Biosorption of Pb(II) and Cu(II) by activated sludge in batch and continuous-flow stirred reactors

Biosorption of Pb(II) and Cu(II) ions in single component and binary systems was studied using activated sludge in batch and continuous-flow stirred reactors. In biosorption experiments, the activated sludge in three different phases of the growth period was used: growing cells; resting cells; dead or dried cells. Because of the low adsorption capacity of the non-viable activated sludge especially in the case of Pb(II) ions, biosorption of the Cu(II) and Pb(II) ions from the binary mixtures was carried out by using the resting cells. The biosorption data fitted better with the Freundlich adsorption isotherm model. Using a mathematical model based on continuous system mass balance for the liquid phase and batch system mass balance for the solid phase, the forward rate constants for biosorption of Pb(II) and Cu(II) ions were 0.793 and 0.242 1 (mmolmin)(-1), respectively.     

Biosorption of Cd(II) and Pb(II) onto brown seaweed, Lobophora variegata (Lamouroux): kinetic and equilibrium studies

The present work deals with the biosorption performance of raw and chemically modified biomass of the brown seaweed Lobophora variegata for removal of Cd(II) and Pb(II) from aqueous solution. The biosorption capacity was significantly altered by pH of the solution delineating that the higher the pH, the higher the Cd(II) and Pb(II) removal. Kinetic and isotherm experiments were carried out at the optimal pH 5.0. The metal removal rates were conspicuously rapid wherein 90% of the total sorption occurred within 90 min. Biomass treated with CaCl₂ demonstrated the highest potential for the sorption of the metal ions with the maximum uptake capacities i.e. 1.71 and 1.79 mmol g⁻¹ for Cd(II) and Pb(II), respectively. Kinetic data were satisfactorily manifested by a pseudo-second order chemical sorption process. The process mechanism consisting of both surface adsorption and pore diffusion was found to be complex. The sorption data have been analyzed and fitted to sorption isotherm of the Freundlich, Langmuir, and Redlich–Peterson models. The regression coefficient for both Langmuir and Redlich–Peterson isotherms were higher than those secured for Freundlich isotherm implying that the biosorption system is possibly monolayer coverage of the L. variegata surface by the cadmium and lead ions. FT-IR studies revealed that Cd(II) and Pb(II) binding to L. variegata occurred primarily through biomass carboxyl groups accompanied by momentous interactions of the biomass amino and amide groups. In this study, we have observed that L. variegata had maximum biosorption capacity for Cd(II) and Pb(II) reported so far for any marine algae. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Biosorption of binary mixtures of copper and cobalt by Penicillium brevicompactum

This work reports on a study of the biosorption of copper and cobalt, both singly and in combination (in equimolar concentrations), by the resting cells of Penicillium brevicompactum. Equilibrium batch sorption studies were carried out at 30 degrees C and pH 5.0 for a contact time of 1 hour to guarantee that equilibrium was reached. The equilibrium data were analyzed using the Langmuir and Freundlich isotherms. The adsorption of binary mixtures of heavy metal solutions on the fungal biomass was found to be of competitive type where the adsorption capacity for any single metal decreased in the presence of the other. The cobalt ions showed a higher affinity for Penicillium brevicompactum than the copper ions.     

Biosorption characteristics of Aspergillus flavus biomass for removal of Pb(II) and Cu(II) ions from an aqueous solution

The Pb(II) and Cu(II) biosorption characteristics of Aspergillus flavus fungal biomass were examined as a function of initial pH, contact time and initial metal ion concentration. Heat inactivated (killed) biomass was used in the determination of optimum conditions before investigating the performance of pretreated biosorbent. The maximum biosorption values were found to be 13.46 +/- 0.99 mg/g for Pb(II) and 10.82 +/- 1.46 mg/g for Cu(II) at pH 5.0 +/- 0.1 with an equilibrium time of 2 h. Detergent, sodium hydroxide and dimethyl sulfoxide pretreatments enhanced the biosorption capacity of biomass in comparison with the heat inactivated biomass. The biosorption data obtained under the optimum conditions were well described by the Freundlich isotherm model. Competitive biosorption of Pb(II) and Cu(II) ions was also investigated to determine the selectivity of the biomass. The results indicated that A. flavus is a suitable biosorbent for the removal of Pb(II) and Cu(II) ions from aqueous solution.     

