Removal of Cs1+, Sr2+ and Co2+ from aqueous solutions by adsorption on natural clinoptilolite

The adsorption properties of local clinoptilolite (Serbia) towards Cs⁺, Co²⁺, and Sr²⁺ were investigated by batch equilibration technique. The influence of equilibration time, initial metal cation concentration, solution pH and presence of EDTA on these properties was studied and discussed. Kinetic data were found to be well fitted with pseudo-second order kinetic model. Cs⁺ is preferably adsorbed by the natural clinoptilolite, followed by Sr²⁺ and Co²⁺. The Langmuir adsorption isotherm was used to determine the adsorption capacities from both single and mixed metal solutions. At pH range of 3–12 the adsorption of Cs⁺ remains almost constant, while at low pH (2–3) the adsorption is lesser. At initial pH range of 2–10 adsorption of Sr²⁺ remains approximately stable, whereas at initial pH > 10 adsorption increases significantly. The adsorption of Co²⁺ is low at low pH but increased remarkably with increasing pH and precipitated at pH > 8. Cs⁺ adsorption on the clinoptilolite was not affected by the presence of EDTA, while the presence of EDTA hinders the adsorption of Co²⁺ and Sr²⁺ on clinoptilolite.     

The assessment of removing strontium and cesium cations from aqueous solutions based on the combined methods of ionic liquid extraction and electrodeposition

The extraction of Sr²⁺ and Cs⁺ from aqueous solutions by using the ionophores dicyclohexano-18-crown-6 (DCH18C6) and calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6), respectively, was demonstrated in the hydrophobic, room-temperature ionic liquid (RTIL), tri-1-butylmethylammonium bis((trifluoromethyl)sulfonyl)imide (Bu₃MeN-TFSI). The water contents of several hydrophobic ionic liquids and the absorption/desorption reversibility of oxygen and moisture in the Bu₃MeN-TFSI ionic liquid were determined by electrochemical techniques. The relationship between the distribution coefficient, D_M, and the concentration ratios of C_ionophore,IL/C_{metal ion,aq} were investigated. The values of D_M increase with increasing the concentration ratios and they are also influenced with the counter ions of Sr²⁺ and Cs⁺ in the aqueous solutions. In the previous study, it was demonstrated that the Sr²⁺ and Cs⁺ cations in the Bu₃MeN-TFSI ionic liquid could be coordinated by DCH18C6 and BOBCalixC6, respectively, and formed the DCH18C6·Sr²⁺ and BOBCalixC6·2Cs⁺ ions, which would be cathodically reduced to Sr- and Cs-amalgam at a mercury film electrode (MFE). In this study, the probability was evaluated if the Sr²⁺ and Cs⁺ cations extracted from the aqueous solutions can be really reduced to respective amalgam.     

Use of chitosan complex with aminophosphonic groups and cobalt for the removal of Sr2+ ions

We briefly describe the adsorbent performance of the chitosan complex with aminophosphonic groups and cobalt in the removal process of Sr²⁺ ions from aqueous solutions. The strontium adsorption was studied as a function of pH, contact time, and initial strontium concentration. Adsorption isotherms such as Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin were used to analyze the equilibrium data at different concentrations. The kinetics of the Sr²⁺ sorption was analyzed using the pseudo-first-order and pseudo-second-order kinetic models. The results clearly indicate that the chitosan complex with aminophosphonic groups and cobalt is an efficient adsorbent with respect to its capacity to absorb Sr²⁺ ions from aqueous solutions.     

Assessment of kinetic and isotherm models for competitive sorption of Cs+ and Sr2+ from binary metal solution onto nanosized zeolite

This study examined the sorption performance of synthesized nanosized zeolite for the elimination of Cs⁺ and Sr²⁺ cations in a binary metal system. The influence of pH, sorbent amount, temperature, and contact time was studied. The relationship between each of these parameters and the removal efficiency was investigated. An analysis of the rate data was performed using both pseudo-first- and second-order reaction models. The ranking of three equilibrium sorption isotherm models used (Redlich–Peterson, Langmuir, and Freundlich) with a variety of numbers of parameters was determined using the corrected Akaike’s information criterion. The results demonstrate that a pseudo-second-order model fits the sorption kinetic data better than a pseudo-first-order model. The isotherm model rank order that best described the data statistically was Redlich–Peterson?>?Langmuir?>?Freundlich for the cesium ions and Langmuir?>?Redlich–Peterson?>?Freundlich for the strontium ions. Our results revealed that the existence of Sr²⁺ caused a significant reduction of Cs⁺ sorption in the binary metal mixture according to a lumped parameter model and vice versa. The results show that the synthesized material’s surface had a relatively stronger affinity for Cs⁺ than for Sr^2+.     

