Batch kinetics and isotherms for biosorption of copper(II) ions onto pre-treated powdered waste sludge (PWS)

Waste sludge samples from different plants were tested for Cu(II) ion biosorption capacities with and without pre-treatment. Waste sludge from a paint industry wastewater treatment plant was found to perform better than the others after pre-treatment with 1% H(2)O(2). Powdered waste sludge (PWS) from the paint industry wastewater treatment plant was used for recovery of Cu(II) ions from aqueous solution by biosorption after pre-treatment with 1% H(2)O(2). Batch kinetics and isotherms of biosorption of Cu(II) ions were investigated at variable initial Cu(II) concentrations between 50 and 400 mg l(-1) with a PWS particle size of 64 microm. The pseudo-first and -second order kinetic models were used to correlate the experimental data. The kinetic constants were determined for both models and the second order kinetic model was found to be more suitable. The Langmuir, Freundlich and the generalized isotherm models were used to correlate the equilibrium biosorption data and the isotherm constants were determined. The Langmuir isotherm was found to fit the experimental data better than the other isotherms tested. The maximum biosorption capacity (116 mg g(-1)) of the pre-treated powdered waste sludge for Cu(II) ions was found to be superior as compared to the other biosorbents reported in literature.     

Adsorption character for removal Cu(II) by magnetic Cu(II) ion imprinted composite adsorbent

A novel magnetic Cu(II) ion imprinted composite adsorbent (Cu(II)-MICA) was synthesized, characterized and applied for the selective removal Cu(II) from aqueous solution in the batch system. The adsorption-desorption and selectivity characteristics were investigated. The maximum adsorption occurred at pH 5-6. The equilibrium time was 6.0h, and a pseudo-second-order model could best describe adsorption kinetics. The adsorption equilibrium data fit Langmuir isotherm equation well with a maximum adsorption capacity of 46.25mg/g and Langmuir adsorption equilibrium constant of 0.0956L/mg at 298K. Thermodynamic parameters analysis predicted an exothermic nature of adsorption and a spontaneous and favourable process that could be mainly governed by physisorption mechanism. The relative selectivity coefficients of Cu(II)-MICA for Cu(II)/Zn(II) and Cu(II)/Ni(II) were 2.31, 2.66 times greater than the magnetic non-imprinted composite adsorbent (MNICA). Results suggested that Cu(II)-MICA was a material of efficient, low-cost, convenient separation under magnetic field and could be reused five times with about 14% regeneration loss.     

Removal of Cu(II) ions by activated poplar sawdust (Samsun clone) from aqueous solutions

In this work, adsorption of Cu(II) ions on sawdust (SD) and activated sawdust (ASD) has been studied by using batch adsorption techniques. The equilibrium adsorption level was determined to be a function of the pH, initial Cu(II) concentration, and adsorbent dosage. The equilibrium nature of Cu(II) adsorption has been described by the Freundlich and Langmuir isotherms. The experimental adsorption data were fitted to the Langmuir adsorption model both sawdust and activated sawdust. The equilibrium capacity of sawdust and activated sawdust were 5.432 and 13.495 mg copper per g adsorbent, respectively at room temperature and natural pH. The maximum adsorption capacity was obtained at the maximum zeta potential value that -74.5 mV (pH 5) for activated sawdust and at -48.4 mV (pH 4) for sawdust. It was observed that activated sawdust was a suitable adsorbent than sawdust for removal of Cu(II) from aqueous solutions.     

Biosorption of Pb(II) ions by modified quebracho tannin resin

In this study, the effect of temperature, pH and initial metal concentration on Pb(II) biosorption on modified quebracho tannin resin (QTR) was investigated. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to investigate QTR structure and morphology. Besides, the specific BET surface area and zeta-potential of the QTR were analysed. Thermodynamic functions, the change of free energy (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) of Pb adsorption on modified tannin resin were calculated as -5.43 kJ mol(-1) (at 296+/-2K), 31.84 kJ mol(-1) and 0.127 J mmol(-1) K(-1), respectively, indicating the spontaneous, endothermic and the increased randomness nature of Pb(2+) adsorption. The kinetic data was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model. The results suggested that the pseudo-second-order model (R(2)>0.999) was the best choice among all the kinetic models to describe the adsorption behavior of Pb(II) onto QTR. Langmuir, Freundlich and Tempkin adsorption models were used to represent the equilibrium data. The best interpretation for the experimental data was given by the Langmuir isotherm and the maximum adsorption capacity (86.207 mg g(-1)) of Pb(II) was obtained at pH 5 and 296 K.     

