A chelating resin containing trihydroxybenzoic acid as the functional group: synthesis and adsorption behavior for Th(IV) and U(VI) ions

A novel glycidyl methacrylate chelating resin has been synthesized through copolymerization of glycidyl methacrylate (GMA) in the presence of divinylbenzene (DVB), the resulting resin was immobilized with 3,4,5-trihydroxybenzoic acid (THBA) to give GMA/DVB/THBA chelating resin. The adsorption of Th(IV) and U(VI) on GMA/DVB/THBA adsorbent was studied as a function of initial concentration, pH, shaking time and temperature. The novel chelating resin shows a high capacity for Th(IV) and U(VI), maximum adsorption of Th(IV) and U(VI) were 56 and 83.6 mg/g, respectively. Kinetic studies showed that the adsorption follows the pseudo second order model referring to the influence of the textural properties of the resin on the rate of adsorption. Thermodynamic parameters such as ?H° and ?S° were studied and indicated an endothermic process.     

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.     

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.     

Preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using low-cost abundantly available sorbent

Olive cake as low-cost abundantly available sorbent has been characterized by N₂ at 77 K adsorption, porosity analysis, elemental analysis and IR spectra and has been used for preconcentrating of uranium(VI) and thorium(IV) ions prior to their determination spectrophotometrically. The optimum pH values for quantitative sorption of U(VI) and Th(IV) are 4–7 and 3–7, respectively. The enrichment factor for the preconcentration of U(VI) and Th(IV) were found to be 125 and 75 in the given order. The sorption capacity of olive cake is in the range of 2,260–15,000 μg g⁻¹ for Th(IV) and in the range of 1,090–17,000 μg g⁻¹ for U(VI) at pH 3–7. The sorbent exhibits good reusability and the uptake and stripping of the studied ions were fairly rapid. The elution of U(VI) and Th(IV) was performed with 0.3–1 M HCl/1–2 M HNO₃ and 0.3–0.8 M HCl/1 M HNO₃, respectively. The precision of the method was 1.8 RSD% for U(VI) and 2.5 RSD% for Th(IV) in a concentration of 1.00 μg mL⁻¹ for 10 replicate analysis. The influence of some electrolytes and cations as interferents was discussed. Separation of U(VI) and Th(IV) from other metal ions in synthetic solution was achieved.     

Simultaneous determination of uranium(VI) and thorium(IV) with carminic acid by derivative spectrophotometry

The reactions of uranium(VI) and thorium(IV) ions with carminic acid have been investigated. These ions react with carminic acid in neutral medium, forming colored complexes. The dark purple or red wine complexes show a high absorption in the visible region (597 nm U(VI) and 616 nm Th(IV)). Chemical variables that affect the reaction have been optimized. The spectral overlapping of the color of complexes has been resolved by first-derivative spectrophotometry. The simultaneous determination of uranium(VI) and thorium(IV) mixtures is accomplished by taking the derivative signal (zero crossing) at 597 nm for U(VI) determination and at 616 nm for Th(IV) determination, respectively. The method has been applied to Tyuyamonite ore, containing in the matrix both ions.     

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.     

Role of solution chemistry on the trapping of radionuclide Th(IV) using titanate nanotubes as an efficient adsorbent

Titanate nanotubes (TNTs) have attracted great interest in multidisciplinary study since their discovery. The adsorption of thorium [Th(IV)] onto TNTs in the absence and presence of humic acid (HA)/fulvic acid (FA) was studied by batch technique. The influence of pH from 2.0 to 10.0, ionic strength from 0.001 to 0.1 mol L^?1 NaClO₄, and coexisting electrolyte cations (Li⁺, Na⁺, K⁺) and antions (ClO₄ ^?, NO₃ ^?, Cl^?) on the adsorption of Th(IV) onto TNTs was tested. The adsorption isotherms of Th(IV) was determined at pH 3.0 and analyzed with Langmuir and Freundlich adsorption models, respectively. The results demonstrated that the adsorption of Th(IV) onto TNTs increases steeply with increasing pH from 2.0 to 4.0. Generally, HA/FA was showed to enhance Th(IV) adsorption onto TNTs at low pH values, but to reduce Th(IV) adsorption onto TNTs at high pH values. The adsorption of Th(IV) onto TNTs was also dependent on coexisting electrolyte ions in aqueous solution under our experimental conditions. The adsorption of Th(IV) onto TNTs is exothermic and spontaneous. The findings indicating that TNTs can be used as a promising candidate for the enrichment and solidification of Th(IV) or its analogue actinides from large volume solution in real work.     

