Measurement of uranium isotope ratios in solid samples using laser ablation and diode laser-atomic absorption spectrometry

A diode laser was used for the selective detection of ²³⁵U and ²³⁸U in a laser-induced plasma ignited by a Nd:YAG laser beam focused onto uranium oxide samples. The diode laser was sequentially tuned to the absorption lines of both isotopes (682.6736 nm for ²³⁵U, and 682.6913 nm for ²³⁸U). The absorption was measured on a pulse-to-pulse basis; the transient absorption peak was used as an analytical signal. Three samples were used with the relative abundance of the minor isotope ²³⁵U of 0.204%, 0.407% and 0.714%. Optimal conditions for the detection of the minor isotope were obtained at a distance of ∼3 mm from the sample surface, an argon pressure of ∼3 kPa and for 7.5 mJ pulse energy of the Nd:YAG laser. Absorption in the wing of the broadened line of the ²³⁸U isotope was found to be the main source of background for the measurement of the absorption of the minor isotope. The limit of detection of the minor isotope, evaluated on the basis of the 3σ criteria was estimated to be 100 μg g⁻¹. At the optimal conditions for the detection of the minor isotope optical thick conditions in the line centre of the main isotope were observed. Therefore, the isotope ratio measurements were performed by rationing the intensity of the net absorption signal measured in the line centre of the minor isotope and the absorption signal measured in the wing of the main isotope. This strategy was checked by determination of the isotope ratios for the two samples with depleted ²³⁵U concentration using the sample with the natural isotope composition (0.714%) as a standard. The accuracy and precision for this measurement strategy was evaluated to approximately 10%.     

Isotope ratio determination of uranium by optical emission spectroscopy on a laser-produced plasma - basic investigations and analytical results

We report in this paper, the first determination of the isotope ratio (238/235) in an uranium sample by optical emission spectroscopy on a laser-produced plasma at reduced pressure (2.67 Pa). Investigations aimed at developing a new application of laser ablation for analytical isotope control of uranium are presented. Optimized experimental conditions allow one to obtain atomic emission spectra characterized by the narrowest possible line widths of the order of 0.01 nm for the investigated transition UII 424.437 nm. We show the possibility to achieve a relative precision in the range of 5% for an enrichment of 3.5% ²³⁵U. The influence of different relevant plasma parameters on the measured line width is discussed.     

Measurement of uranium isotope ratios in solid samples using laser ablation and diode laser-excited atomic fluorescence spectrometry

A diode laser is used for the selective excitation of ²³⁵U and ²³⁸U in a laser-induced plasma applying Nd:YAG laser pulses to UO₂ samples. The diode laser is rapidly scanned immediately following each laser sampling and the resonance atomic fluorescence spectrum for both isotopes is obtained on a pulse-to-pulse basis. Time-integrated measurements, with the diode laser fixed at either isotope, were also made. Optimum signal-to-noise was obtained at a distance of 0.8 cm from the sample surface, a pressure of 0.9 mbar and a Nd:YAG laser pulse energy of 0.5 mJ (880 MW cm⁻²). Three samples with 0.204, 0.407 and 0.714% ²³⁵U were measured. For example, for the UO₂ pellet with the natural uranium isotopic composition (99.281% ²³⁸U and 0.714% ²³⁵U), the accuracy and precision were 7% and 5% (460 shots), respectively, limited by the continuum emission background from the laser-induced plasma.     

Uranium isotope dilution mass spectrometry using NBL certified reference materials as spikes

The isotope dilution mass spectrometry method of analysis is used to determine the elemental uranium contents in a wide variety of uranium bearing materials. The method is based on the mass spectrometric analysis of a mixture prepared by diluting the sample to be analyzed with a spike of distinctly different isotopic composition to that of the sample. In this work, a beginning is made to identify suitable candidates among the multitude of certified reference materials (CRMs) available at the New Brunswick Laboratory to supplant the use of ²³³U which remains now as the preferred spike nuclide. The results of the study presented here identify CRM 112-A (of normal isotopic composition) and CRM 115 (depleted uranium composition) as suitable candidates to replace ²³³U as spike material for determining uranium in high enriched uranium materials, and CRM 116 (²³⁵U mass fraction of >90 %) for determining uranium in materials of low enrichment.     

