Competitive adsorption of Cu (II), Co (II) and Ni (II) from their binary and tertiary aqueous solutions using chitosan-coated perlite beads as biosorbent

A new composite chitosan-coated biosorbent was prepared and was used for the removal and recovery of heavy metals from aqueous solution. In the present investigation, equilibrium adsorption characteristics of Cu (II), Ni (II), and Co (II) from their binary and tertiary solution on newly developed biosorbent chitosan-coated perlite beads were evaluated through batch and column studies. These beads were characterized by using FTIR, EDXRF and surface area analysis techniques. The effect of various biosorption parameters like effect of pH, agitation time, concentration of adsorbate and amount of adsorbent on extent of adsorption was investigated. The adsorption follows Lagergren first order kinetic model. The equilibrium adsorption data were fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters were evaluated. Both the models represent the experimental data satisfactorily. The sorbent loaded with metal was regenerated with 0.1N NaOH solution. Furthermore the column dynamic studies indicate the re-usage of the biosorbent.     

Immobilization of 2,2'-dipyridyl onto bentonite and its adsorption behavior of copper(II) ions

In this study, the immobilization of 2,2'-dipyridyl onto bentonite was firstly carried out and it was then used for the adsorption of copper(II) ions from aqueous solutions. The variation of the parameters of pH, contact time, initial copper(II) concentration and temperature were investigated in the adsorption experiments. The XRD, FTIR, elemental and thermal analyses were performed to observe the immobilization of 2,2'-dipyridyl onto natural bentonite. The adsorption data obtained were well described by the Langmuir adsorption isotherm model at all studied temperatures. The results indicated that the maximum adsorption capacity was 54.07 mg g(-1) from the Langmuir isotherm model at 50 degrees C. The thermodynamic parameters indicated that the adsorption process is spontaneous, endothermic and chemical in nature. The kinetic parameters of the adsorption were calculated from the experimental data. According to these parameters, the best-fit was obtained by the pseudo-second-order kinetic model. The results showed that 2,2'-dipyridyl-immobilized bentonite can be used as the effective adsorbent for the removal of heavy metal contaminants.     

Adsorption of p-chlorophenol from aqueous solutions on bentonite and perlite

The adsorption of p-chlorophenol (p-CP) from aqueous solutions on bentonite and perlite was studied. These materials are available in large quantities in Bulgaria. Model solutions of various concentrations (1–50 mg dm⁻³) were shaken with certain amounts of adsorbent to determine the adsorption capacity of p-CP on bentonite and perlite as well. The influence of several individual variables (initial adsorbate concentration, adsorbent mass) on the rate of uptake of the studied compound on the adsorbent was determined by carrying out experiments at different contact times using the batch adsorber vessel designed according to the standard tank configuration. Rapid adsorption was observed 20–30 min after the beginning for every experiment. After that, the concentration of p-CP in the liquid phase remained constant. The adsorption equilibrium of p-CP on bentonite and perlite was described by the Langmuir and the Freundlich models. A higher adsorption capacity was observed for bentonite (10.63 mg g⁻¹) compared to that for perlite (5.84 mg g⁻¹).     

Copper(II)-EDTA sorption onto chitosan and its regeneration applying electrolysis

Cu(II)-EDTA (ethylendiaminetetraacetate) complexes are widely used in the manufacture of printed circuit boards. In order to avoid the outlet into the environment the sorption of complexes onto chitosan is proposed. The uptake of both Cu(II) and EDTA proceeds in weakly acidic (pH 3-5) and strongly alkaline (pH > 12) solutions. In acidic solutions EDTA sorption prevails. FT-IR investigations have shown that in acidic solutions the amide bonds between -COOH groups of EDTA and -NH2 groups of chitosan were formed. In alkaline solutions the single EDTA sorption does not proceed. In this media the sorption is enhanced by Cu(II) ions. The possible sorption mechanisms are discussed. The uptake of both Cu(II) and EDTA by chitosan depends on the ratio between them in solutions. EDTA sorption in acidic solutions increases with increase in its concentration while that of Cu(II) decreases. In alkaline solutions the sorption of both Cu(II) and EDTA increases with increase in Cu(II) concentration. The use of electrolysis enables to regenerate chitosan and to reuse it. During electrolysis copper is deposited onto the cathode and EDTA is oxidized onto the anode. The current efficiency depends on the current intensity, the load of chitosan and the pH of the background electrolyte. Electrolysis under the most favorable conditions ensures the 10-cycles regeneration without considerable changes in the sorption properties of chitosan. FT-IR spectra of the initial and regenerated chitosans are similar.     

