A new approach to modification of natural adsorbent for heavy metal adsorption

This paper describes modification of a natural adsorbent with Fenton reagent and determines the removal of Cd(II) ions from aqueous solution. Changes of the surface properties of adsorbent materials were determined by the FT-IR analysis after the modification of pine bark. The effect of Fe2+/H2O2 ratio, ORP, pH, and contact time were determined. Different adsorption isotherms were also obtained using concentrations of Cd(II) ions ranging from 0.1 to 100 mg L(-1). The adsorption process follows pseudo-first-order reaction kinetics and follows the Langmuir adsorption isotherm. The paper discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Cd(II) on modified bark, and revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiency obtained was 97% at pH 7 and with a 90-min contact time (for 35 mg L(-1) initial concentration and a 2.5 g L(-1) solid-to-liquid ratio).     

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.     

Adsorption of Cu(II) and Pb(II) onto diethylenetriamine-bacterial cellulose

Diethylenetriamine-bacterial cellulose (EABC) was synthesized by amination with diethylenetriamine on bacterial cellulose (BC). Its adsorption properties for Cu(II) and Pb(II) were investigated. The parameters affecting the metal ions adsorption, such as contact time, solution pH, and initial metal ions concentration have been investigated. The adsorption kinetics and adsorption isotherms were further studied. The results show that the adsorption rate could be well fitted by pseudo-second-order rate model, and adsorption isotherm could be described by the Langmuir model. The regeneration of EABC was also studied. This study provides the relatively comprehensive data for the EABC application to the removal of metal ion in the wastewater.     

Spray-dried chitosan microspheres containing 8-hydroxyquinoline -5 sulphonic acid as a new adsorbent for Cd(II) and Zn(II) ions

In the present study, a new chelating adsorbent was prepared from chitosan microspheres cross-linked with glutaraldehyde by spray drying using 8-hydroxyquinoline -5 sulphonic acid as chelant agent (CTS-SX-CL). Microspheres of the new adsorbent were characterized by Raman spectroscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). The effect of pH, contact time and concentration of metallic ions in solution were evaluated on the adsorption behavior of Cd(II) and Zn(II) by CTS-SX-CL. Adsorption was maximum for both Cd(II) and Zn(II) at pH 8.0. Adsorption kinetic curves were obtained and could be fit by the pseudo second-order adsorption model. An analysis of equilibrium adsorption data using the Langmuir isotherm model indicated that the maximum adsorption capacity of CTS-SX-CL was higher than that of CTS-CL for both ions investigated. The adsorption capacity increased 74% for Cd(II).     

Adsorptive removal of Pb(II) by activated carbon prepared from Spartina alterniflora: Equilibrium,kinetics and thermodynamics

Low-cost activated carbon was prepared from Spartina alterniflora by phosphoric acid activation for the removal of Pb(II) from dilute aqueous solution. The effect of experimental parameters such as pH, initial concentration, contact time and temperature on the adsorption was studied. The obtained data were fitted with the Langmuir and Freundlich equations to describe the equilibrium isotherms. The kinetic data were fitted with the Lagergren-first-order, pseudo-second-order and Elovich models. It was found that pH played a major role in the adsorption process. The maximum adsorption capacity for Pb(II) on S. alterniflora activated carbon (SAAC) calculated from Langmuir isotherm was more than 99 mg g⁻¹. The optimum pH range for the removal of Pb(II) was 4.8–5.6. The Freundlich isotherm model was found to best describe the experimental data. The kinetic rates were best fitted to the pseudo-second-order model. Thermodynamic study showed the adsorption was a spontaneous exothermic process.     

Sorption of Cu(II) and Cd(II) by extracellular polymeric substances (EPS) from Aspergillus fumigatus

