Non-volatile organic analysis of uranium ore concentrates

In support of nuclear safeguards and non-proliferation efforts, Oak Ridge National Laboratory is responsible for characterizing uranium ore concentrate (UOC) samples obtained from two ore mining and milling sites. A sorptive extraction method has been developed for analysis of non-volatile organic compounds that might be used to identify characteristics of the purification process by which uranium was separated from these ores. This method utilizes Gerstel Twister^® stir bars coated with polydimethylsiloxane to extract organic components from aqueous media. A slurry of UOC is extracted with the Twister^® stir bar in 20 % methanol/80 % water containing deuterated internal hydrocarbon standards. Following extraction of non-volatile organics, the Twister^® stir bar is analyzed directly in the inlet of a gas chromatograph fitted with a quadrupole mass spectrometric detector. Results have been consistent and have shown excellent recoveries of internal standards, with the average recovery being 97.5 %. Both qualitative and quantitative differences have been identified between the two sources of UOC utilizing this method. One source contained an increased concentration of amines which commonly are used in the recovery and purification of ores. Amines that were identified in this UOC source include dioctylamine, triisoctylamine, and Alamine^® 336, a common industrial complexant. Also, when comparing both sources, the same UOC source contained various decanol and C20 compounds. Based on the results from this study, non-volatile organic analysis of UOC using sorptive extraction with Twister^® stir bars and GC–MS is a tool that can be used to facilitate sourcing of unknown UOC.     

Alpha spectrometric evaluation of SRM-995 as a potential uranium/thorium double tracer system for age-dating uranium materials

Uranium-233 (t _1/2 ~ 1.59E5 years) is an artificial, fissile isotope of uranium that has significant importance in nuclear forensics. The isotope provides a unique signature in determining the origin and provenance of uranium-bearing materials and is valuable as a mass spectrometric tracer. Alpha spectrometry was employed in the critical evaluation of a ²³³U standard reference material (SRM-995) as a dual tracer system based on the in-growth of ²²⁹Th (t _1/2 ~ 7.34E3 years) for ~35 years following radiochemical purification. Preliminary investigations focused on the isotopic analysis of standards and unmodified fractions of SRM-995; all samples were separated and purified using a multi-column anion-exchange scheme. The ²²⁹Th/²³³U atom ratio for SRM-995 was found to be 1.598E?4 (±4.50 %) using recovery-corrected radiochemical methods. Using the Bateman equations and relevant half-lives, this ratio reflects a material that was purified ~36.8 years prior to this analysis. The calculated age is discussed in contrast with both the date of certification and the recorded date of last purification.     

Radioecology around a closed uranium mine

The uranium mine and mill at ?irovski vrh, Slovenia, operated from 1982 to 1990. After processing, the uranium mill tailings were deposited onto the Bor?t waste pile lying close to the mine. Radioecological studies focused on assessing the mobility and bioavailability of deposited radionuclides were initiated some five years ago. The mobility of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra in soil was studied by applying sequential extraction protocols. The highest activity concentrations were found at the bottom of the waste pile. Uranium isotopes were the most mobile, followed by ²²⁶Ra whose mobility appeared to be suppressed by high sulphate concentrations and ²³⁰Th. The wetland plants grown in soils contaminated with seepage waters from the tailings contained higher levels of ²³⁸U, ²²⁶Ra and ²³⁰Th compared to plants from a control site. The activity concentration of ²²⁶Ra was the highest in all studied plant species. The radiological risk to wildlife around the mine area as assessed by the ERICA Tool was negligible. Activity concentrations in bovine milk from the area of ?irovski vrh were comparable to the reference location, except for uranium where the content was higher. The combined annual effective dose for adults consuming milk from the ?irovski vrh area is 13.0 ± 1.7 μSv a^?1.     

