Amidoxime modified chitosan based ion-imprinted polymer for selective removal of uranyl ions.

Ion-imprinting strategy was utilized in the development of UO2(II) imprinted amidoxime modified chitosan sorbent (U-AOCS) that can selectively remove UO2(II) from water. First, cyanoactic acid was linked to the chitosan -NH2 groups and then the inserted -CN groups were converted into amidoxime moieties, which chelate the UO2(II) ions and then the polymer chains were cross-linked by glyoxal. The UO2(II) ions have been then eluted leaving their matching recognition sites. The prepared U-AOCS along with the control NIP displayed maximum capacities toward the UO2(II) ions around 332 and 186 mg/g, respectively, and the isotherms were interpreted better by the Langmuir model in both adsorbents. Moreover, the selective uptake of the uranyl ions in multi-ionic aqueous solutions containing the tetravalent Th(IV) ions, trivalent Al(III), Eu(III), and Fe(III) ions, beside the divalent Pb(II), Co(II), Ni(II), Cu(II) ions confirmed the successful creation of a considerable UO2(II) ions selectivity in the U-AOCS construction. In addition, the U-AOCS adsorbent displayed economic feasibility by maintaining around 95 % of its initial efficiency after the regeneration and reuse for 5 adsorption/desorption cycles.

Graphene oxide encapsulated polyvinyl alcohol/sodium alginate hydrogel microspheres for Cu (II) and U (VI) removal.

In this work, a novel sodium alginate (SA)/polyvinyl alcohol (PVA)/graphene oxide (GO) hydrogel microspheres were prepared by a simple method. Sodium alginate was physically crosslinked by Ca2+; GO was encapsulated into the composite to strengthen the hydrogels; PVA played a significant role in well dispersing of GO in SA. The SA/PVA/GO (SPG) hydrogels were employed as an efficient adsorbent for removal of Cu (II) and U (VI) from aqueous solution. Batch experiments with the subject of the pH, initial metal ion concentration, competing ions and contact time were investigated. Structure characterization was successfully conducted by FTIR, SEM, EDX, BET and XPS. Furthermore, the sorption kinetics of Cu2+ and UO22+ followed pseudo-second order model and exhibited 3-stage intraparticle diffusion model. Equilibrium data were best described by Langmuir model and the obtained maximum adsorption capacities of SPG hydrogel microspheres for Cu2+ and UO22+ were 247.16 and 403.78 mg/g, respectively. The difference in adsorption capacity can be confirmed by the percentage of elements in EDX spectra and the intension of peak of elements in XPS spectra. The SPG sorbent exhibited excellent reusability after 5 adsorption-desorption cycles. All results suggested that the prepared adsorbents could be considered as effective and promising materials for removal of Cu (II) and U (VI) in wastewater.

Magnetic beads-based DNAzyme recognition and AuNPs-based enzymatic catalysis amplification for visual detection of trace uranyl ion in aqueous environment.

We herein developed a novel biosensor for the visual detection of trace uranyl ion (UO2(2+)) in aqueous environment with high sensitivity and specificity by using DNAzyme-functionalized magnetic beads (MBs) for UO2(2+) recognition and gold nano-particles (AuNPs)-based enzymatic catalysis oxidation of TMB (3,3',5,5'-tetramethylbenzidine sulfate) for signal generation. The utilization of MBs facilitates the magnetic separation and collection of sensing system from complex sample solution, which leads to more convenient experimental operation and more strong resistibility of the biosensor to the matrix of sample, and the utilization of AuNPs-based enzymatic catalysis amplification greatly improved the sensitivity of the biosensor. Compared with the previous DNAzyme-based UO2(2+) sensors, the proposed biosensor has outstanding advantages such as relative high sensitivity and specificity, operation convenience, low cost and more strong resistibility to the matrix of sample. It can be used to detect as low as 0.02 ppb (74 pM) of UO2(2+) in aqueous environment by only naked-eye observation and 1.89 ppt (7.0 pM) of UO2(2+) by UV-visible spectrophotometer with a recovery of 93-99% and a RSD ≤ 5.0% (n=6) within 3h. Especially, the visual detection limit of 0.02 ppb (74 pM) is much lower than the maximum allowable level of UO2(2+) (130 nM) in the drinking water defined by the U.S. Environmental Protection Agency (EPA), indicating that our method meets the requirement of rapid and on-site detection of UO2(2+) in the aqueous environment by only naked-eye observation.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

