A simple method for the determination of uranium and thorium by delayed neutron counting

A simple method for the determination of uranium and thorium by delayed neutron counting is described. One portion of the sample is irradiated in a reactor and the delayed neutrons are counted. Another portion of the sample is mixed with B₄ C powder absorbing the thermal neutrons, and irradiated in the same position. From those data, both uranium and thorium can be calculated when a quantitative calibration has been made beforehand. The detection limits for the pure elements are 0.07 ppm for uranium and 2 ppm for thorium with the minimum analyzing time being 2 min. The accuracy of the method is investigated by comparing results obtained by the method described here with results obtained by epithermal activation analysis.     

Boron in natural waters by atomic absorption spectrometry with electrothermal atomization

Rapid scanning of numerous rock samples when prospecting for uranium and thorium ores can be facilitated by using the shorter-lived nuclides. The samples are activated during short epithermal neutron irradiations and the 20-min activities of ²³⁹U and ²³³Th are observed instrumentally with a small Ge(Li) detector. The detection limits for uranium and thorium are less than 1 ppm and 20 ppm, respectively.     

X射线荧光光谱法同时测定矿石中铀和钍

建立了X射线荧光光谱法测定矿石样品中铀、钍含量的快速分析方法。采用高压粉末制样法,对不同含量的放射性样品的压片压力、粒径、含水率、用量等处理条件到进行单因素实验。在400 MPa压力下压制,克服了低压制样的弊端,制备的样片表面光滑、致密,大幅改善了制样重现性,有效地减少了部分基体效应,铀校准曲线的标准偏差从0.053%降到0.0071%,钍校准曲线的标准偏差从0.062%降到0.0057%。经国家一级标准物质验证,表明方法准确、可靠,能满足样品中铀、钍含量日常分析要求。     

Non-destructive determination of uranium and thorium in geological materials by resonance-neutron activation analysis

A simple method is described for the determination of uranium and thorium in gological materials. The samples are irradiated in a reactor with resonance and fast neutrons behind a cadmium filter. Compared with an irradiation with the whole reactor neutron spectrum, the matrix activities are reduced to about 1%, those of uranium (²³⁹Np) and thorium (²³³Pa) to about only 50 and 25%, respectively. This relative diminution of matrix activities allows the γ-measurement of²³⁹Np and²³³Pa as early as after two days' cooling time; in samples with high uranium contents the determination of²³³Pa requires one month's cooling time. This non-destructive procedure yields a detection limit of 0.1 ppm for uranium and thorium in samples of 200 mg, with an error of ±5%. Dedicated to ProfessorW. Borchert on the occasion of his 60th birthday.     

Solid phase extraction of uranium and thorium on octadecyl bonded silica modified with Cyanex 302 from aqueous solutions

A simple and reliable method for rapid extraction and determination of uranium and thorium using octadecyl-bonded silica modified with Cyanex 302 is presented. Extraction efficiency and the influence of various parameters such as aqueous phase pH, flow rate of sample solution and amount of extractant has been investigated. The study showed that the extraction of uranium and thorium increase with increasing pH value and was found to be quantitative at pH 6; and the retention of ions was not affected significantly by the flow rate of sample solution. The extraction percent were found to be 89.55 and 86.27 % for uranium and thorium, respectively. The maximal capacity of the cartridges modified by 30 mg of Cyanex 302 was found to be 20 mg of uranium and thorium. The method was successfully applied to the extraction and determination of uranium and thorium in aqueous solutions. The percentage recovery of uranium and thorium in a number of natural as well as seawater samples of Iran were also investigated and found to be in the range of 85–95 %.     

Comparison studies adsorption of thorium and uranium on pure clay minerals and local Malaysian soil sediments

Adsorption studies of thorium and uranium radionuclides on 9 different pure clay minerals and 4 local Malaysian soil sediments were conducted. Solution containing dissolved thorium and uranium at pH 4.90 was prepared from concentrate sludges from a long term storage facility at a local mineral processing plant. The sludges are considered as low level radioactive wastes. The results indicated that the 9 clay minerals adsorbed more uranium than thorium at pH ranges from 3.74 to 5.74. Two local Malaysian soils were observed to adsorb relatively high concentration of both radionuclides at pH 3.79 to 3.91. The adsorption value 23.27 to 27.04 ppm for uranium and 33.1 to 50.18 ppm for thorium indicated that both soil sediments can be considered as potential enhanced barrier material for sites disposing conditioned wastes containing uranium and thorium.     