Radiological chronometry of uranium metal samples

Radiological chronometry is an important tool in nuclear forensics that uses several methods to determine the length of time that has elapsed since a material was last purified. One of the chronometers used in determining the age of metallic uranium involves measuring the fractional ingrowth of ²³⁰Th from its parent ²³⁴U with the assumption that the uranium metal contained no impurities, especially thorium, when it was purified. The affects of different etching procedures were evaluated for the removal of surface oxidation with three different types of uranium metal samples to determine whether the etching procedure affects the radiological age. The sample treated with a rigorous etching procedure had exhibited the most reliable radiological age while less rigorous etching yields a radiological age from 15 years to hundreds of years older than the known age. Any excess thorium on the surface of a uranium metal sample presents a bias in age determination and the sample will appear older than the true age. Although this research demonstrates the need for rigorous surface etching, a bias in the radiological age could have arisen if the uranium in the metal was heterogeneously distributed.     

Natural radioactivity around former uranium mine,Gabrovnica in Eastern Serbia

Gabrovnica near Kalna village was the first uranium mine established in Yugoslavia. In 1963, the Nuclear Energy Commission began operating the mine and mill. Between 1964 and 1966, the staff at Kalna extracted and produced an estimated 900 kg of UO₂ and 400 kg of uranium metal. The Kalna ore was of poor quality, containing very low uranium content, which required higher-cost mining and refining methods. That was the main reason for closing this mine. This paper presents results obtained by measuring the activity concentration of soil samples measured by gamma spectrometry and also indoor ²²²Rn activity concentrations in houses in the nearby village Kalna. There is a presence of elevated radioactivity levels in the most of the measured samples. The mine was never officially decommissioned. The results obtained might be useful for the future decommissioning procedure.     

Uranium isotopic signatures measured in samples of dirt collected at two former uranium facilities

Nuclear forensics is a multidisciplinary science that uses a variety of analytical methods and tools to explore the physical, chemical, and isotopic characteristics of nuclear and radiological materials. These characteristics, when evaluated alone or in combination, become signatures that may reveal how and when the material was fabricated. The signatures contained in samples of dirt collected at two different uranium metal processing facilities in the United States were evaluated to determine uranium isotopic composition and compare results with processes that were conducted at these sites. One site refined uranium and fabricated uranium metal ingots for fuel and targets and the other site rolled hot forged uranium and other metals into dimensional rods. Unique signatures were found that are consistent with the activities and processes conducted at each facility and establish confidence in using these characteristics to reveal the provenance of other materials that exhibit similar signatures.     

Determination of uranium concentration in urine of workers in an Iraqi phosphate mine and fertilizer plants

Precise determination of uranium concentration in human urine is quite important in assessment of occupational and public exposure to uranium. In the present work, a pulsed dye nitrogen laser-induced kinetic phosphorescence analysis (KPA) was used to determine uranium in urine of Iraqi phosphate mine and fertilizer plant workers and in the population living near the mining region. A total of 92 urine samples were collected from workers of the Akashat phosphate mine, the Al-Qaim fertilizer complex, and the Akashat residential region. Uranium concentration in urine of all samples ranged between 0.49 to 5.26 μg L^?1 with a total average of 1.47 ± 0.01 μg L^?1. For comparison, all samples were also analyzed using a completely different technique; the nuclear fission track analysis using CR-39 SSNTD. Both techniques were capable of such measurements, although not with an equal degree of uncertainty. KPA technique is found to be more suitable for analysis of urine samples having high concentrations of uranium.     

Assay of actinides in human urine by rapid method

A method using DGA resin (N,N,N′,N′-tetra-n-octyldiglycolamide on an inert support) was developed for the rapid analysis of actinides in urine samples. Samples acidified with HCl to 4 M were loaded directly (without digestion) onto a DGA column. Actinides were stripped simultaneously, α-sources were prepared by co-precipitation with NdF₃. Americium, plutonium and uranium were separated with acceptable high recoveries (40–80%). The americium, plutonium and uranium content of 100–200 ml urine samples was determined within 24 h with detection limits as low as 0.01 Bq l^?1. Based on model experiments using ¹⁴C-spiked urea, it was proven that high urea content can affect americium separation deleteriously due to irreversible fixing of americium on DGA resin.     

