Mg Of Uranium Research Articles

Delayed-neutron activation analysis at NIST

An automated delayed-neutron activation analysis system has been installed at the NIST research reactor. This work involved characterization of the transfer time of the system, evaluation of blanks, and tests of the system’s analytical capabilities through quantitative analysis for uranium in several natural matrix standard reference materials (SRMs). The calibration curve was shown to be linear up to at least 20 μg of uranium, and the well-thermalized reactor irradiation position makes the system insensitive to thorium and oxygen. For SRMs 1646a Estuarine Sediment and 2710a Montana Soil the values determined for this work agree with the reference and certified values, respectively. The mass fraction of uranium in SRM 695 Multi-Nutrient Fertilizer is the first reported for this material. For this system and the irradiation, transfer, and counting times used, the limit of detection for natural uranium is 20 ng, which corresponds to approximately 200 pg of 235U.

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 %.

Binding of uranyl ion by a DNA aptamer attached to a solid support

A UO(2)(2+)-specific DNA aptamer was attached to aminopolystyrene (aminoPS) using sulfo-SMCC as a crosslinking agent in view of high affinity of DNA for uranyl ion. Capacity of the aptamer-conjugated aminoPS resins for uranyl uptake was measured, revealing that about 0.63 μg of uranium can be complexed to 1g of the resins, which clearly demonstrates that most of DNA aptamers introduced to the resins can strongly bind to uranyl ion. In the presence of 21 mM bicarbonate ion at pH 8.01, apparent dissociation constant (K(d)(app)) of about 84.6 pM and log formation constant (K(f)) of about 22.9 were obtained. Results of the present study strongly suggest that modification of the aptamer-containing resins can improve uranyl-binding ability, probably leading to economical recovery of uranium from seawater.

A fast and sensitive method for the determination of uranium in the Thorex Process streams

This paper presents a simple, rapid and sensitive radiometric method for the determination of uranium in Thorex Process stream containing large amount of thorium. This method involves the extraction of uranium into 0.05M tri-n-octyl phosphine oxide (TOPO) in xylene at 2M HNO3. The extraction of thorium is prevented by masking them with suitable quantity of fluoride ions. The optimum experimental parameters for extraction of 233U were evaluated and using the most suitable experimental conditions the extracted uranium is radiometrically determined by α-counting in proportional counter with a prior knowledge of specific activity of uranium. Simultaneously in the same sample uranium was determined by spectrophotometric method using 2-(5bromo-2 pyridylazo)-5-diethylaminophenol (Bromo-PADAP) as chromogenic reagents. Simulated as well as actual samples of dissolver, conditioner and raffinate tank of Thorex stream have been analyzed by both these methods. The method was tested for as low as 0.15 μg of uranium and the results of these analyses were found to be satisfactory within the experimental limits.

Preparation, Certification and Validation of a Stable Solid Spike of Uranium and Plutonium Coated with a Cellulose Derivative for the Measurement of Uranium and Plutonium Content in Dissolved Nuclear Fuel by Isotope Dilution Mass Spectrometry

A stable solid spike for the measurement of uranium and plutonium content in nitric acid solutions of spent nuclear fuel by isotope dilution mass spectrometry has been prepared at the European Commission Institute for Reference Materials and Measurements in Belgium. The spike contains about 50 mg of uranium with a 19.838% (235)U enrichment and 2 mg of plutonium with a 97.766% (239)Pu abundance in each individual ampoule. The dried materials were covered with a thin film of cellulose acetate butyrate as a protective organic stabilizer to resist shocks encountered during transportation and to eliminate flaking-off during long-term storage. It was found that the cellulose acetate butyrate has good characteristics, maintaining a thin film for a long time, but readily dissolving on heating with nitric acid solution. The solid spike containing cellulose acetate butyrate was certified as a reference material with certified quantities: (235)U and (239)Pu amounts and uranium and plutonium amount ratios, and was validated by analyzing spent fuel dissolver solutions of the Tokai reprocessing plant in Japan. This paper describes the preparation, certification and validation of the solid spike coated with a cellulose derivative.

