The effect of increase in concentration of Na(I) ions on biosorption of Cr(III) ions by Enteromorpha prolifera and Spirulina sp

In this study, the effect of the increase in the initial concentration of Na(I) ions in the solution during biosorption of Cr(III) ions by two edible algae: marine macroalga — Enteromorpha prolifera and microalga — Spirulina sp. was investigated. During biosorption, essential elements are exchanged with alkali and alkaline earth metal ions (e.g. Na(I) ions), which are naturally bound with the biomass. The goal of this study was to investigate the effect of the increase in concentration of Na(I) ions on biosorption performance. The equilibrium of the process is described by Langmuir equation. It was found that with the increase in the initial concentration of NaCl (from 132 to 7331 mg L^?1), there was a lower biosorption capacity of Enteromorpha prolifera (from 85.8 to 51.0 mg g^?1) and Spirulina sp. (74.2 to 20.7 mg g^?1) towards Cr(III) ions. It was also possible to determine the number of times the solution used in the biosorption process can be recycled and yet mantain high biosorption capacity. The determined numbers were: 16 for Enteromorpha prolifera and 19 for Spirulina sp.      

ICP-OES and SEM-EDX Analysis of dust and powder produced by the laser-processing of a Cr-Ni-Steel alloy

In this investigation we compared the analytical results obtained by inductively coupled plasma optical emission spectroscopy (ICP-OES) and a scanning electron microscope with an energy dispersive X-ray analysis system (SEM-EDX). The powder and dust, obtained by laser-processing of CRN-14301 steel, was analysed to classify the powder and dust for its final waste disposal. For this reason we analysed the elemental content of the samples. The samples consisted of a mixture of metals and their oxides.The solid powder and dust was analysed directly by SEM-EDX, the ICP-OES analysis was carried out after the solid was dissolved in an acid solution. Both analytical methods were in good agreement.ICP-OES showed a higher precision and lower detection limit than EDX, but SEM-EDX showed a higher amount of information regarding the sample composition.     

Chemical equilibria in wastewaters during toxic metal ion removal by agricultural biomass

After an overview of environmental pollution and the environmental threat posed by metals, this paper focuses on a literature survey of the different analytical methodologies and techniques used to investigate the functional groups involved in metal sorption onto biomass derived from agricultural waste. The recent literature has mainly focused on identifying the binding groups on the biomass surface through the use of different analytical techniques, from the traditional potentiometry to the most innovative and sophisticated solid surface analysis. In most of the biosorption studies, carboxylic group is the main origin for metal uptake, followed by hydroxyl group, aromatic ring and amine. The extent of the use of spectroscopic methods compared to traditional chemical analysis is being questioned. We stress that the study of biosorption mechanisms requires a multidisciplinary approach, and the efforts of analytical chemists and solution equilibrium experts really do contribute to the knowledge and to the optimization of these processes. This is the context in which we present a speciation study of the binding of various toxic metal ions by some coordinating groups on the biomass surface, which allows the classification of sorption mechanisms as a function of the pH dependence of the binding phenomena.     

Enhanced Cu(II) and Cr(VI) biosorption capacity on poly(ethylenimine) grafted aerobic granular sludge

The biosorption characteristics of cations and anions from aqueous solution using polyethylenimine (PEI) modified aerobic granules were investigated. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis exhibit the presence of PEI on the granule surface. Compared with the raw granule, the modified aerobic granules with PEI showed a significant increase in sorption capacity for both metal ions. The monolayer biosorption capacity of granules for Cu(II) and Cr(VI) ions was found to be 71.239 and 348.125mg/g. The optimum solution pH for adsorption of Cu(II) and Cr(VI) from aqueous solutions was found to be 6 and 5.2, respectively. The biosorption data fitted better with the Redlich-Peterson isotherm model. FTIR showed chemical interactions occurred between the metal ions and the amide groups of PEI on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption.     

Performance of Pleurotus ostreatus Mushrooms and Spent Substrate for the Biosorption of Cd(II) From Aqueous Solution

The capacities of Pleurotus ostreatus mushroom and spent substrate were evaluated for the biosorption of cadmium (II) from aqueous solution in order to select the most efficient material for bioremediation. The optimum sorption conditions were optimized, including the pH of the aqueous solution, contact time, biomass dosage, initial metal concentration, and temperature. The sorption of cadmium on both biosorbents was also evaluated by several kinetic, equilibrium, and thermodynamic models. The possible heavy metal biosorption mechanisms were evaluated through point of zero charge (pH_pzc), Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX). Based on the results of column studies, the effectiveness of the P. ostreatus spent substrate was confirmed as a biosorbent for Cd(II) removal from aqueous solutions.     

