Sorption Characteristics of Radioeuropium on Bentonite and Kaolinite

The factors affecting the sorption of radioeuropium(III) by bentonite and kaolinite were studied with the aim to assess the important factors which should be included in modeling of radioeuropium(III) migration in soils and sediments. Europium(III) is an analogue of trivalent actinides. The distribution coefficients of radioeuropium for sorption on bentonite and kaolinite from aqueous solutions were determined by using the batch method, and it was found that they were sensitive to the loading, the pH, the humic substance and the sorption direction. Thus, these sorption characteristics of radioeuropium on bentonite and kaolinite were found to be different from those of radiocobalt¹, and the mathematical modeling of trivalent lanthanides and actinides migration will be more complicated than that of radiocobalt. It is improbable that the migration modeling with a constant distribution coefficient will be successful in the case of trivalent lanthanides and actinides.     

Removal of radiocobalt from aqueous solutions by kaolinite affected by solid content, pH, ionic strength, contact time and temperature

The kaolinite sample was characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray powder diffraction, and was applied as adsorbent for the removal of radiocobalt ions from radioactive wastewater. The results demonstrated that the sorption of Co(II) was strongly dependent on pH and ionic strength at low pH values, and independent of pH and ionic strength at high pH values. The sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange at low pH values, whereas inner-sphere surface complexation was the main sorption mechanism at high pH values. The sorption isotherms were well described by Langmuir, Freundlich and Dubinin–Radushkevich models. The thermodynamic parameters (i.e., ΔG°, ΔS°, ΔH°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on kaolinite was an endothermic and spontaneous process. The results of high sorption capacity of kaolinite suggested that the kaolinite sample was a suitable material for the preconcentration of Co(II) from large volumes of aqueous solutions and as backfill materials in nuclear waste management.     

Factors affecting interaction of radiocobalt with river sediments

The paper aims at the analysis of principal factors affecting interaction of radiocobalt with freshwater solids, important for migration of radiocobalt in surface streams. Uptake and release of radiocobalt by sediment from a small river have been studied as a function of pH and composition of aqueous phase, the cobalt concentration and contact time, using laboratory model experiments. A factor of primary importance is the contact time due to slow and two-step kinetics of radiocobalt uptake, which also strongly depends on the concentration of sediment in suspension. pH exerts the most significant effect on the interaction in the pH region of 5–7.5, where the uptake increases with pH. Ionic strength of water phase (I) and concentration of cobalt in water (c) affect the interaction only at rather high values of I or c and their variation can be neglected in the modelling of radiocobalt transport in streams under ordinary conditions. Desorption by river water of radiocobalt pre-adsorbed on the sediment passes through a maximum with desorption time, decreases with increasing adsorption time and increases upon drying of the sediment prior to desorption. Results obtained are compared with literature data and conclusions are drawn concerning the mechanism of radiocobalt uptake by the sediment.     

Comparison of Linear and Nonlinear Forms of Isotherm Models for Strontium Sorption on a Sodium Bentonite

Sorption on bentonite will play an important role in retarding the migration of radionuclides from a waste repository. Bentonite is characterized by low permeability, water swelling capability and excellent sorption potential for cationic radionuclides. To correctly assess the sorption potential of radionuclides on bentonite is essential for the development of predictive migration models. The sorption isotherm model is usually used to describe the sorption behavior and assess the sorption potential of radionuclides on bentonite. However, there are few studies to investigate the feasibility of isotherm models for the sorption of radionuclides on bentonite. Thus, in this study, we compared the goodness-of-fit of linear and nonlinear forms of two common isotherm models, Langmuir and Freundlich equations. The experimental sorption isotherms of strontium (Sr) on Wyoming bentonite, MX-80, were used for illustration. The results showed that the nonlinear forms of Langmuir and Freundlich isotherm models are more suitable for fitting the experimental sorption isotherms of Sr on MX-80 than are the linear forms. Thus, the nonlinear forms of isotherm models should be primarily adopted to fit experimental isotherms. On the other hand, we also found that the goodness-of-fit of Langmuir model is better than that of Freundlich model. Moreover, based on the theoretical assumptions of Langmuir isotherm model, the parameters M and K _L represent the sorption capacity and affinity, respectively. One can use the values of M and K _L , obtained from fitting the experimental isotherms, to assess the sorption potential of radionuclides in bentonite. Thus, we suggested that the Langmuir isotherm model is more useful for investigating the sorption behavior of radionuclides on bentonite.     

