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).     

Determination of isotopic ratios of uranium samples using passive gamma spectroscopy with multiple detectors

Uranium samples of various enrichments have been passively counted on the University of Texas detector gamma–gamma coincidence system. By observing gamma rays emitted from ²³⁵U and its daughters compared to gamma rays emitted by ²³⁸U daughters and comparing the data to standards of known enrichments, a technique has been developed to take a uranium sample of unknown enrichment and passively count it to determine its uranium isotopic concentration. Because the gamma rays from ²³⁵U are generally in the low-energy regime, there is a strong susceptibility to background interferences, especially from the Compton background produced from higher energy gamma rays. Other interferences, such as those from the decay series of uranium also exist for ²³⁵U gamma rays. In this light, we have collected data using list-mode to produce two-dimensional gamma–gamma coincidence spectra, which allows us to gate the low-energy gamma rays from ²³⁵U with gamma rays that are in coincidence. In doing this, much of the low energy interferences are reduced, and one can analyze the ²³⁵U gamma rays with high precision. Because of the high density of uranium, self-shielding has significant effects especially in the low-energy regime. To correct for this attenuation the detector system has been modeled by MCNP and self-shielding factors have been calculated across the energy spectrum. A big advantage to this method is the capability of performing this analysis with small (<1 g) samples in a non-destructive and relatively inexpensive manner. If necessary, this analysis can be performed within 24 h if an urgent nuclear forensics scenario arises.     

Rapid measurements of concentrations of natural uranium in process stream samples via gamma spectrometry at an extraction facility

A new application of gamma spectrometry in the efficient measurement of natural uranium in the process stream at an extraction plant is described here. The inherent nuclear properties of uranium viz. emanation of characteristic gamma rays (185.7 keV) has been exploited for the determination of concentrations ranging from 5 to 450 g l⁻¹ by passive photon counting of 185.7 keV gamma rays from ²³⁵U isotope for a maximum of 3-10 min per sample. This technique is totally matrix independent unlike other instrumental analytical techniques like wavelength dispersive X-ray fluorescence spectrometry and UV-vis spectrophotometry. Solution samples of aqueous and organic phase can be directly counted without the requirement of sample preparation. A MINIM-based gamma spectrometer consisting of a multichannel pulse height analyzer and a 3 in. × 3 in. well-type NaI(Tl) scintillation detector with an approximately 2 in. thick lead shield has been employed for the measurements. The results are compared with those obtained by potentiometry and wavelength dispersive X-ray fluorescence spectrometry (WD-XRF). Relative standard deviation of 1-5% has been obtained depending upon the concentration of uranium, which is more than adequate for routine process control samples. This paper also discusses in detail the problems associated with the determination of high concentrations of uranium in using 63 and 93 keV gamma rays emanating from ²³⁴Th (t_1/2 24 days) the immediate daughter of ²³⁸U isotope in samples that have attained secular equilibrium and the limitations of these energies in the routine analysis of freshly extracted uranium.     

Comparative determination of uranium in rock phosphates and columbite by ICP-OES,alpha &; gamma spectrometry

During this work selective separation of uranium from rock phosphate and columbite mineral was done before its quantitative estimation by using Inductively Coupled Plasma Optical Emission Spectrometery (ICP-OES). Uranium from the rock phosphate and columubite was extracted by sodium peroxide fusion followed by leaching in 2 M HNO₃. To avoid spectral interference in the estimation of uranium by ICP-OES, the selective separation of uranium from the leachate was carried out by using two different extractants, 30% Tributyl Phophates (TBP) in CCl₄ and a equi-volume mixture of Di(2-ethylhexyl) phosphoric acid (D2EHPA) & TBP in petrofin. Uranium was stripped from the organic phase by using 1 M ammonium carbonate solution. Determination of uranium by ICP-OES was done after dissolving the residue left after evaporation of ammonium carbonate solution in 4% HNO₃. The concentration of the uranium observed in the rock phosphates samples was 40–200 μg g⁻¹ whereas in columbite samples the concentration range was 100–600 μg g⁻¹. Uranium concentration evaluated by ICP-OES was complimented by gamma & alpha spectrometry. Concentration of uranium evaluated by gamma spectrometry in case of rock phosphate and coulmbite was in close agreement with the uranium content obtained by ICP-OES. Uranium determination by alpha spectrometry showed only minor deviation (1–2%) from the results obtained by ICP-OES in case of rock phosphates whereas in case of coulmbites results are off by 20–30%.     