Studies on the adsorption of caesium,thallium, strontium and cobalt radionuclides on activated carbons from aqueous solutions

Individual adsorption studies of Cs⁺, Tl⁺, Sr²⁺ and Co²⁺ on activated carbons from aqueous solutions are reported. The carbon samples were characterised using different techniques. The surface area and the micro-, meso- and macropore volumes of all samples have been calculated. The chemical nature of the surface of the activated carbons was also studied. Optimal conditions for the adsorption of the metal ions have been identified. The adsorption of these cations by the carbon samples was also determined in the presence of a number of different anions. The data suggest the possible use of activated carbons for the preconcentration and separation of some cations.     

Isotopic ion-exchange studies in heteroionic systems

Isotopic ion-exchange studies were carried out for Mn²⁺ ions in the presence of Ba²⁺, Sr²⁺ Cs⁺ and Na⁺ ions, and for Na⁺ ions in the presence Ba²⁺ and Mn²⁺ ions, from 0.1 N chloride solutions. Single Particle Radioactive Tracer technique was employed, and the exchanger Dowex 5OW-X8 was used. The Nernst-Planck model, taking into account the diffusion processes both in the film and in the resin bead, was employed to analyse the data Resin-phase self-diffusion coefficients obtained from the isotopic exchanges in the homo-ionic systems, and liquid-phase diffusion coefficients calculated from limiting ionic conductance data, were used. The computer results agreed well with the experimental data for the following cases: (i), Na⁺ exchange in the presence of Ba²⁺ and Mn²⁺ ions; (ii), Mn²⁺ ion in the presence of Na+ ions; and (iii), Mn²⁺ exchange in the presence of Ba²⁺, Sr²⁺ and Cs⁺ ions at higher fractions of Mn²⁺ ions. However, lower values of diffusion coefficient of Mn²⁺ ions could correlate the data with smaller fractions of Mn²⁺ ions. It has been shown ibat resinphase diffusion mechanism of homovalent ions under similar environments is similar.     

A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Rapid Separation of Tl+ and Pb2+ from Various Binary Cation Mixtures Using Dicyclohexano-18-crown-6 Incorporated into Emulsion Membranes

Abstract

Relative transport rates of metal cation nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, Tl⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺) in a water-toluene-water emulsion membrane system were measured. The toluene component contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6. The aqueous receiving phase contained Li₄P2O₇. When each metal cation was individually present in the aqueous source phase, metal extraction was complete within 10 min with the order of extraction being Tl⁺ > Cs⁺ > Ag⁺ > Rb⁺ > K⁺ ≥m Na⁺ and Pb⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ for uni-and bivalent cations, respectively. Significant extraction was found for all cations except Na⁺, K⁺, and Ba²⁺. Some metal ions were concentrated nearly 10-fold in a 10-min period. Relative transport rates were determined when binary cation mixtures of either Tl⁺ or Pb²⁺ were present at equal concentrations with each of the remaining metal ions in the source phase. Tl⁺, when present with either Na⁺, Cs⁺, or Rb⁺, was selectively extracted from the source phase. Complete and nearly exclusive extraction of Pb²⁺ was observed in the presence of all cations including Tl⁺. The enrichment ratios of Pb²⁺ in the binary mixtures were approximately 10 while those of the second cation were less than 0.5 except for Sr²⁺ which was 0.86. Corresponding separation factors for Pb²⁺ ranged from 1000 to > 6000.     

Electrochemistry of ionophore-coordinated Cs and Sr ions in the tri-1-butylmethylammonium bis((trifluoromethyl)sulfonyl)imide ionic liquid

