Cork biomass as biosorbent for Cu(II), Zn(II) and Ni(II)

The removal of Cu(II), Zn(II) and Ni(II) from solutions using biosorption in cork powder is described. The adsorption isotherms were determined, along with the effect of different variables, such as the solid–liquid ratio, temperature and pH on the removal efficiency of the metals. The potentiometric titration curve of the cork biomass was determined and some zeta-potential studies were carried out. The effect of the pre-treatment by Fisher esterification on the biosorption properties of cork is also presented. It was concluded that the adsorption of the heavy metals was favoured by an increase in pH. The degree of heavy metal removal is directly related to the concentration of cork biomass, and the maximum sorption capacity of cork biomass for Cu(II), Zn(II) and Ni(II) was 0.63, 0.76 and 0.34 meq./g, respectively. It is shown that ion exchange plays a more important role in the sorption of Cu(II) and Ni(II) on cork biomass than in the sorption of Zn(II). The pre-treatment by Fisher esterification confirmed the important role of the carboxylic groups in binding of Cu(II) and Ni(II) and showed that they are the only binding sites for Zn(II).     

Immobilization of heavy metals by Pseudomonas putida CZ1/goethite composites from solution

Bacterial–mineral composites are important in the retention of heavy metals due to their large sorption capacity under a wide range of environmental conditions. This study provides the first quantitative comparison of the metal-binding capacities of P. putida CZ1–goethite composite to its individual components. When the same amount (on a dry weight basis) of living and nonliving cells of P. putida CZ1, goethite or their composites was separately exposed to solutions of 0.5 mM Cu(II) and Zn(II) in 0.01 M KNO₃, the living cells removed the largest quantity of heavy metals. The results of calculated metal retention values indicated that the adsorption of goethite to bacteria has not mask or neutralize chemically reactive adsorption sites normally available to metal ions. Moreover, the nonliving cells–goethite composite retained approximately 82% more Zn than that predicted by their individual behavior. The preferential association of Zn with P. putida CZ1 was observed by TEM and EDS analyses of a mixture consisting of the bacteria and goethite. Desorption of Cu and Zn with 1.0 M CH₃COOK solution from P. putida CZ1 and goethite indicated the differences in the functional groups able to bind heavy metals.     

Biosorption of copper(II) from aqueous solutions by Spirogyra species

Batch studies were conducted to investigate the kinetics and isotherms of Cu(II) biosorption on the biomass of green alga Spirogyra species. It is observed that the biosorption capacity of the biomass strongly depends on pH and algal dose. The maximum biosorption capacity of 133.3 mg Cu(II)/g of dry weight of biomass was observed at an optimum pH of 5 in 120 min with an algal dose of 20 g/L. Desorption studies were conducted with 133.3 mg/g of Cu(II) loaded biomass using different desorption agents including HCl, EDTA, H2SO4, NaCl, and H2O. The maximum desorption of 95.3% was obtained with HCl in 15 min. The results indicate that with the advantages of high metal biosorption capacity and satisfactory recovery of Cu(II), Spirogyra can be used as an efficient and economic biosorbent material for the removal and recovery of toxic heavy metals from polluted water.     

Biosorption of cadmium,copper, lead and zinc by inactive biomass of<Emphasis Type="Italic"> Pseudomonas Putida</Emphasis>

The accumulation of Cd(II), Cu(II), Pb(II) and Zn(II) at mg L(-1) concentration levels by inactive freeze-dried biomass of Pseudomonas Putida has been investigated. These metals could be efficiently removed from diluted aqueous solutions. A contact time of 10 min was sufficient to reach equilibrium. The pH has a strong effect on metal biosorption and the optimal pH values were 6.0, 5.0-6.0, 6.0-6.5 and 7.0-7.5 for Cd(II), Cu(II), Pb(II) and Zn(II) respectively. Under these conditions there was 80% removal for all metals studied. The process of biosorption can be described by a Langmuir-type adsorption model. This model accounts for 98% of the data variance. The K(A) and q(max) parameters for each metal are strongly correlated (at confidence levels greater than 98%) with the metal acidity, quantified by the constant of the corresponding M(OH)(+) complex, thus confirming previous assertions by other authors.     

