Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions

Removal of Pb2+ and Ni2+ from aqueous solutions by sorption onto natural bentonite was investigated. Experiments were carried out as a function of particle size, the amount of bentonite, pH, concentration of metals, contact time, and temperature. The adsorption patterns of metal ions onto followed the Langmuir, Freundlich, and Dubinin-Radushkevich isotherms. This included adsorption isotherms of single-metal solutions at 303 K by batch experiments. The thermodynamic parameters (DeltaH,DeltaS,DeltaG) for Pb2+ and Ni2+ sorption onto bentonite were also determined from the temperature dependence. The adsorptions were endothermic reactions. The results suggested that natural bentonite is suitable as a sorbent material for recovery and adsorption of metal ions from aqueous solutions.     

One-pot synthesis of a novel magnetic activated carbon/clay composite for removal of heavy metals from aqueous solution

Abstract

In the present work, a novel composite consisting of magnetite, activated carbon from spent coffee grounds and natural clay (MACCC) was prepared by a one-pot synthesis method via a simultaneous activation and magnetization processes. Various techniques (XRD, FTIR, SEM, TEM, EDX, BET) were utilized to characterize the synthesized composite before utilizing it as an adsorbent for removal of Cu(II), Ni(II) and Pb(II) ions from aqueous solutions. Conditions for removal of heavy metals were thoroughly optimized as 25?°C, pH of 5.5, adsorbent dosage of 2?g L^?1, and a contact time of 60?min. Three models of pseudo first-, second-order and intraparticle diffusion as well as three models of Langmuir, Freundlich, and Temkin were used to analyze kinetics and isotherms of the adsorption process. Thermodynamics was discussed completely. Regeneration and recyclability of the adsorbent were also evaluated. Based on the analysis of experimental results, a possible adsorption mechanism of heavy metals onto the synthesized composite was proposed. The maximum capacities caculated from Langmuir model followed the order of Pb(II) > Cu(II) > Ni(II) as 143.56, 96.16 and 84.86?mg·g^?1, respectively. The overall results indicated that MACCC is a potential adsorbent for removal of toxic Pb(II), Cu(II) and Ni(II) ions from wastewater due to simple preparation, high removal efficiency and good recyclability.     

Removal of Cu(II) and Zn(II) from industrial wastewater by acid-activated montmorillonite-illite type of clay

An acid-activated montmorillonite-illite type of clay collected from the Gulbarga region of Karnataka, India was examined for removing copper and zinc ions from industrial wastewater containing Cu(II), Zn(II) and minor amounts of Pb(II). Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and competitive Langmuir (two competing ions) isotherms were fitted to experimental data and the goodness of their fit for adsorption was compared. The shapes of isotherms obtained indicated multilayer adsorption of Cu(II) and monolayer adsorption of Zn(II) on the acid-activated clay. Competitive adsorption was found to be significant due to the presence of Cu(II) in the wastewater.     

Adsorption of Pb(II) on a composite material prepared from polystyrene-alumina and activated carbon: Kinetic and thermodynamic studies

The ability of polystyrene-alumina-activated carbon composite as a synthetic adsorbent was investigated for the removal of Pb(II) ions from aqueous solutions. Various physico-chemical parameters such as pH, initial metal ion concentration, adsorbent dosage and contact time were studied. The optimum solution pH for the maximum adsorption of Pb(II) was found to be 4. Kinetic data were best described by pseudo-second-order model. The adsorption process followed both Langmuir and Freundlich adsorption isotherms at 30 °C. Thermodynamic studies indicated that the adsorption was spontaneous and endothermic in nature. Desorption studies were carried out by batch and column operations and it was found that 97% Pb(II) could be recovered by the column process using 0.1 M HCl as eluent.     