Metal ion distribution between water and river sediment: speciation model and spectroscopic validation

Natural sediments show sequestering properties that can lead to a process of self-purification of aquatic environment from metal pollution. The study of the interaction between metal ions and sediment particles enhances what is known about the distribution and bioavailability of heavy metals in natural systems. Our contribution concerns the characterisation of the sequestering ability of a River Po sediment with regard to calcium(II), magnesium(II), cadmium(II), nickel(II) and copper(II), in fixed experimental conditions, through pH-metric and spectrometric measurements. A batch titration procedure was adopted and, in each solution, after equilibration, both pH and pM (M = Ca(II), Mg(II), Cd(II), Ni(II), Cu(II)) (via Inductively Coupled Plasma - Optical Emission Spectroscopy, ICP-OES) values were measured. The experimental data were first processed with a specific software to evaluate the concentration and protonation constants of the sediment ligand site(s). The speciation model was then assessed, together with the values of complexation constants, for the different sediment/metal cation systems. In order to better characterise the copper(II)-sediment interaction and to obtain more information about the nature of ligand site(s) involved, EPR (Electronic Paramagnetic Resonance) measurements were also made on the dry sediment before and after reaction with copper(II) ions.     

Biosorption of lead(II) from aqueous solutions by non-living algal biomass Oedogonium sp. and Nostoc sp.--a comparative study

Industrial wastewaters containing heavy metals pose a major environmental problem that needs to be remedied. The present study reports the ability of two non-living (dried) fresh water algae, Oedogonium sp. and Nostoc sp. to remove lead(II) from aqueous solutions in batch system under varying range of pH (2.99-7.04), contact time (5-300 min), biosorbent dose (0.1-0.8 g/L), and initial metal ion concentrations (100 and 200mg/L). The optimum conditions for lead biosorption are almost same for the two algal biomass Oedogonium sp. and Nostoc sp. (pH 5.0, contact time 90 and 70 min, biosorbent dose 0.5 g/L and initial Pb(II) concentration 200mg/L) however, the biomass of Oedogonium sp. was found to be more suitable than Nostoc sp. for the development of an efficient biosorbent for the removal of lead(II) from aqueous solutions, as it showed higher values of q(e) adsorption capacity (145.0mg/g for Oedogonium sp. and 93.5mg/g for Nostoc sp.). The equilibrium data fitted well in the Langmuir isotherms than the Freundlich isotherm, thus proving monolayer adsorption of lead on both the algal biomass. Analysis of data shows that the process involves second-order kinetics and thermodynamic treatment of equilibrium data shows endothermic nature of the adsorption process. The spectrum of FTIR confirms that the amino and carboxyl groups on the surface of algal biomass were the main adsorption sites for lead removal. Both the biosorbents could be regenerated using 0.1 mol/L HCl solution, with upto 90% recovery. The biosorbents were reused in five biosorption-desorption cycles without a significant loss in biosorption capacity. Thus, this study demonstrated that both the algal biomass could be used as an efficient biosorbents for the treatment of lead(II) bearing wastewater streams.     

Characteristic features of Bacillus cereus cell surfaces with biosorption of Pb(II) ions by AFM and FT-IR

In order to elucidate the potential mechanisms involved in the biosorption of metal ions, atomic force microscopy (AFM) and Fourier transform infrared (FT-IR) spectroscopy were used to characterize the interaction between Pb2+ and Bacillus cereus. AFM imaging of the biomass surfaces exposed to different concentrations of lead ions solution showed a major morphological change occurred after Pb2+ biosorption. The FT-IR spectra indicated the binding characteristics of the lead ions involved the carboxyl, hydroxyl and amino groups in the biomass. Equilibrium biosorption experiments of Pb2+ were carried out to investigate the effects of pH values and the initial metal concentrations. The experimental isotherm data were then modeled using Langmuir, Freundlich, and Redlich-Peterson isotherm equations. As a result, the Redlich-Peterson model yielded the best fit of experimental data. Kinetics experiments showed the biosorption was a rapid process and the pseudo-second-order model was successfully applied to predict the rate constant of biosorption.     

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.     

Biosorption of Metals from Dilute Aqueous Solutions

Dilute aqueous solutions, generated or used by industry, can contain a variety of different metal ions. Various processes are suitable for reclamation of toxic metals and among them, attention is paid here to biosorption. The ability of microorganisms to remove metal ions from solution is a well known phenomenon. Industrial applications of biosorption often make use of dead biomass, which does not require nutrients and can be exposed to environments of high toxicity. Experimental laboratory batch experiments are described for actinomycetes, fungi and for activated sludge, as the metal biosorbents, providing insight into cadmium biosorption. Non-living biomass showed greater binding capacities for cadmium (a priority pollutant) than living biomass. Engineering considerations are central in decisions concerning the commercial future of biosorption and a practical solution is needed for certain problems, such as the efficient separation of metal-loaded biomass.     

