A rapid radiochemical procedure for uranium determination in natural waters

A neutron activation analysis method for the determination of uranium in natural fresh waters is described. The method is based on a preconcentration step by precipitation of the metal oxinate on a phenolphtalein bed followed by instrumental neutron activation analysis. Preliminary investigations with²³⁹U radiotracer were carried cut to set up the best working conditions and to evaluate the chemical yield. The whole procedure has been applied to the determination of uranium in river water.     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

A simple radiochemical determination of90Sr in environmental samples

A simple procedure for the determination of⁹⁰Sr in environmental samples is described. The method uses the different solubilities of the oxalates of calcium and strontium in presence of a large excess of calcium. For this reason the method is especially suited for Ca-rich samples, as e.g., bones or soils. However, after addition of supplementary calcium it works equally well for other types of samples. The method was tested by analyzing the IAEA Certified Reference Materials soil, animal bone and algae.     

Optimization of a radioanalytical procedure for the determination of uranium isotopes in environmental samples

A radiochemical procedure is described for the fast and sensitive measurement of uranium isotopes in gaseous and liquid effluents of nuclear facilities. Equally, this procedure is suitable to measure uranium isotopes in all kinds of environmental samples. Uranium is leached from ashed sample materials with HNO₃, HF, and Al(NO₃)₃ solution and separated from matrix elements by extraction with trioctylphosphinic oxide and backextraction with NH₄F. After radiochemical cleaning by coprecipitation with LaF₃ and anion exchange, uranium isotopes are electroplated on stainless steel discs from HCl/oxalate solution. The preparation is measured by alpha-spectrometry using surface barrier detectors. The detection limit for 1000 minutes of counting time is 2 mBq per sample and nuclide, the chemical yield is in the range of 50 to 80%.     

Simultaneous radiochemical neutron activation analysis of iodine, uranium and mercury in biological and environmental samples

The determination of medium and long-lived nuclides can be combined with short-lived ones if a medium or long irradiation is made prior to the short irradiation and radiochemical processing. Thus, an RNAA method previously developed for determination of iodine based on the reaction¹²⁷I(n,)¹²⁸I (T _1/2=25 m) using oxygen flask ignition of the irradiated sample, followed by solvent extraction with an iodine-iodide redox cycle, was combined with an overnight preirradiation to induce the²³⁵U fission product¹³³I (T _1/2=20.8 h). By reactivating the sample, cooled 1–2 days after the first irradiation, for few minutes both¹²⁸I and¹³³I could be quantified in the separated iodine fraction. Non-combustible inorganic materials (e.g., sediment, soil, etc.) can be successfully ignited after mixing with excess cellulose powder. Chemical yields for iodine were determined spectrophotometrically in the organic phase, while homogeneously spiked Whatman cellulose powder was used as uranium standard. Mercury is also released on ignition and collected in the absorbing solution, from where it was separated by toluene extraction. Its chemical yield was determined for each aliquot using²⁰³Hg tracer and counting on an LEPD. Results for some suitable SRMs are presented, and the general features of the double irradiation technique discussed.     

A new very sensitive LSC procedure for determination of Tc-99 in environmental samples

A new method for the determination of Tc-99 in different environmental samples has been developed. The sample is carefully ashed in a muffle furnace and then fused with Na₂CO₃ and K₂CO₃. The first step is an enrichment and purification of TcO ₄ ^– on an anion exchange resin. The Tc is desorbed as a cationic thiourea complex, which is held on a cation exchange resin. The complex is destroyed by oxidation to TcO ₄ ^– with (NH₄)₂S₂O₈ in sulfuric acid. From this solution TcO ₄ ^– is extracted into TBP/toluene and the organic phase is mixed with a scintillation cocktail and counted in an anticoincidence shielded LSC. Tc-99m is used as a chemical yield tracer. The decontamination factors for all important fission and activation products and naturally occurring radionuclides are in the range between > 10⁵ and > 10⁸. The detection limit is about 5 mBq per sample at a counting time of 1000 minutes. The maximum sample amount of plants is 500 g dry weight and therefore the lowest detection limit achievable is 10 mBq/kg. Ashing and dissolution of the samples takes 24 h and 4 analyses are performed by one technician in 8 hours. The chemical yield ranges from 50 to 80%.     

