Kinetics and equilibrium studies on biosorption of cadmium, lead, and nickel ions from aqueous solutions by intact and chemically modified brown algae

The present study deals with the evaluation of biosorptive removal of Cd (II), Ni (II) and Pb (II) ions by both intact and pre-treated brown marine algae: Cystoseira indica, Sargassum glaucescens, Nizimuddinia zanardini and Padina australis treated with formaldehyde (FA), glutaraldehyde (GA), polyethylene imine (PEI), calcium chloride (CaCl(2)) and hydrochloric acid (HCl). Batch shaking adsorption experiments were performed in order to examine the effects of pH, contact time, biomass concentration, biomass treatment and initial metal concentration on the removal process. The optimum sorption conditions for each heavy metal are presented. One-way ANOVA and one sample t-tests were performed on experimental data to evaluate the statistical significance of biosorption capacities after five cycles of sorption and desorption. The equilibrium experimental data were tested using the most common isotherms. The results are best fitted by the Freundlich model among two-parameter models and the Toth, Khan and Radke-Prausnitz models among three-parameter isotherm models for Cd (II), Ni (II) and Pb (II), respectively. The kinetic data were fitted by models including pseudo-first-order and pseudo-second-order. From the results obtained, the pseudo-second-order kinetic model best describes the biosorption of cadmium, nickel and lead ions.     

Adsorptive removal of methylene blue by tea waste

The potentiality of tea waste for the adsorptive removal of methylene blue, a cationic dye, from aqueous solution was studied. Batch kinetics and isotherm studies were carried out under varying experimental conditions of contact time, initial methylene blue concentration, adsorbent dosage and pH. The nature of the possible adsorbent and methylene blue interactions was examined by the FTIR technique. The pH(pzc) of the adsorbent was estimated by titration method and a value of 4.3+/-0.2 was obtained. An adsorption-desorption study was carried out resulting the mechanism of adsorption was reversible and ion-exchange. Adsorption equilibrium of tea waste reached within 5h for methylene blue concentrations of 20-50mg/L. The sorption was analyzed using pseudo-first-order and pseudo-second order kinetic models and the sorption kinetics was found to follow a pseudo-second order kinetic model. The extent of the dye removal increased with increasing initial dye concentration. The equilibrium data in aqueous solutions were well represented by the Langmuir isotherm model. The adsorption capacity of methylene blue onto tea waste was found to be as high as 85.16mg/g, which is several folds higher than the adsorption capacity of a number of recently studied in the literature potential adsorbents. Tea waste appears as a very prospective adsorbent for the removal of methylene blue from aqueous solution.     

Batch kinetics and isotherms for biosorption of copper(II) ions onto pre-treated powdered waste sludge (PWS)

Waste sludge samples from different plants were tested for Cu(II) ion biosorption capacities with and without pre-treatment. Waste sludge from a paint industry wastewater treatment plant was found to perform better than the others after pre-treatment with 1% H(2)O(2). Powdered waste sludge (PWS) from the paint industry wastewater treatment plant was used for recovery of Cu(II) ions from aqueous solution by biosorption after pre-treatment with 1% H(2)O(2). Batch kinetics and isotherms of biosorption of Cu(II) ions were investigated at variable initial Cu(II) concentrations between 50 and 400 mg l(-1) with a PWS particle size of 64 microm. The pseudo-first and -second order kinetic models were used to correlate the experimental data. The kinetic constants were determined for both models and the second order kinetic model was found to be more suitable. The Langmuir, Freundlich and the generalized isotherm models were used to correlate the equilibrium biosorption data and the isotherm constants were determined. The Langmuir isotherm was found to fit the experimental data better than the other isotherms tested. The maximum biosorption capacity (116 mg g(-1)) of the pre-treated powdered waste sludge for Cu(II) ions was found to be superior as compared to the other biosorbents reported in literature.     

Biosorption of Pb(II) ions by modified quebracho tannin resin

In this study, the effect of temperature, pH and initial metal concentration on Pb(II) biosorption on modified quebracho tannin resin (QTR) was investigated. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to investigate QTR structure and morphology. Besides, the specific BET surface area and zeta-potential of the QTR were analysed. Thermodynamic functions, the change of free energy (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) of Pb adsorption on modified tannin resin were calculated as -5.43 kJ mol(-1) (at 296+/-2K), 31.84 kJ mol(-1) and 0.127 J mmol(-1) K(-1), respectively, indicating the spontaneous, endothermic and the increased randomness nature of Pb(2+) adsorption. The kinetic data was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model. The results suggested that the pseudo-second-order model (R(2)>0.999) was the best choice among all the kinetic models to describe the adsorption behavior of Pb(II) onto QTR. Langmuir, Freundlich and Tempkin adsorption models were used to represent the equilibrium data. The best interpretation for the experimental data was given by the Langmuir isotherm and the maximum adsorption capacity (86.207 mg g(-1)) of Pb(II) was obtained at pH 5 and 296 K.     