Functionalized cotton via surface-initiated atom transfer radical polymerization for enhanced sorption of Cu(II) and Pb(II)

The surface-initiated atom transfer radical polymerization (ATRP) was used to successfully prepare the aminated cotton and polyacrylic acid sodium (P(AA-Na))-grafted cotton for the efficient removal of Cu(II) and Pb(II) from aqueous solution in this study. The modified cotton surfaces were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The grafted long polymers with high density of amine and carboxyl groups on the cotton surfaces were responsible for the enhanced adsorption of heavy metals. The sorption behaviors including sorption kinetics, isotherms and pH effect were investigated. The sorption equilibrium of Cu(II) and Pb(II) was achieved within 1 h on the P(AA-Na)-grafted cotton, much faster than 8 h on the aminated cotton. According to the Langmuir fitting, the maximum sorption capacities of Cu(II) and Pb(II) on the P(AA-Na)-grafted cotton were 2.45 and 2.44 mmol/g, respectively, higher than many adsorbents reported in the literature. The P(AA-Na)-grafted cotton had better adsorption behaviors for Cu(II) and Pb(II) than the aminated cotton.     

A sustainable generated hydrochar from pomegranate residues for remediation of process water contaminated with Cu(II) ions

An eco-friendly, flexible and sustainable valorization of pomegranate residue (PR) was studied by hydrothermal technology. PR was used as a feedstock for producing hydrochar (PRHC) and the effects of treatment temperature (TT; 180, 200, 220 °C) and treatment time (Tt; 6, 12, 24 h) on the elemental composition, yield, higher heating value (HHV) and energy density (D_E) parameters were examined. The most suitable production conditions were recommended as TT of 220 °C and Tt of 12 h with a HHV of 23.23 MJ/kg and D_E of 1.22 GJ/m³. A broad spectral survey including FTIR, SEM/EDX, XPS, XRD, Raman and ¹³C MAS-NMR techniques were performed to define its physicochemical characteristics. PRHC was applied as an adsorbent for removal of Cu(II) ions from water and adsorption kinetics indicated well-suitability of the data to the pseudo second order model while the Langmuir model best described the equilibrium data with a 113.64 mg/g. Thermodynamics evaluation displayed the spontaneous, feasible and endothermic adsorption of Cu(II) ions. In addition, regeneration studies have shown efficiently usage of PRHC for multiple times in wastewater treatment.     

Adsorption of lead(II) ions onto 8-hydroxy quinoline-immobilized bentonite

In this study, the immobilization of 8-hydroxy quinoline onto bentonite was carried out and it was then used to investigate the adsorption behavior of lead(II) ions from aqueous solutions. The changes of the parameters of pH, contact time, initial lead(II) ions concentration and temperature were tested in the adsorption experiments. The XRD, FTIR, elemental and thermal analyses were done to observe the immobilization of 8-hydroxy quinoline onto natural bentonite. The adsorption was well described by the Langmuir adsorption isotherm model at all studied temperatures. The maximum adsorption capacity was 142.94mgg(-1) from the Langmuir isotherm model at 50 degrees C. The thermodynamic parameters implied that the adsorption process is spontaneous and endothermic. The kinetic data indicate that the adsorption fits well with the pseudo-second-order kinetic model. 8-Hydroxy quinoline-immobilized bentonite can be used as well respective adsorbent for the removal of the heavy metal pollutants according to the results.     