Thermal stability and IR-laser-driven selective photochemistry of a volatile uranyl compound at natural abundance

Molecular beam mass spectrometric measurements have been carried out to investigate the IR-laser chemistry of bis(1,1,1,5,5,5,-hexafluoropentane-2,4-dionato)dioxouranium(VI) tetrahydrofuran [UO₂[(CF₃CO)₂CH]₂] · THF. The compound has been characterized and shown to be stable in the gas phase up to 95°C. An isotope selectivity, factor for ²³⁸U species as high as three was obtained in on-line dissociations of this compound (with natural abundance of uranium isotopes) using the 10P(6) line of a TEA CO₂ laser IR-laser dissociation studies have also been carried out with the vapour in static or flowing condition in a cell. Negligible isotope selectivity is observed in the cell experiments.     

Study of uranium isotopic composition in groundwater and deviation from secular equilibrium condition

Uranium concentration in groundwater reflect both redox conditions and uranium content in host rock. In the present study an attempt has been made to study the uranium concentration and activity ratios of uranium isotopes to present the geochemical conditions of the groundwater in Malwa region of Punjab state, India and the reason for high uranium levels and variation of activity ratios from secular equilibrium conditions. Uranium concentration in groundwater samples was found to be in the range of 13.9 ± 1.2 to 172.8 ± 12.3 μg/l with an average value of 72.9 μg/l which is higher than the national and international guideline values. On the basis of uranium concentration, the groundwater of the study region may be classified as oxidized aquifer on normal uranium content strata (20 %) or oxidized aquifer on enhanced uranium content strata (80 %). The ²³⁸U, ²³⁵U and ²³⁴U isotopic concentration in groundwater samples was found to be in the range of 89.2–1534.5, 4.4–68.5, and 76.4–1386.2 mBq/l, respectively. Activity ratios of ²³⁴U/²³⁸U varies from 0.94 to 1.85 with a mean value of 1.11 which is close to unity that shows secular equilibrium condition. High value of ²³⁴U isotope than ²³⁸U may be due to alpha recoil phenomenon. The plot of AR of ²³⁴U/²³⁸U against the total uranium content in log scale reveals that the groundwaters of the study region either belongs to stable accumulation or normal oxidized aquifer.     

Non-denaturating isoelectric focusing gel electrophoresis for uranium–protein complexes quantitative analysis with LA-ICP MS

A non-denaturating isoelectric focusing (ND-IEF) gel electrophoresis protocol has been developed to study and identify uranium (U)–protein complexes with laser ablation–inductively coupled plasma mass spectrometry (LA-ICP MS) and electrospray ionization mass spectrometry (ESI-MS). The ND-IEF-LA-ICP MS methodology set-up was initiated using in vitro U–protein complex standards (i.e., U–bovine serum albumin and U–transferrin) allowing the assessment of U recovery to 64.4?±?0.4 %. This methodology enabled the quantification of U–protein complexes at 9.03?±?0.23, 15.27?±?0.36, and 177.31?±?25.51 nmol U L^?1 in digestive gland cytosols of the crayfish, Procambarus clarkii, exposed respectively to 0, 0.12, and 2.5 μmol of waterborne depleted U L^?1 during 10 days. ND-IEF-LA-ICP MS limit of detection was 19.3 pmol U L^?1. Elemental ICP MS signals obtained both in ND-IEF electropherograms and in size exclusion chromatograms of in vivo U–protein complexes revealed interactions between U- and Fe- and Cu-proteins. Moreover, three proteins (hemocyanin, pseudohemocyanin-2, and arginine kinase) out of 42 were identified as potential uranium targets in waterborne-exposed crayfish cytosols by microbore reversed phase chromatography coupled to molecular mass spectrometry (µRPC-ESI-MS/MS) after ND-IEF separation.