Sorption of Cu(II) and Cd(II) onto the extracellular polymeric substances (EPS) produced by Aspergillus fumigatus was investigated for the initial pH of the solution, EPS concentrations, contact time, NaCl concentration, initial metal ion concentration and the presence of other ions in the solution. The results showed that the adsorption of metal ions was significantly affected by pH, EPS concentrations, initial metal concentration, NaCl concentration and co-ions. The sorption of Cu(II) and Cd(II) increased with increasing pH and initial metal ion concentration but decreased with an increase in the NaCl concentration. The maximum sorption capacities of A. fumigatus EPS calculated from the Langmuir model were 40 mg g⁻¹ EPS and 85.5 mg g⁻¹ EPS for Cu(II) and Cd(II), respectively. The binary metal sorption experiments showed a selective metal binding affinity in the order of Cu(II) > Pb(II) > Cd(II). Both the Freundlich and Langmuir adsorption models described the sorption of Cu(II) and Cd(II) by the EPS of A. fumigatus adequately. Fourier transform infrared spectroscopy (FTIR) analysis revealed that carboxyl, amide and hydroxyl functional groups were mainly correlated with the sorption of Cu(II) and Cd(II). Energy dispersive X-ray (EDX) system analysis revealed that the ion-exchange was an important mechanism involved in the Cu(II) and Cd(II) sorption process taking place on EPS.     

Removal of Fe(II) ions from aqueous solution by Calabrian pine bark wastes

The ability of Calabrian pine bark wastes (Pinus brutia Ten) for the removal of Fe(II) ions from aqueous solution at different concentrations and temperatures at a fixed pH was investigated. While the amounts of Fe(II) ions adsorbed onto the bark increased with increasing concentration, it increased slightly with increasing the temperature. Kinetics studies showed that adsorption process followed the first-order kinetic model as well as intra-particle diffusion kinetics. Adsorption isotherm followed both Langmuir and Freundlich models. And it was determined that the adsorption was favorable from a dimensionless factor, R(L). Furthermore, the thermodynamic parameters demonstrated that the removal of Fe(II) by the bark was a physical process.     

Characterization of Aqueous Pb(II) and Cd(II) Biosorption on Native and Chemically Modified Alstonia macrophylla Saw Dust

This study was conducted in order to understand the mechanism of Cd and Pb adsorption in aqueous solutions by raw and modified saw dust (SD) of Alstonia macrophylla. The biosorbent was characterized by Boehm titration, specific surface area, scanning electron microscopy (SEM), X-ray energy dispersion (EDAX), and Fourier transform infrared (FTIR) analyses. SD was treated using organic acids and bases. Batch studies were conducted for raw and modified SD to determine the effect of initial concentration, pH, ionic strength, and contact time on metal adsorption. The specific surface area and total basic and acidic groups of SD were 77 m²/g and 1521 and 2312 μmol/g, respectively. The adsorption of both metals onto SD was pH dependent. No ionic strength dependency was observed in adsorption of Cd and Pb at pH >6, indicating inner sphere surface complexation. Monolayer adsorption is dominant in both metal sorptions by SD. Furthermore, there is no competition between metals on adsorption and raw SD was found to be suitable for removal of Cd and Pb as compared to organic acid– or base-treated SD. Maximum adsorption capacity of SD for Cd and Pb were 30.6 and 204.2 mg/g, respectively. Results indicate that the A. macrophylla SD can be considered as a potential material for metal ion removal from wastewater.     

Biosorption of cadmium(II), lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium

The biosorption from artificial wastewaters of heavy metals (Cd(II), Pb(II) and Cu(II)) onto the dry fungal biomass of Phanerochaete chryosporium was studied in the concentration range of 5-500 mg l(-1). The maximum absorption of different heavy metal ions on the fungal biomass was obtained at pH 6.0 and the biosorption equilibrium was established after about 6 h. The experimental biosorption data for Cd(II), Pb(II) and Cu(II) ions were in good agreement with those calculated by the Langmuir model.     

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.     

Equilibrium isotherm studies for the uptake of cadmium and lead ions onto sugar beet pulp