The biosorption of heavy metals from aqueous solution by Spirogyra and Cladophora filamentous macroalgae

The aim of this research was to develop a low cost adsorbent for wastewater treatment. The prime objective of this study was to search for suitable freshwater filamentous algae that have a high heavy metal ion removal capability. This study evaluated the biosorption capacity from aqueous solutions of the green algae species, Spirogyra and Cladophora, for lead (Pb(II)) and copper (Cu(II)). In comparing the analysis of the Langmuir and Freundlich isotherm models, the adsorption of Pb(II) and Cu(II) by these two types of biosorbents showed a better fit with the Langmuir isotherm model. In the adsorption of heavy metal ions by these two types of biosorbents, chemical and physical adsorption of particle surfaces was perhaps more significant than diffusion and adsorption between particles. Continuous adsorption-desorption experiments discovered that both types of biomass were excellent biosorbents with potential for further development.     

Application of Freundlich and Langmuir models to multistage purification process to remove heavy metal ions by using Schizomeris leibleinii

The adsorption of iron(III), lead(II) and cadmium(II) ions onto Schizomeris leibleinii, a green alga, was studied with respect to initial pH, temperature, initial metal ion and biomass concentration to determine the optimum adsorption conditions. Optimum initial pH for iron(III), lead(II) and cadmium(II) ions were 2.5, 4.5 and 5.0 at optimum temperature 30°C, respectively. The initial adsorption rates increased with increasing initial iron(III), lead(II) and cadmium(II) ion concentrations up to 100, 100 and 150 mg l⁻¹, respectively. The Freundlich and Langmuir adsorption isotherms were developed at various initial pH and temperature values. The adsorption of these metal ions to S. leibleinii was investigated in a two-stage mixed batch reactor. The residual metal ion concentrations (C_eq) at equilibrium at each stage for a given ‘quantity of dried algae (X₀)/volume of solution containing heavy metal ion (V₀)’ ratio were calculated using Freundlich and Langmuir isotherm constants. The experimental biosorption equilibrium data for iron(III), lead(II) and cadmium(II) ions were in good agreement with those calculated by both Freundlich and Langmuir models. The adsorbed iron(III), lead(II) and cadmium(II) ion concentrations increased with increasing X₀/V₀ ratios while the adsorbed metal quantities per unit mass of dried algae decreased.     

Biosorption of Pb(II) and Cr(III) from aqueous solution by lichen (Parmelina tiliaceae) biomass

The biosorption characteristics of Pb(II) and Cr(III) ions from aqueous solution using the lichen (Parmelina tiliaceae) biomass were investigated. Optimum biosorption conditions were determined 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 P. tiliaceae biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The monolayer biosorption capacity of P. tiliaceae biomass for Pb(II) and Cr(III) ions was found to be 75.8 mg/g and 52.1mg/g, respectively. From the D-R isotherm model, the mean free energy was calculated as 12.7 kJ/mol for Pb(II) biosorption and 10.5 kJ/mol for Cr(III) biosorption, indicating that the biosorption of both metal ions was taken place by chemical ion-exchange. The calculated thermodynamic parameters (delta G degrees , delta H degrees and delta S degrees ) showed that the biosorption of Pb(II) and Cr(III) ions onto P. tiliaceae 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 and Desorption of Lead(II) by Hydrilla verticillata

The potential of nonliving biomass of Hydrilla verticillata to adsorb Pb(II) from an aqueous solution containing very low concentrations of Pb(II) was determined in this study. Effects of shaking time, contact time, biosorbent dosage, pH of the medium, and initial Pb(II) concentration on metal-biosorbent interactions were studied through batch adsorption experiments. Maximum Pb(II) removal was obtained after 2 h of shaking. Adsorption capacity at the equilibrium increased with increasing initial Pb(II) concentration, whereas it decreased with increasing biosorbent dosage. The optimum pH of the biosorption was 4.0. Surface titrations showed that the surface of the biosorbent was positively charged at low pH and negatively charged at pH higher than 3.6. Fourier transform infrared (FT-IR) spectra of the biosorbent confirmed the involvement of hydroxyl and C?O of acylamide functional groups on the biosorbent surface in the Pb(II) binding process. Kinetic and equilibrium data showed that the adsorption process followed the pseudo-second-order kinetic model and both Langmuir and Freundlich isothermal models. The mean adsorption energy showed that the adsorption of Pb(II) was physical in nature. The monolayer adsorption capacity of Pb(II) was 125 mg g^?1. The desorption of Pb(II) from the biosorbent by selected desorbing solutions were HNO₃ > Na₂CO₃ > NaOH > NaNO₃.     