Application of ion-exchange separations to determination of trace elements in natural waters-IX: simultaneous isolation and determination of uranium and thorium

A method is described for the determination of uranium and thorium in samples of natural waters. After acidification with citric acid the water sample is filtered and sodium citrate and ascorbic acid are added. The resulting solution of pH 3 is passed through a 4-g column of Dowex 1 x 8 (citrate form) on which both uranium and thorium are adsorbed as anionic citrate complexes. Thorium is eluted with 8M hydrochloric acid and separated from co-eluted substances by anion-exchange in 8M nitric acid medium on a separate 2-g column of the same resin in the nitrate form. After complete removal of iron by washing with a mixture consisting of IBMK, acetone and 1M hydrochloric acid (1:8:1 v v ) and treatment of the resin with 6M hydrochloric acid, the uranium is eluted from the 4-g column with 1M hydrochloric acid. In the eluate thorium is determined spectrophotometrically (arsenazo III method) while fluorimetry is employed for the assay of uranium. The procedure was used for the determination of uranium and thorium in numerous water samples collected in Austria, including samples of mineral-waters. The results indicate that a simple relationship exists between the uranium and thorium contents of waters which makes it possible to calculate the approximate thorium content of a sample on the basis of its uranium concentration and vice versa.     

Validation of scanning electron microscope (SEM), energy dispersive X-ray (EDX) and gamma spectrometry to verify source nuclear material for safeguards purposes

Ten ore samples, two unpurified yellow cake samples and natural uranyl nitrate hexahydrate sample were analyzed by Scanning Electron Microscope (SEM) and Energy Dispersive X-ray (EDX) method to verify source nuclear material. Samples represent source nuclear material as possible. All samples were scanned at ideal conditions; working distance = 10 mm, voltage = 30 kV, magnification value = × 100, spot size = 50 to screen samples for the presence of uranium and thorium, Also Hyper pure germanium (HPGe) gamma spectrometers were applied to estimate the uranium and thorium contents in Bq/kg (ppm). For the ore samples uranium-238 ranges from 1,049.23 Bq/kg (85.30 ppm) to 2,096.06 Bq/kg (170.41 ppm), uranium-235 ranges from 47.51 to 105.61 Bq/kg and thorium-232 ranges from 22.84 Bq/kg (5.65 ppm) to 41.78 Bq/kg (10.34 ppm). For the yellow cake samples and uranyl nitrate hexahydrate uranium-238 ranges from 42.99 Bq/kg (3.50 ppm) to 71,887.2 Bq/kg (5,844.49 ppm) and thorium-232 is 4.78 Bq/kg (1.83 ppm) and the other two samples are lower than the detection limit.     

Fast sensitive analysis of uranium and thorium in natural samples based on delayed neutron counting using an ultrafast conveyor tube system

A fast, sensitive and routine methode for quantitative analysis of uranium and thorium in natural samples is described. The identification is done by counting the delayed neutrons of mainly the short living fission products after sample-irradiation with and without cadmium shielding. The rabbit system used is installed at the Forschungsreaktor Neuherberg, type TRIGA Mark III. The limits of detection (relative to 2 g of sample weight) were specified to be 20 ppb (U) and 3 ppm (Th) using puls irradiations, 150 ppb (U) and 15 ppm (Th) using 1 MW steady state reactor power. A single determination is done within less than 60 s. The methods were proved by about 3000 measurements also including comparison experiments.     

Determination of uranium and thorium in complex samples using chromatographic separation, ICP-MS and spectrophotometric detection

The paper describes a research of possible application of UTEVA and TRU resins and anion exchanger AMBERLITE CG-400 in nitrate form for the isolation of uranium and thorium from natural samples. The results of determination of distribution coefficient have shown that uranium and thorium bind on TRU and UTEVA resins from the solutions of nitric and hydrochloric acids, and binding strength increases proportionally to increase the concentration of acids. Uranium and thorium bind rather strongly to TRU resin from the nitric acid in concentration ranging from 0.5 to 5 mol L⁻¹, while large quantities of other ions present in the sample do not influence on the binding strength. Due to the difference in binding strength in HCl and HNO₃ respectively, uranium and thorium can be easily separated from each other on the columns filled with TRU resin. Furthermore, thorium binds to anion exchanger in nitrate form from alcohol solutions of nitric acid very strongly, while uranium does not, so they can be easily separated. Based on these results, we have created the procedures of preconcentration and separation of uranium and thorium from the soil, drinking water and seawater samples by using TRU and UTEVA resins and strong base anion exchangers in nitrate form. In one of the procedures, uranium and thorium bind directly from the samples of drinking water and seawater on the column filled with TRU resin from 0.5 mol L⁻¹ HNO₃ in a water sample. After binding, thorium is separated from uranium with 0.5 mol L⁻¹ HCl, and uranium is eluted with deionised water. By applying the described procedure, it is possible to achieve the concentration factor of over 1000 for the column filled with 1 g of resin and splashed with 2 L of the sample. Spectrophotometric determination with Arsenazo III, with this concentration factor results in detection limits below 1 μg L⁻¹ for uranium and thorium. In the second procedure, uranium and thorium are isolated from the soil samples with TRU resin, while they are separated from each other on the column filled with anion exchanger in alcohol solutions. Anion exchanger combined with alcohol solutions enables isolation of thorium from soil samples and its separation from a wide range of elements, as well as spectrophotometric determination, ICP-MS determination, and other determination techniques.     

