Selective extraction of Th(IV) over U(VI) and other co-existing ions using eosin B-impregnated Amberlite IRA-410 resin beads

A new chelating polymeric sorbent as an extractant impregnated resin (EIR) has been developed using eosin B and Amberlite IRA-410 resin. The impregnation process was characterized by FT-IR spectroscopy. The eosin B-impregnated resin showed superior binding affinity for Th(IV) over U(VI) and many co-existing ions. The influence of various physicochemical parameters on the recovery of Th(IV) were optimized by both static and dynamic methods. The Langmuir adsorption isotherm gave a satisfactory fit of the equilibrium data. The kinetic studies performed for Th(IV) sorption revealed that <20 min was sufficient for reaching equilibrium metal ion sorption. A preconcentration factor of 100 was found for the column-mode extraction. The accuracy of the developed method in conjunction with Arsenazo III procedure was tested by analyzing geological reference materials and seawater sample, which are prepared, synthetically. Furthermore, the above procedure has been successfully employed for the analysis of natural water samples.     

Kinetics of the reaction of U(VI) with benzene-1,2-diphosphonic acid

The kinetics of the reaction between dioxouranium(VI) and benzene-1,2-diphosphonic acid (BzDPA) has been investigated by stopped-flow spectrophotometry. The rate of reaction of uranyl ions with Arsenazo III (2,7-bis(2,2'-arsonophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid) in 50:50 methanol-water solutions was also determined. Both formation and dissociation rate constants for the 1:1 complex between uranyl-BzDPA in acidic solutions were resolved. To gain insight into the effect of solvation on the progress of the reaction, the system was studied in triply distilled water, in 50:50 methanol-water, 80:20 methanol-water and in 50:50 tert-butanol-water as a function of temperature at pH 1.0. The rates of complex formation and dissociation reactions decrease as methanol substitutes for water in the medium and further decrease as tert-butanol replaces methanol as co-solvent. Activation parameters are most consistent with an associative process governing the progress of both complex formation and dissociation reactions. Introduction of alcoholic co-solvents results in notably more negative activation entropies for both complex formation and dissociation reactions, while the activation enthalpies are only slightly reduced in the mixed methanol-water medium. These results are compared with the kinetic features of other U(VI) systems.     

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.     

Preconcentration of U(VI) ions on few-layered graphene oxide nanosheets from aqueous solutions

Graphene oxide nanosheets have attracted multidisciplinary attention due to their unique physicochemical properties. Herein, few-layered graphene oxide nanosheets were synthesized from graphite using a modified Hummers method and were characterized by TEM, AFM, Raman spectroscopy, XPS, FTIR spectroscopy, TG-DTA and acid-base titrations. The prepared few-layered graphene oxide nanosheets were used as adsorbents for the preconcentration of U(VI) ions from large volumes of aqueous solutions as a function of pH, ionic strength and temperature. The sorption of U(VI) ions on the graphene oxide nanosheets was strongly dependent on pH and independent of the ionic strength, indicating that the sorption was mainly dominated by inner-sphere surface complexation rather than by outer-sphere surface complexation or ion exchange. The abundant oxygen-containing functional groups on the surfaces of the graphene oxide nanosheets played an important role in U(VI) sorption. The sorption of U(VI) on graphene oxide nanosheets increased with an increase in temperature and the thermodynamic parameters calculated from the temperature-dependent sorption isotherms suggested that the sorption of U(vi) on graphene oxide nanosheets was an endothermic and spontaneous process. The maximum sorption capacities (Q(max)) of U(VI) at pH 5.0 ± 0.1 and T = 20 °C was 97.5 mg g(-1), which was much higher than any of the currently reported nanomaterials. The graphene oxide nanosheets may be suitable materials for the removal and preconcentration of U(VI) ions from large volumes of aqueous solutions, for example, U(VI) polluted wastewater, if they can be synthesized in a cost-effective manner on a large scale in the future.     

Hydration structures of U(III) and U(IV) ions from ab initio molecular dynamics simulations

We apply DFT+U-based ab initio molecular dynamics simulations to study the hydration structures of U(III) and U(IV) ions, pertinent to redox reactions associated with uranium salts in aqueous media. U(III) is predicted to be coordinated to 8 water molecules, while U(IV) has a hydration number between 7 and 8. At least one of the innershell water molecules of the hydrated U(IV) complex becomes spontaneously deprotonated. As a result, the U(IV)-O pair correlation function exhibits a satellite peak at 2.15 A? associated with the shorter U(IV)-(OH(-)) bond. This feature is not accounted for in analysis of extended x-ray absorption fine structure and x-ray adsorption near edge structure measurements, which yield higher estimates of U(IV) hydration numbers. This suggests that it may be useful to include the effect of possible hydrolysis in future interpretation of experiments, especially when the experimental pH is close to the reported hydrolysis equilibrium constant value.     

