Immobilized chitosan as biosorbent for the removal of Cd(II), Cr(III) and Cr(VI) from aqueous solutions

The generation of layer-by-layer silicate-chitosan composite biosorbent was studied. The films were evaluated on its stability regarding the polymer leakage and its capability in the removal of Cd(II), Cr(III) and Cr(VI) from an aqueous solution. SEM, EDAX and ATR-IR techniques were applied for material characterization. Silicate-chitosan films with a final layer of silicate demonstrated chitosan retention and had better sorption capacities than those without it. For metal species, such as Cd(II) and Cr(III), the greatest adsorption was obtained when the pH of the solution was 7. When Cr(VI) was evaluated, pH 4 was the optimal for its adsorption. Langmuir and Freundlich isotherms were modeled for the equilibrium data. An 80% of the adsorbed metal was recovered by HNO(3) incubation. This non-covalent immobilization method allowed chitosan surface retention and did not affect its adsorption properties. The use of a coated surface would facilitate sorbent removal from medium after adsorption.     

Application of Arthrospira (Spirulina) platensis biomass for silver removal from aqueous solutions

The cyanobacterium Arthrospira (Spirulina) platensis was used to study the process of silver biosorption. Effects of various parameters such as contact time, dosage of biosorbent, initial pH, temperature, and initial concentration of Ag(I) were investigated for a batch adsorption system. The optimal biosorption conditions were determined as pH 5.0, biosorbent dosage of 0.4 g, and initial silver concentration of 30 mg/L. Equilibrium adsorption data were analyzed by the Langmuir and Freundlich models – however, the Freundlich model provided a better fit to the experimental data. The kinetic data fit the pseudo-second-order model well, with a correlation coefficient of 0.99. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the adsorption process of silver ion by spirulina biomass was exothermic and spontaneous (ΔG° < 0), and exothermic (ΔH° < 0) process. The biosorption capacity of biomass A. platensis serves as a basis for the development of green technology for environmental remediation.     

Continuous removal of Cr(VI) from aqueous solution catalysed by palladised biomass of Desulfovibrio vulgaris

Growth-decoupled cells of Desulfovibrio vulgaris NCIMB 8303 can be used to reduce Pd(II) to cell-bound Pd(0) (Bio-Pd(0)), a bioinorganic catalyst capable of reducing hexavalent chromium to less toxic Cr(III), using formate as the electron donor. Magnetic resonance imaging showed that Bio-Pd(0), immobilized in chitosan and agar beads, is distinguishable from the surrounding gel and is evenly dispersed within the immobilization matrix. Agar-immobilized Bio-Pd(0) and 'chemical Pd(0)' were packed into continuous-flow reactors, and challenged with a solution containing 100 microM Cr(VI) (pH 7) at a flow rate of 2.4 ml h(-1). Agar-immobilized chemical Pd(0) columns lost Cr(VI) reducing ability by 160 h, whereas columns containing immobilized Bio-Pd(0) maintained 90% reduction until 680 h, after which reduction efficiency was gradually lost.     

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.     

The removal of As(III) and As(V) from aqueous solutions by waste materials

The use of different waste materials such as Atlantic Cod fish scale, chicken fat, coconut fibre and charcoal in removing arsenic [As(III) and As(V)] from aqueous solutions was investigated. Initial experimental runs, conducted for both As(III) and As(V) with the aforementioned materials, demonstrated the potential of using Atlantic Cod fish scale in removing both species of arsenic from aqueous streams. Therefore, the biosorbent fish scale was selected for further investigations and various parameters such as residence time, adsorbent dose, initial concentration of adsorbate, grain size of the adsorbent and pH of the bulk phase were studied to establish optimum conditions. The maximum adsorption capacity was observed at pH value 4.0. The equilibrium adsorption data were interpreted by using both Freundlich and Langmuir models. Rapid small-scale column tests (RSSCT) were also performed to determine the breakthrough characteristics of the arsenic species with respect to packed biosorbent columns.     

Continuous removal of Cr(VI) from aqueous solution catalysed by palladised biomass of Desulfovibrio vulgaris

Growth-decoupled cells of Desulfovibrio vulgaris NCIMB 8303 can be used to reduce Pd(II) to cell-bound Pd(0) (Bio-Pd⁰), a bioinorganic catalyst capable of reducing hexavalent chromium to less toxic Cr(III), using formate as the electron donor. Magnetic resonance imaging showed that Bio-Pd⁰, immobilized in chitosan and agar beads, is distinguishable from the surrounding gel and is evenly dispersed within the immobilization matrix. Agar-immobilized Bio-Pd⁰ and `chemical Pd⁰' were packed into continuous-flow reactors, and challenged with a solution containing 100 m Cr(VI) (pH 7) at a flow rate of 2.4 ml h^–1. Agar-immobilized chemical Pd⁰ columns lost Cr(VI) reducing ability by 160 h, whereas columns containing immobilized Bio-Pd⁰ maintained 90% reduction until 680 h, after which reduction efficiency was gradually lost.     