Adsorption of indole and 2-methylindole on ligand-exchange matrix

The adsorption of indole and its 2-methyl derivative from aqueous solutions onto cobalt(II)-carboxylated diaminoethane sporopollenin (CDAE-sporopollenin) was studied using a fixed-bed column at 25+/-0.1 degrees C. Minicolumn adsorption studies showed that the breakthrough and the total adsorption capacities of CDAE-sporopollenin in the concentration range we have studied increased with increasing external ligand concentration. The characteristics of the adsorption process were investigated using Scatchard plot analysis, where the equilibrium binding data for indole on ligand exchanger gave rise to a linear plot. However, for 2-methylindole, divergence from the Scatchard plot was evident, consistent with the participation of secondary equilibrium effects in the adsorption process. The adsorption behaviors of ligands on CDAE-sporopollenin were expressed by both the Langmuir and Freundlich isotherms. The adsorption isotherm data for these ligands on the resin can be satisfactorily fitted to the Freundlich isotherm within the concentration range studied. However, in the case of 2-methylindole, the experimental data did not fit the Langmuir model, especially when a high ligand concentration range is used; this is probably due to the nonspecific interactions between the ligand exchange matrix and the methyl group present. Ligand adsorption constants and correlation coefficients for the ligands were calculated from the Langmuir and Freundlich isotherms.     

Isotherm, kinetic and thermodynamic studies of lead and copper uptake by H2SO4 modified chitosan

The kinetic and thermodynamic adsorption and adsorption isotherms of Pb(II) and Cu(II) ions onto H₂SO₄ modified chitosan were studied in a batch adsorption system. The experimental results were fitted using Freundlich, Langmuir and Dubinin–Radushkevich isotherms; the Langmuir isotherm showed the best conformity to the equilibrium data. The pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were employed to analyze the kinetic data. The adsorption behavior of Pb(II) and Cu(II) was best described by the pseudo-second order model. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined; the adsorption process was found to be both spontaneous and exothermic. No physical damage to the adsorbents was observed after three cycles of adsorption/desorption using EDTA and HCl as eluents. The mechanistic pathway of the Pb(II) and Cu(II) uptake was examined by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The equilibrium parameter (R_L) indicated that chitosan–H₂SO₄ was favorable for Pb(II) and Cu(II) adsorption.     

Kinetic and equilibrium studies of lead(II) adsorption from aqueous media by KIT-6 mesoporous silica functionalized with –COOH

An organic–inorganic hybrid mesoporous silica was synthesized via post-grafting of KIT-6 with 4-(triethoxysilyl)butyronitrile. All samples were characterized using their N₂ adsorption–desorption isotherms, XRD, FT–IR, TEM, SEM, and PT. The adsorption potential of this material for removing Pb(II) from aqueous solutions was investigated via the batch technique, and the effects of pH and contact time were studied. Experimental data showed that the maximum Pb(II) adsorption, 76%, occurred in the pH range around 6. The adsorption equilibrium was reached within 40 min for 10 wt.%COOH/KIT-6. The adsorption data were fitted using the Langmuir and Freundlich isotherms, and the obtained modeling equilibrium adsorption data suggested that the 10 wt.%COOH/KIT-6 sample contained homogeneous adsorption sites that fit the Langmuir adsorption model well. The pseudo-second-order model described well the 10 wt.%COOH/KIT-6 adsorption process. The desorption and regeneration experiments indicated that ≈95% of the metal desorbed and the adsorbent could be regenerated via an acid treatment without altering its properties.     

Kinetics and equilibrium adsorption study of lead(II) onto activated carbon prepared from coconut shell

Removal of lead from aqueous solutions by adsorption onto coconut-shell carbon was investigated. Batch adsorption experiments were performed to find out the effective lead removal at different metal ion concentrations. Adsorption of Pb2+ ion was strongly affected by pH. The coconut-shell carbon (CSC) exhibited the highest lead adsorption capacity at pH 4.5. Isotherms for the adsorption of lead on CSC were developed and the equilibrium data fitted well to the Langmuir, Freundlich, and Tempkin isotherm models. At pH 4.5, the maximum lead adsorption capacity of CSC estimated with the Langmuir model was 26.50 mg g(-1) adsorbent. Energy of activation (Ea) and thermodynamic parameters such as DeltaG, DeltaH, and DeltaS were evaluated by applying the Arrhenius and van't Hoff equations. The thermodynamics of Pb(II) on CSC indicates the spontaneous and endothermic nature of adsorption. Quantitative desorption of Pb(II) from CSC was found to be 75% which facilitates the sorption of metal by ion exchange.     