Adsorption of Uranium on a Novel Bioadsorbent-Chitosan-Coated Perlite

Chitosan was coated on an inert substrate, perlite, and was prepared as spherical beads for adsorption of uranium from aqueous solutions. The uptake capacity of chitosan-coated perlite beads for uranium varied from 98.9 to 149 000 μg/g when the equilibrium concentration of uranium in the solution ranged from 11 ppb (11 μg/l) to 1000 ppm (10 × 106 μg/l) and the solution pH was 5. The adsorption capacity of chitosan-coated perlite beads for uranium decreased by 75% in the presence of 0.45 M NaCl, whereas the adsorption capacity decreased by 55% when TiO2 was added to the beads during their preparation. The adsorption capacity of TiO2-containing chitosan beads for uranium was found to be in the range of 2.5 to 40 μg of uranium per gram of beads when the concentration of uranium was 39 to 734 μg/l in the presence of 0.45 M NaCl. It was in the range of 18 to 302 μg of uranium per gram of beads when the concentration was 990 to 47 000 μg/l in the presence of 0.45 M Na2CO3. Chitosan-coated beads were found to preferentially adsorb uranium, Cd, and Cr from a mixture containing these ions along with Sr and Cs. Only a negligible amount of Sr and Cs was adsorbed by chitosan-coated beads. The data suggest that the chitosan-coated beads can be used for both extraction of uranium from waste streams and also from a highly acidic medium such as a reprocessing stream that uses nitric acid.

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.

Synthesis of salicylaldehyde-modified mesoporous silica and its application as a new sorbent for separation, preconcentration and determination of uranium by inductively coupled plasma atomic emission spectrometry

A new functionalized mesoporous silica (MCM-41) using salicylaldehyde was utilized for the separation, preconcentration and determination of uranium in natural water by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of U(VI) were optimized. The preconcentration factor was 100 (1.0 mL of elution for a 100 mL sample volume). The analytical curve was linear in the range 2–1000 μg L −1 and the detection limit was 0.5 ng mL −1. The relative standard deviation (R.S.D.) under optimum conditions was 2.5% ( n = 10). Common coexisting ions did not interfere with the separation and determination of uranium at pH 5. The sorbent exhibited excellent stability and its sorption capacity under optimum conditions has been found to be 10 mg of uranium per gram of sorbent. The method was applied for the recovery and determination of uranium in different water samples.

Photofission tomography of nuclear waste packages

Quantifying the mass of actinides in large concrete waste packages using non-destructive methods is a major challenge for the management and the storage of packages in appropriate facilities. Since the beginning of 1990s, our team in CEA has been working on the development of a method based on interrogation with high-energy photons to assay actinides in large concrete waste package. The method consists in using photons of high energy (bremsstrahlung radiation) in order to induce photofission reactions on the fissile nuclei present in the wastes. The measurement of the delayed neutrons emitted by fission products allows us to quantify the actinides present in the wastes. The accuracy of the method can be deeply improved by carrying out a tomography, i.e. computing the three-dimensional spatial distribution of the actinide mass inside the nuclear waste package. This paper presents the first experimental results of a tomography carried out on a 1.2 t real concrete waste package. Measurements associated with reconstruction algorithms and Monte Carlo simulations have allowed to locate an equivalent mass of 690 mg of uranium 238 centered in a disc of 20–25 cm of diameter at 75 cm height. These measurements have been performed in the SAPHIR irradiation facility at CEA/Saclay. This facility houses a pulsed linear electron accelerator (energy range from 15 to 30 MeV, pulse duration of 2.5 μs, peak current of 130 mA). The located mass has been subsequently confirmed by a destructive analysis of the package.

Preconcentration of uranium(VI) by solid phase extraction onto dicyclohexano-18-crown-6 embedded benzophenone

The preparation of a solid phase extractant (SPE), dicyclohexano-18-crown-6 embedded benzophenone, for preconcentration of uranium(VI) is described. The uranium(VI) can be quantitatively retained from 0.5 l solution on 1% dicyclohexano-18-crown-6 embedded benzophenone in the pH range 6.0-7.0, and then eluted with 5.0 ml of 1M HCl. Uranium(VI) content of the eluent was determined spectrophotometrically by Arsenazo III. Calibration graphs are rectilinear over the uranium(VI) concentration in the range of 0.004-0.4mg.ml-1. Five replicate determinations of 40mg of uranium(VI) present in 0.5 l sample gave a mean absorbance of 0.185 with a relative standard deviation of 2.45%. The detection limit corresponding to three times the standard deviation of the blank was found to be 2.0mg.l-1. The accuracy of the developed preconcentration procedure was tested by analyzing standard marine sediment reference material. The uranyl ion content of soils and sediments was estimated spectrophotometrically after the preconcentration procedure and compared to the results gained by standard inductively coupled plasma mass spectrometry (ICP-MS).

