Sorption of cesium ions by nanostructured calcium aluminosilicates

Data on the sorption properties of synthetic calcium aluminosilicates (CASes) with Al: Si ratios of 2: 2, 2: 6, and 2: 10, fabricated within the multicomponent system CaCl₂–AlCl₃–KОН–SiO₂–H₂O, are presented. Isotherms of the sorption of Cs⁺ ions from aqueous solutions with Cs⁺ concentrations of 0.2 to 6.0 mmol L^–1 are analyzed. The CAS maximum sorption capacity and the Langmuir constants are determined. Kinetic data are obtained, and the energy of cation-exchange activation upon the sorption of Cs⁺ ions is determined. The effect of a salt background (1% KCl + 6% NaCl) has on the values of distribution coefficient (K_d) and the degree of Cs⁺ ion removal is established.     

Equilibrium in adsorption of lead (Pb<Superscript>2+</Superscript>) and manganese (Mn<Superscript>2+</Superscript>) ions from solutions onto natural and synthetic sorbents

The patterns of static equilibrium sorption of Pb²⁺ and Mn²⁺ ions from solutions simulating a composition of industrial liquid waste, onto modified bentonite and zeolite were researched. Na-bentonite and Na-clinoptilolite demonstrate high sorption activity with respect to Pb²⁺ and Mn²⁺ ions are recommended instead of a commercial synthetic KU-2-8 for a sorption after-treatment of liquid wastes from toxic Pb²⁺ and Mn²⁺ ions.     

Sorption of Cd<Superscript>2+</Superscript> with the product formed by alkali treatment of boron production wastes

Experiments on sorption of Cd²⁺ ions from aqueous CdCl₂ solutions with calcium hydrosilicate prepared from borogypsum (boron production waste) showed that this cheap sorbent can be used for effi cient sorption of Cd²⁺ ions in a wide range of solid: liquid ratios.     

Adsorption of strontium ions from aqueous solution using hydrous,amorphous MnO2–ZrO2 composite: a new inorganic ion exchanger

Hydrous, amorphous MnO₂–ZrO₂ composite was prepared as a new inorganic composite material under various conditions for removal of Sr²⁺ ion from aqueous solutions. The physico-chemical characterization was carried out by Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy and thermogravimetry. The maximum sorption capacity for synthesized composite was evaluated as 1.5 meq/g sorbent and batch experiments were carried out as a function of contact time, aqueous phase pH, temperature and initial metal ions concentration of adsorptive solution. The results indicated that under optimal conditions, Sr²⁺ ions could be efficiently removed using MnO₂–ZrO₂ composite from aqueous solutions when pH > 5. The equilibrium isotherms were determined and the sorption data were successfully modeled using Langmuir model. Kinetics of the process was studied by considering a pseudo second-order model. This model predicted chemisorption as the adsorption mechanism. The results of thermodynamic investigation reveal that the adsorption process of the studied ion is entropy driven.     

Incorporation of Mg<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, Ba<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> into aragonite and comparison with calcite

We have investigated the presence of foreign ions into the bulk structure and the external surfaces of aragonite using periodic ab-initio methods. Four cations isovalent to Ca²⁺ were studied: Mg²⁺, Sr²⁺, Ba²⁺ and Zn²⁺. The calculations were performed at structures (bulk, surface) that contain four and eight CaCO₃ units. Our results, at the Hartree-Fock level, show that the incorporation of those ions into aragonite depends strongly on their size. Mg²⁺ and Zn²⁺, due to their smaller size, can substitute Ca²⁺ ions in the crystal lattice while the incorporation of Sr²⁺ and Ba²⁺ into aragonite is energetically less favoured. Examination of the [011], [110] and [001] surfaces of aragonite revealed that the surface incorporation reduces the energetic cost for the larger ions. These systems provide challenging examples for most shape analysis methods applied in Mathematical Chemistry.     

