Utilization of an exopolysaccharide produced by Chryseomonas luteola TEM05 in alginate beads for adsorption of cadmium and cobalt ions

Cadmium and cobalt adsorption from aqueous solution onto calcium alginate, sodium alginate with an extracellular polysaccharide (EPS) produced by the activated sludge bacterium Chryseomonas luteola TEM05 and immobilized C. luteola TEM05 was studied. In addition, solutions containing both of these ions were prepared and partial competitive adsorption of these mixtures was investigated. Metal adsorption onto gel beads was carried out at pH 6.0 and 25 degrees C. The maximum adsorption capacities determined by fitting Langmuir isotherms to the data for calcium alginate, calcium alginate+EPS, calcium alginate + C. luteola TEM05 and calcium alginate + EPS + C. luteola TEM05 were 45.87, 55.25, 49.26, 51.81 mg g(-1) for Co(II) and 52.91, 64.10, 62.5, 61.73 mg g(-1) for Cd(II), respectively. The biosorption capacity of the carrier for both metal ions together in competition was lower than those obtained when each was present alone.     

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.     

Biosorption of Chromium,Cadmium, and Cobalt from Aqueous Solution by Immobilized Living Cells of Chryseomonas luteola TEM 05

Abstract

In this work, the potential use of the immobilized cells of Chryseomonas luteola TEM 05 for the removal of Cr⁺⁶, Cd⁺² and Co⁺² ions from aqueous solutions was investigated. The living cells of C. luteola TEM 05 were firstly entrapped both in carrageenan and chitosan coated carrageenan gels and then used in biosoption of the metal ions in batch reactors at pH 6.0, 25°C, in 100 mg L^?1 of each metal solution. Besides this, a process of competitive biosorption of these metal ions was also described and compared to single metal ion adsorption in solution. According to the immobilization results, the replacement of KCl by KCl-chitosan as gelling agent improved the mechanical strength and thermal stability of the gel. In addition, the C. luteola TEM 05 immobilized carrageenan-chitosan gel system was quite more efficient for the fast adsorption of metal ions from aqueous solution than the carrageenan gels without biomass.     

Chromium and aluminum biosorption on<Emphasis Type="Italic"> Chryseomonas luteola</Emphasis> TEM05

Cr(VI) and Al(III) are environmental pollutants that are frequently encountered together in industrial wastewaters, e.g., from mining iron-steel, metal cleaning, plating, metal processing, automobile parts, and the manufacturing and dye industries. In this work, several variables that affect the capacity for chromium and aluminum biosorption by Chryseomonas luteola TEM05 were studied, particularly the effects of pH, metal concentration and contact time. Optimum adsorption pH values of Cr(VI) and Al(III) were determined as 4.0 and 5.0, respectively. The biosorption equilibrium was described by Freundlich and Langmuir adsorption isotherms. The value of Q ^o appears to be significantly higher for the Al(III) C. luteola TEM05 system. Langmuir parameters of C. luteola TEM05 also indicated a maximum adsorption capacity of 55.2 mg g^–1 for Al(III) and 3.0 mg g^–1 for Cr(VI).     

Comparison of Rhizopus nigricans in a pelleted growth form with some other types of waste microbial biomass as biosorbents for metal ions

Biosorption of metal ions (Li⁺, Ag⁺, Pb²⁺, Cd²⁺, Ni²⁺, Zn²⁺, Cu²⁺, Sr²⁺, Fe²⁺, Fe³⁺ and Al³⁺) by Rhizopus nigricans biomass was studied. It was shown that metal uptake is a rapid and pH-dependent process, which ameliorates with increasing initial pH and metal concentrations. Different adsorption models: Langmuir, Freundlich, split-Langmuir and combined nonspecific-Langmuir adsorption isotherm were applied to correlate the equilibrium data. The maximum biosorption capacities for the individual metal ions were in the range from 160 to 460 mol/g dry weight. Scatchard transformation of equilibrium data revealed diverse natures of biomass metal-binding sites. The binding of metals was also discussed in terms of the hard and soft acids and bases principle. The maximum biosorption capacities and the binding constant of R. nigricans were positively correlated with the covalent index of metal ions.The following types of waste microbial biomass originating as by-products from industrial bioprocesses were tested for biosorption of metal ions: Aspergillus terreus, Saccharomyces cerevisiae, Phanerochaete chrysosporium, Micromonospora purpurea, M. inyoensis and Streptomyces clavuligerus. The determined maximum biosorption capacities were in the range from 100 to 500 mol/g dry weight. The biosorption equilibrium was also represented with Langmuir and Freundlich sorption isotherms.     