Chronic ingestion of uranyl nitrate perturbs acetylcholinesterase activity and monoamine metabolism in male rat brain

Recent animal studies have shown that uranium can reach the brain after chronic exposure. However, little information is available on the neurological effects of chronic long-term exposure to uranium. In the present study, the effects during 1.5, 6 and 9-month periods of chronic ingestion of uranyl nitrate (UN) in drinking water (40 mg of uranium per litre) on cholinergic acetylcholinesterase (AChE) activity and on dopaminergic and serotoninergic metabolisms were investigated in several areas of male Srague Dawley rat brains. Uranium brain accumulation and distribution was also investigated after 1.5 and 9 months. Both after 1.5, 6 and 9 months of exposure, AChE activity was unaffected in the striatum, hippocampus and frontal cortex. Nevertheless, AChE activity was transitionally perturbed in the cerebellum after 6 months of exposure. After 1.5 months of exposure, DA level increased in hypothalamus. After 6 months of exposure, a tiny but significant modification of the DAergic turnover ratio was detected in the frontal cortex. And after 9 months, UN produced a significant decrease in the 5HIAA level and the 5HTergic turn-over ratio in the frontal cortex and also a decrease in the DOPAC level and DAergic turn-over ratio in the striatum. Uranium brain accumulation was statistically significant in striatum after 1.5 months and in striatum, hippocampus and frontal cortex after 9 months of exposure. Although neurochemical changes did not always correlated with increased accumulation of uranium in specific areas, these results suggest that chronic ingestion of UN can cause chronic and progressive perturbations of physiological level of neurotransmitter systems. Considering previous reports on behavioural uranium-induced effects and the involvement of neurotransmitters in various behavioural processes, it would be crucial to determine whether these neurochemical disorders were accompanied by neurobehavioral deficits even at 40 mg of uranium per litre exposure.

A method for the separation of beryllium from spectral interfering elements in inductively coupled plasma-atomic emission spectroscopic analysis

A quick, simple and effective chromatographic method for the separation of beryllium from a wide range of elements is described. The elements selected comprise elements which can interfere with the determination of beryllium by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and elements which commonly occur in environmental and industrial sample matrices. Beryllium is separated from all possible ICP-AES spectral interfering elements using a single extraction chromatographic (EXC) cartridge containing an acidic chelating organophosphorus extractant, Dipex ®, sorbed onto an inert polymeric substrate. The separation method has been evaluated using simulated samples generated using several different digestion methods currently employed in beryllium analyses performed in Department of Energy (DOE) facilities. Incorporating a guard cartridge containing either 2-ethyl-1-hexylphosphonic acid mono 2-ethyl-1-hexyl ester or bis(2,4,4-trimethylpentyl)phosphinic acid to selectively remove U(VI) allows the isolation of beryllium from samples containing over 100 mg of uranium without changing the load, rinse or strip conditions of the method.

Determination of Uranium by Packed-Column Supercritical Fluid Chromatography with 1-Phenyl-3-methyl-4-benzoylpyrazolin-5-one

A new procedure for the determination of uranium by packed-column supercritical chromatography is proposed here. 1-Phenyl-3-methyl-4-benzoylpyrazolin-5-one (HPMBP) is chosen, as it can easily extract uranium from a nitric acid aqueous phase in the presence of a synergistic agent. Eighteen columns packed with C18-grafted silica have been tested. Adding the chelating agent directly to the mobile phase greatly improves the elution peak shapes. Trioctylphophine oxide (TOPO), diphenyl sulfoxide, and phenanthrene have been studied as synergistic agents. The influence of the injection solvent is also shown, and a calibration curve is obtained for uranium in the range of 20 ng to 2 μg injected. The limit of detection is 2 μg of uranium. The accuracy of the method is 4%, and the repeatability measured (1σ) is 3%.