The adsorption of Cd2+ and Pb2+ on sugar beet pulp (SBP), a low-cost material, has been studied. In the present work, the abilities of native (SBP) to remove cadmium (Cd2+) and lead (Pb2+) ions from aqueous solutions were compared. The (SBP) an industrial by product and solid waste of sugar industry were used for the removal of Cd2+ and Pb2+ ions from aqueous water. Batch adsorption studies were carried out to examine the influence of various parameters such as initial pH, adsorbent dose, initial metal ion concentration, and time on uptake. The sorption process was relatively fast and equilibrium was reached after about 70 min of contact. As much as 70-75% removal of Cd2+ and Pb2+ ions for (SBP) are possible in about 70 min, respectively, under the batch test conditions. Uptake of Cd2+ and Pb2+ ions on (SBP) showed a pH-dependent profile. The overall uptake for the (SBP) is at a maximum at pH 5.3 and gives up to 46.1 mg g(-1) for Cd2+ and at pH 5.0 and gives 43.5 mg g(-1) for Pb2+ for (SBP), which seems to be removed exclusively by ion exchange, physical sorption and chelation. A dose of 8 gL(-1) was sufficient for the optimum removal of both the metal ions. The Freundlich represented the sorption data for (SBP). In the presence of 0.1M NaNO3 the level of metal ion uptake was found to reach its maximum value very rapidly with the speed increasing both with the (SPB) concentration and with increasing initial pH of the suspension. The reversibility of the process was investigated. The desorption of Cd2+ and Pb2+ ions which were previously deposited on the (SBP) back into the deionised water was observed only in acidic pH values during one day study period and was generally rather low. The extent of adsorption for both metals increased along with an increase of the (SBP) dosage. (SBP), which is cheap and highly selective, therefore seems to be a promising substrate to entrap heavy metals in aqueous solutions.     

Rapid Adsorption of Copper(II) and Lead(II) by Rice Straw/Fe3O4 Nanocomposite: Optimization,Equilibrium Isotherms,and Adsorption Kinetics Study

Rice straw/magnetic nanocomposites (RS/Fe₃O₄-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.     

Impact of Humin on Soil Adsorption and Remediation of Cd(II), Pb(II), and Cu(II)

In situ immobilization constitutes a promising technology for the mitigation of contaminants, through the reduction of metal bioavailability and mobility. This study investigated the adsorption isotherms and kinetic characteristics of humin extracted from peat soils. We also studied the influences of the pH, ionic strengths, and soluble organic matter concentrations of soil solutions on the adsorptive properties of humin, and compared its ability to detoxify potentially toxic metals in both actual and simulated soil solutions. The study results indicated that humin contains a massive population of oxygen-containing functional groups. Its adsorption capacity for Pb(II) was greater than that for Cu(II), which exceeded that for Cd(II). The adsorption of humin for Pb(II) conformed to the Freundlich model, while the adsorption of humin for Cd(II) and Cu(II) followed the Langmuir model. The adsorption kinetics of humin with respect to potentially toxic metals aligned well with second-order kinetics equations. As the pH was elevated, the potentially toxic metal adsorption by humin increased rapidly. Electrolyte ions and tartaric acids in solution both inhibited the adsorption of potentially toxic metals by humin, and its ability to inactivate potentially toxic metals. This was shown to be improved in actual field soil solutions in contrast to simulated soil solutions.     

Experimental and theoretical approaches for Cd(II) biosorption from aqueous solution using Oryza sativa biomass

Biomass of Oryza sativa (OS) was tested for the removal of Cd(II) ions from synthetic and real wastewater samples. Batch experiments were conducted to investigate the effects of operating parameters on Cd(II) biosorption. Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to examine the surface characteristics of the Cd(II)-loaded biomass. The maximum removal efficiency of Cd(II) was 89.4% at optimum pH 6.0, biosorbent dose 10.0 g L^?1, initial Cd(II) 50 mg L^?1, and biosorbent particle size 0.5 mm. The applicability of Langmuir and Freundlich isotherms to the sorbent system implied the existence of both monolayer and heterogeneous surface conditions. Kinetic studies revealed that the adsorption process of Cd(II) followed the pseudo-second-order model (r2: 0.99). On the theoretical side, an adaptive neuro-fuzzy inference system (ANFIS) was applied to select the operating parameter that mostly influences the Cd(II) biosorption process. Results from ANFIS indicated that pH was the most influential parameter affecting Cd(II) removal efficiency, indicating that the biomass of OS was strongly pH sensitive. Finally, the biomass was confirmed to adsorb Cd(II) from real wastewater samples with removal efficiency close to 100%. However, feasibility studies of such systems on a large-scale application remain to be investigated.     

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.     

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.     

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.     