Batch studies on the removal of gold(III) from aqueous solution by Azolla filiculoides

Azolla filiculoides removed 86% and 100% of gold(III) from initial metal solutions of 2–10 mg gold l^–1 increasing with increased initial concentrations of gold(III). The biomass gave greater than 95% removal efficiency from solution at all biomass concentrations measured. Complete removal of gold occurred at pH 2, with 42% removal at pH 3 and 4, and 63% and 73% removal at pH 5 and 6, respectively. No temperature-dependence removal was observed.     

Mercury removal from aqueous solution by dried biomass of indigenous Vibrio parahaemolyticus PG02: Kinetic,equilibrium, and thermodynamic studies

In this study, for the first time the potential use of dried Vibrio parahaemolyticus PG02 to remove mercury from synthetic effluent was investigated by considering equilibrium, kinetic, and thermodynamic aspects. The results indicated that Hg²⁺ biosorption was best described by the pseudo-second order model. In addition, it was found that intraparticle diffusion was not the sole rate-limiting step. The ion-exchange mechanism was a predominant biosorption mechanism in the first 15 min of contact. The Langmuir isotherm better described the equilibrium data of Hg²⁺ biosorption than the Freundlich isotherm. According to this model, the maximum biosorption capacity was found to be 9.63 × 10⁻⁴ mol g⁻¹ at optimum conditions (pH = 6.0 and temperature =35 °C).     

Kinetics of Cr(III) and Cr(VI) removal from water by two floating macrophytes

The aim of this work was to compare Cr(III) and Cr(VI) removal kinetics from water by Pistia stratiotes and Salvinia herzogii. The accumulation in plant tissues and the effects of both Cr forms on plant growth were also evaluated. Plants were exposed to 2 and 6 mg L^?1 of Cr(III) or Cr(VI) during 30 days. At the end of the experiment, Cr(VI) removal percentages were significantly lower than those obtained for Cr(III) for both macrophytes. Cr(III) removal kinetics involved a fast and a slow component. The fast component was primarily responsible for Cr(III) removal while Cr(VI) removal kinetics involved only a slow process. Cr accumulated principally in the roots. In the Cr(VI) treatments a higher translocation from roots to aerial parts than in Cr(III) treatments was observed. Both macrophytes demonstrated a high ability to remove Cr(III) but not Cr(VI). Cr(III) inhibited the growth at the highest studied concentration of both macrophytes while Cr(VI) caused senescence. These results have important implications in the use of constructed wetlands for secondary industrial wastewater treatment. Common primary treatments of effluents containing Cr(VI) consists in its reduction to Cr(III). Cr(III) concentrations in these effluents are normally below the highest studied concentrations in this work.     

Potential use of green algae as a biosorbent for hexavalent chromium removal from aqueous solutions

The hexavalent chromium Cr(VI) poses a threat as a hazardous metal and its removal from aquatic environments through biosorption has gained attention as a viable technology of bioremediation. We evaluated the potential use of three green algae (Cladophora glomerata, Enteromorpha intestinalis and Microspora amoena) dry biomass as a biosorbent to remove Cr(VI) from aqueous solutions. The adsorption capacity of the biomass was determined using batch experiments. The adsorption capacity appeared to depend on the pH. The optimum pH with the acid-treated biomass for Cr(VI) biosorption was found to be 2.0 at a constant temperature, 45?°C. Among the three genera studied, C. glomerata recorded a maximum of 66.6% removal from the batch process using 1.0?g dried algal cells/100?ml aqueous solution containing an initial concentration of 20?mg/L chromium at 45?°C and pH 2.0 for 60?min of contact time. Langmuir and Freundlich isotherm equations fitted to the equilibrium data, Freundlich was the better model. Our study showed that C. glomerata dry biomass is a suitable candidate to remove Cr(VI) from aqueous solutions.     

