Biosorption of heavy metals by the exopolysaccharide produced by <Emphasis Type="Italic">Paenibacillus jamilae</Emphasis>

The biosorption of several toxic heavy metals (Pb, Cd, Co, Ni, Zn and Cu) by the exopolysaccharide (EPS) produced by Paenibacillus jamilae, a potential biosorbent for metal remediation and recovery was studied. Firstly, the biochemical composition of this bacterial polymer was determined. Glucose was the most abundant neutral sugar, followed by galactose, rhamnose, fucose and mannose. The polymer presented a high content of uronic acids (28.29%), which may serve as binding sites for divalent cations. The presence of carboxylic groups was also detected by infrared spectroscopy. The EPS presented an interesting affinity for Pb in comparison with the other five metals. Lead biosorption (303.03 mg g⁻¹) was tenfold higher (in terms of mg of metal adsorbed per gram of EPS) than the biosorption of the rest of metals. Biosorption kinetics, the effect of pH and the effect of competitive biosorption were determined. Finally, we found that the EPS was able to precipitate Fe(III), but the EPS-metal precipitate did not form with Fe(II), Pb(II), Cd(II), Co(II), Ni(II), Cu(II) and Zn(II).     

Biosorption of nickel and cadmium by metal resistant bacterial isolates from agricultural soil irrigated with industrial wastewater

Agricultural soil irrigated with industrial wastewater (more than two decades) analysed for heavy metals revealed high levels of Fe, Cr, Cu, Zn, Ni and Cd. Out of a total of 40 bacterial isolates obtained from these soils, 17 belonged to the family enterobacteriaceae and 10 were Pseudomonas spp. A maximum MIC of 200 for Cd, 400 for Zn and Cu, 800 for Ni, and 1600 microg/ml for Pb was observed. Biosorption of Ni and Cd studies over a range of metal ion concentrations with Escherichia coli WS11 both in single and bi-metal systems showed that the adsorption of Cd and Ni was dependent on the concentrations and followed the Freundlich adsorption isotherm. The biosorption of Ni increased from 6.96 to 55.31 mg/g of cells, and Cd from 4.96 to 45.37 mg/g of cells at a concentration ranging from 50 to 400 microg/ml after 2h of incubation in a single metal solution. A further increase in incubation time had no significant effect on the biosorption of metals.     

酵母菌对重金属离子吸附的研究

以６属３３株酵母菌的活菌或死菌对重金属离子Ｃｕ２＋、Ｃｄ２＋和Ｎｉ２＋进行了吸附能力的初步研究。结果显示∶吸附时间、吸附温度、溶液的ｐＨ、共存离子和菌体的生理状态对吸附作用都有明显的影响。在优化组合后发现一株假丝酵母菌对三种重金属离子的吸附比为Ｃｄ２＋＞Ｃｕ２＋＞Ｎｉ２＋,每克活菌体吸附量分别为１７．２３ｍｇ＞１０．５７ｍｇ＞３．２ｍｇ。干菌体对三种重金属的吸附量较明显的低于活菌体的吸附量。     

Biosorption of Heavy Metals from Wastewater by Biosolids

In a study where the removal of heavy metals from wastewater is the primary aim, the biosorption of heavy metals onto biosolids prepared as Pseudomonas aeruginosa immobilized onto granular activated carbon was investigated in batch and column systems. In the batch system, adsorption equilibriums of heavy metals were reached between 20 and 50 min, and the optimal dosage of biosolids was 0.3 g/L. The biosorption efficiencies were 84, 80, 79, 59 and 42 % for Cr(VI), Ni(II), Cu(II), Zn(II) and Cd(II) ions, respectively. The rate constants of biosorption and pore diffusion of heavy metals were 0.013–0.089 min^–1 and 0.026–0.690 min^–0.5. In the column systems, the biosorption efficiencies for all heavy metals increased up to 81–100 %. The affinity of biosorption for various metal ions towards biosolids was decreased in the order: Cr = Ni > Cu > Zn > Cd.     