Sorption characteristics of137Cs onto clay minerals: Effect of mineral structure and ionic strength

The sorption behavior of¹³⁷Cs onto kaolinite, bentonite, illite, and zeolite was studied at different ionic strengths of Na⁺, K⁺, Ca²⁺. A significant effect of ionic strengths on the sorption has been observed. Clay minerals with 21 structure (bentonite, illite) showed much higher sorption than that of 11 structure (kaolinite). Zeolite showed high selectivity for¹³⁷Cs sorption. Sorption behavior of¹³⁷Cs on clay minerals can be explained by their surface charge characteristics originated from mineral structure.     

Modeling of radionickel sorption on MX-80 bentonite as a function of pH and ionic strength

MX-80 bentonite was detected using acid-based titration, XRD and FTIR in detail. The sorption behavior of 63Ni(Ⅱ) from aqueous solution to MX-80 bentonite was investigated as a function of solid content, ionic strength and pH by using batch technique. The experimental data of 63Ni(Ⅱ) sorption on MX-80 bentonite was obtained using the diffuse layer model (DLM) with the aid of FITEQL 3.1 program. The results indicated that the sorption of 63Ni(Ⅱ) on MX-80 bentonite was mainly dominated by surface complexation...     

Partitioning of clay colloids at air-water interfaces

Colloid sorption onto air-water interfaces in a variety of natural environments has been previously recognized, but better quantification and understanding is still needed. Affinities of clay colloids for the air-water interface were measured using a bubble-column method and reported as partition coefficients (K). Four types of dilute clay suspensions were measured in NaCl solutions under varying pH and ionic strength conditions: kaolinite KGa-1, illite IMt-2, montmorillonite SWy-2, and bentonite. The K values of three types of polystyrene latex particles with different surface-charge properties were also measured for comparison. Kaolinite exhibited extremely high affinity to the air-water interface at pH values below 7. Illite has lower affinity to air-water interfaces than kaolinite, but has similar pH dependence. Na-montmorillonite and bentonite clay were found excluded from the air-water interface at any given pH and ionic strength. Positively and negatively charged latex particles exhibited sorption and exclusion, respectively, at the air-water interface. These results show the importance of electrostatic interactions between the air-water interface and colloids, especially the influence of pH-dependent edge charges, and influence of particle shape.     

Sorption and desorption of radiostrontium on powdered bentonite: Effect of pH and fulvic acid

The effect of pH and fulvic acid on the sorption of Sr on bentonite was investigated by using batch experiments. The sorption and desorption isotherms of Sr on bentonite were determined at room temperature, at pH 6.0±0.2 and in presence of 0.1M NaCl. It was found that the sorption of Sr is independent at pH<8, and then increases slightly with increasing pH. Fulvic acid increases the sorption of Sr significantly on bentonite at low pH, but decreases the sorption of Sr at pH>8. The sorption of Sr on bentonite can be described by a reversible sorption process and the sorption mechanism consists mainly of ion exchange. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparative study on sorption of radiocobalt to montmorillonite and its Al-pillared and cross-linked samples: Effect of pH,ionic strength and fulvic acid

Effects of pH, ionic strength and fulvic acid on sorption of radiocobalt on montmorillonite and its Al-pillared and cross-linked samples were studied using batch technique. The results indicate that the sorption of cobalt is strongly dependent on pH values and independent of ionic strength. Fulvic acid enhances the sorption of cobalt slightly at low pH, but has no influence at high pH values. Surface complexation is considered the main mechanism of cobalt sorption to montmorillonite. The sequences of FA/Co²⁺ additions to the system did not affect cobalt sorption.     

