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.     

Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

Sorption isotherm studies of Cd(II) ions using living cells of the marine microalga Tetraselmis suecica (Kylin) Butch

The present work reports the use of living cells of the marine microalga Tetraselmis suecica for the biosorption of cadmium ions. For a better understanding of the biosorption characteristics, three fractions of removed cadmium (total, bioadsorbed and intracellular) were measured in the cells after 24 and 72 h of exposure to different initial cadmium concentrations (0.6–45 mg L^?1). Both the Langmuir and Freundlich models were suitable for describing the sorption of cadmium ions by this microalga. The maximum sorption capacity was estimated to be 40.22 mg Cd g^?1 after 72 h using the Langmuir sorption model. In the lower cadmium concentrations, metal removed intracellularly was higher than that removed on the microalgal cell surface. Therefore, the intracellular fraction contributed more to the total removed cadmium than the fraction bioadsorbed to the cellular surface. The results showed that the cadmium removal capacity using living biomass could be much more effective than with non-living biomass due to the intracellular bioaccumulation. According to the microorganism selected and its tolerance to the toxic effect of the metal, the cadmium content in the intracellular fraction can become very significant, just like it happened with Tetraselmis.     

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.     

Equilibrium studies of copper ion adsorption onto palm kernel fibre

The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin–Radushkevich (D–R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r², and the non-linear Chi-square, χ² error analysis.The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH_PZC of the palm kernel fibre with an optimum dose of 10 g/dm³. The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 × 10^?4 mol/g at 339 K. The sorption equilibrium constant, K_a, increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B₁, with increasing temperature. The Dubinin–Radushkevich (D–R) isotherm parameter, free energy, E, was in the range of 15.7–16.7 kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO₃ and CH₃COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic.     

Biosorption of lead by maize (Zea mays) stalk sponge

This study investigated the removal of Pb(II) from aqueous solutions by a maize (Zea mays) stalk sponge. Equilibrium and kinetic models for Pb(II) sorption were developed by considering the effect of the contact time and concentration at the optimum pH of 6 ± 0.2. The Freundlich model was found to describe the sorption energetics of Pb(II) by Z. mays stalk sponge, and a maximum Pb(II) loading capacity of 80 mg g^?1 was determined. The kinetic parameters were obtained by fitting data from experiments measuring the effect of contact time on adsorption capacity into pseudo-first and second-order equations. The kinetics of Pb(II) sorption onto Z. mays biosorbent were well defined using linearity coefficients (R²) by the pseudo-second-order equation (0.9998). The results obtained showed that Zea may stalk sponge was a useful biomaterial for Pb(II) sorption and that pH has an important effect on metal biosorption capacity.     

Fly ash for the treatment of Zn(II) rich effluents

Summary The ability of fly ash to remove Zn(II) from water by adsorption has been tested at different concentrations, temperatures and pH of the solution. It was found that low adsorbate concentration, small particle size of adsorbent and higher temperature favoured the removal of Zn(II) from aqueous solution. The Langmuir isotherm was used to represent the equilibrium data at different temperatures. The apparent heat of adsorption has been found to be 17.325 Kcal mol^–1, which indicates the process to be endothermic. The uptake of Zn(II) is diffusion controlled and the mass transfer coefficient is 3.56 × 10^–5 cm s ^–1.The maximum removal was noted at pH 7.5. Dr V.N. Singh is Professor and Head of the Department of Applied Chemistry, Dr A.K. and Prof. D.P. Singh are members of the Department of Mining Engineering; all are situated in the Institute of Technology at Banaras Hindu University.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Removal of phosphorus from aqueous solutions using chemically modified sawdust of Aleppo pine (<Emphasis Type="Italic">Pinus halepensis Miller</Emphasis>): kinetics and isotherm studies

In the present study, chemically modified Aleppo pine (Pinus halepensis Miller) sawdust was used for the removal of phosphate from water. Biosorbent preparation process included size fractionation, extraction for surface activation, acid prehydrolysis, and treatment with urea. Sorption of phosphate ions onto biosorbent was studied using the batch technique. The effect of different parameters such as contact time, adsorbate concentration, and temperature was investigated. The adsorption kinetics data were best described by the pseudo-second-order rate equation, and equilibrium was achieved after 40 and 80 min for modified and unmodified sawdust, respectively. The Langmuir and Freundlich equations for describing adsorption equilibrium were applied to data. The constants and correlation coefficients of these isotherm models were calculated and compared. The adsorption isotherms obey the Freundlich equation. The thermodynamic parameters like free energy, enthalpy, and entropy changes for the adsorption of phosphate ions have been evaluated, and it has been found that the reaction was spontaneous and endothermic in nature. The low value of activated energy of adsorption, 3.088–3.540 kJ mol⁻¹, indicates that the phosphate ions are easily adsorbed on the sawdust. Results suggest that the prepared chemically modified Aleppo pine sawdust has potential in remediation of contaminated waters by phosphate.     

Comparison of biosorbents with inorganic sorbents for removing copper(II) from aqueous solutions

In comparison with several other reported inorganic sorbents, Camellia tree leaf and primary sludge obtained from a settling tank as a pretreatment to the activated sludge system in a Hong Kong sewage treatment plant were evaluated for removing Cu(II) from aqueous solutions. Experimental data were modeled by the Langmuir isotherm equation to estimate the maximum sorption capacity (q_max). Results show that, at pH 5.6, biosorbents, Camellia tree leaf and primary sludge in particular, exert higher sorption capacities (q_max > 40 mg g⁻¹) than inorganic sorbents, Na-montmorillonite (q_max = 33.3 mg g⁻¹), fly ash (q_max = 18.8 mg g⁻¹), and goethite powder (10.3 mg g⁻¹). Furthermore, a pseudo second-order kinetic model was found to properly describe the experimental data for both bio- and inorganic sorbents. Sorption of Cu(II) on the Camellia tree leaf and primary sludge were much faster than that on the inorganic sorbents. In addition, desorption tests revealed that the desorption capacities of the two biomaterials are higher than the other selected materials; and much more Cu(II) can be retrieved from the Cu(II)-loaded biosorbents. Finally, increasing solution pH was found to greatly increase q_max and accelerate sorption processes.     