Assessment of natural uranium and 226Ra concentration in ground water around the uranium mine at Narwapahar, Jharkhand, India and its radiological significance

A brief study on dissolved radionuclides in aquatic environment, especially in ground water, constitutes the key aspect for assessment and control of natural exposure. In the present study the distribution of natural uranium and ²²⁶Ra concentration were measured in ground water samples collected within a 10 km radius around the Narwapahar uranium mine in the Singhbhum thrust belt of Jharkhand, India in 2007–2008. The natural uranium content in the ground water samples in this region was found to vary from 0.1 to 3.75 μg L^?1 with an average of 0.87 ± 0.73 μg L^?1 and ²²⁶Ra concentration was found to vary from 5.2 to 38.1 mBq L^?1 with an average of 13.73 ± 7.34 mBq L^?1. The mean annual ingestion dose due to intake of natural uranium and ²²⁶Ra through drinking water pathway to male and female adults population was estimated to be 6.55 and 4.78 μSv y^?1, respectively, which constitutes merely a small fraction of the reference dose level of 100 μSv y^?1 as recommended by WHO.     

A novel method of synthesizing solid phase adsorbent silica modified with xylenol orange: application for separation, pre-concentration and determination of uranium in calcium rich hydro-geochemical samples and sea water—Part 1

A novel, single-step route has been developed for the synthesis of solid phase adsorbent silica modified with xylenol orange. The addition of cationic surfactant cetyl tri-methylammonium bromide during the synthesis of the adsorbent supports the formation of a stable coating of xylenol orange on silica. The adsorbent showed no signs of degradation in contact with organic solvents and with solutions of varying pH between 1 and 9. This adsorbent has been used for separation and pre-concentration of uranium from hydro-geochemical samples with high calcium content and from sea water. Quantitative sorption of uranium was observed above pH 3 and complete desorption can be achieved using 0.2 M sodium pyrophosphate solution. The uranium content in the extract was determined by laser fluorimetric technique. The equilibration time is 30 min. The sorption capacity of the adsorbent for uranium is 10 mg g^?1. An enrichment factor of 50 was obtained by this procedure taking 500 mL of sample solution. Uranium concentrations down to 0.05 ng mL^?1 can be determined after pre-concentration using this method. The relative standard deviation at an 0.1 ng mL^?1 level is ±15%.     

Using the 186-keV peak for 226Ra activity concentration determination in Hungarian coal-slag samples by gamma-ray spectroscopy

The uranium isotopic abundance and the ²³⁸U–²²⁶Ra secular equilibrium were determined in nine Hungarian coal slag samples. The ²²⁶Ra activity concentration was measured based on the radon decay products and also the ²²⁶Ra peak at 186 keV. Secular equilibrium existed in eight samples, whereas one sample showed a slight disequilibrium. The direct and fast measurement using only the 186 keV peak was validated which can be used after measuring the uranium isotopic ratio and verifying the ²³⁸U–²²⁶Ra secular equilibrium. This method can be used to measure the ²²⁶Ra content of high number of samples from the same geochemical background.     

Bioremediation of effluent from a uranium mill tailings repository in South China by <Emphasis Type="Italic">Azolla</Emphasis>–<Emphasis Type="Italic">Anabaena</Emphasis>

Hydroponic experiments were conducted on the removal of uranium, heavy metals and nutrients from the effluent of a uranium mill tailings repository in South China by Azolla–Anabaena. The plant–microbe symbiont was kept in the effluent for 30 days, and it was found that U, Fe, Mn, Cu, Zn, Pb, Cd, total phosphorus (TP), total nitrogen (TN) and SO₄^2? reduced by 87.6, 99.1, 98.8, 88.2, 91, 78.3, 77.5, 93.4, 98.7 and 76.7%, respectively. Specifically, the concentration of uranium reduced to 0.039 mg L^?1, which is below the limits of contaminants by the Department of Environmental Protection of China. The concentration of Fe, Cu, Zn, Pb, TP and TN in the effluent reached the quality standard for drinking water. The results showed that Azolla–Anabaena can be used for the bioremediation of the effluent from the uranium mill tailings repository.     

