Synthesis and application of a highly efficient tetraester calix[4]arene based resin for the removal of Pb from aqueous environment

The present study describes the Pb²⁺ sorption potential of newly synthesized tetraester calix[4]arene (TC4) based resin from aqueous media. The TC4 resin was synthesized through diazotization reaction of TC4 with Amberlite XAD-4 in the presence of sodium nitrite in acidic medium. The TC4 resin was characterized by using different analytical techniques such as FT-IR, elemental analysis and scanning electron microscopy (SEM). The Pb²⁺ removal ability of the resin from the aqueous environment has been evaluated by both batch adsorption as well as column studies. The experiments have been conducted involving the determination of effect of pH, adsorbate concentration, adsorbent dosage, contact time and temperature. Moreover, on the basis of kinetic studies, the pseudo-first-order and pseudo-second-order adsorption kinetics were calculated. The thermodynamic parameters of lead adsorption were also calculated. Equation isotherms such as Langmuir (L), Freundlich (F), and Dubinin-Radushkevich (D-R) were successfully used to model the experimental data. From the D-R isotherm parameters, it was considered that the uptake of Pb²⁺ by TC4 resin is ion exchange mechanism. From the results it has been found that the TC4 resin is a versatile adsorbent for the removal of Pb²⁺ from the aqueous environment. The study also confers its impact on human health, reinstate of polluted sites and other fields of material science.     

Efficiency of Acacia Gummifera powder as biosorbent for simultaneous decontamination of water polluted with metals

Biosorbent materials represent an interesting alternative to classic methods of metal removal from industrial effluents. Acacia biomass showed a higher absorption capacity for heavy metals than living biomass. This study aimed to evaluate the bioadsorption of Lead and Cadmium onto Acacia Gummifera gum, using batch experiment. The structural characterization of the biosorbent was carried out using FT-IR, SEM, BET, TGA and DSC analysis. The adsorption equilibrium was reached within 15 min. A maximum uptake of 18.3 mg.g⁻¹ Pb²⁺ and 9.57 mg.g⁻¹ Cd²⁺ was achieved at pH 6.5. The metal ions seemed to be removed exclusively by ion exchange, physical sorption and chelation. The biomass of A. Gummifera powder was found to be effective for lead and cadmium removal with respectively 97% and 86% sorption efficiency at a concentration of 100 mg/L, in aqueous media. Parameters affecting adsorption capacities such as biosorbent dosage, initial metal concentration, temperature, and pH are discussed in detail. Furthermore, adsorption thermodynamics, kinetics, and equilibrium were studied and fitted by different models. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms were used to compare adsorption data at equilibrium. The adsorption kinetics data were found to be best fitted by the pseudo-second-order model, and the adsorption isotherm was well fitted with the Langmuir model. The calculated thermodynamic parameters (ΔG⁰, ΔS⁰ and ΔH⁰) indicated a spontaneous and exothermic biosorption of both metal ions onto Acacia Gummifera. Moreover, chromatograms obtained by size exclusion chromatography coupled with multi-angle laser light scattering detection system (SECMALLS) showed the formation of complexes between the arabinogalactan-peptide (AGP) and glycoprotein (GP) Acacia moieties and the two studied metal ions. The analysis of the FTIR spectra of dried Acacia and that of Acacia loaded with lead and cadmium in aqueous media suggests that the surface functional groups such as amides and carboxy groups might be involved in the metal removal process.The extent of adsorption for both metals increased along with an increase of the A. Gummifera biomass dosage. A. Gummifera biomass, which is safe, of low-cost, and highly selective, seems therefore to be a promising substrate for simultaneous trapping of Pd and Cd ions in aqueous solutions.     

A comparative study of microwave and chemically treated Acacia nilotica leaf as an eco friendly adsorbent for the removal of rhodamine B dye from aqueous solution

The use of cheap and eco friendly adsorbents prepared from freely and abundantly available Acacia nilotica leaves have been investigated by batch methods. Microwave treated A. nilotica leaves (MVM) are more effective than chemically treated A. nilotica leaves (CVM) for the removal of rhodamine B (RH B) from aqueous solution. The effect of initial pH, contact time and initial dye concentration of RH B onto CVM and MVM has been investigated. The applicability of the linear form of Langmuir model to CVM and MVM was proved by the high correlation coefficients R² = 0.9413 and 0.9681 for RH B adsorption. The R² values were greater than 0.994 for all RH B concentrations, which indicates the applicability of the pseudo-second-order kinetic model. The recycling ability of MVM is greater than CVM. The preparation of MVM does not require an additional chemical treatment step and it attains rapid equilibrium. Hence it is agreeing with the principles of green chemistry and less time is required to possess high adsorption of RH B. Therefore, the eco friendly adsorbent MVM is expected to be environmentally and economically feasible for the removal of RH B from aqueous solutions.     