Extraction of uranium(VI) and thorium(IV) from nitric acid solution by N-alkylcaprolactam

Extraction of uranium(VI), thorium(IV) from nitric acid has been studied with N-octylcaprolactam and N-(2-ethyl)hexylcaprolactam. Distribution coefficients of U(VI), Th(IV) and HNO₃ as a function of aqueous NHO₃ concentration, extractant concentration and temperature have been studied. The compositions of extracted species, thermodynamic parameters of extraction have been evaluated. Third phase formation in extraction of U(VI) has been studied. Back extraction behavior of U(VI) and Th(IV) from the organic phase has also been tested. The results obtained are compared with those obtained by using TBP under the same experimental conditions.     

Ion exchange separation of Eu(III), Th(IV), U(VI) and Pu(IV) ions on Amberlyst A-15 in non-aqueous solutions

Distribution ratios of europium(III), thorium(IV), uranium(VI) and plutonium(IV) ions on Amberlyst A-15, a macroreticular polystyrene sulfonate resin, after extraction in HTTA-TBP-Shell Sol-T and HTTA-TOPO-benzene solutions have been determined as a function of the aqueous acidity. The affinity orders were EuPu>Th>U and Eu>Th>Pu>U in the former and the latter solutions, respectively. Separation factors were computed from the observed K_d values. A procedure for the separation of a mixture of Eu(III), Th(IV), and U(VI) ions in HTTA-TOPO-benzene solution in an ion-exchange column is described.     

Liquid-liquid extraction and separation studies of uranium(vi)

Summary Separation of uranium(VI) from iron(III), molybdenum(VI), vanadium (V), bismuth(III), zirconium(IV) and thorium(IV) is achieved by liquid-liquid extraction with 4-methyl-3-pentene-2-one (mesityl oxide; MeO) from sodium salicylate media (0.1M, pH 6.0). The extracted species is UO₂(HO·C₆H₄COO)₂·2MeO. A procedure for separating 50g of uranium from mg amounts of the other metals is described.

---

Flüssig-flüssig-Extraktion und Trennung von Uran(VI)

Zusammenfassung Die Trennung des U(VI) von Fe(III), Mo(VI), V(V), Bi(III), Zr(IV) und Th(IV) läßt sich durch Flüssig-flüssig-Extraktion mit 4-Methyl-3-penten-2-on] (Mesityloxid, MeO) aus 0,1M Natriumsalicylat bei pH 6,0 durchführen. Die extrahierte Verbindung ist UO₂(HO·C₆H₄COO)2·2MeO. Ein Verfahren zur Abtrennung von 50g Uran von Milligrammengen der anderen Metalle wurde beschrieben.

     

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.     

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,characterization, and application of polystyrene adsorbents containing tri-n-butylphosphate for solid-phase extraction of uranium (VI) from aqueous nitrate solutions

Polystyrene adsorbent for solid-phase extraction of U(VI) was developed through in situ copolymerization of styrene and divinylbenzene in the presence of tri-n-butylphosphate and its magnetic form was obtained by addition of fine particles of magnetite in an amount of 15 wt% of the total monomers used. The obtained adsorbents were characterized by means of scanning electron microscope, FTIR spectroscopy and X-ray powder diffraction. The adsorption behavior of U(VI) from aqueous nitrate solutions onto non-magnetic adsorbent RI (St–DVB–TBP) and its magnetic form RII (St–DVB–TBP–Fe₃O₄) at different experimental condition was studied using batch method. The adsorption results were found to fit Langmuir model. The magnetite-containing adsorbent showed higher uptake values relative to the corresponding magnetite-free one. The adsorption of U(VI) onto RI followed pseudo-first order kinetics whereas the adsorption onto RII followed pseudo-second order. Thermodynamic studies revealed that the adsorption process was a spontaneous exothermic reaction. Desorption of the loaded U(VI) was carried out using distilled water and found to be 97 and 93 % for RI and RII, respectively.     

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.     