Electrochemical separation of uranium and cerium in molten LiCl–KCl

The electrochemical separation of uranium from cerium in LiCl–KCl eutectic and the electrochemical behavior of Ce(III) were studied. According to the cyclic voltammogram of Ce(III) and the former result of U(III), electrodeposition potential was determined at ?1.65 V (vs Ag/AgCl). The uranium metal was successfully deposited and separated from cerium. The morphology of deposit and cross section of electrode were investigated by SEM, firstly uranium deposit alloys with stainless steel and forms a thin transition layer, and secondly the uranium metal layer grows from the transition layer. The separation factors of uranium/cerium on different recovery ratios were determined through a series of steps. It was found that the content of cerium in the deposit and separation factors declined with increasing the initial concentration of U³⁺ in molten salts; the separation factors remained stable at around 20 in different uranium recovery ratios.     

Optimization of operating parameters and rate of uranium bioleaching from a low-grade ore

In this study the bioleaching of a low-grade uranium ore containing 480 ppm uranium has been reported. The studies involved extraction of uranium using Acidithiobacillus ferrooxidans derived from the uranium mine samples. The maximum specific growth rate (µ ^max) and doubling time (t _d) were obtained 0.08 h^?1 and 8.66 h, respectively. Parameters such as Fe²⁺ concentration, particle size, temperature and pH were optimized. The effect of pulp density (PD) was also studied. Maximum uranium bio-dissolution of 100 ± 5 % was achieved under the conditions of pH 2.0, 5 % PD and 35 °C in 48 h with the particles of d ₈₀ = 100 μm. The optimum concentration of supplementary Fe²⁺ was dependent to the PD. This value was 0 and 10 g of FeSO₄·7H₂O/l at the PD of 5 and 15 %, respectively. The effects of time, pH and PD on the bioleaching process were studied using central composite design. New rate equation was improved for the uranium leaching rate. The rate of leaching is controlled with the concentrations of ferric and ferrous ions in solution. This study shows that uranium bioleaching may be an important process for the Saghand U mine at Yazd (Iran).     

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.     

Uranium concentration in blood samples of Southern Iraqi leukemia patients using CR-39 track detector

The simple and effective technique of fission track etch has been applied to determine trace concentration of uranium in human blood samples taken from two groups of male and female participants: leukemia patients and healthy subjects group. The blood samples of leukemia patients and healthy subjects were collected from three key southern governorates namely, Basrah, Muthanna and Dhi-Qar. These governorates were the centers of intensive military activities during the 1991 and 2003 Gulf wars, and the discarded weapons are still lying around in these regions. CR-39 track detector was used for registration of induced fission tracks. The results show that the highest recorded uranium concentration in the blood samples of leukemia patients was 4.71 ppb (female, 45 years old, from Basrah) and the minimum concentration was 1.91 ppb (male, 3 years old, from Muthanna). For healthy group, the maximum uranium concentration was 2.15 ppb (female, 55 years old, from Basrah) and the minimum concentration was 0.86 ppb (male, 5 years old, from Dhi-Qar). It has been found that the uranium concentrations in human blood samples of leukemia patients are higher than those of the healthy group. These uranium concentrations in the leukemia patients group were significantly different (P < 0.001) from those in the healthy group.     

Determination of ultratrace amounts of plutonium in high saline groundwater by inductively coupled plasma mass spectrometry

For determination of ultratrace amounts of plutonium in high saline groundwater, large-volume sampling and preconcentration are necessary. However, traditional co-precipitation methods, such as Fe(OH)₃, Ca(OH)₂–Mg(OH)₂ and hydroxide-carbonate co-precipitation, are unable to meet the requirements of preconcentration of the ultratrace plutonium in high saline groundwater. In this paper, the ultratrace plutonium in high saline groundwater was concentrated by sequential co-precipitation with MnO₂ and Fe(OH)₃, and purified by two-stage anion-exchange separation on Dowex1 × 4 resin column. Quadrupole ICP-MS was employed for the determination of ²³⁹Pu with ²⁴²Pu spiked. After co-precipitation and purification, the major matrix elements were significantly decreased to μg mL^?1 level and decontamination factor of uranium is better than 10⁶. The detection limit for ²³⁹Pu in 50 L high saline water is 2.1 × 10^?16 g L^?1. Three high saline fountain samples (total dissolved solids more than 20 g L^?1) from Dunhuang region of China were analyzed using this method. The concentrations of ²³⁹Pu in these samples were 0.48 ± 0.2 × 10^?15, 1.40 ± 0.10 × 10^?15 and 2.13 ± 0.21 × 10^?15 g L^?1 respectively. The recovery obtained for 7 pg of ²⁴²Pu spiked into real high saline-water samples was all above 70 %.     