Interaction between tetracycline and smectite in aqueous solution

The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d₀₀₁ spacing. The TC adsorption capacity was equivalent to 0.74–1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H⁺, resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H⁺ resulted in the ratio of H⁺ adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H⁺ could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H⁺ adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.     

Insight from adsorption properties of Xylidyl Blue embedded hydrogel for effective removal of uranyl: Experimental and theoretical approaches

Applications of a hybrid material consisting of polyacrylamide (PAA) and Xylidyl Blue (XB) for the removal of uranyl ions from aqueous solutions has been investigated with all details. Adsorption experiments were performed at batch mode and constant temperature. Experimental parameters affecting adsorption process such as pH, initial uranyl concentration, time and temperature were studied on the removal of the uranyl ions. The isotherms assays were carried out with synthetic solutions and adsorption data were evaluated by using Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Morphological and chemical characterizations of new synthesized material were investigated by UV-VIS-NIR spectroscopy and SEM/EDX techniques and pH_pzc experiments. The results of the kinetic experiments are consistent with pseudo-second-order models and intra-particle diffusion models with a slightly better fit to the latter. Equilibrium was achieved within 3 h. The value of rate constant for adsorption process was calculated as 1.055 mol⁻¹ kg min⁻¹ at 318 K. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) indicated that the adsorption of uranyl ions onto XB@PAA was feasible, spontaneous and endothermic nature under the studied temperature. The developed material has also a potential as a sensor because its color turn from pink to red by adsorption of uranyl ions.     

Development of hybrid adsorbent for effective aqueous phase sorptive removal of copper

Alginate beads (ABs) immobilized with hydrous zirconium oxide (ZO) were used as a hybrid adsorbent (ZO@AB) for the effective removal of copper ions [Cu(II)] from aqueous phase. ZO@AB was characterized using X‐ray photoelectron spectroscopy to confirm the impregnation of ABs with ZO and the adsorption of Cu(II) onto ZO@AB. The maximum equilibrium sorption capacity of ZO@AB for Cu(II) was 63.1 mg·g⁻¹ at pH 5. The Cu(II) removal rate was high at the beginning of reaction, with >90% adsorption within 24 hours, and equilibrium was achieved within 48 hours. The adsorption of Cu(II) onto ZO@AB was well described by pseudo‐second‐order kinetic model (R² > 0.99), and the monolayer nature of sorption was supported by the Langmuir model (R² > 0.99). The sorption process was endothermic, favorable, and spontaneous in nature. Regarding the reusability of the adsorbent, its sorption capacity remained satisfactory (>90%) throughout the 5 consecutive cycles (regeneration in 0.1 mol·L⁻¹ HCl). The stoichiometric ratio of released calcium ions [Ca(II)] to adsorbed copper ions [Cu(II)] was approximately 1:1, confirming that ion exchange was the main mechanism for removal of Cu(II) from aqueous phase. The developed adsorbent (ZO@AB) shows promise as a candidate for the effective and selective removal of Cu(II) from aqueous phase.     

Evaluation of Acacia nilotica as a non conventional low cost biosorbent for the elimination of Pb(II) and Cd(II) ions from aqueous solutions

In the present study a biomass derived from the leaves of Acacia nilotica was used as an adsorbent material for the removal of cadmium and lead from aqueous solution. The effect of various operating variables, viz., adsorbent dosage, contact time, pH and temperature on the removal of cadmium and lead has been studied. Maximum adsorption of cadmium and lead arises at a concentration of 2 g/50 ml and 3 g/50 ml and at a pH value of 5 and 4, respectively. The sorption data favored the pseudo-second-order kinetic model. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were applied to describe the biosorption isotherm of the metal ions by A. nilotica biomass. Based on regression coefficient, the equilibrium data found were fitted well to the Langmuir equilibrium model than other models. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) have been calculated, respectively revealed the spontaneous, endothermic and feasible nature of adsorption process. The activation energy of the biosorption (Ea) was estimated as 9.34 kJ mol⁻¹ for Pb and 3.47 kJ mol⁻¹ for Cd from Arrhenius plot at different temperatures.     

