Uranium(VI) and Thorium(IV) Adsorption Studies on Chelating Resin Containing Pentaethylenehexamine as a Functional Group

A new chelating resin (glycidyl methacrylate/divinylbenzene/pentaethylenehexamine (GMA/DVB/PEHA)) for uranium(VI) and thorium(IV) has been developed by functionalizing GMA/DVB with PEHA. The adsorption of U(VI) and Th(IV) ions onto the functionalized GMA/DVB/PEHA were investigated as a function of pH value, contact time, and temperature using batch adsorption technique. The results showed that U(VI) and Th(IV) adsorption onto GMA/DVB/PEHA was strongly dependent on pH. Kinetic studies revealed that the adsorption process achieved equilibrium within 15 and 90 minutes for Th(IV) and U(VI), respectively, and followed a pseudo-second-order rate equation. The isothermal data correlated with the Langmuir model better than the Freundlich model. Thermodynamic data indicated the spontaneous and endothermic nature of the process. The maximum adsorption capacity of U(VI) and Th(IV) were found to be 114 and 78 mg/g, respectively. Quantitative recovery of uranium and thorium were achieved by desorbing the loaded GMA/DVB/PEHA with 0.5 M HNO₃      

Selective Separation of Uranium(VI), Thorium(IV), and Lanthanum(III) from Their Aqueous Solutions using a Chelating Resin Containing Amine Functionality

A glycidyl methacrylate/divinylbenzene resin containing triethylenetetramine functional group was synthesized. The adsorption behavior of the obtained resin toward U(VI), Th(IV), and La(III) in aqueous solutions was investigated by batch and column techniques at different experimental conditions. Kinetic and thermodynamic characteristics of the adsorption process have been investigated. The regeneration of the loaded resin was also studied.     

A novel extractant-impregnated resin containing carminic acid for selective separation and pre-concentration of uranium(VI) and thorium(IV)

The present work proposes the use of a novel extractant-impregnated resin (EIR) as an adsorbent in trace separation and pre-concentration of U(VI) and Th(IV) ions. The new EIR was prepared by impregnating carminic acid onto Amberlite XAD-16 resin beads. The morphology of new EIR was studied by BET surface area measurements and SEM micrographs. A column packed with CA/XAD-16 was used for selective separation and pre-concentration of the metal ions. Maximum adsorption of Th(IV) and U(VI) ions occurred at pHs of 3.50–5.75 and 3.75–6.50, respectively. The adsorbed metals could be eluted sequentially using 0.55?mol?L^?1 HCl for U(VI) and 2.25?mol?L^?1 HCl for Th(IV). The dynamic capacity of EIR was found to be 0.832 and 0.814?mmol?g^?1 for Th(IV) and U(VI), respectively. The tolerance limit of some foreign ions was also studied. The proposed method showed a good performance in analyzing geological reference materials and a synthetic seawater sample. Furthermore, the above procedure was successfully employed for the analysis of natural water samples.     

Synthesis of phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin and its adsorption properties of uranium(VI)

A new phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin (PS–N–P) was synthesized by P,P-dichlorophenylphosphine oxide modified commercially available ammoniated polystyrene beads, and characterized by Fourier transform infrared spectroscopy and elemental analysis. The adsorption properties of PS–N–P toward U(VI) from aqueous solution were evaluated using batch adsorption method. The effects of the contact time, temperature, pH and initial uranium concentration on uranium(VI) uptake were investigated. The results show that the maximum adsorption capacity (97.60 mg/g) and the maximum adsorption rate (99.72 %) were observed at the pH 5.0 and 318 K with initial U(VI) concentration 100 mg/L and adsorbent dose 1 g/L. Adsorption equilibrium was achieved in approximately 4 h. Adsorption kinetics studied by pseudo second-order model stated that the adsorption was the rate-limiting step (chemisorption). U(VI) adsorption was found to barely decrease with the increase in ionic strength. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as ?G ₀, ?H ₀ and ?S ₀ were derived to predict the nature of adsorption. Adsorbed U(VI) ions on PS–N–P resin were desorbed effectively (about 99.39 %) by 5 % NaOH–10 % NaCl. The synthesized resin was suitable for repeated use.     