Linear alkyl diamine-uranium-phosphate systems: U(VI) to U(IV) reduction with ethylenediamine

Mild-hydrothermal reactions in acidic medium using 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane as structure directing agents led to three-dimensional (3D) uranyl phosphates (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C3U5P4), (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C4U5P4) and (CH?)5(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C5U5P4). The structures of (C4U5P4) and (C5U5P4) were solved in the space group Cmc2? using single-crystal X-ray diffraction data. The compounds are isostructural to the corresponding uranyl vanadates and contain the same 3D inorganic framework built from uranyl-phosphate layers of uranophane-type anion topology pillared by [UO?(H?O)] pentagonal bipyramids. In neutral or basic medium the alkyl diamines decompose to give ammonium uranyl phosphate trihydrate. In the same conditions by using ethylenediamine, unexpected reduction of uranium(VI) to uranium(IV) occurs leading to the formation of (CH?)?(NH?)?[U(PO?)?] (C2UP2) single crystals. C2UP2 undergoes a reversible phase transition from triclinic to monoclinic symmetry at about 230 °C. The structure of the two forms results from the stacking of inorganic layers (∞)1[U(PO?)?]2?, and organic layers containing ethylene diammonium ions, the two layers being linked by hydrogen bonds. Single crystals of (CH?)?(NH?)?[PO?OH] (C2HP) are formed by evaporation of the solution after filtering of C2UP2 single crystals. The structure of C2HP contains infinite (∞)1[PO?OH]2? chains connected by (CH?)?(NH?)?2? ions through hydrogen bonds.     

Sorption and complexation of uranium(VI) and thorium(IV) with reagents Arsenazo III and Arsenazo M on fibrous filled sorbents

The possibility of the highly sensitive sorption-spectrometric determination of Th(IV) and U(VI) in the presence of each other on the solid phase of fibrous anion-exchange materials with Arsenazo M and Arsenazo III was examined. Polyacrylonitrile fiber filled with an exchanger AN-31, ANKB-50, or EDE-10p was used as the solid phase. It was demonstrated that the studied systems allow the selective determination of thorium in the presence of one-to twofold amounts of uranium. On PANV-EDE-10p with immobilized Arsenazo III, the detection limit of thorium in 2–10 M HCl is 0.002 μg/mL, and in 10 M HCl the presence of up to twofold amounts of uranium is permissible. A high sensitivity of the determination of uranium in 2–7 M HCl of 0.005 μg/mL, which has not been reported before, was attained. The time of the analysis of five or six samples is no longer than 20 min.     

Determination of U(VI) and U(IV) concentrations in aqueous samples containing strong luminescence quenchers using TRLFS

Novel luminescence (LM) spectroscopy-based uranium (U) analysis methods are developed for aqueous samples containing strong LM quenchers. Reducing agents often found in biological samples, such as thiols, ascorbate and Fe(II) ions, are identified as the major strong quencher species. A strategy to selectively oxidize the reducing moieties of the quencher species using monopersulfate (the selected oxidant) is employed to rapidly reduce the LM quenching effects. Without requiring conventional sample pre-processing (ashing) procedures this method improves the limit of detection of U(VI) (~nM levels) and enables rapid and simultaneous determination of U(VI) and U(IV) dissolved in biological samples containing strong quenchers.     

Preconcentration of U(VI) from aqueous solutions after sorption using Sorel’s cement in dynamic mode

Summary Mg(OH)₂ was identified as a component of Sorel’s cement being a very strong sorbent for uranium. Sorel’s cement is a mixture of MgO, MgCl₂ and water. The optimal conditions for the adsorption of U(VI) was studied by the batch method. A contact time of 2 hours was found to be optimum. Maximum U(VI) uptake was observed in a pH range of 5.5-6.5 with a sorption constant of K_ads = 0.9 h^-1 at initial concentration of 20 ppm. Polypropylene columns filled with 2 g of Sorel’s cement at a mesh size of 35 were used for the preconcentration of uranium by passing 8 l of water containing 10 ppb U(VI). A flow rate of 0.25 ml/min and a bed height of 5 cm were found to be the optimum for the U(VI) separation. A 5 wt% triphenylphosphine oxide solution in toluene was used as an organic solvent for the separation of uranium from interfering elements such as iron(III) and thorium(IV), prior to spectrophotometric analysis. The determination of U(VI) was accomplished by adding Arsenazo III as a coloring reagent to the solution and using a UV-160A spectrophotometer.     