The selective extraction of Cs⁺ and Sr²⁺ from aqueous solutions by using the ionophores calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) and dicyclohexano-18-crown-6 (DCH18C6), respectively, was demonstrated in the hydrophobic, room-temperature ionic liquid (RTIL), tri-1-butylmethylammonium bis((trifluoromethyl)sulfonyl)imide (Tf₂N⁻). The electrochemistry of Cs⁺ coordinated by BOBCalixC6 and Sr²⁺ coordinated by DCH18C6 was examined at a mercury film electrode (MFE) in this ionic liquid by using cyclic staircase voltammetry, sampled current voltammetry at a rotating electrode, and chronoamperometry. Both BOBCalixC6·2Cs⁺ and DCH18C6·Sr²⁺ exhibit well-defined reduction waves at approximately −2.4 and −2.9 V versus the ferrocene/ferrocenium (Fc/Fc⁺) couple, respectively, in which the coordinated ions are reduced to their respective amalgams, permitting the recycling of the ionophores. The diffusion coefficients of BOBCalixC6·2Cs⁺ and DCH18C6·Sr²⁺ are (2.7 ± 0.1) × 10⁻⁹ and (2.1 ± 0.1) × 10⁻⁹ cm² s⁻¹, respectively, at 30 °C. The coulometric efficiency for the reduction and stripping of Cs at mercury pool electrodes was about 90% and was independent of the deposition time, whereas the efficiency for Sr was slightly less than 90% at short times and decreased with the deposition time, probably due to the formation of a passive layer of Sr(Tf₂N)₂.     

Glycolamide-functionalized ionic liquid: Synthesis and actinide ion extraction studies

A glycolamide-functionalized ionic liquid (G-FIL) was synthesized for the first time and was evaluated for the extraction of actinide ions such as Am³⁺, Pu⁴⁺ and UO₂²⁺ and fission product element ions such as Eu³⁺, Sr²⁺ and Cs⁺. The extraction of the trivalent metal ions was found to be exceptionally high at low acid concentrations, which rapidly decreased with increasing acidity. In view of the high viscosity of the G-FIL, the studies were carried out using its diluted solution in a commercial ionic liquid, viz. 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₄mim][Tf₂N]).     

Use of chitosan derivatives as solid phase extractors for metal ions

This paper shows a comparative study between the two radiation grafted chitosan derivatives viz. cross-linked chitosan (CRC) and cross-linked chitosan after hydrolysis (CRCH). These chitosan derivatives were used as solid phase extractors for several radionuclides. The uptake of ¹³⁷Cs, ^85,89Sr, ¹⁵²Eu, ²⁴¹Am, ²³⁴Th and ²³³U by CRCH and CRC was studied using batch and column methods. The K_d, exchange capacity, breakthrough capacity for different metal ions with the functionalized polymers were determined. The uptake followed the following trend: UO₂²⁺>Th⁴⁺>Cs⁺>Eu³⁺>Am³⁺>Sr²⁺ for both sorbents. It was seen that CRCH has a greater uptake of metal ions compated to CRC but CRC was more selective of the two.     

In situ immobilization properties and mechanism of geopolymer microspheres after adsorbing Sr2+ and Cs+ (Sr/Cs@GPMs)

Herein, in situ immobilization properties and mechanism of the pre-prepared geopolymer microspheres after adsorption of Sr²⁺/Cs⁺ (Sr/Cs@GPMs) were studied. The Sr²⁺ and Cs⁺ were solidified via calcination and a GP slurry coating strategies. The conditions for leaching experiments were H₂O, 0.1 mol/L (NaCl, NaOH, and HCl). The calcination results showed that the pore volume of the two adsorbents gradually decreased with increasing temperature and the order of leaching rate of Sr²⁺/Cs⁺ in calcination of Sr/Cs@GPMs was: HCl > NaCl > NaOH > H₂O, while the leaching rate decreased with increasing temperature and met the national standards. The in situ immobilization mechanism revealed that the pores of the adsorbent disappeared after high-temperature calcination or ceramic reaction. The results of the GP slurry coating experiment showed that the leaching rates of Sr²⁺/Cs⁺ decreased with leaching cycles. The solidified slag-based GP with Sr/Cs@GPMs (12%) adsorbent in 0.1 mol/L HCl leaching environment had the 28-day leaching rate (R₂₈) and cumulative leaching fractions (P₂₈) for Sr²⁺ of 1.26 × 10^-3 cm/d and 0.057 cm, respectively, and 1.51 × 10^-3 cm/d and 0.127 cm for Cs⁺, respectively. These metrics met the requirements of the national standard, thus indicating that slag-based GP has value in treating radionuclides.     

