Surface complexation modeling of uranium(VI) sorbed onto lanthanum monophosphate

Sorption/desorption are basic processes in the field of contaminant transport. In order to develop mechanistically accurate thermodynamic sorption models, the simulation of retention data has to take into account molecular scale informations provided by structural investigations. In this way, the uranyl sorption constants onto lanthanum monophosphate (LaPO(4)) were determined on the basis of a previously published structural investigation. The surface complexation modeling of U(VI) retention onto LaPO(4) has been performed using the constant capacitance model included in the FITEQLv3.2 program. The electrical behavior of the solid surface was investigated using electrophoretic measurements and potentiometric titration experiments. The point of zero charge was found to be 3.5 and surface complexation modeling has made it possible to calculate the surface acidity constants. The fitting procedure was done with respect to the spectroscopic results, which have shown that LaPO(4) presents two kinds of reactive surface sites (lanthanum atoms and phosphate groups). The uranyl sorption edges were determined for two surface coverages: 40 and 20% of the surface sites that are occupied, assuming complete sorption. The modeling of these experimental data was realized by considering two uranyl species ("free" uranyl and uranyl nitrate complex) sorbed only onto phosphate surface groups according to the previously published structural investigation. The obtained sorption constants present similar values for both surface complexes and make it possible to fit both sorption edges: logK(U)=9.4 for z.tbnd;P(OH)(2)+UO(2)(2+)<-->z.tbnd;P(OH)(2)UO(2)(2+) and logK(UN)=9.7 for z.tbnd;P(OH)(2)+UO(2)NO(3)(+)<-->z.tbnd;P(OH)(2)UO(2)NO(3)(+).     

Surface and bulk sorption of uranium(VI) onto granite rock

Surface and bulk sorption of U(VI) onto granite rock with different types of surfaces were carried out and the results were compared for the different surfaces such as crushed granite, machined core granite, and core granite with fractured surface. The sorption behavior of U(VI) dependent on surface types was investigated and discussed for contacting time, pH, constituent minerals, and surface area. Results from the sorption experiments were also compared each other in order to analyze the differences in sorption behaviors of U(VI) and to correlate the surface sorption coefficient K_a and the bulk sorption coefficient K_d. The effect of contact time and pH on the sorption of U(VI) onto fractured surfaces was larger than that onto the machined fresh surfaces but smaller than that onto the crushed surfaces. As expected, it was noticed that the surface sorption coefficients of U(VI) for the natural fracture surfaces were greater than those of the machined fresh surfaces due to the higher content of secondary minerals such as calcite and chlorite which acted as stronger sorbents. It is presumed that there are many micro-fractures or micro-pores available for the uranium sorption on the granite surfaces, even on the machined fresh surfaces, and there can be an intrinsic difference between the surface and the bulk sorption due to the different types of surfaces.     

Structural environment of uranium (VI) species sorbed onto ZrP2O7: X-ray absorption spectroscopy study

The structure of the surface complex formed during the sorption of UO₂²⁺_aq ion onto the selected phosphate solid has been investigated mainly using X-ray absorption spectroscopy. Samples were prepared by batch experiments. L_III U edge measurements have shown that uranyl ions are sorbed on the phosphate surface as a mononuclear bidentate inner-sphere complex.     

The removal of uranium(VI) from aqueous solutions onto activated carbon: kinetic and thermodynamic investigations

The adsorption of uranium(VI) from aqueous solutions onto activated carbon has been studied using a batch adsorber. The parameters that affect the uranium(VI) adsorption, such as contact time, solution pH, initial uranium(VI) concentration, and temperature, have been investigated and optimized conditions determined (contact time 240 min; pH 3.0+/-0.1; initial uranium concentration 100 mg/L; temperature 293.15 K). The experimental data were analyzed using sorption kinetic models (pseudo-first- and pseudo-second-order equations) to determine the equation that fits best our experimental results. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of activated carbon and experimental results showed this to be 28.30 mg/g. The Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) models have been applied and the data correlate well with Freundlich model and that the sorption is physical in nature (the activation energy Ea=7.91 kJ/mol). Thermodynamic parameters (DeltaHads0=-50.53 kJ/mol, DeltaSads0=-98.76 J/mol K, DeltaGads(293.15 K)0=-21.61 kJ/mol) showed the exothermic heat of adsorption and the feasibility of the process.     

