The efficiency of the red alga Mastocarpus stellatus for remediation of cadmium pollution

This work reports the results of the study for cadmium binding by the dead red macroalga Mastocarpus stellatus. Kinetics sorption experiments demonstrated the high rate of metal biosorption: the system attained over 50% of the total biomass cadmium uptake within 2 min of contact and over 90% in the first 9 min. The kinetic data were successfully described by a pseudo-second order model with rate constants ranging from 1.06 to 10 gmmol(-1)min(-1), as a function of initial metal concentration and temperature. The equilibrium binding was accurately represented in terms of Langmuir and Langmuir-Freundlich models. The sorption isotherms at constant pH showed uptake values as 0.49 mmol g(-1) (at pH 2.4), 0.56 mmol g(-1) (at pH 4) and 0.59 mmol g(-1) (at pH 6), while the affinity constant values were between 0.6 and 5 mmol(-1) L (Langmuir fit). The acid-base properties of the alga were also studied, obtaining the total number of acid groups, 2.5 mmol g(-1), and their apparent pK value, 1.56, using the Katchalsky model. Desorption studies were conducted employing different HNO(3) concentrations and desorption times.     

Equilibrium and Kinetic Studies of Cd2+ Biosorption by the Brown Algae Sargassum fusiforme

A fundamental investigation of the biosorption of Cd²⁺ from aqueous solution by the edible seaweed Sargassum fusiforme was performed under batch conditions. The influences of experimental parameters, such as the initial pH, sorption time, temperature, and initial Cd²⁺ concentration, on Cd²⁺ uptake by S. fusiforme were evaluated. The results indicated that the biosorption of Cd²⁺ depended on the initial Cd²⁺ concentration, as well as the pH. The uptake of Cd²⁺ could be described by the Langmuir isotherm model, and both the Langmuir biosorption equilibrium constant and the maximum biosorption capacity of the monolayer decreased with increasing temperature, thereby confirming the exothermic character of the sorption process. The biosorption kinetics follows the pseudo-second-order kinetic model, and intraparticle diffusion is the sole rate-limiting step for the entire biosorption period. These fundamental equilibrium and kinetic results can support further studies to the removal of cadmium from S. fusiforme harvested from cadmium-polluted waters.     

Biosorption of cadmium and lead ions by ethanol treated waste baker's yeast biomass

The biosorption of cadmium and lead ions from artificial aqueous solutions using waste baker's yeast biomass was investigated. The yeast cells were treated with caustic, ethanol and heat for increasing their biosorption capacity and the highest metal uptake values (15.63 and 17.49 mg g(-1) for Cd(2+) and Pb(2+), respectively) were obtained by ethanol treated yeast cells. The effect of initial metal concentration and pH on biosorption by ethanol treated yeast was studied. The Langmuir model and Freundlich equation were applied to the experimental data and the Langmuir model was found to be in better correlation with the experimental data. The maximum metal uptake values (qmax, mg g(-1)) were found as 31.75 and 60.24 for Cd(2+) and Pb(2+), respectively. Competitive biosorption experiments were performed with Cd(2+) and Pb(2+) together with Cu(2+) and the competitive biosorption capacities of the yeast biomass for all metal ions were found to be lower than in non-competitive conditions.     

Kinetic modeling and equilibrium studies during cadmium biosorption by dead Sargassum sp. biomass

A basic investigation on the removal of cadmium(II) ions from aqueous solutions by dead Sargassum sp. was conducted in batch conditions. The influence of different experimental parameters; initial pH, shaking rate, sorption time, temperature and initial concentrations of cadmium ions on cadmium uptake was evaluated. Results indicated that cadmium uptake could be described by the Langmuir adsorption model, being the monolayer capacity negatively affected with an increase in temperature. Analogously, the adsorption equilibrium constant decreased with increasing temperature. The kinetics of the adsorption process followed a second-order adsorption, with characteristic constants increasing with increasing temperature. Activation energy of biosorption could be calculated as equal to 10 kcal/mol. The biomass used proved to be suitable for removal of cadmium from dilute solutions. Its maximum uptake capacity was 120 mg/g. It can be considered an optimal result when compared to conventional adsorbing materials. Thus Sargassum sp. has great potential for removing cadmium ions especially when concentration of this metal is low in samples such as wastewater streams.     

