A methodological approach to the application of a vermiculite modified carbon paste electrode in interaction studies: Influence of some pesticides on the uptake of Cu(II) from a solution to the solid phase

A new methodological approach, for studying metal ion binding interactions with a clay mineral is presented. A carbon paste electrode (CPE) modified with vermiculite clay mineral was used as a model for a soil-like solid phase and Cu(II) ions were chosen as the test ions. The application of this model is demonstrated and explained by investigating the influence of seven pesticides (bromofenoxim, fenamiphos, phenmedipham, atrazine and its three natural degradation products) on the uptake of Cu(II) ions from a solution to the vermiculite, included in a CPE. Different conditions (pH, concentration, exposure time etc.) were considered and the amount of bound copper, accumulated when no potential was applied, was then determined by stripping voltammetry.     

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying pre-electrolysis at –0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fast on-site testing of polluted soils.     

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.     

Molecular-level investigation into copper complexes on vermiculite: effect of reduction of structural iron on copper complexation

In this paper we present results that describe the speciation of Cu sorbed to the clay mineral vermiculite, with special attention to the effects of reduction on Cu sorption complexes. Sorption complexes were studied using powdered extended X-ray absorption fine structure (EXAFS) spectroscopy, polarized EXAFS spectroscopy, and X-ray diffraction (XRD). Ionic strength (I), background ion, and clay reduction (structural iron) were varied in the sorption samples. At low I EXAFS results indicate that Cu was surrounded by up to six water molecules sorbed in the interlayer of reduced vermiculite. EXAFS results from Cu-equilibrated reduced vermiculite with high I Ca background electrolyte revealed that Cu was surrounded by 4 O atoms at 1.95 Angatroms and 8 second shell O atoms at 3.14 Angstroms. Angular dependence of the second shell O atoms interpreted from the polarized-EXAFS spectra indicated that the atoms are out of plane from the basal plane of the vermiculite (inclined approximately 25 degrees from the ab plane). The local atomic environment and angular dependence of the EXAFS spectra suggest that the Cu atoms are adsorbed above the hexagonal cavities of the reduced clay mineral and form a Cu dimer in the interlayer. This adsorption mechanism was not observed in the non-reduced vermiculite under identical equilibration conditions. Our results provide molecular level evidence that Cu sorption mechanisms on vermiculite are dependent on solution conditions, such as redox potential and background electrolyte. These results can be used to develop better models of Cu sorption mechanisms on clay mineral surfaces.     

An insight to the filtration mechanism of Pb(II) at the surface of a clay ceramic membrane through its preconcentration at the surface of a graphite/clay composite working electrode

The use of cyclic voltammetry (CV) and linear scan anodic stripping voltammetry (LSASV) to predict the selectivity of microfiltration ceramic membranes made from a lump of local clay towards Pb(II) ions filtration is described. The membranes were characterized by different techniques followed by CV analysis of the Fe(CN)₆^3-/Fe(CN)₆^4- redox couple and Pb(II) on bare graphite, raw clay, and clay-modified carbon paste electrode (clay-modified CPE). The effect of clay loading in the range of 1–10 % (w/w) on the electrodes is studied, where an enhanced peak current is observed for 5 % w/w clay. Moreover, a decrease in the peak current can be seen for bare graphite electrodes, suggesting that the clay mineral had played a substantial role in the sieving of heavy metal ions through the ceramic membrane. The electroactive surface area of 5% w/w raw clay towards Fe(II) ions was found to be in the order of 3.07 × 10^-2 cm² and higher than 5% w/w clay sintered to 1000 °C and bare graphite. CV analysis shows that both, 5 % w/w raw clay and 5 % w/w clay sintered to 1000 °C exhibited high peak currents towards Pb(II) ions. The mobility of the Pb(II) ions is found to increase when 5% w/w clay sintered to 1000 °C is utilized as membrane/electrode, leading to an increase in the amount of reduced Pb(II) ions on the surfaces of the clay membranes/electrodes. The study suggests successful filtration of Pb(II) ions through the proposed membrane/electrode and a much better accumulation than Fe(II) at the surface of the membrane/electrode before being subjected to filtration.     