In-Capillary Derivatization and Preconcentration for CE of Metal Ions as Their Phenanthroline Complexes

A simple and automated method involving in-capillary derivatization and in-capillary preconcentration was developed for the simultaneous determination of metal ions by capillary zone electrophoresis. Fe(II), Zn(II), Cu(II) and Cd(II) were derivatized using 1,10-phenanthroline as the derivatizing agent. The in-capillary derivatization and in-capillary preconcentration via large volume injection were performed sequentially as follows: 60 mmol L^?1 1,10-phenanthroline was first hydrodynamically injected (0.2 psi) for 2 s; metal ions were introduced by hydrodynamic injection (0.5 psi) for 60 s; 0.2 mol L^?1 acetate pH 5.5 containing 20 % methanol was used as the running buffer. Four metal ions can be determined within 8 min using 16 kV. The resulting preconcentration factors were in the range 12–21. Good linearity was obtained for concentrations of 0.1–8.0 mg L^?1 (r ² > 0.990). The mean recoveries of the metal ions evaluated by fortification of wine samples were in the range 90–102 %. The limits of detection ranged from 0.05 to 0.2 mg L^?1. The proposed method can be applied for directly determining metal ions in wine samples.     

Effects of compression molding on meltability of uranium dendrites for ingot consolidation in a pyroprocess

Compression molding was carried out to enhance the meltability of uranium dendrites. Uranium dendrites were successfully compressed, increasing their bulk density more than 9 times from 1.1 to 10 g/cm³. The average bulk density was about 8.7 g/cm³ which was almost half of the material density. The compressed dendrites were favorably melted at a temperature of 1,400 °C in an induction furnace. 3 kg of the compressed dendrites were consolidated into an ingot form, showing 96.7 % yield. About 3 % of dross was formed during the melting test in the form of fine powder which was characterized as a uranium oxide. This compression molding method was compared to the supplemental charge method in which uranium dendrites were poured into a molten metal pool produced from a uranium ingot. The capacity of dendrite melting was higher in the compression molding method than in the supplemental charge method. We consider that the higher capacity can be attributed to enhanced thermal conductivity as the bulk density was increased by the compression. These results suggest the high feasibility of the compression molding method for uranium melting in a pyroprocess at an engineering scale.     

Removal, preconcentration and spectrophotometric determination of U(VI) from water samples using modified maghemite nanoparticles

Arsenazo III modified maghemite nanoparticles (A-MMNPs) was used for removing and preconcentration of U(VI) from aqueous samples. The effects of contact time, amount of adsorbent, pH and competitive ions was investigated. The experimental results were fitted to the Langmuir adsorption model in the studied concentration range of uranium (1.0 × 10^?4–1.0 × 10^?2 mol L^?1). According to the results obtained by Langmuir equation, the maximum adsorption capacity for the adsorption of U(VI) on A-MMNPs was 285 mg g^?1 at pH 7. The adsorbed uranium on the A-MMNPs was then desorbed by 0.5 mol L^?1 NaOH solution and determined spectrophotometrically. A preconcentration factor of 400 was achieved in this method. The calibration graph was linear in the range 0.04–2.4 ng mL^?1 (1.0 × 10^?10–1.0 × 10^?8 mol L^?1) of U(VI) with a correlation coefficient of 0.997. The detection limit of the method for determination of U(VI) was 0.01 ng mL^?1 and the relative standard deviation (R.S.D.) for the determination of 1.43 and 2.38 ng mL^?1 of U(VI) was 3.62% and 1.17% (n = 5), respectively. The method was applied to the determination of U(VI) in water samples.