Biosorption of copper(II) and cadmium(II) by a novel exopolysaccharide secreted from deep-sea mesophilic bacterium

The biosorption behaviors and mechanisms of a novel exopolysaccharide (EPS), which is secreted by a mesophilic bacterium (namely Wangia profunda (SM-A87)) isolated from deep-sea sediment, for heavy metals Cu(II) and Cd(II) have been studied in this paper. The effects of SM-A87 EPS concentration, solution pH and ionic strength on the metal uptake were investigated by employing batch adsorption techniques, respectively. The optimum biosorption capacities were observed at pH 5.0 for Cu(II) with 48.0 mg/g and pH 6.0 for Cd(II) with 39.75 mg/g, respectively. Addition of salts decreased Cu(II) or Cd(II) uptake in the order of K⁺ < Na⁺ < Ca²⁺. Langmuir and Freundlich models were employed to describe the biosorption equilibrium data, indicating the favorable biosorption occurs and larger biosorption capacity and intensity for Cu(II) than for Cd(II). The biosorption kinetics for both metals can be well described by pseudo-second-order kinetic model, compared with pseudo-first-order and intraparticle diffusion kinetic models. The competitive biosorption was also studied, indicating that in two-component solution with different metal ratios, the selective biosorption of SM-A87 EPS for Cu(II) was much higher than for Cd(II). The Fourier transform infrared spectroscopy (FT-IR) analysis indicated possible functional groups (e.g., OH, COO and COC) of SM-A87 EPS involved in metal biosorption process, which indicated the potential of using SM-A87 EPS as an effective sorbent for Cu(II) or Cd(II) removal from water.     

Competitive biosorption of zinc(II) and cobalt(II) in single- and binary-metal systems by aerobic granules

The biosorption process for removal of cobalt(II) and zinc(II) by aerobic granules was characterized. Single component and binary equimolar systems were studied at different pH values. The equilibrium was well described by Redlich-Peterson adsorption isotherm. The maximal adsorption capacity of the granules, in single systems (55.25 mg g(-1) Co; 62.50 mg g(-1) Zn) compared with binary systems (54.05 mg g(-1) Co; 56.50 mg g(-1) Zn) showed reduction in the accumulation of these metals onto aerobic granules. The kinetic modelling of metal sorption by granules has been carried out using Lagergren equations. The regression analysis of pseudo second-order equation gave a higher R(2) value, indicating that chemisorption involving valent forces through the sharing or exchange of electrons between sorbent and sorbate may be the rate limiting step. The initial biosorption rate indicated that aerobic granules can adsorb Co(II) more rapidly than Zn(II) from aqueous solutions. Meanwhile, FTIR and XPS analyses revealed that chemical functional groups (e.g., alcoholic and carboxylate) on aerobic granules would be the active binding sites for biosorption of Co(II) and Zn(II).     

Adsorption of zinc(II) and copper(II) to Shirasu (pyroclastic flow)

A fundamental study on the adsorption of metal elements on Shirasu, a pyroclastic flow deposit distributed in southern Kyushu, Japan, has been conducted. The adsorption experiment was carried out by a batch method, and by using Zn(II) and Cu(II) under several conditions; the effects of the initial concentration of metal ions, grain size, and pH were investigated. At smaller grain sizes, the amount of Zn(II) and Cu(II) adsorbed increased. At higher pH values, the amount of Zn(II) and Cu(II) adsorbed increased. Plots of the adsorption isotherm indicated that the adsorption of Zn(II) and Cu(II) on Shirasu followed the Langmuir isotherm model, and the Langmuir isotherm constants, W(0) and b, were obtained. W(0) at pH 5.0 was approximately two-times larger than that at pH 3.0. This may reflect an increase in the number of anionic binding sites on the surface of Shirasu with an increase in the pH. The b value for Zn hardly changed with an increase in the pH, and for Cu the value decreased with an increase in the pH. These observations suggest that anionic binding sites have a low stability constant, since the apparent stability constant, b, is obtained as the average of stability constant of all sites on the Shirasu surface.     

Enhanced Removal of Cu(II) and Pb(II) from Aqueous Solutions by Pretreated Biomass of Fusarium Solani

This study investigated the feasibility of Fusarium solani biomass as a biosorbent for Cu(II) and Pb(II) removal from aqueous solutions. Batch sorption experiments were carried out for Cu(II) and Pb(II) to quantify the sorption kinetics, pH, biosorbent dose and pretreatment of F. solani biomass. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. The maximum biosorption by F. solani biomass was obtained with solutions having pH 5 for both metal ions. An enhanced Cu(II) removal (96.53%) was observed for aluminum hydroxide pretreated biomass. Maximum Pb(II) removal (95.48%) was observed with native biomass. Time dependence experiments for the metal ions uptake showed that adsorption equilibrium reached almost 240 min after metal addition. The kinetic studies showed that the biosorption process followed the pseudo second‐order rate model for Cu(II) and Pb(II). The equilibrium data fitted well to the Langmiur isotherm model.     