Mass transfer, kinetics and equilibrium studies for the biosorption of methylene blue using Paspalum notatum

Batch experiments were carried out for the sorption of methylene blue onto Paspalum notatum. The operating variables studied were initial dye concentration, initial solution pH, adsorbent dosage and contact time. Experimental equilibrium data were fitted to Freundlich, Langmuir and Redlich-Peterson isotherms by non-linear regression method. Six error functions was used to determine the optimum isotherm by non-linear regression method. The present study shows r2 as the best error function to determine the parameters involved in both two- and three-parameter isotherms. Langmuir isotherm was found to be the optimum isotherm for methylene blue onto P. notatum. The monolayer methylene blue sorption capacity of P. notatum was found to be 31 mg/g. The kinetics of methylene blue onto P. notatum was found to follow a pseudo second order kinetics. A Boyd plot confirms the external mass transfer as the rate-limiting step in the dye sorption process. The influence of initial dye concentration on the dye sorption process was represented in the form of dimensionless mass transfer numbers (Sh/Sc0.33) and was found to vary as C(0)-5x10(-6).     

Posidonia oceanica (L.) fibers as a potential low-cost adsorbent for the removal and recovery of orthophosphate

Adsorption efficiency of orthophosphate from aqueous solution onto Posidonia oceanica fibers (POF) as a raw, natural and abundant material was investigated and compared with other common natural materials. A series of batch tests were undertaken to assess the effect of the system variables, i.e. initial aqueous orthophosphate concentration, contact time, adsorbent dosage, pH and temperature. Results indicate that orthophosphate uptake increased with increasing initial orthophosphate concentration, temperature and adsorbent dosage and decreased with increasing pH values. The maximum adsorption capacity (Q(m)) determined from the Langmuir isotherm was calculated to be 7.45 mg g(-1) for the studied orthophosphates concentration range of 15-100 mg L(-1), pH 7; adsorbent dosage of 2 g L(-1) and temperature of 20±2°C. The adsorption data were very well described by the pseudo-second order model predicting a chemisorption process. The energy dispersive spectroscopy (EDS) and FTIR analysis before and after adsorption of orthophosphate onto POF showed that the main involved mechanisms are ligand exchange between orthophosphate and Cl(-), SO(4)(2-) and OH(-) and precipitation with calcium. In comparison with other natural adsorbents, raw POF could be considered as one of the most efficient natural materials for the removal of orthophosphate with the possibility of agronomic reuse.     

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.     

Physical and chemical modification of distillery sludge for Pb(II) biosorption

The waste distillery sludge from sugar-cane industry was pretreated physically (boiled, heated and autoclaved) as well as chemically (HCl, H(2)SO(4), H(3)PO(4), NaOH, Ca(OH)(2), Al(OH)(3), C(6)H(6), HCHO, CH(3)OH and C1(2)H(25)OSO(3)Na (sodium dodecyl sulphate (SDS)) for assessing the comparative sorption capacity of untreated and modified distillery sludge for Pb(II) biosorption from aqueous solutions. Experiments were conducted in shake flasks on a batch basis to access the effect of different experimental parameters such as pH, biosorbent dosage, biosorbent size, initial Pb(II) concentration and contact time. The uptake capacity 'q' (mg/g) of untreated and pretreated distillery sludge was in following order: NaOH (51.29+/-1.21)>HCl (49.82+/-1.22)>HCHO (49.56+/-1.14)>H(2)SO(4) (47.71+/-1.20)>HgCl(2) (45.32+/-1.06)>Ca(OH)(2) (44.01+/-1.18)>MeOH (43.73+/-1.23)>C(6)H(6) (42.72+/-1.19)>H(3)PO(4) (42.01+/-1.17)>SDS (40.87+/-1.27)>autoclaved (40.23+/-1.24)>Boiled (39.95+/-1.19)>heated (38.87+/-1.32)>Al (OH)(3) (38.30+/-1.14)>untreated (37.76+/-1.21). In further parameter studies, the optimized biosorbent size was 0.250 mm at pH 5 and best dose was 0.05 g of biosorbent. The applicability of the Langmuir and Freundlich models for sorption process was tested and best fitted model was Langmuir with the coefficient of determination (R(2)) value, 0.97, the process followed second order kinetic mechanism.     