Evaluation of batch adsorption of chromium ions on natural and crosslinked chitosan membranes

Removal of chromium ions from aqueous solutions by using natural and crosslinked chitosan membranes was achieved using batch adsorption experiments. The effect of pH (6.0 and 2.0), concentration of chromium ions and crosslinking agents (glutaraldehyde: GLA and epichlorohydrin: ECH) on the adsorption properties of chitosan membranes was analyzed. The experimental equilibrium data was fitted to Langmuir and Freundlich models. Through the model curves, it was possible to observe that the amount of chromium ions adsorbed was significantly higher for crosslinked membranes compared to non-crosslinked chitosan. The maximum adsorbed amount was about 1400 mg g(-1) for ECH-crosslinked chitosan at pH 6.0. The adsorption rates for crosslinked chitosan membranes with glutaraldehyde and epichlorohydrin were similar for natural chitosan. Desorption study using NaCl (1 mol L(-1)) solution was performed on chitosan membranes, in order to recover chromium ions and to determine the suitable number of cycles for repeated use of these membranes without considerable decrease in their adsorption capacity. The desorption results showed that chromium ions could be more effectively removed at pH 2.0 than pH 6.0, mainly for ECH-crosslinked chitosan.     

Preparation of porous chitosan gel beads for copper(II) ion adsorption

In this paper, chitosan porous beads were prepared by using a phase inversion technique, and then used for the adsorption and removal of copper(II) ions. The porosity, diameter and other characteristics were characterized. With the increase of chitosan and NaOH concentration used to prepare the beads, the amount of adsorbed Cu2+ per gram of the beads decreased. A maximum adsorption amount was observed at a pH value of 6.0 for the cross-linked porous chitosan beads. The amount of the adsorbed Cu2+ increased with the Cu2+ concentration used in the adsorption experiments. By the relationship of the ratio of the equilibrium Cu2+ concentration in the solution (C(e)) to the adsorbed equilibrium amount (P(e)) (C(e)/P(e)) and C(e), we concluded that the adsorption of Cu2+ to the porous chitosan beads was Langmuir adsorption. The Cu2+-loaded porous chitosan beads were stable in water, which is useful for further study on selectively adsorption of IgG. The results suggested that the porous chitosan beads were useful adsorbents for copper ions removal in water treatment, and the Cu2+-loaded beads may be good sorbents for IgG removal in blood purification.     

Adsorption of platinum(IV) and palladium(II) from aqueous solution by thiourea-modified chitosan microspheres

The chitosan microparticles were prepared using the inverse phase emulsion dispersion method and modified with thiourea (TCS). TCS was characterized by scanning electron microscope (SEM), the Fourier transform infrared (FT-IR) spectra, sulfur elemental analysis, specific surface area and pore diameter. The effects of various parameters, such as pH, contact time, initial concentration and temperature, on the adsorption of Pt(IV) and Pd(II) by TCS were investigated. The results showed that the maximum adsorption capacity was found at pH 2.0 for both Pt(IV) and Pd(II). TCS can selectively adsorb Pt(IV) and Pd(II) from binary mixtures with Cu(II), Pb(II), Cd(II), Zn(II), Ca(II), and Mg(II). The adsorption reaction followed the pseudo-second-order kinetics, indicating the main adsorption mechanism of chemical adsorption. The isotherm adsorption equilibrium was well described by Langmuir isotherms with the maximum adsorption capacity of 129.9 mg/g for Pt(IV) and 112.4 mg/g for Pd(II). The adsorption capacity of both Pt(IV) and Pd(II) decreased with temperature increasing. The negative values of enthalpy (ΔH°) and Gibbs free energy (ΔG°) indicate that the adsorption process is exothermic and spontaneous in nature. The adsorbent was stable without loss of the adsorption capacity up to at least 5 cycles and the desorption efficiencies were above 95% when 0.5 M EDTA–0.5 M H₂SO₄ eluent was used. The results also showed that the preconcentration factor for Pt(IV) and Pd(II) was 196 and 172, respectively, and the recovery was found to be more than 97% for both precious metal ions.     