Isotope ratio analysis on micron-sized particles in complex matrices by Laser Ablation-Absorption Ratio Spectrometry

Laser ablation has been combined with dual tunable diode laser absorption spectrometry to measure ¹⁵²Gd:¹⁶⁰Gd isotope ratios in micron-size particles. The diode lasers are tuned to specific isotopes in two different atomic transitions at 405.9 nm (¹⁵²Gd) and 413.4 nm (¹⁶⁰Gd) and directed collinearly through the laser ablation plume, separated on a diffraction grating, and detected with photodiodes to monitor transient absorption signals on a shot-by-shot basis. The method has been characterized first using Gd metal foil and then with particles of GdCl₃·xH₂0 as binary and ternary mixtures with ¹⁵²Gd:¹⁶⁰Gd isotope ratios ranging from 0.01 to 0.43. These particulate mixtures have been diluted with Columbia River sediment powder (SRM 4350B) to simulate environmental samples and we show the method is capable of detecting a few highly-enriched particles in the presence of a >100-fold excess of low-enrichment particles, even when the Gd-bearing particles are a minor component (0.08%) in the SRM powder and widely dispersed (1178 particles detected in 800,000 ablation laser shots). The implications for monitoring ²³⁵U:²³⁸U enrichment ratios in airborne particle samples, as related to the nuclear industry, are discussed.     

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.     

Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS

Data evaluation is a crucial step when it comes to the determination of accurate and precise isotope ratios computed from transient signals measured by multi-collector–inductively coupled plasma mass spectrometry (MC-ICPMS) coupled to, for example, laser ablation (LA). In the present study, the applicability of different data evaluation strategies (i.e. ‘point-by-point’, ‘integration’ and ‘linear regression slope’ method) for the computation of ²³⁵U/²³⁸U isotope ratios measured in single particles by LA-MC-ICPMS was investigated. The analyzed uranium oxide particles (i.e. 9073-01-B, CRM U010 and NUSIMEP-7 test samples), having sizes down to the sub-micrometre range, are certified with respect to their ²³⁵U/²³⁸U isotopic signature, which enabled evaluation of the applied strategies with respect to precision and accuracy. The different strategies were also compared with respect to their expanded uncertainties. Even though the ‘point-by-point’ method proved to be superior, the other methods are advantageous, as they take weighted signal intensities into account. For the first time, the use of a ‘finite mixture model’ is presented for the determination of an unknown number of different U isotopic compositions of single particles present on the same planchet. The model uses an algorithm that determines the number of isotopic signatures by attributing individual data points to computed clusters. The ²³⁵U/²³⁸U isotope ratios are then determined by means of the slopes of linear regressions estimated for each cluster. The model was successfully applied for the accurate determination of different ²³⁵U/²³⁸U isotope ratios of particles deposited on the NUSIMEP-7 test samples.     

Nuclear analytical application of thermionic mass spectrometry

Summary The relative uncertainty on the isotope abundance ratio measurements of uranium and plutonium samples by means of thermionic mass spectrometry at the Central Bureau for Nuclear Measurements (CBNM) in Geel, Belgium, has decreased to a level of about 2 · 10^–4.The improvement was mainly achieved through the preparation of synthetic isotope mixtures of uranium and plutonium, to a relative uncertainty of 0.01% (computed on a 2s basis) on the ratios of isotopes with major abundances. This allowed to determine some error sources more precisely, such as: — isotope fractionation, — non-linearity of the ion beam current measuring system.As a consequence CBNM is able to prepare certified uranium isotopic reference materials (U IRM's) for distribution, with a relative uncertainty of 0.07% (computed on a 2s basis) on the²³⁵U isotope abundance and to provide reference values on samples for the (European) Interlaboratory Measurement Evaluation Programmes (REIMEP).

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Nuklearanalytische Anwendung der Thermionen-Massenspektrometrie

     

New methodology for uranium analysis in swipe samples for nuclear safeguards purposes

Environmental swipe sampling for safeguards purpose has been used by International Atomic Energy Agency since 1997, being a powerful tool to detect undeclared materials and activities. This work describes a new methodology for swipe samples analysis based on ultrasound-assisted acid leaching and compares it with traditional total digestion bulk analysis. The proposed method requires few preparation steps, decreasing the risk of contamination, reduced amounts of reagents and a good option to extract uranium from swipe sample. In a real case study, the swipe samples were collected in a conversion plant at IPEN/CNEN, Brazil. The measurements were carried out by ICP-MS and the results showed relative error lower than 0.96 % for uranium isotopic ratios for the certified reference material (NBS U200). The uncertainties were estimated by following the ISO GUM, with a confidence level of 95 %. The uncertainties percentage for n(²³⁵U)/n(²³⁸U) ratio of the samples ranged from 2.5 to 4.3 %. The values of uranium isotopic ratio obtained for each method demonstrate the viability of using the methodology proposed in this work.     