Sorption profile of Cd(II) ions onto beach sand from aqueous solutions

Sorption of traces of Cd(II) ions onto beach sand is investigated as a function of nature and concentration of electrolyte (10(-4) to 10(-2)M nitric, hydrochloric and perchloric acids, pH 2-10 buffers and deionized water), shaking time 5-40min, shaking speed 50-200strokes/min, dosage of sand (50-1000mg/15cm(3)), concentration of sorbate (1.04x10(-6) to 1.9x10(-4)M) and temperature (293-323K). Maximum sorption of Cd(II) ions (approximately 66%) is achieved from deionized water using 300mg/15cm(3) sand in 20min. The data are successfully tested by Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The values for characteristic Langmuir constants Q=13.31+/-0.20micromol/g and of b=(6.56+/-0.53)x10(3)dm(3)/mol, Freundlich constants A=2.23+/-1.16mmol/g and 1/n=0.70+/-0.05 of (D-R) constants beta=-0.005068+/-0.000328kJ(2)/mol(2), X(m)=46.91+/-11.91micromol/g and energy E=9.92+/-0.32kJ/mol have been estimated. Kinetics of sorption has been studied by applying Morris-Weber, Richenberg and Lagergren equations. The sorption follows first order rate equation resulting 0.182+/-0.004min(-1) The thermodynamic parameters DeltaH=32.09+/-2.92kJ/mol, DeltaS=111.0+/-9.5J/molK and DeltaG=-1.68+/-0.02kJ/mol are evaluated. The influence of common ions on the sorption of Cd(II) ions is also examined. Some common ions reduce the sorption while most of the ions have very little effect. It can be concluded that beach sand may be used as an alternative for the expensive synthetic sorbents.     

Biosorption of cadmium (II) and lead (II) from aqueous solutions using mushrooms: A comparative study

Sorption capacity of oyster mushroom (Pleurotus platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe indica) were evaluated on biosorption of heavy metals, viz. cadmium (II) and lead (II) from aqueous solutions. The optimum sorption conditions were studied for each metal separately. The desired pH of the aqueous solution was found to be 6.0 for the removal of cadmium (II) and 5.0 for removal of lead (II) for all the mushrooms. The percent removal of both the metals was found to increase with the increase in biosorbent dosage and contact time. The fitness of the biosorption data for Langmuir and Freundlich adsorption models was investigated. It was found that biosorption of cadmium (II) and lead (II) ions onto the biomass of the three mushrooms were better suitable to Langmuir than Freundlich adsorption model. P. platypus showed the highest metal uptake potential for cadmium (q_max 34.96 mg/g) whereas A. bisporus exhibited maximum potential for lead (q_max 33.78 mg/g). Milky mushroom showed the lowest metal uptake capacity for both the metals. The present data confirms that mushrooms may be used as efficient biosorbent for the removal of cadmium (II) and lead (II) ions from aqueous solution.     

Copper(II)-EDTA sorption onto chitosan and its regeneration applying electrolysis

Cu(II)-EDTA (ethylendiaminetetraacetate) complexes are widely used in the manufacture of printed circuit boards. In order to avoid the outlet into the environment the sorption of complexes onto chitosan is proposed. The uptake of both Cu(II) and EDTA proceeds in weakly acidic (pH 3-5) and strongly alkaline (pH > 12) solutions. In acidic solutions EDTA sorption prevails. FT-IR investigations have shown that in acidic solutions the amide bonds between -COOH groups of EDTA and -NH2 groups of chitosan were formed. In alkaline solutions the single EDTA sorption does not proceed. In this media the sorption is enhanced by Cu(II) ions. The possible sorption mechanisms are discussed. The uptake of both Cu(II) and EDTA by chitosan depends on the ratio between them in solutions. EDTA sorption in acidic solutions increases with increase in its concentration while that of Cu(II) decreases. In alkaline solutions the sorption of both Cu(II) and EDTA increases with increase in Cu(II) concentration. The use of electrolysis enables to regenerate chitosan and to reuse it. During electrolysis copper is deposited onto the cathode and EDTA is oxidized onto the anode. The current efficiency depends on the current intensity, the load of chitosan and the pH of the background electrolyte. Electrolysis under the most favorable conditions ensures the 10-cycles regeneration without considerable changes in the sorption properties of chitosan. FT-IR spectra of the initial and regenerated chitosans are similar.     