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

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

Equilibrium and kinetic studies on biosorption potential of charophyte biomass to remove heavy metals from synthetic metal solution and municipal wastewater

The risk of heavy metal contamination in domestic water causes serious health and environmental problems. Biosorption has been considered as an efficient and alternative way for treatment of heavy metal–contaminated wastewater. The potentials of dried charophytes, Chara aculeolata and Nitella opaca, to biosorb lead (Pb), cadmium (Cd), and zinc (Zn) from synthetic solutions and municipal wastewater were investigated. The efficiency of metal removal was studied under varied conditions in different sorbent dosages, pH, and contact times. Biosorption isotherm and kinetics were used to clarify heavy metal preference and biosorption mechanism. C. aculeolata and N. opaca performed well in the biosorption of all three metal ions, with preference towards Pb, followed by Cd and Zn, in the single-metal solutions. Pb adsorption onto algal biomass followed first-order rate kinetics (N. opaca) and intraparticle diffusion (C. aculeolata and N. opaca). These results indicated physical adsorption process between Pb ions and both algal biomasses. Cd and Zn biosorption kinetics fitted the second-order rate model, indicating chemical adsorption between metal ions and both algae. The experimental data of three-metal biosorption fitted well to Langmuir isotherm model, suggesting that the metal ion adsorption occurred in a monolayer pattern on a homogeneous surface. C. aculeolata exhibited slightly higher maximum uptake of Pb, Cd, and Zn (105.3 mgPb/g, 23.0 mgCd/g, 15.2 mgZn/g) than did N. opaca (104.2 mgPb/g, 20.5 mgCd/g, 13.4 mgZn/g). In multi-metal solutions, antagonistic effect by metal competition was observed. The ability of charophytes to remove Pb and Zn was high in real municipal water (81–100%). Thus, the charophytic biomass may be considered for the treatment of metal contamination in municipal wastewater.     

Cadmium, zinc and copper biosorption mediated by Pseudomonas veronii 2E

Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents. Experimental conditions (pH, time, cellular mass, volume, metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E. Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes, silicone rubber and polyurethane foam. Biosorption experiments were carried out at 32 °C and controlled pH; maximal Cd(II) retention was observed at pH 7.5. The isotherm followed the Langmuir model (K_d = 0.17 mM and q_max = 0.48 mmol/g cell dry weight). Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II). In addition, biosorption of 40% Cu(II) (pH 5 and 6.2) and 50% Zn(II) and 50% Cd(II) (pH 7.5) was observed from mixtures of Cu(II), Zn(II) and Cd(II) 0.5 mM each.     

The metal specificity and selectivity of ZntA from Escherichia coli using the acylphosphate intermediate

ZntA from Escherichia coli is a P-type ATPase that confers resistance to Pb(II), Zn(II), and Cd(II) in vivo. We had previously shown that purified ZntA shows ATP hydrolysis activity with the metal ions Pb(II), Zn(II), and Cd(II). In this study, we utilized the acylphosphate formation activity of ZntA to further investigate the substrate specificity of ZntA. The site of phosphorylation was Asp-436, as expected from sequence alignments. We show that in addition to Pb(II), Zn(II), and Cd(II), ZntA is active with Ni(II), Co(II), and Cu(II), but not with Cu(I) and Ag(I). Thus, ZntA is specific for a broad range of divalent soft metal ions. The activities with Ni(II), Co(II), and Cu(II) are extremely low; the activities with these non-physiological substrates are 10-20-fold lower compared with the values obtained with Pb(II), Zn(II), and Cd(II). Similar results were obtained with DeltaN-ZntA, a ZntA derivative lacking the amino-terminal metal binding domain. By characterizing the acylphosphate formation reaction in ZntA in detail, we show that a step prior to enzyme phosphorylation, most likely the metal ion binding step, is the slow step in the reaction mechanism in ZntA. The low activities with Ni(II), Co(II), and Cu(II) are because of a further decrease in the rate of binding of these metal ions. Thus, metal ion selectivity in ZntA and possibly other P1-type ATPases is based on the charge and the ligand preference of particular metal ions but not on their size.     