Practical synthetic routes to solvates of U(OTf)3: X-ray crystal structure of [U(OTf)3(MeCN)3]n, a unique U(III) coordination polymer

The reaction of UH3 or U metal with triflic acid results in the formation of a mixture of species including U(OTf)4 and leads to the reproducible isolation of the mononuclear U(IV) hydroxo complex [U(OTf)3(OH)(py)4] (1) and the U(IV) dinuclear mu-oxo-complex [{U(OTf)2(py)3}2{mu-O}{mu-OTf}2] (2). The X-ray crystal structures of these complexes have been determined. Analytically pure complex 1 can be prepared in a 17-27% yield providing a good precursor for the synthesis and study of the reactivity of the hydroxo complexes with different coordination environments. Two practical synthetic methods for the preparation of Lewis base adducts of U(OTf)3 are described. Analytically pure [U(OTf)3(py)4] (4) was easily and reproducibly prepared (50-60% yield) by protonolysis of the amide U{N(SiMe3)2}3 with pyridinium triflate in pyridine. Salt metathesis of UI3(thf)4 with potassium triflate in acetonitrile resulted in the complete substitution of the iodide counterions by triflate producing the acetonitrile solvate [U(OTf)3(MeCN)3]n (3). The solid-state structure of 3 shows the formation of a unique U(III) coordination polymer in which the metal ions are connected by three triflates acting as bidentate bridging ligands to form a 1D chain.     

Adsorptivity of polyvinylpolypyrrolidone for selective separation of U(VI) from nitric acid media

Adsorptivity of polyvinylpolypyrrolidone (PVPP), a candidate resin with selectivity to U(VI) in HNO₃ media, to various metal ions was examined. It was found that PVPP has a strong adsorptivity to U(VI) in wide concentration range of HNO₃. The Scatchard plot analysis revealed that the adsorption of U(VI) by PVPP occurs at plural binding sites. The infrared spectroscopic analysis suggested that the strong binding site is due to the coordination of the carbonyl oxygen atom and the nitrogen atom in the pyrrolidone ring to UO₂ ²⁺. It was also found that fission product ions except Re(VII) as the simulant of Tc(VII) and Pd(II) are not adsorbed onto PVPP. The adsorptivities to Tc(VII) and Pd(II) species are weak, indicating that U(VI) can be separated from other metal ions by PVPP.     

Use of pyrocatechol violet modified sodium dodecyl sulfate coated on alumina for separation and preconcentration of uranium(VI)

A sensitive and selective solid phase extraction procedure for the determination of trace of uranium(VI) has been developed. An alumina-sodium dodecyl sulfate coated on with pyrocatechol violet was used for preconcentration and determination of uranyl ions by spectrophotometry method using Arsenazo III reagent. Sorbed ions were quantitatively eluted using 5 mL of 0.25 mol L⁻¹ HNO₃. The effects of parameters such as pH, amount of alumina, amount of ligand, flow rate, type and concentration of elution agent were examined. The capacity of the sorbent for U(VI) was found to be 0.92 mmol g⁻¹. The relative standard deviation was 1.28% for 10 replicate determinations of U(VI) ion in a solution with a concentration of 1.0 μg mL⁻¹. The practical applicability of the developed sorbent was examined using synthetic and real samples such as standard reference material 2709 (San Joaquin Soil) and 2711 (Montana Soil).     

Structure and hydrolysis of the U(IV), U(V), and U(VI) aqua ions from ab initio molecular simulations

Ab initio molecular dynamics simulations at 300 K, based on density functional theory, are performed to study the hydration shell geometries, solvent dipole, and first hydrolysis reaction of the uranium(IV) (U(4+)) and uranyl(V) (UO(2)(+)) ions in aqueous solution. The solvent dipole and first hydrolysis reaction of aqueous uranyl(VI) (UO(2)(2+)) are also probed. The first shell of U(4+) is coordinated by 8-9 water ligands, with an average U-O distance of 2.42 ?. The average first shell coordination number and distance are in agreement with experimental estimates of 8-11 and 2.40-2.44 ?, respectively. The simulated EXAFS of U(4+) matches well with recent experimental data. The first shell of UO(2)(+) is coordinated by five water ligands in the equatorial plane, with the average U═O(ax) and U-O distances being 1.85 ? and 2.54 ?, respectively. Overall, the hydration shell structure of UO(2)(+) closely matches that of UO(2)(2+), except for small expansions in the average U═O(ax) and U-O distances. Each ion strongly polarizes their respective first-shell water ligands. The computed acidity constants (pK(a)) of U(4+) and UO(2)(2+) are 0.93 and 4.95, in good agreement with the experimental values of 0.54 and 5.24, respectively. The predicted pK(a) value of UO(2)(+) is 8.5.     

Enhancing U(eff) in oxime-bridged [Mn(III)6Ln(III)2] hexagonal prisms

The first 3d-4f clusters built using derivatised salicylaldoximes (R-saoH(2)) describe unusual hexagonal prisms. Replacement of the paramagnetic Gd(III) ions with diamagnetic Ln(III) ions allows for a more thorough understanding of the magnetic properties, whilst replacement with Tb(III) doubles U(eff).     

