A review and experimental verification of using chitosan and its derivatives as adsorbents for selected heavy metals

A literature survey on liquid-phase adsorption of selected heavy metals including Cu(II), Zn(II), Ni(II), Cd(II), Pb(II), Hg(II), and Cr(VI) on chitosan (CTS) and its derivatives was made from the viewpoint of adsorption capacity. This parameter was obtained from the Langmuir fit of isotherm data. The magnitude of adsorption capacity of heavy metals on pristine CTS was also used to discuss the mechanism of adsorption; that is, how many amino groups in CTS chains would coordinate with one heavy metal ion. Furthermore, a newly defined parameter, the approaching equilibrium factor R_L, was proposed to quantitatively indicate the favorability of the related adsorption process and to judge the correctness of adsorption capacity determined by the Langmuir equation.     

Cellulose-based anion exchanger with tertiary amine functionality for the extraction of arsenic(V) from aqueous media

A novel cellulose-based anion exchanger (Cell-AE) with tertiary amine functionality was synthesized by graft polymerization reaction of cellulose and glycidyl methacrylate using N,N′-methylene-bis-acrylamide as a crosslinker and benzoyl peroxide as an initiator, followed by dimethylamine (amination) and acid (HCl) treatment. The chemical modification was confirmed by infrared spectroscopy and CHN analysis. The anion exchanger was used in batch processes to study AS(V) adsorption in solutions. The operating variables studied were pH, contact time, initial As(V) concentration, sorbent mass, and ionic strength. The process was affected by solution pH with an optimum adsorption occurring at pH 6.0. Adsorption equilibrium was achieved within 1 h. Increasing ionic strength of solution negatively affected the arsenic uptake. The adsorption process performed more than 99.0% of As(V) removal from an initial concentration of 25.0 mg/L. The process of adsorption followed pseudo-second-order kinetics. The adsorption equilibrium isotherm data were analyzed using the Langmuir, Freundlich, Redlich–Peterson and Langmuir–Freundlich equations. The Langmuir–Freundlich isotherm described the adsorption data over the concentration range 25–400 mg/L. The adsorption mechanism appears to be a ligand-exchange process. A simulated groundwater sample was treated with Cell-AE to demonstrate its efficiency in removing As(V). The adsorbed As(V) ions were desorbed effectively by a 0.1 M NaOH solution.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Utilization of powdered waste sludge (PWS) for removal of textile dyestuffs from wastewater by adsorption

Acid pre-treated powdered waste sludge (PWS) was used for removal of textile dyestuffs from aqueous medium by adsorption as an alternative to the use of powdered activated carbon (PAC). The rate and extent of dysetuff removals were determined for four different dyestuffs at different PWS concentrations varying between 1 and 6 gl(-1). Biosorbed dyestuff concentrations at equilibrium decreased with increasing PWS concentration for all dyestuffs tested. PWS was more effective for adsorption of Remazol red RR and Chrisofonia direct yellow 12 as compared to the other dyestuffs tested. More than 80% percent dyestuff removal was obtained for all dyestuffs at PWS concentrations above 4 gl(-1) after 6h of incubation. Similar to percent dyestuff removal, the rate of adsorption was maximum at a PWS concentration of 4 gl(-1). Kinetics of adsorption of dyestuffs was investigated by using the first- and second-order kinetic models and the kinetic constants were determined. Second-order kinetics was found to fit the experimental data better than the first-order model for all dyestuffs tested. Adsorption isotherms were established for all dyestuffs used and the isotherm constants were determined by using the experimental data. Langmuir and the generalized adsorption isotherms were found to be more suitable than the Freundlich isotherm for correlation of equilibrium adsorption data. Acid pre-treated PWS was proven to be an effective adsorbent for dyestuff removal as compared to the other adsorbents reported in literature studies.     