Cloud point extraction preconcentration for capillary electrophoresis of metal ions

The application of the cloud point extraction (CPE) technique for capillary electrophoresis (CE) determination of metal ions was demonstrated using Cu(II) and Co(II) as model metal ions. The preconcentration of Cu(II) and Co(II) in aqueous solution was achieved by CPE with 1-(2-pyridylazo)-2-naphthol (PAN) as the chelating agent and Triton X-114 as the extractant. Baseline separation of the PAN chelates of Cu(II) and Co(II) was realized by CE with a photodiaode array detector in a  μm i.d. fused-silica capillary at 17 kV. A 50 mM NH₄Ac buffer solution (pH 8.0) containing 0.2 mM of PAN in 80% (v/v) of acetonitrile and 20% (v/v) doubly deionized water (DDW) was used as the separation medium to avoid the adsorption of hydrophobic substances and nonionic surfactant Triton X-114 onto the inner surface of the separation capillary, ensuring the separation efficiency and reproducibility. The precision (relative standard deviation (R.S.D.), n=5) for five replicate injections of a mixture of 20 μg/l of Co(II) and Cu(II) were 0.74 and 1.8% for the migration time, 3.1 and 0.64% for the peak area measurement, respectively. The apparent concentration factor, which is defined as the concentration ratio of the analyte in the final diluted surfactant-rich extract ready for CE separation and in the initial solution, was 15.9 for Co(II) and 16.3 for Cu(II). The linear concentration range was from 3 to 100 μg/l for both Co(II) and Cu(II). The detection limits of Co(II) and Cu(II) were 0.12 and 0.26 μg/l, respectively. The developed method was successfully applied to the determination of Co(II) and Cu(II) in tap water, snow water, and flavor wines.     

Sorption and preconcentration of some heavy metals by 2-mercaptobenzothiazole-clay

2-Mercaptobenzothiazole loaded on previously treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II), Pb(II), Zn(II), Cd(II), Cu(II) and Mn(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorption isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II), Cu(II) and Mn(II) were also present.     

Pt‐Nanoparticle Incorporated Carbon Paste Electrode for the Determination of Cu(II) Ion by Anodic Stripping Voltammetry

Pt‐nanoparticles were synthesized and introduced into a carbon paste electrode (CPE), and the resulting modified electrode was applied to the anodic stripping voltammetry of copper(II) ions. The synthesized Pt‐nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy and X‐ray photoelectron spectroscopy techniques to confirm the purity and the size of the prepared Pt‐nanoparticles (ca. 20 nm). This incorporated material seems to act as catalysts with preconcentration sites for copper(II) species that enhances the sensitivity of Cu(II) ions to Cu(I) species at a deposition potential of ?0.6 V in an aqueous solution. The experimental conditions, such as, the electrode composition, pH of the solution, pre‐concentration time, were optimized for the determination of Cu(II) ion using as‐prepared electrode. The sensitivity changes on the different binder materials and the presence of surfactants in the test solution. The interference effect of the coexisted metals were also investigated. In the presence of surfactants, especially TritonX‐100, the Cu(II) detection limit was lowered to 3.9×10^?9 M. However, the Pt‐nanoparticle modified CPE begins to degrade when the period of deposition exceeds to 10 min. Linear response for copper(II) was found in the concentration range between 3.9×10^?8 M and 1.6×10^?6 M, with an estimated detection limit of 1.6×10^?8 M (1.0 ppb) and relative standard deviation was 4.2% (n=5).     

Adsorption of heavy metals on vermiculite: influence of pH and organic ligands

The sorption behaviour of vermiculite has been studied with respect to cadmium, copper, lead, manganese, nickel, and zinc as a function of pH and in the presence of different ligands. The continuous column method was used in order to evaluate the feasibility to use the clay in wastewater purification systems. The total capacity of vermiculite was found to decrease in the following order: Mn > Ni > Zn > Cd > Cu > Pb. The adsorption of metal ions on vermiculite decreases with decreasing pH and increasing ionic strength. In general, the metal uptake on the clay was hindered by the presence of strong complexing agents in solution and it decreases with increasing of the complexation constants of the ligands with exception of cysteine and tiron. It is necessary, hence, to consider all these factors to effectively predict the uptake efficiency of this sorbent. However, it is possible to conclude that the vermiculite has good potentialities for cost-effective treatments of metal-contaminated wastewaters.     