Binding of uranyl ion by 2,2′-dihydroxyazobenzene attached to crosslinked polystyrenes covered with highly populated quaternary ammonium cations

2,2′-Dihydroxyazobenzene (DHAB) derivatives were attached to poly(chloromethylstyrene-co-divinylbenzene) (PCD) because of the high affinity of DHAB for uranyl ion. Chloromethyl groups of PCD were converted to quaternary ammonium ions by treating them with tertiary amines. Two strategies were adopted to improve the uranyl-binding ability of the immobilized DHAB: (1) the creation of a highly cationic microenvironment around the DHAB moieties and (2) the introduction of electron-withdrawing groups to DHAB. Capacity of the resins for uranyl uptake was measured, revealing that about 10 to 46 mg of uranium could be complexed to 1 g of the resins. Formation constants (Kf) for the uranyl complexes of the resins were determined. In the presence of ≥0.02 M bicarbonate ion at pH 8.02, log Kf values of 14.3 to 15.8 were obtained. Uranium extraction from seawater with two kinds of resins prepared in this study was carried out on the east coast of the Korean peninsula. The amount of uranium extracted from seawater was up to 150 μg/g resin. Thus, the uranium-extracting capability of the DHAB-containing polystyrene resins was improved significantly by the structural modifications. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4117–4125, 1999

A Rapid Method for the Extraction and Separation of Uranium from Thorium and Other Accompanying Elements Using Octadecyl Silica Membrane Disks Modified by Tri-n-octyl Phosphine Oxide

A simple method for rapid and selective separation of uranyl ion from Th4+ and other accompanying elements by using octadecyl silica membrane disks modified with tri-n-octyl phosphine oxide (TOPO) in the presence of 0.5 M HNO3 is presented. The influences of type and concentration of acid, nature of ligands, flow rates, and nature of stripping agents have been investigated. Maximum capacity of the membrane disks modified by 50 mg TOPO was found to be 938 μg of uranium. The method was applied to the recovery of uranyl ion from two different soil samples.

Binding of uranyl ion by 2,2′‐dihydroxyazobenzene attached to crosslinked polystyrenes covered with highly populated quaternary ammonium cations

2,2′-Dihydroxyazobenzene (DHAB) derivatives were attached to poly(chloromethylstyrene-co-divinylbenzene) (PCD) because of the high affinity of DHAB for uranyl ion. Chloromethyl groups of PCD were converted to quaternary ammonium ions by treating them with tertiary amines. Two strategies were adopted to improve the uranyl-binding ability of the immobilized DHAB: (1) the creation of a highly cationic microenvironment around the DHAB moieties and (2) the introduction of electron-withdrawing groups to DHAB. Capacity of the resins for uranyl uptake was measured, revealing that about 10 to 46 mg of uranium could be complexed to 1 g of the resins. Formation constants (Kf) for the uranyl complexes of the resins were determined. In the presence of ≥0.02 M bicarbonate ion at pH 8.02, log Kf values of 14.3 to 15.8 were obtained. Uranium extraction from seawater with two kinds of resins prepared in this study was carried out on the east coast of the Korean peninsula. The amount of uranium extracted from seawater was up to 150 μg/g resin. Thus, the uranium-extracting capability of the DHAB-containing polystyrene resins was improved significantly by the structural modifications. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4117–4125, 1999

Binding of uranyl ion by 2,2?-dihydroxyazobenzene attached to a partially chloromethylated polystyrene

A 2,2′-dihydroxyazobenzene (DHAB) derivative was attached to a chloromethylated cross-linked polystyrene derivative in view of high affinity of DHAB for uranyl ion. Chloromethyl groups of the resin were converted to quaternary ammonium ions by treating with tertiary amines. Capacity of the resins for uranyl-uptake was measured, revealing that about 20 mg of uranium can be complexed to 1 g of the resins. Formation constants (Kf) for uranyl complexes of the resins were determined. In the presence of >0.1 M bicarbonate ion at pH 8.10, log Kf of about 15 was obtained. As bicarbonate concentration was lowered, Kf decreased considerably. Degrees of uranyl-uptake from rapidly flowing uranyl solutions were measured, and the results suggested that rate of uranyl-uptake may not impose a major barrier to application of the resins in uranium extraction from seawater. Uranium extraction from seawater with the resins was carried out on the east coast of Korean peninsula. The amount of uranium extracted from seawater was about 10 µg/g resin. This is not satisfactory for economical processes of uranium recovery from seawater. Results of the present study, however, suggested that modification of the DHAB-containing resins can improve uranyl-binding ability, probably leading to economical recovery of uranium from seawater. In addition, simulation of uranyl-binding processes in seawater with the laboratory procedures developed in this study was satisfactory. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3169–3177, 1999