Synergistic Removal of Pb(II), Cd(II) and Humic Acid by Fe3O4@Mesoporous Silica-Graphene Oxide Composites

The synergistic adsorption of heavy metal ions and humic acid can be very challenging. This is largely because of their competitive adsorption onto most adsorbent materials. Hierarchically structured composites containing polyethylenimine-modified magnetic mesoporous silica and graphene oxide (MMSP-GO) were here prepared to address this. Magnetic mesoporous silica microspheres were synthesized and functionalized with PEI molecules, providing many amine groups for chemical conjugation with the carboxyl groups on GO sheets and enhanced the affinity between the pollutants and the mesoporous silica. The features of the composites were characterized using TEM, SEM, TGA, DLS, and VSM measurements. Series adsorption results proved that this system was suitable for simultaneous and efficient removal of heavy metal ions and humic acid using MMSP-GO composites as adsorbents. The maximum adsorption capacities of MMSP-GO for Pb(II) and Cd (II) were 333 and 167 mg g⁻¹ caculated by Langmuir model, respectively. HA enhances adsorption of heavy metals by MMSP-GO composites due to their interactions in aqueous solutions. The underlying mechanism of synergistic adsorption of heavy metal ions and humic acid were discussed. MMSP-GO composites have shown promise for use as adsorbents in the simultaneous removal of heavy metals and humic acid in wastewater treatment processes.     

Kinetic analysis of metal uptake by dry and gel alginate particles

The kinetics of metal uptake by gel and dry calcium alginate beads was analysed using solutions of copper or lead ions. Gel beads sorbed metal ions faster than the dry ones and larger diffusivities of metal ions were calculated for gel beads: approximately 10⁻⁴ cm²/min vs. 10⁻⁶ cm²/min for dry beads. In accordance, scanning electron microscopy and nitrogen adsorption data revealed a low porosity of dry alginate particles. However, dry beads showed higher sorption capacities and a mechanical stability more suitable for large-scale use. Two sorption models were fitted to the kinetic results: the Lagergren pseudo-first order and the Ho and McKay pseudo-second order equations. The former was found to be the most adequate to model metal uptake by dry alginate beads and kinetic constants in the orders of 10⁻³ and 10⁻² min⁻¹ were obtained for lead solutions with concentrations up to 100 g/m³. The pseudo-first order model was also found to be valid to describe biosorbent operation with a real wastewater indicating that it can be used to design processes of metal sorption with alginate-based materials.     

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.     

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.     

Anions effects on biosorption of Mn(II) by extracellular polymeric substance (EPS) from Rhizobium etli

Microbial extracellular polymeric substances (EPS) are potential biosorbents for metal remediation and recovery. The Langmuir and Freundlich kinetics of Mn(II) binding by the EPS from a novel Mn(II) oxidising strain of Rhizobium etli were determined. Maximum manganese specific adsorptions (q _max) decreased in the sequence: sulphate (62 mg Mn per g EPS) > nitrate (53 mg g^–1) > chloride (21 mg g^–1). Consideration of the anion during kinetic studies is usually neglected but is important in providing more practical and comparable data between different biosorbent systems.     

Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by mercerized cellulose and mercerized sugarcane bagasse chemically modified with EDTA dianhydride (EDTAD)

This work describes the preparation of new chelating materials derived from cellulose and sugarcane bagasse for adsorption of Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous solutions. The first part involved the mercerization treatment of cellulose and sugarcane bagasse with NaOH 5 mol/L. Non- and mercerized cellulose and sugarcane bagasse were then reacted with ethylenediaminetetraacetic dianhydride (EDTAD) in order to prepare different chelating materials. These materials were characterized by mass percent gain, X-ray diffraction, FTIR, and elemental analysis. The second part consisted of evaluating the adsorption capacity of these modified materials for Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous single metal solutions, whose concentration was determined by atomic absorption spectroscopy. These materials showed maximum adsorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ ions ranging from 38.8 to 92.6 mg/g, 87.7 to 149.0 mg/g, and 192.0 to 333.0 mg/g, respectively. The modified mercerized materials showed larger maximum adsorption capacities than modified non-mercerized materials.     

