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.     

Sorption of U(VI) on granite

The sorption-desorption of uranium (VI) on Grimsel granite of Switzerland was studied under oxidizing conditions with an initial uranium concentration range of between 9.7·10^–7 and 4.5·10^–4M, using a batch technique. The sorption coefficients varied between 8.0 and 0.4 ml/g and sorption was not fully reversible. The data could be fitted to a Freundlich isotherm. By fitting the data with the Dubinin-Radushkevich equation, a mean energy of sorption of 10.7 kJ/mol was calculated, which corresponds to the energy of ion exchange reactions. The kinetic data could be interpreted by assuming diffusion into the crushed granite particles. The calculated pore diffusion coefficient was between 2.0·10^–11–7.7·10^–11 m²/s.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.     

Sorption of Co, Cs, Sr and I onto argillaceous rock as studied by radiotracers</p> </p>

Summary Sorption of⁶⁰Co,⁸⁵Sr, 137Cs and¹²⁵I have been studied on samples originated from Boda (siltstone-) claystone formation (BCF) (Hungary). The distribution of K_dvalues have been determined in static batch experiments using natural groundwater. The order of sorption of isotopes was Co>Cs>Sr>I, where iodine exhibits sorption properties in a modest extent. The sorption isotherm was determined for Cs from measurements carried out in 10^-5-10^-1M initial concentration range. The isotherm can be described with non-linear Freundlich approximation in the range of</o:p></p> 10^-7-10^-4M equilibrium concentration. At concentrations >10^-2M the isotherm achieves saturation. Hence, it is suggested that sorption of Cs on BCF is dominated by cation-exchange reactions on the illite mineral component. In the case of Co and Sr, precipitation reactions occurred during the experiments performed with carrier-containing solutions. This can be attributed to the low values of solubility product constants of SrCO₃, SrSO₄and Co(OH)₂, formed from anions present in the natural groundwater.</p> </p>     

Influences of salt concentration,loading and pH on strontium adsorption

The adsorption of Sr on clay which contains zeolites and montmorillonite mixtures was investigated in solutions of NaCl by means of a batch technique. Sr retention was reduced with increasing NaCl concentration from 5·10^–4 to 5·10^–1M. Distribution coefficients (K _d ) linearly increased with pH in the acidic region but they were almost independent of pH in neutral and alkaline solutions. By fitting the data of the Dubinin-Radushkevich (D-R) isotherm, the mean energies of adsorption and adsorption capacities of Sr at different pH values were calculated. The results showed that the mode of adsorption below pH 4.5 is ion exchange, while above that value a multilayer adsorption occurs. Adsorption data were fitted to the Freundlich isotherm and from empirical Freundlich parameters a site distribution function was calculated.     

Modeling of iron adsorption on HTTA-loaded polyurethane foam using Freundlich,Langmuir and D-R isotherm expressions

The sorption of Fe(III) at low pH range from 1 to 4.5 on open cell polyether type HTTA-loaded polyurethane foam has been carried out using batch technique. The optimum shaking time for 2.5· 10^–4M solution of Fe(III) was found to be 30 minutes. The concept of macropore and micropore nature of polyurethane foam sorbent offers unique advantages of adsorption. Freundlich and Langmuir adsorption isotherms are followed at low concentration range from 1·10^–4 to 3·10^–4M solution of Fe(III). The Freundlich constant (1/n=0.46±0.013 andK=9.16±1.39 mg·g^–1) and Langmuir isotherm constants(M=21.78 mg·g^–1 andb=88.41±9.731·g^–1) were established. The sorption mean free energyE=12.22±0.09 kJ·mol^–1 and loading capacityC _m =145.21±6.1 mg·g^–1 were evaluated using Dubinin-Radushkevich isotherm, which suggested that the adsorption mechanism was chemisorption.     

Adsorption of Strontium on Illite

Adsorption of strontium on illite type clay has been studied as a function of shaking time, the ratio of solution volume to weight of clay and the concentration of adsorbate, using ⁹⁰Sr as a tracer. The adsorption experiments were carried out using the batch method and initial Sr²⁺ ion concentrations ranged from 10^–6 to 10^–1 M. The influence of Ca²⁺ and Ba²⁺ cations on Sr adsorption were also studied. These effects are correlated with the ionic radii of alkaline earth ions present in the solution. The Freundlich and Dubinin Radushkevich (D-R) isotherm have been applied to the data and the parameters of the isotherm equations were calculated. The mean energy of adsorption, E was also calculated from the adsorption energy constant, K and maximum capacity X _m values were determined from linearized D-R equation. From empirical Freundlich parameters a site distribution function was calculated.     

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.     

