Sorption of cesium from water solutions on potassium nickel hexacyanoferrate-modified <Emphasis Type="Italic">Agaricus bisporus</Emphasis> mushroom biomass

In order to gain biosorbent that would have the ability to bind cesium ions from water solution effectively, potassium nickel hexacyanoferrate(II) (KNiFC) was incorporated into the mushroom biomass of Agaricus bisporus. Cesium sorption by KNIFC-modified A. bisporus biosorbent was observed in batch system, using radiotracer technique using ¹³⁷Cs radioisotope. Kinetic study showed that the cesium sorption was quite rapid and sorption equilibrium was attained within 1 h. Sorption kinetics of cesium was well described by pseudo-second order kinetics. Sorption equilibrium was the best described by Freundlich isotherm and the distribution coefficient was at interval 7,662–159 cm³ g⁻¹. Cesium sorption depended on initial pH of solution. Cesium sorption was very low at pH₀ 1.0–3.0. At initial pH 11.0, maximum sorption of cesium was found. Negative effect of monovalent (K⁺, Na⁺, NH₄ ⁺) and divalent (Ca²⁺, Mg²⁺) cations on cesium sorption was observed. Desorption experiments showed that 0.1 M potassium chloride is the most suitable desorption agent but the complete desorption of cesium ions from KNiFC-modifed biosorbent was not achieved.     

Cesium sorption on mylonite

As part of the laboratory support program for the field migration experiment at the Grimsel Test Site (GTS) in the Swiss Alps, the sorption behaviour of cesium on Grimsel mylonite was studied. Batch sorption experiments were carried out in N₂ atmosphere (<3 ppm O₂). The adsorption isotherms were reversible and non-linear for cesium concentrations of between 3.2·10^–8 and 5.0·10^–4M. Two different sites appear to be involved in sorption depending on whether Cs loading was high (10^–6–10^–3 meq/g) or low (10^–7–10^–6 meq/g). At low Cs loadings adsorption was considered to occur mainly at the crystal edges of mica particles. Selectivity coefficients for exchange between cesium and potassium were calculated for different Cs loadings. It was suggestd that by varying the potassium concentration of the solution and by making some assumptions, a K_d value for cesium at the migration site could be estimated. Data were fitted to both Freundlich and Dubinin-Radushkevich isotherms. The empirical Freundlich parameters enabled a site distribution function to be calculated and a mean energy of sorption of about 12 kJ/mol was found using Dubinin-Radushkevich isotherms approach.     

Application of Thermal Analysis for Explaining the Sorption of Benzene and N-Hexane on Silicalite

The origin of kinks (steps) on sorption isotherms was examined for the sorption of benzene and n-hexane on silicalite-1. In both cases sorption revealed the existence of two different binding sites. There was no equilibrium (or a very slow one), between molecules bound at different sites. Sorption energies within particular centres display more or less wide overlapping distributions leading to a single resultant isotherm. Depending on differences in binding energies and degree of overlapping, the resulting isotherms exhibit steps (benzene) or no steps (n-hexane). In fact, the sorption isotherm of benzene being a sum of two elemental isotherms (Ω₁ and Ω₂) of different shapes is characterized by a ‘kink’, in contrast to n-hexane the elemental isotherms of which are of the same shape. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic and thermodynamic studies of cesium(I) sorption on hydrous silica

Summary Batch sorption experiments of cesium, Cs⁺, on SiO₂ ^. xH₂O (silica gel) have been conducted with variable times of equilibration, amounts of silica gel (0.10-1.00 g), cesium concentrations (5.00 ^. 10^-5-2.40 ^. 10^-3M), ionic strengths (0.20-1.40M NaClO₄), pH (2.50-7.70), and temperatures (273-333 K). The diffusion coefficient of Cs⁺ ion was calculated to be (9.19±0.86) ^. 10^-11 m^{2 .} s^-1 under particle diffusion-controlled conditions. The sorption rate was (3.94±0.65) ^. 10^-3 s^-1 at 298 K, pH 7.70±0.05 in 0.20M NaClO₄. The sorption data fits the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Cesium sorption on 0.20 g silica gel decreased with ionic strength from (40.42±0.34)% in 0.20M NaClO₄ to (6.35±0.40)% in 1.40M NaClO₄, at pH_(initial) 8.20±0.05. A gradual decrease in pH with increased ionic strength is consistent with a cation-exchange mechanism. Sorption of Cs⁺ on silica gel decreased with increased temperature, indicating an exothermic enthalpy. The presence of anions such as fluoride, carbonate, phosphate and oxalate in the aqueous medium did not influence the cesium sorption profile.     

