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.     

Removal of Cu(II), Cd(II) and Cr(III) ions from aqueous solution by dam silt

The removal of heavy metals, such as Cu(II), Cd(II) and Cr(III) from aqueous solution was studied using Chorfa silt material (Mascara, Algeria). The main constituents of silt sediment are quartz, calcite and mixture of clays. The experimental data were described using Freundlich, Langmuir, Dubinin–Radushkevich (D–R) and Langmuir–Freundlich models. The adsorbed amounts of chromium and copper ions were very high (95% and 94% of the total concentration of the metal ions), whereas cadmium ion was adsorbed in smaller (55%) amounts. The Langmuir–Freundlich isotherm model was the best to describe the experimental data. The maximum sorption capacity was found to be 26.30, 11.76 and 0.35 mg/g for Cr³⁺, Cu²⁺ and Cd²⁺, respectively. The results of mean sorption energy, E (kJ/mol) calculated from D–R equation, confirmed that the adsorption of copper, chromium and cadmium on silt is physical in nature.     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.     

Development of a sequential injection anodic stripping voltammetry (SI-ASV) method for determination of Cd(II), Pb(II) and Cu(II) in wastewater samples from coatings industry

This paper describes the development and validation of a sequential injection (SI) anodic stripping voltammetry (ASV) method using the hanging mercury drop electrode for accumulation of the heavy metal cations Cu(II), Pb(II) and Cd(II). The method was applied to wastewater samples after proper acid digestion in open vessels to eliminate matrix effects. For a deposition time of 90 s at the flow rate of 10 μl s⁻¹, the detection limits of the method were 0.06, 0.09 and 0.16 μmol L⁻¹ for Cd, Pb and Cu, respectively. Under these conditions the linear dynamic range was between 0.20 and 9.0 μmol L⁻¹ and the sampling frequency was 30 analyses per hour. The relative standard deviation of the method was 3%(n=7) at the concentration level of 2.0 μmol L⁻¹. The accuracy of the method was evaluated by spiking the samples with known amounts of the metal cations, and by comparison with an independent analytical technique, the inductively coupled plasma atomic emission spectroscopy (ICP-AES). Average recoveries were around of 84%, and the results showed no evidence of systematic errors in comparison to the ICP-AES.     

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.     

Modification of silica nanoparticles with 1-hydroxy-2-acetonaphthone as a novel composite for the efficient removal of Ni(II), Cu(II), Zn(II), and Hg(II) ions from aqueous media

In this paper, a novel composite based on the formation of Schiff base on silica nanoparticles was facilely synthesized. Firstly, silica nanoparticles, which contain silanol groups (Si-OH), were modified with (3-aminopropyl)trimethoxysilane. Then, the modified silica reacted with 1-hydroxy-2-acetonaphthone to form a novel Schiff base/silica composite. The synthesized composite was characterized using several tools such as XRD, FT-IR, FE-SEM, N₂ adsorption/desorption analyzer, and CHN analyzer. The considerable reduction at 2θ = 21.9° in the intensity of the XRD peak of the composite is owing to the formation of the Schiff base. Also, the observed FT-IR bands in the composite at 3440 and 1604 cm^?1 are owing to the stretching and bending vibrations of OH and/or CN, respectively. The FE-SEM images confirmed that the silica includes irregular shapes whereas the composite possesses a flaky surface owing to the formation of the Schiff base. Elemental analysis of the composite demonstrated that the % C, % H, and % N are 15.26, 3.24, and 1.65 %, respectively. The BET surface area and total pore volume of the composite were reduced because the formed Schiff base blocks the pores of silica. The synthesized composite was employed for the efficient removal of Ni(II), Cu(II), Zn(II), and Hg(II) ions from aqueous media. The maximum uptake capacity of the composite toward Cu(II), Hg(II), Zn(II), and Ni(II) ions is 68.630, 50.942, 45.126, and 40.420 mg/g, respectively. The adsorption processes of the studied metal ions were spontaneous, chemical, and well described using the pseudo-second-order kinetic model and Langmuir equilibrium isotherm. The synthesized composite can be successfully regenerated and utilized various times in the removal of studied metal ions from aqueous media.     