Development and tailoring of amino-functionalized activated carbon based Cucumerupsi manni Naudin seed shells for the removal of nitrate ions from aqueous solution

The removal of nitrate ions with ethylenediamine (EDA)-functionalized activated carbon (AC-NH₂) was studied in this work. Activated carbon prepared from Cucumerupsi manni Naudin seed shells using ZnCl₂ (ACZ) was functionalized with EDA via a nitric acid oxidation followed by acyl chlorination and amidation process. The effect of pH, contact time, initial concentration and co-existing ions on the adsorption of nitrate ions have been investigated. The FTIR and elemental analysis revealed that amino groups were successfully grafted onto the ACZ after functionalization. The surface area and average pore of ACZ were found to be 1008.99 m²/g and 2.02 nm respectively. However, it was noticed that, after functionalization (AC-NH₂), its surface area decreases to 113.43 m²/g meanwhile, its pore diameter increases to 2.48 nm. The experimental results of adsorption showed that AC-NH₂ exhibit excellent nitrate ions uptake performance compared to ACZ which is attributed to the presence of the grafted amino groups on the ACZ. Nitrate adsorption follows pseudo-first-order kinetic model while the equilibrium adsorption data was best fitted the Freundlich isotherm suggesting that the adsorption process was predominated by physisorption. This study demonstrates that the prepared AC-NH₂ is a promising adsorbent for nitrate ions removal from aqueous media.     

Analysis of the role of various biochar in the remediation of heavy metals in contaminated water and its kinetics study

Biochar prepared from agricultural wastes has gained great attention as a cost-effective treatment for metal-contaminated water. In this study, the effectiveness of corn cob and sugarcane bagasse-derived biochar for metals (Pb, Ni, and Cu) removal from an aqueous medium was examined following their physical, chemical, and structural characterization. Batch sorption experiments were carried out by employing the Langmuir and Freundlich equations. The results indicated that separation factor (R_L) values lay in the range of 0 and 1 representing the productive adsorption. The optimum dosage for metal adsorption can be recommended as 30 g L^?1. The optimum adsorption conditions were found at 6.5 and 5.5 pH, 1.5 g adsorbent dose, and at 180 min equilibrium time, for both corn cob and sugarcane bagasse biochars. At pH 6.5, adsorption capacities of Pb, Ni, and Cu were found maximum i.e., 11.34, 15.71, and 11.96 mg kg^?1 for corn cob and 8.96, 15.46, and 12 mg kg^?1, for sugarcane bagasse biochars, respectively. The metal adsorption kinetics was analyzed via four different types of the pseudo-second-order kinetic model. Moreover, the corn cob biochar showed a more pronounced activity in the removal of metals compared to sugarcane bagasse biochar. Hence, it was concluded that corncob and sugarcane bagasse-derived biochars could be utilized as economical bio-adsorbents for the heavy metals removal from wastewater.     

Preparation of Quercus mongolica leaf-derived porous carbon with a large specific surface area for highly effective removal of dye and antibiotic from water

Quercus mongolica leaf (QL), an easily available biomass, was used as the precursor for preparing the hierarchical porous carbon with a large specific surface area and high adsorption capacities toward the representative dye and antibiotic. After being carbonized, QL was further chemically activated, and potassium hydroxide was proved to be a better activator than sodium hydroxide. The QL-derived porous carbon (PCQL) exhibited abundant micro- and mesopores, and the specific surface area reached 3275 m² g^?1. The performances of PCQL were evaluated through adsorbing rhodamine B (RhB) and tetracycline hydrochloride (TC) from water. Four adsorption isotherm models (the Langmuir, Freundlich, Sips, and Redlich-Peterson models), three adsorption kinetic models (the pseudo-first-order, pseudo-second-order, and intra-particle diffusion models), and the thermodynamic equations were used to investigate the adsorption processes. The pseudo-second-order kinetic model and the Sips isotherm model fitted the experimental data well, which indicates that the adsorption processes were controlled by the amount of adsorption active sites on the surface of PCQL, and these adsorption active sites had different affinities for the adsorbates. The maximum adsorption capacities of PCQL toward RhB and TC were 1946.0 and 1479.6 mg g^?1, respectively, based on the Sips model. The thermodynamic analysis indicates that the adsorption of PCQL toward adsorbents was spontaneous physical processes accompanied by the increasing disorder degree. The adsorption mechanism was attributed to the combination of the pore-filling, hydrogen bond, and π-π interactions. Moreover, in the fixed-bed experiments, the Yoon-Nelson model fitted the breakthrough curves well, and about 8 L wastewater containing RhB (200 mg L^?1) may be effectively treated by 1.0 g of PCQL. Above results indicate that QL is a promising precursor for preparing functional porous carbon materials.     