The direct total evaporation (DTE) method for TIMS analysis

The total evaporation (TE) method is an established analytical method for safeguards measurements of uranium and plutonium isotope-amount ratios using thermal ionization mass spectrometry. As fractionation effects are minimized in this analytical method, it is a method of choice in many practical applications that require high accuracy and precision isotope abundance ratio measurements. The speed of signal regulation is a critical parameter for a steady sample evaporation process. Standard TE methods use the data system to read the ion signal and its difference from the target intensity is used to determine the increment in which the filament is heated. The new, hardware-driven proprietary direct total evaporation method uses an analog regulator in the filament power supply with direct feedback of the detector intensity. Only target values are set by the data system initially. The filament heating and sample evaporation process is then carried out by the hardware. The data system just monitors, collects, and calculates the data. Due to the nature of electronic regulation the ion signal is kept stable for the duration of the run until the whole sample is consumed. For routine uranium isotopic analyses of the major isotope-amount ratio n(²³⁵U)/n(²³⁸U) using a modified MAT261 instrument with SPECTROMAT? hardware and software upgrades, precision (relative standard deviation, expressed as a percent) and accuracy (relative difference, expressed as a percent) of 0.05 % are obtained for low enriched and high enriched uranium certified reference materials.     

A method for dating small amounts of uranium

In this study we describe a method for uranium dating (i.e. determination of the date of the last chemical purification undergone by the material) by measurement of the ²³⁰Th/²³⁴U ratio, applicable to sub-microgram quantities. The chosen protocol (AG1x8 resin in hydrochloric acid medium) has been tested on separation microcolumns (100 μl). This ‘microchemistry’ technique considerably limits the risks of contamination by reagents or the environment. Thorium extraction efficiencies were greater than 90 % and reproducible. The quantities of ²³⁰Th introduced by the chemical purification procedure were negligible. Using an ultra-sensitive inductively coupled plasma mass spectrometry measurement technique, detection limits of the order of femtograms (10^?15 g) of ²³⁰Th were obtained. The complete procedure, chemical separation and isotope measurement, was successfully tested and validated on a few micrograms of uranium.     

Laser ablation isotope ratio mass spectrometry for enhanced sensitivity and spatial resolution in stable isotope analysis

Stable isotope analysis permits the tracking of physical, chemical, and biological reactions and source materials at a wide variety of spatial scales. We present a laser ablation isotope ratio mass spectrometry (LA‐IRMS) method that enables δ¹³C measurement of solid samples at 50 µm spatial resolution. The method does not require sample pre‐treatment to physically separate spatial zones. We use laser ablation of solid samples followed by quantitative combustion of the ablated particulates to convert sample carbon into CO₂. Cryofocusing of the resulting CO₂ coupled with modulation in the carrier flow rate permits coherent peak introduction into an isotope ratio mass spectrometer, with only 65 ng carbon required per measurement. We conclusively demonstrate that the measured CO₂ is produced by combustion of laser‐ablated aerosols from the sample surface. We measured δ¹³C for a series of solid compounds using laser ablation and traditional solid sample analysis techniques. Both techniques produced consistent isotopic results but the laser ablation method required over two orders of magnitude less sample. We demonstrated that LA‐IRMS sensitivity coupled with its 50 µm spatial resolution could be used to measure δ¹³C values along a length of hair, making multiple sample measurements over distances corresponding to a single day's growth. This method will be highly valuable in cases where the δ¹³C analysis of small samples over prescribed spatial distances is required. Suitable applications include forensic analysis of hair samples, investigations of tightly woven microbial systems, and cases of surface analysis where there is a sharp delineation between different components of a sample. Copyright © 2011 John Wiley & Sons, Ltd.     