The analysis of uranium-232: comparison of radiochemical techniques and an improved method by alpha spectrometry

Uranium-232 is an isotope of interest for nuclear forensic studies because it can provide information on the irradiation history of a sample of uranium. The isotope is formed in uranium materials through several pathways and is typically found at ultra-trace levels (usually ng/g or smaller) in typical uranium materials. The low abundance of this isotope in irradiated materials makes it very difficult to measure accurately and precisely. Many different methods have been proposed for the analysis of ²³²U using radiochemical methods including alpha and gamma spectrometry. In this paper, literature methods will be discussed and an improved method using alpha spectrometry will be presented. Alpha spectrometry offers a direct analysis technique for measuring ²³²U, with few interferences that can be removed via separations. Results from our improved method will be presented and compared to results obtained from a non-destructive gamma spectrometry method that utilizes an indirect measurement. LA-UR-12-20186.     

Dissolution of resistate minerals containing uranium and thorium: Environmental implications

Summary Minerals in the soil range from those that easily weather to those that are very resistant to the weathering processes. The minerals used in this study are referred to as “resistates” because of their resistance to natural weathering processes.¹ It is also known that there are some resistate minerals that have a tendency to contain uranium and thorium within their crystal structure. These resistates can contain as much as 15-20% of the total uranium and thorium present in the soil.⁹ Do resistates dissolve in acids, particularly in the HF/HNO₃ procedures, if not what can be done to the HF/HNO₃ process to dissolve more of the resistate minerals? How would these acid techniques compare to the fusion method used for mineral dissolution? Could the resistate minerals contain considerable amount of uranium and thorium? These were the questions addressed in this research. The comparative data indicate that the use of H₂SO₄ in the dissolution process resulted in ~25% overall increase in the minerals dissolving therefore resulting in a higher yield of extracted uranium and thorium.     

A comparison of two nuclear analytical techniques for determination of 210Pb-specific activity in solid environmental samples

Two nuclear analytical techniques for determination of ²¹⁰Pb-specific activity in solid environmental samples have been validated and compared. The first technique depends on determination of ²¹⁰Pb via its alpha emitting daughter ²¹⁰Po using alpha-particle spectrometry, while the second technique is based on direct determination of ²¹⁰Pb by measuring its activity at the 46-keV gamma line by low-energy gamma-ray spectrometry. Detection limits, repeatability, reproducibility, and surrogate recovery were the main validation parameters. Measurement uncertainties were estimated and compared for both techniques. Results of this study have shown that the expected activity of ²¹⁰Pb in the environmental samples and the required measurement uncertainty are the main factors influencing a selection of the appropriate method for the application.     

Fluorimetric determination of uranium in certain refractory minerals,environmental samples and industrial waste materials

Summary A simple sample decomposition and laser fluorimetric determination of uranium at trace level is reported in certain refractory minerals, like ilmenite, rutile, zircon and monazite; environmental samples viz. soil and sediments; industrial waste materials, such as, coal fly ash and red mud. Ilmenite sample is decomposed by heating with ammonium fluoride. Rutile, zircon and monazite minerals are decomposed by fusion using a mixture of potassium bifluoride and sodium fluoride. Environmental and industrial waste materials are brought into solution by treating with a mixture of hydrofluoric and nitric acids. The laser induced fluorimetric determination of uranium is carried out directly in rutile, zircon and in monazite minerals and after separation in other samples. The determination limit was 1 μg ^. g^-1 for ilmenite, soil, sediment, coal fly ash and red mud samples, and it is 5 μg ^. g^-1 for rutile, zircon and monazite. The method is also developed for the optical fluorimetric determination of uranium (determination limit 10 μg ^. g^-1) in ilmenite, rutile, zircon and monazite minerals. The methods are simple, accurate, and precise and they require small quantity of sample and can be applied for the routine analysis.     

Performance of alpha spectrometry in the analysis of uranium isotopes in environmental and nuclear materials

The accuracy of alpha spectrometry in the determination of uranium isotopes at various concentrations levels and with various isotope ratios was tested in a round robin international intercomparison exercise. Results of isotope activity/mass and isotope mass ratios obtained by alpha spectrometry were accurate in a wide range of uranium masses and in isotopic ratios typical of depleted, natural, and low enriched uranium samples. Determinations by alpha spectrometry compared very satisfactorily in accuracy with those by mass spectrometry. For example, determination of U isotopes in natural uranium by alpha spectrometry agreed with mass spectrometry determinations at within ±1%. However, the ²³⁶U isotope, particularly if present in activities much lower than ²³⁵U, might not be determined accurately due to overlap in the alpha particle energies of these two uranium isotopes.     