Raw and treated marble wastes reuse as low cost materials for phosphorus removal from aqueous solutions: Efficiencies and mechanisms

Phosphorus removal from synthetic solutions by raw and calcined powdered marble wastes (RPMW and CPMW) has been investigated in batch mode under different experimental conditions. The results showed that RPMW and CPMW have high removal efficiencies, especially in acidic media. The maximum phosphorus removal capacities were evaluated to 103.9 and 181.2 mg·g⁻¹ at an initial pH and an aqueous concentration of 5 and 350 mg·L⁻¹, respectively. Phosphorus removal by RPMW occurred mainly through adsorption. However, for CPMW, phosphorus was removed not only by adsorption, but also by precipitation as calcium phosphate complexes. Specific analyses using scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy confirmed that this precipitate is most probably hydroxyapatite. On the other hand, CPMW have demonstrated an important ability in removing phosphorus from highly concentrated dairy wastewater (C_0,P = 1000 mg·L⁻¹) since only one dosage of 10 g·L⁻¹ was enough to ensure more than 97% of phosphorus removal.     

Evaluation of CO2 adsorption capacity of solid sorbents

The CO₂ adsorption capacity of the low-cost solid sorbents of waste tire char (TC) and chicken waste char (CW) was compared with commercial active carbon (AC) and 5 ? zeolite (ZA) using thermogravimetric analysis (TG), pressurized TG, and differential scanning calorimetry (DSC). The sorbents were degassed in a TG up to 150 °C to release all gases on the surface of the sample, then cooled down to the designed temperature for adsorption. TG results indicated that the CO₂ adsorption capacity of TC was higher than that of CW, but lower than those of AC and ZA. The maximum adsorption rate of TC at 50 °C was 0.61% min⁻¹, lower than that of AC, but higher than that of CW, 0.44% min⁻¹. The maximum adsorption rate of ZA at 50 °C was 3.1% min⁻¹. When the pressure was over 4 bar, the adsorption rate of ZA was lower than that of TC and AC. At 30 bar, the total CO₂ uptake of TC was 20 wt%, higher than that of CW and ZA but lower than that of AC. The temperature, nitrogen concentration, and water content also influenced the CO₂ adsorption capacity of sorbents to some extent. DSC results showed that adsorption was an exothermic process. The heat of CO₂ adsorption per mole of CO₂ of TC at 50 °C was 24 kJ mol⁻¹ while the ZA had the largest heat of adsorption at 38 kJ mol⁻¹. Comparing the characteristics of TC and CW, TC may be a promising sorbent for removal of CO₂.     

Iron-modified light expanded clay aggregates for the removal of arsenic(V) from groundwater

Iron modified materials have been proposed as a filter medium to remove arsenic compounds from groundwater. This research investigated the removal of arsenate, As(V) from aqueous solutions by iron-coated light expanded clay aggregates (Fe-LECA). Arsenic is effectively adsorbed by Fe-LECA in the optimum pH range 6-7 by using a 10 mg mL^− 1 adsorbent dose. Kinetics experiments were performed to investigate the adsorption mechanisms. Electrostatic attraction and surface complexation were proposed to be the major arsenic removal mechanisms. The experimental data fitted the pseudo-first-order equation of Lagergren. For an arsenic concentration of 1 mg L^− 1, the rate constant (k₁) of pseudo-first-order was 0.098 min^− 1, representing a rapid adsorption in order to reach equilibrium early. Equilibrium sorption isotherms were constructed from batch sorption experiments and the data was best described by the Langmuir isotherm model. Large scale column experiments were conducted under different bed depths, flow rates, coating duration and initial iron salts concentration to determine the optimal arsenic removal efficiency by Fe-LECA column. Volumetric design as well as higher hydraulic detention time was proposed to optimize the efficiency of the column to remove arsenic. In addition, concentrated iron salts and longer coating duration were also found to be crucial parameters for arsenic removal. The maximum arsenic accumulation was 3.31 mg of As g^− 1 of Fe-LECA when the column was operated at a flow rate of 10 mL min^− 1 and the LECA was coated with 0.1 M FeCl₃ suspension for a 24 h coating duration.     