Synthesis and characterization of ion-imprinted resin for selective removal of UO2 (II) ions from aqueous medium.

In this work, uranyl ion-imprinted resin based on 2-(((4-hydroxyphenyl)amino)methyl)phenol was synthesized by condensation polymerization of its uranyl complex in presence of resorcinol and formaldehyde cross-linkers. Numerous instrumental techniques including elemental analysis, Fourier transform infrared spectroscopy, ultraviolet, (1) H along with (13) C nuclear magnetic resonance spectroscopy have been employed for complete characterization of the synthesized ligand and its uranyl complex. Additionally, the obtained ion-imprinted and non-imprinted resins were investigated using scanning electron microscope and Fourier transform infrared spectroscopy. The effects of various essential parameters such as pH, temperature and contact time on removal of uranyl ions have been examined, and the results indicated that the obtained resin exhibited the optimum activity at pH 5. Furthermore, the adsorption process was spontaneous at all studied temperatures and followed the second-order kinetics model. Also, Langmuir adsorption isotherm exhibited the best fit with the experimental results with maximum adsorption capacity 139.3 mg/g. Moreover, the selectivity studies revealed that the ion-imprinted resin exhibited an obvious affinity toward the uranyl ions in presence of other metal ions compared with the non-imprinted resin.

Application of DGT to high pH environments: uptake efficiency of radionuclides of different oxidation states onto Chelex binding gel.

The DGT Chelex binding phase has not been tested for binding efficiency over the extreme high pH range (i.e., 10 to 13). Here, we examined the uptake efficiency of the gel-encapsulated Chelex cation exchange resin binding phase when in direct contact with solutions of radionuclides of different oxidation states over the circumneutral to high pH range (∼7 to 13). Results show that the Chelex binding gel is suitable for Eu(3+) for circumneutral pH, for UO2(2+) up to at least pH 10.7 and for NpO2(+) up to at least pH 11.7. Application may be appropriate at higher pH values but testing of complete solution deployment units will be required. This work provides the framework to use DGT as a tool for the study of high pH radionuclide systems.

The synthesis of (N2O2S2)-Schiff base ligands and investigation of their ion extraction capability from aqueous media.

Two new Schiff bases (I) and (II) containing nitrogen-sulfur-oxygen donor atoms were designed and synthesized in a multi-step reaction sequence. The Schiff base (I) was used in solvent extraction of metal chlorides such as Cu2+ and Cr3+ as well as metal picrates such as Hg2+ and UO2(2+) from aqueous phase to the organic phase. The influences of the parameter functions, such as pH, solvent, ionic strength of aqueous phase, aqueous to organic phase and concentration of the extractant were investigated to shed light on their chemical extracting properties upon the extractability of metal ions. The effect of chloroform, dichloromethane and nitrobenzene as organic solvents over the metal chlorides extraction was investigated at 25±0.1 °C by using flame atomic absorption and the result is that the ability of extraction in solvents as follows: C6H5NO2>CHCl3>CH2Cl2 and the compositions of the extracted species have been determined. The metal picrate extraction was investigated at 25±0.1 °C by using UV-visible spectrometry. As well that the extraction of picrates metal such as UO2(2+) and Hg2+ with Schiff base(I) in absence and presence of 2-(2-aminoethyl) pyridine was investigated in chloroform. The extraction results revealed the presence of neutral donors 2-(2-aminoethyl) pyridine shifts the extraction percentage curves towards higher pH region, indicating a synergistic effect of this donors on extraction of UO2(2+) and Hg2+ by the studied Schiff base (I).