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.     

Application of Artificial Neural Network and Particle Swarm Optimization for modelling and optimization of biosorption of Lead(II) and Nickel(II) from wastewater using dead cyanobacterial biomass

Removal of heavy metals through biosorption using biomass offers several advantages over other conventional techniques such as low cost, high efficiency, environmentally friendly, etc. In the present article, biosorption of Nickel(II) and Lead(II)was investigated using dried biomass of cyanobacterial consortium. OFAT (one-factor-at-a-time) analysis was used to assess the effect of input parameters on the removal of potentially toxic elements by varying initial metal ion concentration (2–10 mgL⁻¹), adsorbent dose (0.1–1.0 gL^-1), pH (for Pb(II): 2–6, for Ni(II): 2–8) and temperature (25°C–45°C) individually, at constant shaking speed of 150 ​rpm. Results showed that removal using biomass attained highest values in as short time as 15 ​min. The investigations also showed the removal is highly effective at lower initial concentrations of heavy metals. Maximum removal of Lead(II) (87.27 ​± ​1.75%) and Nickel(II) (92.57 ​± ​0.77%) was obtained at pH 6 and 45°C and at pH 7 and 25°C, respectively, within 15 ​min with 0.1 gL^-1 biomass. Both the Langmuir model and Freundlich model were seen to fit the equilibrium data. Further, Artificial Neural Network was used to model the biosorption process. Subsequently, Particle Swarm Optimization was applied to optimize the operating conditions for the removal of both the metals.     

Amberlite XAD-7 impregnated with Xylenol Orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS

A new chelating resin, Xylenol Orange coated Amberlite XAD-7, was prepared and used for preconcentration of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) prior to their determination by flame atomic absorption spectrophotometry. The optimum pH values for quantitative sorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) are 4.5-5.0, 4.5, 4.0-5.0, 4.0, 5.0 and 5.0-7.0, respectively, and their desorptions by 2 mol L(-1) HCl are instantaneous. The sorption capacity of the resin has been found to be 2.0, 2.6, 1.6, 1.6, 2.6 and 1.8 mg g(-1) of resin for Cd, Co, Cu, Fe, Ni and Zn, respectively. The tolerance limits of electrolytes, NaCl, NaF, NaI, NaNO3, Na2SO4 and of cations, Mg2+ and Ca2+ in the sorption of the six metal ions are reported. The preconcentration factor was between 50 and 200. The t1/2 values for sorption are found to be 5.3, 2.9, 3.2, 3.3, 2.5 and 2.6 min for the six metals, respectively. The recoveries are between 96.0 and 100.0% for the different metals at preconcentration limits between 10 to 40 ng mL(-1). The preconcentration method has been applied to determine the six metal ions in river water samples after destroying the organic matter (if present in very large amount) with concentrated nitric acid (RSD < or = 8%, except for Cd for which it is upto 12.6%) and cobalt content of vitamin tablets with RSD of approximately 3.0%.     

Adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto fine powder of Typha latifolia L. root: kinetics and isotherm studies

Fine powder of Typha latifolia L. root was used for adsorption of copper and zinc ions from buffered and nonbuffered aqueous solutions. The adsorption reached equilibrium in 60 min. During this time, more than 90 % of the adsorption process was completed. The effect of initial pH, initial concentration of metal ion, and contact time was investigated in a batch system at room temperature. The optimum adsorption performance was observed at pH 5.00 and 4.25 for nonbuffered solutions of Cu(II) and Zn(II), respectively, while for buffered solutions it occurred at pH 6.00. The total metal uptake decreased on application of ammonium acetate buffer, from 37.35 to 17.00 mg g^?1 and 28.80 to 9.90 mg g^?1 for Cu(II) and Zn(II) solutions, respectively, with 100 mg L^?1 initial concentration. The pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models were used to describe the adsorption kinetics. The experimental data followed the pseudo-second-order kinetic model. The biosorption equilibrium was well described by Langmuir and Freundlich isotherm models.     