Biosorption of Ni, Cr and Cd by metal tolerant Aspergillus niger and Penicillium sp. using single and multi-metal solution

Fungi including Aspergillus and Penicillium, resistant to Ni2+, Cd2+, and Cr6+ were isolated from soil receiving long-term application of municipal wastewater mix with untreated industrial effluents of Aligarh, India. Metal tolerance in term of minimum inhibitory concentration (MIC) was 125-550 microg/ml for Cd, 300-850 microg/ml for Ni and 300-600 microg/ml for Cr against test fungi. Two isolates, Aspergillus niger and Penicillium sp. were tested for their Cr, Ni and Cd biosorption potential using alkali treated, dried and powdered mycelium. Biosorption experiment was conducted in 100 ml of solution at three initial metal concentrations i.e., 2, 4 and 6 mM with contact time (18 hr) and pretreated fungal biomass (0.1g) at 25 degrees C. Biosorption of all metals was found higher at 4 mM initial metal concentration as compared to biosorption at 2 and 6 mM concentrations. At 4 mM initial metal concentration, chromium biosorption was 18.05 and 19.3 mg/g of Aspergillus and Penicillium biomasses, respectively. Similarly, biosorption of Cd and Ni ions was also maximum at 4 mM initial metal concentration by Aspergillus (19.4 mg/g for Cd and 25.05 mg/g of biomass for Ni) and Penicillium (18.6 mg/g for Cd and 17.9 mg/g of biomass for Ni). In general, biosorption of metal was influenced by initial metal concentration and type of the test fungi. The results indicated that fungi of metal contaminated soil have high level of metal tolerance and biosorption properties.     

Biotechnological potential of Microcystis sp. in Cu, Zn and Cd biosorption from single and multimetallic systems

This paper provides information on biosorption of Cu, Zn and Cd by Microcystis sp. in single, bi and trimetallic combination. Highest biosorption of Cu followed by Zn and Cd in single as well as in mixtures containing two or three metals was noticed. The order of inhibition of Cu, Zn and Cd biosorption in bi and trimetallic combinations was suggestive of screening or competition for the binding sites on the cell surface. This observation was reconfirmed by Freundlich adsorption isotherm. K_f values were maximum for Cu (K_f=45.18), followed by Zn (K_f=16.71), and Cd (K_f=15.63) in single metallic system. The K_f values for each test metal was reduced in solution containing more than one metal. Further, the reduction in biosorption of each metal ion due to presence of other metal ion was of greater magnitude at relatively higher concentrations of interfering metal ion. The biosorption of Cu at saturation was less affected when secondary metal (Cd or Zn) was added in the medium. Above results suggest that Microcystis holds great potential for metal biosorption from mixture.     

Differential pulse polarography: a method of directly measuring uptake of metal ions by live bacteria without separation of biomass and medium

Abstract The technique of differential pulse polarography is shown here for the first time to be applicable to monitoring directly the uptake of metal ions from solution by live bacteria in the chamber of the polarograph. The potential at which the polarographic current peak is observed is characteristic of the metal, whereas peak height is proportional to metal concentration. Adding solutions of Cd(II) or Zn(II) to a suspension of Pseudomonas cepacia in 50 mM Hepes buffer (pH 7.4) in the chamber gave polarographic peaks of lower amplitude than those observed when these metal solutions were added to buffer alone, due to metal binding or uptake by cells. Langmuir plots gave binding capacities of 0.13 and 0.20 mmol metal (Dd or Zn, respectively) per g (dry weight) biomass. Ni(II) uptake was biphasic. Metal uptake increased with pH. The value of polarography for rapid assessment of metal removal by cells and the ability to measure uptake from multi-metal solutions is demonstrated.     

Metal tolerance and biosorption potential of filamentous fungi isolated from metal contaminated agricultural soil

Heavy metal analysis of agricultural field soil receiving long-term (>20 years) application of municipal and industrial wastewater showed two- to five-fold accumulation of certain heavy metals as compared to untreated soil. Metal-resistant fungi isolated from wastewater-treated soil belonged to genera Aspergillus, Penicillium, Alternaria, Geotrichum, Fusarium, Rhizopus, Monilia and Trichoderma. Minimum inhibitory concentrations (MIC) for Cd, Ni, Cr, Cu, and Co were determined. The MIC ranged from 0.2 to 5 mg ml(-1) for Cd, followed by Ni (0.1-4 mg ml(-1)), Cr (0.3-7 mg ml(-1)), Cu (0.6-9 mg ml(-1)) and for Co (0.1-5 mg ml(-1)) depending on the isolate. Aspergillus and Rhizopus isolates were tested for their metal biosorption potential for Cr and Cd in vitro. Biosorption experiments were conducted with initial metal concentrations of 2, 4, 6 and 8 mM with a contact time of 4 h and wet fungal biomass (1-5 g) at 25 degrees C. Maximum biosorption of Cr and Cd ions was found at 6 mM initial metal concentration. Aspergillus sp.1 accumulated 1.20 mg of Cr and 2.72 mg of Cd per gram of biomass. Accumulation of these two metals by very tolerant Aspergillus sp.2 isolate was at par with relatively less tolerant Aspergillus sp.1 isolate. Rhizopus sp. accumulated 4.33 mg of Cr and 2.72 mg of Cd per g of biomass. The findings indicated promising biosorption of cadmium and chromium by the Rhizopus and Aspergillus spp. from aqueous solution. There is little, if any, correlation between metal tolerance and biosorption properties of the test fungi.     