Removal of Cu(II) and Zn(II) from industrial wastewater by acid-activated montmorillonite-illite type of clay

An acid-activated montmorillonite-illite type of clay collected from the Gulbarga region of Karnataka, India was examined for removing copper and zinc ions from industrial wastewater containing Cu(II), Zn(II) and minor amounts of Pb(II). Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and competitive Langmuir (two competing ions) isotherms were fitted to experimental data and the goodness of their fit for adsorption was compared. The shapes of isotherms obtained indicated multilayer adsorption of Cu(II) and monolayer adsorption of Zn(II) on the acid-activated clay. Competitive adsorption was found to be significant due to the presence of Cu(II) in the wastewater.     

One-pot synthesis of a novel magnetic activated carbon/clay composite for removal of heavy metals from aqueous solution

Abstract

In the present work, a novel composite consisting of magnetite, activated carbon from spent coffee grounds and natural clay (MACCC) was prepared by a one-pot synthesis method via a simultaneous activation and magnetization processes. Various techniques (XRD, FTIR, SEM, TEM, EDX, BET) were utilized to characterize the synthesized composite before utilizing it as an adsorbent for removal of Cu(II), Ni(II) and Pb(II) ions from aqueous solutions. Conditions for removal of heavy metals were thoroughly optimized as 25?°C, pH of 5.5, adsorbent dosage of 2?g L^?1, and a contact time of 60?min. Three models of pseudo first-, second-order and intraparticle diffusion as well as three models of Langmuir, Freundlich, and Temkin were used to analyze kinetics and isotherms of the adsorption process. Thermodynamics was discussed completely. Regeneration and recyclability of the adsorbent were also evaluated. Based on the analysis of experimental results, a possible adsorption mechanism of heavy metals onto the synthesized composite was proposed. The maximum capacities caculated from Langmuir model followed the order of Pb(II) > Cu(II) > Ni(II) as 143.56, 96.16 and 84.86?mg·g^?1, respectively. The overall results indicated that MACCC is a potential adsorbent for removal of toxic Pb(II), Cu(II) and Ni(II) ions from wastewater due to simple preparation, high removal efficiency and good recyclability.     

Modeling of copper(II) and lead(II) adsorption on kaolinite-based clay minerals individually and in the presence of humic acid

The aim of this study is to explain how clay minerals adsorb heavy metals individually and in the presence of humic acid, and to model heavy metal adsorption specifically based on surface-metal binary and surface-metal-ligand ternary complexation. The adsorption of Cu(II) and Pb(II) on kaolinite-based clay minerals has been modeled by the aid of the FITEQL3.2 computer program using single- and double-site binding models of the Langmuir approach. Potentiometric titrations and adsorption capacity experiments were carried out in solutions containing different concentrations of the inert electrolyte NaClO4; however, the modeling of binary and ternary surface complexation was deliberately done at high ionic strength (0.1 M electrolyte) for eliminating adsorption onto the permanent negatively charged sites of kaolinite. A "two-site, two pKa" model was adapted, and as for the two surface sites responsible for adsorption, it may be arbitrarily assigned that [triple bond]S1OH sites represent silanol and organic functional groups such as carboxyl having pKa values close to that of silanol, and [triple bond]S2OH sites represent aluminol and organic functional groups such as phenolics whose pKa values are close to that of aluminol, as all the studied clays contained organic carbon. Copper(II) showed a higher adsorption capacity and higher binding constants, while lead(II), being a softer cation (in respect to HSAB theory) preferred the softer basic sites with aluminol-phenol functional groups. Heavy metal cations are assumed to bind to the clay surface as the sole (unhydrolyzed) M(II) ion and form monodentate surface complexes. Cu(II) and Pb(II) adsorption in the presence of humic acid was modeled using a double-site binding model by the aid of FITEQL3.2, and then the whole system including binary surface-metal and surface-ligand and ternary surface-metal-ligand complexes was resolved with respect to species distributions and relevant stability constants. Electrostatic effects were accounted for using a diffuse layer model (DLM) requiring minimum number of adjustable parameters. Metal adsorption onto clay at low pH increased in the presence of humic acid, and the metal adsorption vs pH curves of metal-kaolinite-humic acid suspensions were much steeper (and distinctly S shaped) compared to the wider pH-gradient curves observed in binary clay-metal systems. The clay mineral in the presence of humic acid probably behaved more like a chelating ion-exchanger sorbent for heavy metals rather than being a simple inorganic ion exchanger.     

