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.     

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.     

Removal of Ni(II), Zn(II) and Cr(VI) from aqueous solution by Alternanthera philoxeroides biomass

Alternanthera philoxeroides biomass, a type of freshwater macrophyte, was used for the sorptive removal of Ni(II), Zn(II) and Cr(VI) from aqueous solutions. Variables of the batch experiments include solution pH, contact time, particle size and temperature. The biosorption capacities are significantly affected by solution pH. Higher pH favors higher Ni(II), Zn(II) removal, whereas higher uptake of Cr(VI) is observed as the pH is decreased. A two-stage kinetic behavior is observed in the biosorption of Ni(II), Zn(II) and Cr(VI): very rapid initial biosorption in a few minutes, followed by a long period of a slower uptake. It is noted that an increase in temperature results in a higher Ni(II), Zn(II) and Cr(VI) loading per unit weight of the sorbent. Decreasing the particle sizes of the Alternanthera philoxeroides biomass leads to an increase in the Ni(II), Zn(II) and Cr(VI) uptake per unit weight of the sorbent. All isothermal data are fairly well fitted with Langmuir equations. The thermodynamic parameter, DeltaG degrees, were calculated. The negative DeltaG degrees values of Cr(VI), Ni(II) and Zn(II) at various temperatures confirm the adsorption processes are spontaneous.     

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.     

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.     

Silica gel functionalized with 4-phenylacetophynone 4-aminobenzoylhydrazone: Synthesis of a new chelating matrix and its application as metal ion collector

The silica gel surface immobilized with 4-phenylacetophynone 4-aminobenzoylhydrazone (PAAH) after surface modification by 3-chloropropyltrimethoxysilane (CPTS). The modified silica gel was used for sorption of Cu(II), Ni(II) and Co(II) in aqueous solution. The effect of solution pH, sorption time, temperature and initial metal ion concentration onto metal ions sorption was investigated. The characteristics of the sorption process were evaluated by using the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) adsorption isotherms. The sorption of metal ions onto modified silica gel correlated well with the Langmuir type adsorption isotherm and adsorption capacities were found to be 0.012, 0.014 and 0.018 mmol g⁻¹ for Cu(II), Ni(II) and Co(II) metal ions, respectively. From the D–R adsorption isotherms, it was concluded that chemical interactions and chelating effects were playing an important role in the sorption of metal ions onto modified silica gel.

Thermodynamic parameters such as the standard free energy change (ΔG)°, enthalpy change (ΔH°) and entrophy change (ΔS°) were calculated to determine the nature of sorption process. From these parameters, ΔH° were found to be endothermic values: 38.39, 18.0, and 14.7 kJ mol⁻¹ for the same sequence of divalent cations and ΔS° values were calculated to be positive for the sorption of each metal ion onto the modified silica gel. Negative ΔG° values indicated that sorption process for all metal ions were spontaneous in nature although they presented an endothermic enthalpy for the interaction, resulting in an entropically favoured process.     

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.     

Biosorption of cadmium(II), zinc(II) and lead(II) by Penicillium simplicissimum: Isotherms, kinetics and thermodynamics

The isotherms, kinetics and thermodynamics of Cd(II), Zn(II) and Pb(II) biosorption by Penicillium simplicissimum were investigated in a batch system. The effects of pH, initial metal ions concentration, biomass dose, contact time, temperature and co-ions on the biosorption were studied. Adsorption data were well described by both the Redlich–Peterson and Langmuir model. Chemical ion-exchange was found to be an important process based on free energy value from Dubini–Radushkevich isotherm for all metal ions. The results of the kinetic studies of all metal ions at different temperature showed that the rate of adsorption followed the pseudo second-order kinetics well. The thermodynamics constants ΔG°, ΔH° and ΔS° of the adsorption process showed that biosorption of Cd(II), Zn(II) and Pb(II) ions on Penicillium simplicissimum were endothermic and spontaneous.     