Cadmium uptake by algal biomass in batch and continuous (CSTR and packed bed column) adsorbers

In this work, the properties of marine algae Gelidium, algal waste from agar extraction industry and a composite material were investigated for cadmium(II) biosorption. Equilibrium experiments were performed at three pH values (4, 5.3 and 6.5). Equilibrium data were well described by the Langmuir and Langmuir–Freundlich isotherms. Two models predicting the pH influence in the cadmium biosorption (discrete and continuous models) have been developed in order to better describe the equilibrium. The continuous model also considers a heterogeneous distribution of carboxylic groups, determined by potentiometric titration. The results of batch kinetic experiments performed at different pH values were well fitted by two mass transfer models and the homogeneous diffusion coefficients for the cadmium ions inside the biosorbent were obtained. Continuous stirred tank reactor (CSTR) and packed bed column configurations were also examined for the biosorption of cadmium ions. A strong acid (0.1 M HNO₃) was used as eluant to regenerate the biosorbents in the column. Several mass transfer models were applied with success to describe the biosorption process in batch mode, CSTR and fixed bed column.     

Metals sorption from aqueous solutions by Kluyveromyces marxianus: Process optimization,equilibrium modeling and chemical characterization

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0–1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.     

Immobilization of blue green microalgae on loofa sponge to biosorb cadmium in repeated shake flask batch and continuous flow fixed bed column reactor system

Summary An indigenous strain of blue green microalga, Synechococcus sp., isolated from wastewater, was immobilized onto loofa sponge discs and investigated as a potential biosorbent for the removal of cadmium from aqueous solutions. Immobilization has enhanced the sorption of cadmium and an increase of biosorption (21%) at equilibrium was noted as compared to free biomass. The kinetics of cadmium biosorption was extremely rapid, with (96%) of adsorption within the first 5 min and equilibrium reached at 15 min. Increasing initial pH or initial cadmium concentration resulted in an increase in cadmium uptake. The maximum biosorption capacity of free and loofa immobilized biomass of Synechococcus sp. was found to be 47.73 and 57.76 mg g⁻¹ biomass respectively. The biosorption equilibrium was well described by Langmuir adsorption isotherm model. The biosorbed cadmium was desorbed by washing the immobilized biomass with dilute HCl (0.1 M) and desorbed biomass was reused in five biosorption–desorption cycles without an apparent decrease in its metal biosorption capacity. The metal removing capacity of loofa immobilized biomass was also tested in a continuous flow fixed-bed column bioreactor and was found to be highly effective in removing cadmium from aqueous solution. The results suggested that the loofa sponge-immobilized biomass of Synechococcus sp. could be used as a biosorbent for an efficient removal of heavy metal ions from aqueous solution.     

Kinetic and Equilibrium Studies of Cr(VI) Biosorption by Dead <Emphasis Type="Italic">Bacillus licheniformis</Emphasis> Biomass

Many studies have been carried out on the biosorption capacity of different kinds of biomass. However, reports on the kinetic and equilibrium study of the biosorption process are limited. In our experiments, the removal of Cr(VI) from aqueous solution was investigated in a batch system by sorption on the dead cells of Bacillus licheniformis isolated from metal-polluted soils. Equilibrium and kinetic experiments were performed at various initial metal concentrations, pH, contact time, and temperatures. The biomass exhibited the highest Cr(VI) uptake capacity at 50°C, pH 2.5 and with the initial Cr(VI) concentration of 300 mg/g. The Langmuir and Freundlich models were considered to identify the isotherm that could better describe the equilibrium adsorption of Cr(VI) onto biomass. The Langmuir model fitted our experimental data better than the Freundlich model. The suitability of the pseudo first-order and pseudo second-order kinetic models for the sorption of Cr(VI) onto Bacillus licheniformis was also discussed. It is better to apply the pseudo second-kinetic model to describe the sorption system.     

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 lead, cadmium, and zinc by Citrobacter strain MCM B-181: characterization studies

The biosorption process for removal of lead, cadmium, and zinc by Citrobacter strain MCM B-181, a laboratory isolate, was characterized. Effects of environmental factors and growth conditions on metal uptake capacity were studied. Pretreatment of biomass with chemical agents increased cadmium sorption efficiency; however, there was no significant enhancement in lead and zinc sorption capacity. Metal sorption by Citrobacter strain MCM B-181 was found to be influenced by the pH of the solution, initial metal concentration, biomass concentration, and type of growth medium. The metal sorption process was not affected by the age of the culture or change in temperature. Equilibrium metal sorption was found to fit the Langmuir adsorption model. Kinetic studies showed that metal uptake by Citrobacter strain MCM B-181 was a fast process, requiring <20 min to achieve >90% adsorption efficiency. The presence of cations reduced lead, zinc, and cadmium sorption to the extent of 11. 8%, 84.3%, and 33.4%, respectively. When biomass was exposed to multimetal solutions, metals were adsorbed in the order Co2+ < Ni2+ < Cd2+ < Cu2+ < Zn2+ < Pb2+. Among various anions tested, only phosphate and citrate were found to hamper metal sorption capacity of cells. Biosorbent beads prepared by immobilizing the Citrobacter biomass in polysulfone matrix exhibited high metal loading capacities. A new mathematical model used for batch kinetic studies was found to be highly useful in prediction of experimentally obtained metal concentration profiles as a function of time. Metal desorption studies indicated that Citrobacter beads could, in principle, be regenerated and reused in adsorption-desorption cycles. In an expanded scale trial, biosorbent beads were found to be useful in removal/recovery of metals such as lead from industrial wastewaters.     

