Sorption of thorium(IV) from aqueous solutions by graphene oxide

Graphene oxide (GO) is one of the most important carbon nano-materials. In this paper, GO was synthesized from flake graphite and characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The sorption of Th(IV) on GO was investigated as a function of contact time, solid-to-liquid ratio, pH, ionic strength, and in the presence of fulvic acid (FA) and humic acid (HA) by batch experiments. The sorption percentage of Th(IV) on GO decreased with increasing ionic strength and decreasing solid-to-liquid ratio. The sorption edge of Th(IV) in the presence of FA/HA is much lower than that in the absence of FA/HA. Furthermore, the sorption processes of Th(IV) can be described by a pseudo-second order rate model. Based on the Langmuir model, the maximum sorption capacities (Cs_max) of Th(IV) were about 5.80 × 10^?4 mol/L. From thermodynamic investigation, sorption of Th(IV) on GO is spontaneous and endothermic in nature. The rapid sorption rate and high sorption capacity suggest that GO is a promising adsorbent for Th(IV).     

Removal of uranium(VI) and thorium(IV) ions from aqueous solutions by functionalized silica: kinetic and thermodynamic studies

Adsorption behavior of uranyl and thorium ions from synthetic radioactive solutions onto functionalized silica as sorbent has been investigated. The effect of contact time, initial concentration of radioactive solutions, sorbent mass, pH value and temperature on the adsorption capacity of the sorbent was investigated. Negative values of Gibbs free energy of adsorption suggested the spontaneity of the adsorption process on both functionalized silica with –NH₂ groups and with –SH groups. Positive values obtained for ΔH° indicates that the adsorption is an endothermic process. The adsorption isotherms were better fitted by Freundlich model and the adsorption kinetic was well described by the pseudo-second order equation. Desorption studies indicated that the most favorable desorptive reagents for UO₂ ²⁺ is HNO₃ 1 M and for Th⁴⁺ is EDTA 1 M solutions.     

Removal of thorium from aqueous solutions by sodium clinoptilolite

Adsorptive behavior of natural clinoptilolite was assessed for removal of thorium from aqueous solutions. Natural zeolite was characterized by X-ray diffraction and X-ray fluorescence. The zeolite sample composed mainly of clinoptilolite. Na-exchanged form of zeolite was prepared and its sorption capacity for removal of thorium from aqueous solutions was examined. The effects of relevant parameters, including initial concentration, contact time, solid to liquid ratio, temperature and initial pH on the removal efficiency were investigated in batch studies. The pH strongly influenced thorium adsorption capacity and maximal capacity was obtained at pH 4.0. Kinetics and isotherm of adsorption were also studied. The pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion models were used to describe the kinetic data. The pseudo-second-order kinetic model provided excellent kinetic data fitting (R ² > 0.999) with rate constant of 1.25, 1.37 and 1.44 g mmol⁻¹ min⁻¹ respectively for 25, 40 and 55 °C. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms for thorium uptake and the Langmuir model agrees very well with experimental data. Thermodynamic parameters were determined and are discussed.     

Sorption of praseodymium(III) ions from aqueous solutions by a natural clinoptilolite-containing tuff

The equilibrium and kinetics of sorption of praseodymium(III) ions from sulfate solutions by a natural clinoptilolite-containing tuff are studied. It is shown that praseodymium is completely extracted from dilute solutions (<0.002 M). The kinetic parameters of the sorption process are determined.     

Sorption and desorption of thorium from aqueous solutions by montmorillonite

The sorption and desorption of thorium on a West Anatolian montmorillonite has been studied by application of a batch technique. Experimental procedures are outlined and results for thorium contacted with montmorillonite are reported and discussed. The thorium concentration range was between 200–4000 ppm (8.5×10^–4–1.7×10^–2M). The sorption and desorption coefficients varied between 1.586–0.216 ml g^–1 and 0.829–0.168 ml g^–1, respectively, and sorption was not fully reversible. The data could be fitted to Freundlich and Langmuir isotherms. The quantity of the sorbed thorium was much lower than its theoretical CEC. This was attributed to a blocking of montmorillonite's CEC by thorium islands in the interlayer.     