Cu(II)-catalyzed THM formation during water chlorination and monochloramination: A comparison study

The catalytic effect of Cu(II) on trihalomethane (THM) formation during chlorination and monochloramination of humic acid (HA) containing water was comparatively investigated under various pH conditions. Results indicate that in the presence of Cu(II), the formation of THMs was significantly promoted as pH decreased in both chlorination and monochloramination. More THMs were formed during Cu(II)-catalyzed monochloramination which was partially due to enhanced hydroxyl radical (OH) generation as demonstrated by electron spin resonance (ESR) analysis. To discriminate the reactive moieties of HA, nine model compounds, which approximately represented the chemical structure of HA, were individually oxidized by chlorine or monochloramine. Results show that Cu(II) could promote THM formation through reacting with citric acid and similar structures in HA. During chlorination and monochloramination of citric acid in the absence of Cu(II), major intermediates including chlorocarboxylic acid, chloroacetone and chloroacetic anhydride were identified. However, the catalysis of Cu(II) did not produce any new intermediate. The complexation of Cu(II) with model compounds was characterized via FTIR analysis. The reaction mechanism for Cu(II)-catalyzed THM formation was proposed to comprise two pathways: (1) indirect catalysis in which OH oxidizes the large molecules of HA into small ones to enhance THM formation; and (2) direct catalysis in which Cu(II) complexes with HA to accelerate the decarboxylation steps for THM formation.     

Prediction of biosorption efficiency for the removal of copper(II) using artificial neural networks

Various low-cost adsorbents have been used for removing Cu(II) ions from aqueous solutions for the treatment of copper containing wastewaters to remove organic compounds and color. Sawdust is an impressive adsorbent in terms of adsorption efficiency, cost and availability; hence the use of sawdust as biosorbent has been widely studied. Many earlier investigations tried to correlate the experimental data with available models or some modified empirical equations, but these results were unable to predict the values of parameters from a single equation. Artificial neural networks (ANN) are effective in modeling and simulation of highly non-liner multivariable relationships. A well-designed and very well trained network can converge even on multiple number of variables at a time without any complex modeling and empirical calculations. In this present work ANN is applied for the prediction of percentage adsorption efficiency for the removal of Cu(II) ions from aqueous solutions by sawdust. Artificial neural network model, based on multilayered partial recurrent back-propagation algorithm has been used. The performance of the network for predicting the sorption efficiency of sawdust for copper is found to be very impressive.     

Removal of Cu(II) from aqueous solution by adsorption onto acid-activated palygorskite

A series of activated palygorskite clay by HCl with different concentrations was prepared and applied as adsorbents for removal of Cu(II) from aqueous solutions. The effects of contact time, adsorbent dosages and pHs of suspension on the adsorption capacities for Cu(II) were investigated. The results showed that adsorption capacity of activated palygorskites increased with increasing the HCl concentration and the maximum adsorption capacity with 32.24 mg/g for Cu(II) is obtained at 12 mol/L of HCl concentration. The variations in IR spectra and pH of solution after adsorption Cu(II) confirmed that the numerous amount of silanol groups (Si-OH) originated by acid treatment were mainly responsible for Cu(II) adsorption onto acid-activated palygorskite. Kinetic studies indicated that the adsorption mechanisms in the Cu(II)/acid-activated palygorskite system followed the pseudo-second-order kinetic model with a relatively small contribution of film diffusion. Equilibrium data fitted well with Freundlich isotherm model compared to Langmuir isotherm model, indicating that adsorption takes place on heterogeneous surfaces of the acid-activated palygorskite. Adsorption-desorption studies presented that activated palygorskite has lower adsorption and desorption efficiencies using Cu(CH3COO)2 than that of other inorganic copper salts, such as CuSO4, Cu(NO3)2, and CuCl2.     