黏土矿物中重金属离子的吸附规律及竞争吸附

采用等温吸附法,研究了重金属铜、铅、镉、镍在膨润土中的吸附特征,发现膨润土对铜、铅的吸附明显强于镉、镍,吸附强度大小顺序为Pb2 >Cu2 >Ni2 >Cd2 。Langmuir和Freundlich方程对这4种金属离子等温吸附的拟合均呈极显著关系。Pb2 、Cd2 、Ni2 分别与Cu2 的双组分竞争吸附表明,黏土矿物对4种离子具有"选择性吸附"。在Pb2 、Ni2 、Cd2 的存在条件下,黏土矿物对Cu2 的吸附产生不同程度的下降;100mg/LCu2 对Pb2 的影响不大,但可完全抑制Ni2 、Cd2 的吸附。建立了IAS和LCA模型来预测Pb2 与Cu2 的双组分竞争吸附,并对LCA模型进行修正,提出了更符合实际情况的竞争吸附模型。文章最后用LCA修正模型对Pb2 与Cu2 的双组分竞争吸附进行了模拟。     

A comparative study on heavy metal biosorption characteristics of some algae

The biosorption of copper(II), nickel(II) and chromium(VI) from aqueous solutions on dried (Chlorella vulgaris, Scenedesmus obliquus and Synechocystis sp.) algae were tested under laboratory conditions as a function of pH, initial metal ion and biomass concentrations. Optimum adsorption pH values of copper(II), nickel(II) and chromium(VI) were determined as 5.0, 4.5 and 2.0. respectively, for all three algae. At the optimal conditions, metal ion uptake increased with initial metal ion concentration up to 250 mg l⁻¹. Experimental results also showed the influence of the alga concentration on the metal uptake for all the species. Both the Freundlich and Langmuir adsorption models were suitable for describing the short-term biosorption of copper(II), nickel(II) and chromium(VI) by all the algal species.     

Comparative biosorption of mercuric ions from aquatic systems by immobilized live and heat-inactivated Trametes versicolor and Pleurotus sajur-caju

Trametes versicolor and Pleurotus sajur-caju mycelia immobilized in Ca-alginate beads were used for the removal of mercuric ions from aqueous solutions. The sorption of Hg(II) ions by alginate beads and both immobilized live and heat-killed fungal mycelia of T. versicolor and P. sajur-caju was studied in the concentration range of 0.150-3.00 mmol dm(-3). The biosorption of Hg(II) increased as the initial concentration of Hg(II) ions increased in the medium. Maximum biosorption capacities for plain alginate beads were 0.144+/-0.005 mmol Hg(II)/g; for immobilized live and heat-killed fungal mycelia of T. versicolor were 0.171+/-0.007 mmol Hg(II)/g and 0.383+/-0.012 mmol Hg(II)/g respectively; whereas for live and heat-killed P. sajur-caju, the values were 0.450+/-0.014 mmol Hg(II)/g and 0.660+/-0.019 mmol Hg(II)/g respectively. Biosorption equilibrium was established in about 1 h and the equilibrium adsorption was well described by Langmuir and Freundlich adsorption isotherms. Between 15 and 45 degrees C the biosorption capacity was not affected and maximum adsorption was observed between pH 4.0 and 6.0. The alginate-fungus beads could be regenerated using 10 mmol dm(-3) HCl solution, with up to 97% recovery. The biosorbents were reused in five biosorption-desorption cycles without a significant loss in biosorption capacity. Heat-killed T. versicolor and P. sajur-caju removed 73% and 81% of the Hg(II) ions, respectively, from synthetic wastewater samples.     

Potential capacity of Beauveria bassiana and Metarhizium anisopliae in the biosorption of Cd2+ and Pb2+

In this study Beauveria bassiana and Metarhizium anisopliae were used as inexpensive and efficient biosorbents for Pb(II) and Cd(II) from aqueous metal solutions. The effects of various physicochemical factors on Pb(II) and Cd(II) biosorption by B. bassiana and M. anisopliae were studied. The optimum pH for Cd(II) and Pb(II) biosorption by two fungal species was achieved at pH 6.0 for Pb(II) and 5.0 Cd(II) at a constant time of 30 min. The nature of fungal biomass and metal ion interactions was evaluated by Fourier transform infrared. The maximum adsorption capacities (q(max)) calculated from Langmuir isotherms for Pb(II), and Cd(II) uptake by B. bassiana were 83.33±0.85, and 46.27±0.12 mg/g, respectively. However, the q(max) obtained for Pb(II) uptake by M. anisopliae was 66.66±0.28 mg/g, and 44.22±0.13 mg/g for Cd(II). B. bassiana showed higher adsorption capacity compared to M. anisopliae. The data obtained imply the potential role of B. bassiana and M. anisopliae for heavy metal removal from aqueous solutions.     