Removal of Cu(II) from aqueous solution by adsorption onto acid-activated palygorskite

A series of activated palygorskite clay by HCl with different concentrations was prepared and applied as adsorbents for removal of Cu(II) from aqueous solutions. The effects of contact time, adsorbent dosages and pHs of suspension on the adsorption capacities for Cu(II) were investigated. The results showed that adsorption capacity of activated palygorskites increased with increasing the HCl concentration and the maximum adsorption capacity with 32.24 mg/g for Cu(II) is obtained at 12 mol/L of HCl concentration. The variations in IR spectra and pH of solution after adsorption Cu(II) confirmed that the numerous amount of silanol groups (Si-OH) originated by acid treatment were mainly responsible for Cu(II) adsorption onto acid-activated palygorskite. Kinetic studies indicated that the adsorption mechanisms in the Cu(II)/acid-activated palygorskite system followed the pseudo-second-order kinetic model with a relatively small contribution of film diffusion. Equilibrium data fitted well with Freundlich isotherm model compared to Langmuir isotherm model, indicating that adsorption takes place on heterogeneous surfaces of the acid-activated palygorskite. Adsorption-desorption studies presented that activated palygorskite has lower adsorption and desorption efficiencies using Cu(CH3COO)2 than that of other inorganic copper salts, such as CuSO4, Cu(NO3)2, and CuCl2.     

Adsorption of p-chlorophenol from aqueous solutions on bentonite and perlite

The adsorption of p-chlorophenol (p-CP) from aqueous solutions on bentonite and perlite was studied. These materials are available in large quantities in Bulgaria. Model solutions of various concentrations (1–50 mg dm⁻³) were shaken with certain amounts of adsorbent to determine the adsorption capacity of p-CP on bentonite and perlite as well. The influence of several individual variables (initial adsorbate concentration, adsorbent mass) on the rate of uptake of the studied compound on the adsorbent was determined by carrying out experiments at different contact times using the batch adsorber vessel designed according to the standard tank configuration. Rapid adsorption was observed 20–30 min after the beginning for every experiment. After that, the concentration of p-CP in the liquid phase remained constant. The adsorption equilibrium of p-CP on bentonite and perlite was described by the Langmuir and the Freundlich models. A higher adsorption capacity was observed for bentonite (10.63 mg g⁻¹) compared to that for perlite (5.84 mg g⁻¹).     

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.     

The removal of an anionic red dye from aqueous solutions using chitosan beads-the role of experimental factors on adsorption using a full factorial design

A factorial design was employed to evaluate the quantitative removal of an anionic red dye from aqueous solutions on epichlorohydrin-cross-linked chitosan. The experimental factors and their respective levels studied were the initial dye concentration in solution (25 or 600 mg L⁻¹), the absence or the presence of the anionic surfactant sodium dodecylbenzenesulfonate (DBS) and the adsorption temperature (25 or 55 °C). The adsorption parameters were analyzed statistically using modeling polynomial equations. The results indicated that increasing the dye concentration from 25 to 600 mg L⁻¹ increases the dye adsorption whereas the presence of DBS increases it. The principal effect of temperature did not show a high statistical significance. The factorial results also demonstrate the existence of statistically significant binary interactions of the experimental factors. The adsorption thermodynamic parameters, namely Δ_adsH, Δ_adsG and Δ_adsS, were determined for all the factorial design results. Exothermic and endothermic values were found in relation to the Δ_adsH. The positive Δ_adsS values indicate that entropy is a driving force for adsorption. The Δ_adsG values are significantly affected by an important synergistic effect of the factors and not by the temperature changes alone.     

Bromine pretreated chitosan for adsorption of lead (II) from water

Pollution by heavy metals like lead (II) is responsible for health hazards and environmental degradation. Adsorption is a prevalent method applied for removal of heavy metal pollutants from water. This study explored adsorption performances of 30% bromine pretreated chitosan for lead (II) abatement from water. Bromine pretreatment alters porosity and specific surface area of chitosan by means of physicochemical interaction with cationic sites of chitosan skeleton, besides imparting anionic alteration at amino linkages of chitosan, to remove lead (II) by chemical interactions on superfluous active sites as characterized by FTIR, SEM, DTA and elemental analysis. Lead adsorptions were studied in batch mode by varying parameters viz. pH, bromine loading, sorbent dosage, initial lead concentration, contact time and temperature. The adsorption equilibrium data was well fitted to Freundlich isotherm and maximum sorption capacity of 30% bromine pretreated chitosan sorbent was 1·755 g/kg with 85–90% lead removal efficiency. Though cost and applicability of sorbent is unproven, yet contrast to raw chitosan derivatives, activated carbons and some resins, 30% bromine pretreated chitosan endow benign and efficient lead abatement technique.     