A rapid radiochemical procedure for indium

A rapid radiochcmical procedure was developed for the separation of indium radionuclides from a mixed fission-product solution. An alcoholic pyridine solution is added to a uranium solution containing indium and tin carriers. The resulting tin precipitate is separated from the indium-containing solution by filtering through a cellulose membrane filter. The decontamination factor for tin is 2·10³. Other fission products are only partially removed. The chemical yield of indium is about 44%, and the time required for the separation is about 10 sec. After the tin-separated indium has decayed, the tin daughters of indium are removed from all the other fission products at a specified time and measured, so that the amount of indium present at the time of the tin precipitation is determined.     

Rubidium uranium trisulphate: A new chemical assay standard for uranium

Rubidium uranium trisulphate [Rb₂U(SO₄)₃] was prepared as a high purity compound of uranium in different lots of 250 g each. The compound was characterised and evaluated by chemical, atomic spectrosopic, infrared, X-ray diffraction and thermogravimetric methods for its use as a chemical assay standard for uranium. The compound is stoichiometric, pure, homogeneous and stable in atmospheric conditions. The solubility studies showed that Rb₂U(SO₄)₃ is easily soluble in mineral acids. An experiment based on Randomised Block Design was carried out to assign a value to the uranium content in Rb₂U(SO₄)₃ from the statistically analysed chemical data. The assigned value of [34.167±0.042]% to the uranium content is in close agreement with the theoretical value of 34.152%. Based on these studies, Rb₂U(SO₄)₃ is recommended as a chemical assay standard for uranium.     

A sensitive radiochemical assay for Coenzyme A

Summary A simple and sensitive assay for Coenzyme A (CoA) is described. The method is based on coupling the enzymatic reactions of acetyl-CoA synthetase and acetyl-CoA carboxylase. CoA is converted into acetyl-CoA with acetyl-CoA synthetase in the presence of excess ATP and acetate. Acetyl-CoA is subsequently converted into malonyl-CoA with acetyl-CoA carboxylase in the presence of excess ATP and KH¹⁴CO₃. The formation of labelled acid-stable material (i.e. malonyl-CoA) is determined. Under conditions of the assay CoA is quantitatively converted into malonyl-CoA. This procedure permits the detection of as little as 15 pmoles of CoA in biological samples. Elimination of acetyl-CoA synthetase from the reaction mixture allows for the determination of acetyl-CoA.

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Empfindlicher radiochemischer Assay für Coenzym A

Zusammenfassung Ein einfacher und empfindlicher Assay für Coenzym A (CoA) wird beschrieben, der auf einer Kopplung der enzymatischen Reaktionen von Acetyl-CoA-synthetase und Acetyl-CoA-carboxylase beruht. CoA wird mit Hilfe von Acetyl-CoA-synthetase in Gegenwart von überschüssigem ATP und Acetat zu Acetyl-CoA umgesetzt. Dieses wird anschließend mit Acetyl-CoA-carboxylase in Gegenwart von überschüssigem ATP und KH¹⁴CO₃ zu Malonyl-CoA umgewandelt. Die Bildung von markierter säurestabiler Substanz (d.h. Malonyl-CoA) wird bestimmt. Unter den Versuchsbedingungen ist die Umsetzung von CoA zu Malonyl-CoA quantitativ. Noch 15 pMol CoA können in biologischem Material erfaßt werden. Durch Entfernung von Acetyl-CoA-synthetase aus dem Reaktionsgemisch kann auch Acetyl-CoA bestimmt werden.

