Removal and recovery of heavy metals from aqueous solution using Ulmus carpinifolia and Fraxinus excelsior tree leaves

Ulmus carpinifolia and Fraxinus excelsior tree leaves, which are in great supply in Iran, were evaluated for removal of Pb(II), Cd(II) and Cu(II) from aqueous solution. Maximum biosorption capacities for U. carpinifolia and F. excelsior were measured as 201.1, 172.0 mg/g for Pb(II), 80.0, 67.2 mg/g for Cd(II) and 69.5, 33.1 mg/g for Cu(II), respectively. For both sorbents the most effective pH range was found to be 2-5 for Pb(II), 3-5 for Cd(II) and 4-5 for Cu(II). Metal ion biosorption increased as the ratio of metal solution to the biomass quantity decreased. Conversely, biosorption/g biosorbent decreased as the quantity of biomass increased. The biosorption of metal ions increased as the initial metal concentration increased. Biosorption capacities of metal ions were in the following order: Pb(II)>Cd(II)>Cu(II). The equilibrium data for Pb(II) and Cu(II) best fit the Langmuir adsorption isotherm model. Kinetic studies showed that the biosorption rates could be described by a second-order expression. Both the sorbents could be regenerated using 0.2 M HCl during repeated biosorption-desorption cycles with no loss in the efficiency of the Cu(II) removal observed. Biosorption of Pb(II), Cd(II) and Cu(II) was investigated in the presence of Na, K, Mg and Ca ions. The results from these studies show a novel way of using U. carpinifolia and F. excelsior tree leaves to remove Pb(II), Cd(II) and Cu(II) from metal-polluted waters.     

Biosorption of lead from aqueous solutions by green algae Spirogyra species: kinetics and equilibrium studies

Biosorption is the effective method for the removal of heavy metal ions from wastewaters. Results are presented showing the sorption of Pb(II) from solutions by biomass of commonly available, filamentous green algae Spirogyra sp. Batch experiments were conducted to determine the biosorption properties of the biomass and it was observed that the maximum adsorption capacity of Pb(II) ion was around 140mgmetal/g of biomass at pH 5.0 in 100min with 200mg/L of initial concentration. Temperature change in the range 20-40 degrees C affected the adsorption capacity and the nature of the reaction was found to be endothermic in nature. Uptake kinetics follows the pseudo-second-order model and equilibrium is well described by Langmuir isotherm. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change, enthalpy change and entropy change. Various properties of the algae, as adsorbent, explored in the characterization part were chemical composition of the adsorbent, thermal analysis by TGA, surface area calculation by BET method, surface morphology with scanning electron microscope images and surface functionality by FTIR. FTIR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which are responsible for biosorption of metal ions. The results indicated that the biomass of Spirogyra sp. is an efficient biosorbent for the removal of Pb(II) from aqueous solutions.     

Comparative study of the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto S. cerevisiae: determination of biosorption heats

In this study, the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto inactive Saccharomyces cerevisiae was investigated as a function of initial pH, initial metal ion concentration and temperature. The Langmuir model was applied to experimental equilibrium data of Pb(II), Ni(II) and Cr(VI) biosorption depending on temperature and the maximum metal ions uptake at optimum biosorption temperature of 25 °C, were found to be 270.3, 46.3 and 32.6 mg g⁻¹, respectively. Using the Langmuir constant, b values obtained at different temperatures, the biosorption heats of Pb(II), Ni(II) and Cr(VI) were determined as −1.125, −1.912 and −2.89 kcal mol⁻¹, respectively. The results indicated that the biosorption of Pb(II), Ni(II) and Cr(VI) ions to S. cerevisiae is by the physical adsorption and has an exothermic nature.     

Equilibrium, kinetic and thermodynamic study of the biosorption of uranium onto Cystoseria indica algae

Biosorption equilibrium, kinetics and thermodynamics of binding of uranium ions to Cystoseria indica were studied in a batch system with respect to temperature and initial metal ion concentration. Algae biomass exhibited the highest uranium uptake capacity at 15 °C at an initial uranium ion concentration of 500 mg l⁻¹ and an initial pH of 4. Biosorption capacity increased from 198 to 233 mg g⁻¹ with an decrease in temperature from 45 to 15 °C at this initial uranium concentration. The Langmuir isotherm model were applied to experimental equilibrium data of uranium biosorption depending on temperature. Equilibrium data fitted very well to the Langmuir model C. indica algae in the studied concentration range of Uranium ions at all the temperatures studied. The saturation type kinetic model was applied to experimental data at different temperatures changing from 15 to 45 °C to describe the batch biosorption kinetics assuming that the external mass transfer limitations in the system can be neglected and biosorption is chemical sorption controlled. The activation energy of biosorption (E_A) was determined as −6.15 using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption (ΔG°, ΔH° and ΔS°) were also evaluated.     