Biosorption of cadmium (II) ions by immobilized cells of Pycnoporus sanguineus from aqueous solution

Biosorption of cadmium (II) ions from aqueous solution onto immobilized cells of Pycnoporus sanguineus (P. sanguineus) was investigated in a batch system. Equilibrium and kinetic studies were conducted by considering the effect of pH, initial cadmium (II) concentration, biomass loading and temperature. Results showed that the uptake of cadmium (II) ions increased with the increase of initial cadmium (II) concentration, pH and temperature. Langmuir, Freundlich and Redlich-Peterson isotherm models were used to analyze the equilibrium data at different temperatures. Langmuir isotherm model described the experimental data well followed by Redlich-Peterson and Freundlich isotherm models. Biosorption kinetics data were fitted using pseudo-first, pseudo-second-order and intraparticle diffusion. It was found that the kinetics data fitted well the pseudo-second-order followed by intraparticle diffusion. Thermodynamic parameters such as standard Gibbs free energy (Delta G0), standard enthalpy (Delta H0) and standard entropy (Delta S0) were evaluated. The result showed that biosorption of cadmium (II) ions onto immobilized cells of P. sanguineus was spontaneous and endothermic nature.     

Removal of cadmium(II) ion from aqueous system by dry biomass, immobilized live and heat-inactivated Oscillatoria sp. H1 isolated from freshwater (Mogan Lake)

Oscillatoria sp. H1 (Cyanobacteria, microalgae) isolated from Mogan Lake was used for the removal of cadmium ions from aqueous solutions as its dry biomass, alive and heat-inactivated immobilized form on Ca-alginate. Particularly, the effect of physicochemical parameters like pH, initial concentration and contact time were investigated. The sorption of Cd(II) ions on the sorbent used was examined for the cadmium concentrations within the range of 25-250 mg/L. The biosorption of Cd(II) increased as the initial concentration of Cd(II) ions increased in the medium up to 100 mg/L. Maximum biosorption capacities for plain alginate beads, dry biomass, immobilized live Oscillatoria sp. H1 and immobilized heat-inactivated Oscillatoria sp. H1 were 21.2, 30.1, 32.2 and 27.5 mg/g, respectively. Biosorption equilibrium was established in about 1 h for the biosorption processes. The biosorption was well described by Langmuir and Freundlich adsorption isotherms. Maximum adsorption was observed at pH 6.0. The alginate-algae beads could be regenerated using 50 mL of 0.1 mol/L HCl solution with about 85% recovery.     

Biosorption of heavy metals by Fucus spiralis

The sorption uptake of cadmium, nickel, zinc, copper and lead by marine brown alga Fucus spiralis was investigated in bimetallic, trimetallic and multimetallic solutions. The experimental data fitted very well to Langmuir model. In bimetallic systems, the affinity of biomass for lead and copper increased and the sorption uptake of these metals was not affected by increasing concentrations of cadmium, nickel or zinc. However, in solutions with both metals there was a significant mutual decrease of their sorption levels at high concentrations of the other metal. The sorption uptake of cadmium, nickel and copper was investigated in trimetallic aqueous systems. Based on the kinetic parameter b, the affinity of F. spiralis for copper was considerably higher than for cadmium or nickel: bCd=6.39, bNi=1.82 and bCu=17.89. In all tests, the maximum sorption uptake remained practically constant around 1 mmol/g, indicating that the number of active sites on the biomass was limited. Tests with four and five metals showed that copper was preferentially adsorbed. The differences between the experimental sorption data and those given by the chemical speciation program PHREEQCI were negligible. In general, the software used provided satisfactory estimated data for each metal and hence can be a useful tool to predict or simulate the real process.     

Cadmium removal from water environment by a fungus Volveriella volvacea

Biosorption technique was used for removal of cadmium under different conditions from water environment using a biosorbent, Volveriella volvaceas, locally growing fruit bodies of mushroom. Effects of different parameters like pH, sorbent concentration, ionic strength on the removal efficiency of cadmium by V. volvacea were carried out in continuation with adsorption kinetics and equilibrium isotherm experiments. From the kinetics studies it was found that nearly 95% of the total cadmium removal was achieved from cadmium spiked distilled water within first 15 minutes. Isotherm data was best fitted to linearised Langmuir equation and the sorption capacity was found to be varying from 9.13 to 9.33 mg/g for different sizes of sorbent. The uptake of cadmium(II) is a function of pH of the solution and increases with the increasing pH. Increasing ionic strength and the presence of soluble complexing agents such as ethylene diamine tetraacetic acid (EDTA) decrease the sorption of cadmium (II). The presence of other diavalent cations like calcium and magnesium impedes the uptake of cadmium (II). The presence of chloride ion has no significant effect on cadmium (II) removal. The spent biosorbent can effectively be regenerated with acid and can then be reused.The present work was carried out by the financial support in terms of fellowship under the cultural exchange programme of the Indo-Bangladesh government. Special thanks to the Director, Bangladesh Institute of Technology, Dhaka, Bangladesh, for providing leave, which enabled the author in carrying out the research work.     