Adsorptive Removal and Recovery of U(VI), Cu(II), Zn(II), and Co(II) from Water and Industry Effluents

Tamarind fruit shell (TFS) was converted to a cation exchanger (PGTFS-SP-COOH) having a carboxylate functional group at the chain end by grafting poly(hydroxyethylmethacrylate) onto TFS (a lignocellulosic residue) using potassium peroxydisulfate-sodium thiosulfate redox initiator, and in the presence of N, N ′-methylenebisacrylamide as a cross-linking agent, followed by functionalization. The chemical modification was investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), and potentiometric titrations. The feasibility of PGTFS-SP-COOH for the removal of heavy metals such as U(VI), Cu(II), Zn(II), and Co(II) ions from aqueous solutions was investigated by batch process. The optimum pH range for the removal of meal ions was found to be 6.0. For all the metal ions, equilibrium was attained within 2 h. The kinetic and isotherm data, obtained at optimum pH value 6.0, could be fitted with pseudo-second-order equation and Sips isotherm model, respectively. The Sips maximum adsorption capacity for U(VI), Cu(II), Zn(II), and Co(II) ions at 30°C was found to be 100.79, 65.69, 65.97, and 58. 81 mg/g, respectively. Increase of ionic strength decreased the metal ion adsorption. Different wastewater samples were treated with PGTFS-SP-COOH to demonstrate its efficiency in removing metal ions from wastewater. The adsorbed metal ions on PGTFS-SP-COOH can be recovered by treating with 1.0 M NaCl + 0.5 M HCl for U(VI) ions and 0.2 M HCl for Cu(II), Co(II), and Zn(II) ions. Four adsorption/desorption cycles were performed without significant decrease in removal capacity. The results showed that PGTFS-SP-COOH developed in this study exhibited considerable adsorption potential for the removal of U(VI), Cu(II), Zn(II), and Co(II) ions from water and wastewaters.     

Biosorption of Pb(II) from contaminated water onto Moringa oleifera biomass: kinetics and equilibrium studies

Abstract

The present study aims at evaluating a batch scale biosorption potential of Moringa oleifera leaves (MOL) for the removal of Pb(II) from aqueous solutions. The MOL biomass was characterized by FTIR, SEM, EDX, and BET. The impact of initial concentrations of Pb (II), adsorbent dosage, pH, contact time, coexisting inorganic ions (Ca²⁺, Na⁺, K⁺, Mg²⁺, CO₃^2?, HCO₃^?, Cl^?), electrical conductivity (EC) and total dissolved salts (TDS) in water was investigated. The results revealed that maximum biosorption (45.83?mg/g) was achieved with adsorbent dosage 0.15?g/100?mL while highest removal (98.6%) was obtained at adsorbent biomass 1.0?g/100?mL and pH 6. The presence of coexisting inorganic ions in water showed a decline in Pb(II) removal (8.5% and 5%) depending on the concentrations of ions. The removal of Pb(II) by MOL decreased from 97% to 89% after five biosorption/desorption cycles with 0.3?M HCl solution. Freundlich model yielded a better fit for equilibrium data and the pseudo-second-order well described the kinetics of Pb(II) biosorption. FTIR spectra showed that –OH, C–H, –C–O, –C?=?O, and –O–C functional groups were involved in the biosorption of Pb(II). The change in Gibbs free energy (ΔG = ?28.10?kJ/mol) revealed that the biosorption process was favorable and thermodynamically driven. The results suggest MOL as a low cost, environment-friendly alternative biosorbent for the remediation of Pb(II) contaminated water.     

Investigation of complexation of immobilized metallothionein with Zn(II) and Cd(II) ions using piezoelectric crystals

The aim of this study is to investigate complexation of metallothionein (MT) with cadmium and zinc ions. An oligopeptide (i.e. Lys-Cys-Thr-Cys-Cys-Ala), a fragment of MT was covalently immobilized onto piezoelectric crystals, which were first treated with ethylene diamine plasma in a glow-discharge apparatus, and then were chemically reacted with glutaraldehyde. Complexation of the immobilized MT with Zn(II) and Cd(II) ions in aqueous media was followed by recording the changes of the frequency shifts of the piezoelectric quartz crystals. The amount of Cd(II) ions interacted with the immobilized MT molecules was the highest at pH 7.4, and decreased with an increase in the pH of the medium, in parallel to the decrease in the amount of immobilized MT. The number of Zn(II) ions interacted with the immobilized MT molecules was higher than the number of Cd(II) ions when the adsorption was from solutions containing a single-metal ion with the same ion concentrations. In consecutive adsorption studies, we observed that the type of metal ions used in the first interaction is important. These experiments showed also that there is an exchange between the metal ions, and competition provokes adsorption of both ions due to synergistic-antagonistic effects.