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.     

Recovery of actinides extracted by Truex solvent from high level waste using complexing agents

The sorption and migration of radiostrontium in a calcareous soil from Yu Zhong county of Gansu province (China) was studied using batch and column experiments. Sorption isotherms, breakthrough curves and concentration profiles for the untreated soil and the soil treated to remove CaCO₃ were determined, respectively. It was found that radiostrontium is a relatively mobile nuclide in calcareous soil and removal of CaCO₃ from the soil slightly increases the retention ability for radiostrontium. The breakthrough curves were fitted to the analytical solution of a one-dimensional convection-dispersion transport model that assumes a reversible linear isotherm. Good agreement was obtained between the measured and predicted concentration profiles.     

Retention of Cs on zeolite, bentonite and their mixtures

The sorption behavior of cesium on zeolite and bentonite minerals and their mixtures was studied by means of a batch method and a tracer technique. All experiments were carried out in the presence of CsCl spiked with ¹³⁷Cs and NaCl as a supporting electrolyte in varying concentrations. The distribution coefficients (K _D) did not show significant differences at low Cs⁺ loadings while they decreased in the high loading region. Freundlich and D-R isotherms were applied to the adsorption data of zeolite and bentonite. Adsorption capacities and mean energies calculated from D-R isotherm parameters decreased by increasing ionic strength on both minerals. The identification of the specific uptake sites was attempted on the basis of the Freundlich isotherm. Experimentally observed distribution coefficients of Cs on two mineral mixtures were smaller than theoretically calculated values, except at the highest NaCl concentration.     

Sorption of Paraquat and 2,4-D by an Oscillatoria Sp.-Dominated Cyanobacterial Mat

The present study characterises sorption of two pesticides, namely, paraquat (PQ) and 2,4-dichlorophenoxyacetic acid (2,4-D) by an Oscillatoria sp.-dominated cyanobacterial mat. Sorption of PQ onto the test mat was not significantly affected by the pH of the solution within the pH range 2–7. However, 2,4-D sorption was strongly influenced by the solution pH and was maximum at pH 2. Whereas PQ sorption increased with increase in temperature, 2,4-D sorption showed an opposite trend. The sorption of PQ and 2,4-D achieved equilibrium within 1 h of incubation, independent of concentration of pesticide and mat biomass in the solution. The pseudo-second-order kinetic model better defined PQ sorption than the pseudo-first-order model, whereas 2,4-D sorption was well defined by both the models. Sorption isotherms of both the pesticides showed L-type curve. Freundlich model more precisely defined PQ sorption than Langmuir model, thereby suggesting heterogeneous distribution of PQ binding sites onto the biomass surface. However, the Langmuir model more correctly defined 2,4-D sorption, thus, indicating homogeneous distribution of 2,4-D binding sites onto the biomass surface. The test biomass is a good sorbent for the removal of PQ because it could, independent of pH of the solution, sorb substantial amount of PQ (q _max = 0.13 mmol g⁻¹).     

Removal of cesium and strontium from acid solution using a composite of zirconium molybdate and zirconium tungstate

A composite mixture of zirconium molybdate and zirconium tungstate was prepared and studied for the sorption of cesium and strontium as a function of nitric acid, metal ion concentration, time and temperature. The distribution coefficient (K_d) of 7000 ml/g (~90% sorption) and 70 ml/g (~20% sorption) was obtained for the sorption of cesium and strontium in 0.1M nitric acid, respectively. Experimental sorption capacity, b for cesium was found to be 50 mg/g from 0.1M HNO₃ and 30 mg/g for strontium from 0.001M nitric acid. The sorption of strontium on the sorbent was accompanied by the absorption of heat but the sorption of Cs⁺ results in the liberation of heat. Column studies were conducted by following a breakthrough (BT) curve of cesium and strontium up to C/C₀=1 and the results are reported.     

Structure of copper-potassium hexacyanoferrate (II) and sorption mechanisms of cesium

A mixed potassium-copper hexacyanoferrate (II) K₂CuFe(CN)₆ was prepared by local growth on solid cupric sulfate in an aqueous solution of potassium hexacyanoferrate (II) and by growth in a gel. Powders having this composition and separable by filtration could not be obtained by normal precipitation from aqueous solution. This compound has a triclinic P-1 structure, described for the first time, and made up of non-linear -Fe-C-N-Cu-chains which form a puckered layered network. Sorption mechanisms for cesium have been studied in batch experiments including kinetics and isotherms, X-ray diffraction, infra-red spectroscopy and scanning electron microscopy. In neutral solutions the initial crystal structure is maintained and sorption proceeds through a K/Cs ion exchange. In acid solutions, even without addition of cesium, the initial structure is destroyed. The main phase formed in acidic media is Cu₂Fe(CN)₆. In the presence of cesium the structure is also destroyed and new solid phases are formed. All these processes have slow kinetics, the evolution of the solid being observed over a period of 6 months. This study confirms previous results, which have shown that the sorption mechanisms on hexacyanoferrates strongly depend on the composition and structure of the solid, together with the composition of the solution. Sorption mechanisms have considerable consequences on the use of these products for the decontamination of radioactive wastes.     