Removal of Pb(II) ions from aqueous solutions on few-layered graphene oxide nanosheets

Few-layered graphene oxide (FGO) was synthesized from graphite by using the modified Hummers method, and was characterized by scanning electron microscopy, atomic force microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. The prepared FGO was used to adsorb Pb(II) ions from aqueous solutions. The abundant oxygen-containing groups on the surfaces of FGO played an important role in Pb(II) ion adsorption on FGO. The adsorption of Pb(II) ions on FGO was dependent on pH values and independent of ionic strength. The adsorption of Pb(II) ions on FGO was mainly dominated by strong surface complexation. From the adsorption isotherms, the maximum adsorption capacities (C(smax)) of Pb(II) ions on FGO calculated from the Langmuir model were about 842, 1150, and 1850 mg g(-1) at 293, 313, and 333 K, respectively, higher than any currently reported. The FGO had the highest adsorption capacities of today's nanomaterials. The thermodynamic parameters calculated from the temperature dependent adsorption isotherms indicated that the adsorption of Pb(II) ions on FGO was a spontaneous and endothermic process.     

Adsorptive accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from water on montmorillonite: influence of acid activation

The present work investigates the influence of acid activation of montmorillonite on adsorption of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) from aqueous medium and comparison of the adsorption capacities with those on parent montmorillonite. The clay-metal interactions were studied under different conditions of pH, concentration of metal ions, amount of clay, interaction time, and temperature. The interactions were dependent on pH and the uptake was controlled by the amount of clay and the initial concentration of the metal ions. The adsorption capacity of acid-activated montmorillonite increases for all the metal ions. The interactions were adsorptive in nature and relatively fast and the rate processes more akin to the second-order kinetics. The adsorption data fitted both Langmuir and Freundlich isotherms, indicating that strong forces were responsible for the interactions at energetically nonuniform sites. The Langmuir monolayer capacity of the acid-activated montmorillonite is more than that of the parent montmorillonite (Cd(II): 32.7 and 33.2 mg/g; Co(II): 28.6 and 29.7 mg/g; Cu(II): 31.8 and 32.3 mg/g; Pb(II): 33.0 and 34.0 mg/g; and Ni(II): 28.4 and 29.5 mg/g for montmorillonite and acid-activated montmorillonite, respectively). The thermodynamics of the rate processes showed the adsorption of Co(II), Pb(II), and Ni(II) to be exothermic, accompanied by decreases in entropy and Gibbs free energy, while the adsorption of Cd(II) and Cu(II) was endothermic, with an increase in entropy and an appreciable decrease in Gibbs free energy. The results have established the potential use for montmorillonite and its acid-activated form as adsorbents for Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions from aqueous media.     

Theoretical,Equilibrium, Kinetics and Thermodynamic Investigations of Methylene Blue Adsorption onto Lignite Coal

The interaction of methylene blue (MB) dye with natural coal (collected from coal landfills of the Kosovo Energy Corporation) in aqueous solutions was studied using adsorption, kinetics, and thermodynamic data, and Monte Carlo (MC) calculations. In a batch procedure, the effects of contact duration, initial MB concentration, pH, and solution temperature on the adsorption process were examined. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D–R) isotherms were used to examine the equilibrium adsorption data. The equilibrium data fit well to the Freundlich and Langmuir adsorption isotherm models; however, the Freundlich model suited the adsorption data to a slightly better extent than the Langmuir model. The kinetics experimental data was fitted using pseudo-first-order, first-order, pseudo-second-order, second-order, Elvoich equation, and diffusion models. The pseudo-second-order rate model manifested a superlative fit to the experimental data, while the adsorption of MB onto coal is regulated by both liquid film and intraparticle diffusions at the same time. Thermodynamic parameters, such as Gibbs free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰) were calculated. The adsorption of MB was confirmed to be spontaneous and endothermic. The theoretical results were in agreement with the experimental ones.     