New trends in removing heavy metals from industrial wastewater

Innovative processes for treating industrial wastewater containing heavy metals often involve technologies for reduction of toxicity in order to meet technology-based treatment standards. This article reviews the recent developments and technical applicability of various treatments for the removal of heavy metals from industrial wastewater. A particular focus is given to innovative physico-chemical removal processes such as; adsorption on new adsorbents, membrane filtration, electrodialysis, and photocatalysis. Their advantages and limitations in application are evaluated. The main operating conditions such as pH and treatment performance are presented. Published studies of 94 cited references (1999–2008) are reviewed.It is evident from survey that new adsorbents and membrane filtration are the most frequently studied and widely applied for the treatment of metal-contaminated wastewater. However, in the near future, the most promising methods to treat such complex systems will be the photocatalytic ones which consume cheap photons from the UV-near visible region. They induce both degradation of organic pollutants and recovery of metals in one-pot systems. On the other hand, from the conventional processes, lime precipitation has been found as one of the most effective means to treat inorganic effluent with a metal concentration of >1000 mg/L. It is important to note that the overall treatment cost of metal-contaminated water varies, depending on the process employed and the local conditions. In general, the technical applicability, plant simplicity and cost-effectiveness are the key factors in selecting the most suitable treatment for inorganic effluent     

Modification of sodium aluminum silicate hydrate by thioglycolic acid as a new composite capable of removing and preconcentrating Pb(II), Cu(II), and Zn(II) ions from food and water samples

In this paper, sodium aluminum silicate hydrate was synthesized using rice husk as a silicon source and scrap aluminum cans as an aluminum source. Afterward, with the aid of microwave heating, a composite of sodium aluminum silicate hydrate and (3-aminopropyl)trimethoxysilane was facilely synthesized then modified by thioglycolic acid to produce a new composite. Besides, characterization of the synthesized composite was carried out using XRD, FT-IR, TEM, CHN elemental analyzer, nitrogen gas sorption analyzer, and SEM. The XRD pattern of the produced composite shows that there is a halo at 2θ = 25.0°, which means that there is a crystalline structure that is combined with an amorphous background. The SEM and TEM studies indicate that the synthesized composite has a structure similar to cotton. The synthesized composite was utilized for the efficient removal and preconcentration of Pb(II), Cu(II), and Zn(II) ions from food and water samples prior to determination by flame atomic absorption spectrometry. The produced composite has a maximum adsorption capacity of 185.53, 168.92, and 125.94 mg/g for Pb(II), Cu(II), and Zn(II) ions, respectively. The recovery findings demonstrate that the process is accurate, adaptable, and resulted in quantitative separation (greater than95 percent). Furthermore, the % RSD was less than 3.5 percent, indicating good reproducibility. The Langmuir isotherm and pseudo-second-order model fit the experimental results well. The thermodynamic studies established that the adsorption process is spontaneous, chemical, and exothermic. The produced composite was successfully regenerated and used multiple times to remove the metal ions under investigation from aqueous solutions.     

A review on industrial wastewater treatment via electrocoagulation processes

Every year, a large amount of wastewater is discharged from various industries into the environment, and various methods are used to treat wastewater to reduce the amount of pollutants. Electrocoagulation (EC) is an electrochemically based technique that generates coagulant species in situ from the electrodissolution of sacrificial anodes, usually made of iron or aluminum destabilizes suspended, dissolved, or emulsified pollutants by using an electric current. It has a potential in removing various kinds of pollutants including organic and inorganic contaminants for various types of wastewater. The effectiveness of EC process depends on various parameters including pH, electrode, operation time, and current density. The goal of this study is to review the most relevant literatures that were published recently. The main challenges associated with the EC process are electrode passivation and energy consumption. EC compared with other common methods has advantages such as reducing energy consumption and reducing operating costs.     

Selective removal of Cd(II), As(III), Pb(II) and Cr(III) ions from water resources using novel 2-anthracene ammonium-based magnetic ionic liquids

Facile synthesis of two 2-anthracene ammonium-based magnetic ionic liquids (MILs), 2-anthracene ammonium tetrachloroferrate (III) ([2A-A]FeCl₄) and 2-anthracene ammonium trichlorocobaltate (II) ([2A-A]CoCl₃) was performed by protonation of 2-aminoanthracene, followed complexation with FeCl₃/CoCl₂. The MILs were tested in the adsorptive removal of Cd²⁺, As³⁺, Pb²⁺ and Cr³⁺ from water sources. Upon treatment with 10 mg dosage of MILs in 10 mL aqueous solution of 50 ppm each of Cd²⁺, As³⁺, Pb²⁺ and Cr³⁺, adsorption capacity (mg/g) in the range of 5.73–55.5 and 23.6–56.8 for [2A-A]FeCl₄ and [2A-A]CoCl₃ respectively were recorded. Thus, the optimization, kinetic and isotherms studies were conducted using the [2A-A]CoCl₃ adsorbent. The [2A-A]CoCl₃ was more effective in pH 7–9, and equilibrium adsorption was achieved after 60 min contact time. The adsorption process proceeded via the Pseudo-second order pathway and the Langmuir isotherm model is the best fit for the adsorption process (with q_max = 227 – 357 mg/g) of all the targeted metal ions. The [2A-A]CoCl₃ adsorbent demonstrated practicality with large distribution and selectivity coefficients of the targeted ions, and up to six times regeneration.     