Evaluation of cesium sorption on natural mordenite

The kinetic and equilibrium sorption behaviors of Cs⁺ on mordenite, a zeolite which can sorb cesium well, were investigated by using the batch method. Cesium-137 and the stable CsNO₃ were used as tracer and carrier to study the influences on Cs⁺ sorption behaviors by changing Cs⁺ initial concentration, pH value, particle size of mordenite and experimental temperature. The equilibrium was reached in 3 days and the saturated amount of cesium sorbed is about 0.19 kg Cs/kg NM. The sorption data at 25°C and 90°C were fitted to Freundlich sorption model and nonlinear isotherms were found. However, linear isotherm was applicable with a Cs⁺ initial concentration less than 10^–3M. The decrease of Cs⁺ sorption at elevated temperature suggested the sorption reaction was exothermic. The use of centrifugation to separate the liquid from solid phases in traditional batch techniques was not suitable to the kinetic experiment of Cs sorbed by mordenite for lower concentrations.     

Investigation of cesium uptake from aqueous solutions using new titanium phosphates ion-exchangers

The uptake of cesium from aqueous solutions (pH 5) using titanium phosphates was investigated in the absence and presence of background electrolyte (0.1 M NaNO₃) using a batch technique. The determination of cesium was performed by gamma spectroscopy using ¹³⁷Cs as tracer. The obtained sorption isotherms could be satisfactorily reproduced by a Langmuir sorption equation. The maximum uptake capacity values (q _max) calculated fitting the experimental data by this equation were 167 and 118 mg/g for solutions of initial pH 5 in the absence and presence of background electrolyte. Kinetics data obtained at 293, 308 and 323 K could satisfactorily reproduced by the pseudo-second order equation. It was demonstrated that the new synthesized materials can remove considerable amounts of cesium from aqueous solutions and ion exchange is considered to be the principal mechanism for cesium removal. Toxicity characteristic leaching procedure and desorption tests provided data about the application of the sorbents in environmental remediation.     

Synthetic calcium aluminosilicates and their sorption properties with respect to Sr<Superscript>2+</Superscript> ions

Sorption characteristics of synthetic calcium aluminosilicates (CAS) obtained in the multicomponent CaCl₂–AlCl₃–KOH–SiO₂–H₂O system are presented. The isotherms of Sr²⁺ sorption on CAS from aqueous solutions containing no additional salts were measured for Sr²⁺ concentration from 0.5 to 11.1 mmol/L and solid to liquid phase ratio S: L = 1: 100. The maximum sorption capacity of synthetic CAS was determined, the phase distribution constants of Sr²⁺ ions at different S: L ratios were found. The recoveries of Sr²⁺ ions from solutions containing 0.01 mol/L Ca(NO₃)₂ and from a solution simulating water of the Mayak plant sewage pond No. 11 were determined.     

Anaerobic and aerobic sorption of cesium and selenium on mudrock

This study is focused on sorption and determination of distribution ratios (R _d) of cesium and selenium on mudrock, which is the potential host rock for waste disposal in Taiwan. Batch tests including sorption kinetic and isotherms tests have been performed in synthetic groundwater at aerobic and anaerobic conditions which might be found in the deep geologic environment. It is found that R _d for sorption of cesium did not have an obvious difference in both conditions with various contact time. However, R _d in anaerobic condition for sorption of selenium was greater than that in aerobic condition. Selenium is a redox sensitive element and its solubility in reducing conditions is controlled by the formation of metallic or precipitable selenium. It demonstrated variation of R _d with time in both conditions for Se sorption kinetic experiments was equal (10 ml/g) and indicated a part formation (10%) of precipitable selenium (Se⁰, FeSe or FeSe₂) in the solution. Moreover, it was not enough to form precipitable selenium completely in reducing condition as to insufficient experimental period (2 weeks) and in the presence of Fe²⁺. The Freundlich and Langmuir isotherm for the concentration ranges (i.e., 10⁻³–10⁻⁷M) conducted in both conditions seem to be adequate to quantitatively describe the sorption of cesium and selenium, respectively.     