Sorption of Eu(III) onto Gaomiaozi bentonite by batch technique as a function of pH, ionic strength, and humic acid

The bentonite from Gaomiaozi county (Inner Mongolia, China) (denoted as GMZ bentonite) was characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The effect of pH, contact time, ionic strength, humic acid (HA) and Eu(III) concentrations on Eu(III) sorption to the GMZ bentonite was studied by batch technique under ambient conditions. The sorption of Eu(III) on GMZ bentonite was strongly dependent on pH and independent of ionic strength. The sorption of Eu(III) on GMZ bentonite was mainly dominated by surface complexation rather than by ion exchange. The presence of HA enhanced Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. The enhanced sorption of Eu(III) on GMZ bentonite at low pH was attributed to the strong complexation of Eu(III) with surface adsorbed HA on GMZ bentonite and the reduced sorption of Eu(III) at high pH was attributed to the formation of soluble HA–Eu complexes in aqueous solution. The strong sorption of Eu(III) on GMZ bentonite suggested that the GMZ bentonite could be used as the backfill material in nuclear waste disposal.     

Physicochemical characterization of the retardation of aqueous Cs+ ions by natural kaolinite and clinoptilolite minerals

The aim of this study was to carry out kinetic, thermodynamic, and surface characterization of the sorption of Cs+ ions on natural minerals of kaolinite and clinoptilolite. The results showed that sorption followed pseudo-second-order kinetics. The activation energies were 9.5 and 13.9 kJ/mol for Cs+ sorption on kaolinite and clinoptilolite, respectively. Experiments performed at four different initial concentrations of the ion revealed that the percentage sorption of Cs+ on clinoptilolite ranged from 90 to 95, compared to 28 to 40 for the kaolinite case. At the end of a 1 week period, the percentage of Cs+ desorption from clinoptilolite did not exceed 7%, while it amounted to more than 30% in kaolinite, indicating more stable fixation by clinoptilolite. The sorption data were best described using Freundlich and D-R isotherm models. Sorption showed spontaneous and exothermic behavior on both minerals, with deltaH(0) being -6.3 and -11.4 kJ/mol for Cs+ uptake by kaolinite and clinoptilolite, respectively. Expanding the kaolinite interlayer space from 0.71 to 1.12 nm using DMSO intercalation, did not yield a significant enhancement in the sorption capacity of kaolinite, indicating that the surface and edge sites of the clay are more energetically favored. EDS mapping and elemental analysis of the surface of kaolinite and clinoptilolite revealed more intense signals on the surface of the latter with an even distribution of sorbed Cs+ onto the surfaces of both minerals.     

蒙脱土和高岭土对Pb2+的吸附

选择带结构负电荷的蒙脱土和带微量结构负电荷的高岭土,研究了其对Pb2+的吸附性能,并探讨了吸附机理。 研究表明,蒙脱土和高岭土吸附Pb2+的动力学曲线符合准二级动力学方程,吸附等温线符合Langmuir方程。 Pb2+同时以内层络合和外层配合形式吸附,其相对量与pH值有关。 在pH值小于4和大于8的范围内,以内层配合物为主;而pH值在4～8范围内外层配合物比例增大。 Pb2+能进入蒙脱土的层间,而不能进入高岭土的层间;部分Pb2+可进入黏土颗粒的微孔中被固定。 蒙脱土对Pb2+的吸附能力和饱和吸附量明显高于高岭土。     

Preliminary selection of clay minerals for the removal of pharmaceuticals,bisphenol A and triclosan in acidic and neutral aqueous solutions