Transport and sorption of <Superscript>85</Superscript>Sr and <Superscript>125</Superscript>I in crushed crystalline rocks under dynamic flow conditions

Transport and sorption of water-soluble ⁸⁵Sr²⁺ and ¹²⁵I⁻ in the columns with beds of crushed crystalline rocks from synthetic groundwater has been studied under dynamic flow conditions. Samples of crystalline rocks: diorite-I, diorite-II, gabbro, granite and tonalite, having the grain size between 0.25 and 0.80 mm, were used. Plastic syringes of 8.8 cm length and 2.1 cm in diameter were applied as columns. The synthetic groundwater was pumped downward through the columns with a seepage velocity of about 0.2 cm/min and the given radioactive nuclide was added into the water stream individually in a form of a short pulse. In case of ⁸⁵Sr, desorption from diorite-I was also studied using an artificial acid rainfall and then, the longitudinal distribution of the residual ⁸⁵Sr activity along the bed was measured. Retardation, distribution and hydrodynamic dispersion coefficients were determined by the evaluation of respective breakthrough curves. A corrected integral form of a simple advection–dispersion equation was derived and used for fitting the experimental data. The K _d-parameters resulting from dynamic experiments were also compared with the results of static sorption experiments.     

Migration and sorption of <Superscript>137</Superscript>Cs and <Superscript>152,154</Superscript>Eu in crushed crystalline rocks under dynamic conditions

In migration experiments, sorption of ¹³⁷Cs and ^152,154Eu in the columns of crushed crystalline rocks of 0.25–0.8 mm grain size under dynamic flow conditions from the synthetic groundwater (SGW) has been studied. Five samples of crystalline rocks from Cavernous Gas Reservoir near Příbram were taken. Plastic syringes of 8.8 cm length and 2.1 cm in diameter were used as columns. The water phase was pumped downward through the columns, using a multi-head peristaltic pump, with a seepage velocity of about 0.2 cm/min. The radioactive nuclides, containing chemical carriers, were added into the water stream individually in the form of a short pulse. Desorption experiments were carried out with 2:1 (v/v) mixture of H₂SO₄ and HNO₃. In the columns the longitudinal distribution of the residual ¹³⁷Cs and ^152,154Eu activities was also determined. By the evaluation of respective breakthrough and displacement curves, the experimental and theoretical retardation factors, distribution coefficients and hydrodynamic dispersion coefficients were determined using the integrated analytical form of a simple advection-dispersion equation (ADE). Dynamic sorption experiments were also compared with the results of static sorption experiments. The paper was presented in part as a poster No. PB1-1 at the 11th International Conference Migration’ 07, held in Munich, Germany, August 26–31, 2007, Abstracts, p. 212.     

A new phosphor with flower-like structure and luminescent properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> long afterglow materials by sol–gel method

The flower-like phosphors of Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ with high brightness and long afterglow were obtained by sol–gel method. X-ray diffraction pattern (XRD) shows that single-phased Sr₂MgSi₂O₇ phosphor is prepared by sol–gel method under 1250 °C. Scanning electron microscope (SEM) indicates that the phosphor consists of nano-sized whiskers which are detected for the first time in Eu²⁺ and Dy³⁺ co-doped long-lasting phosphorescence silicates. Furthermore, the investigation on the mechanism indicates that the internal structure and gas, liquid and solid phase effect play important roles in the formation of flower-like Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ nanostructure. Finally, the optical properties of flower-like Sr₂MgSi₂O₇ nanostructure have been characterized by photoluminescence (PL) spectra.     

Study of Complex Formation between Kryptofix 21 with La<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> Cations in Some Binary Mixed Non-Aqueous Solvents Using the Conductometric Method

The complexation reactions between La³⁺, Y³⁺ and Ce³⁺ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La³⁺, Y³⁺ and Ce³⁺ metal cations, but in the case of Y³⁺ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML₂] and 1: 3 [ML₃] complexes are formed in solution. In the case of Ce³⁺cation, a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed between the ligand and La³⁺ and Ce³⁺ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between log_{K f} of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y³⁺ > La³⁺ > Ce³⁺ and La³⁺ > Y³⁺ > Ce³⁺, respectively. The values of the standard thermodynamic quantities (ΔH _c ^° and ΔS _c ^° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La³⁺, Y³⁺ and Ce³⁺ cations, is affected by the nature and composition of the mixed solvents systems.     