     

Evaluation of a new generation quadrupole-based ICP-MS for uranium isotopic measurements in environmental samples

We compare the analytical performance of a modern quadrupole-based ICP-MS (“X-Series”, Thermo-Electron, Winsford, UK) with a single-collector double-focusing sector-field ICP-MS (“Axiom”, VG Elemental, Winsford, UK) for uranium isotopic measurements in environmental samples. We focus on the precision and accuracy obtained with both instruments for the ²³⁵U/²³⁸U isotopic ratios and on the abundance sensitivity that is a key parameter for low ²³⁶U/²³⁸U isotopic ratios measurements. We observe that isotopic measurements are more precise accurate with the “X-Series” than with the “Axiom”. Besides, we demonstrate that the “Axiom’s” higher abundance sensitivity limits its capability to measure ²³⁶U/²³⁸U ratio below a few ppm.     

An improved radiochemical procedure for low-level measurements of americium in environmental matrices

The chemical yield and accuracy of measurements of (241)Am at low levels in marine environmental matrices have been substantially improved by applying the extraction procedure with DDCP (dibutyl-N,N-diethylcarbamylphosphonate). The improved procedure is described, and its advantages over the conventional procedure are discussed.     

Development of a radiochemical neutron activation analysis procedure for determination of rhenium in biological and environmental samples at ultratrace level

Summary Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed for accurate determination of rhenium in biological and environmental samples at the sub-ng ^. g^-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng ^. g^-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng ^. g^-1 was found. Significantly elevated values of Re, up to 90 ng ^. g^-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated ⁹⁹Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process.     

Determination of uranium isotopes in environmental samples

The determination of isotopes of uranium by alpha spectrometry in different environmental components (sediments, soil, water, plants and phosphogypsum) is presented and discussed in this paper. The alpha spectrometry is a very convenient and good technique for activity concentration of natural uranium isotopes (²³⁴U, ²³⁵U, ²³⁸U) in environmental samples and provides the most accurate determination of isotopic activity ratios between ²³⁴U and ²³⁸U. The analysis were provided information about possible sources of high concentrations of uranium in the examined sites determined by anthropogenic sources. The calculation of values ²³⁴U/²³⁸U in all analyzed samples was applied to identifying natural or anthropogenic uranium origin. Activity concentration of uranium isotopes in analyzed environmental samples shows that measurement of uranium levels is of great importance for environmental and safety assessment especially in contaminated areas (phosphogypsum waste heap).     

Development of radiochemical analysis of uranium isotopes in highly contaminated soil samples

An accurate and reliable analytical technique of uranium isotopes in highly contaminated soil samples was developed and applied to the IAEA reference samples. The conventional TBP method of uranium isotopes is insufficient to completely purify uranium from actinides such as plutonium and americium isotopes in highly contaminated soil samples. For overcoming the demerits of the conventional TBP extraction method, sample materials were decomposed with HNO₃ and HF, and uranium isotopes were purified by TBP extraction and anion exchange columns and extraction chromatography. Among the purifying methods of uranium, with a TRU Spec resin column after TBP solvent extraction, uranium was completely separated from the radionuclides in a highly contaminated samples. With the modified TBP extraction method, it was found that the concentrations of uranium isotopes were consistent with the reference values reported by the IAEA.     

A rapid iodine radiochemical procedure

A radiochemical procedure was developed to determine fission yields and radiation characteristics of short-lived iodine fission products.Iodine was separated from other fission products of uranium in less than 10 sec after completion of irradiation. High decontamination factors of iodine from Sn, Sb, Te, Xe, Cs and Ba, and high chemical yields were obtained. The sample was prepared by dissolving uranium peroxide in molten periodic acid; the melt was cooled, ground and mixed with activated carbon. After irradiation, the periodic acid was decomposed by heat and the gaseous iodine formed was collected in carbon tetrachloride or in a cooled counting chamber. Higher temperatures could be used than in conventional aqueous systems, thus enhancing the exchange of carrier and fission product iodine.     

