Influence of pH and ionic strength on Cu(II) biosorption by aerobic granular sludge and biosorption mechanism

BACKGROUND: To elucidate the process and mechanism of Cu(II) biosorption onto aerobic granules, the influence of pH and ionic strength (IS) on the Cu(II) biosorption capacity and biosorption mechanism was studied. RESULTS: The biosorption of Cu(II) onto aerobic granules under different conditions of pH (3, 4 and 5), IS (0, 0.1 and 0.5 mol L^?1) and Cu(II) concentration (25–250 mg L^?1) was investigated. The correlation coefficients of the pseudo‐second‐order kinetic model were , while those of the Langmuir and Freundlich models were and respectively. The biosorption of Cu(II) increased with increasing pH, while the effect of IS on the biosorption was complicated, which could be explained by the competition among different metallic ions, colloidal chemistry theory or Derjaguin, Landau, verwey and Overbeek (DLVO) theory. About 70% of the solid phase Cu(II) was exchanged by Na(I), Ca(II) and Mg(II) released from the aerobic granules at pH 4 and 5. The results revealed that ion exchange is the most important biosorption mechanism but that other mechanisms also play a part. CONCLUSION: The sorption performance can be optimised by adjusting the pH and IS. Aerobic granules can be used as an alternative effective, economical and practical biosorbent for heavy metal removal. Copyright © 2008 Society of Chemical Industry     

Kinetics of ligand exchange reaction of Cu(II)-ammine complex with poly(vinyl alcohol) in aqueous solution

The kinetics of the ligand exchange reaction of the Cu(II)-ammine complex with poly(vinyl alcohol) (PVA) has been studied by a stopped-flow method at pH 9–10, at μ=0.1 (NH₄Cl) and at 25°C. The reaction is initiated by the formation of unstable [Cu(NH₃)₃]²⁺ by the attack of H⁺ on Cu(II)-ammine complex, and proceeds through the mixed complex {[Cu(NH₃)₃(O?PVA)]²⁺}. This step may be rate-determining, followed by a rapid reaction. Finally, the Cu(II) ion is taken up by PVA. The rate is given by d[Cu(II)?PVA]/dt=k[H⁺]{[Cu(NH₃)₄]²⁺}[PVA]/[NH₄Cl], where k=k₁ + k′₂[H⁺], k₁=4.25× 10s^?1 and k′₂=5.20× 10¹¹l mol^?1s^?1.     

A novel magnetic ion imprinted polymer for selective adsorption of trace amounts of lead(II) ions in environment samples

In this work a novel ion imprinted polymer (IIP) based on 4-(vinylamino)pyridine-2,6-dicarboxylicacid (VPyDC), was coated on Fe₃O₄ nano-particles. The application of this magnetic sorbent was investigated for preconcentration and determination of trace Pb(II) ions by flame atomic absorption spectrometry. Effects of various parameters such as sample pH, adsorption/desorption time and eluent were investigated during this study. The relative standard deviation and limit of detection of the method were found to be 1.8% and 0.9 ng mL⁻¹, respectively. The accuracy of this method was confirmed using various standard reference materials, then it was used for Pb(II) determination in environmental samples.     

Zinc(II) modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticles for its determination in water samples