Tailored functionalized polymer nanoparticles using gamma radiation for selected adsorption of barium and strontium in oilfield wastewater

To improve oil recovery from oilfield wells mineral scales derived by insoluble BaSO₄ and SrSO₄ salts during oil extraction should be diminished. In this work, adsorption selectivity of Barium (Ba²⁺) and Strontium (Sr²⁺) ions associated with saline formation waters was examined for the first time using nano-sized bi-functional polymer blend synthesized by Cobalt-60 (⁶⁰Co) γ-rays, as green technology. A bifunctional polymer formed from poly(acrylonitrile)/(styrene-butadiene rubber) homogenous blend is functionalized by -SO₃H and -COOH terminal groups (termed as SASB). Those functional groups were selected based on systematic calcium (Ca²⁺) ions adsorption studies of carboxylate containing molecules. Main and binary interactive effects of solution pH (3–9), adsorbents dose (1-3 g/L), total dissolved salts (TDS, up to 30 g/L), initial Ba²⁺ and Sr²⁺ concentrations (10-500 mg/L) and temperature (20–50 ^oC) on the adsorption selectivity were examined and optimized using Plackett-Burman factorial design (PBD) combined with multiple regression analysis. The regression statistics revealed the significance of quadratic polynomial model to optimize interactive sorption conditions from salty waters with high accuracy level ($R^2$≈ 0.99) rather than linear and two-way interactive models at 95% confidence level. Interestingly finding, the regression and experimental data proved that the presence of up to 10 g/L TDS from alkali metal ions had a significant effect on the enhancement sorption capacity of Ba²⁺ and Sr²⁺ when using the prepared sorbent. The SASB adsorbent showed higher sorption selectivity with maximum equilibrium capacity ($q_{\mathit{mg}/g}$) of 175.3 mg Ba⁺² and 210.5 mg Sr⁺² per each gram sorbent used in kinetic study. Adsorption kinetics of Ba²⁺ and Sr²⁺ sorption by both adsorbents obey pseudo-first and pseudo-second order kinetics, respectively. In sum, the adsorptive power of SASB sorbent is found to be in reverse order of the electronegativity and the hydration radii of the metal ions.     

Complex formation involving Hg<Superscript>2+</Superscript> ions on the surface of the polysiloxane xerogels functionalized by 3-mercaptopropyl groups

The influence of parameters of the porous structure and the surface layer composition of the xerogels containing 3-marcaptopropyl and alkyl groups on their sorption properties toward the Hg²⁺ ions and the stability constants of the formed complexes, which are calculated using the model of chemical reactions, is studied. An increase in the overall surface concentration of the functional groups is shown to induce a change in the composition of the formed complexes. At the concentration of the functional groups lower than 0.01 mmol/m² the [HgS(CH₂)₃Si≡]⁺ complexes are formed, and above 0.01 mmol/m² the composition of the complexes depends on the mercury(II) content in the starting solution: at low contents the [Hg{S(CH₂)₃Si≡}₂] complexes are formed, whereas at higher concentrations the composition of the complexes becomes simpler. Only the [Hg{S(CH₂)₃Si≡}₂] complexes are formed on the nearly nonporous xerogel with the polymeric structure of the surface layer (the functional group concentration is 0.38 mmol/m²). This, in turn, leads to the situation that the maximum static sorption capacity (590–620 (mg of Hg²⁺)/(g of sorbent)) is observed for the xerogels with a rather low content of the 3-mercaptopropyl groups (3.0–3.8 mmol/g). The stability of the formed complexes also depends on the surface concentration of the functional groups: the stability constant of the 1: 1 Hg(II) complexes decreases with an increase in the concentration of thiol groups. The introduction of alkyl groups into the surface layer also decreases the stability of the complexes formed. The [Hg{S(CH₂)₃Si≡}₂] complexes formed in the surface layer of the xerogels are characterized by similar stability constants.     

