Removal of Cu(II) and Fe(III) from aqueous solutions by dead sulfate reducing bacteria

The biosorption properties of dead sulfate reducing bacteria (SRB) for the removal of Cu(II) and Fe(III) from aqueous solutions was studied. The effects of the biosorbent concentration, the initial pH value and the temperature on the biosorption of Cu(II) and Fe(III) by the SRB were investigated. FTIR analysis verified that the hydroxyl, carbonyl and amine functional groups of the SRB biosorbent were involved in the biosorption process. For both Cu(II) and Fe(III), an increase in the SRB biosorbent concentration resulted in an increase in the removal percentage but a decrease in the amount of specific metal biosorption. The maximum specific metal biosorption was 93.25 mg?g^–1 at pH 4.5 for Cu(II) and 88.29 mg?g^–1 at pH 3.5 for Fe(III). The temperature did not have a significant effect on biosorption. In a binary metal system, the specific biosorption capacity for the target metal decreased when another metal ion was added. For both the single metal and binary metal systems, the biosorption of Cu(II) and Fe(III) onto a SRB biosorbent was better represented by a Langmuir model than by a Freundlich model.     

Chelation of Cu(II), Zn(II), and Fe(II) by Tannin Constituents of Selected Edible Nuts

The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by ~90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested.     

Ru(III)-catalyzed oxidation of N-acetyl-L-cysteine by methylene blue in absence and in presence of Cu(II) in acidic medium: influence of solvent and morphology

N-acetyl l-cysteine (NAC), the substrate used presently has got diverse medicinal applications and is widely used as a mucolytic agent. The oxidation of bioactive molecules, in general, involves metal ion catalysis facilitated by the participation of metal nanoparticles. In view of this, the oxidation of NAC by a phenothiazine dye methylene blue (MB), a model electron receptor, catalyzed by Ru(III) in the absence and in the presence of Cu(II) has been investigated in acidic medium. The concentration order in MB is zero, while the order in NAC is one and two in Ru(III)-catalyzed and Ru(III)-Cu(II)-catalyzed reactions, respectively. Hydrogen ions retard the rate in Ru(III)-Cu(II)-catalyzed reaction, whereas the rate increases linearly with increasing [Ru(III)] in both the systems. The rate increases with increasing [Cu(II)] and attains a limiting value. The addition of the reaction products does not affect the rate of reaction. The reaction is characterized by a large negative entropy of activation. The kinetic deviations of the reaction, explained by presuming the participation of a reactive form of the NAC molecule or its new conformational polymorph reported recently, indicate the regulatory influence of the morphology of nanoparticles.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Synthesis and characterization of resins with ligands containing guanidinine derivatives. Cu(II) sorption and coordination properties

A new modification direction of acrylonitrile, vinyl acetate and divinylbenzene terpolymers (A, B) are presented. The aminolysis of nitrile groups of the terpolymers using ethylenediamine or hydroxylamine hydrochloride was a first stage of the modification. The resulting amine groups reacted with dicyandiamide (DCDA), cyanamide (CA) and sodium dicyanimide (SDC) in order to obtain the biguanidyl, guanidyl or nitrilguanidyl derivatives in the polymer side chain, respectively. The properties of all obtained resin such as water regain, nitrogen content, amine and carboxyl group concentration and sorption properties towards Cu(II) from nitric acid solutions were determined. The studies of IR spectra of all the resins were performed. Structures of ligand complexes with Cu(II) were studied using electron paramagnetic resonance spectroscopy.     

Novel dicopper(II)-tetracarboxylates as catalysts for selective oxidation of benzyl alcohols with aqueous TBHP

A few dicopper(II) tetracarboxylate complexes viz. [Cu₂(µ-O₂CC₆H₅)₄(4-Etpy)₂] (1), [Cu₂(µ-O₂CC₆H₅)₄(4-DMAP)₂] (2), [Cu₂(µ-O₂CC₆H₅)₄(4-CNpy)₂] (3) and [Cu₂(µ-O₂CCH₃)₄(4-CNpy)₂] (4) have been utilised as catalysts for oxidation of benzyl alcohols using aqueous tert-butyl hydroperoxide as the oxidant. Complexes 1 and 2 have shown better catalytic activity than the other two. Unlike other catalysts, these dicopper complexes can catalyse oxidation of alcohols at a very low concentration (0.5 mol%).     

