing the labor and time requirements of analysis; this is very important in the case of a large scale NAA.     

Simultaneous determination of tantalum and hafnium in silicates by neutron activation analysis

A neutron activation procedure suitable for the routine determination of tantalum and hafnium in silicates is described. The irradiated sample is fused with sodium peroxide and leached, and the insoluble hydroxides are dissolved in dilute hydrofluoric acid-hydrochloric acid. After LaF₃ and AgCl scavenges, tantalum and hafnium are separated by anion exchange. Tantalum is obtained radiochemically pure; ²³³Pa and ⁹⁵Zr contaminants in the hafnium fraction are resolved by γ-ray spectrometry. The chemical yield of the procedure is detemined after counting by re-irradiation. Values for the 8 U.S. Geological Survey standard rocks are reported.     

Separation of Carrier-Free 176,177W and 176,177Ta Produced in 16O Irradiated Holmium Target

Carrier-free radionuclides of tungsten and tantalum, ^176,177W and ^176,177Ta have been produced by heavy ion activation of holmium target with 97 MeV ¹⁶O⁵⁺ beam. Radiochemical separation scheme has been developed to isolate tungsten and tantalum radionuclides from the holmium target matrix.     

7LiOH solution — A suitable reagent to collect volcanic gas samples for NAA

Commercially available⁷LiOH was used for collecting volcanic gas samples on the island of Vulcano, Southern Italy, to determine trace elements by NAA. The high -background activity, which is induced when NaOH solutions are used as collecting agents was avoided in this way. While several elements (Cl, Br, I, As) could be determined in the collected samples, activation products of impurities in⁷LiOH produced considerable -background and this prevented the determination of other trace elements. An ion-exchange procedure for reducing impurities in⁷LiOH solutions, in particular of Hg, Ta and W, was then developed and is described here. This procedure, supplemented by steps to eliminate interference from¹⁸F in the irradiated samples due to small amounts of⁶Li in the⁷LiOH employed will allow very sensitive determinations of further trace elements in volcanic gases.     

Determination of silicon in high purity metals by radiochemical NAA and CPAA

The indicator radionuclide³¹Si produced in neutron and deuteron activation analysis for silicon via the reactions³⁰Si(n,) and³⁰Si(d,p), respectively, is specifically separated from the irradiated sample by distillation as³¹SiF₄. In the case of aluminium, the distillation is carried out from a HF(HNO₃)H₂O₂ medium and in the case of molybdenum, niobium, tantalum, titanium and vanadium from a HF/HNO₃/HBr/H₂SO₄ medium. Using liquid scintillation counting, the achievable detection limits for neutron activation analysis are, depending on the type of the matrix, between 4–50 ng/g, and for the deuteron activation analysis of tantalum the detection limit is 5 ng/g.