Biosorption of heavy metals by lyophilized cells of <Emphasis Type="Italic">Pseudomonas stutzeri</Emphasis>

Biosorptive capacity of Pb(II), Cd(II) and Cu(II) by lyophilized cells of Pseudomonas stutzeri was investigated based on Langmuir and Freundlich isotherms. Biosorptive capacity for Pb(II), Cd(II) and Cu(II) decreased with an increase of metal concentration, reaching 142, 43.5 and 36.2 mg/g at initial concentration of 300 mg/l, respectively. Biosorption capacity for metal ions increased with increasing pH. The optimum pH for biosorption rate of Cd(II) and Cu(II) were 5.0, and 6.0 for Pb(II) biosorption. The experimental data showed a better fit with the Langmuir model over the Freundlich model for metal ions throughout the range of initial concentrations. The maximum sorptive capacity (q _max) obtained from the Langmuir equation for Pb(II), Cd(II) and Cu(II) were 153.3 (r ²  = 0.998), 43.86 (r ²  = 0.995), and 33.16 (r ²  = 0.997) for metal ions, respectively. The selectivity order for metal ions towards the biomass of P. stutzeri was Pb(II) > Cd(II) > Cu(II) for a given initial metal ions concentration. The interactions between heavy metals and functional groups on the cell wall surface of bacterial biomass were confirmed by FTIR analysis. The results of this study indicate the possible removal of heavy metals from the environment by using lyophilized cells of P. stutzeri.     

Entrapment of white-rot fungus Trametes versicolor in Ca-alginate beads: preparation and biosorption kinetic analysis for cadmium removal from an aqueous solution

The biosorption of cadmium ions onto entrapped Trametes versicolor mycelia has been studied in a batch system. The maximum experimental biosorption capacities for entrapped live and dead fungal mycelia of T. versicolor were found as 102.3 +/- 3.2 mg Cd(II) g(-1) and 120.6 +/- 3.8 mg Cd(II) g(-1), respectively. Biosorption equilibrium was established in about 1 h and biosorption was well described by the Langmuir and Freundlich biosorption isotherms. The change in the biosorption capacity with time was found to fit the pseudo-second-order equation. Since the biosorption capacities were relatively high for both entrapped live and dead forms, those fungal forms could be considered as suitable biosorbents for the removal of cadmium in wastewater-treatment systems. The biosorbents were reused in three consecutive adsorption/desorption cycles without a significant loss in the biosorption capacity.     

Improvement of heavy metal biosorption by mycelial dead biomasses (Rhizopus arrhizus, Mucor miehei and Penicillium chrysogenum): pH control and cationic activation

Abstract: Fungal mycelial by-products from fermentation industries present a considerable affinity for soluble metal ions (e.g. Zn, Cd, Ni, Pb, Cr, Ag) and could be used in biosorption processes for purification of contaminated effluents. In this work the influence of pH on sorption parameters is characterized by measuring the isotherms of five heavy metals (Ni, Zn, Cd, Ag and Pb) with Rhizopus arrhizus biomass under pH-controlled conditions. The maximum sorption capacity for lead was observed at pH 7.0 (200 mg g^-l), while silver uptake was weakly affected. The stability of metal-biosorbent complexes is regularly enhanced by pH neutralization, except for lead. A transition in sorption mechanism was observed above pH 6.0. In addition, comparison of various industrial fungal biomasses ( R. arrhizus, Mucor miehei and Penicillium chrysogenum indicated important variations in zinc-binding and buffering properties (0.24, 0.08 and 0.05 mmol g^−l, respectively). Without control, the equilibrium pH (5.8, 3.9 and 4.0) is shown to be related to the initial calcium content of the biosorbent, pH neutralization during metal adsorption increases zinc sorption in all fungi (0.57, 0.52 and 0.33 mmol g-l) but an improvement was also obtained (0.34, 0.33 and 0.10 mmol g⁻¹) by calcium saturation of the biomass before heavy metal accumulation. Breakthrough curves of fixed bed biosorbent columns demonstrated the capacity of the biosorbent process to purify zinc and lead solutions in continuous-flow systems, and confirmed the necessity for cationic activation of the biosorbent before contact with the heavy-metal solution.     