Kinetic and thermodynamic aspects of U(VI) and Th(IV) sorption on a zeolitic volcanic tuff

Summary The sorption behavior of U(VI) and Th(IV) from simulated waste solutions on a zeolitic volcanic tuff from Nereju (Vrancea, Romania) has been studied in the absence of the ionic competition as a function of contact time, radioactive ions concentration, temperature and pH using a batch mode technique. The effect of the above-mentioned parameters on the sorption efficiency was discussed. The apparent thermodynamic parameters of the sorption of uranium and thorium onto the considered volcanic tuff were calculated, showing that the process is endothermic and higher temperatures favor the sorption process.     

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.     

Adsorption of U(VI) ions from low concentration uranium solution by thermally activated sodium feldspar

The thermally activated sodium feldspar (TASF), a novel material, was prepared by calcinating the micron sodium feldspar (SF) at 450 °C for 45 min. The TASF and the SF were characterized using X-ray diffraction and mercury injection porosimetry, and the TASF was found to have larger specific surface area and larger porosity than SF. The effects of the initial pH, temperature, contact time and initial U(VI) ions concentration on the adsorption of U(VI) ions from the low concentration uranium solution by TASF were investigated. The maximum adsorption efficiency of TASF for 0.5 mg/L uranium solution amounted to 95.49 % when the initial pH was 5.0, the temperature, 318 K, and and the contact time, 600 min. The relationship between the adsorption capacity q _e and equilibrium concentration C _e can well be described by Freundlich equation. Adsorption isotherm and the analysis by FT-IR coupled with SEM revealed that U(VI) ions were adsorbed onto the surface of TASF in multimolecular or cluster states, and that the intraparticle diffusion occurred in spontaneous process. The basic thermodynamic parameters including free energy change, entropy change and enthalpy change were calculated to comprehend the intrinsic features and spontaneous nature of the adsorption process. The FT-IR spectroscopic characterization for the TASF indicated that many groups were involved in the adsorption process of U(VI) ions, and the –OH group played a more important role. The experimental results suggested that TASF had great adsorption efficiency and strong potentiality of enrichment and recovery for the low concentration U(VI).     

Stability constants of uranium(VI) and thorium(IV) complexes formed with 8-hydroxyquinoline and its 5-sulfonic acid derivative

In this study, the stability constants of uranium(VI) and thorium(IV) complexes formed with 8-hydroxyquinoline (8-HOQ) and its 5-sulfonic acid (8-HOQ-5-SO₃H) derivative have been determined using the Irving-Rossotti method, computing the Calvin-Bjerrum pH-titration data. As a result, it is determined that the thorium(IV) complexes are considerably more stable than the corresponding uranium(VI) complexes. On the other hand, the complexes formed between 8-HOQ-5-SO₃H and uranium(VI) or thorium(IV) are less stable than the corresponding 8-HOQ complexes.     

Adsorptive removal of U(VI) from aqueous solution by hydrothermal carbon spheres with phosphate group

The phosphorylated hydrothermal carbon spheres (HCS-PO₄) were developed by functionalizing hydrothermal carbon spheres (HCS) with o-phosphoethanolamine, and the structure and textural property were characterized by SEM and FT-IR. The parameters that affect the uranium(VI) sorption, such as solution pH, initial U(VI) concentration, contact time, and temperature, had been investigated. The HCS-PO₄ showed the highest uranium sorption capacity at initial pH 6.0 and contact time of 120 min. The adsorption kinetics was better described by the pseudo-second-order model, and the adsorption process could be well defined by the Langmuir isotherm and the maximum monolayer adsorption capacity increased from 80.00 to 434.78 mg/g after phosphorylation. The thermodynamic parameters, ?G° (298 K), ?H° and ?S°, demonstrated shown that the sorption process of U(VI) onto HCS-PO₄ was feasible, spontaneous and endothermic in nature. The spent HCS-PO₄ could be effectively regenerated by 0.1 mol/L EDTA solution for the removal and recovery of U(VI) and reused for ten cycles at least. Selective adsorption studies showed that the HCS-PO₄ could selectively remove U(VI), and the selectivity coefficients of HCS in the presence of co-existing ions, Mg(II), Na(I), Zn(II), Mn(II),Co(II), Ni(II), Sr(II), Cs(I) and Hg(II) improved after functionalization.     

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by α-benzoin oxime modified Amberlite XAD-2000 resin

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with α-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48 μg L⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.