Alumina-supported Mn(II), Co(II), Ni(II) and Cu(II) N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine complexes: Synthesis, characterization and catalytic oxidation of cyclohexene with tert-butylhydroperoxide and hydrogen peroxide

New square-planar manganese(II), copper(II), nickel(II) and cobalt(II) complexes of a tetradentate Schiff-base ligand “N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine, H₂[salpnMe₂]” have been prepared and characterized by elemental analyses, IR, UV–Vis, conductometric and magnetic measurements. The results suggest that the symmetrical Schiff-base is a bivalent anion with tetradentate N₂O₂ donors derived from the phenolic oxygen and azomethine nitrogen. The formulae was found to be [M(salpnMe₂)] for the 1:1 non-electrolytic complexes. Alumina-supported metal complexes (ASMC; [M(salpnMe₂)/Al₂O₃]) catalyze the oxidation of cyclohexene with tert-buthylhydroperoxide (TBHP) and hydrogen peroxide. Oxidation of cyclohexene with TBHP gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene whereas, oxidation with H₂O₂ resulted in the formation of cyclohexene oxide and cyclohexene-1,2-diol. Manganese(II) complex supported on alumina “[Mn(salpnMe₂]–Al₂O₃” shows significantly higher catalytic activity than other catalysts.     

New polymeric structures designed for the removal of Cu(II) ions from aqueous solutions

New polymeric structures obtained by chemical transformations of maleic anhydride/dicyclopentadiene copolymer with triethylenetetraamine, p‐aminobenzoic acid, and p‐aminophenylacetic acid were used for the removal Cu(II) ions from aqueous solutions. The experimental values prove the importance of the chelator nature and of the macromolecular chain geometry for the retention efficiency. The retention efficiency (η_r), the retention capacity (Q _e ), and the distribution coefficient of the metal ion into the polymer matrix (K _d ) are realized by evaluation of residual Cu(II) ions in the effluent waters, by atomic adsorption. Also are discussed the influence of pH, the thermal stability of the polymer, and their polymer–metal complex, as well as the particular aspects regarding the contact procedure and the batch time. Based on the polymers and polymer–metal complexes characterization a potential retention mechanism is proposed. All polymer supports as well theirs metal–complexes are characterized by ATD and FTIR measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1397–1405, 2007     

Electrochemical oxidation of hydrogen peroxide at a bromine adatom-modified gold electrode in alkaline media

Bromine (Br)-adatom (Br_(ads)) was in situ fabricated onto polycrystalline gold (Au (poly)) electrode in Br⁻-containing alkaline media. The surface coverage of Br_(ads) (Γ_Br) varied only in the submonolayer coverage within the investigated potential window under potentiodynamic condition because of the coadsorption of hydroxyl ion (OH⁻) in alkaline media. The in situ fabricated Br_(ads)-submonolayer-coated Au (poly) electrode was successfully used for the electrochemical oxidation of hydrogen peroxide (H₂O₂). About five times higher oxidation current was achieved at the modified electrode as compared with the bare electrode. The enhancement of the electrode activity towards the electrochemical oxidation of H₂O₂ was explained based on the enhanced electrostatic attraction between the anionic HO₂⁻ molecules and Br_(ads)-adlayer-induced positively polarized Au (poly) electrode surface.     

Removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound

ABSTRACT

Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.     