Characterization of hexavalent chromium interaction with Sargassum by X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and quantum chemistry calculation

Hexavalent chromium represents higher toxicity in aqueous solutions. It can be removed by such low-cost biosorbents as Sargassum sp. In this study, X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and quantum chemistry (QC) calculation were used to study the interactions between hexavalent chromium and Sargassum sp. during the biosorption. It was found that most of the adsorbed Cr(VI) ions were reduced to Cr(III) after the biosorption. The electrons for the reduction of Cr(VI) were possibly supplied from the Sargassum biomass, some organic compounds of which were oxidized. Cr(III) ions were coordinated with the oxygen atoms from either carboxyl or hydroxyl functional groups to form an octahedral structural metal complex. The coordination numbers of the formed Cr complex were 4-6, and bond length of Cr-O was 1.98?. QC calculation proved the possible formation of the Cr(III) metal complex, and revealed that carboxyl from biomass could be strongly bound with Cr(III). A three-step removal mechanism of Cr(VI) by Sargassum was proposed.     

Biosorption of Pb(II) and Cd(II) ions by Agave sisalana (sisal fiber)

The present work proposes the use of Agave sisalana (sisal fiber) as an natural adsorbent for ions Pb(II) and Cd(II) biosorption from natural waters. The flame atomic absorption spectrometry was used for quantitative determination and study of the ions Pb(II) and Cd(II) adsorption on the solid phase. The Fourier transform infrared spectroscopy (FT IR) was used to investigate the sisal structure and the specific BET surface area was analyzed. The biosorption potential of sisal as biosorbent for the removal of the ions Pb(II) and Cd(II) from aqueous solution was investigate considering the followings parameters: pH, biomass amount and contact time. Langmuir and Freundlich isotherms were used to evaluate adsorption behavior of the ions on this solid phase. The results showed that sisal has a surface area to adsorption of 0.0233 m² g^{− 1}, and the OH and CO functional groups are the main involved in the biosorption. The best interpretation for the experimental data was given by Freundlich isotherm that proposes a monolayer sorption with a heterogeneous energetic distribution of active sites, accompanied by interactions between sorbed molecules. The maximum monolayer biosorption capacity was found to be 1.85 mg g^{− 1} for Cd (II) and 1.34 mg g^{− 1} for Pb (II) at pH 7 and 296 K. This phase solid can be used for biosorption of cadmium and lead in polluted natural waters.     

Biosorption of Co(II), Cr(III), Cd(II), and Pb(II) Ions from Aqueous Solution Using Nonliving Neochloris Pseudoalveolaris Deason & Bold: Equilibrium,Thermodynamic, and Kinetic Study

In this study, biosorption of cobalt(II), chromium(III), cadmium(II), and lead(II) ions from aqueous solution was studied using the algae nonliving biomass (Neochloris pseudoalveolaris, Np) as natural and biological sorbents. The effect of pH, contact time, temperature, and metal concentration on the adsorption capacity of metal ions was investigated. The maximum adsorption capacities for Co(II), Cr(II), Cd(II), and Pb(II) were found to be 20.1, 9.73, 51.4 and 96.2 mg/g at the optimum conditions, respectively. The experiments showed that when pH increased, an increase in the adsorption capacity of the biomass was observed too. The kinetic results of adsorption obeyed a pseudo second-order model. Freundlich and Langmuir isotherm models were applied to experimental equilibrium data of metal ions adsorption and the value of R _L for Pb(II), Cb,(II), Co(II), and Cr(III) was found to be 0.376, 0271, 0872, and 096, respectively. The thermodynamic parameters related to the adsorption process such as E _a , ΔG ⁰, ΔH ⁰, and ΔS ⁰ were calculated. ΔH ⁰ values (positive) showed that the adsorption mechanism was endothermic. Weber-Morris and Urano-Tachikawa diffusion models were also applied to experimental equilibrium data. The algae biomass was effectively used as a sorbent for the removal of metal ions from aqueous solutions.     

Equilibrium,kinetic and thermodynamic biosorption studies of Hg(II) on red algal biomass of Porphyridium cruentum

Among a variety of microbial materials employed for biosorption, algae have added advantages of non-toxic and autotrophic nature. In this study, biosorption of Hg(II) was studied with red algal biomass of Porphyridium cruentum. The parameters affecting biosorption such as dosage of biosorbent, pH, contact time, initial metal concentration, temperature and effect of foreign metal cations in binary system were evaluated. Kinetic data were described with the help of pseudo-first-order and pseudo-second-order kinetic models. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models were applied to adsorption equilibrium data. According to the results, the maximum removal capacity (q_max) was 2.62?mg/g observed at pH 7 with 0.25?g/L of biosorbent dosage for Hg(II) solution containing 10?mg/L of metal ions. The Langmuir isotherm model fits best to the adsorption data while the kinetic data followed the pseudo-second-order model. Thermodynamics studies showed that the biosorption process of Hg(II) on P. cruentum was exothermic in nature.     