Biosorption of copper(II) by nonliving lichen biomass of Cladonia rangiformis hoffm

Biosorption of heavy metals can be an effective process for the removal of heavy metal ions from aqueous solutions. In this study, the adsorption properties of lichen biomass of Cladonia rangiformis hoffm. for copper(II) were investigated by using batch adsorption techniques. The effects of initial metal ion concentration, initial pH, biosorbent concentration, stirring speed and contact time on biosorption efficiency were studied. In the experiments the optimum pH value was found out 5.0 which was the native pH value of solution. The experimental adsorption data were fitted to the Langmuir adsorption model. The highest metal uptake was calculated from Langmuir isotherm and found to be 7.6923 mg Cu(II)/g inactivated lichen at 15 degrees C. The results indicated that the biomass of C. rangiformis is a suitable biosorbent for removing Cu(II) from aqueous solutions.     

Kinetic and thermodynamic studies of the biosorption of Cr(VI) by Pinus sylvestris Linn

Biosorption equilibrium, kinetics and thermodynamics of chromium(VI) ions onto cone biomass were studied in a batch system with respect to temperature and initial metal ion concentration. The biosorption efficiency of chromium ions to the cone biomass decreased as the initial concentration of metal ions was increased. But cone biomass of Pinus sylvestris Linn. exhibited the highest Cr(VI) uptake capacity at 45 degrees C. The biosorption efficiency increased from 67% to 84% with an increase in temperature from 25 to 45 degrees C at an initial Cr(VI) concentration of 300 mg/L. The Langmuir isotherm model was applied to experimental equilibrium data of Cr(VI) biosorption depending on temperature. According to Langmuir isotherm, the monolayer saturation capacity (Q(max)) is 238.10 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data for initial Cr(VI). The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order kinetic model. The activation energy of biosorption (E(a)) was determined as 41.74 kJ/mol using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption (DeltaG(0), DeltaH(0) and DeltaS(0)) were also evaluated.     

Equilibrium and kinetic modelling of cadmium(II) biosorption by nonliving algal biomass Oedogonium sp. from aqueous phase

The biosorption of cadmium(II) ions on Oedogonium sp. is studied in a batch system with respect to initial pH, algal dose, contact time and the temperature. The algal biomass exhibited the highest cadmium(II) uptake capacity at 25 degrees C, at the initial pH value of 5.0 in 55 min and at the initial cadmium(II) ion concentration of 200 mg L(-1). Biosorption capacity decreased from 88.9 to 80.4 mg g(-1) with an increase in temperature from 25 to 45 degrees C at this initial cadmium(II) concentration. Uptake kinetics follows the pseudo-second-order model and equilibrium is well described by Langmuir isotherm. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change, enthalpy change and entropy change. FTIR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which are responsible for biosorption of metal ions. Acid pretreatments did not substantially increase metal sorption capacity but alkali like NaOH pretreatment slightly enhanced the metal removal ability of the biomass. During repeated sorption/desorption cycles at the end of fifth cycle, Cd(II) sorption decreased by 18%, with 15-20% loss of biomass. Nevertheless, Oedogonium sp. appears to be a good sorbent for removing metal Cd(II) from aqueous phase.     

Investigation of nickel(II) biosorption on Enteromorpha prolifera: optimization using response surface analysis

In this study, the biosorption of nickel(II) ions on Enteromorpha prolifera, a green algae, was investigated in a batch system. The single and combined effects of operating parameters such as initial pH, temperature, initial metal ion concentration and biosorbent concentration on the biosorption of nickel(II) ions on E. prolifera were analyzed using response surface methodology (RSM). The optimum biosorption conditions were determined as initial pH 4.3, temperature 27 degrees C, biosorbent concentration 1.2 g/L and initial nickel(II) ion concentration 100 mg/L. At optimum biosorption conditions, the biosorption capacity of E. prolifera for nickel(II) ions was found to be 36.8 mg/g after 120 min biosorption. The Langmuir and Freundlich isotherm models were applied to the equilibrium data and defined very well both isotherm models. The monolayer coverage capacity of E. prolifera for nickel(II) ions was found as 65.7 mg/g. In order to examine the rate limiting step of nickel(II) biosorption, such as the mass transfer and chemical reaction kinetics, the intraparticle diffusion model, external diffusion model and the pseudo second order kinetic model were tested with the experimental data. It was found that for both contributes to the actual biosorption process. The pseudo second order kinetic model described the nickel(II) biosorption process with a good fitting.     