Sorption of europium on zirconium oxide from aqueous solutions

Sorption of europium on zirconium oxide has been studies as a function of shaking time, concentration and nature of electrolyte. The effect of initial europium concentration and the amount of adsorbent has been investigated in the range from 6.6·10^–10 to 6.6·10^–8 mol·dm^–3 and between 10 to 200 mg of the oxide. Maximum sorption (>99.8%) from pH 10 buffer and low sorption (<3%) was observed from 0.01 mol·dm^–3 nitric or perchloric acid solution. Citrate, sulfate, EDTA and carbonate reduced the sorption significantly. Under optimal conditions Ag(I), Cs(I), Tc(VII), Sb(V), Cu(II), Nd(III), Fe(III), and especially Nd and Fe showed low distribution coefficients. The data followed both Dubinin-Radushkevich and Langmuir-type isotherms. The mean free energy, of sorption was evaluated to be 10.1 kJ mol^–1 and the sorption capacity was found to be 22.2 mmol g^–1, using the Dubinin-Radushkevich isotherm.     

Modeling the Proton Transport in Orthoperiodic and Orthotelluric Acids and Their Salts

Orthoperiodic and orthotelluric acids, their salts MIO₆H₄ (M = Li, Rb, Cs) and CsH₅TeO₆, and dimers of the salt · acid type are calculated within density functional theory B3LYP and basis set LanL2DZ complemented by the polarizationd,p-functions. According to calculations, the salt · acid dimerization is energetically favorable for compounds MIO₆H₄ · H₅IO₆ (M = Rb, Cs) and CsIO₆H₄ · H₆TeO₆. The dimerization energy is equal to 138–146 kJ mol^–1. With relatively small activation energies equal to 4 kJ mol^–1 (M = Li) and 11 kJ mol^–1 (M = Rb, Cs), possible is rotation of octahedron IO₆ relative to the M atom in monomers of salt molecules. The proton transfer along an octahedron occurs with activation energies of 63–84 kJ mol^–1. The activation energy for the proton transfer between neighboring octahedrons of the type salt · acid acid · salt equals 8–17 kJ mol^–1. Quantum-chemical calculations nicely conform to x-ray diffraction and electrochemical data.     

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.     

A Microcalorimetric Study of Water Vapor Sorption on Morphine Sulphate

Water vapor sorption on morphine sulphate was studied in a twin double sorption microcalorimeter at 25°C. The vapor sorption isotherm and the differential heats of sorption were determined simultaneously from dry condition to a water activity of 0.99. Two well resolved hydration steps were obtained on the sorption isotherm at water activities of 0.01 and 0.22 corresponding to the formation of dihydrate and pentahydrate of morphine sulphate. They were accompanied by constant values of the differential heats of sorption: –24 kJ mol^–1(H₂O) for the dihydrate formation and –10 kJ mol^–1(H₂O) for the pentahydrate formation.The calorimetrically obtained sorption isotherms were compared with the results of Karl Fisher titrations of morphine sulphate samples equilibrated at different water activities. The appearance of a liquid phase in the morphine sulphate at high water activities is discussed on the basis of the obtained differential heats of sorption and measured heat capacities of morphine sulphate at different water activities.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.     

Adsorption behavior of cesium on montmorillonite-type clay in the presence of potassium ions

The adsorption behavior of Cs ions on a montmorillonite-type clay was investigated in the presence of potassium ions, using a radiotracer technique. The initial concentration of K⁺ added to the CsCl was between 10^-4 and 10^-1 mol/l. The addition of K⁺ to the CsCl solution at different concentrations (10^-6-10^-2 mol/l) reduced the amount of Cs⁺ adsorbed on clay. The maximum ratio of Cs⁺ exchanged, calculated from a linearized form of Langmuir plot was in agreement with the ion exchange isotherms of Cs-K ions. Sorption energy evaluated from the graph of corrected selectivity coefficients vs. equivalent fraction of Cs in the solid phase was compared to the energy values obtained from Dubinin-Radushkevich (D-R) isotherms. Freundlich isotherm parameters were used to characterize a site distribution function, which provides information about the affinity ratio of the adsorption sites of Cs⁺ and K⁺ ions. The ion exchange isotherm of Cs-K systems exhibited a Langmuir type curve for all K⁺ concentrations.     

Kinetic exchange studies of metal ion substitution in EDTA chelates Fe(III)- UO2 EDTA exchange

A kinetic study of the exchange reaction between UO₂EDTA complex and Fe(III), at a constant ionic strength of 0.1, over the concentration range of 5×10^–3–1×10^–2 M of each reactant and pH 4.5–5.5 has been carried out radiometrically. The rate of the exchange process can be expressed by the equation: R=k₁[UO₂EDTA][Fe]+k₂[EDTA][H⁺]^–1. The activation parameters calculated were H^*=25.95 kJ mol^–1 and S^*=0.67 kJ mol^–1 K^–1.     