Particle isolation for analysis of uranium minor isotopes in individual particles by secondary ion mass spectrometry

A new technique to measure ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope ratios for individual particles in environmental samples was developed, which was a combination of particle isolation under scanning electron microscope (SEM) and secondary ion mass spectrometry (SIMS). The technique was verified by measuring ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope ratios in individual particles in a simulated environmental sample containing uranium standard (NBL CRM U010) and Pb metal particles. When the uranium particles were not isolated, the relative deviations of the measured isotope ratios from the reference values increased with increasing the signal intensity ratio of ²⁰⁸Pb to ²³⁸U, which was due to the molecular ion interferences by the Pb particles co-existing in the sputtered area. By the isolation of individual uranium particles, the interferences were eliminated and the measured isotope ratios were in good agreement with the reference values. The maximum relative deviations among 20 particles were 8.9% for ²³⁴U/²³⁸U and 13.1% for ²³⁶U/²³⁸U isotope ratios, respectively. The technique was also successfully applied to the analysis of a real swipe sample containing various kinds of elements.     

High accuracy determination of235U in nondestructive assay standards by gamma spectrometry

High precision gamma spectrometry measurements have been made on five sets of uranium isotope abundance reference materials for nondestructive assay (NDA). These sets are intended for international safeguards use as primary reference materials for the determination of the²³⁵U abundance in homogeneous uranium bulk material by gamma spectrometry. The measurements were made to determine the count rate uniformity of the²³⁵U 185.7 keV gamma-ray as well as the²³⁵U isotope abundance for each sample. Since the samples were packaged such that the U₃O₈ is infinitely thick for the 185.7 keV gamma-ray, the measured count rate was not dependent on the material density. In addition, the activity observed by the detector was collimated to simulate calibration conditions used to measure bulk material in the field. The sample-to-sample variations observed within the 5 sets of samples ranged between 0.005–0.11% (1s) with standard deviations of the mean ranging from 0.01–0.02%. This observed variation appears to be due predominantly to counting statistics and not to material inhomogeneity and/or packaging. The results of this study indicate that accuracy of²³⁵U determinations via gamma spectrometry, in the range of few hundredths of a percent (2), is achievable. The main requirement for achieving this level of accuracy is a set of standards whose²³⁵U isotope abundances are known to within 0.01% (2).     

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.     

Distribution of uranium in groundwaters of Bathinda and Mansa districts of Punjab,India: inferences from an isotope hydrochemical study

This paper presents the isotope hydrochemical results of groundwaters from southwest Punjab for assessing the uranium contamination and evaluating the factors leading to elevated uranium concentration. A total of 35 samples covering shallow and deep zones were collected for hydrochemistry and isotopes. Uranium concentration ranges between 2.3 and 357 µg L^?1 and 66% of the samples are contaminated. Both shallow and deep zones show U contamination but high incidences are noticed in shallow zone. Hydrochemical correlations infer geological sources rather than anthropogenic sources responsible for U contamination. Isotopically there is no clear distinction between high and low U groundwater.     

Precise isotope ratio measurements for uranium, thorium and plutonium by quadrupole-based inductively coupled plasma mass spectrometry

Precise long-term measurements of uranium and thorium isotope ratios was carried out in 1 μg/L solutions using a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS). The isotopic ratios of uranium (²³⁵U/ ²³⁸U = 1, 0.02 and 0.00725) were determined using a cross-flow nebulizer (CFN, at solution uptake rate of 1 mL/min) and a low-flow microconcentric nebulizer (MCN, at solution uptake rate of 0.2 mL/min) over 20 h. For 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) relative external standard deviations (RESDs) of 0.05% and 0.044% using CFN and MCN, respectively, can be achieved. Additional short term isotope ratio measurements using a direct injection high-efficiency nebulizer (DIHEN) of 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) at a solution uptake rate of 0.1 mL/min yielded an RSD of 0.06–0.08%. The sensitivity of solution introduction by DIHEN for uranium, thorium and plutonium (145 MHz/ppm, 150 MHz/ppm and 177 MHz/ppm, respectively) increased significantly compared to CFN and MCN and the solution uptake rate can be reduced to 1 μL/ min in DIHEN-ICP-MS. Isotope ratio measurements at an ultralow concentration level (e.g. determination of ²⁴⁰Pu/ ²³⁹Pu isotope ratio in a 10 ng/L Pu waste solution) were carried out for the characterization of radioactive waste and environmental samples.