U(VI) Complexes of oxine and derivatives

Infrared bands due to the hydrogen-bonded (+)N-H cdots, three dots, centered O system in the oxine adduct of U(VI) have been identified and found to occur in the spectra of several newly prepared U(VI) adducts of oxine derivatives. Interligand steric effects in the U(VI) complexes of most 7-substituted oxines prevent the formation of the 1:3 adduct. Complexes of the type ML(2)X, where X is a small co-ordinating species present in solution, are formed instead. With 2-substituted oxines, steric interactions between the 2-substituent and co-ordinated water result in destabilization of the complex and subsequent hydrolysis as the pH of the solution is raised. Experiments involving the use of [(14)C]-oxine were found to distinguish between co-ordinated and lattice-held oxine and are potentially valuable in studies of oxine adducts formed by other metal ions.     

Preconcentration and determination of ultra-trace amounts of U(VI) and Th(IV) using titan yellow-impregnated Amberlite XAD-7 resin

A simple and sensitive method for the determination of ultra trace amounts of U(VI) and Th(IV) ions by spectrophotometric method after solid-phase extraction on a new extractant-impregnated resin (EIR) has been reported. The new EIR was synthesised by impregnating a weakly polar polymeric adsorbent, Amberlite XAD-7, with titan yellow (TY) as extractant. The analytical method is based on the simultaneous adsorption of analyte ions in a mini-column packed with TY/XAD-7 and performing sequential elution with 0.5% (w/v) Na₂CO₃ for uranium and 2.0 M HCl for thorium. The influences of the analytical parameters including pH, salting out agent and sample volume were investigated. The interference effects of foreign ions on the retention of the analyte ions were also explored. The limits of detection for U(VI) and Th(IV) were as low as 50 and 25 ng L^?1, respectively. Relative standard deviations (n = 7) for U(VI) and Th(IV) were 3.1% and 2.9%, respectively. The method was successfully applied to the determination of ultra trace amounts of U(VI) and Th(IV) in different real matrices including industrial wastewater samples and environmental waters. The proposed method was validated using three certified reference materials and the results were in good agreement with the certified values.     

Flow Injection Manifold for Simultaneous Spectrophotometric Determination of Bi (III), Pb (II)

Abstract

A FIA assembly producing a carrier with pH which can be adjusted to the desired pH value is propposed. It is based on the merging of two different solutions, one of them at constant flow-rate and the other at variable flow-rate. This manifold has been used for the simultaneous determination of Bi(III) and Pb(II) with Arsenazo III. Calibration curves are linear in the 1.0-11.0 ppm Bi (III) range at pH 0.25 and 1.0-12.1 ppm Pb (II) at pH 2.15. The effect of foreign ions is also reported.     

Selective sorption of protactinium on aminopolystyrene azo derivative chelating resins

The sorption of protactinium on chelating resins, containing arsono groups, or other salt-forming groups on an aminopolystyrene lattice, is discussed. The chelating resins were synthesized by coupling diazotizedp-aminopolystyrene witho-hydroxyphenylarsonic acid, 2-arsonobenzene-(1-azo-2)-1,8-dihydroxynaphthalene-3,6-disulphonic acid (Arsenazo I) and some other monoazo derivatives of chromotropic acid. The dependence of sorption of Pa, Zr, Nb and Ta was investigated from hydrochloric acid and sulphuric acid solutions under static conditions as a function of the concentration of the acid. The feasibility of separating Pa from Fe, U, Zr, Nb, Th and Po is shown, using a solution 10N in respect to sulphuric acid and 0.3M in respect to oxalic acid and employing a resin obtained by coupling diazotized aminopolystyrene with Arsenazo I.     

Preparation and structures of homoleptic Pu(III) and U(III) acetonitrile salts

Nine-coordinate homoleptic acetonitrile solvate complexes of Pu(III) and U(III) ions have been prepared through oxidation of Pu metal suspended in acetonitrile with metal-hexafluorophosphate salts and dissolution of UI3(THF)4 in acetonitrile, respectively.     

Effect of arsenate and phosphate ions on the adsorption and complexation of uranium(VI) with Arsenazo III on the solid phase of the ion exchanger PAN-EDE-10p fibrous anion exchanger

The effect of arsenate and phosphate ions on the adsorption and color reaction of uranium(VI) with Arsenazo III on the solid phase of a fibrous material filled with the EDE-10p anion exchanger was studied in different adsorption processes. We selected the optimum conditions for the system of U(VI)-AsO ₄ ^3? (H₂PO ₄ ^? )-PANV-EDE-10p-Arsenazo III and used this system for the adsorption-spectrophotometric determination of (0.03–0.3) 10^?3 M arsenate, (0.004–0.06) 10^?3 M phosphate, and 0.01–0.1 μg/mL uranyl ions.