A modified method for the determination of uranium in Nb/Ta minerals by LED fluorimetry

A modified LED fluorimetry determination of uranium in Nb/Ta minerals has been developed. The mineral is brought into solution by fusion with mixed phosphate flux (NaH₂PO₄, H₂O and Na₂HPO₄). Iron quenches uranium fluorescence when it is present above the ratio of (iron to uranium) 100. Uranium is separated in ethyl acetate by solvent extraction and then stripped back into pyrophosphate buffer (pH ~ 7) prior to its LED fluorimetry determination. This modified method has been applied for the determination of uranium in synthetic mixtures and Nb/Ta minerals including Certified Reference Materials (X1807) with high degree of accuracy and precision.

     

A quick method to determine uranium concentration by gamma spectroscopy: Its application for extraction of uranium from wet phosphoric acid

A rapid and accurate method to measure uranium was established using gamma spectroscopy with a high purity germanium detector. This can be done by measuring the gamma radiation intensity at 186 keV which corresponds to the concentration of ²³⁵U only since all the ²²⁶Ra which also shows a peak at this energy level, remains in the solid phosphogypsum. The method was proved to be accurate when compared with other methods. It has also the advantage of measuring uranium concentrations over a wide range suitable to the operation of the pilot plant for extraction of uranium from wet process phosphoric acid without the need to dilution or concentration. It can also measure the uranium in the different media such as acid, organic or alkaline media found in the pilot plant at different stages.     

Instrumental neutron activation determination of rare earth,noble and other elements in mineral raw materials of The Socialist Republic of Vietnam

The possibilities of multielement neutron activation analysis of the mineral raw materials of the Socialist Republic of Vietnam, have been studied. Samples were activated by a²⁵²Cf neutron source (yield 4·10⁹ n·s^–1). The induced activity was measured by coaxial Ge(Li) and planar Ge detectors. The content of gold, thorium, uranium, rare earths and other elements, was determined and evaluated in ores and concentrates by an absolute method.     

Advances in technologies for the measurement of uranium in diverse matrices

An overview of the advances in technologies, which can be used in the field as well as in a laboratory for the measurement of uranium in diverse matrices like, waters, minerals, mineralized rocks, and other beneficiation products for its exploration and processing industries is presented. Laser based technologies, ion chromatography, microsample X-ray analysis method followed by energy dispersive X-ray fluorescence technique (MXA-EDXRF), sensors for electrochemical detection followed by cyclic voltammogram and alpha liquid scintillation counting techniques are the most promising techniques. Among these techniques, laser fluorimetry/spectrofluorimetry, in particular, is the technique of choice because of its high performance qualification (PQ), inherent sensitivity, simplicity, cost effectiveness, minimum generation of analytical waste, rapidity, easy calibration and operation. It also fulfills the basic essential requirements of reliability, applicability and practicability (RAPs) for the analysis of uranium in solution of diverse matrices in entire nuclear fuel cycle. A very extensive range of uranium concentrations may be covered. Laser fluorimetry is suitable for direct determination of uranium in natural water systems within the μg L⁻¹ and mg L⁻¹ range while differential technique in laser fluorimetry (DT-LIF) is suitable for mineralized rocks and concentrates independent of matrix effects (uranium in samples containing >0.01% uranium). The most interesting feature of TRLIF is its capability of performing speciation of complexes directly in solution as well as remote determination via fiber optics and optrode. Future trend and advances in lasers, miniaturization and automation via flow injection analysis (FIA) has been discussed.     

Extraction and quantitation of furanic compounds dissolved in oils

There is often a need to calculate isotopic uranium activities from total uranium mass or gamma spectrometry measurement data. This calculation is based on a model of the relationship of the²³⁴U activity to that of²³⁵U since both are enriched together in the normal gaseous diffusion enrichment process. This paper presents equations for calculating these activities that have been developed from several sources of data. These equations have been used for several characterization studies and have produced very good results when compared to results from actual isotopic uranium analyses. However, because the variability in the model causes significant uncertainty in the calculated results, alpha-spectrometry is recommended for critical applications.     

A gamma–gamma coincidence spectrometric method for rapid characterization of uranium isotopic fingerprints

This paper reports on initial efforts for uranium isotopic analysis using gamma-rays and X-ray fluorescence coincidence. In this study, a gamma–gamma coincidence spectrometry was developed. The spectrometry consists of two NaI(Tl) scintillators and XIA LLC Digital Gamma Finder (DGF)/Pixie-4 software and card package. The developed spectrometry was optimized according to the considerations of output count rate and gamma peak energy resolution. It has been demonstrated that the spectrometry provides an effective method of assessing the content of uranium isotopes for nuclear materials. The main advantages of this approach over the conventional gamma spectrometry include the fact that ²³⁵U enrichment can be graphically characterized by its unique coincidence “fingerprints”. The method could be further developed for fast uranium isotope verification with an established gamma–gamma coincidence spectral imaging library by various nuclear materials.     