Removal of copper(II) and lead(II) from aqueous solution by manganese oxide coated sand II. Equilibrium study and competitive adsorption

The adsorption equilibrium of MOCS and the Cu(II) and Pb(II) ions removal capacity by MOCS in single-(non-competitive) and binary-(competitive) component sorption systems from aqueous solutions were investigated. The equilibrium data were analyzed using the Langmuir, Freundlich, Temkin and Redlich-Peterson isotherms. The characteristic parameters for each isotherm were determined. The Langmuir and Redlich-Peterson isotherms provided the best correlation for both Cu(II) and Pb(II) onto MOCS. From the Langmuir isotherms, maximum adsorption capacities of MOCS towards Cu(II) and Pb(II) are determined at different temperature. The maximum adsorption capacity of Cu(II) and Pb(II) per gram MOCS in single component sorption systems were from 5.91 and 7.71 micromol to 7.56 and 9.22 micromol for the temperature range of 288-318 K, respectively. The order of affinity based on a weight uptake by MOCS was as follows: Pb(II)>Cu(II). The same behavior was observed during competitive adsorption that is in the case of adsorption from their binary solution. The thermodynamic parameters (DeltaG degrees , DeltaH degrees , and DeltaS degrees) for Cu(II) and Pb(II) sorption on MOCS were also determined from the temperature dependence. This competitive adsorption showed that the uptake of each metal was considerably reduced with an increasing concentration of the other, the adsorption of Cu(II) being more strongly influenced by Pb(II) than vice versa due to the higher affinity of MOCS for the latter.     

Chitosan selectivity for removing cadmium (II), copper (II), and lead (II) from aqueous phase: pH and organic matter effect

The aim of this study was to investigate the selectivity of chitosan for cadmium, copper and lead in the presence and absence of natural organic matter (NOM) in different pH solutions. Adsorption isotherms of one and three adsorbates at initial concentration of 5-100mg/L were carried out in batch reactors at pH 4, 5, or 7 and 25 degrees C in reactive and clarified water. The chitosan employed had a MW of 107.8 x 10(3)g/mol and degree of acetylation (DA) of 33.7%. The chitosan adsorption capacity at pH 4 in reactive water was 0.036, 0.016, 0.010mmol/g for Pb(2+), Cd(2+), and Cu(2+), respectively, and it decreased for Pb(2+) and Cd(2+) in clarified water. Conversely, experiments carried out in clarified water showed that the cadmium adsorption capacity of chitosan was enhanced about three times by the presence of NOM at pH 7: an adsorption mechanism was proposed. Furthermore, it was found that the biosorbent selectivity, in both reactive and clarified water at pH 4, was as follows Cu(2+)>Cd(2+)>Pb(2+). Finally, the preliminary desorption experiments of Cd(2+) conducted at pH 2 and 3 reported 68 and 44.8% of metal desorbed, which indicated that the adsorption mechanism occurred by electrostatic interactions and covalent bonds.     

Phase transition in copper(II) pyrovanadate

A new phase Cu₂V₂O₇ synthesized, exhibits phase transitions between 475°C and 500°C. These phase transitions are reversible with ease in contrast toα →β phase transition at 712°C of Cu₂V₂O₇ phase reported earlier. These phase transitions are identified by DTA technique and characterized by detailed XRD investigations at different temperatures. The crystal structures of these Cu₂V₂O₇ phases are related to either thortveitite (Sc₂Si₂O₇) type or a modification of it.     

Sorption of copper(II) ion from aqueous solution by Tectona grandis l.f. (teak leaves powder)

Studies on a batch sorption system using Tectona grandis l.f. as adsorbent was investigated to remove copper(II) from aqueous solutions. The adsorption experiments were performed under various conditions such as different initial concentrations, pH, adsorbent dosage and adsorbent particle size. The data showed that 0.1 g of Tectona grandis l.f. was found to remove 71.66% of 20 mg/L copper(II) from 30 mL aqueous solution in 180 min. The experimental equilibrium data were adjusted by the adsorption isotherms from Langmuir and Freundlich models and their equilibrium parameters were determined. The best-adjusted model to the experimental equilibrium data for Tectona grandis l.f. was the Langmuir model. Using the Langmuir model equation, the monolayer sorption capacity of Tectona grandis l.f. was evaluated and found to be 95.40 mg/g. The optimum pH value was found to be 5.5. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data. The dynamic data fitted the pseudo-second-order kinetic model.     