Synthesis of N,N′-dimethyl-N,N′-dibutyl malonamide functionalized polymer and its sorption affinities towards U(VI) and Th(IV) ions

A novel chelating polymeric material was synthesized by chemical anchoring of N,N′-dimethyl-N,N′-dibutyl malonamide (DMDBMA) with chloromethylated polystyrene-divinyl benzene polymer. The polymeric material thus prepared was characterized by ¹³C NMR, FT-IR spectroscopy and CHN elemental analysis. The fabricated polymeric material exhibited superior binding for hexa-valent and tetra-valent metal ions such as U(VI) and Th(IV). Various physico-chemical properties of the functionalized polymer like phase adsorption kinetics, metal sorption mechanism and metal sorption capacity was studied in the static method. Adsorption kinetics studies show that <20 min was sufficient for >99.99% adsorption of Th(IV) and U(VI). The kinetics for adsorption of U(VI) and Th(IV) was found to follow the first order Lagergren rate kinetics. Adsorption of U(VI) on the malonamide functionalized polymer followed the Langmuir adsorption isotherm. The Langmuir monolayer adsorption phenomenon was also confirmed by the theoretical approach calculated based on the adsorption kinetics. The metal sorption capacities for uranium and thorium were found to be 18.78 ± 1.53 mg and 15.74 ± 1.59 mg/g of the chelating polymer at 3 M HNO₃, respectively.     

Preparation of a novel magnetic resin for effective removal of both natural organic matter and organic micropollutants

A novel,bifunctional,hypercrosslinked.magnetic resin W2 was prepared using divinylbenzene(DVB) and glycidyl methacrylate(GMA) as comonomers in three steps(i.e.,suspension polymerization, amination and post-crosslinking reactions).To evaluate the adsorption of natural organic matter(NOM) and organic micropollutants(OMPs) on the obtained resin W2,two magnetic resins Wl(the precursor of W2 before post-crosslinking) and WO(the precursor of Wl before amination) were chosen for comparison.The results indicated that W2 would be a promising material for the removal of both NOM and OMPs from aquatic environments.     

Adsorptive removal of U(VI) and Th(IV) from aqueous solutions using polymer-based electrospun PEO/PLLA fibrous membranes

Fibrous membranes based on poly(ethylene oxide) and poly(l-lactide) fabricated by electrospinning were evaluated for the first time as substrates for the adsorption of tetravalent thorium (Th(IV)) and hexavalent uranium (U(VI)) from aqueous media. The membranes consisted of microfibers with diameters of approximately 2 μm as revealed by scanning electron microscopy. The adsorption of Th(IV) and U(VI) on the membrane was investigated as a function of pH, ionic strength and initial metal concentration under normal atmospheric conditions. The experimental data indicated increased affinity of the membrane for Th(IV) and U(VI), which was pH depended and reaches maximum values (>90 %) for Th(IV) and U(VI) at pH 3 and pH 6.5, respectively. The maximum adsorption capacity (q _max) at optimum conditions was evaluated from the Langmuir isotherm and was found to amount 50.08 and 9.3 mmol kg^?1 for Th(IV) and U(VI), respectively. In addition, studies on the effect of ionic strength on the adsorption efficiency did not show any significant effect indicating that the adsorption of Th(IV) and U(VI) on the membrane was most probably based on specific interactions and the formation of inner-sphere surface complexes. The significantly higher adsorption efficiency of the membrane for Th(IV) in acidic media (pH ≤ 3) could be utilized for a pH-triggered, selective separation of Th(IV) from U(VI) from aqueous media.     

Simultaneous preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using a chelating calix[4]arene anchored chloromethylated polystyrene solid phase

A new chelating polymeric sorbent is developed using Merrifield chloromethylated resin anchored with calix[4]arene-o-vanillinsemicarbazone for simultaneous separation and solid phase extractive preconcentration of U(VI) and Th(IV). The “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone was covalently linked to Merrifield resin and characterized by FT-IR and elemental analysis. The synthesized chelating polymeric sorbent shows superior binding affinity towards U(VI) and Th(IV) under selective pH conditions. Various physico-chemical parameters that influence the quantitative extraction of metal ions were optimized. The optimum pH range and flow rates for U(VI) and Th(IV) were 6.0-7.0 and 1.0-4.0 ml min⁻¹ and 3.5-4.5 and 1.5-4.0 ml min⁻¹, respectively. The total sorption capacity found for U(VI) and Th(IV) was 48734 and 41175 μg g⁻¹, respectively. Interference studies carried out in the presence of diverse ions and electrolyte species showed quantitative analyte recovery (98-98.5%) with lower limits of detection, 6.14 and 4.29 μg l⁻¹ and high preconcentration factors, 143 and 153 for U(VI) and Th(IV), respectively. The uptake and stripping of these metal ions on the resin were fast, indicating a better accessibility of the metal ions towards the chelating sites. The analytical applicability of the synthesized polymeric sorbent was tested with some synthetic mixtures for the separation of U(VI) and Th(IV) from each other and also from La(III), Cu(II) and Pb(II) by varying the pH and sequential acidic elution. The validity of the proposed method was checked by analyzing these metal ions in natural water samples, monazite sand and standard geological materials.     