Treatment of effluents from uranium oxide production.

The nuclear fuel cycle comprises a series of industrial processes which involve the production of electricity from uranium in nuclear power reactors. In Brazil the conversion of uranium hexafluoride (UF6) into uranium dioxide (UO2) takes place in Resende (RJ) at the Nuclear Fuel Factory (FCN). The process generates liquid effluents with significant concentrations of uranium, which might be treated before being discharged into the environment. This study investigates the recovery of uranium from three distinct liquid effluents: one with a high carbonate content and the other with an elevated fluoride concentration. This paper also presents a study on carbonate removal from an effluent that consists of a water-methanol solution generated during the filtration of the yellow cake (ammonium uranyl tricarbonate). The results showed that: (1) the uranium from the carbonated solution can be recovered through the ion exchange technique using the strong base anionic resin IRA 910-U, as the carbonate has been removed as CO2 after heating; (2) the most suitable technique to recover uranium from the fluoride solution is its precipitation as (NH4)2UO4F2 (ammonium fluorouranate peroxide), (3) the solution free of carbonate can be added to the fluoride solution and the uranium from the final solution can be recovered by precipitation as ammonium fluorouranate peroxide as well; (4) the carbonate from the water-methanol solution can be recovered as calcium carbonate through the addition of calcium chloride, or it can be recovered as ammonium sulphate through the addition of sulphuric acid. The ammonium sulphate product can be used as a fertilizer.

Adsorption characteristics of UO(2)(2+) and Th(4+) ions from simulated radioactive solutions onto chitosan/clinoptilolite sorbents.

Adsorption features of UO(2)(2+) and Th(4+) ions from simulated radioactive solutions onto a novel chitosan/clinoptilolite (CS/CPL) composite as beads have been investigated compared with chitosan cross-linked with epichlorohydrin. The effects of contact time, the initial metal ion concentration, sorbent mass and temperature on the adsorption capacity of the CS-based sorbents were investigated. The adsorption kinetics was well described by the pseudo-second order equation, and the adsorption isotherms were better fitted by the Sips model. The maximum experimental adsorption capacities were 328.32 mg Th(4+)/g composite, and 408.62 mg UO(2)(2+)/g composite. The overall adsorption tendency of CS/CPL composite toward UO(2)(2+) and Th(4+) radiocations in the presence of Cu(2+), Fe(2+) and Al(3+), under competitive conditions, followed the order: Cu(2+)>UO(2)(2+)>Fe(2+)>Al(3+), and Cu(2+)>Th(4+)>Fe(2+)>Al(3+), respectively. The negative values of Gibbs free energy of adsorption indicated the spontaneity of the adsorption of radioactive ions on both the CS/CPL composite and the cross-linked CS. The desorption level of UO(2)(2+) from the composite CS/CPL, by using 0.1M Na(2)CO(3), was around 92%, and that of Th(4+) ions, performed by 0.1M HCl, was around 85%, both values being higher than the desorption level of radiocations from the cross-linked CS, which were 89% and 83%, respectively.

Use of amidoximated hydrogel for removal and recovery of U(VI) ion from water samples.

Poly(acrylamidoxime-co-2-acrylamido-2-methylpropane sulfonic acid) (PAMSA) hydrogel was prepared by copolymerization of acrylonitrile and 2-acrylamido-2-methylpropane sulfonic acid as monomer, N,N'-methylenebis(acrylamide) as crosslinking agent and potassium peroxodisulfate as initiator. Amidoximated copolymer network was prepared by the reaction of copolymer network with hydroxylamine hydrochloride. A batch procedure was used for the determination of the characteristics of the U(VI) solid phase extraction from the amidoximated hydrogel. The determination of U(VI) was performed by spectrophotometric method using arsenazo-III as complexing agent. Optimal pH value for the quantitative preconcentration was 3, and full desorption was achieved with 3 mol L(-1) HClO(4). The adsorption process can be well described by the pseudo-second-order kinetic model, and the equilibrium adsorption isotherm was closely fitted with the Langmuir model. A preconcentration factor of 20 and the three sigma detection limit of 2.8 µg L(-1) (n=20) were achieved for uranium(VI) ions. The PAMSA hydrogel was used for separating and preconcentrating the uranyl ion existing in sea water samples, thermal spring water samples and the certified reference materials (TMDA 64; fortified lake water sample).