Possible Utilization of Silica Gel Sludge for the Removal of Phenol from Aqueous Solutions: Laboratory Studies

This paper discusses the adsorption capacity of silica gel sludge for phenol removal from aqueous solution. Kinetic experiments showed that phenol adsorption was completed after 2 h. Adsorption isotherms were measured for phenol from aqueous solution onto silica gel sludge under various pHs and temperatures. Results showed that the adsorption capacities for phenol was increased as pH decreased from 6.5 to 2. Temperature also was found to affect the adsorption isotherm. As temperature increases from 30 to 50°C, the adsorption capacity increases. The adsorption equilibrium of phenol on silica gel sludge was described by the linear Freundlich and Langmuir models. Furthermore, results showed that the isotherm parameters fit both linearized Langmuir and Freundlich adsorption isotherms. The Freundlich and Langmuir parameters at optimum pH was found as K _f=2.89, 1/n=0.23 and K _d=22.0, q _m=7.98, respectively. Whereas, for those at optimum temperature it was observed as K _f=2.87, 1/n=0.16 and K _d=20.93, q _m=7.91, respectively.     

Removal of basic dye (Astrazon Blue FGRL) using macroalga Caulerpa lentillifera

The macroalga Caulerpa lentillifera was found to have adsorption capacity for a basic dye, Astrazon Blue FGRL. For the whole range of concentrations employed in this work (20-1280 mgl(-1)), the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second-order kinetic model where the rate constants decreased as initial dye concentrations increased. At low dye concentrations (20-80 mgl(-1)), an increase in the adsorbent dosage resulted in a higher removal percentage of the dye, but a lower amount of dye adsorbed per unit mass (q). The adsorption isotherm followed both the Langmuir and Freundlich models within the temperature range employed in this work (18-70 degrees C). The highest maximum adsorption capacity (q(m)) was obtained at 50 degrees C. The enthalpy of adsorption was estimated at 14.87 kJmol(-1) suggesting a chemical adsorption mechanism.     

Lead removal from contaminated water using mineral adsorbents

This study records experiments undertaken to determine the suitable conditions for the use of naturally occurring minerals (talc, chalcopyrite and barite) as an adsorbent for the removal of lead ions from liquid wastes. The adsorption of lead ions from solutions containing different initial lead concentrations (50, 100, 200, 400, 600, 800 and 1000 mg l^–1 Pb as lead nitrate) using different size fractions (<63 m, 63–150 m) of talc, chalcopyrite and barite at different pH (3, 5, 7 and 9) and different adsorption times (24, 48, 72 and 96 hr) was examined. The results revealed that of the studied minerals, the chalcopyrite fraction at 63–150 m showed the highest adsorption capacity. The adsorption data of Pb ions was also analyzed with the help of the Langmuir and Freundlich models to evaluate the mechanistic parameters associated with the adsorption process. The adsorption isotherms obtained from the Langmuir and Freundlich equations were generally linear and the adsorption of Pb by the studied minerals was correlated with the adsorption maximum and binding energy constant of the Langmuir equation and equilibrium partition constant and binding partition coefficient of the Freundlich equation. It was concluded that the equilibrium time of adsorption was 72 hr at an optimum pH from 7 to 9. This technique might be successfully used for the removal of lead ions from liquid industrial wastes and wastewater.     

Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Adsorption characteristics of Cu and Ni on Irish peat moss

Peat has been widely used as a low cost adsorbent to remove a variety of materials including organic compounds and heavy metals from water. Various functional groups in lignin allow such compounds to bind on active sites of peat. The adsorption of Cu(2+) and Ni(2+) from aqueous solutions on Irish peat moss was studied both as a pure ion and from their binary mixtures under both equilibrium and dynamic conditions in the concentration range of 5-100mg/L. The pH of the solutions containing either Cu(2+) or Ni(2+) was varied over a range of 2-8. The adsorption of Cu(2+) and Ni(+2) on peat was found to be pH dependent. The adsorption data could be fitted to a two-site Langmuir adsorption isotherm and the maximum adsorption capacity of peat was determined to be 17.6 mg/g for Cu(2+) and 14.5mg/g for Ni(2+) at 298 K when the initial concentration for both Cu(2+) and Ni(2+) was 100mg/L, and the pH of the solution was 4.0 and 4.5, respectively. Column studies were conducted to generate breakthrough data for both pure component and binary mixtures of copper and nickel. Desorption experiments showed that 2mM EDTA solution could be used to remove all of the adsorbed copper and nickel from the bed.     