Modeling, simulation, and experimental validation for continuous Cr(VI) removal from aqueous solutions using sawdust as an adsorbent

Continuous adsorption experiments were performed in a fixed-bed adsorption column to evaluate the performance of low-cost adsorbent (sawdust) developed for the removal of Cr(VI) from aqueous solutions. The effects of influencing parameters such as flow rate, mass of adsorbent, initial Cr(VI) concentration were studied and the corresponding breakthrough curves were obtained. The fixed-bed adsorption process parameters such as breakthrough time, total percentage removal of Cr(VI), adsorption exhaustion rate and fraction of unused bed-length were obtained. A mathematical model for fixed-bed adsorption column was proposed by incorporating the effect of velocity variation along the bed-length in the existing model. Pore and solid diffusion models were used to describe the intra-particle mechanism for Cr(VI) adsorption. The proposed mathematical model was validated with the literature data and the experimental data obtained in the present study and the model was found to be good for explaining the behavior of breakthrough curves.     

Removal of Cr(VI) from aqueous solutions by adsorption onto hazelnut shell activated carbon: kinetic and equilibrium studies

The adsorption Cr(VI) from aqueous solutions onto hazelnut shell activated carbon was carried out by varying the parameters such as pH, initial Cr(VI) concentration and temperature. The experimental data fitted well to the pseudo first-order kinetic model and then the rate constants were evaluated. The Langmuir isotherm provided the best correlation for Cr(VI) onto the activated carbon. Adsorption capacity was calculated from the Langmuir isotherm as 170 mg/g at an initial pH of 1.0 for the 1000 mg/l Cr(VI) solution. Thermodynamic parameters were evaluated and the adsorption is endothermic showing monolayer adsorption of Cr(VI).     

The removal of Cu(II) from aqueous solutions by Ulothrix zonata

In this work, adsorption of copper(II) ions on alga has been studied by using batch adsorption techniques. The equilibrium biosorption level was determined as a function of contact time at several initial metal ion concentrations. The effect of adsorbent concentration on the amount adsorbed was also investigated. The experimental adsorption data were fitted to the Langmuir adsorption model. The free energy change (deltaG0) for the adsorption process was found to be -12.60 kJ/mol. The results indicated that the biomass of Ulothrix zonata is a suitable biosorbent for both the removal and recovery of heavy metals from wastewater.     

Biosorption of Nickel(II) from aqueous solution by the fungal mat of Trametes versicolor (rainbow) biomass: equilibrium, kinetics, and thermodynamic studies

This study investigates the equilibrium, kinetics and thermodynamics of Nickel(II) biosorption from aqueous solution by the fungal mat of Trametes versicolor (rainbow) biomass. The optimum biosorption conditions like pH, contact time, biomass dosage, initial metal ion concentration and temperaturewere determined in the batch method. The biosorbent was characterized by FTIR, SEM and BET surface area analysis. The experimental data were analyzed in terms of pseudo-first-order, pseudo-secondorder and intraparticle diffusion kinetic models, further it was observed that the biosorption process of Ni(II) ions closely followed pseudo-second-order kinetics. The equilibrium data of Ni(II) ions at 303, 313, and 323 K were fitted to the Langmuir and Freundlich isotherm models. Langmuir isotherm provided a better fit to the equilibrium data andthe maximum monolayer biosorption capacity of the T. versicolor(rainbow) biomass for Ni(II) was 212.5 mg/g at pH 4.0. The calculated thermodynamic parameters, ΔG^○, ΔH^○, and ΔS^○, demonstrated that the biosorption of Ni(II) ions onto the T. versicolor (rainbow) biomass was feasible, spontaneous and endothermic at 303 ～ 323 K. The performance of the proposed fungal biosorbent was also compared with that of many other reported sorbents for Nickel(II) removal and it was observed that the proposed biosorbent is effective in terms of its high sorption capacity.     

Senna auriculata L. flower petal biomass: An alternative green biosorbent for the removal of fluoride from aqueous solutions

Fluoride contamination in groundwater is a major concern in many parts of India and all over the world. Researches paying attention for the removal of fluoride through the application of biosorbents prepared from different parts of plants are finding greater scope and importance. The present research work focuses on Senna auriculata L., flower petal biomass as biosorbent, and evaluated its feasibility for fluoride ion elimination from aqueous solutions. Batch experiments were conducted to remove fluoride under different experimental conditions have been optimized for the maximum removal of fluoride; 80% removal was observed at pH: 6, sorbent dosage: 0.25 g/100 mL, time of agitation: 90 min, and initial concentration of the fluoride ions: 5 mg/L. Characterization studies of the biosorbent revealed its favorability towards the sorption of fluoride. In the isothermal modeling studies, Langmuir isotherm model was obeyed by the biosorption process with R² value of 0.98 and from a kinetic perspective, the biosorption of fluoride onto the biosorbent observed the pseudo-second-order reaction with R² value of 0.98. The developed biosorbent has been applied to real field fluoride-contaminated water samples and found to be successful.     