Pharmaceuticals, personal care products and endocrine disruptors demonstrate huge potential to cause adverse ecological health effects at very low concentration in aquatic environment. There is a need to improve current purification technologies used in sewage and drinking-water treatment plants. This article aims at providing new insights into the recent development of natural and modified clay-based sorbents for the removal of aqueous contaminants such as pharmaceuticals and personal care products. The removal of six widely used pharmaceuticals: ibuprofen, diclofenac, ketoprofen, carbamazepine, as well as endocrine disrupting chemicals – bisphenol A and a bactericidal agent, triclosan – was examined by sorption onto eight adsorbents. Sorption was performed using natural and modified clay minerals – montmorillonite (Mt), vermiculite (VER), bentonite (B), kaolinite (K), commercial acid activated montmorillonites K10 and K30, and two carbonaceous-mineral nanocomposites, MtG5%T, BAlG3%C. This study showed that among the tested natural clays, vermiculite is the most promising sorbent for the removal of pharmaceuticals in purification processes. Among the modified clay minerals, the best results were achieved for carbonaceous bentonite and two acid activated montmorillonites K10 and K30. However, the removal of acidic pharmaceuticals on montomorillonite K10 and carbonaceous bentonite was strongly dependent on the pH value. In the case of vermiculite and acid-modified montmorillonite K30, the sorption of the selected compounds was not significantly affected by pH, which is crucial in wastewater treatment. The sorption constant divided by the specific surface area (K_d/A) is proposed to assess whether the surface area or chemical properties of the materials control the sorption process. K_d/A values were relatively high in the case of vermiculite, so it should be noticed that individual and specific surface properties of vermiculite were of crucial importance for sorption.     

Thermal behavior and immersion heats of selected clays from Turkey

Four clays (two bentonites and two kaolinites) from Turkey were investigated by X-ray diffraction (XRD), thermal analysis (DTA/TG-DSC) and surface area measurement techniques. Mineralogically bentonite samples were characterized low concentration of montmorillonite and high level of impurities. Both kaolinite samples mainly contained kaolinite and quartz as major mineral. TG-DTA curves of all clay samples were measured in the temperature range 30–1200 °C. The total % weight losses for the bentonite samples (B1 and B2) and the kaolinite samples (K1 and K2) were determined as 14.50, 13.42, 5.55 and 11.85%, respectively. Differential Scanning Calorimeter (DSC) analyses of samples were carried out by heating the samples from 30 to 550 °C. The immersion heats of clay samples were measured using with a Calvet-type C-80 calorimeter. The higher exothermic Q_imm values were determined for bentonite samples compared to kaolinite samples.     

U(VI) sorption on kaolinite: effects of pH,U(VI) concentration and oxyanions

U(VI) sorption on kaolinite was studied as functions of contact time, pH, U(VI) concentration, solid-to-liquid ratio (m/V) by using a batch experimental method. The effects of sulfate and phosphate on U(VI) sorption were also investigated. It was found that the sorption kinetics of U(VI) can be described by a pseudo-second-order model. Potentiometric titrations at variable ionic strengths indicated that the titration curves of kaolinite were not sensitive to ionic strength, and that the pH of the zero net proton charge (pH_PZNPC) was at 6.9. The sorption of U(VI) on kaolinite increased with pH up to 6.5 and reached a plateau at pH >6.5. The presence of phosphate strongly increased U(VI) sorption especially at pH <5.5, which may be due to formation of ternary surface complexes involving phosphate. In contrast, the presence of sulfate did not cause any apparent effect on U(VI) sorption. A double layer model was used to interpret both results of potentiometric titrations and U(VI) sorption on kaolinite.     

Removal of radiocobalt form aqueous solutions by inorganic exchangers

The sorption of radiocobalt from aqueous as well as organic solvents by natural and treated clays has been investigated. The effect of many factors, such as time, pH, carrier concentration, etc., were studied. In was found that the uptake is maximum in neutral, or slightly alkaline solutions. The rate of sorption depends on the velocity of shaking, which may indicate the operation of the film-diffusion mechanism, in addition to some contribution from particle-diffusion mechanism, but the dependence of the rate on shaking velocity could be attributed to an increase in the surface area of the clays. The conclusion is that natural clays are well suited for the removal of radioactive cobalt with slight, if any modification. These clays may be considered superior to synthetic exchangers for the removal of⁶⁰Co, if the availibility and prices of the former are taken into account.     