In the present study newly developed potentiometric sensors for determination of zinc(II) are presented. The proposed potentiometric method was based on the fabrication of modified carbon paste (MCPE; electrode X) and modified gold nanoparticles-carbon paste (GNPs-CPE; electrode IX) sensors. A mercapto compound of 1,4-bis(5-mercaptopentyloxy)-benzene (BMPB) alone or self-assembled on gold nanoparticles was used as modifier to construct electrode (X) and electrode (IX) sensors, respectively. The prepared electrodes exhibit Nernstian slope of 29.93 ± 0.4 and 26.0 ± 1.02 mV decade⁻¹ towards Zn(II) ion over a wide concentration range of 6.8 × 10⁻¹⁰ to 2.9 × 10⁻² and 1.0 × 10⁻⁷ to 1.0 × 10⁻² mol L⁻¹ for electrode (IX) and electrode (X) sensors, respectively. The limit of detection of the electrode (IX) and electrode (X) sensors was found to be 6.8 × 10⁻¹⁰ and 1.0 × 10⁻⁷ mol L⁻¹, respectively. The potentiometric response of the electrode (IX) and electrode (X) based on GNPs-BMPB and BMPB are independent of pH of test solution in the pH range of 2.5–8.1 and 3–7 with a response time of 6 and 8 s for electrode (IX) and electrode (X) sensors, respectively. The proposed sensors showed fairly good discriminating ability towards Zn(II) ion in comparison with many hard and soft metal ions. Finally, the proposed electrodes were successfully used as indicator electrodes in potentiometric titration of zinc ion with sodium tetraphenylborate (NaTPB) and in direct determination of Zn(II) ion in some water samples. The results obtained compared well with those obtained using atomic absorption spectrometry.     

Solid-phase extraction for simultaneous separation and preconcentration of Fe(III) and Zn(II) traces using three chelatants and Ramelak bark-derived activated carbon as a new bio-sorbent

This article introduces a comparative study for the simultaneous separation and preconcentration of Fe(III) and Zn(II) traces in various water samples using three well-known ligands as chelating agents and activated carbon (AC) derived from Ramelak bark as a new bio-sorbent prior to the determination by ?ame atomic absorption spectrometry. The chelating agents were 4,4’-[(4-Cyano-phenyl)methylene]bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) (CMBM), diethyldithiocarbamate (DDTC) and ammonium pyrrolidine dithiocarbamate (APDC). CMBM was synthesized by a procedure reported in the literature. The newly prepared AC was characterized by Scanning Electron Microscopy (SEM) and Fourier-Transform Infrared (FTIR) Spectrometry. The analytical parameters affecting the separation efficiency of the analytes including pH, shaking time, chelating agent volume (concentration), sorbent mass, sample ?ow rate and elution conditions were investigated and discussed. Common coexisting ions did not seriously interfere with the separation, showing the good selectivity of the proposed method. The calibration graph was linear in the range of 0.35–70, 0.50–80, 0.9–100, 0.55–75, 0.75–90 and 1.0–120 ng mL^?1 for Fe-CMBM, Fe-DDTC, Fe-APDC, Zn-CMBM, Zn-DDTC and Zn-APDC, respectively. Under optimized conditions, the limits of detection were 0.11, 0.13, 0.27, 0.16, 0.22 and 0.30 ng mL^?1 for Fe-CMBM, Fe-DDTC, Fe-APDC, Zn-CMBM, Zn-DDTC and Zn-APDC, respectively. The proposed method has been applied to the determination of Fe(III) and Zn(II) in different water samples with satisfactory recovery percentages. The developed method, validated with standard reference materials, was used successfully in determining the concentrations of metal ions in water samples.     

Synthesis and thermal behavior of poly(methyl methacrylate)/Maghnia bentonite nanocomposite prepared at room temperature via in situ polymerization initiated by a new Ni(II)α‐benzoinoxime complex

Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/clay nanocomposite (PMMA/OBT) were successfully prepared in dioxan at room temperature via in situ radical polymerization initiated by a new Ni(II)α‐ Benzoinoxime complex as a single component in presence of 3% by weight of an organically modified bentonite (OBT) (originated from Maghnia, Algeria) and characterized by FTIR, ¹H‐NMR and viscometry. Mainly intercalated and partially exfoliated PMMA/OBT nanocomposite was elaborated and evidenced by X‐Ray diffraction (XRD) and transmission electron microscopy (TEM). The intrinsic viscosity of PMMA/OBT nanocomposite is much higher than the one of pure PMMA prepared under the same conditions. Differential scanning calorimetry (DSC) displayed an increase of 10°C in the glass transition temperature of the elaborated PMMA/OBT nanocomposite relative to the one of pure PMMA. Moreover, the TGA analysis confirms a significant improvement of the thermal stability of PMMA/OBT nanocomposite compared to virgin PMMA: the onset degradation temperature of the nanocomposite, carried out under nitrogen atmosphere, increased by more than 45°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