Surface complexation modeling of zinc sorption onto ferrihydrite

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.     

The influence of the temperature on the carbonate complexation of uranium(VI): a spectroscopic study

The interaction of uranium(VI) with carbonate ions was studied with absorption spectroscopy and time-resolved laser-induced fluorescence spectroscopy due to the importance of these complexes in environmental relevant waters. In the pH range from 2 to 11 the influence of the temperature on the spectra was studied to check changes in the abundances of several binding forms. It was found that several binding forms are predominant at different temperatures and pH values. This observation can be explained by speciation changes due to the dependence of chemical equilibria on the temperature. Furthermore photoluminescence spectra of aqueous solutions of uranyl carbonate complexes were observed at ambient temperatures for the first time and single component absorption spectra of the uranyl carbonate complexes UO₂(CO₃)₃ ⁴⁻ and UO₂(CO₃)₂ ²⁻ were derived.     

Surface complexation modeling of Sr(II) and Eu(III) adsorption onto oxidized multiwall carbon nanotubes

Acid-base titrations of oxidized multiwall carbon nanotubes (MWCNTs), Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs were conducted to investigate the surface charge characteristics of oxidized MWCNTs and the surface complexation interactions between Sr(II)/Eu(III) and oxidized MWCNTs. The results suggested that Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs increased with increasing pH, and decreased with increasing ionic strength, and the affinity of oxidized MWCNTs for Eu(III) was much higher than that for Sr(II). The diffuse layer model (DLM) fitted the experimental data of Sr(II) and Eu(III) adsorptions well with the aid of FITEQL 3.2.     

Dynamic adsorption of uranium(VI) and zirconium(IV) on silica gel

Adsorption of uranium(VI) and zirconium(IV) from aqueous nitric acid solution on silica gel has been investigated under dynamic conditions. The influence of temperature, nitric acid concentration (pH), and solution flow rates was studied. If the nitric acid concentration in the solution is higher than 0.05 mol/l, then it is possible to achieve separation of uranium(VI) and zirconium(IV) by passing the solution through a column filled with silicagel.     

Effect of pH,fulvic acid and temperature on sorption of Th(IV) on zirconium oxophosphate

Sorption of Th(IV) on Zr₂O(PO₄)₂ as a function of contact time, reaction temperature, pH, ionic strength and solid-to-liquid ratio (m/V) is studied under ambient condition by using batch technique. Effects of fulvic acid (FA), phosphate, sulfate and citrate on Th(IV) sorption are investigated in detail. A pseudo-second-order rate equation is used to simulate the kinetic sorption. The removal of Th(IV) increases with increasing pH and hardly depends on ionic strength. Sorption of Th(IV) increases with increasing m/V and reaction temperature. The presence of FA and phosphate enhances the sorption of Th(IV) on Zr₂O(PO₄)₂ while sulfate and citrate decrease the sorption. The Langmuir and Freundlich models are used to simulate the sorption isotherm of Th(IV) on Zr₂O(PO₄)₂ at different temperatures. The thermodynamic data (i.e., ∆H ⁰, ∆S ⁰, ∆G ⁰) are calculated from temperature dependent sorption isotherms. The results suggest that the sorption process of Th(IV) on Zr₂O(PO₄)₂ is spontaneous and endothermic.     

Fluorescence spectroscopic study on complexation of uranium(VI) by glucose: a comparison of room and low temperature measurements

Cryogenic techniques are currently used in scanning tunnelling microscopy (STM) and single molecule spectroscopy. Recently such cryogenic devices have also been adapted to time resolved laser-induced fluorescence spectroscopy (TRLFS) systems applied to uranium(VI). In our study, we interpret TRLFS results obtained for the uranyl(VI) glucose system at room temperature (RT) and under cryogenic conditions of 153 K (cryo-TRLFS). A uranyl(VI) glucose complex was only identified by cryo-TRLFS measurements at pH 5 and not by RT measurements. The uranyl(VI) glucose complex was characterized by five emission bands at 499.0, 512.1, 525.2, 541.7, and 559.3 nm and a fluorescence lifetime of 20.9 ± 2.9 μs. The uranyl(VI) glucose complex formation constant was calculated for the first time to be logß_I=0.1 M = 15.25 ± 0.96. Cryo-TRLFS investigation opens up new possibilities for the determination of complex formation constants since interfering quenching effects often encounter at RT are suppressed by measurements at cryogenic conditions.     