Binding of the Activating Ion Co(II) to myo-Inositol Monophosphatase Monitored by Fluorescence and Phosphorescence Spectroscopy

Two extrinsic probes, pyrene-maleimide and eosin-maleimide, were used to label specific SH groups of the enzyme myo-inositol monophosphatase. The fluorescence of pyrene-monophosphatase is enhanced upon addition of the activating metal ions Co(II) and Mg(II). Co(II) ions bind with a dissociation constant of 4 M, whereas the apparent activation constant K _a is 0.4 mM. Energy transfer measurements demonstrated that the pyrene chromophore, covalently linked to Cys-218, is within 9 Å of the metal ion Tb(III) coordinated to the metal-binding site. The phosphorescence emitted by eosin covalently linked to the protein is quenched by the addition of the activating cations Co(II) and Mg(II). Phosphorescence titrations conducted under anaerobic conditions were used to determine a dissociation constant of approximately 3 M for the binding of Co(II) ions. The results are consistent with the hypothesis that two activating ions per monomeric subunit participate in the catalytic mechanism. The affinity of the tightly bound ion is at least 100-fold greater than the affinity of the weakly bound ion.     

Role of extracellular polymeric substance (EPS) in toxicity response of soil bacteria Bacillus sp. S3 to multiple heavy metals

Heavy metal resistant bacteria are of great interest because of their potential use in bioremediation. Understanding the survival and adaptive strategies of these bacteria under heavy metal stress is important for better utilization of these bacteria in remediation. The objective of this study was to investigate the role of bacterial extracellular polymeric substance (EPS) in detoxifying against different heavy metals in Bacillus sp. S3, a new hyper antimony-oxidizing bacterium previously isolated from contaminated mine soils. The results showed that Bacillus sp. S3 is a multi-metal resistant bacterial strain, especially to Sb(III), Cu(II) and Cr(VI). Toxic Cd(II), Cr(VI) and Cu(II) could stimulate the secretion of EPS in Bacillus sp. S3, significantly enhancing the adsorption and detoxification capacity of heavy metals. Both Fourier transform infrared spectroscopy (FTIR) and three-dimensional excitation–emission matrix (3D-EEM) analysis further confirmed that proteins were the main compounds of EPS for metal binding. In contrast, the EPS production was not induced under Sb(III) stress. Furthermore, the TEM–EDX micrograph showed that Bacillus sp. S3 strain preferentially transported the Sb(III) to the inside of the cell rather than adsorbed it on the extracellular surface, indicating intracellular detoxification rather than extracellular EPS precipitation played an important role in microbial resistance towards Sb(III). Together, our study suggests that the toxicity response of EPS to heavy metals is associated with difference in EPS properties, metal types and corresponding environmental conditions, which is likely to contribute to microbial-mediated remediation.

     

Adsorption of lead(II) from aqueous solution onto Hydrilla verticillata

The adsorption of Pb(II) onto Hydrilla verticillata was examined in aqueous solution with parameters of pH, adsorbent dosage, contact time and temperature. The linear Langmuir and Freundlich models were applied to describe equilibrium isotherms, and both models fitted well. The monolayer adsorption capacity of Pb(II) was found as 104.2 mg/g at pH 4 and 25°C. Dubinin–Radushkevich (D–R) isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (15.81 kJ/mol) indicated that the adsorption of Pb(II) onto H. verticillata may be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, free energy (ΔG ⁰), enthalpy (ΔH ⁰) and entropy (ΔS ⁰) of adsorption were also calculated. These parameters showed that the adsorption of Pb(II) onto H. verticillata was a feasible, spontaneous and exothermic process in nature. The influence of Cd²⁺, Cu²⁺ and Ni²⁺ on adsorption of Pb²⁺ onto H. verticillata was studied, too. In the investigated range of operating conditions, it was found that the existence of Cd ²⁺, Cu ²⁺ and Ni ²⁺ had no impact on the adsorption of Pb²⁺.     