Biosorption of total chromium from aqueous solution by red algae (Ceramium virgatum): equilibrium, kinetic and thermodynamic studies

This study focused on the biosorption of total chromium onto red algae (Ceramium virgatum) biomass from aqueous solution. Experimental parameters affecting biosorption process such as pH, contact time, biomass dosage and temperature were studied. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were applied to describe the biosorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The biosorption capacity of C. virgatum biomass for total chromium was found to be 26.5 mg/g at pH 1.5 and 10 g/L biomass dosage, 90 min equilibrium time and 20 °C. From the D–R isotherm model, the mean free energy was calculated as 9.7 kJ/mol, indicating that the biosorption of total chromium was taken place by chemisorption. The calculated thermodynamic parameters (ΔG°, ΔH°and ΔS°) showed that the biosorption of total chromium onto C. virgatum biomass was feasible, spontaneous and exothermic at 20–50 °C. Kinetic evaluation of experimental data showed that the biosorption processes of total chromium followed well pseudo-second-order kinetics.     

Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste

In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73mgg(-1), respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23kJ/mol for BY 28 and 18.15kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents.     

Removal of methylene blue from aqueous solution by chaff in batch mode

A new adsorbent system for removing methylene blue (MB) from aqueous solutions has been investigated. This new adsorbent is cereal chaff, an agriculture product in middle-west region in China. Variables of the system, including biosorption time, chaff dose, pH, salt concentration and initial MB concentration, were adopted to study their effects on MB removal. The results showed that as the dose of chaff increased, the percentage of MB sorption increased accordingly. There was no significant difference in the dye concentration remaining when the pH was increased from 4.0 to 11.0. The salt concentration has negative effect on MB removal. At the experimental range of MB concentration, the amount of MB adsorbed onto per unit mass of chaff (q(e)) is direct ratio to MB initial concentration (c(0)). The equilibrium data were analyzed using five equilibrium models, the Langmuir, the Freundlich, the Redlich-Peterson, the Koble-Corrigan and the Temkin isotherms. The results of non-linear regressive analysis are that the isotherms of Langmuir, Redlich-Peterson and Koble-Corrigan are better fit than the isotherms of Freundlich and Temkin at different temperatures according to the values of determined coefficients (R(2)) and Chi-square statistic (chi(2)). The maximum equilibrium capacities of chaff from Langmuir models are 20.3, 25.3 and 26.3 mg g(-1) at 298, 318 and 333K, respectively. Using the equilibrium concentration constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics parameters of MB/chaff system indicate spontaneous and endothermic process. It was concluded that an increase in temperature results in a bigger MB loading per unit weight of the chaff.     

Biosorptive uptake of methylene blue using Mediterranean green alga Enteromorpha spp.

Batch biosorption experiments were carried out for the removal of methylene blue, a basic dye, from aqueous solution using raw and dried Enteromorpha spp., Mediterranean green alga. A series of assays were undertaken to assess the effect of the system variables, i.e. contact time, solution pH and sorbent amount. The results had showed that sorption capacity was optimal using 6–10 solution pH range (i.e. maximum adsorption capacity of 274 mg/g). The minimum sorbent concentration experimentally found to be sufficient to reach the total removal of the dye molecules from the aqueous solution was 5 g/L. Besides, equilibrium data were fitted using five linearisable isotherm models. The related results showed that the experimental data were very well represented by the Langmuir model for the linear regression analysis and both the Langmuir and Redlich–Peterson isotherm models for the non-linear analysis. In both cases, such modelling behaviour confirms the monolayer coverage of methylene blue molecules onto energetically homogenous Enteromopha surface. In addition, an exhaustive comparative study was done to situate this marine biomass among other proposed sorbents.     

Biosorption of heavy metals from aqueous solutions by chemically modified orange peel

Equilibrium, thermodynamic and kinetic studies were carried out for the biosorption of Pb(2+), Cd(2+) and Ni(2+) ions from aqueous solution using the grafted copolymerization-modified orange peel (OPAA). Langmuir and Freundlich isotherm models were applied to describe the biosorption of the metal ions onto OPAA. The influences of pH and contact time of solution on the biosorption were studied. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. According to the Langmuir equation, the maximum uptake capacities for Pb(2+), Cd(2+) and Ni(2+) ions were 476.1, 293.3 and 162.6 mg g(-1), respectively. Compared with the unmodified orange peel, the biosorption capacity of the modified biomass increased 4.2-, 4.6- and 16.5-fold for Pb(2+), Cd(2+) and Ni(2+), respectively. The kinetics for Pb(2+), Cd(2+) and Ni(2+) ions biosorption followed the pseudo-second-order kinetics. The free energy changes (ΔG°) for Pb(2+), Cd(2+) and Ni(2+) ions biosorption process were found to be -3.77, -4.99 and -4.22 kJ mol(-1), respectively, which indicates the spontaneous nature of biosorption process. FTIR demonstrated that carboxyl and hydroxyl groups were involved in the biosorption of the metal ions. Desorption of Pb(2+), Cd(2+) and Ni(2+) ions from the biosorbent was effectively achieved in a 0.05 mol L(-1) HCl solution.     