Salvadora Persica branches biomass adsorbent for removal of uranium(VI) and thorium(IV) from aqueous solution: kinetics and thermodynamics study

Adsorption isotherms of U(VI) and Th(IV) in water were obtained and removal kinetics was studied. The main functional groups on the surface of Salvadora Persica branches adsorbent were identified using a Fourier-transform infrared and the surface morphology of adsorbent was characterized by a Scanning Electron Microscope. Effects of the U(VI) and Th(IV) initial concentrations, contact time, the mass of adsorbent loading, pH of the solution were investigated at 25?±?0.3 °C. The efficiencies with which this adsorbent removes U(VI) and Th(IV) from their solutions in water are reported. The adsorption isotherm fitted the Freundlich model. The adsorption of U(VI) and Th(IV) follows the pseudo-second order kinetic with squared correlation coefficients (R²) close to 1.0. The thermodynamic parameters (i.e. the free energy (\(\Delta G_{\text{ads}}^{o}\)), the enthalpy (\(\Delta H_{\text{ads}}^{o}\)) and the entropy of adsorption (\(\Delta S_{\text{ads}}^{o}\)) for the adsorption of U(VI) and Th(IV) on the Salvadora Persica branches adsorbent were reported.

     

Competitive adsorption of uranium(VI) and thorium(IV) ions from aqueous solution using triphosphate-crosslinked magnetic chitosan resins

The triphosphate-crosslinked magnetic chitosan resins (TPP-MCR) with a diameter range of 200–350 nm were synthesized for the adsorption of U(VI) and Th(IV) ions from aqueous solutions. The adsorption experiments were conducted in both mono-component systems with pure actinide solution and bi-component systems with different U/Th mass ratios. The maximum adsorption capacities in mono-component systems determined by Langmuir model were 169.5 and 146.8 mg g^?1 for U(VI) and Th(IV), respectively. In bi-component systems, U(VI) and Th(IV) adsorption capacities were reduced significantly, and the combined sorption capacities were substantially lower (almost halved) compared to those obtained by the addition of sorption capacities using mono-component solutions, indicating that U(VI) and Th(IV) compete for the same sorption sites. Adsorption–desorption experiments for five cycles illustrated the feasibility of the repeated use of TPP-MCR for the adsorption of U(VI) and Th(IV) ions.     

Sorption behaviour of lanthanum(III), neodymium(III), terbium(III), thorium(IV) and uranium(VI) on Amberlite XAD-4 resin functionalized with bicine ligands

The complexing properties (capacity, pH effect, breakthrough curve) of a chelating resin, containing bicine ligands, were investigated for La(III), Nd(III), Tb(III), Th(IV) and U(VI). Trace amounts of these metal ions were quantitatively retained on the resin and recovered by eluting with 1 M hydrochloric acid. The capacity of the resin for La(III), Nd(III), Tb(III), Th(IV) and U(VI) was found to be 0.35, 0.40, 0.42, 0.25 and 0.38 mmol g(-1), respectively. Separation of U(VI) and Th(IV) from Ni(II), Zn(II), Co(II) and Cu(II) in a synthetic solution was carried out.     

Poly-L-Histidine Attached Poly(glycidyl methacrylate) Cryogels for Heavy Metal Removal

Poly-L-histidine immobilized poly(glycidyl methacrylate) (PGMA) cryogel discs were used for the removal of heavy metal ions [Pb(II), Cd(II), Zn(II) and Cu(II)] from aqueous solutions. In the first step, PGMA cryogel discs were synthesized using glycidyl methacrylate (GMA) as a basic monomer and methylene bisacrylamide (MBAAm) as a cross linker in order to introduce active epoxy groups through the polymeric backbone. Then, the metal chelating groups are incorporated to cryogel discs by immobilizing poly-L-histidine (mol wt ≥ 5000) having poly-imidazole ring. The swelling test, fourier transform infrared spectroscopy and scanning electron microscopy were performed to characterize both the PGMA and poly-L-histidine immobilized PGMA [P-His@PGMA] cryogel discs. The effects of the metal ion concentration and pH on the adsorption capacity were studied. These parameters were varied between 3.0–6.0 and 10–800 mg/L for pH and metal ion concentration, respectively. The maximum adsorption capacity of heavy metal ions of P-His@PGMA cryogel discs were 6.9 mg/g for Pb(II), 6.4 mg/g for Cd(II), 5.6 mg/g for Cu(II) and 4.3 mg/g for > Zn(II). Desorption of heavy metal ions was studied with 0.1 M HNO₃ solution. It was observed that cryogel discs could be recurrently used without important loss in the adsorption amount after five repetitive adsorption/desorption processes. Adsorption isotherms were fitted to Langmuir model and adsorption kinetics were suited to pseudo-second order model. Thermodynamic parameters (i.e. ΔH° ΔS°, ΔG°) were also calculated at different temperatures.     