Simultaneous Spectrophotometric Determination of Uranium and Thorium Using Arsenazo III by H‐Point Standard Addition Method and Partial Least Squares Regression

Simultaneous determination of uranium and thorium using arsenazo III as a chromogenic reagent at pH 1.70 by H‐point standard addition method (HPSAM) and partial least squares (PLS) calibration is described. Under optimum conditions, the simultaneous determinations of uranium and thorium by HPSAM were performed. The absorbencies at one pair of wavelengths, 649 and 669 nm, were monitored with the addition of standard solutions of uranium. The results of applying the HPSAM showed that uranium and thorium can be determined simultaneously with weight concentration ratios of uranium to thorium varying from 20:1 to 1:15 in the mixed sample. By multivariate calibration methods such as PLS, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. In this study, the calibration model is based on absorption spectra in the 600–750 nm range for 25 different mixtures of uranium and thorium. Calibration matrices contained 0.10–21.00 and 0.25–18.5 μg mL^?1 of uranium and thorium, respectively. The RMSEP for uranium and thorium were 0.7400 and 0.7276, respectively. Both proposed methods (HPSAM and PLS) were also successfully applied to the determination of uranium and thorium in several synthetic and real matrix samples.     

Separation behavior of U(VI) and Th(IV) on a cation exchange column using 2,6-pyridine dicarboxylic acid as a complexing agent and its application for the rapid separation and determination of U and Th by ion chromatography

The retention behavior of U and Th as their 2,6-pyridine dicarboxylic acid (PDCA) complexes on a cation exchange column was investigated under low pH conditions. Based on the observed retention characteristics, an ion chromatographic method for the rapid separation of uranium and thorium in isocratic elution mode using 0.08 mM PDCA and 0.24 M KNO(3) in 0.22 M HNO(3) as the eluent was developed. Both uranium and thorium were eluted as their PDCA complexes within 2 min, whereas the transition and lanthanide metal cations were eluted as an unresolved broad peak after thorium. Under the optimized conditions both U and Th have no interference either from alkali and alkaline earth elements up to a concentration ratio of 1:500 or from other elements up to 1:100. The detection limits (LOD) of U and Th were calculated as 0.04 and 0.06 ppm, respectively (S/N=3). The precision in the measurement of peak area of 0.5 ppm of both U and Th was better than 5% and a linear calibration in the concentration range of 0.25-25 ppm of U and Th was obtained. The method was successfully applied to determine U and Th in effluent water samples.     

Solid phase extraction and preconcentration of uranium(VI) and thorium(IV) on Duolite XAD761 prior to their inductively coupled plasma mass spectrometric determination

A simple and effective method is presented for the separation and preconcentration of thorium(IV) and uranium(VI) by solid phase extraction on Duolite XAD761 adsorption resin. Thorium(IV) and uranium(VI) 9-phenyl-3-fluorone chelates are formed and adsorbed onto the Duolite XAD761. Thorium(IV) and uranium(VI) are quantitatively eluted with 2 mol L⁻¹ HCl and determined by inductively coupled plasma-mass spectrometry (ICP-MS). The influences of analytical parameters including pH, amount of reagents, amount of Duolite XAD761 and sample volume, etc. were investigated on the recovery of analyte ions. The interference of a large number of anions and cations has been studied and the optimized conditions developed have been utilized for the trace determination of uranium and thorium. A preconcentration factor of 30 for uranium and thorium was achieved. The relative standard deviation (N = 10) was 2.3% for uranium and 4.5% for thorium ions for 10 replicate determinations in the solution containing 0.5 μg of uranium and thorium. The three sigma detection limits (N = 15) for thorium(IV) and uranium(VI) ions were found to be 4.5 and 6.3 ng L⁻¹, respectively. The developed solid phase extraction method was successively utilized for the determination of traces thorium(IV) and uranium(VI) in environmental samples by ICP-MS.     