Uptake of cesium and strontium cations by potassium-depleted phlogopite

Phlogopite mica was equilibrated with 1.0 N sodium chloride (NaCl)–0.2 N sodium tetraphenylborate (NaTPB)–0.01 M disodium ethylenediaminetetraacetic acid (EDTA) solution at room temperature resulting in an almost complete removal (92%) of the mica's interlayer K. X-ray powder diffraction analysis provides additional evidence that hydrated Na⁺ ions had almost completely replaced the interlayer K⁺. Following equilibration, the c-axis spacing of the mica increased from 10.0 Å to approximately 12.2 Å. Cesium and Sr ion exchange isotherms indicate that K-depleted phlogopite is highly selective for both elements, the Cs⁺ exchange capacity is 1.26 meq/g or 65% of the theoretical cation exchange capacity and the Sr²⁺ exchange capacity is 1.94 meq/g or 100% of the theoretical exchange capacity of the mica. Kielland plots indicated that the mica was selective for Cs⁺ when the equivalent exchange capacity of Cs⁺ in the exchanger phase (X¯_Cs) was < 0.66 and selective for Sr²⁺ when X¯_Sr < 0.41. At equivalent fractions greater than these levels, layer collapse and/or steric effects limit the diffusion of these ions into the interlayers of the mica. Analysis of the Cs⁺ equilibrated mica utilizing XRD indicated that a collapse of the c-axis spacing had occurred. Based on the high selectivity of < 45-μm K-depleted phlogopite for Sr²⁺ and Cs⁺, this material may prove useful as an inorganic ion exchanger for these radioactive isotopes.     

Kinetics of Exchange of Cs+, Co2+ and Sr2+ on Synthetic Hydrous Titanium Oxides

Abstract

In the present work, a study of the kinetics of adsorption of Cs⁺, Co²⁺, and Sr²⁺ on four hydrous titanium oxides, prepared in different media, and designated as Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, was carried out. In the aqueous medium, the internal diffusion coefficients, D_i for Cs⁺ were found to be equal to 3.7×10^?9, 3.7×10^?9, 2.3×10^?9, and 1.5?10^?9 cm²/s, in Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, respectively. For Co²⁺ and Sr²⁺, these values are equal to 0.96×10^?9 and 0.64×10^?9 cm²/s, respectively for Ti‐IV. In Ti‐IV, D_i for all ions generally increases on adding methanol or propanol. This is probably due to greater dehydration, leading to faster ion diffusion, and, hence, to a decrease of ion mobility due to stronger interaction with the surface. In all media in Ti‐IV, the order: D_i(Cs⁺)>D_i(Co²⁺)≥D_i(Sr²⁺) was found which is due to a stronger interaction of the bivalent ions with the exchange sites.     

Adsorption Kinetics and Equilibria of Strontium onto Kaolinite

Adsorption of Sr²⁺ onto kaolinite has been studied by means of a radiotracer technique using the ⁹⁰Sr isotope. Bangham’s and McKay models have been applied to kinetic results in Sr²⁺ concentrations between trace ?0.1 mol.L^?1. The magnitudes of film and intra-particle diffusion coefficients are 10?10 and 10?14 m²·s^?1, respectively. Concentration dependence of diffusion coefficients indicated that Sr²⁺ ions are adsorbed on two different adsorption sites by an exothermic and spontaneous process. The Freundlich isotherm parameters and exchange equilibrium constants derived from selectivity coefficients indicate that Sr adsorption are depressed by competing cations in the order of Na⁺< Mg²⁺< Al³⁺.     

Gold Recovery from HCl Solutions using Cyphos IL‐101 (a Quaternary Phosphonium Ionic Liquid) Immobilized in Biopolymer Capsules

Tetraalkyl phosphonium chloride (Cyphos IL‐101), an ionic liquid (IL), was tested for gold recovery from HCl solutions: first in liquid/liquid extraction systems (using toluene and hexane as solvent) and in a second step, after being immobilized in a biopolymer composite matrix. SEM‐EDAX analysis was used for the characterization of the resins. The sorption capacity reached up to 140 mg Au(III) g^?1 in 1 M HCl solutions. Base metals that do not form anionic chlorocomplexes and nitrate or chloride ions (at 5 g L^?1) did not interfere with Au(III) binding. Gold binding probably occurs through the interaction of R₃R'P⁺ with AuCl₄ ^?. The kinetics of sorption was carried out varying agitation speed, metal concentration, IL content, and resin drying. Intraparticle diffusion played an important role on the control of sorption kinetics. Gold could be desorbed from the loaded IL‐impregnated resin using thiourea (in HCl solutions). The resin could be re‐used for at least 4 cycles. The resins are specially adapted for the recovery of gold from low metal concentrations.     