Effect of salinity on metal-complex dye biosorption by Rhizopus arrhizus

In this study the biosorption of Yellow RL, a metal-complex anionic dye, by dried Rhizopus arrhizus, a filamentous fungus, was investigated as a function of initial solution pH, initial dye concentration and initial salt (sodium chloride) concentration. The fungus exhibited the maximal dye uptake at pH 2 in the absence and in the presence of salt. Dye uptake increased with the dye concentration up to 1000 mg l^?1 and diminished considerably in the presence of increasing concentrations of salt up to 50 g l^?1. The fungus biosorbed 85.4 mg dye g^?1of dried biomass at 100 mg l^?1 initial dye concentration in the absence of salt. When 50 g l^?1 salt was added to the biosorption medium, this value dropped to 60.8 mg g^?1 resulting in 28.8% reduction in biosorption capacity. The Redlich–Peterson and Langmuir–Freundlich were the most suitable adsorption models for describing the biosorption equilibrium data of the dye both individually and in salt containing medium. The pseudo-second-order and saturation type kinetic models depicted the biosorption kinetics accurately for all cases studied. Equilibrium and kinetic constants varied with the level of salt were expressed as a function of salt concentration.     

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.     

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.     

Determination of model parameters for zinc (II) ion biosorption onto powdered waste sludge (PWS) in a fed-batch system

Biosorption of zinc (II) ions onto pre-treated powdered waste sludge (PWS) was investigated using a completely mixed tank operating in fed-batch mode instead of an adsorption column. Experiments with variable feed flow rate (0.05-0.5 L h(-1)), feed Zn(II) ion concentrations (37.5-275 mg L(-1)) and amount of adsorbent (1-6 g PWS) were performed using fed-batch operation at pH 5 and room temperature (20-25 degrees C). Break-through curves describing variations of aqueous (effluent) zinc ion concentrations with time were determined for different operating conditions. Percent zinc removal from the aqueous phase decreased, but the biosorbed (solid phase) zinc ion concentration increased with increasing feed flow rate and zinc concentration. A modified Bohart-Adams equation was used to determine the biosorption capacity of PWS (q'(s)) and the rate constant (K) for zinc ion biosorption. Biosorption capacity (q'(s)=57.7 g Zn kg(-1) PWS) of PWS in fed-batch operation was found to be comparable with powdered activated carbon (PAC) in column operations. However, the adsorption rate constant (K=9.17 m(3) kg(-1) h(-1)) in fed-batch operation was an order of magnitude larger than those obtained in adsorption columns because of elimination of mass transfer limitations encountered in the column operations. Therefore, a completely mixed tank operated in fed-batch mode was proven to be more advantageous as compared to adsorption columns due to better contact between the phases yielding faster adsorption rates.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

Biosorption of Cu and Zn from aqueous solutions by dried marine green macroalga Chaetomorpha linum

The biosorption of the heavy metals Cu²⁺ and Zn²⁺ by dried marine green macroalga (Chaetomorpha linum) was investigated. The biosorption capacities of the dried alga for copper and zinc were studied at different solution pH values (2–6), different algal particle sizes (100–800 μm) and different initial metal solution concentrations (0.5–10 mM). An optimum pH value of 5 was found suitable for both metal ions biosorption for both metal ions. At the optimum particle size (100–315 μm), biosorbent dosage (20 g/l) and initial solution pH (pH 5), the dried alga produced maximum copper and zinc uptakes values (q_max) of 1.46 and 1.97 mmol/g respectively (according to the Langmuir model). The kinetic data obtained at different initial metal concentrations indicated that the biosorption rate was fast and most of the process was completed within 120 min. This study illustrated an alternative technique for the management of unwanted biological materials using processed algal material. C. linum is one of the fast-growing marine algae in the lake of Tunis and could be utilized as a biosorbent for the treatment of Cu²⁺ and Zn²⁺ contaminated wastewater streams.     

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.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.     

Experimental investigation of adsorption capacity of anthill in the removal of heavy metals from aqueous solution

In the present work, the adsorption capacity of anthill was investigated as a low‐cost adsorbent to remove the heavy metal ions, lead (II) ion (Pb²⁺), and zinc (II) ion (Zn²⁺) from an aqueous solution. The equilibrium adsorption isotherms of the heavy metal ions were investigated under batch process. For the study we examined the effect of the solution's pH and the initial cations concentrations on the adsorption process under a fixed contact time and temperature. The anthill sample was characterized using a scanning electron microscope (SEM), X‐ray fluorescence (XRF), and Fourier transform infrared (FTIR) techniques. From the SEM analysis, structural change in the adsorbent was a result of heavy metals adsorption. Based on the XRF analysis, the main composition of the anthill sample was silica (SiO₂), alumina (Al₂O₃), and zirconia (ZrO₂). The change in the peaks of the spectra before and after adsorption indicated that there was active participation of surface functional groups during the adsorption process. The experimental data obtained were analyzed using 2‐ and 3‐parameter isotherm models. The isotherm data fitted very well to the 3‐parameter Radke–Prausnitz model. It was noted that Pb²⁺ and Zn²⁺ can be effectively removed from aqueous solution using anthill as an adsorbent.