Photocatalytic Behavior of a New Series of In0.8M0.2TaO4 (M = Ni, Cu, Fe) Photocatalysts in Aqueous Solutions

A new series of photocatalysts, In_0.8M_0.2TaO₄ (M = Ni, Cu, Fe), were synthesized by a solid-state reaction and characterized by powder X-ray diffraction and Rietveld structure refinement. No apparent structural variation has been recognized with the change of doping atoms. However, the rate of H₂ evolution from Pt/CH₃OH/H₂O solution under UV irradiation significantly changed with the change of doping atoms. In_0.8Ni_0.2TaO₄ showed much higher activity than the non-doped InTaO₄ photocatalyst. Furthermore, we found that under visible light irradiation ( > 420 nm) In_0.8Ni_0.2TaO₄ exhibited also higher activity than the non-doped InTaO₄ photocatalyst.     

Preparation and characterization of an IPN type chelating resin containing amino and carboxyl groups for removal of Cu(II) from aqueous solutions

A novel IPN type chelating resin, amino-functionalized poly (glycidyl methacrylate)/poly (acrylic acid), (pGMA/pAA), was synthesized by a combination of serial reactions including, conventional radical polymerization, amination and photopolymerization. To assess the efficacy and characteristics of the resin in removal of Cu (II), batch adsorption experiments were carried out, and the effects of different parameters such as contact time, adsorbent dosage, initial metal ion concentration, temperature, and pH on the adsorption process were investigated. The results showed that 0.5 g/L dosage and pH 5 are the optimum values to achieve the maximum adsorption capacity and the adsorption kinetic of Cu (II) was well represented by pseudo-second-order kinetic model. In addition, it was found that the adsorption was mainly controlled by the film diffusion mechanism, along with a considerable contribution of the intra-particle diffusion mechanism, and Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models can be used for interpreting the adsorption process. Moreover, FT-IR analysis results and the mean free energies of adsorption clearly indicate that the ion exchange and chelation mechanisms took place as dominating mechanisms simultaneously during the adsorption process. It was also found to be that IPN resin could be used at least four times without losing its original activity.     

Electrochemical synthesis of Cr(II) at carbon electrodes in acidic aqueous solutions

The electrochemical synthesis of Cr(II) has been investigated on a vitreous carbon rotating disc electrode and a graphite felt electrode using cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results show that in 0.1 M Cr(III) + 0.5 M sulphuric acid and in 0.1 M Cr(III) + 1 M hydrochloric acid over an electrode potential range of –0.8 to 0.8 V vs SCE, the electrochemical reaction at carbon electrodes is essentially a surface process of proton adsorption and desorption, without significant hydrogen evolution and chromium(II) formation. At electrode potentials more negative than –0.8 V vs SCE, both hydrogen evolution and chromium(II) formation occurred simultaneously. At electrode potentials –0.8 to –1.2 V vs SCE, the electrochemical reduction of Cr(III) on carbon electrodes is controlled mainly by charge transfer rather than mass transport. Measurements on vitreous carbon and graphite felt electrodes in 1 M HCl, with and without 0.1 M CrCl₃, allowed the exchange current density and Tafel slope for hydrogen evolution, and for the reduction of Cr(III) to Cr(II), to be determined. The chromium(III) reduction on vitreous carbon and graphite electrodes can be predicted by the extended high field approximation of the Butler–Volmer equation, with a term reflecting the conversion rate of Cr(III) to Cr(II).     

The intermolecular interaction studies in the complexes of isothiocyanic acid (HNCS) and its derivatives with H2S: a computational study

The computational investigations are carried out on the complexes of isothiocyanic acid (HNCS) and its derivatives with H₂S through MP2/aug-cc-PVTZ//MP2/aug-cc-PVDZ level. Five, four, three and four structures are located on the potential energy surface of the HNCS?H₂S, HSCN? H₂S, HCNS? H₂S and HSNC?H₂S heterodimers, respectively. The calculated results reveal that the most stable heterodimers among all heterodimers obtained for the HNCS?H₂S, HSCN?H₂S, HCNS?H₂S and HSNC?H₂S systems belong to HSCN?H₂S system. Therefore, HSCN?H₂S system has a key role in the atmosphere.     