Utilization of olive pomace in nano MgO modification for sorption of Ni(II) and Cu(II) metal ions from aqueous solutions

Magnesium oxide nanoparticles were synthesized and modified by olive pomace (NMOOP700) as a novel sorbent and characterized using Fourier Transform Infrared Spectra, Scanning Electron Microscope, Transmission Electron Microscope, X-ray Diffraction, Differential Thermal Analysis and Thermal Gravimetric Analysis. Sorption of Cu (II) or Ni (II) ions were achieved taking into account important parameters including initial pH of the medium, contact time, initial metal ion concentration and temperature. A comparative study between Magnesium oxide nanoparticles and NMOOP700 material for the sorption of Cu (II) or Ni (II) ions was implemented. The obtained data revealed that the sorption process is significantly improved using NMOOP700. The monolayer capacity of Ni (II) and Cu (II) metal ions on NMOOP700 at pH 5 were found to be 149.93 ± 4.4 and 186.219 ± 6.3 mg/g, respectively. Findings of the present work highlight the potential use of NMOOP700 as a novel and effective sorbent material for the removal of Cu (II) or Ni (II) ions from the liquid phase.     

Removal of Cd(II) and Pb(II) from aqueous solution by modified attapulgite clay

Three low-cost adsorbents (purified raw attapulgite (A-ATP), high-temperature-calcined attapulgite (T-ATP), and hydrothermal loading of MgO (MgO-ATP)) were prepared as adsorbents for the removal of Cd(II) and Pb(II). By evaluating the effect of the initial solution pH, contact time, initial solution concentration, temperature and coexistence of metal ions on Cd(II) and Pb(II) adsorption, the experimental results showed that MgO-ATP was successfully prepared by hydrothermal reaction and calcination as well as appearing to be a promising excellent adsorbent. At an initial pH of 5.0, A-ATP, T-ATP and MgO-ATP reached maximum adsorption amounts of 43.5, 53.9 and 127.6 mg/g for Pb(II) and 10.9, 11.2, and 25.3 mg/g for Cd(II) at 298 K, respectively. The Cd(II) adsorption on A-ATP was fitted by the Freundlich model, while the adsorption of Pb(II) and Cd(II) on T-ATP and MgO-ATP as well as Pb(II) adsorption on A-ATP agreed with the Langmuir model. All kinetic experimental data favored pseudo second-order model. The calculated thermodynamic parameters suggested that Pb(II) adsorption onto MgO-ATP was spontaneous and exothermic. When considering foreign metal ions, the three adsorbents all presented preferential adsorption for Pb (II). Chemical adsorption had a high contribution to the removal of Cd(II) and Pb(II) by modified attapulgite. In summary, the adsorption was greatly enhanced by the hydrothermal loading of MgO. It aimed to provide insights into the MgO-ATP, which could be able to efficiently remove Cd(II) and Pb(II) and serve as an economic and promising adsorbent for heavy metal-contaminated environmental remediation.     

Removal of heavy metal ions from water by using poly(ethyleneglycol dimethacrylate-co-acrylamide) beads

Poly(ethyleneglycol dimethacrylate-co-acrylamide) (poly(EDGMA-co-AAm)) copolymer beads have been prepared for use in the separation Pb(II), Hg(II), and Cd(II), metal ions in aqueous solution by a batch equilibration technique. Adsorption capacity were increased with pH for Pb(II), Cd(II) and Hg(II) and then reached almost plateau value around 6.0. The high initial rate of metal ions uptake (<10 min) suggests that the adsorption occurs mainly at the bead surface. The metal uptake results show that poly(EGDMA-co-AAm) can be used for the adsorption of the following metals in the indicated order: Pb(II) > Cd(II) > Hg(II) expressed on a molar basis. However, when the uptake was expressed in terms of the amount of metal removed from solution was as follows: Pb(II) > Hg(II) > Cd(II). The beads still showed preference toward Pb(II) when this metal was in a mixture with Hg(II) and Cd(II). A linearized form of the Freundlich and the Langmuir isotherm model fits the experimental equilibrium concentration data of Hg(II) and Cd(II) better than isotherm type model of Pb(II). The recovery of the metal ions after adsorption and the regeneration of the adsorbent can be carried out by treatment of the loaded beads with either 0.5 M NaCl, or 1 M HNO₃.     