Biosorption of nickel and copper onto treated alga (Undaria pinnatifida): application of isotherm and kinetic models

Biosorption of nickel and copper ions from aqueous solution onto treated alga biomass Undaria pinnatifida has been studied and the Langmuir, Freundlich and Temkine equilibrium isotherms, pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic model were determined respectively. Within the test range (initial concentration 5–50 mg/L, biosorption doze 0.1–0.5 g, pH 3–7), biosorption performance for metal ions showed an increase in specific metal uptake capacity with an increasing in initial ions concentration and decreasing in biosorbent doze. The optimized condition of pH value for nickel and copper is 4.7 and 4.0, respectively, while contact time is about 100 min. At equilibrium, the maximum total uptake by U. pinnatifida was 24.71 mg/g for nickel and 38.82 mg/g for copper. The results for nickel and copper fit well to the Langmuir and the Temkin isotherm, respectively. Pseudo-second-order model described well the sorption kinetic of nickel and copper ions in comparison to pseudo-first-order and intra-particle diffusion kinetic model.     

Adsorption of Pb(II) and Cd(II) metal ions from aqueous solutions by mustard husk

The adsorption of Pb(II) and Cd(II) metal ions on mustard husk has been found to be concentration, pH, contact time, adsorbent dose and temperature dependent. The adsorption parameters were determined using Langmuir and Freundlich isotherm models. The adsorption isotherm studies clearly indicated that the adsorptive behavior of Pb(II) and Cd(II) metal ions on mustard husk satisfies not only the Langmuir assumptions but also the Freundlich assumptions, i.e. multilayer formation on the surface of the adsorbent with an exponential distribution of site energy. Ion exchange and surface complexation are the major adsorption mechanisms involved.

The applicability of Lagergren kinetic model has also been investigated. Thermodynamic constant (k_ad), free energy change (ΔG), enthalpy change (ΔH) and entropy change (ΔS) were calculated for predicting the nature of adsorption. The results indicate the potential application of this method for effluent treatment in industries and also provide strong evidence to support the adsorption mechanism proposed.     

Adsorptive removal of heavy metals from aqueous solution by treated sawdust (Acacia arabica)

The removal of Cr(VI), Pb(II), Hg(II) and Cu(II), by treated sawdust has been found to be concentration, pH, contact time, adsorbent dose and temperature dependent. The adsorption parameters were determined using both Langmuir and Freundlich isotherm models. Adsorption capacity for treated sawdust, i.e. Cr(VI) (111.61 mg/g), Pb(II) (52.38 mg/g), Hg(II) (20.62 mg/g), and Cu(II) (5.64 mg/g), respectively. Surface complexation and ion exchange are the major removal mechanisms involved. The adsorption isotherm studies clearly indicated that the adsorptive behaviour of metal ions on treated sawdust satisfies not only the Langmuir assumptions but also the Freundlich assumptions. The applicability of Lagergren kinetic model has also been investigated. The adsorption follows first-order kinetics. Thermodynamic constant (k_ad), standard free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated for predicting the nature of adsorption. The percentage adsorption increases with pH to attain a maximum at pH 6 and thereafter it decreases with further increase in pH. The results indicate the potential application of this method for effluent treatment in industries and also provide strong evidence to support the adsorption mechanism proposed.     

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.     

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.     

Synthesis of some ferromagnetic composite resins and their metal removal characteristics in aqueous solutions

In this study, a procedure for synthesis of new organic-inorganic magnetic composite resins was established. The procedure was based upon immobilization of magnetite (Mag) as a ferromagnetic material within the polymer poly(acrylic acid acrylonitrile) P(AA-AN) and the ion exchange resin (Amberlite IR120). The produced magnetic resins, IR120-PAN-Mag (R1) and P(AA-AN)-Mag (R2) were assessed as sorbents for Cr(VI). Various factors influencing the sorption of Cr(VI), e.g., pH, equilibrium time, initial concentration and temperature were studied. The sorption process was very fast initially and maximum sorption was achieved within 3 h and pH 5.1. The kinetic of the system has been evaluated with pseudo first order model, second order model, Elovich model, intra-particle diffusion model and liquid film diffusion model. Chromium interaction with composite particles followed second-order kinetics with a correlation coefficient extremely high and closer to unity and rate constant (k_s) has the values 1.68 × 10⁻⁴ and 1.9 × 10⁻⁴ g (mg⁻¹ min⁻¹) for R1 and R2, respectively. The values of equilibrium sorption capacity (q_e) are consistent with the modeled data and attain the range 893–951 mg g⁻¹. Kinetically, both pore diffusion and film diffusion are participating in ruling the diffusion of Cr(VI) ions. The sorption data gave good fits with Temkin and Flory–Huggins isotherm models. The isotherm parameters related to the heat of sorption are in the range 8–16 kJ mol⁻¹ which is the range of bonding energy for ion exchange interactions and so suggest an ion exchange mechanism for removal of Cr(VI) by the composite sorbents. The adsorption process was exothermic with ΔH in the range of −73 to −97 kJ mol⁻¹. The negative values of Gibbs free energy confirm the feasibility and the spontaneous nature of Cr(VI) removal with these novel composites.     