Biosorption of zinc from aqueous solution using Azadirachta indica bark: equilibrium and kinetic studies

The removal of zinc ions from aqueous solutions on the biomass of Azadirachta indica bark has been studied by using batch adsorption technique. The biosorption studies were determined as a function of contact time, pH, initial metal ion concentration, average biosorbent size and biosorbent dosage. The equilibrium metal uptake was increased and percentage biosorption was decreased with an increase in the initial concentration and particle size of biosorbent. The maximum zinc biosorption occurred at pH 6 and percentage biosorption increases with increase in the biosorbent dosage. Experimental data obtained were tested with the adsorption models like Langmuir, Freundlich and Redlich-Peterson isotherms. Biosorption isothermal data were well interpreted by Langmuir model with maximum biosorption capacity of 33.49mg/g of zinc ions on A. indica bark biomass and kinetic data were properly fitted with the pseudo-second-order kinetic model.     

Biosorption of copper (II) onto immobilized cells of Pycnoporus sanguineus from aqueous solution: equilibrium and kinetic studies

The ability of white-rot fungus, Pycnoporus sanguineus to adsorb copper (II) ions from aqueous solution is investigated in a batch system. The live fungus cells were immobilized into Ca-alginate gel to study the influence of pH, initial metal ions concentration, biomass loading and temperature on the biosorption capacity. The optimum uptake of Cu (II) ions was observed at pH 5 with a value of 2.76mg/g. Biosorption equilibrium data were best described by Langmuir isotherm model followed by Redlich-Peterson and Freundlich models, respectively. The biosorption kinetics followed the pseudo-second order and intraparticle diffusion equations. The thermodynamic parameters enthalpy change (10.16kJ/mol) and entropy change (33.78J/molK) were determined from the biosorption equilibrium data. The FTIR analysis showed that OH, NH, CH, CO, COOH and CN groups were involved in the biosorption of Cu (II) ions onto immobilized cells of P. sanguineus. The immobilized cells of P. sanguineus were capable of removing Cu (II) ions from aqueous solution.     

Biosorption of mercury from aqueous solutions by powdered leaves of castor tree (Ricinus communis L.)

A new biosorbent produced from castor leaves powder [Ricinus communis L.] was used to remove mercury(II) from aqueous solutions. The initial mercury concentrations, contact time and initial pH were evaluated. The ability of castor leaves to remove mercury at various pH (2-8) was studied. The maximum capacity (Qmax) of biomass was found to be 37.2mg Hg(II)/g at pH 5.5. Biosorption equilibrium was established in approximately 1h. The equilibrium data were described well by Langmuir and Freundlich models. The adsorbed mercury on biomass was desorbed using 10 ml of 4M HCl solution. The biomass could be reused for other biosorption assays. The ability of biomass to adsorb mercury(II) in a column was investigated. These studies consider the possibility of using leaves of castor tree as an inexpensive adsorbent for the removal of Hg(II) from contaminated chemical and mining industry wastewaters. It is also suggested that the dried biomass might be simply kept and used in a very low cost metal ion removal system.     

Untreated coffee husks as biosorbents for the removal of heavy metals from aqueous solutions

The objective of this work was to propose an alternative use for coffee husks (CH), a coffee processing residue, as untreated sorbents for the removal of heavy metal ions from aqueous solutions. Biosorption studies were conducted in a batch system as a function of contact time, initial metal ion concentration, biosorbent concentration and pH of the solution. A contact time of 72 h assured attainment of equilibrium for Cu(II), Cd(II) and Zn(II). The sorption efficiency after equilibrium was higher for Cu(II) (89-98% adsorption), followed by Cd(II) (65-85%) and Zn(II) (48-79%). Even though equilibrium was not attained in the case of Cr(VI) ions, sorption efficiency ranged from 79 to 86%. Sorption performance improved as metal ions concentrations were lowered. The experimental sorption equilibrium data were fitted by both Langmuir and Freundlich sorption models, with Langmuir providing the best fit (R2>0.95). The biosorption kinetics was determined by fitting first and second-order kinetic models to the experimental data, being better described by the pseudo-second-order model (R2>0.99). The amount of metal ions sorbed increased with the biosorbent concentration in the case of Cu(II) and Cr(VI) and did not present significant variations for the other metal ions. The effect of the initial pH in the biosorption efficiency was verified in the pH range of 4-7, and the results showed that the highest adsorption capacity occurred at distinct pH values for each metal ion. A comparison of the maximum sorption capacity of several untreated biomaterial-based residues showed that coffee husks are suitable candidates for use as biosorbents in the removal of heavy metals from aqueous solutions.     