Preconcentration of Cr(III), Co(II), Cu(II), Fe(III) and Pb(II) as calmagite chelates on cellulose nitrate membrane filter prior to their flame atomic absorption spectrometric determinations

A method for the preconcentration and determination of Cr(III), Co(II), Cu(II), Fe(III) and Pb(II) ions by atomic absorption spectrometry has been described. The method was based the collection of metal-calmagite complexes on a soluble cellulose nitrate membrane filter. The detection of the solution was obtained by flame atomic absorption spectrometry (FAAS) after completely dissolving the membrane with 0.5 ml of nitric acid at 80 degrees C. The metal ions were recovered quantitatively at pH 8. Various factors which affect the collection and determination of metal ions such as, type and size of the membrane filter, solvent for dissolution of the species retained on the filter were investigated. The detection limits were varying 0.06 mug l(-1) for Cu to 2.5 mug l(-1) for Cr. An application of the proposed method for analyte ions in mineral and tap water samples was also described with satisfactory results (recoveries >95%, relative standard deviations <10%).     

Intercalation Compounds of Cu2+ and Nl2+ — Exchanged Montmorillonite Clay with 8-Hydroxyquinoline

Montmorillonite clay mineral shows remarkable ion exchange, intercalation and swelling properties. It can act as a good host for large organic molecules. Intercalated coordination compounds can be prepared in the interlayer spaces of montmorillonite structure. Cu(II)- and Ni(II)- exchanged montmorillonite sorb 8-hydroxyquinoline (oxine) to form corresponding coordination compounds of the exchanged metal ions. Such compounds have been characterised by means of elemental analysts, infrared spectroscopy, magnetic susceptibility data and X-ray diffraction. These compound show good thermal stability.     

Sensing System Integrating Lanthanum Hydroxide Nanowires with Copper(II) Ion for Uracil and its Application

Abstract

A sensing system for uracil was constituted by using lanthanum hydroxide nanowires (LNW) as a modifier to obtain LNW modified carbon paste electrode (LNW/CPE) and by introducing copper(II) ion into supporting electrolyte to transform electroinactive uracil to electroactive uracil‐Cu(II) complex. The voltammetric behaviors of uracil in the presence of Cu(II) ion at LNW/CPE were investigated. A reduction peak of the uracil‐Cu(II) complex at ?0.18 V was the two‐electron reduction of Cu(II) ion in the uracil‐Cu(II) complex; while a new oxidation peak at 0.22 V was the one‐electron oxidation of the uracil‐Cu(I) complex. Additionally, the voltammetric responses of all the complexes at LNW/CPE were more sensitive than that at carbon and multiwall carbon nanotube paste electrodes, which resulted from both the large surface effect of LNW and the chemical coordination of uracil with La(III) ion in LNW. With the sensitive oxidation peak of the uracil‐Cu(I) complex at LNW/CPE, a linear range of 4.0×10^?9?3.0×10^?8 mol/l for uracil was obtained along with a detection limit of 2.0×10^?10 mol/l. The proposed system was evaluated by the determination of uracil derivatives, anticancer drug 5‐flurouracil, in pharmaceutical preparations.     