Comparison of cadmium biosorption by Gram-positive and Gram-negative bacteria from activated sludge

Summary Gram-positive and Gram-negative bacteria were isolated from activated sludge and used to evaluate differences in cadmium biosorption. Gram-positive bacteria exhibited approximately 20% more cadmium biosorption at 30°C and pH 6.6 than Gram-negatives. Biosorption was largely passive in both cases, although metabolic uptake appeared to occur to a higher extent with Gram-positive bacteria.     

Biosorption of Arsenic from Contaminated Water onto Solid Psidium guajava Leaf Surface: Equilibrium,Kinetics, Thermodynamics,and Desorption Study

A batch study on the removal of As(III) and As(V) ions from contaminated water by biosorption using powdered Psidium guajava (Guava) leaf as biosorbent was carried out in the present work. FT-IR (Fourier transform infrared) and SEM (scanning electron microscopy) were used to characterize the surface of the biosorbent. The effect of sorption parameters such as pH, temperature (T _c), adsorbent dose (D _c), and contact time (t _c) were studied. At optimum treatment conditions, the maximum uptake of 1.06 mg of As(III) per gram and 2.39 mg of As(V) per gram onto the surface of biosorbent were obtained. Langmuir and Freundlich isotherm models were examined for sorption equilibrium at various temperatures. The sorption isotherm was favorable with the Freundlich model with the experimental data. Furthermore, higher uptake kinetics was tested for the pseudo-first-order and pseudo-second-order models. The pseudo-second-order model appeared to be the more suitable model to describe arsenic biosorption. ΔG ₀ values were negative at all temperatures, confirming the feasible and spontaneous nature of the biosorption process. Solvent desorption studies help in understanding the mechanism of the adsorption process and also to check the stability of the loaded/spent adsorbents. HCl was found to show maximum effectiveness in the desorption of both As(III) and As(V) with the comparison of other solvents.     

Uptake of cationic dyes from aqueous solution by biosorption onto granular kohlrabi peel

A new, low cost, locally available biomaterial was tested for its ability to remove cationic dyes from aqueous solution. Granules prepared from kohlrabi peel had been utilized as a sorbent for uptake of three cationic dyes, methylene blue (MB), neutral red (NR) and acridine orange (AO). The effects of various experimental parameters (e.g., dye concentration, particle size, initial pH, contact time and other factors) were investigated and optimal experimental conditions were ascertained. Above the value of initial pH 4, three dyes studied could be removed effectively. The isothermal data fitted the Langmuir model in the case of NR sorption and the Freundlich model for all three dyes sorption. The biosorption processes followed the pseudo-first-order rate kinetics. The results in this study indicated that kohlrabi peel was an attractive candidate for removing cationic dyes from the dye wastewater.     

Biosorption of nickel(II) ions by baker's yeast: kinetic, thermodynamic and desorption studies

In this study, the biosorption of nickel(II) ion on deactivated protonated yeast was investigated as a function of temperature at different initial metal ion concentrations. The effect of temperature on the sorption was more significant at lower nickel(II) ion concentrations compared to higher concentrations. The protonated yeast biomass exhibited the highest nickel(II) ion uptake capacity at 27 degrees C at an initial nickel(II) ion concentration of 400mg/l and an initial pH of 6.75. The biosorption capacity decreased from 9.8 to 9.3mg/g at an initial nickel(II) ion concentration of 400mg/l, while at a lower initial concentration of 100mg/l, it decreased from 8.2 to 4.9 mg/g, as the temperature was increased from 27 degrees C to 60 degrees C. The equilibrium data fit better to the Freundlich and Redlich-Peterson isotherm models compared to the Langmuir model in the concentration range studied (10-400mg/l). Kinetic models applied to the sorption data at different temperatures showed that nickel(II) ion uptake process followed the pseudo-second order rate model and the adsorption rate constants decreased with increasing temperature. The activation energy of biosorption (Ea) was determined to be -13.3 kJ/mol using the pseudo-second order rate constants. The results indicated that the biosorption of nickel(II) ion on to baker's yeast was spontaneous and exothermic in nature. Desorption studies revealed that the protonated yeast biomass can be regenerated using 0.1N HCl and reused.