Adsorption of copper (II), chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti sawdust

The present study proposed the use of meranti sawdust in the removal of Cu(II), Cr(III), Ni(II) and Pb(II) ions from synthetic aqueous solutions. Batch adsorption studies showed that meranti sawdust was able to adsorb Cu(II), Cr(III), Ni(II) and Pb(II) ions from aqueous solutions in the concentration range 1–200 mg/L. The adsorption was favoured with maximum adsorption at pH 6, whereas the adsorption starts at pH 1 for all metal ions. The effects of contact time, initial concentration of metal ions, adsorbent dosage and temperature have been reported. The applicability of Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm was tried for the system to completely understand the adsorption isotherm processes. The adsorption kinetics tested with pseudo-first-order and pseudo-second-order models yielded high R² values from 0.850 to 0.932 and from 0.991 to 0.999, respectively. The meranti sawdust was found to be cost effective and has good efficiency to remove these toxic metal ions from aqueous solution.     

Copper(II) and zinc(II) biosorption on Pinus sylvestris L

The biosorption properties of copper(II) and zinc(II) onto a cone biomass of Pinus sylvestris L. was investigated by using batch techniques. The biosorption studies carried out with single metal solutions. The removal of copper(II) and zinc(II) from aqueous solution increased with pH and sharply decreased when pH of the solution was decreased. The maximum biosorption efficiency of P. sylvestris was 67% and 30% for Cu(II) and Zn(II), respectively. Batch kinetic and isotherm of biosorption metal ions were investigated. The second-order kinetic model was used to correlate the experimental data. The Freundlich and Langmuir model can describe the adsorption equilibrium of metal(II) on cone biomass. The biosorption constants were found from the Freundlich and Langmuir isotherms at 25 degrees C. It is found that the biosorption data of metals on cone biomass fitted both the Freundlich and Langmuir adsorption models.     

Pb(II) biosorption from hazardous aqueous streams using Gossypium hirsutum (Cotton) waste biomass

Studies on the biosorptive ability of Gossypium hirsutum (Cotton) waste biomass outlined that smaller size of biosorbent (0.355mm), higher biomass dose (0.20g), 5 pH and 100mg/L initial Pb(II) concentration were more suitable for enhanced Pb(II) biosorption from aqueous medium. The Langmuir isotherm model and pseudo second order kinetic model fitted well to the data of Pb(II) biosorption. Highly negative magnitude of Gibbs free energy (DeltaG degrees ) indicated that the process was spontaneous in nature. In addition to this surface coverage and distribution coefficient values of Pb(II) biosorption process were also determined. At optimized conditions Pb(II) uptake was more rapid in case of industrial effluents in comparison to synthetic solutions. FTIR spectroscopic analysis revealed that the main functional groups involved in the uptake of Pb(II) on the surface of G. hirsutum biomass were carboxyl, carbonyl, amino and alcoholic.     

Removal of copper(II) and chromium(VI) from aqueous solution using sorghum roots (<Emphasis Type="Italic">S. bicolor</Emphasis>): a kinetic and thermodynamic study

Biosorption of toxic metal ions from industrial effluents using different plant parts is an important branch of environmental chemistry. Biosorption of copper(II) and chromium(VI) ions from aqueous solution onto sorghum root (SR) powder have been investigated under batch mode. The optimum pH and temperature for biosorption of both the metals was found to be 2 and 20 °C, respectively. The maximum biosorption capacity q _e for Cu(II) and Cr(VI) is 18.6 and 18.39 mg/g, respectively. The Langmuir model gave a better fit than other two models. The kinetic studies indicated that the biosorption process of the metal ions followed well pseudo-second-order model. The thermodynamic parameters were also calculated and the values indicated that the biosorption process was exothermic, spontaneous, and feasible in nature. Desorption experiments with 1 M HCl and 1 M HNO₃ inferred the reusability of biomass. The results showed that SRs have excellent adsorption properties and thus can be used as an effective and low cost biosorbent for the removal of Cu(II) and Cr(VI) ions from aqueous solution.     

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.