Biosorption of Au (III) and Cu (II) from aqueous solution by a non-living Cetraria islandica (L.) Ach

Biosorption of Au(III) and Cu(II) from dilute aqueous solutions was investigated by biomass of the non-living Cetraria islandica (L.) Ach. The removal and recovery of gold and copper were studied by applying batch technique. The experimental parameters such as the pH of the solution, contact time, the amount of Cetraria islandica (L.) Ach. (dried lichen), the concentration of metals on retention and eluents kind and amount have been investigated. Au(III) and Cu(II) were adsorbed on the dried lichen at pH 3 and pH 8, respectively. Quantitative retention (> or = 90%) was obtained within 60 minutes for metals. Maximum capacity of 1.0 g of dried lichen for biosorption of Au(III) and Cu(II) were found as 7.4 mg of Au(III) and 19.2 mg of Cu(II). It was seen that the adsorption equilibrium data conformed well to the Langmuir model and Freundlich equation for Au(III) and only Freundlich equation for Cu(II). The method proposed in this study was applied to spiked mineral water analysis and metals adsorbed on the lichens were quantitatively (> or = 90%) recovered from mineral water samples by using 0.5 mol L(-1) HCl.     

Amberlite XAD-7 impregnated with Xylenol Orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS

A new chelating resin, Xylenol Orange coated Amberlite XAD-7, was prepared and used for preconcentration of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) prior to their determination by flame atomic absorption spectrophotometry. The optimum pH values for quantitative sorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) are 4.5–5.0, 4.5, 4.0–5.0, 4.0, 5.0 and 5.0–7.0, respectively, and their desorptions by 2 mol L^–1 HCl are instantaneous. The sorption capacity of the resin has been found to be 2.0, 2.6, 1.6, 1.6, 2.6 and 1.8 mg g^–1 of resin for Cd, Co, Cu, Fe, Ni and Zn, respectively. The tolerance limits of electrolytes, NaCl, NaF, NaI, NaNO₃, Na₂SO₄ and of cations, Mg²⁺ and Ca²⁺ in the sorption of the six metal ions are reported. The preconcentration factor was between 50 and 200. The t_1/2 values for sorption are found to be 5.3, 2.9, 3.2, 3.3, 2.5 and 2.6 min for the six metals, respectively. The recoveries are between 96.0 and 100.0% for the different metals at preconcentration limits between 10 to 40 ng mL^–1. The preconcentration method has been applied to determine the six metal ions in river water samples after destroying the organic matter (if present in very large amount) with concentrated nitric acid (RSD ≤ 8%, except for Cd for which it is upto 12.6%) and cobalt content of vitamin tablets with RSD of ～ 3.0%.     

自然水体生物膜有机组分对Pb(2+)的吸附特性及其影响因素

生物膜在天然水环境和工程处理中起着重要的作用．关于自然水体生物膜对重金属的吸附作用已有很多报道．但多数报道认为，生物膜中的无机物即铁锰氧化物对重金属的吸附起着主要作用，而对于生物膜的重要组成部分——有机组分对重金属吸附影响的研究则很少．     

Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions by adsorption onto natural bentonite

In this study, the removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions using the adsorption process onto natural bentonite has been investigated as a function of initial metal concentration, pH and temperature. In order to find out the effect of temperature on adsorption, the experiments were conducted at 20, 50, 75 and 90 °C. For all the metal cations studied, the maximum adsorption was observed at 20 °C. The batch method has been employed using initial metal concentrations in solution ranging from 15 to 70 mg L⁻¹ at pH 3.0, 5.0, 7.0 and 9.0. A flame atomic absorption spectrometer was used for measuring the heavy metal concentrations before and after adsorption. The percentage adsorption and distribution coefficients (K _d) were determined for the adsorption system as a function of adsorbate concentration. In the ion exchange evaluation part of the study, it is determined that in every concentration range, adsorption ratios of bentonitic clay-heavy metal cations match to Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR) adsorption isotherm data, adding to that every cation exchange capacity of metals has been calculated. It is shown that the bentonite is sensitive to pH changes, so that the amounts of heavy metal cations adsorbed increase as pH increase in adsorbent-adsorbate system. It is evident that the adsorption phenomena depend on the surface charge density of adsorbent and hydrated ion diameter depending upon the solution pH. According to the adsorption equilibrium studies, the selectivity order can be given as Zn²⁺>Cu²⁺>Co²⁺. These results show that bentonitic clay hold great potential to remove the relevant heavy metal cations from industrial wastewater. Also, from the results of the thermodynamic analysis, standard free energy ΔG ⁰, standard enthalpy ΔH ⁰ and standard entropy ΔS ⁰ of the adsorption process were calculated.     