Mechanism of N-vinylcarbazole polymerization on Co(II)–13X molecular sieve

Kinetics of polymerization of N-vinylcarbazole over Co(II)-13X molecular sieves in toluene have been studied. The rate of polymerization (R_p) has been found to be second order with respect to percent exchange level of Co(II) and also to the NVC concentration at all the reaction temperatures of 40, 50 and 60°C. The rate increases with decreasing pH of the original exchanging salt solution up to a pH of about 3.5, beyond which it falls. The overall activation energy of polymerization has been found to decrease with increase in monomer concentration, exchange level of Co(II), and the hydrogen ion concentration of the original exchange solution. Average degree of polymerization also follows a similar trend. A mechanism of polymerization involving simultaneous propagation on both metal ion Co(II) and proton on a zeolite surface has been suggested. The two propagation routes are characterized by an average activation energy of 10.36 kcal/mol and 5.40 kcal/mol on the metal ion and proton centers, respectively.     

Adsorption of Eu(III) from aqueous solution using mesoporous molecular sieve

The adsorption behavior of Eu(III) from aqueous solution to mesoporous molecular sieves (Al-MCM-41) is investigated as a function of contact time, solid content, ionic strength, pH, foreign ions and temperature by using batch technique. The experimental results show that Eu(III) adsorption is strongly dependent on pH values, but independent of ionic strength and foreign cations under our experimental conditions. The kinetic process is described by a pseudo-second-order rate model very well. The adsorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (∆G°, ∆S°, ∆H°) are calculated from the temperature dependent adsorption isotherms at 293, 313 and 333 K, respectively, and the results suggest that the adsorption of Eu(III) on Al-MCM-41 is a spontaneous and endothermic process. Desorption studies indicate that the adsorbed Eu(III) is very difficult to be desorbed from the solid surface. Al-MCM-41 is a suitable material for the preconcentration and solidification of Eu(III) from large volumes of aqueous solutions.     

Selective preconcentration of trace thorium from aqueous solutions with Th(IV)-imprinted polymers prepared by a surface-grafted technique

A novel ion-imprinted adsorbent for selective solid phase extraction of thorium(IV) based on the surface of silica gel was prepared by a surface-grafted technique with methacrylic acid (MAA) as a functional monomer. After removal of Th(IV) ions with 3?mol?L^?1 HCl solution, the obtained imprinted particles for Th(IV) exhibited specific recognition and relatively rapid kinetic process. The maximum static and total dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 33.2 and 17.3?mg?g^?1, respectively. A comparison of the selectivity coefficient of the imprinted polymers with that of non-imprinted polymers showed that the imprinted matrix for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III) and Th(IV)/Zr(IV) was 58.8, 107, 106.4 and 151.7 times greater than non-imprinted matrix, respectively. With a series of samples loading flow rate of 3?mL?min^?1 for preconcentration, an enrichment factor of 14.6 and the detection limit of 0.59?µg?L^?1 were obtained. The relative standard deviation of the method under optimum conditions was 2.1% (n?=?7). The developed method was successfully applied to the determination of trace Th(IV) in real water samples with satisfactory results.     

The removal of thorium from aqueous solutions using zeolites

The ability of zeolites to remove thorium-232 from naturally radioactive thorium nitrate solutions was studied by ion exchange, adsorption and surface phenomena. The best zeolites were a clinoptilolite from Mudhills, California, USA and a mordenite rich tuff from Eastgate, Nevada, USA. As the concentration of thorium in solution was increased the mechanism of thorium removal switches from that of partial ion-exchange to a surface precipitation. This was confirmed by electron probe microanalysis (EPMA) in conjunction with XRD and Energy Dispersive X-ray analysis (EDX). A Langmuir-type of adsorption occurred with the thorium-232 daughter isotopes at the same time as partial exchange/precipitation of the thorium parent which is in regular equilibrium with its natural daughters. Some experiments with²³⁴Th were carried out to confirm this hypothesis as well as column experiments to confirm the usefulness of the Th removal.     

Structural studies on thorium(IV)-titriplex IV-interacted 13X zeolite

A new zeolite derivative has been prepared by interacting Th(IV) and complexone in HCl medium and neutralising with aqueous ammonia. The amorphous and siliceous derivative showed a total mass loss of 29.25% in TG for stepwise dehydration, dehydroxylation and decomposition. Heats of reaction were 1167.6 J g^–1 at 88.7°C and 75.167 J g^–1 at 492.5°C for loss of volatile components and decomposition respectively.²⁹Si and²⁷Al MAS NMR spectra as well as XRD data of the derivative before and after calcination indicate presence of both four-coordinated and six-coordinated Al in varying ratios and the total loss of crystallinity.The author is grateful to Dr. Alan Dyer of the Department of Chemistry and Applied Chemistry, Salford University and to Dr. Jacek Klinowski of the Department of Chemistry, Cambridge University for providing the thermal data and NMR spectra respectively. He also acknowledges the comments received from Dr. N. Suryaprakash of the Sophisticated Instrument Facility, I.I.Sc., Bangalore on the²⁷Al and²⁹Si spectra of the derivatives.     