Determination of uranium isotopic composition in aqueous solutions by combined gamma-spectrometry and X-ray fluorescence

The possibility of use of combined gamma spectrometry and X-ray fluorescence for uranium isotopic analysis in dilute aqueous solutions has been studied. Uranium K X-rays were excited by gamma-rays of⁵⁷Co radionuclide source and were measured together with 185.7 keV gamma-rays of²³⁵U using a planar pure Ge detector. Uranium K_α1 fluorescent X-rays were used for the evaluation. The method was proved to be independent of total uranium concentration in the region of 8–20 mg U/ml. The procedure making use of measurement of 7 ml samples and allowing to achieve an accuracy better then 1% in the region of 0.4–4.5 at. % of²³⁵U is proposed.     

Analysis of Ores and its Purified Constituents by γ‐Spectrometry with Calculation of Uranium Isotopic Atom,Mass, and Activity Ratios

The physical verifications, that the national and international inspectors carry out in order to perform a credibility control, often consist in the measurement of physical quantities, related to the declared nuclear material properties, by Non‐destructive Assay (NDA). Analysis of ores and its purified constituent's samples has been carried out in this work using non‐destructive gamma assay technique. The spectrometer based on HpGe detector and its electronics was calibrated using standard IAEA multi‐lines gamma sources. The efficiency calibration curve was plotted for broad gamma energies; 50–2600 keV. The gamma transition of ²³⁵U (143.7, 163.3, 185.7, and 205.3 keV) and ²³⁸U (63, 766.3, and 1001.03 keV) were used for qualitative and quantitative assay of the samples. The specific activities of the samples were calculated based on the determined efficiency, branching ratio (emission probability per disintegration), mass of sample and count rate of the characteristics gamma transitions of uranium isotopes at fixed geometrical conditions. A simplified equation was derived for calculation of ²³⁵U atom ratios. The results of calculation show natural origin of the analyzed samples; around 0.72 %. Where, the anthropogenic ²³⁶U was not detected at all in the spectra. The uranium activity ratios (²³⁵U/²³⁸U) were calculated based on the measured activity. The uranium isotopic mass and total uranium content of the investigated samples were also calculated. The results obtained are depicted, tabulated and discussed in comparison with recent published national and international works.     

238U, 234U and 226Ra concentrations in mineral waters and their contribution to the annual committed effective dose in Turkey

Activity concentrations of ²³⁴U, ²³⁸U and ²²⁶Ra in mineral waters were determined on the basis of nine water bottling facilities using alpha particle spectrometry. The mineral water samples were collected from three geographic regions of Turkey. The radiochemical separation used in the uranium analysis is based on the isolation of uranium radioisotopes from other radionuclides such as Th, Am, Pu and Np using UTEVA resin. Alpha sources were prepared using electrodeposition method. The activity concentration of ²²⁶Ra was determined after deposition on a membrane using BaSO₄ co-precipitation method. The activity concentrations (mBq L^?1) of ²²⁶Ra, ²³⁸U and ²³⁴U ranged from <0.56 to 165, from <0.42 to 439 and from <0.42 to 464, respectively. The measured activity concentrations were used for the calculation of the average total annual effective ingestion doses for children and adults. The committed effective doses were calculated for three different scenarios according to mineral water consumption rate. In the most extreme scenario (for age group 12–17), all water samples except MW1 and MW2 cause annual committed effective doses below the reference level (0.1 mSv year^?1) recommended by World Health Organization (WHO).     

Application of two-tracer isotope dilution mass spectrometry in the determination of uranium in geological samples

The determination of the uranium concentration in mineral samples using two tracer (²³³U and ²³⁵U) mass spectrometric isotope dilution techniques is described. The precision and accuracy are discussed and results are compared with those obtained by x-ray fluorescence and instrumental neutron activation methods. Based on the two independent values obtained for the same dilution, parameters such as the chemical procedures adopted, effect of mass fractionation and uranium distribution in minerals are evaluated. The ability of the method to distinguish between the analytical errors and heterogeneous distribution of uranium is discussed.     

Interferences in uranium oxidation states during dissolution of solid phases

The effects of iron on uranium oxidation states during sample dissolution were studied. A mineral acid mixture in anaerobic conditions was used for the dissolution the sample and the uranium oxidation states were determined by ion exchange. The first experiments were performed with pure iron chloride compounds. In the second stage, study was made of common iron-containing minerals. Uranium oxidation states were affected when the content of iron compound was as low as 10^-5M. In the case of the natural minerals, pyrite caused uranium to change to an increasingly reduced state, whereas goethite caused it to change to an increasingly oxidized state as the amount of mineral was increased. The interferences of the silicates fell between those of pyrite and goethite. The results indicate that a wide range of common bulk rocks with less than 20 wt% of iron-containing minerals can be reliable chemically analyzed for uranium oxidation state.