Spectrophotometric study of the complexation equilibria of uranium(VI) with 1,4-bis(4′-methylanilino)anthraquinone and determination of uranium(VI)

The reaction of U(VI) with 1,4-bis(4′-methylanilino)anthraquinone (quinizarin green) in water-dimethylformamide medium was investigated spectrophotometrically. The complexation equilibria in solution were demonstrated. The study of the reaction in presence of equimolar concentrations or in solutions containing metal or ligand excess gave evidence for the formation of complexes with stoichiometric ratios of UO₂:L = 1:1 and 1:2 in dependence on the pH of the medium. Their thermodynamic stabilities and the values of their molar absorption coefficients were determined. The optimum conditions for spectrophotometric determination of U(VI) with this reagent were found.     

Capillary zone electrophoretic (CZE) study of uranium(VI) complexation with humic acids

The interaction of UO₂ ²⁺ with various humic acids (HA's) has been studied by capillary zone electrophoresis (CZE). The experiments were done in 10 mM acetate buffer with pH 3.3 and 4.0, to avoid hydrolysis of uranium. It was found that in slightly acidic media and low HA concentration (<3 mM), two complexes with uranium(VI) are formed by fast kinetics and uranyl migrates as cationic species. Electrophoretic mobilities are decreasing with the increasing HA/uranium ratio and a low soluble neutral compound is also formed. In addition, it was found that at HA concentrations higher than 3 mM negatively charged species are formed. Similar results were obtained for HA's of different origin (soil, peat, coal derived, IHSS standards). Conditional stability constants of the complexes UO₂ ²⁺-HA for Fluka I HA, were estimated to be log ₁ = 4.18±0.06 and log ₂ = 7.28±0.18.     

Efficient uranium(VI) biosorption on grapefruit peel: kinetic study and thermodynamic parameters

The uranium(VI) biosorption by grapefruit peel was studied from aqueous solutions. Batch experiments was conducted to evaluate the effect of contact time, initial uranium(VI) concentration, initial pH, adsorbent dose, salt concentration and temperature. The equilibrium process was well described by the Langmuir, Redlich–Peterson and Koble–Corrigan isotherm models, with maximum sorption capacity of 140.79 mg g⁻¹ at 298 K. The pseudo second order model and Elovish model adequately describe the kinetic data in comparison to the pseudo first order model and the process involving rate-controlling step is much complex involving both boundary layer and intra-particle diffusion processes. The effective diffusion parameter D _i and D _f values were estimated at different initial concentration and the average values were determined to be 1.167 × 10⁻⁷ and 4.078 × 10⁻⁸ cm² s⁻¹. Thermodynamic parameters showed that the biosorption of uranium(VI) onto grapefruit peel biomass was feasible, spontaneous and endothermic under studied conditions. The physical and chemical properties of the adsorbent were determined by SEM, TG-DSC, XRD and elemental analysis and the nature of biomass–uranium (VI) interactions was evaluated by FTIR analysis, which showed the participation of COOH, OH and NH₂ groups in the biosorption process. Adsorbents could be regenerated using 0.05 mol L⁻¹ HCl solution at least three cycles, with up to 80% recovery. Thus, the biomass used in this work proved to be effective materials for the treatment of uranium (VI) bearing aqueous solutions.     