Adsorptive recovery of UO2(2+) from aqueous solutions using collagen-tannin resin.

Collagen-tannin resin (CTR), as a novel adsorbent, was prepared via reaction of collagen with black wattle tannin and aldehyde, and its adsorption properties to UO(2)(2+) were investigated in detail, including pH effect, adsorption kinetics, adsorption equilibrium and column adsorption kinetics. The adsorption of UO(2)(2+) on CTR was pH-dependent, and the optimal pH range was 5.0-6.0. CTR exhibited excellent adsorption capacity to UO(2)(2+). For instance, the adsorption capacity obtained at 303 K and pH 6.0 was as high as 0.91 mmol UO(2)(2+)/g when the initial concentration of UO(2)(2+) was 1.0 mmol/L. In kinetics studies, the adsorption equilibrium can be reached within 300 min, and the experimental data were well fitted by the pseudo-second-order rate model, and the equilibrium adsorption capacities calculated by the model were almost the same as those determined by experiments. The adsorption isotherms could be well described by the Freundlich equation with the correlation coefficients (R(2)) higher than 0.99, the adsorption behaviors of UO(2)(2+) on CTR column were investigated as well. Present study suggested that the CTR can be used for the adsorptive recovery of UO(2)(2+) from aqueous solutions.

Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay.

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6+/-2.1 and 94.7+/-3.3% was observed for an initial concentration of 50 and 100 mg L(-1), respectively at pH 6.0 and an adsorbent dose of 2.0 g L(-1). Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68+/-5.04 mg g(-1). An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (approximately = 100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.

Sizing alpha emitting particles of aged plutonium on personal air sampler filters using CR-39 autoradiography.

Methods have been developed to assess the size distribution of alpha emitting particles of reactor fuel of known composition captured on air sampler filters. The sizes of uranium oxide and plutonium oxide particles were determined using a system based on CR-39 solid-state nuclear track detectors. The CR-39 plastic was exposed to the deposited particles across a 400 microm airgap. The exposed CR-39 was chemically etched to reveal clusters of tracks radially dispersed from central points. The number and location of the tracks were determined using an optical microscope with an XY motorised table and image analysis software. The sample mounting arrangement allowed individual particles to be simultaneously viewed with their respective track cluster. The predicted diameters correlated with the actual particle diameters, as measured using the optical microscope. The efficacy of the technique was demonstrated with particles of natural uranium oxide (natUO2) of known size, ranging from 4 to 150 microm in diameter. Two personal air sampler (PAS) filters contaminated with actinide particles were placed against CR-39 and estimated to have size distributions of 0.8 and 1.0 microm activity median aerodynamic diameter (AMAD).

Validation of the integrity of a HEPA filter system.

The objective of this study was to establish a delayed air sampling method to verify the integrity of an existing HEPA filter system in a ventilated fume hood. (238U,232Th)O2 microspheres were generated to fabricate cement nuclear fuel pellets in a HEPA-filtered hood. To comply with the air effluent concentration limits by NRC, the capture efficiency of the HEPA filter was examined. An in-line isokinetic air sampling system was installed downstream of the HEPA filter. Utilizing a gas flow proportional counter, 212Pb was used as a surrogate to indicate any possible penetration of the (238U,232Th)O2 particles through the HEPA filter. Based on the experimental results, this delayed sampling method proved to be an easy and effective way to validate the integrity of the HEPA filter.