Effect of temperature on the sorption behavior of sodium potassium fluorophlogopite with respect to the heavy metal ions Cd<Superscript>2+</Superscript>, Hg<Superscript>2+</Superscript>, and Pb<Superscript>2+</Superscript>

The effect of temperature on the sorption behavior of a synthesized gel structurally close to the fluorine mica mineral, sodium potassium fluorophologopite, was studied for the heavy metal ions Cd²⁺, Hg²⁺, and Pb²⁺. The synthesized gel was characterized by X-ray powder pattern, energy dispersive spectrometry, infrared spectroscopy, and thermogravimetric analysis and was found to have the composition Na_0.5K_0.5Mg(AlSi₃O₁₀)F₂·6H₂O. The effect of temperature on sorption was studied with respect to varying concentrations of metal ions. The overall sorption capacity of the synthesized gel was found to depend on the number of ion active groups per unit weight of the material. The data were expressed in terms of distribution coefficients (K _d). Sorption data followed Freundlich adsorption isotherms. Studies showed that sorption decreased as the concentration of metal ions increased and increased as the temperature grew, which was evidence that the process was endothermic. The text was submitted by the authors in English.     

Ion exchange with silica-titania gels

Silica-titania gels containing 25, 50 and 75 mol% TiO₂ were prepared and the sorption of alkali and alkaline earth metal ions by these materials has been studied. Distribution coefficient values for Cs⁺ and Sr²⁺ ions were found to pass through broad maxima as a function of TiO₂ content except in the case of Sr under alkaline conditions where there was a continuous increase. Capacity values also increased with TiO₂ content and samples containing 50% (for K⁺ and Cs⁺), 75% (for Li⁺ and Na⁺) and 25%/50% (for Ca²⁺, Sr²⁺ and Ba²⁺) TiO₂ exhibited maximum capacities. However, unlike with alkali metals, capacities of a given sorbent for the three alkaline earth ions were almost the same. Large capacities obtained for the latter ions seem to indicate a mineral-forming reaction with 25% and 50% materials. On the other hand, the 25% TiO₂ gel seems to sorb Sr at trace level by an ion exchange mechanism. Coupled with its Cs sorption capability, this material may find potential use in large scale decontamination of low level waste solutions.     

Sorption behavior of Am<Superscript>3+</Superscript> on suspended pyrite

Sorption behavior of ²⁴¹Am (~10⁻⁹ M) on naturally occurring mineral pyrite (particle size: ≤70 μm) has been studied under varying conditions of pH (2–11), and ionic strength (0.01–1.0 M (NaClO₄)). The effects of humic acid (2 mg/L), other complexing anions (1 × 10⁻⁴ M CO₃ ²⁻, SO₄ ²⁻, C₂O₄ ²⁻ and PO₄ ³⁻), di- and trivalent metal ions (1 × 10⁻³ M Mg²⁺, Ca²⁺ and Nd³⁺) on sorption behavior of Am³⁺ at a fixed ionic strength (I = 0.10 M (NaClO₄)) have been studied. The sorption of ²⁴¹Am on pyrite increased with pH from 2.8 (84%) to 8.1 (97%). The sorption of ²⁴¹Am decreased with ionic strength at low pH values (2 ≤ pH ≤ 4), but was insensitive in the pH range of 4–10, suggesting the formation of outer-sphere complexes on pyrite surface at lower pH, and inner-sphere complexes at higher pH values. The sorption of ²⁴¹Am increased in the presence of (i) humic acid (5 < pH < 7.5), and (ii) C₂O₄ ²⁻ (2 < pH < 3). By contrast, other complexing anions such as (carbonate, phosphate, and sulphate) showed negligible influence on ²⁴¹Am sorption. The presence of Mg²⁺, Ca²⁺ ions showed marginal effect on the sorption profile of ²⁴¹Am; while the presence of Nd³⁺ ion suppressed its sorption significantly under the conditions of present study. The sorption of ²⁴¹Am on pyrite decreased with increased temperature indicating an exothermic process.     