Nickel (II) ions sensing properties of dimethylglyoxime/poly(caprolactone) electrospun fibers

A novel dimethylglyoxime (DMG)/poly(caprolactone) (PCL) blend was electrospun into fibers to serve as an optical sensor for the nickel detection based on the formation of a red Ni(DMG)₂ complex. DMG was mixed with PCL at 10, 20 and 30% (w/w) in a mixture of N, N-dimethylformamide (DMF) and dichloromethane (DCM) (50/50, v/v) prior electrospunning process. The best fibers were prepared under an electric field of 20 kV and a distance between needle and collector of 20 cm. From scanning electron microscopy (SEM), the average diameter of the fibers remained nearly constant with increasing amount of DMG. The optimum mass ratio of DMG and PCL was found to be 20:80 as it produced fibers with the smallest diameter distribution and the best sensing property. The formation of the Ni(DMG)₂ complex was confirmed by Fourier transform infrared spectroscopy (FT-IR). The colorimetric response of the PCL/DMG electrospun fibers were then tested against the nickel ions over a concentration range of 1-10 ppm using reflectance spectroscopy. Good linearity between the reflectance values at 547 nm and the concentrations was obtained (R² = 0.9925). These proposed DMG and PCL fibers could be used as the naked-eye sensor for nickel in waste water.     

Water-soluble magnetic-carbon nanotubes nanocomposites for efficient adsorption of Cu(II) from aqueous solution

In this study, the water-soluble magnetic-multi-walled carbon nanotubes nanocomposites were fabricated via a facile and efficient approach and were characterized by X-ray diffraction, energy-dispersive X-ray, and transmission electron microscopy in detail. The nanocomposites could be employed as an effective adsorbent for removal of heavy metal ions, Cu(II) ions, from aqueous solution. It is noteworthy that the novel adsorbent displayed good water-dispersibility, rapid absorption rate, high absorption capacity, and convenient magnetic separation. Furthermore, the nanocomposites could be recovered and recycled for 10 consecutive trials without significant loss of its activity.     

Reduction of Cu(II) to Cu(I) in solid CsCuCl3

The solid state reaction Cu + Cu²⁺ → 2Cu⁺ in CsCuCl₃ was studied at 499 K using a cell in which the Cu(II) sample was put between two copper discs. Mass changes, thickness of the product layer and the total electrical resistance of the cell were measured as a function of time, both with and without (spontaneous) applied voltage.     

Biosorption of Pb(II) and Cd(II) from aqueous solution using green alga (Ulva lactuca) biomass

The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the green alga (Ulva lactuca) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by U. lactuca biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The monolayer biosorption capacity of U. lactuca biomass for Pb(II) and Cd(II) ions was found to be 34.7mg/g and 29.2mg/g, respectively. From the D-R isotherm model, the mean free energy was calculated as 10.4kJ/mol for Pb(II) biosorption and 9.6kJ/mol for Cd(II) biosorption, indicating that the biosorption of both metal ions was taken place by chemisorption. The calculated thermodynamic parameters (DeltaG degrees , DeltaH degrees and DeltaS degrees ) showed that the biosorption of Pb(II) and Cd(II) ions onto U. lactuca biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both metal ions followed well pseudo-second-order kinetics.     

The adsorption of Cd(II) ions on sulphuric acid-treated wheat bran

The adsorption of Cd(II) ions which is one of the most important toxic metals by using sulphuric acid-treated wheat bran (STWB) was investigated. The effects of solution pH and temperature, contact time and initial Cd(II) concentration on the adsorption yield were studied. The equilibrium time for the adsorption process was determined as 4 h. The adsorbent used in this study gave the highest adsorption capacity at around pH 5.4. At this pH, adsorption capacity for an initial Cd(II) ions concentration of 100 mg/L was found to be 43.1 mg/g at 25 degrees C for contact time of 4 h. The equilibrium data were analysed using Langmuir and Freundlich isotherm models to calculate isotherm constants. The maximum adsorption capacity (qmax) which is a Langmuir constant decreased from 101.0 to 62.5 mg/g with increasing temperature from 25 to 70 degrees C. Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the adsorption process. The enthalpy change (deltaH(o)) for the process was found to be exothermic. The free energy change (deltaG(o)) showed that the process was feasible. The kinetic results indicated that the adsorption process of Cd(II) ions by STWB followed first-order rate expression and adsorption rate constant was calculated as 0.0081 l/min at 25 degrees C. It was observed that the desorption yield of Cd(II) was highly pH dependent.