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.     

The removal of Cu,Ni, and Zn in industrial soil by washing with EDTA-organic acids

In order to improve the heavy metal removal ability of traditional single washing agents and explore the removal mechanism of heavy metals. Then, the washing reagents that mixed by low-molecular weight organic acids (citric acid, oxalic acid, and tartaric acid) and artificial chelating compound ethylenediaminetetraacetic acid disodium (EDTA) were selected. Furthermore, the effect of soil washing parameters, the variation of leaching toxicity, mobility, stability and speciation of heavy metals were also considered. The results of soil washing experiments showed that mixing an equal volume of 0.05 M EDTA and 0.2 M organic acids (citric acid, oxalic acid, and tartaric acid) could remove more than about 80% heavy metals from soil under the optimal conditions. In addition, the soil leaching toxicity was decreased and the stability of remaining heavy metals was increased, indicating that EDTA-organic acid washing reagents could effectively reduce the ecological risk of contaminated soil. EDTA had a stronger chelating ability with heavy metals than the organic acids, and the organic acids could not only chelate heavy metals but also decrease the pH of the mixture for promoting the desorption of heavy metals. Thus, mixing EDTA and organic acids was advisable method to improve soil washing technology.     

Removal of methylene blue with hemicellulose/clay hybrid hydrogels

In this study, we chose corn stover hemicellulose for the preparation of hydrogels with admirable adsorption properties under mild alkaline conditions. Clay nanosheets were introduced to this system and hemicellulose/clay hybrid hydrogels were prepared. Morphological, mechanical properties and the methylene blue adsorption behaviors of the prepared hydrogels were studied. Results suggested that the addition of clay not only improved the mechanical strength of hemicellulose-based hydrogels, but also increased the adsorption capacity on methylene blue. Moreover, the adsorptions were confirmed to follow pseudo-second order equation for both gels with and without clay. The maximum adsorption capacities on methylene blue for hemicellulose-based hydrogels with or without clay reached 148.8 and 95.6 mg/g, respectively. These results implied that hemicellulose-based hydrogels could be used as promising adsorbents for the removal of methylene blue from waste water.     

Simultaneous Determination of Zn(II), Cu(II), Cd(II) and Pb(II) in Soil Samples Employing an Array of Potentiometric Sensors and an Artificial Neural Network Model

A sensor array of 9 potentiometric PVC sensors has been employed for the simultaneous determination of heavy metals in soil. Sensors were firstly characterized in their response: Nernstian behavior, a concentration range from ca. 10^?6 to 10^?2 M and selectivity coefficients confirming that all sensors had cross‐response for the target ions. The mixed response system was modeled employing Artificial Neural Networks. The proposed tool was applied to the determination of Pb²⁺, Cd²⁺, Cu²⁺ and Zn²⁺ in soils at the mg kg^?1 level with satisfactory performance. Results were compared and validated against AAS reference methodology, with correlations R²>0.948 for the four heavy metals considered.     

Removal of zinc metal ion (Zn) from its aqueous solution by kaolin clay mineral: A kinetic and equilibrium study

A laboratory batch study has been performed to study the effect of various physic-chemical factors such as initial metal ion concentration, solution pH, and amount of adsorbent, contact time and temperature on the adsorption characteristics of zinc (Zn²⁺) metal ions onto kaolin. It has been found that the amount of adsorption of zinc metal ion increases with initial metal ion concentration, contact time, solution pH but decreases with the amount of adsorbent and temperature of the system. Kinetic experiments clearly indicate that adsorption of zinc metal ion (Zn²⁺) on kaolin is a two steps process: a very rapid adsorption of zinc metal ion to the external surface is followed by possible slow decreasing intra-particle diffusion in the interior of the adsorbent which has also been confirmed by intra-particle diffusion model. The equilibrium time is found to be in the order of 60 min. Overall the kinetic studies showed that the zinc adsorption process followed pseudo-second-order kinetics among pseudo-first-order and intra-particle diffusion model. The different kinetic parameters including rate constant are determined at different initial metal ion concentration, solution pH, amount of adsorbent and temperature respectively. The equilibrium adsorption results are analyzed by both Langmuir and Freundlich models to determine the mechanistic parameters associated with the adsorption process. The value of separation factor, R_L from Langmuir equation also gives an indication of favorable adsorption. Finally thermodynamic parameters are determined at three different temperatures and it has been found that the adsorption process is exothermic due to negative ΔH° accompanied by decrease in entropy change and Gibbs free energy change (ΔG°).