The removal of chromium(VI) from aqueous solutions by Fagus orientalis L

The removal of chromium(VI) from aqueous solution under different conditions using an adsorbent was investigated. This adsorbent is Beech (Fagus orientalis L.) sawdust studied by using batch techniques. Batch studies indicated that the percent adsorption decreased with increasing initial concentration of chromium(VI). A contact time of 80 min was found to be optimum. Maximum chromium(VI) removal was observed near a pH of 1.0. Adsorption conformed to the Freundlich and Langmuir isotherms.     

The use of flocculating brewer's yeast for Cr(III) and Pb(II) removal from residual wastewaters

The use of inexpensive biosorbents to sequester heavy metals from aqueous solutions, is one of the most promising technologies being developed to remove these toxic contaminants from wastewaters. Considering this challenge, the viability of Cr(III) and Pb(II) removal from aqueous solutions using a flocculating brewer's yeast residual biomass from a Portuguese brewing industry was studied. The influence of physicochemical factors such as medium pH, biomass concentration and the presence of a co-ion was characterised. Metal uptake kinetics and equilibrium were also analysed, considering different incubation temperatures. For both metals, uptake increased with medium pH, being maximal at 5.0. Optimal biomass concentration for the biosorption process was determined to be 4.5?g dry weight/l. In chromium and lead mixture solutions, competition for yeast binding sites was observed between the two metals, this competition being pH dependent. Yeast biomass showed higher selectivity and uptake capacity to lead. Chromium uptake kinetic was characterised as having a rapid initial step, followed by a slower one. Langmuir model describes well chromium uptake equilibrium. Lead uptake kinetics suggested the presence of mechanisms other than biosorption, possibly including its precipitation.     

Spectroscopic studies of aqueous gallium(III) and aluminum(III) citrate complexes

Aqueous gallium(III) citrate complexes have been studied in the 10(-2) M concentration range with extended X-ray absorption fine structure (EXAFS) and FTIR techniques. From EXAFS data, one mononuclear and one oligomeric species were identified at different Ga(III) to citrate ratios. The first shell of the mononuclear complex was found to be distorted, with average Ga-O bond lengths of 1.95 and 2.06 A, in agreement with the solid-state structure of Ga(Cit)2(3-) (Cit=citrate). Also the oligomeric species was found to have a distorted first shell, with average Ga-O bond lengths of 1.95 and 2.04 A. This complex was found to contain two Ga-Ga distances at 3.03 and 3.56 A, typical for edge and corner sharing GaO6 octahedra, respectively. The gallium(III) and aluminum(III) citrate systems were compared by means of FTIR, and were found to be analogous. The IR results suggest that the bond lengths derived from EXAFS for the 1:2 gallium(III) citrate complex also provide a good estimate of the corresponding distances in the mononuclear 1:1 complex. Direct coordination of citrate to the metal ions in the oligomeric gallium(III) citrate complex was indicated from both EXAFS and IR results, and this complex is stoichiometrically analogous to the Al3(H-1Cit)3(OH)(H2O)4- complex, which has been structurally determined. However, while the formation of the aluminum trimer has been shown to be slow, the gallium trimer was significantly more labile with a rate of formation indicated to be in the order of seconds or faster.     

Removal of lead from aqueous solutions by Penicillium biomass

The removal of lead ions from aqueous solutions by adsorption on nonliving Penicillium chrysogenum biomass was studied. Biosorption of the Pb(+2) ion was strongly affected by pH. Within a pH range of 4 to 5, the saturated sorption uptake of Pb(+2) was 116 mg/g dry biomass, higher than that of activated charcoal and some other microorganisms. At pH 4.5, P. chrysogenum biomass exhibited selectivity for Pb(+2) over other metal ions such as Cd(+2), Cu(+2), Zn(+2), and As(+3) Sorption preference for metals decreased in the following order: Pb > Cd > Cu > Zn > As. The sorption uptake of Pb(+2) remained unchanged in the presence of Cu(+2) and As(+3), it decreased in the presence of Zn(+2), and increased in the presence of Cd(+2). (c) 1993 John Wiley & Sons, Inc.     

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.