Studies on the applicability of alginate-entrapped Chryseomonas luteola TEM 05 for heavy metal biosorption

Chryseomonas luteola TEM 05 cells were entrapped both in alginate and chitosan coated alginate beads. Biosorption of metal ions on alginate beads was investigated by using a batch stirred system at pH 6.0, 25 degrees C, in initial metal concentration of 1.92 mM of Cr6+, 0.89 mM Cd2+ and 1.69 mM Co2+. Then, a process of competitive biosorption of these metal ions was described and compared to single metal ion adsorption in solution. The apparent equilibrium biosorption was reached within the 180 min of contact for all metals. Although the competitive biosorption capacities of the beads for all metal ions were lower than those of single conditions, Cd2+ biosorption on alginate and alginate-chitosan beads did not change significantly.     

Biosorption of Pb(II) and Cd(II) from aqueous solution using green alga (Ulva lactuca) biomass

The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the green alga (Ulva lactuca) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by U. lactuca biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The monolayer biosorption capacity of U. lactuca biomass for Pb(II) and Cd(II) ions was found to be 34.7mg/g and 29.2mg/g, respectively. From the D-R isotherm model, the mean free energy was calculated as 10.4kJ/mol for Pb(II) biosorption and 9.6kJ/mol for Cd(II) biosorption, indicating that the biosorption of both metal ions was taken place by chemisorption. The calculated thermodynamic parameters (DeltaG degrees , DeltaH degrees and DeltaS degrees ) showed that the biosorption of Pb(II) and Cd(II) ions onto U. lactuca biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both metal ions followed well pseudo-second-order kinetics.     

Biosorption of Reactive Black 5 dye by Penicillium restrictum: the kinetic study

Biosorption of Reactive Black 5 (RB 5) dye onto dried Penicillium restrictum biomass was studied with respect to pH, contact time, biosorbent and dye concentrations. The effect of temperature on the biosorption efficiency was also carried out and the kinetic parameters were determined. Optimum initial pH, equilibrium time and biomass concentration for RB 5 dye were found to be 1.0, 75 min and 0.4 g dm(-3) at 20 degrees C, respectively. The maximum biosorption capacities (q(max)) of RB 5 dye onto dried P. restrictum biomass were 98.33 and 112.50mg (g biomass)(-1) at 175 mg dm(-3) initial dye concentration at 20 and 50 degrees C, respectively, and it was 142.04 mg (g biomass)(-1) at 200 mg dm(-3) initial dye concentration at 35 degrees C. The results indicate that the biosorption process obeys a pseudo-second-order kinetic model.     

Biosorption of heavy metal ions on immobilized white-rot fungus Trametes versicolor

Trametes versicolor mycelia were immobilized in carboxymethylcellulose, CMC, beads via entrapment, and the bead containing immobilized fungus spores were incubated at 30 degrees C for 3 days to attain uniform growth on the bead surface. After incubation, the live and heat inactivated immobilized fungus on the CMC beads were used for the biosorption of Cu(2+), Pb(2+) and Zn(2+) ions.Plain CMC beads were used as a control system. The biosorption of Cu(2+), Pb(2+) and Zn(2+) ions by the CMC and both live and inactivated immobilized preparations increased as the initial concentration of Cu(2+), Pb(2+) and Zn(2+) ions in the medium increased. The maximum biosorption capacities for both immobilized live and heat inactivated Trametes versicolor were 1.51 and 1.84mmol Cu(2+), 0.85 and 1.11mmol Pb(2+) and 1.33 and 1.67mmol Zn(2+) per g of dry biosorbents, respectively. Biosorption equilibrium was established in about 1.0h and the equilibrium was well described by Langmuir and Freundlich isotherms. A temperature change in the range of 15-45 degrees C did not affect the biosorption capacity. The affect of pH was also investigated and the maximum adsorption of Cu(2+), Pb(2+) and Zn(2+) ions on the CMC and both live and inactivated immobilized fungal biomass was observed between pH 4.0 and 6.0. The CMC beads with the immobilized fungus can be regenerated using 10mM HCl, with up to 97% recovery of the metal ions; the biosorbents reused up to five biosorption-desorption cycles without any major loss in the biosorption capacity.     