A column system for the selective extraction of U(VI) and Th(IV) using a new chelating sorbent

A new method has been developed using (bis-3,4-dihydroxy benzyl)p-phenylene diamine functionalized to XAD-16 (a polystyrene divinyl benzene copolymer) matrix, to preconcentrate mainly U(VI) and Th(IV) from synthetic and real samples. The developed method is free from matrix interference due to alkali and alkaline metal ions and preconcentrates the actinides with a high degree of selectivity, with consistent trace recoveries. The new chelating resin provides dramatic improvement in metal exchange rate, with half value saturation time (t_1/2) of less than 1.6 min. The developed method was superior in its metal loading capacity for U(VI) and Th(IV), with values of 0.666 and 0.664 mmol g⁻¹, respectively. Various physio-chemical properties like effect of solution pH, kinetic studies, resin loading capacity, sample breakthrough volume, matrix effects etc., on metal ion sorption to sorbent phase, were studied using both batch and column method. The new chelatogen was applied to extract U(VI) from near neutral real water samples. Preconcentration and separation of metal ions were possible through pH variation and also by varying the eluant concentration. A high preconcentration factor value of 350 with a lower limit of detection of 20 and 30 ng cm⁻³ was obtained for U(VI) and Th(IV), respectively. The practical applicability of the developed resin was examined using synthetic and real samples such as sea/well water samples. The method provides low relative standard deviation values of <3.5% for all analytical measurements, reflecting on the reproducibility and accuracy of the developed method. The new resin is quite durable with recycling time >35 cycles, without any major change in its quantitative metal uptake nature.     

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.     

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.     

Biosorption of uranium (VI) and thorium (IV) onto Ulva gigantea (K��tzing) bliding: discussion of adsorption isotherms, kinetics and thermodynamic

Ulva gigantea (Kützing) bliding (UGB) obtained from sea inlet of Izmir-Turkey has been studied as a biosorbent for removal of radioactive metals from water. In this study, unmodified UGB and modified UGB with glutaraldehyde (GUGB) characterized by FTIR spectroscopy were used as biosorbents for removal of U(VI) and Th(IV) ions from aqueous solution. Adsorption experiments performed under batch process with initial pH, contact time, adsorbent mass and temperature as variables. In order to determine the adsorption characteristics, Langmuir, Freundlich and Dubinin-Raduschkevich adsorption isotherms were applied to the adsorption data. Adsorption experiments showed that the adsorption isotherms correlated well with the Freundlich model. The sorption followed pseudo-second-order kinetics. The thermodynamic parameters such as variations of ??H°, ??G° and ??S° were estimated as a function of temperature. The thermodynamics of the adsorption of U(VI) and Th(IV) onto UGB and GUGB indicates that the spontaneous and exothermic nature of the process. The results showed that UGB and GUGB were potential for application in removal of U(VI) and Th(IV) from aqueous solution.     

Selective uranium adsorption using modified acrylamide resins

Polymeric matrices composed of N,N′-Methylenebis(acrylamide)/glycidyl methacrylate was prepared and modified producing two resins (GMA/MBA/OH and GMA/MBA/SO₃H). The adsorption of U(VI) ions onto the modified acrylamide resins was studied from synthetic and granite samples. For better understanding around the uranium mineralization and the rock-forming minerals of the hosted granitic rocks, to facilitate the choice of the appropriate ore-processing techniques, it was necessary to identify the mineral composition and the radiometric specifications of the used granitic rock. The synthesized adsorbents revealed a promising selective adsorption toward the U(VI) ions from its bearing solutions even with the competence of other cations.