Thermodynamic and kinetic investigations of uranium adsorption on soil

In order to understand the mobility of uranium it is very important to know about its sorption kinetics and the thermodynamics behind the sorption process on soil. In the present study the sorption kinetics of uranium was studied in soil and the influence parameters to the sorption process, such as initial uranium concentration, pH, contact time and temperature were investigated. Distribution coefficient of uranium on soil was measured by laboratory batch method. Experimental isotherms evaluated from the distribution coefficients were fit to Langmuir, Freundlich and Dubinin?CRadushkevich (D?CR) models. The sorption energy for uranium from the D?CR adsorption isotherm was calculated to be 7.07?kJ?mol^?1.The values of ??H and ??S were calculated to be 37.33?kJ?mol^?1 and 162?J?K^?1?mol^?1, respectively. ??G at 30?°C was estimated to be ?11.76?kJ?mol^?1. From sorption kinetics of uranium the reaction rate was calculated to be 1.6?×?10^?3?min^?1.     

Kinetic study of Cr(VI) sorption on MnO2

The kinetics of adsorption of chromate ions has been investigated radiometrically over a wide range of concentration of chromate ions (10^–6–10^–2M) and temperature (303–323 K). The kinetics of the process follows essentially a first order rate law with respect to adsorptive concentration and obeys the Freundlich adsorption isotherm in the concentration range studied. In addition, the kinetics of desorption of the preadsorbed species also follows a first order rate law and the activation energy for desorption is greater than that of the adsorption process. On the basis of an adsorption kinetic study, the thermodynamic parameters have been calculated. Infrared spectroscopy has shown the chemical interaction of chromate ions on the surface of MnO₂.     

Sorption of hafnium on hydrous titanium oxide using radiotracer technique

The sorption of hafnium on hydrous titanium oxide (TiO₂·1.94 H₂O) has been studied in detail. Maximum sorption of hafnium can be achieved from a pH 7 buffer solution containing boric acid and sodium hydroxide using 50 mg of the oxide after 30 minutes shaking. The value ofk _d, the rate constant of intraparticle transport for hafnium sorption, from 0.01M hydrochloric and perchloric acid and pH 7 buffer solutions has been found to be 17 mmole·g^–1·min^–2. The kinetics of hafnium sorption follows Lagergren equation in 0.01M HCl solution only. The values of the overall rate constantK=6.33·10^–2 min^–1 and of the rate constant for sorptionk ₁=6.32·10^–2 min^–1 and desorptionk ₂=2.28·10^–5 min^–1 have been evaluated using linear regression analysis. The value of correlation factor() is 0.9824. The influence of hafnium concentration on its sorption has been examined from 4.55·10^–5 to 9.01·10^–4 M from pH 7 buffer solution. The sorption data followed only the Langmuir sorption isotherm. The saturation capacity of 9.52 mmole·g^–1 and of a constant related to sorption energy have been estimated to be 2917 dm³·mole^–1. Among all the additional anions and cations tested only citrate ions reduce the sorption significantly. Under optimal experimental conditions selected for hafnium sorption, As(III), Sn(V), Co(II), Se(IV) and Eu(III) have shown higher sorption whereas Mn(II), Ag(I) and Sc(III) are sorbed to a lesser extent. It can be concluded that a titanium oxide bed can be used for the preconcentration and removal of hafnium and other metal ions showing higher sorption from their very dilute solutions. The oxide can also be employed for the decontamination of radioactive liquid waste and for pollution abatement studies.     

Radiochemical studies of the sorption behavior of strontium and barium

The sorption behavior of strontium and barium on kaolinite, bentonite and chlorite-illite mixed clay was studied by radioanalytical techniques using the batch method.⁹⁰Sr (29.1 y) and¹³³Ba (10.5 y) were used as radiotracers. Characterization of the solid matrices was done by FTIR and XRD spectrometries and specific surface area measurements. Synthetic groundwater was used as the aqueous phase. The variation of the distribution ratioR _d, as a function of metal ion loading was examined. The sorption isotherms were fitted to various isotherm models. The sorption energies were calculated to be in the range of 8–10 kJ/mol suggesting an ion exchange type of sorption mechanism. In detailed experiments, chlorite-illite mixed clay was first presaturated with K⁺, Sr²⁺, Ca²⁺ and Al³⁺ ions, respectively, prior to sorption studies with Ba²⁺ ions. The results of Ca²⁺ pretreated chlorite-illite were very similar to those of natural chlorite-illite, suggesting that the Ba²⁺ ion exchanges primarily with the Ca²⁺ ion on the clay minerals.     

Distribution coefficients of137Cs and85Sr by mixtures of clay and humic material

Distribution coefficients K_d for the sorption of Cs and Sr on mixtures of a clay mineral (Ca-saturated bentonite) and humic material (Ca-humate) have been measured and were compared with calculated values obtained from the K_d-values observed for the pure components. The concentration of Sr and Cs in the solution was varied between 1·10^–6 and 0.01N and the distribution of the elements determined by using radioactive tracers. All experiments were carried out in pure water as well as in the presence of a supporting electrolyte (0.01N CaCl₂). It was found that the differences between the observed and calculated K_d-values were, if present, always negative if Cs was sorbed, and positive if Sr was sorbed.