A selective colorimetric and fluorescence chemosensing sensor for Cr<Superscript>3+</Superscript> based on a rhodamine base derivative

A rhodamine-conjugated coumarin (L) was used in designing a selective fluorescence chemosensor for the determination of trace amounts of Cr³⁺ ions in acetonitrile–water (MeCN/H₂O (90:10, %v/v) solutions. The intensity of the fluoresce emission of the chemosensor is intensified upon addition of Cr³⁺ ions in MeCN/H₂O (90:10, %v/v) solutions, due to the formation of a selective 1:1 complex between L and Cr³⁺ ions. The fluorescence enhancement versus Cr³⁺ concentration has been found to be linear from 1.0?×?10^?7 to 1.8?×?10^?5 M and a detection limit of 7.5?×?10^?8 M. The proposed fluorescent probe proved to be highly selective towards Cr³⁺ ions as compared to other common metal ions and could be successfully applied to the determination of Cr³⁺ concentrations in some water and wastewater samples.     

A new chelating resin containing 2-aminothiophenol: Synthesis characterization and determination of mercury in waste water using <Superscript>203</Superscript>Hg radiotracer

A new stable chelating resin was synthesized by incorporating 2-aminothiophenol into Merrifield polymer through C-N covalent bond and characterized by elemental analysis, IR and thermal study. The sorption capacity of the newly formed resin for Hg²⁺ as a function of pH has been studied using ²⁰³Hg radioisotope. The resin exhibits no affinity to alkali or alkaline earth metal ions and common anions. The separation of mercury(II) in presence of different alkali and alkaline earth metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), common anions (ClO₄ ⁻, SO₄ ²⁻) and other diverse ions (Ag⁺, Cu²⁺, Pb²⁺, Fe³⁺, Ni²⁺ and Zn²⁺) has been checked. In column operation it has been observed that Hg²⁺ content of the waste water can be removed at usual pH of natural water. Mercury was determined by isotope dilution method and the concentration of Hg²⁺ in the waste water spiked with ²⁰³Hg was found to be 0.05 to 0.09 μg/ml.     

Factors affecting the sorption behavior of Cs<Superscript>+</Superscript> and Sr<Superscript>2+</Superscript> using biosorbent material

In this study, saw dust has been used as precursor for production of low cost activated carbon using potassium hydroxide (KOH) and steam activation technique. The activated carbon was used to remove Cs⁺ and Sr²⁺ ions from aqueous solutions by batch operation, and the extent of adsorption was investigated as a function of solution pH, temperature, shaking time, and initial concentration. The influence of interfering ions was also investigated. The removal of metal ions was pH dependent and the adsorption capacity reaches its maximum 43% and 61.5% at pH 5.0 and 6.0 for Cs⁺ and Sr²⁺ ions, respectively. Thermodynamic studies showed different behaviours where an endothermic, non-spontaneous process was shown for Cs⁺ while an exothermic, spontaneous process was obtained for Sr²⁺. The kinetic data of both ions was described well by pseudo-second order rate equation. The two equilibrium models (Langmuir and Freundlich) have been also applied. Desorption studies indicated that HCl was the most effective desorbing eluent. The investigated adsorbent showed good results towards cesium and strontium removal from aqueous media that could be a promising method due to its low-cost and good efficiency.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Sorption of Cs<Superscript>+</Superscript> and Sr<Superscript>2+</Superscript> by ion exchanger based on titanium phosphate

Sorption capacity of a composite ion exchanger based on titanium phosphate for Cs⁺ and Sr²⁺ cations was studied. The effect of pH and concentration of salts and, in particular, sodium chloride in solution on the sorption efficiency and distribution coefficient was analyzed. The diffusion coefficients were calculated for the Cs⁺ and Sr²⁺ cations and the time of half-exchange of the Na⁺ cation for the Cs⁺ and Sr²⁺ cations was found.     

Specific features of absorption of Cu<Superscript>2+</Superscript>, Zn<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>, and Pb<Superscript>2+</Superscript> cations from aqueous solutions by calcium phosphates

Kinetic characteristics of the interaction of trisubstituted calcium phosphate Ca₃(PO₄)₂ · xH₂O with Cu²⁺, Zn²⁺, Co²⁺, and Pb²⁺ ions in aqueous solutions were studied.