Current oscillations during chronoamperometric and cyclic voltammetric measurements in alkaline Cu(II)-citrate solutions

It is demonstrated that current oscillations can be observed during chronoamperometric and cyclic voltammetric experiments in solutions containing 0.4 M CuSO₄ and 1.2 M citrate at pH 11 and 50 °C. The oscillations, which are shown to originate from local variations in the pH, result in the deposition of nanostructured Cu and Cu₂O materials. It is concluded that the current oscillations are analogous to the previously described potential oscillations obtained under controlled current conditions in alkaline Cu(II)-lactate, -tartrate and -citrate solutions. Rotating disk electrode results clearly show that the reduction of the Cu(II)-complexes is kinetically controlled and that the rate of the reduction increases with increasing pH and temperature. It is also shown that the presence of a cathodic peak on the anodic scan in the cyclic voltammograms can be used to identify the experimental conditions leading to the spontaneous current (or potential) oscillations. Electrochemical quartz crystal microbalance results indicate that the cathodic peak stems from an increased rate of the reduction of the Cu(II)-citrate complexes due to a rapid increase in the local pH. This causes Cu₂O rather than Cu to be deposited which, however, results in a decrease in the local pH and a decreasing current. In situ ellipsometry data confirm that Cu₂O deposition replaces that of Cu in the potential region of the cathodic peak. The present findings should facilitate syntheses of nanolayered materials based on spontaneous potential or current oscillations.     

Oxidation of Cu(II)-EDTA in supercritical water—Experimental results and modeling

Copper complex ethylenediamine tetraacetic acid (Cu(II)-EDTA) was oxidized in supercritical water in a continuous tubular reactor at temperatures 420–500 °C, residence times 57–144 s, and a pressure 25 MPa. The major carbon-containing products were CO₂ and CO. The TOC conversions increased steadily with reaction temperature and residence time, and the yield of CO can be effectively reduced at elevating temperatures. Ammonia was determined to be the main refractory nitrogen-containing intermediate, whose oxidation was supposed to be enhanced by the copper in Cu(II)-EDTA. In addition, the copper transformed into copper oxides (CuO and Cu₂O), and was removed from the Cu(II)-EDTA solution with high efficiency. Based on the experimental results and the analysis of reaction pathways, a global Arrhenius kinetic model was proposed to predict the removal of TOC and the yield of the intermediates NH₃ and CO. With this kinetic model, a computational fluid dynamic (CFD) model of the tubular reactor was implemented to assist the experimental study. The composition profiles of TOC, CO, and CO₂ along the reactor were simulated and compared with the experimental results. Operating parameters, reaction temperature and oxygen flow rate, were optimized based on the simulation results.     

The diffusion coefficient of Cu(II) ions in sulfuric acid–aqueous and methanesulfonic acid–methanol solutions

When using a copper working electrode to study the diffusion of Cu(II) ions it is necessary to polish the electrode between experiments to maintain a smooth surface. To eliminate the required polishing, a platinum working electrode can be used. The copper layer established on the electrode surface during experimentation can be removed between experiments by anodic stripping. When using a platinum disk working electrode, the most reliable method of analysis involves double potential step chrono-amperometry method as opposed to voltammetry. By applying this method diffusion coefficients for Cu(II) ions in sulphuric acid – aqueous and methanesulfonic acid (HMSA) – methanol solutions were determined.     

Temperature programmed oxidation of Cu/ZnO catalysts with N2O: an attempt for characterization of copper catalysts

For characterization of the surface structure of metallic copper formed on the support, temperature programmed oxidation (TPO) with N₂O was carried out over various Cu/ZnO catalysts. Four peaks of the N₂ formation (, , and ) were observed at 223, 400, 545 and 600 K in the TPO runs. The average copper crystallite size estimated from the sum of the amount of - and -peaks agreed fairly with those determined by X-ray diffraction and transmission electron microscopy. It was concluded that - and -peaks resulted from the oxidation of metallic copper atoms on the steps, corners and/ or defect sites, and on the flat sites of the surface of copper crystallites, respectively, while - and -peaks resulted from the bulk oxidation of copper.