Cadmium(II) sorption from water samples by powdered marble wastes

Abstract

A series of batch adsorption experiments were carried out, with the aim of removing cadmium ions from aqueous solutions and water samples using powdered marble wastes (PMW) as an effective inorganic sorbent. PMW is inexpensive, widespread, and may be considered as environmental problem. The main parameters (i.e. solution pH, sorbent and cadmium concentrations, stirring time, and temperature) influencing the sorption process were investigated. The results obtained for sorption of cadmium ions onto PMW are well described by the Freundlich and Langmuir models. The Dubinin-Radushkevick (D–R) isotherm model was applied to describe the nature of the adsorption of the metal ion; it was found that the adsorption process was chemical in nature. The thermodynamic parameters were also calculated from the Gibbs free energy change (ΔG°), enthalpy (AH°) and entropy (ΔS°). These parameters indicated that the adsorption process of cadmium(II) ions on PMW was spontaneous and endothermic in nature. Under the optimum experimental conditions employed the removal of ca ~100% of Cd²⁺ ions was attained. The procedure was successfully applied to removal of the cadmium ions from aqueous and various natural water samples. The adsorption mechanism is discussed.     

Biosorption and Bioreduction of Trivalent Aurum by Photosynthetic Bacteria <Emphasis Type="Italic">Rhodobacter capsulatus</Emphasis>

Biosorption has been shown to be an eco-friendly approach to remove heavy metal ions. In this study, the photosynthetic bacteria Rhodobacter capsulatus was screened and found to have strong ability to adsorb Au(III). The maximum specific uptake of living cells was over 92.43 mg HAuCl₄/g dry weight of cell in the logarithmic phase. Biosorpion ability would be enhanced by an acidic environment. As the main cations, during biosorption the quantity of Mg²⁺ exchanged was more than Na⁺. Biosorbed Au(III) could be reduced by carotenoid and enzymes embedded and/or excreted by R. capsulatus, which might be the mechanism of photosynthtic bacteria metal tolerance.     

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.     

Demonstration of Levan and Alginate in Bean Plants (Phaseolus vulgaris) Infected by Pseudomonas syringae pv. phaseolicola

A simple method for the extraction of extracellular polysaccharides (EPS) from plant tissue was developed. The polysaccharides of bacterial and plant origin present in the crude leaf extracts were separated by column chromatography on DEAE-fractogel, and the bacterial polymers were identified by IR spectroscopy. In extracts from infected leaves as well as in exudates (ooze) from leaf axils, alginate (an acetylated mannuronan) and levan (β-2,6-fructofuranan) were detected as the major components amounting up to 80% of the crude extracts. A race-1 isolate of P. phaseolicola synthesized both levan and alginate in about equal amounts in planta, whereas a race-2 strain produced EPS composed almost solely of alginate. Extraction of healthy leaves yielded low amounts of complex polysaccharides. These consisted mainly of galactose, arabinose, and galacturonic acid. Neither fructose nor mannuronic acid were detected. Kinetic studies indicated that the main production of bacterial EPS in planta was correlated with the appearance of the water-soaked symptom in leaves. However, before water-soaking became apparent, alginate was detected in infected leaves (1, day after inoculation). The high amount of extractable material (ca. 50 mg levan plus alginate per g of dry weight of diseased tissue) suggests that the bacterial EPS is responsible for the typical water-soaked appearance of lesions after bacterial infection. Since alginate was predominantly synthesized by the more virulent race-2 isolate, this component of bacterial EPS was suspected to be a decisive factor of virulence of P. phaseolicola. A possible function of alginate during pathogenesis is discussed.     

The use ofZoogloea ramigera in waste water treatment containing Cr(VI) and Cd(II) ions

Summary Optimum fermentation conditions forZ. ramigera were determined and various parameters which affected adsorption rates of chromium and cadmium ions onZ. ramigera were investigated. At 25°C the optimum adsorption pH of Cr(VI) and Cd(II) ions were 2.0 and 6.0 respectively. The adsorption rate of chromium and cadmium ion increased by increasing initial metal ion concentration up to 75 and 50 ppm respectively: at higher initial metal ion concentrations, the adsorption rates decreased.     

Behavior of human immunoglobulin G adsorption onto immobilized Cu(II) affinity hollow‐fiber membranes

Iminodiacetic acid (IDA) and tris(2‐aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow‐fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA‐Cu(II) or TREN‐Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini‐cartridge in a cross‐flow filtration mode (52.5 and 298.4 mg g^?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g^?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively). When mini‐cartridges were used, the dynamic adsorption capacity of IDA‐Cu(II) was the same for both mini‐cartridge and agarose gel. Copyright © 2013 John Wiley & Sons, Ltd.