SELECTIVE UPTAKE OF CESIUM BY AMMONIUM TUNGSTOPHOSPHATE (AWP) - CALCIUM ALGINATE COMPOSITES

ABSTRACT

The fine crystals of ammonium tungstophosphate (AWP) exchanger were immobilized in the biopolymer consisting of calcium alginate (CaALG) gels. The uptake rate of Cs⁺ for the AWP-CaALG composite was fairly fast and the uptake percentage of Cs^? was above 90 % within 30 min even in the presence of 5 M HNO₃ In a wide HNO₃concentration region of 0.1 - 5 M, the distribution coefficient of Cs^? for the composite was about 10⁴ cm³/g, while those for other nuclides, Na⁺, Sr²⁺, Co²⁺, Eu³⁺ and Am³⁺, were less than 10 cm³/g. The uptake of Cs⁺ followed a Langmuir-type adsorption equation, and the maximum uptake capacity of Cs⁺ increased with the content of AWP immobilized in the composite. The trace amounts of ¹³⁷Cs in the presence of 5 M NaNO₃-l M HNO₃ were selectively adsorbed on the composite column. The AWP-CaALG composite proved to be effective for the selective removal of radioactive cesium from waste solutions containing HNO₃ and NaNO₃     

Two-Phase Calorimetry. II. Studies on the Thermodynamics of Cesium and Strontium Extraction by Mixtures of H+CCD− and PEG-400 in FS-13

Abstract

Thermochemical characterization of the partitioning of cesium and strontium from nitric acid solutions into mixtures of the acid form of chlorinated cobalt dicarbollide (H⁺CCD^?) and polyethylene glycol (PEG-400) in FS-13 diluent has been completed using isothermal titration microcalorimetry and radiotracer distribution methods. The phase transfer reaction for Cs⁺ is a straightforward (H⁺ for Cs⁺) cation exchange reaction. In contrast, the extraction of Sr²⁺ does not proceed in the absence of the co-solvent molecule PEG-400. This molecule is believed to facilitate the dehydration of the Sr²⁺ aquo cation to overcome its resistance to partitioning. The phase transfer reactions for both Cs⁺ and Sr²⁺ are enthalpy driven (exothermic), but partially compensated by an unfavorable entropy. The results of the calorimetry studies suggest that the PEG-400 functions as a stoichiometric phase transfer reagent rather than acting simply as a phase transfer catalyst or phase modifier. The calorimetry results also demonstrate that the extraction of Sr²⁺ is complex, including evidence for both the partitioning of Sr(NO₃)⁺ and endothermic ion pairing interactions in the organic phase that contribute to the net enthalpic effect. The thermodynamics of the liquid-liquid distribution equilibria are discussed mainly considering the basic features of the ion solvation thermochemistry.     

Adsorption from aqueous solution by δ-manganese dioxide I. Adsorption of the alkaline-earth cations

The adsorption isotherms of M²⁺ ions (M = Mg, Ca, Sr or Ba) were determined at pH 7.0 and at different temperatures. The adsorbent, δ-MnO₂, was converted to the K⁺ form prior to adsorption and about 1.5 mol K⁺ ions were released per mol of M²⁺ ions adsorbed. The adsorption capacity at a given temperature increased in the series: Mg²⁺ < Ca²⁺ ≦ Sr²⁺ < Ba²⁺. This was explained by an ion exchange mechanism between hydrated ions: K⁺ ions in the outer Helmholtz layer and M²⁺ ions in the bulk of the solution. The radii of the hydrated ions decreased in the series: Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺. The adsorption of M²⁺ ions at pH values below the point of zero charge (pH 3.3) was significant for Mg²⁺ ions only. Although adsorption was not strictly reversible, the results fitted the Langmuir isotherm and ‘apparent heats of adsorption’, Q, were calculated. The endothermic heats (Q = 20,18, 11 and 5 kJ mol^?1 for Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ adsorption respectively) indicated positive entropy contributions which are expected for the adsorption mechanism suggested. The decrease in Q down the alkaline-earth group was correlated to the entropy effects and to the hydration numbers of the cations.     

Design and Evaluation of Chelating Resins through EDTA- and DTPA-Modified Ligands

Ion-exchange resins through EDTA or DTPA moieties are synthesized and evaluated for the co-extraction of Cs⁺ and Sr²⁺ radionuclides for wastewater treatment. EDTA-bis(amide) and DTPA-bis(amide) derivatives bearing phenol or catechol moieties obtained from tyramine or dopamine, respectively, were used as building blocks to prepare ion-exchange resins. Their synthesis involved the condensation of formaldehyde with various phenolic rings, catechol (C), resorcinol (R), or calixresorcinarene (CR) under alkaline conditions. The resulting formo-phenolic-like resins have both ion-exchange and chelating groups in their structure and are indeed efficient in the remediation of Cs⁺ and Sr²⁺, even in salted aqueous solutions.