Quartzite an efficient adsorbent for the removal of anionic and cationic dyes from aqueous solutions

Quartzite obtained from local source was investigated for the removal of anionic dye congo red (CR) and cationic dye malachite green (MG) as an adsorbent from aqueous solution in batch experiment. The adsorption process was studied as a function of dye concentration, contact time, pH and temperature. Adsorption process was described well by Langmuir and Freundlich isotherms. The adsorption capacity remained 666.7 mg/g for CR dye and 348.125 mg/g for MG dye. Data was analyzed thermodynamically, ΔH⁰ and ΔG⁰ values proved that adsorption of CR and MG is an endothermic and spontaneous process. Adsorption data fitted best in the pseudo-first order kinetic model. The adsorption data proved that quartzite exhibits the best adsorption capacity and can be utilized for the removal of anionic and cationic dyes.     

Optimization of cadmium adsorption from aqueous solutions by functionalized graphene and the reversible magnetic recovery of the adsorbent using response surface methodology

Novel functionalized graphene adsorbent was prepared and characterized using different techniques. The prepared adsorbent was applied for the removal of cadmium ions from aqueous solution. A response surface methodology was used to evaluate the simple and combined effects of the various parameters, including adsorbent dosage, pH, and initial concentration. Under the optimal conditions, the cadmium removal performance of 70% was achieved. A good agreement between experimental and predicted data in this study was observed. The experimental results revealed of cadmium adsorption with high linearity follow Langmuir isotherm model with maximum adsorption capacity of 502 mg g^?1, and the adsorption data fitted well into pseudo‐second order model. Thermodynamic studies showed that adsorption process has exothermic and spontaneous nature. The recommended optimum conditions are: cadmium concentration of 970 mg L^?1, adsorbent dosage of 1 g L^?1, pH of 6.18, and T = 25 °C. The magnetic recovery of the adsorbent was performed using a magnetic surfactant to form a noncovalent magnetic functionalized graphene. After magnetic recovery of the adsorbent both components (adsorbent and magnetic surfactant) were recycled by tuning the surface charges through changing the pH of the solution. Desorption behavior studied using HNO₃ solution indicated that the adsorbent had the potential for reusability.     

Rapid reductive degradation of dye contaminated water by using a core-shell nano zerovalent iron (nZVI)

We report on the synthesis of zero valent iron nano particles (nZVI) via chemical reduction method. The large peak visible in the XRD pattern reveals the presence of an amorphous phase of iron. SEM and TEM images signify the dendritic morphology and core-shell-like structure of manufactured nZVI particles respectively. Methylene blue dye (MB) was used as model contaminant to assess the reductive degradation proficiency of nZVI. With complete elimination of MB, the fresh synthesized nZVI exhibited the best performance (97%), while the regenerated nZVI had an 85.1% MB removal efficiency after five regenerations. The equilibrium data of adsorption were fitted to eight different kinetic and isothermal models. The effects of critical operating factors such as pH, varied amounts of nZVI and dye concentration, adsorption temperature, and adsorption time were also studied. A presumptive reaction mechanism and function of core-shell construction in contaminant sequestration has also been investigated.     

Experimental design,machine learning approaches for the optimization and modeling of caffeine adsorption