Application of simplified desorption method to study on sorption of americium(III) on bentonite

To elucidate the sorption behavior of americium(III) on bentonite, which is a mixture of montmorillonite clay, quartz and other minerals, simplified desorption experiments were applied to the solid phases collected after the sorption experiments. The sorption–desorption behavior was examined in the final pH range from 2 to 8. The desorption experiments revealed that most of the Am was sorbed on the montmorillonite moiety of the bentonite. The sorption of Am on montmorillonite was divided into two types: one was the “exchangeable” sorption, in which the sorbed Am was desorbed with a 1 M KCl aqueous solution, and the rest was the “unexchangeable” sorption. The exchangeable sorption was ion exchange of mostly Am³⁺. The unexchangeable sorption was the strong sorption of Am hydroxides. An accessory iron mineral, pyrite, might be involved in the Am sorption on bentonite at neutral pH.     

Investigation of sequestration mechanisms of radionuclide 63Ni(II) on kaolinite in aqueous solutions

To better understand the application of kaolinite as an adsorbent for the decontamination of Ni(II) from radionuclide contaminated aqueous systems, herein, the sorption behavior of radionuclide ⁶³Ni(II) on kaolinite as a function of contacting time, pH, coexistent electrolyte ions, adsorbent concentration, fulvic acid and humic acid was investigated using batch technique. At low pH values, ion exchange and/or outer-sphere surface complexation was the main mechanism of Ni(II) sorption on kaolinite, whereas, the sorption of Ni(II) was dominated by inner-sphere surface complexation at high pH values. The presence of different electrolyte ions can enhance or inhibit the sorption of Ni(II) on kaolinite to some extent. The Langmuir and Freundlich models were used to simulate the sorption isotherms of Ni(II) at three different temperatures of 288, 313 and 338 K. The thermodynamic parameters (i.e., ΔS°, ΔH°, and ΔG°) calculated from the temperature-dependent sorption isotherms indicated that the sorption reaction of Ni(II) on kaolinite was endothermic and spontaneous. The findings in this present study demonstrates that the kaolinite can be used as a cost-effective adsorbent for the solidification and pre-concentration of Ni(II) from large volumes of aqueous systems.     

Sorption and diffusion of 90Sr2+in compacted bentonite investigated by a capillary method

Summary The effects of bentonite density and fulvic acid on the sorption and diffusion of ⁹⁰Sr²⁺in compacted bentonite were investigated by using a capillary method. The experiments were carried out at pH 7.0±0.1 in the presence of 0.01M NaClO₄. The results suggest that the sorption and diffusion of ⁹⁰Sr²⁺in compacted bentonite decreases with increasing the density of compacted bentonite. The presence of FA enhances the sorption of Sr²⁺, but reduces the diffusion of Sr²⁺in compacted bentonite. The porosity of the compacted bentonite plays an important role in the sorption and diffusion behavior of ⁹⁰Sr²⁺. Using the calculated effective diffusion coefficients the long-term relative concentration distribution of strontium was evaluated in compacted bentonite.     

Characterization of MX-80 bentonite and its sorption of radionickel in the presence of humic and fulvic acids

MX-80 bentonite is considered as one of the best backfill materials for high-level radioactive nuclear waste. Herein, the bentonite is characterized by using XRD and FTIR techniques. Sorption of radionickel to MX-80 bentonite in the presence/absence of humic acid (HA) or fulvic acid (FA) as a function of pH is investigated. The results indicate that the presence of HA or FA decreases the sorption of Ni²⁺ obviously. The different experimental processes do not affect the sorption of nickel to FA/HA bound bentonite. The sorption of Ni²⁺ on FA/HA-bound bentonite decreases with the increasing FA/HA content in the systems. The mechanism of nickel sorption is also discussed in detail.