Petiolar felt-sheath of palm: a new biosorbent for the removal of heavy metals from contaminated water.

Biosorption of heavy metals such as Pb2+, Ni2+, Cd2+, Cu2+, Cr3+ and Zn2+ by petiolar felt-sheath of palm (PFP) from contaminated water was examined. PFP was found to efficiently remove all the toxic metal ions with selectivity order of Pb2+ > Cd2+ > Cu2+ > Zn2+ > Ni2+ > Cr3+. The uptake was rapid, with more than 70% completed within 15 min. The bound metal ions were successfully desorbed and the PFP fibrous-biomass remained effective after several adsorption-desorption cycles.     

Study of the biosorption of different heavy metal ions onto Kraft lignin

The ability of Kraft lignin, a waste product of paper production, for removing copper, zinc, cadmium and chromium ions from water was investigated. The studies were conducted by a batch method to determine equilibrium parameters. The adsorbed heavy metal ions followed the order: Cr(VI) ? Cd(II) > Cu(II) > Zn(II). The influence of other ions such as Ni(II), Cd(II) and Pb(II), on Cu(II) adsorption by Kraft lignin was evaluated. Obtained results support the idea that adsorption behaviour of heavy metal ions have to be perceived from the aspect of possible influence of interfering ion species.     

Comparison of the Heavy Metal Biosorption Capacity of Active,Heat‐Inactivated and NaOH‐Treated Phanerochaete chrysosporium Biosorbents

Three different kinds of Phanerochaete chrysosporium (NaOH‐treated, heat‐inactivated and active) biosorbent were used for the removal of Cd(II) and Hg(II) ions from aquatic systems. The biosorption of Cd(II) and Hg(II) ions on three different forms of Phanerochaete chrysosporium was studied in aqueous solutions in the concentration range of 50–700 mg/L. Maximum biosorption capacities of NaOH‐treated, heat‐inactivated and active Phanerochaete chrysosporium biomass were found to be 148.37 mg/g, 78.68 mg/g and 68.56 mg/g for Cd(II) as well as 224.67 mg/g, 122.37 mg/g and 88.26 mg/g for Hg(II), respectively. For Cd(II) and Hg(II) ions, the order of affinity of the biosorbents was arranged as NaOH‐treated > heat‐inactivated > active. The order of the amount of metal ions adsorbed was established as Hg(II) > Cd(II) on a weight basis, and as Cd(II) > Hg(II) on a molar basis. Biosorption equilibriums were established in about 60 min. The effect of the pH was also investigated, and maximum rates of biosorption of metal ions on the three different forms of Phanerochaete chrysosporium were observed at pH 6.0. The reusability experiments and synthetic wastewater studies were carried out with the most effective form, i.e., the NaOH‐treated Phanerochaete chrysosporium biomass. It was observed that the biosorbent could be regenerated using 10 mM HCl solution, with a recovery of up to 98%, and it could be reused in five biosorption‐desorption cycles without any considerable loss in biosorption capacity. The alkali‐treated Phanerochaete chrysosporium removed 73% of Cd(II) and 81% of Hg(II) ions from synthetic wastewater.     