Immobilisation of lead(II) ions from aqueous solutions on natural coal

The immobilisation of lead(II) ions from aqueous solutions on natural coal was investigated to compare calculated and measured adsorption enthalpies. For this purpose, adsorption isotherms were measured at temperatures of 303, 333 and 353 K. Adsorption enthalpy ΔH was evaluated from temperature dependence of the equilibrium constant of adsorption using the van‘t Hoff equation. Thus, the value of ΔH = 27 kJ mol^?1 was obtained manifesting endothermic effect of lead(II) immobilisation on the coal. However, based on the flow and immersion calorimetric measurements, the exothermic character of lead(II) adsorption on the studied coal was proven with a value of about ?7 kJ mol^?1.     

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.     

Uptake of silver from AgNO3 salt by Zeolite-13X

Isotherms of silver uptake by zeolite-13X from AgNO₃ at temperatures /323-563 K/ around the melting point of the nitrate are reported. Measurements of silver uptake have been carried out by a neutron activation method. At temperatures below the melting point the Ag⁺ uptake is exchange dominant while above the melting point the exchange accompanies substantial AgNO₃ inclusion. The overall process of Ag⁺ uptake from both the powder and the melt is endothermic within the temperature range employed.     

Polysulfobetaines as extractants for Sr(II) ions from its aqueous solutions

In the present paper, we communicate sorption of Sr(II) ions on novel polysulfobetaines. N‐vinyl imidazole was modified by crosslinking it with four different crosslinkers: N,N‐methylene bisacrylamide, ethylene glycol dimethacrylate, divinyl benzene, and tripropylene glycol diacrylate. All the crosslinked networks were treated with sodium 2‐bromoethane sulfonate to obtain novel polysulfobetaines. The polymers were characterized by FTIR, elemental analysis and SEM to find evidence of network formation and quaternization. These polymers were used as Sr(II) sorbents. Sr(II) uptake was determined by using a colorimetric method using Rose Bengal anionic dye and 0.1 N HCl as the eluent. SEM‐EDS analysis of Sr(II)‐loaded polymers as well as after elution on treatment with 0.1 N HCl was recorded to ascertain the uptake of Sr(II) ions. The experimental isotherm data were analyzed using the Freundlich and Temkin equations. The experimental data also were analyzed using pseudo‐second order sorption kinetic model. Results show that the equilibrium data fit well in the Freundlich isotherm. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrosorption of ions from aqueous solutions by nanostructured carbon aerogel

Electrosorption is generally defined as potential-induced adsorption on the surface of charged electrodes. After polarization of the electrodes, ions are removed from the electrolyte solution by the imposed electric field and adsorbed onto the surface of the electrodes. Experimental and modeling studies were conducted using two types of carbon aerogel composites of different surface areas to provide a better understanding on the mechanisms of electrosorption. The experimental results revealed that no significant specific adsorption of F- ions occurred, while strong specific adsorption was observed for NO3- and Cu2+ ions. In addition, although the two types of carbon aerogel electrodes had different surface areas, their capacities were found to be very similar because of the electrical double-layer overlapping effect in micropores. An electrical double-layer model developed in our previous work (16), in which the electrical double-layer overlapping correction is included, is expanded in the present work by considering the effect of the specific adsorption on the electrosorption process. Modeling results were compared with experimental data obtained under various conditions. When the overlapping effect and specific adsorption were considered, the model provided results that were in good agreement with experimental data.     

干湿循环中水对13X分子筛机械强度劣化和晶格畸变

本文选用化工过程中常用的13X分子筛为模型,详细研究了在不同湿度下以及在干湿循环后分子筛机械强度的变化,发现经历干湿循环后分子筛的强度明显下降。经过干湿循环处理后的分子筛结构分析和表征结果显示,13X分子筛X射线衍射特征峰向高角度发生较显著的位移,这种位移与强度劣化有明显的正相关。干湿循环后分子筛的吸附-脱附特征也发生明显变化,对应的红外、核磁等表征结果也与强度下降、吸脱附特征变化、结构畸变有明显的对应关系。本文的结果表明,干湿循环过程中水分子可能诱发了13X分子筛晶格畸变,导致或者诱导了分子筛体相晶格有序度破坏,致使其机械强度大幅度降低。本文的结果对于改进分子筛载体的强度和理解分子筛载体失效有一定的指导意义。     

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.