Studies of phosphate anion sorption using the soil samples

The paper presents the results of studies of phosphate anion sorption on various types of soil taken up from the Lublin Province (Poland). Anions belong to the group of ions witch undergo insignificant sorption according to the soil science. As follows from the studies anion sorption depends insignificantly on pH. Sorption isotherms can be described using the Freundlich equation. Sorption extent depends on concentration of iron ions and organic substances in the sample. Specific sorption (chemisorptions) plays the greatest role in the process under investigation.     

Mercury(II) Biosorption Using <Emphasis Type="Italic">Lessonia</Emphasis> sp. Kelp

Lessonia nigrescens and Lessonia trabeculata kelps have been tested for the sorption of mercury from aqueous solutions. A pretreatment (using CaCl₂) allowed stabilizing the biomass that was very efficient for removing Hg(II) at pH 6–7. Sorption isotherms were described by the Langmuir equation with sorption capacities close to 240–270 mg Hg g⁻¹ at pH 6. The temperature had a negligible effect on the distribution of the metal at equilibrium. The presence of chloride anions had a more marked limiting impact than sulfate and nitrate anions. The uptake kinetics were modeled using the pseudo-second-order equation that fitted better experimental data than the pseudo-first-order equation. The particle size hardly influenced sorption isotherms and uptake kinetics, indicating that sorption occurs in the whole mass of the biosorbent and that intraparticle mass transfer resistance was not the limiting rate. Varying the sorbent dosage and the initial metal concentration influenced the equilibrium, but the kinetic parameters were not drastically modified. Metal can be eluted with hydrochloric acid, citric acid, or acidic KI solutions.     

Sorption studies of europium(III) on hydrous silica

Summary Sorption behavior of europium, Eu³⁺, on SiO₂ ^. xH₂O (silica gel) has been investigated as a function of time, the amount of silica gel, Eu³⁺ concentration, the ionic strength, and pH (in absence and in presence of carbonate). The sorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The sorption capacity of silica gel was determined to be in the range of (2.62-8.00) ^. 10^-7 mol/g at pH 5.30±0.05 and 0.20M NaClO₄. The mean energy of sorption was calculated to be 13.50±0.05 kJ/mol from the D-R isotherm, suggesting the involvement of ion-exchange reactions in the sorption process. Sorption of Eu³⁺ decreased with increased ionic strength. A gradual decrease in pH with increased ionic strength supports the involvement of an ion-exchange mechanism in the sorption process. The diffusion coefficient of Eu³⁺ ion on silica gel was calculated as (3.98±0.12) ^. 10^-13 m^{2 .} s^-1 under the particle diffusion-controlled conditions.     

Argon sorption and partial molar volume in poly(ethyl methacrylate) above and below the glass transition temperature

Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (T_g=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above T_g follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above T_g (about 40 cm³/mol), whereas the volumes below T_g are smaller and dependent on both temperature and concentration (19–26 cm³/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 ų, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm³ from the temperature dependence of the dual-mode parameters.     

Sorption of cadmium in some arable and forest soils

The sorption of cadmium labeled with ¹⁰⁹Cd in nitrate form, from aqueous solutions in different horizons of some arable and forest soils was studied under static (batch) conditions. Before sorption, a method of sequential soil treatment was applied, which consist in the consecutive removal of individual soil components by the use of appropriate reagents and procedures. Three sorption isotherms were tested. Kinetic studies showed that the sorption of cadmium is rather rapid and it can be well described by a Freundlich or a linear isotherm, whereas the closeness of Langmuir isotherm to the experimental results is lower. From the different sorption isotherms, it would also be possible to estimate the effect of individual components on the sorption of cadmium in soils. It was found that the untreated soils exhibit the highest sorption and the sorption decreases in the order of untreated > acetate treated > water treated > peroxide treated > dithionite treated soil. Sorption of cadmium increases with the depth of the studied soils disregarding their chemical treatment.This revised version was published online in November 2005 with corrections to the Cover Date.     

Specific adsorption of cesium on silica-titania

The amphoteric nature of hydrous silica-titania gel and its sorption behaviour towards cesium were studied. In NaNO₃ solution, the point of zero change (pH_pzc) of the gel was found to be 4.22 by pH-titration. The fraction of protonated, deprotonated and neutral surface hydroxyl groups as a function of pH have been computed. Sorption of cesium increased with the increase of pH, reached maximum at a pH of 7 followed by a plateau. Significant uptake of cesium was observed even when the pH was less than pH_pzc. Nearly 70% sorption was observed at pH_pzc. The free energy of specific adsorption was found to be –18.7 kJ·mol^–1.