Surface complexation modeling of Fe(3)O(4)-H(+) and Mg(II) sorption onto maghemite and magnetite

New fluorinated copolymers of poly(methyl methacrylate)-b-poly(butyl methacrylate) or poly(n-octadecyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (PMMA(x)-b-PBMA(y)-ec-PFMA(z) or PMMA(x)-b-PODMA(y)-ec-PFMA(z)) were synthesized by living atom transfer radical polymerization. Thin films made of PMMA(230)-b-PODMA(y)-ec-PFMA(1) were characterized by differential scanning calorimetry, angle-resolved X-ray photoelectron spectroscopy and X-ray diffraction. These films were found to exhibit robust surface segregation of the end groups. Furthermore, the fluorine enrichment factor at the film surface was found to increase linearly with increasing degree of polymerization of poly(n-octadecyl methacrylate) and its increasing fusion enthalpy in the second block, which enhances the segregation of the fluorinated moieties.     

The removal of uranium (VI) from aqueous solutions onto natural sepiolite

The adsorption of uranium (VI) from aqueous solutions onto natural sepiolite has been studied using a batch adsorber. The parameters that affect the uranium (VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, and temperature, have been investigated and optimized conditions determined. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of sepiolite and experimental results showed this to be 34.61 mg · g^?1. The experimental results were correlated reasonably well by the Langmuir adsorption isotherm and the isotherm parameters (Q_o and b) were calculated. Thermodynamic parameters (ΔH° = ?126.64 kJ · mol^?1, ΔS° = ?353.84 J · mol^?1 · K^?1, ΔG° = ?21.14 kJ · mol^?1) showed the exothermic heat of adsorption and the feasibility of the process. The results suggested that sepiolite was suitable as sorbent material for recovery and adsorption of uranium (VI) ions from aqueous solutions.     

Biosorption studies of uranium (VI) on cross-linked chitosan: isotherm,kinetic and thermodynamic aspects

The cross-linked chitosan (CS) gels synthesized by using glutaraldehyde (GLA), epichlorohydrin (EC), and ethylene glycol diglycidyl ether (EGDE) as cross-linkers respectively were used to investigate the adsorption of U(VI) ions in an aqueous solution. The pure chitosan (PCS) and the cross-linked chitosan gels were characterized by FTIR and SEM analysis. The kinetic, thermodynamic adsorption and adsorption isotherms of U(VI) ions onto unmodified and modified cross-linked chitosan were studied in a batch adsorption experiments. The effect of pH, contact time and temperature on the adsorption capacity were also carried out. At the optimum pH, the maximum adsorbed amount of PCS, GLACS, ECCS and EGDECS were 483.05, 147.05, 344.83 and 67.56 mg/g, respectively. The uranium (VI) adsorption process of PCS and ECCS followed better with pseudo-second-order kinetic model, while GLACS and EGDECS followed pseudo-first-order kinetic model well. The results obtained from the equilibrium isotherms adsorption studied of U(VI) ions were analyzed in two adsorption models, namely, Langmuir and Freundlich isothms models, the results showed that the Langmuir isotherm had better conformity to the equilibrium data. The thermodynamic parameters such as enthalpy (ΔHo), entropy (ΔSo), and Gibbs free energy (ΔGo) showed that the adsorption process was both spontaneous and endothermic.     

Uranyl(VI) and lanthanum(III) thio-diglycolamides complexes: Synthesis and structural studies involving nitrate complexation

New tri-functional ligands of the type R₂NCOCH₂SCH₂CONR₂ (where R = iso-propyl, n-butyl or iso-butyl) were prepared and characterized. The coordination chemistry of these ligands with uranyl and lanthanum(III) nitrates was studied by using the IR, ¹HNMR and elemental analysis methods. Structures for the compounds [UO₂(NO₃)₂(ⁱPr₂NCOCH₂SCH₂CONⁱPr₂)] [UO₂(NO₃)₂(ⁱBu₂NCOCH₂SCH₂CONⁱBu₂)], [La(NO₃)₃(ⁱPr₂NCOCH₂SCH₂CONⁱPr₂)₂] and [La(NO₃)₃(ⁱBu₂NCOCH₂SCH₂CONⁱBu₂)₂] were determined by single crystal X-ray diffraction. These structures show that the ligand acts as a bidentate chelating ligand and bonds through both the carbamoyl groups to the uranyl and lanthanum(III) nitrate groups. Solvent extraction studies show that the ligand can extract the uranyl ion from the nitric acid medium but does not show any ability to extract the americium (III) ion.