Characterization and determination of the thermodynamic and kinetic properties of the adsorption of the molybdenum(VI)-calmagite complex onto active carbon

The extraction of the Mo(VI)-calmagite complex by adsorption onto active carbon is investigated in the present paper. Thermodynamic and kinetic properties and different adsorption isotherms were determined. The adsorption studies have shown that both the empirical Freundlich and the classical Langmuir isotherms successfully fit the experimental results. The overall adsorption process was exothermic and spontaneous in the temperature range from 283 to 323 K; namely, DeltaH(0) and DeltaS(0) values were found to be -8.15 kJ mol(-1) and -3.86 J mol(-1) K, respectively. The high activation energy demanded for desorption of the Mo(VI)-calmagite complex surface indicated that the overall process was controlled by the slow desorption, while a fast and low activated adsorption of the complex onto active carbon surface was fairly favored. These features indicate that active carbon may be very useful for preconcentration of molybdenum from diluted solutions.     

Removal of Pb(II) and malachite green from aqueous solution by modified cellulose

A low-cost, highly efficient and eco-friendly cellulose-based adsorbent (CMGT) was synthesized and used to uptake Pb(II) and malachite green (MG) from aqueous solutions. The CMGT was characterized by FTIR, SEM, TGA and XRD. Different experimental parameters were evaluated in batch adsorption experiments to determine the optimal adsorption conditions. The optimal pHs for Pb(II) and MG were 5.5 and 7.0, respectively; the optimal contact times for Pb(II) and MG were 60 and 180 min, respectively. Among the Langmuir, Freundlich and Temkin isotherm models, the Langmuir model fitted the adsorption data best for both Pb(II) and MG adsorption. In theory, the maximum adsorption capacities of Pb(II) and MG were 584.80 and 131.93 mg g^?1, respectively. The pseudo-second-order model fitted the experimental data very well, and the thermodynamics were also used to discuss the mechanism in depth. Additionally, desorption tests showed that CMGT could be effectively regenerated by 0.2 mol L^?1 HCl solution and could be reused for at least six cycles successively with a stable sorption ability in the dynamic adsorption process.     

Potential application of termite mound for adsorption and removal of Pb(II) from aqueous solutions

The morphological and mineralogical composition of a termite mound from Ilorin, Nigeria was investigated with a view to understand its sorption properties. The termite hill soil was subjected to some spectroscopic analyses such as X-ray fluorescence (XRF) and Scanning Electron Microscopy. The XRF results revealed that the adsorbent contains a large fraction of Silicon, Iron and Aluminium minerals. The organic matter (OM) content expressed as percentage carbon was 3.45% while the high value of cation exchange capacity of 14.0?meq/100?g is in agreement with high percentage OM, which signifies high availability of exchangeable ions. The maximum Pb(II) adsorption capacity of the mound was found to be 15.5?mg/g. Batch adsorption experiments were carried out as a function of contact time, ionic strength and pH. Maximum and constant adsorption was observed in the pH range of 2?C5.5. The experimental results of Pb(II) adsorption were analyzed using Langmuir, Freundlich, and Temkin isotherms. The Langmuir and Temkin isotherms were found to fit the measured sorption data better than Freundlich. The constants obtained from the Langmuir model are maximum sorption value, Q _m?=?18.18 and Langmuir energy of adsorption constant, b?=?0.085, while the constants of the Freundlich model are the intensity of adsorption constant, n?=?0.134, and maximum diffusion constant, K _f?=?1.36. The adsorption data for Pb(II) was found to fit well into the pseudo-second order model. Desorption experiment was conducted using different concentrations of leachant and this was repeated three times to determine the life span of the adsorbent. It was observed that 0.2?M HCl had the highest desorption efficiency for reuse.     

Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies

The aim of this paper is to study the adsorption of the heavy metals (Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II)) from aqueous solutions by a natural Moroccan stevensite called locally rhassoul. We carried out, first, a mineralogical and physicochemical characterization of stevensite. The surface area is 134 m2/g and the cation exchange capacity (CEC) is 76.5 meq/100 g. The chemical formula of stevensite is Si3.78Al0.22Mg2.92Fe0.09Na0.08K0.08O10(OH)2.4H2O. Adsorption tests of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in batch reactors were carried out at ambient temperature and at constant pH. Two simplified models including pseudo-first-order and pseudo-second- order were used to test the adsorption kinetics. The equilibrium time and adsorption rate of adsorption were determined. The increasing order of the adsorption rates follows the sequence Mn(II) > Pb(II) > Zn(II) > Cu(II) > Cd(II). The Dubinin-Radushkevich (D-R), Langmuir, and Redlich-Peterson (R-P) models were adopted to describe the adsorption isotherms. The maximal adsorption capacities at pH 4.0 determined from the D-R and Langmuir models vary in the following order: Cu(II) > Mn(II) > Cd(II) > Zn(II) > Pb(II). The equilibrium data fitted well with the three-parameter Redlich-Peterson model. The values of mean energy of adsorption show mainly an ion-exchange mechanism. Also, the influence of solution pH on the adsorption onto stevensite was studied in the pH range 1.5-7.0.     

Potato peels as solid waste for the removal of heavy metal copper(II) from waste water/industrial effluent

A new sorbent potato peels, which are normally discarded as solid waste for removing toxic metal ion Cu(II) from water/industrial waste water have been studied. Potato peels charcoal (PPC) was investigated as an adsorbent of Cu(II) from aqueous solutions. Kinetic and isotherm studies were carried out by studying the effects of various parameters such as temperature, pH and solid liquid ratios. The optimum pH value for Cu(II) adsorption onto potato peels charcoal (PPC) was found to be 6.0. The thermodynamic parameters such as standard Gibb's free energy (Delta G degrees ), standard enthalpy (Delta H degrees ) and standard entropy (DeltaS degrees ) were evaluated by applying the Van't Hoff equation. The thermodynamics of Cu(II) adsorption onto PPC indicates its spontaneous and exothermic nature. The equilibrium data at different temperatures were analyzed by Langmuir and Freundlich isotherms.     

Biosorption of Pb(II) and Cd(II) ions by Agave sisalana (sisal fiber)

The present work proposes the use of Agave sisalana (sisal fiber) as an natural adsorbent for ions Pb(II) and Cd(II) biosorption from natural waters. The flame atomic absorption spectrometry was used for quantitative determination and study of the ions Pb(II) and Cd(II) adsorption on the solid phase. The Fourier transform infrared spectroscopy (FT IR) was used to investigate the sisal structure and the specific BET surface area was analyzed. The biosorption potential of sisal as biosorbent for the removal of the ions Pb(II) and Cd(II) from aqueous solution was investigate considering the followings parameters: pH, biomass amount and contact time. Langmuir and Freundlich isotherms were used to evaluate adsorption behavior of the ions on this solid phase. The results showed that sisal has a surface area to adsorption of 0.0233 m² g^{− 1}, and the OH and CO functional groups are the main involved in the biosorption. The best interpretation for the experimental data was given by Freundlich isotherm that proposes a monolayer sorption with a heterogeneous energetic distribution of active sites, accompanied by interactions between sorbed molecules. The maximum monolayer biosorption capacity was found to be 1.85 mg g^{− 1} for Cd (II) and 1.34 mg g^{− 1} for Pb (II) at pH 7 and 296 K. This phase solid can be used for biosorption of cadmium and lead in polluted natural waters.     

Removal of methyl violet from aqueous solution by perlite

The use of perlite for the removal of methyl violet from aqueous solutions at different concentration, pH, and temperature has been investigated. Adsorption equilibrium is reached within 1 h. The capacity of perlite samples for the adsorption of methyl violet was found to increase with increasing pH and temperature and decrease with expansion and increasing acid-activation. The adsorption isotherms are described by means of the Langmuir and Freundlich isotherms. The adsorption isotherm was measured experimentally at different conditions and the experimental data were correlated reasonably well by the adsorption isotherm of Langmuir. The order of heat of adsorption corresponds to a physical reaction. It is concluded that the methyl violet is physically adsorbed onto the perlite. The removal efficiency (P) and dimensionless separation factor (R) have shown that perlite can be used for removal of methyl violet from aqueous solutions, but unexpanded perlite is more effective.