Effect of Cu(II), Cd(II) and Zn(II) on Pb(II) biosorption by algae Gelidium-derived materials

Biosorption of Pb(II), Cu(II), Cd(II) and Zn(II) from binary metal solutions onto the algae Gelidium sesquipedale, an algal industrial waste and a waste-based composite material was investigated at pH 5.3, in a batch system. Binary Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II) solutions have been tested. For the same equilibrium concentrations of both metal ions (1 mmol l(-1)), approximately 66, 85 and 86% of the total uptake capacity of the biosorbents is taken by lead ions in the systems Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II), respectively. Two-metal results were fitted to a discrete and a continuous model, showing the inhibition of the primary metal biosorption by the co-cation. The model parameters suggest that Cd(II) and Zn(II) have the same decreasing effect on the Pb(II) uptake capacity. The uptake of Pb(II) was highly sensitive to the presence of Cu(II). From the discrete model it was possible to obtain the Langmuir affinity constant for Pb(II) biosorption. The presence of the co-cations decreases the apparent affinity of Pb(II). The experimental results were successfully fitted by the continuous model, at different pH values, for each biosorbent. The following sequence for the equilibrium affinity constants was found: Pb>Cu>Cd approximately Zn.     

Ni(II) removal from aqueous solutions using cone biomass of Thuja orientalis

The biomass of terrestrial-plant materials has high removal capacities for a number of heavy metal ions. The Ni(II) biosorption capacity of the cone biomass of Thuja orientalis was studied in the batch mode. The biosorption equilibrium level was determined as a function of contact time, pH, temperature, agitation speed at several initial metal ion and adsorbent concentrations. The removal of Ni(II) from aqueous solutions increased with adsorbent concentration, temperature and agitation speed of the solution were increased. The biosorption process was very fast; 90% of biosorption occurred within 3 min and equilibrium was reached at around 7 min. It is found that the biosorption of Ni(II) on the cone biomass was correlated well (R2 > 0.99) with the Langmuir equation as compared to Freundlich, BET Temkin and D-R isotherm equation under the concentration range studied. According to Langmuir isotherm, the monolayer saturation capacity (Q(o)) is 12.42 mg g(-1). The pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models were applied to test the experimental data for initial Ni(II) and cone biomass concentrations. The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order and intraparticle diffusion kinetic models. The activation energy of biosorption (E(a)) was determined as 36.85 kJ mol(-1) using the Arrhenius equation. This study indicated that the cone biomass of T. orientalis can be used as an effective and environmentally friendly adsorbent for the treatment of Ni(II) containing aqueous solutions.     

Kinetic and equilibrium studies of biosorption of Pb(II) and Cd(II) from aqueous solution by macrofungus (Amanita rubescens) biomass

The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the macrofungus (Amanita rubescens) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by A. rubescens biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The maximum biosorption capacity of A. rubescens for Pb(II) and Cd(II) was found to be 38.4 and 27.3mg/g, respectively, at optimum conditions of pH 5.0, contact time of 30min, biomass dosage of 4 g/L, and temperature of 20 degrees C. The metal ions were desorbed from A. rubescens using both 1M HCl and 1M HNO(3). The recovery for both metal ions was found to be higher than 90%. The high stability of A. rubescens permitted ten times of adsorption-elution process along the studies without a decrease about 10% in recovery of both metal ions. The mean free energy values evaluated from the D-R model indicated that the biosorption of Pb(II) and Cd(II) onto A. rubescens biomass was taken place by chemical ion-exchange. The calculated thermodynamic parameters, DeltaG degrees , DeltaH degrees and DeltaS degrees showed that the biosorption of Pb(II) and Cd(II) ions onto A. rubescens biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both Pb(II) and Cd(II) followed well pseudo-second-order kinetics. Based on all results, It can be also concluded that it can be evaluated as an alternative biosorbent to treatment wastewater containing Pb(II) and Cd(II) ions, since A. rubescens is low-cost biomass and has a considerable high biosorption capacity.     

Study of Cu(II) biosorption by dried activated sludge: effect of physico-chemical environment and kinetics study

Biosorption is a recent technology used to remove heavy metal ions from aqueous solutions. The biosorption of copper ions from aqueous solution by dried activated sludge was investigated in batch systems. Effect of solution pH, initial metal concentration and particle size range were determined. The suitable pH and temperature for studied conditions were determined as 4.0 and 20 °C, respectively. The theoretical max biosorption capacity of activated sludge was 294 mg g⁻¹ at 20 °C for <0.063 mm particle size. The equilibrium data fitted very well to both Langmuir and Freundlich isotherm models. The pseudo first and second-order kinetic models were used to describe the kinetic data. The experimental data fitted to second-order kinetic model. The particle size and initial metal concentration were effected the biosorption capacity of dried activated sludge. An increase in the initial metal concentration increases of biosorption capacity, which also increases with decreasing particle size. Dried activated sludge has different functional groups according to the FT-IR results.