Combined procedure using radiochemical separation of plutonium,americium and uranium radionuclides for alpha-spectrometry

Radiochemical separation of Pu, Am and U was tested from synthetic solutions and evaporator concentrate samples from nuclear power plants for isolation of each of them for alpha-spectrometry analysis. The separation was performed by anion-exchange chromatography, extraction chromatography, using TRU resin, and precipitation techniques. The aim of the study was to develop a sensitive analytical procedure for the sequential determination of ²⁴²Pu^{, 238}Pu, ^239+240Pu, ²⁴¹Am and ^{235, 238}U in radioactive wastes. ²³⁸Pu, ²⁴²Pu, ²⁴³Am and ²³²U were used as tracers. The measurements of α emitting radionuclides were performed by semiconductor detector that is used especially when spectrometric information is needed. For synthetic solutions the chemical recovery was based on associated iron concentration and was about 93%.     

A new adsorbent for trace organic analysis in environmental samples

Summary Graphite fluoride has been evaluated as an adsorbent for use in concentrating organic impurities in air and water samples. This material has been shown to yield large breakthrough volumes for most organics and should be useful for trace analysis in environmental chemistry.     

Determination of uranium isotopes in environmental samples by alpha-spectrometry

A new and accurate method for the determination of uranium isotopes (²³⁸U, ²³⁴U and ²³⁵U) in environmental samples by alpha-spectrometry has been developed. Uranium is preconcentrated from filtered water samples by coprecipitation with iron(III) hydroxide at pH 9-10 using an ammonia solution and the precipitate is dissolved in HNO₃ and mineralized with H₂O₂ and HF; uranium in biological samples is ashed at 600 °C, leached with Na₂CO₃ solution and mineralised with HNO₃, HF and H₂O₂; uranium in soil samples is fused with Na₂CO₃ and Na₂O₂ at 600 °C and leached with HCl, HNO₃ and HF. The mineralized or leaching solution in 2M HNO₃ is passed through a Microthene-TOPO (tri-octyl-phosphine oxide) column; after washing, uranium is directly eluted into a cell with ammonium oxalate solution, electrodeposited on a stainless steel disk and measured by alpha-spectrometry. The lower limits of detection of the method is 0.37 Bq^.kg^-1 (soil) and 0.22 mBq^.l^-1 (water) for ²³⁸U and ²³⁴U and 0.038 Bq^.kg^-1 (soil) and 0.022 mBq^.l^-1 (water) for ²³⁵U if 0.5 g of soil and 1 litre of water are analyzed. Five reference materials supplied by the IAEA have been analyzed and reliable results are obtained. Sample analyses show that, the ²³⁸U, ²³⁴U and ²³⁵U concentrations are in the ranges of 0.30-103, 0.49-135 and 0.02-4.82 mBq^.l^-1 in waters, of 1.01-7.14, 0.85-7.69 and 0.04-0.32 Bq^.kg^-1 in mosses and lichens, and of 25.6-53.1, 26.4-53.8 and 1.18-2.48 Bq^.kg^-1 in sediments. The average uranium yields for waters, mosses, lichens and sediments are 74.5±9.0%, 80.5±8.3%, 77.8±4.9% and 89.4±9.7%, respectively.     

Simultaneous determination of trace uranium and vanadium in biological samples by radiochemical neutron activation analysis

Summary A radiochemical neutron activation analysis (RNAA) for simultaneous determination of uranium and vanadium in a single sample at trace levels is described. The method is based on post-irradiation wet-ashing and solvent extraction of vanadium with N-benzoyl-N-phenyl-hydroxylamine reagent. From the remaining aqueous phase, uranium is extracted into a toluene solution of tri-n-butyl phosphate. The chemical yields are determined spectrophotometrically for vanadium and by gamma-counting of the added natural uranium carrier for uranium. The method was evaluated by the analysis of reference materials and the results showed a good agreement with the certified values. The method was applied to the determination of vanadium and uranium in five military total diet samples in Slovenia.