Kinetic and equilibrium isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk ash

The present study deals with the adsorption of Brilliant Green (BG) on rice husk ash (RHA). RHA is a solid waste obtained from the particulate collection equipment attached to the flue gas lines of rice husk fired boilers. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH0), contact time, adsorbent dose and initial concentration (C0) on the removal of BG. Optimum conditions for BG removal were found to be pH0 approximately 3.0, adsorbent dose approximately 6 g L(-1) of solution and equilibrium time approximately 5 h for the C0 range of 50-300 mg L(-1). Adsorption of BG followed pseudo-second-order kinetics. Intra-particle diffusion does not seem to control the BG removal process. Equilibrium isotherms for the adsorption of BG on RHA were analyzed by Freundlich, Langmuir, Redlich-Peterson (R-P), Dubnin-Radushkevich (D-R), and Temkin isotherm models using a non-linear regression technique. Langmuir and R-P isotherms were found to best represent the data for BG adsorption onto RHA. Adsorption of BG on RHA is favourably influenced by an increase in the temperature of the operation. Values of the change in entropy (DeltaS0) and heat of adsorption (DeltaH0) for BG adsorption on RHA were positive. The high negative value of change in Gibbs free energy (DeltaG0) indicates the feasible and spontaneous adsorption of BG on RHA.     

Physicochemical characterization of hydroxyapatite and its application towards removal of nitrate from water

A laboratory study was conducted to investigate the efficiency of hydroxyapatite (HAP) towards removal of nitrate from synthetic nitrate solution. In the present research HAP synthesized from egg-shell was characterized using SEM, XRD, FTIR and TGA–DSC. The removal of nitrate was 96% under neutral conditions, using 0.3 g of adsorbent in 100 mL of nitrate solution having an initial concentration of 100 mg/L. An adsorption kinetic study revealed that the adsorption process followed first order kinetics. Adsorption data were fitted to a linearly transformed Langmuir isotherm with correlation coefficient (R²) > 0.98. Thermodynamic parameters were also calculated to study the effect of temperature on the removal process. In order to understand the adsorption type, equilibrium data were tested with the Dubinin–Radushkevich isotherm. The process was rapid and equilibrium was established within the first 40 min.     

A two stage batch adsorber design for methylene blue removal to minimize contact time

The adsorption of methylene blue onto bentonite in a batch adsorber has been studied. Three kinetic models, the intraparticle diffusion equation and the pseudo first and second order equations, were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption of methylene blue onto bentonite could be described by the pseudo second order equation. Adsorption of methylene blue onto bentonite followed the Langmuir isotherm. A model has been developed for the design of a two stage batch adsorber based on pseudo second order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total contact time to achieve a specified amount of methylene blue removal using a fixed mass of adsorbent. The results of two stage batch adsorber design studies showed that the required times for specified amounts of methylene blue removal significantly decreased. This design is particularly suitable for low-cost adsorbents/adsorption systems when minimising contact time is a major operational and design criterion and a significant volume of effluent needs to be treated in the minimum amount of time.     

Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin

Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Application of cupuassu shell as biosorbent for the removal of textile dyes from aqueous solution

The cupuassu shell (Theobroma grandiflorum) which is a food residue was used in its natural form as biosorbent for the removal of C.I. Reactive Red 194 and C.I. Direct Blue 53 dyes from aqueous solutions. This biosorbent was characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption/desorption curves. The effects of pH, biosorbent dosage and shaking time on biosorption capacities were studied. In acidic pH region (pH 2.0) the biosorption of the dyes were favorable. The contact time required to obtain the equilibrium was 8 and 18 h at 298 K, for Reactive Red 194 and Direct Blue 53, respectively. The Avrami fractionary-order kinetic model provided the best fit to experimental data compared with pseudo-first-order, pseudo-second-order and chemisorption kinetic adsorption models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Radke-Prausnitz isotherm models. For both dyes the equilibrium data were best fitted to the Sips isotherm model.     

Removal of Pb(II) from wastewater using wheat bran

The adsorption of Pb(II) ions from aqueous solutions on wheat bran (WB) has been investigated as a function of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time and pH of solution. The equilibrium process was described well by the Langmuir isotherm model with maximum sorption capacities of 69.0, 80.7 and 87.0 mgg(-1) of Pb(II) on wheat bran at 20, 40 and 60 degrees C, respectively. Thermodynamic parameters, i.e. DeltaG(0), DeltaH(0) and DeltaS(0) have also been calculated for the system and the sorption process was found to be endothermic. Good correlation coefficients were obtained for the pseudo second-order kinetic model. The metal ion could be stripped by addition of 0.5M HCl, making the adsorbent regeneration and its reutilization possible.     