Ratiometric fluorescent sensor proteins with subnanomolar affinity for Zn(II) based on copper chaperone domains

The ability to image the concentration of transition metals in living cells in real time is important for further understanding of transition metal homeostasis and its involvement in diseases. The goal of this study was to develop a genetically encoded FRET-based sensor for copper(I) based on the copper-induced dimerization of two copper binding domains involved in human copper homeostasis, Atox1 and the fourth domain of ATP7B (WD4). A sensor has been constructed by linking these copper binding domains to donor and acceptor fluorescent protein domains. Energy transfer is observed in the presence of Cu(I), but the Cu(I)-bridged complex is easily disrupted by low molecular weight thiols such as DTT and glutathione. To our surprise, energy transfer is also observed in the presence of very low concentrations of Zn(II) (10(-)(10) M), even in the presence of DTT. Zn(II) is able to form a stable complex by binding to the cysteines present in the conserved MXCXXC motif of the two copper binding domains. Co(II), Cd(II), and Pb(II) also induce an increase in FRET, but other, physiologically relevant metals are not able to mediate an interaction. The Zn(II) binding properties have been tuned by mutation of the copper-binding motif to the zinc-binding consensus sequence MDCXXC found in the zinc transporter ZntA. The present system allows the molecular mechanism of copper and zinc homeostasis to be studied under carefully controlled conditions in solution. It also provides an attractive platform for the further development of genetically encoded FRET-based sensors for Zn(II) and other transition metal ions.     

Chemically modified silica gel with p-dimethylaminobenzaldehyde for selective solid-phase extraction and preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) by ICP-OES

Silica gel-bound amines phase modified with p-dimethylaminobenzaldehyde (p-DMABD) was prepared based on chemical immobilization technique. The product (SG-p-DMABD) was used as an adsorbent for the solid-phase extraction (SPE) Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The uptake behaviors of SG-p-DMABD for extracting these metal ions were studied using batch and column procedures. For the batch method, the optimum pH range for Cr(III) and Ni(II) extraction was ≥ 3, for Cu(II), Pb(II) and Zn(II) extraction it was ≥ 4. For simultaneous enrichment and determination of all the metals on the newly designed adsorbent, the pH value if 4.0 was selected. All the metal ions can be desorbed with 2.0 mL of 0.5 mol L^− 1 of HCl. The results indicate that SG-p-DMABD has rapid adsorption kinetics using the batch method. The adsorption capacity for these metal ions is in the range of 0.40-1.15 mmol g^− 1, with a high enrichment factor of 125. The presence of commonly coexisting ions does not affect the sorption capacities. The detection limits of the method were found to be 1.10, 0.69, 0.99, 1.10 and 6.50 μg L^− 1 for Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 5.0% (n = 8) for all metal ions. The method was applied to the preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) from the certified reference material (GBW 08301, river sediment) and water samples with satisfactory results.     

Simultaneous removal of copper(II), lead(II), zinc(II) and cadmium(II) from aqueous solutions by multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were used successfully for the removal of heavy metals from aqueous solution. Characterization techniques showed the carbon as nanotubes with an average diameter between 40 and 60 nm and a specific surface area of 61.5 m² g^?1. The effect of carbon nanotubes mass, contact time, metal ions concentration, solution pH, and ionic strength on the adsorption of Cu(II), Pb(II), Cd(II) and Zn(II) by MWCNTs were studied and optimized. The adsorption of the heavy metals from aqueous solution by MWCNTs was studied kinetically using different kinetic models. A pseudo-second order model and the Elovich model were found to be in good agreement with the experimental data. The mechanism of adsorption was studied by the intra-particle diffusion model, and the results showed that intra-particle diffusion was not the slowest of the rate processes that determined the overall order. This model also revealed that the interaction of the metal ions with the MWCNTs surface might have been the most significant rate process. There was a competition among the metal ions for binding of the active sites present on the MWCNTs surface with affinity in the following order: Cu(II) > Zn(II) > Pb(II) > Cd(II).