Heavy metal removal from aqueous solution by wasted biomass from a combined AS-biofilm process

This study evaluated the capability of metal biosorption by wasted biomass from a combined anaerobic-anoxic-oxic (A2O)-biofilm process with simultaneous nitrogen and phosphorus removal. Zinc, cadmium and nickel were rapidly adsorbed in 20 min by the harvested sludge from a continuous-flow pilot-plant. Biosorption equilibrium was then reached in 6h. The biosorption isotherm showed that metal biosorption behavior had fitted well to the Freundlich isotherm, but not Langmuir isotherm. The capacity constants k of Freundlich model for nickel, zinc and cadmium were 0.471, 0.298 and 0.726, respectively; the affinity constants 1/n were 0.444, 0.722 and 0.718, respectively. The order of metal affinity for the wasted biomass was Zn > Cd > Ni, which was in conformity to the other biosorption results with different biological sludge.     

Interactions of metal cations with anionic groups on the cell wall of the macroalga Vaucheria sp.

The aim of this article was to investigate the interactions of metal cations in aqueous solutions with the biomass of the freshwater macroalga Vaucheria sp. This problem is important when elaborating new applications of biosorption, e.g. the production of mineral feed additives for livestock from the biomass of algae enriched with microelement ions. Potentiometric titration was applied as a quick and cheap screening test to search for new efficient biosorbents. It revealed a variety of functional groups capable of cation exchange on the macroalgal surface, including carboxyl, phosphate, hydroxyl or amino groups. Fourier transform infrared spectroscopy on natural and chromium‐loaded Vaucheria sp. confirmed that carboxyl groups played a dominant role in the biosorption. The study also showed that Ca(II), Na(I), K(I), and Mg(II) ions were released from the biomass after biosorption of Cu(II), Mn(II), Zn(II), and Co(II) ions, indicating that ion exchange was a key mechanism in the biosorption of metal ions by Vaucheria sp. biomass. It was noticed that the mass of the microelement cations bound by the macroalga was proportional to the total mass of light metal ions [Na(I), K(I), Ca(II), and Mg(II)] released from the biomass.     

Edible macroalga <Emphasis Type="Italic">Ulva prolifera</Emphasis> as microelemental feed supplement for livestock: the fundamental assumptions of the production method

In the present paper, the possibility of the application of marine macroalga Ulva (Enteromorpha) prolifera, as microelemental feed supplement for livestock, was evaluated. The concept was based on two facts: the natural macroalga contains high concentrations of microelements and there is a possibility to greatly increase this content via biosorption. In order to characterize the biosorption process of metal ions by U. prolifera, preliminary experiments were conducted with Cr(III) ions. The effect of temperature, pH and the biomass concentration on the equilibrium of biosorption was investigated. For further experiments (biosorption of Mn(II), Zn(II), Cu(II), Co(II)), the following experimental conditions were chosen: pH 5, 25°C, the biomass concentration 1.0 g l⁻¹. Equilibrium of the biosorption process could be described by the Langmuir equation. The theoretical maximum biosorption capacity was also determined by potentiometric titration of the biomass. The investigation of the external structure of the macroalga and atomic concentration of elements on the surface of the biomass was analyzed using scanning electron microscopy. The content of microelements in the biomass after biosorption increased 110,555; 44,228; 21,177; 2,281 and 1,458 times for Co(II), Cr(III),Cu(II), Zn(II), Mn(II), respectively. Therefore, biomass of U. prolifera enriched with individual microelements, mixed in the proper proportion could be used as feed supplement in animal feeding to cover the nutrient requirements for microelements.     

Biosorption of Copper by Paenibacillus polymyxa Cells and their Exopolysaccharide

Summary Biosorption of heavy metals by gram-positive, non-pathogenic and non-toxicogenic Paenibacillus polymyxa P13 was evaluated. Copper was chosen as a model element because it is a pollutant originated from several industries. An EPS (exopolysaccharide)-producing phenotype exhibited significant Cu(II) biosorption capacity. Under optimal assay conditions (pH 6 and 25 °C), the adsorption isotherm for Cu(II) in aqueous solutions obeyed the Langmuir model. A high q value (biosorption capacity) was observed with whole cells (q_max=112 mgCu g⁻¹). EPS production was associated with hyperosmotic stress by high salt (1 M NaCl), which led to a significant increase in the biosorption capacity of whole cells (q_max=150 mgCu g⁻¹). Biosorption capacity for Cu(II) of the purified EPS was investigated. The maximum biosorption value (q) of 1602 mg g⁻¹ observed with purified EPS at 0.1 mg ml⁻¹ was particularly promising for use in field applications.