     

Selective extraction of U(VI) over Th(IV) from acidic streams using di-bis(2-ethylhexyl) malonamide anchored chloromethylated polymeric matrix

A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with di-bis (2-ethylhexyl) malonamide (DB2EHM). The modified resin was characterized by CPMAS NMR spectroscopy, FT-NIR-FIR spectroscopy, CHN elemental analysis and also by thermo gravimetric analysis. The fabricated sorbent showed superior binding affinity for U(VI) over Th(IV) and other diverse ions, even under high acidities. Various physio-chemical parameters, like solution acidity, phase exchange kinetics, metal sorption capacity, electrolyte tolerance studies, etc., influencing the resin’s metal extractive behavior were studied by both static and dynamic method. Batch extraction studies performed over a wide range of solution acidity (0.01-10 M) revealed that selective extraction of U(VI) could be achieved even up to 4 M acidity with distribution ratios (D) in the order of ∼10³. The phase exchange kinetics studies performed for U(VI) and Th(IV) revealed that time duration of <15 min was sufficient for >99.5% extraction. But similar studies when preformed for trivalent lanthanides gave very low D values (<50), with the extraction time extending up to 60 min. The metal sorption studies performed for U(VI) and Th(IV) at 5 M HNO₃ was found to be 62.5 and 38.2 mg g⁻¹,respectively. Extraction efficiency in the presence of inferring electrolyte species and inorganic cations were also examined. Metal ion desorption was effective using 10-15 mL of 1 M (NH₄)₂CO₃ or 0.5 M α-hydroxy isobutyric acid (HIBA). Extraction studies performed on a chromatographic column at 5 M acidity were found to give enrichment factor values of 310 and 250 for U(VI) and Th(IV), respectively. The practical utility of the fabricated chelating sorbent and its efficiency to extract actinides from acidic waste streams was tested using a synthetic nuclear spent fuel solution. The R.S.D. values obtained on triplicate measurements (n = 3) were within 5.2%.     

Extraction and thermodynamic behavior of U(VI) and Th(IV) from nitric acid solution with tri-isoamyl phosphate

The extraction behavior of U(VI) and Th(IV) with tri-isoamyl phosphate–kerosene (TiAP–KO) from nitric acid medium was investigated in detail using the batch extraction method as a function of aqueous-phase acidity, TiAP concentration and temperature, then the thermodynamic parameters associated with the extraction were derived by the second-law method. It could be noted that the distribution ratios of U(VI) or Th(IV) increased with increasing HNO₃ concentration until 6 or 5 M from 0.1 M. However, a good separation factor (D _U(VI)/D _Th(IV)) of 88.25 was achieved at 6 M HNO₃, and the stripping of U(VI) from TiAP–KO with deionized water or diluted nitric acid was easier than that of Th(IV). The probable extracted species were deduced by log D-log c plot at different temperatures as UO₂(NO₃)₂·(TiAP)_(1–2) and Th(NO₃)₄·(TiAP)_(2–3), respectively. Additionally, △H, △G and △S for the extraction of U(VI) and Th(IV) revealed that the extraction of U(VI) by TiAP was an exothermic process and was counteracted by entropy change, while the extraction of Th(IV) was an endothermic process and was driven by entropy change.     

Removal of La(III) by amino-phosphonic acid functionalized polystyrene microspheres prepared via electron beam irradiation

A new aminophosphonic acid chelating resin was successfully prepared via electron beam irradiation grafting combined with chemical modification and used for the efficient removal of La(III). Firstly, glycidyl methacrylate (GMA) was grafted to polystyrene microspheres (PS) via electron beam co-radiation to obtain PS-PGMA microspheres, then followed by the amination with diethylenetriamine (DETA) to formed PS-PGMA-DETA (PGD) microspheres through nucleophilic substitution between amino and epoxy group, and finally PS-PGMA-DETA-PA (PGDP) microspheres was obtained by phosphorylation with phosphorous acid (PA). The obtained chelating resin absorbent was characterized by Fourier-transform infrared (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), which demonstrated that the millimetric aminophosphonic acid chelating resin were successfully prepared with well-defined morphology and enhanced thermal stability. The X-ray photoelectron spectroscopy (XPS) characterization results confirmed a possible adsorption mechanism, which is mainly based on the chelation and coordination of N and O in PDGP with La(III) in the solution. A series of parameters were taken into account in the adsorption experiment, such as absorbed dose, GMA concentration, dosage of PGDP, pH, contact time, temperature, and the initial concentrations of La(III). The maximum adsorption capacity obtained from the research can be achieved 288.69 mg/g at 298.15 K, pH = 6. The kinetic sorption for for La(III) fitted the type 1 pseudo-second-order (R² = 0.9981), which revealed that the La(III) are chemisorbed on the surface of the PGDP. It was concluded that the La(III) adsorption conformed to the Freundlich equation, indicating a multilayer adsorption process. Thermodynamic data indicated that the La(III) uptake process was a spontaneous and endothermic. In addition, this research provided a new irradiation grafting method for rare earth ions removal.