Efficient photodegradation of methylene blue (MB) under solar radiation by ZrC nanoparticles

Due to increase in water pollution, there is a need to dwindle this problem for a clean and green future. Photocatalysts like ZnO, CaO and TiO₂ have proved to be triumphant in removal of environmental contaminants. In this present work, ZrC nanopowder has been synthesized using a single-step reduction technique by heating zirconium oxide (ZrO₂) and hexane (C₆H₁₄) in metallic Mg powder and is used as a photocatalyst for the degradation of methylene blue (MB) dye under solar radiation. Optimization of synthesis parameters (temperature, holding time and carbon content) has been done to obtain single phase ZrC. Various characterization techniques like X-ray diffraction (XRD), transmission electron microscope (TEM), differential scanning calorimetry/thermal gravimetric analysis (DSC/TGA) and X-ray photoelectron spectroscopy (XPS) were studied for various structural, thermal and surface characteristics of as-synthesized samples. The effect of synthesis parameters on crystal distortion of ZrC particles was studied with the help of Double Voigt analysis. Further, the comparative catalytic activity as photodegradation of MB dye with the help of optimized sample was studied under UV and solar radiations. As an effect of illumination source with the same concentration of catalyst and dye, 80% degradation was observed under solar radiations which is quite higher than that observed under UV in 5?h.     

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.     

Immobilization of Trichoderma viride for enhanced methylene blue biosorption: Batch and column studies

An efficient dye biosorbent was developed by entrapping a fungus mold, Trichoderma viride, within loofa sponge (LS) matirx. Immobilization enhanced the sorption of dye by 30% at equilibrium as compared with T. viride free biomass (TVFB). The maximum dye biosorption capacity of T. viride immobilized onto loofa sponge (TVILS) and TVFB was found to be 201.52 and 155.06 mg g⁻¹ biomass, respectively. The kinetics of dye removal by TVILS was rapid, with 84.3% sorption within the first 30 min and equilibrium after 90 min, whereas sorption by TVFB was slower as 61.4% dye was removed in first 30 min and equilibrium was achieved in 120 min. Biosorption kinetics and equilibria followed the pseudo-second-order and Langmuir adsorption models. FTIR spectroscopy of T. viride biomass showed that amine, hydroxyl, carbonyl and amide bonds were involved in the sorption of dye. Dye desorption from dye-laden TVILS with 0.1 M HCl was 99%. Regenerated TVILS was reusable without any appreciable decrease in its biosorption capacity during five repeated cycles. The dye removing capacity of TVILS in a continuous-flow column bioreactor was better than in batch-scale procedures. The study shows that TVILS has the potential of application as an efficient biosorbent for the removal of methylene blue 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.     

Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies

Bamboo, an abundant and inexpensive natural resource in Malaysia was used to prepare activated carbon by physiochemical activation with potassium hydroxide (KOH) and carbon dioxide (CO(2)) as the activating agents at 850 degrees C for 2h. The adsorption equilibrium and kinetics of methylene blue dye on such carbon were then examined at 30 degrees C. Adsorption isotherm of the methylene blue (MB) on the activated carbon was determined and correlated with common isotherm equations. The equilibrium data for methylene blue adsorption well fitted to the Langmuir equation, with maximum monolayer adsorption capacity of 454.2mg/g. Two simplified kinetic models including pseudo-first-order and pseudo-second-order equation were selected to follow the adsorption processes. The adsorption of methylene blue could be best described by the pseudo-second-order equation. The kinetic parameters of this best-fit model were calculated and discussed.     

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.     

Equilibrium and kinetic studies for the biosorption system of copper(II) ion from aqueous solution using Tectona grandis L.f. leaves powder

The biosorption of copper(II) ions from aqueous solution by Tectona grandis L.f. was studied in a batch adsorption system as a function of pH, metal ion concentration, adsorbent concentration and adsorbent size. The biosorption capacities and rates of copper(II) ions onto T. grandis L.f. were evaluated. The Langmuir, Freundlich, Redlich-Peterson and Temkin adsorption models were applied to describe the isotherms and isotherm constants. Biosorption isothermal data could be well interpreted by the Langmuir model with maximum adsorption capacity of 15.43 mg/g of copper(II) ion on T. grandis L.f. leaves powder. The kinetic experimental data properly correlated with the second-order kinetic model. Various thermodynamic parameters such as deltaG(o), deltaH(o), and deltaS(o) were calculated indicating that this system was a spontaneous and exothermic process.