In the current research, the sorption of caffeine on fresh and calcined Cu–Al layered double hydroxide was comparatively studied based on adsorption parameters, adsorption kinetics, and adsorption isotherm. Response surface methodology (RSM), support vector machine (SVM) and artificial neural network (ANN), as data mining methods, were applied to develop models by considering various operating variables. Different characterization methods were exploited to conduct a comprehensive analysis of the characteristics of HDL in order to acquire a thorough understanding of its structural and functional features. The Langmuir model was employed to accurately describe the maximum monolayer adsorption capacity for calcined sample (q_max) of 152.99 mg/g mg/g with R² = 0.9977. The pseudo-second order model precisely described the adsorption phenomenon (R² = 0.999). The thermodynamic analysis also reveals a favorable and spontaneous process. The ANN model predicts adsorption efficiency result with R² = 0.989. The five-fold cross-validation was achieved to evaluate the validity of the SVM. The predication results revealed approximately 99.9% accuracy for test datasets and 99.63% accuracy for experiment data. Moreover, ANOVA analysis employing the central composite design-response surface methodology (CCD-RSM) indicated a good agreement between the quadratic equation predictions and the experimental data, which results in R² of 0.9868 and the highest removal percentages in optimized step were obtained for RSM (pH 5.05, mass of adsorbent 20 mg, time of 72 min, and caffeine concentrations of 22 mg/L). On the whole, the findings confirm that the proposed machine learning models provided reliable and robust computer methods for monitoring and simulating the adsorption of pollutants from aqueous solutions by Cu–Al–LDH.     

Al-centered functionalized inorganic–organic hybrid sorbent containing N and S donor atoms for effective removal of cadmium

A new aluminium-incorporated layered inorganic–organic hybrid material (Al-GPTS-TU) has been successfully synthesized by using sol–gel based precursor under mild temperature condition and silylaing agent (GPTS-TU) derived from the reaction of 3-glycidoxypropyltrimethoxysilane (GPTS) and thiourea (TU). The hybrid material was characterized by using various instrumentation techniques and the result confirmed the attachment of organic functionality to the inorganic silicon network. The inter-lamellar distance for the hybrid material was found to be 41.33 Å. The synthesized hybrid was used for the removal of cadmium from dilute aqueous solution with variation of solution parameters. Thermodynamic parameters ΔH and ΔS, evaluated for the adsorption of cadmium from water solution, were found to be 73.68 kJ mol^?1 and 282.9 J mol^?1 K^?1, respectively, indicating adsorption process to be endothermic in nature. The negative value of ΔG indicated the feasibility and spontaneity of ongoing adsorption process. The hybrid material containing multiple coordination sites such as S and N in the attached organic functionality can find potential applications for the removal of various metal toxicants from water bodies to prevent the eco-system.     

Modified bentonite by polyhedral oligomeric silsesquioxane and quaternary ammonium salt and adsorption characteristics for dye

To remove methylene blue dye from water by adsorption, bentonites were modified by polyhedral oligomeric silsesquioxane (POSS) and three kind of quaternary ammonium surfactants (dodecyl trimethyl ammonium bromide, tetrabutyl ammonium bromide, cetyl trimethylammonium bromide) in aqueous solution. Systematic adsorption experiments were carried out, the adsorption mechanism was studied, and the factors governing the adsorption of methylene blue on modified bentonite were discussed. The adsorption capacity of methylene blue on all three modified bentonites in 1000 mg·L⁻¹ solutions quickly reached equilibrium within 2000 s, and the removal rate was basically 100%; however, the removal rate in raw bentonite samples was only 60%. The pseudo second-order kinetic model can provide satisfactory kinetic data fitting. The obtained adsorption isotherms fit well with the Dubinin-Radushkevich isotherm model. The thermodynamic results showed that the adsorption process was a spontaneous endothermic physical adsorption process. With increasing pH and KCl concentration, the removal of methylene blue increased significantly. The results of this study confirmed that the modified bentonite is a candidate material as a cationic dye adsorbent.     

Removal of thorium from aqueous solutions by sodium clinoptilolite

Adsorptive behavior of natural clinoptilolite was assessed for removal of thorium from aqueous solutions. Natural zeolite was characterized by X-ray diffraction and X-ray fluorescence. The zeolite sample composed mainly of clinoptilolite. Na-exchanged form of zeolite was prepared and its sorption capacity for removal of thorium from aqueous solutions was examined. The effects of relevant parameters, including initial concentration, contact time, solid to liquid ratio, temperature and initial pH on the removal efficiency were investigated in batch studies. The pH strongly influenced thorium adsorption capacity and maximal capacity was obtained at pH 4.0. Kinetics and isotherm of adsorption were also studied. The pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion models were used to describe the kinetic data. The pseudo-second-order kinetic model provided excellent kinetic data fitting (R ² > 0.999) with rate constant of 1.25, 1.37 and 1.44 g mmol⁻¹ min⁻¹ respectively for 25, 40 and 55 °C. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms for thorium uptake and the Langmuir model agrees very well with experimental data. Thermodynamic parameters were determined and are discussed.