Biosorption behaviors of biosorbents based on microorganisms immobilized by Ca-alginate for removing lead (II) from aqueous solution

Multiple microorganisms directly or treated with NaOH were immobilized by using Ca-alginate embedding to form biosorbents I and II, successively. The biosorption behaviors of biosorbents I and II for Pb(II) from aqueous solution were investigated in a batch system. Effects of solution pH, initial metal concentration, biosorbent dosage, contact time, temperature, and ionic strength on the adsorption process were considered to study the biosorption equilibrium, kinetics, thermodynamics, and mechanism of Pb(II) ion adsorption on the 2 types of biosorbents. The results showed that the adsorption capacity of biosorbent II for Pb(II) was higher than that of biosorbent I, and biosorbent II had a faster adsorption rate for Pb(II) ions. According to FTIR spectra, the carboxyl, amine, and hydroxyl groups on the biomass surface were involved in the biosorption of Pb(II). EDX analysis showed that ion exchange may be involved in the biosorption process, and the morphology observed by SEM micrograph of biosorbent I was completely different from that of biosorbent II. Desorption and regeneration experiments showed that the 2 types of biosorbents could be reused for 3 biosorption-desorption cycles without significant loss of their initial biosorption capacities.     

Enhancement of Lead(II) Biosorption by Microalgal Biomass Immobilized onto Loofa (Luffa cylindrica) Sponge

A unicellular green microalga, Chlorella sorokiniana, was immobilized on loofa (Luffa cylindrica) sponge and successfully used as a new biosorption system for the removal of lead(II) ions from aqueous solutions. The biosorption of lead(II) ions on both free and immobilized biomass of C. sorokiniana was investigated using aqueous solutions in the concentration range of 10–300 mg/L. The biosorption of lead(II) ions by C. sorokiniana biomass increased as the initial concentration of lead(II) ions increased in the medium. The maximum biosorption capacity for free and immobilized biomass of C. sorokiniana was found to be 108.04 and 123.67 mg lead(II)/g biomass, respectively. The biosorption kinetics were found to be fast, with 96 % of adsorption within the first 5 min and equilibrium reached at 15 min. The adsorption of lead(II) both by free and immobilized C. sorokiniana biomass followed the Langmuir isotherm. The biosorption capacities were detected to be dependent on the pH of the solution; and the maximum adsorption was obtained at a solution pH of about 5. The effect of light metal ions on lead(II) uptake was also studied and it was shown that the presence of light metal ions did not significantly affect lead(II) uptake. The loofa sponge‐immobilized C. sorokiniana biomass could be regenerated using 0.1 M HCl, with up to 99 % recovery. The desorbed biomass was used in five biosorption‐desorption cycles, and no noticeable loss in the biosorption capacity was observed. In addition, fixed bed breakthrough curves for lead(II) removal were presented. These studies demonstrated that loofa sponge‐immobilized biomass of C. sorokiniana could be used as an efficient biosorbent for the treatment of lead(II) containing wastewater.     

Biosorptive removal of cadmium from contaminated groundwater and industrial effluents

The cadmium removing capacity of a biosorbent Calotropis procera, a perennial wild plant, is reported here. The biomass was found to possess high uptake capacity of Cd(II). Adsorption was pH dependent and the maximum removal was obtained at two different pH i.e. pH 5.0 and 8.0. Maximum biosorption capacity in batch and column mode was found to be 40 and 50.5 mg/g. The adsorption equilibrium (> or =90% removal) was attained within 5 min irrespective of the cadmium ion concentration. Interfering ions viz. Zn(II), As(III), Fe(II), Ni(II) interfered only when their concentration was higher than the equimolar ratio. The Freundlich isotherm best explained the adsorption, yet the monolayer adsorption was also noted at lower concentrations of Cd(II). The FTIR analysis indicates the involvement of hydroxyl (-OH), alkanes (-CH), nitrite (-NO(2)), and carboxyl group (-COO) chelates in metal binding. The complete desorption of the cadmium was achieved by 0.1M H(2)SO(4) and 0.1M HCl. The C. procera based Cd(II) removal technology appears feasible.     

Heavy metal adsorption properties of a submerged aquatic plant (Ceratophyllum demersum)

Heavy metals can be adsorbed by living or non-living biomass. Submerged aquatic plants can be used for the removal of heavy metals. In this paper, lead, zinc, and copper adsorption properties of Ceratophyllum demersum (Coontail or hornwort) were investigated and results were compared with other aquatic submerged plants. Data obtained from the initial adsorption studies indicated that C. demersum was capable of removing lead, zinc, and copper from solution. The metal biosorption was fast and equilibrium was attained within 20 min. Data obtained from further batch studies conformed well to the Langmuir Model. Maximum adsorption capacities (q(max)) onto C. demersum were 6.17 mg/g for Cu(II), 13.98 mg/g for Zn(II) and 44.8 mg/g for Pb(II). Kinetics of adsorption of zinc, lead and copper were analysed and rate constants were derived for each metal. It was found that the overall adsorption process was best described by pseudo second-order kinetics. The results showed that this submerged aquatic plant C. demersum can be successfully used for heavy metal removal under dilute metal concentration.