The adsorption of Cu(II) ions on bentonite--a kinetic study

The kinetics of sorption of Cu(2+) on a Saudi clay mineral (bentonite) was investigated at 20+/-0.5 degrees C using different weights of the clay (0.5, 1.0, 1.5, and 2 g). Each weight represents a certain sample size. The order of the process appeared to be 1 with respect to the Cu(2+), and 112 with respect to the clay surface area. The rate was found to depend on internal diffusion.,which produced a decrease in the specific rate of sorption as a function of time. Sorption characteristics were described using two site Langmuir isotherms. The desorption experiments proved that Cu(2+) ions are chemisorbed on the bentonite surface. The maximum adsorption obtained was 909 mg Cu(2+)/g clay. This value is of great significance, as it is much higher than any reported one.     

Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

Adsorptive accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from water on montmorillonite: influence of acid activation

The present work investigates the influence of acid activation of montmorillonite on adsorption of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) from aqueous medium and comparison of the adsorption capacities with those on parent montmorillonite. The clay-metal interactions were studied under different conditions of pH, concentration of metal ions, amount of clay, interaction time, and temperature. The interactions were dependent on pH and the uptake was controlled by the amount of clay and the initial concentration of the metal ions. The adsorption capacity of acid-activated montmorillonite increases for all the metal ions. The interactions were adsorptive in nature and relatively fast and the rate processes more akin to the second-order kinetics. The adsorption data fitted both Langmuir and Freundlich isotherms, indicating that strong forces were responsible for the interactions at energetically nonuniform sites. The Langmuir monolayer capacity of the acid-activated montmorillonite is more than that of the parent montmorillonite (Cd(II): 32.7 and 33.2 mg/g; Co(II): 28.6 and 29.7 mg/g; Cu(II): 31.8 and 32.3 mg/g; Pb(II): 33.0 and 34.0 mg/g; and Ni(II): 28.4 and 29.5 mg/g for montmorillonite and acid-activated montmorillonite, respectively). The thermodynamics of the rate processes showed the adsorption of Co(II), Pb(II), and Ni(II) to be exothermic, accompanied by decreases in entropy and Gibbs free energy, while the adsorption of Cd(II) and Cu(II) was endothermic, with an increase in entropy and an appreciable decrease in Gibbs free energy. The results have established the potential use for montmorillonite and its acid-activated form as adsorbents for Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions from aqueous media.     

Equilibrium and kinetics studies of Cu(II) ions adsorption on polyamidoamine dendrimer starch

A polyamidoamine dendrimer starch (PSt) was prepared with epichlorohydrin as cross-linking agent and characterized by FTIR and scanning electron microscopy. The adsorption behavior of PSt for Cu(II) ions was then studied. Effects of adsorption time, initial concentration of Cu(II) ions, and temperature on the adsorption of Cu(II) ions by PSt were researched, and the equilibrium, kinetics and thermodynamics of the adsorption process were further investigated. The results showed that PSt can effectively adsorb Cu(II) ions from the solution. The adsorption process can be well described by Langmuir isotherm and Freundlich isotherm, and the maximum adsorption capacities of G1PSt, G2PSt, and G4PSt were 3.0571, 3.4228, and 3.9527 mmol/g, respectively. The adsorption of Cu(II) ions on PSt was endothermic in nature. In addition, the pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model.     

Mechanochemical Adsorption of Phenol by Tot Swelling Clay Minerals

The mechanochemical adsorption of phenol by laponite, saponite, montmorillonite, beidellite and vermiculite was studied by IR and X-ray spectroscopy. Mixtures containing phenol and clay in the ratio of 6:10 were manually ground by a mortar and pestle for 1,3,5 and 10 min and the ground mixtures were investigated. Depending on the basicity of the clay mineral and the time of grinding, two different associations between interlay er cations, water and phenol were identified. In these associations phenol can act either as a proton acceptor or donor (Configurations I and II, respectively). The phenol is more acidic than water and in most cases phenol acts as a proton donor. With montmorillonite and beidellite phenol acts as a proton acceptor. In this association the aromatic ring forms π bonds with atoms of the oxygen planes of the tetrahedral sheets which donate electrons to the anti-bonding π orbitals of the phenol.