Uranium, thorium and potassium contents and radioactive equilibrium states of the uranium and thorium series nuclides in phosphate rocks and phosphate fertilizers

Uranium, thorium and potassium contents and radioactive equilibrium states of the uranium and thorium series nuclides have been studied for 2 phosphate rocks and 7 phosphate fertilizers. Uranium contents were found to be rather high (39-117 ppm) except for phosphate rock from Kola. The uranium series nuclides were found to be in various equilibration states, which can be grouped into following three categories. Almost in the equilibrium state, 238U approximately 230Th greater than 210Pb greater than 226Ra and 238U greater than 230Th greater than 210Pb greater than 226Ra. Thorium contents were found to be, in general, low and appreciable disequilibrium of the thorium series nuclides was not observed except one sample. Potassium contents were also very low (less than 0.3% K2O) except for complex fertilizers. Based on the present data, discussions were made for the radiation exposure due to phosphate fertilizers.     

Determination of thorium,uranium and plutonium isotopes in atmospheric samples

A new procedure for the radiochemical measurements of thorium, uranium and plutonium in atmospheric samples is described. Analysis involves coprecipitation of these actinides with iron hydroxide from a 40-to 50-dm³ sample of rainwater, followed by radiochemical separation and purification procedures by the use of ion exchange chromatography (Dowex AG1×8) and solvent extraction. The new procedure enables one to determine the isotopes of thorium, uranium and plutonium, which are found in rainwater at extremely low concentrations, with a chemical yield ranging from 60 to 80%.     

Untersuchungen an Geologischen Materialien Durch Messung der Natürlichen Gamma-aktivität

Investigations of natural activity of several geological materials by γ-spectrometry using a Ge(Li)-detector are described. The determination of thorium and uranium contents is possible up to minimum concentrations of about 10 ppm Th and 1 ppm U. The results of this method are compared with results of different methods of activation analysis. In the most cases the agreement is very well. If the decay-chain of²³⁸U is not in equilibration, it is possible to estimate the geological oldness of the sample in a range between about 20 000 and 200 000 years.     

A titrimetric method for the sequential determination of thorium and uranium

A method for the sequential determination of thorium and uranium has been developed. In the sample solution containing thorium and uranium, thorium is first determined by complexometric titration with ethylenediaminetetraacetic acid (EDTA) and then in the same solution uranium is determined by redox titration employing potentiometry. As EDTA interferes in uranium determination giving positive bias, it is destroyed by fuming with HClO₄ prior to the determination of uranium. A precision and accuracy of better than ±0.15% is obtained for thorium at 10mg level and uranium ranging from 5 mg to 20 mg in the aliquot.     

Determination of uranium,thorium and potassium contents of rock samples in Yemen

Uranium, thorium and potassium contents in 16 different rock samples from various sites in Republic of Yemen were determined using three different techniques of analysis: γ-spectrometry, Instrumental neutron activation analyses (INAA) and X-ray fluorescence (XRF). The concentration range for thorium, uranium and potassium were found to be from 9,810 ± 272 to 3.6 ± 1.3 ppm, 1,072 ± 40 to 1.2 ± 0.7 ppm and 11 ± 1 to 0.26 ± 0.05%, respectively.     

Fluorimetric estimation of U(VI) in the presence of a large excess of Th(IV)

A fluorescence based method has been developed for the determination of trace amounts of uranium in thorium matrix using a mixture of phosphoric acid (H₃PO₄) and sulfuric acid (H₂SO₄), as fluorescence enhancing reagent for uranyl (UO₂ ²⁺) ion fluorescence. Synthetic samples mimicking the composition of ThO₂ fuel were prepared and the concentration of U(VI) was estimated. Satisfactory results are obtained when uranium is present at a concentration of 10 ppm in solid thorium samples with good precision.     

Direct determination of thorium in uranium oxide by X-ray fluorescence

Summary Thorium in uranium is determined directly at trace levels by an XRF method. Uranium oxide samples are put in the form of double layer pellets and analysed by using Philips PW-1220 X-ray spectrometer. The typical value of the precision of the method at 200 ppm level is ±10% and estimation range is 50–1000 ppm of thorium in uranium.

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Direkte Bestimmung von Thorium in Uranoxid durch Röntgenfluorescenz-Spektrometrie

Zusammenfassung Mit Hilfe der beschriebenen Methode kann Th in Spurenkonzentrationen direkt bestimmt werden. Die Uranoxidproben werden als Doppelschicht-Tabletten eingesetzt und mit Hilfe eines Philips PW-1220 Röntgenspektrometers analysiert. Die Genauigkeit im Bereich von 200 ppm beträgt ±10%. Der Anwendungsbereich liegt bei 50–1000 ppm.