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 Cd(II), Cr(III), and Cr(VI) by saltbush (Atriplex canescens) biomass: thermodynamic and isotherm studies

The biosorption data of Cd(II), Cr(III), and Cr(VI) by saltbush leaves biomass were fit on the Freundlich and Langmuir adsorption isotherms at 297 K. The Cd(II) and Cr(III) solutions were adjusted to pH 5.0 and the Cr(VI) solution was adjusted to pH 2.0. The correlation coefficient values indicated that the data fit better the Freundlich model. The maximal capacities (K(F)) were found to be 5.79 x 10(-2), 3.25 x 10(-2), and 1.14 x 10(-2) mol/g for Cr(III), Cd(II), and Cr(VI), respectively. Similar results were obtained using the Langmuir and the Dubinin-Radushkevick equations. Thermodynamic parameters calculated from the Khan and Singh equation and from the q(e) vs C(e) plot show that the equilibrium constants for the biosorption of the metals follow the same order of the maximal capacities. The negative Gibbs free energy values obtained for Cd(II) and Cr(III) indicated that these ions were biosorbed spontaneously. The mean free energy values calculated from the Dubinin-Radushkevick equation (10.78, 9.45, and 9.05 for Cr(III), Cr(VI), and Cd(II), respectively) suggest that the binding of Cd(II), Cr(III), and Cr(VI) by saltbush leaves biomass occurs through an ionic exchange mechanism.     

Simultaneous determination of seven metal ions in water samples by solid-phase extraction on polyacrylonitrile activated carbon fibres

A new solid-phase extraction method utilising polyacrylonitrile activated carbon fibres (PAN-ACFs) as adsorbent was developed for the preconcentration of trace metal ions prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The PAN-ACFs oxidised with nitric acid were characterised by FT-IR, XRD, SEM and BET analysis. Then the resulting PAN-ACFs were used as solid-phase adsorbent for simultaneously determination of trace Al(III), Be(II), Bi(III), Cr(III), Cu(II), Fe(III) and Pb(II) ions in aqueous solutions. The influences of the analytical parameters on the recoveries of the studied ions were investigated. The optimum experimental conditions of the proposed method were pH: 6.0; eluent concentration and volume: 3.0 mL of 1.5 mol L^?1 nitric acid; flow rates of sample and eluent solution: 1.5 mL min^?1. The preconcentration factors were found to be 67 for Al(III), Bi(III); 83 for Cr(III), Cu(II), Fe(III) and 50 for Be(II), Pb(II). The precision of this method was in range of 1.5%~3.5% and the detection limit of this metal ions was between 0.06~1.50 μg L^?1. The developed method was validated by the analysis of a certified reference sample and successfully applied to the determination of trace metal ions in water samples with satisfactory results.     

Controlled-pore silica glass modified with N-propylsalicylaldimine for the separation and preconcentration of trace Al(III), Ag(I) and Hg(II) in water samples.

Controlled-pore silica glass modified with N-propylsalicylaldimine (SCPSG) has been investigated as a surface-active matrix for the separation of some metal ions. The porous silica glass base was confirmed to have better stability towards hydrolysis in aqueous solution buffered at pH=9 in comparison to silica gel, which showed twice the surface area of controlled-pore silica glass. The different analytical parameters affecting the batch mode separation and preconcentration of trace Al(II), Ag(I) and Hg(II) in environmental samples using SCPSG, prior to their determination using inductively coupled plasma mass spectrometry (ICP-MS), were studied. The optimum conditions are pH 9.0 +/- 0.1, time of stirring 30 min and the eluent concentration 0.5 mol dm(-3) HNO3. The ion-exchange capacity of SCPSG with respect to Al(III), Ag(I) and Hg(II) was 0.27, 0.18 and 0.23 mmol g(-1), respectively. The recovery values for the metal ions were 96.8 +/- 0.86, 98.1 +/- 0.60 and 96.2 +/- 1.06%, and the analytical detection limits were 26.1, 1.49 and 0.44 pg cm(-3), respectively, for a preconcentration factor of 100. The method has been applied to the determination of the investigated metal ions in natural water samples as well as certified and reported samples and the results were found to be accurate.     

重金属的生物吸附机理及吸附平衡模式研究*

各种生物吸附剂包括海洋微生物、发酵工业的菌丝体废渣及活性污泥的提取物等对金属离子的吸附特性已被广泛研究,本文就生物体对金属离子的吸附机理及吸附平衡模式研究进行了综述,阐明了今后的研究方向。