Release of uranium and emission of radiation from uranium-glazed dinnerware

Samples of orange, yellow, beige, ivory and blue-green ceramic dinnerware glazed with uranium compounds have been examined. Measurements at glaze surfaces yielded exposure rates of 3.8–16 mR/h (1–4 μC/kgh) for orange glazes and rates of 0.04–1.3 mR/h (0.01–0.3 μC/kgh) for ivory beige, and yellow glazes. Whole body exposure from a shelf display of 40 orange dishes was estimated to be 0.1–0.5 mR/h (0.03–0.13 μC/kgh), or up to 50 times the room background radiation level, at a distance of 1 meter. Twenty-four hour leaching tests of orange, yellow, and ivory dishes were carried out with various concentrations of acetic and citric acids. Uranium concentrations in leachates of some orange dishes exceeded 450 mg/l. Uranium is a chemical nephrotoxin and the United States Environmental Protection Agency has proposed a maximum contaminant level for drinking water of 0.020 mg/l. Based on this value a person consuming, 2.2 l of drinking water per day would ingest 0.31 mg of uranium per week. A person eating once a week from an orange glazed dish could easily ingest 10 or more times this amount.

205 Analysis of the glutamate binding site on the NR2B subunit of NMDA receptor

A dialkyl amide with branched alkyl group, viz. N,N-di(2-ethylhexyl)-propionamide (D2EHPrA) was used as the organic extractant in an extraction chromatographic resin prepared for the first time and evaluated for the separation of uranium from acidic feeds. The distribution coefficient measurements, carried out at varying HNO3 concentrations, indicated an increase in the UO22+ ion sorption with increasing nitric acid concentration. The UO22+ ion sorption kinetics and sorption isotherms with this resin were investigated in details. The column studies indicated that 8.3 mg of uranium could be loaded on a 2.1 cm3 column bed volume containing 0.35 g resin. Batch distribution data for other actinides such as Np4+ and Pu4+ indicated that the resin can also be used for effective separation of these metal ions from acidic feeds. Though the resin showed effectiveness for Np and Pu, detailed investigations dealing with macro concentrations of metal ions (in gm quantities) were restricted to uranium only due to hazardous nature of plutonium and limited availability of neptunium. The encouraging results reported in this work is an indication of the possible application of this resin for the recovery or pre-concentration of UO22+, Np4+ and Pu4+ ions from large volumes of aqueous solutions of moderate acidity.

The effect of pulse voltage and capacitance on biosorption of uranium by biomass derived from whiskey distillery spent wash

Biosorption of uranium by residual biomass from The Old Bushmill's Distillery Co. Ltd., Bushmills, Co. Antrim, Northern Ireland, following exposure to short and intense electric pulses has been examined. The biomass was prepared from the distillery spent wash and consisted of non-viable yeast and bacterial cells. As shown previously, untreated biomass had a maximum biosorption capacity of 170 mg uranium/g dry weight biomass. When biosorption reactions were placed between two electrodes and exposed to electric pulses with field strengths ranging from 1.25–3.25 kV/cm at a capacitance of 25 μF, biosorption increased from 170 mg of uranium to 275 mg uranium/g dry weight biomass. The data were obtained from biosorption isotherm analyses and taken as the degree of biosorption at residual uranium concentrations of 3 mM. In addition, when the capacitance of the electric pulses increased from 0.25 μF to 25 μF at a fixed pulse field strength the degree of biosorption increased from 210 mg uranium to 240 mg uranium/g dry weight biomass. The results suggest that application of short and intense electric pulses to biosorption reactions may play an important role in enhancing microbial biosorption of toxic metals/radionuclides from waste water streams.