Etude de l'élimination des ions Cu (II) de la solution aqueuse par sorption sur la zéolithe a study of the removal of Cu (II) from aqueous solution by sorption on Zeolite A

The objective of this study is to present the results of removal of copper by the method of sorption on zeolite A. The batch experiments were conducted for both the kinetics for the sorption isotherms. The experimental variables studied were pH, contact time at different initial concentrations, the amount of sorbent, temperature and stirring speed. The sorption capacity depends on the pH and mass of sorbent, but the temperature and stirring rate showed no influence. Several mechanisms of retention of copper on the zeolite could be competitive (ion exchange, complexation or precipitation and sorption). The modeling of experimental data on kinetics showed that the model of pseudo‐second order describes satisfactorily the sorption on the zeolite, and that the limiting step of the speed distribution intraparticle. Statistical analysis of the constants for Langmuir‐Freundlich equation has shown that this model seems most appropriate to describe this phenomenon of sorption, which indicates the heterogeneity of the surface sorption of the zeolite. Copyright © 2011 Canadian Society for Chemical Engineering     

Studies on the activation of hydrogen peroxide for color removal in the presence of a new Cu(II)-polyampholyte heterogeneous catalyst

In this work we describe the application of a new non-soluble and non-porous complex with copper ion based on ethylene glycol diglycidyl ether (EGDE), methacrylic acid (MAA) and 2-methylimidazole (2MI) in the decolorization of an azo dye Methyl Orange (MO) as a model pollutant at room temperature.The complex with copper ion was studied by ESR and SEM and was tested as a heterogeneous catalyst for H₂O₂ activation. A possible mechanism of interaction involves the production of hydroxyl radicals (confirmed by ESR), dioxygen and water.The Cu(II)-polyampholyte/H₂O₂ system acted efficiently in the color removal of MO. The adsorption and oxidative degradation of the azo-based dye followed pseudo-first-order kinetic profiles, and the rate constant for degradation had a second-order dependence on copper ion content in the mixture.A removal of MO higher than 90% was achieved in 20 min at pH 7.0, combining 0.8 mM of complexed copper ions in the mixture with 24 mM hydrogen peroxide.The dye adsorbed on the polyampholyte following a L4-type isotherm with 4.9 μmol g⁻¹ maximum loading capacity and 3.1 μM dissociation constant for the first monolayer.     

Preparation and characterisation of a poly(acrylamidoglycolic acid-co-acrylamide) hydrogel for selective binding of Cu and application to diffusive gradients in thin films measurements

A poly(acrylamidoglycolic acid-co-acrylamide) [poly(AAGA-co-AAm)] hydrogel was prepared by copolymerising 2-acrylamidoglycolic acid (AAGA) with acrylamide (AAm). The copolymer hydrogel composition and structure was characterised by FTIR spectroscopy and elemental microanalysis and found to contain 3.5 AAGA monomer units for each AAm monomer unit. This was similar to the monomer ratios used in the synthesis. The metal ion binding properties of the hydrogel were characterised for a range of metal ions (Cu²⁺, Cd²⁺, K⁺, Na⁺, Mg²⁺ and Ca²⁺) under varying conditions of pH, ionic strength, metal concentration and time. The hydrogel was shown to bind Cu²⁺ and Cd²⁺ strongly under non-competitive binding conditions, with binding capacities of 5.3 and 5.1 μmol cm⁻², respectively. The binding capacity of each metal decreased, under competitive binding conditions (with a range of metal ions present at 17.8 μN), to 1.3 and 0.17 μmol cm⁻², respectively, indicating stronger selectivity for Cu²⁺. The metal ions were readily recovered (>94%) by eluting with 2 M nitric acid solution for 24 h. The binding capacities for Cu²⁺ and Cd²⁺ were also found to decrease with increasing ionic strength and at pH values <5. The copolymer was found to have an equilibrium swelling ratio (q_w) of over 500 at a maxima of pH 5.4 and at low ionic strengths. Finally, the copolymer hydrogel was tested as a binding phase with the diffusive gradients in thin films technique. A linear mass vs. time relationship was observed for Cu²⁺ in synthetic Windermere water with a recovery of approximately 100%.     