The adsorption of Cd(II) ions on sulphuric acid-treated wheat bran

The adsorption of Cd(II) ions which is one of the most important toxic metals by using sulphuric acid-treated wheat bran (STWB) was investigated. The effects of solution pH and temperature, contact time and initial Cd(II) concentration on the adsorption yield were studied. The equilibrium time for the adsorption process was determined as 4 h. The adsorbent used in this study gave the highest adsorption capacity at around pH 5.4. At this pH, adsorption capacity for an initial Cd(II) ions concentration of 100 mg/L was found to be 43.1 mg/g at 25 degrees C for contact time of 4 h. The equilibrium data were analysed using Langmuir and Freundlich isotherm models to calculate isotherm constants. The maximum adsorption capacity (qmax) which is a Langmuir constant decreased from 101.0 to 62.5 mg/g with increasing temperature from 25 to 70 degrees C. Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the adsorption process. The enthalpy change (deltaH(o)) for the process was found to be exothermic. The free energy change (deltaG(o)) showed that the process was feasible. The kinetic results indicated that the adsorption process of Cd(II) ions by STWB followed first-order rate expression and adsorption rate constant was calculated as 0.0081 l/min at 25 degrees C. It was observed that the desorption yield of Cd(II) was highly pH dependent.     

Application of chitosan as flocculant for coprecipitation of Mn(II) and suspended solids from dual-alkali FGD regenerating process

Heavy metals and suspended solid (SS) needed to be removed from the recirculation of dual-alkali flue gas desulfurization (FGD) system. The feasibility of coprecipitation of heavy metal and SS by water-soluble chitosan was studied in a lab scale experiment. The association between chitosan and metal ions was verified through DSC and FT-IR. The pH investigation revealed that at the pH ranged from 5 to 9, there were three stages for different actions: adsorption of chitosan for Mn(II), precipitation of manganese hydroxide and coprecipitation of manganese hydroxide and chitosan-Mn(II) complex. The ion selectivity experiments showed that the occurrence of Ca(II) in the solution had little influence on the adsorption of chitosan for Mn(II). The decrease rate of adsorption capacity was about 0.0023 mmol g(-1) per 1 mg L(-1) Ca(II). When adsorption and flocculation of chitosan occurred at the same time and at the sufficient addition of chitosan, chitosan not only made solids flocculate but also enhanced sorption capacity of chitosan. Application of chitosan for coprecipitation of Mn(II) and SS could remove Mn(II) efficiently and improve the settling characteristics of SS from dual-alkali FGD regenerating process.     

Thermodynamics and kinetics of Zn(II) adsorption on crosslinked starch phosphates

Crosslinked starch phosphates (CSP) with different contents of phosphate groups were used to adsorb Zn(II) from aqueous solution. Effects of adsorption time, initial concentration of Zn(II) ion, and temperature on the adsorption of Zn(II) by CSP were studied, and the equilibrium, thermodynamics and kinetics of the adsorption process were further investigated. It showed that crosslinked starch phosphates can effectively remove Zn(II) from the solution. The adsorption equilibrium data correlate well with the Langmuir isotherm model with a maximum adsorption capacity of 2.00mmolg(-1). The adsorption of Zn(II) on CSP is endothermic in nature. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model.     

Removal of Cu(II) ions by activated poplar sawdust (Samsun clone) from aqueous solutions

In this work, adsorption of Cu(II) ions on sawdust (SD) and activated sawdust (ASD) has been studied by using batch adsorption techniques. The equilibrium adsorption level was determined to be a function of the pH, initial Cu(II) concentration, and adsorbent dosage. The equilibrium nature of Cu(II) adsorption has been described by the Freundlich and Langmuir isotherms. The experimental adsorption data were fitted to the Langmuir adsorption model both sawdust and activated sawdust. The equilibrium capacity of sawdust and activated sawdust were 5.432 and 13.495 mg copper per g adsorbent, respectively at room temperature and natural pH. The maximum adsorption capacity was obtained at the maximum zeta potential value that -74.5 mV (pH 5) for activated sawdust and at -48.4 mV (pH 4) for sawdust. It was observed that activated sawdust was a suitable adsorbent than sawdust for removal of Cu(II) from aqueous solutions.