A comparative study on the properties,mechanisms and process designs for the adsorption of non-ionic or anionic dyes onto cationic-polymer/bentonite

The adsorption properties and mechanisms of a cationic-polymer/bentonite complex (EPI-DMA/bentonite), prepared from polyepicholorohydrin-dimethylamine and bentonite, for non-ionic dyes (Disperse Blue SBL and Vat Scarlet R) and anionic dyes (Reactive Violet K-3R and Acid Dark Blue 2G) were investigated in this study. The solution pH, presence of salt and surfactant can significantly affect the dye removal efficiency. The equilibrium data were analyzed using the Langmuir and Freundlich models. The Langmuir model is the most suitable to describe non-ionic dye adsorption, but for anionic dyes the Freundlich model is best. The kinetic data for the adsorption of different dyes were analyzed using pseudo first- and second-order equations, and the experimental data conformed to the pseudo second-order kinetic model better. The possibility of intraparticle diffusion was also examined by using the intraparticle diffusion equation. The single-stage batch adsorber design for the adsorption of both types of dyes onto EPI-DMA/bentonite was studied based on the Langmuir isotherm model for non-ionic dyes and the Freundlich isotherm model for anionic dyes. The results showed that the required amount of EPI-DMA/bentonite for 95% dye removal in 5 L dye solution with a concentration of 50 mg/L is 378.0 g for DB SBL, 126.5 g for VS R, 9.7 g for RV K-3R and 15.5 g for ADB 2G.     

Binding of heavy metal contaminants onto chitosans--an evaluation for remediation of metal contaminated soil and water

The binding efficiency of chitosan samples for Ag(+), Cd(2+), Cu(2+), Pb(2+) and Zn(2+) has been evaluated in order to consider their application to remediate metal contaminated soil and water. The sorption behaviour of metal ions was assessed using a batch technique at different contact time and initial metal concentration with different background electrolytes. The kinetics followed a pseudo-second-order model, while the equilibrium data correlated well with the Freundlich and Langmuir isotherm models. For example, the maximum sorption capacity (Q) for chitosan was estimated as 1.93 mmol/g for Ag(+), 1.61 mmol/g for Cu(2+), 0.94 mmol/g for Zn(2+), 0.72 mmol/g for Cd(2+) and 0.64 mmol/g for Pb(2+). Covalent interaction between metal ions and functional groups (amino and hydroxyl) of the chitosans was the main binding mechanism. Ion exchange is not an important process. Chitosan and cross-linked chitosans were able to bind metal ions in the presence of K(+), Cl(-) and NO(3)(-). The nature of Cl(-) and NO(3)(-) ions did not affect Zn(2+) binding by the chitosans. Even at 11x dilution, the chitosans were able to retain metal ions on their surfaces.     

Sorption and desorption of Cd, Cu and Pb using biomass from an eutrophized habitat in monometallic and bimetallic systems

This work examines the sorption capacity of a natural biomass collected from an irrigation pond. The biomass mainly consisted of a mixture of chlorophyte algae with caducipholic plants. Biosorption experiments were performed in monometallic and bimetallic solutions containing different metals commonly found in industrial effluents (Cd, Cu and Pb). The biosorption process was slightly slower in the binary system comparing with monometallic system which was related to competition phenomena between metal cations in solution. The biosorbent behaviour was quantified by the sorption isotherms fitting the experimental data to mathematical models. In monometallic systems, the Langmuir model showed a better fit with the following sorption order: Cu ~ Pb > Cd; and biomass-metal affinity order: Pb > Cd ~ Cu. In bimetallic systems, the binary-type Langmuir model was used and the sorption order obtained was: Pb ~ Cu > Cd. In addition, the effectiveness of the biomass was investigated in several sorption-desorption cycles using HCl and NaHCO(3). The recovery of metal was higher with HCl than with NaHCO(3), though the sorption uptake of the biomass was sensitively affected by the former desorption agent in subsequent sorption cycles.