Copper-alginates: a biopolymer supported Cu(II) catalyst for 1,3-dipolar cycloaddition of alkynes with azides and oxidative coupling of 2-naphthols and phenols in water

Copper(II) ions immobilized onto a biopolymer (sodium alginate) is an effective heterogeneous catalyst for 1,3-dipolar cycloaddition of alkynes with azides and oxidative coupling of 2-naphthols and phenols in water to afford the 1,4-disubstituted 1,2,3-triazoles and biaryl compounds respectively in good yields. The catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity.     

In situ radiotracer and voltammetric study of the formation of surface adlayers in the course of Cr(VI) reduction on polycrystalline and (1 1 1) oriented platinum

This paper is focused on the in situ radiotracer and voltammetric studies of the induced HSO₄⁻/SO₄²⁻ adsorption at Pt(poly) and Pt(1 1 1) surfaces in 0.1 mol dm⁻³ HClO₄ solution in the course of Cr(VI) electroreduction. Besides this, the sorption behavior of HSO₄⁻/SO₄²⁻ ions on bare Pt(poly) and Pt(1 1 1) electrodes is compared and discussed. From the experimental results it can be stated that: (i) although the extent of bisulfate/sulfate adsorption is strongly dependent upon the crystallographic orientation of Pt surfaces, the maximum coverage on the Pt(1 1 1) does not exceed 0.2 monolayer; (ii) the Cr(VI) electroreduction on both poly- and (1 1 1) oriented platinum proceeds via a ce (chemical-electron-transfer) mechanism to yield Pt surfaces covered with intermediate surface adlayers containing Cr(VI) particles (and reduced Cr-containing adspecies) and ‘strongly bonded’ HSO₄⁻/SO₄²⁻ ions; (iii) while the coverage of platinum surfaces by the intermediate complexes formed in the course of Cr(VI) electroreduction at E > 0.20 V is basically independent of the crystallographic orientation of the Pt electrode, the onset for rapid Cr(VI) reduction is highly affected by the nature and crystallographic orientation of the electrode.     

Determination of Cr ions in biological and environmental samples by a chromium(III) membrane sensor based on 5-amino-1-phenyl-1H-pyrazole-4-carboxamide

A highly Cr³⁺-selective ionophore, based on 5-amino-1-phenyl-1H-pyrazole-4-carboxamide (APC) as a carrier, was synthesized in order to obtain a Cr³⁺ ion-selective electrode. The demonstrated characteristics of the sensor included a linear dynamic range between 1.0 × 10^− 6 and 1.0 × 10^− 1 M with a near Nernstian slope of 19.6 ± 0.4 mV per decade, a detection limit of 5.3 × 10^− 7 M, a very good selectivity for Cr³⁺ over other cations in a wide pH range (3.2-6.3). Furthermore, the newly-designed electrode presented a fast response time of 10 s with a lifetime of at least 2 months indicating no considerable potential divergence. The sensor accuracy was investigated by the potentiometric titration of a Cr(III) solution with EDTA as well as the monitoring of Cr(III) in mixtures of three and five different ions. As a result, the developed sensor provided satisfactory results after its application in the Cr³⁺ determination in biological samples (urine and synthetic plasma) and also in wastewater of chromium electroplating industries.