Adsorptive removal of Cu(II) and Pb(II) onto mixed-waste activated carbon: kinetic,thermodynamic, and competitive studies and application to real wastewater samples

This work aimed to investigate the adsorption characteristics, both kinetically and thermodynamically, of Cu(II) and Pb(II) removal from aqueous solutions onto mixed-waste activated carbon, as well as to study the competitive behavior found in mixed heavy metal solution systems. This study shows that activated carbon prepared from mixed waste is an effective adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions, with the aim of detoxifying industrial effluents before their safe disposal onto water surfaces. The adsorption process was characterized in terms of kinetic and thermodynamic studies. In addition, the influence of presence of Cu(II) and Pb(II) in a competitive system was investigated. The results showed that the maximum adsorption capacities were gained at a pH of 6 with a contact time of 180 min, a metal solution concentration of 300 ppm, and an adsorbent dose of 0.3 g/L. The adsorption process was found to follow a pseudo-first-order kinetic model. Thermodynamic parameters such as ΔG ^o, ΔH ^o, and ΔS ^o showed that the sorption process was spontaneous and endothermic in nature. A competitive study demonstrated the applicability of mixed-waste activated carbon to adsorb Cu(II) and Pb(II) from a solution of mixed metals. In addition, the adsorption capacity was found to be as effective as other adsorbents reported in the literature. The developed adsorptive removal procedure was applied for treatment of real wastewater samples and showed high removal efficiency.     

Adsorption of aqueous Pb(II), Cu(II), Zn(II) ions by amorphous tin(VI) hydrogen phosphate: an excellent inorganic adsorbent

Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pH_ZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H⁺ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly.     

Equilibrium studies on removal of lead (II) ions from aqueous solution by adsorption using modified red mud

In the present experimental study, solid waste was used as an adsorbent and the effectiveness of the adsorbent was increased by novel treatment methods. Red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were used for the removal of lead (II). The structural and functional groups were identified to confirm the removal of lead (II) by powder X-ray diffraction and Fourier transform infrared spectroscopy analyses. The enhancement of surface area was confirmed by Brunauer–Emmett–Teller analysis. Batch adsorption experiment was also conducted, and various parameters such as the effect of adsorbent dosage, pH, contact time and initial ion concentration were analyzed and reported. Adsorption equilibrium data were investigated using Langmuir, Freundlich and Dubinin–Radushkevich isotherm models with three parameters, and the rate of reaction was examined through kinetic models. The results indicate that in particular a novel modified form of red mud, namely iron oxide-coated acid-treated activated red mud was well fitted in lead (II) removal compared with reported adsorbents. The Langmuir isotherm shows that the maximum adsorption of adsorbate per gram was greater than other adsorbents (27.02 mg/g). In Freundlich isotherm, the Freundlich constant n values lie between 1 and 10 indicate the favorable adsorption. The calculated n values for normal red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were found to be 1.9, 2.1 and 2.0 respectively. The correlation coefficient value was higher and the rate of reaction follows the pseudo-second-order kinetic model.     

Preparation and solubility of northupite from brine and its adsorption properties for Cu(II) and Cd(II) in seawater

The mineral northupite Na₃Mg(CO₃)₂Cl was synthesized from a solar Adriatic seawater brine pond to which Na₂CO₃ was added at 373°K. The precipitated northupite had a surface area (P) of 6.0 ± 0.4 m²g⁻¹, and the thermodynamic solubility product was estimated to be log K Na₃Mg(CO₃)₂Cl = −4.8 ± 0.3 at 25°C. This value was used to calculate the interfacial energy (σ = 50 erg cm⁻²) for the homogeneous nucleation of northupite. The solubility constant determined in this study has been used to examine the saturation state of Mahega Lake and Lake Katwe (Uganda). The waters from Lake Katwe were found to be supersaturated with respect to northupite.The adsorption of Cu and Cd onto northupite particles was studied in seawater. Both metals are strongly adsorbed. Adsorption constants and the specific area of northupite occupied by Cd and Cu using Langmuir adsorption isotherms and equilibrium constants for surface complex formation have been determined.     

Adsorption kinetic models for the removal of Cu(II) from aqueous solution by clay liners in landfills

Liners are commonly used in engineered waste disposal landfill to minimize the potential contamination of the aquatic environment. The adsorption behavior of Cu(II) from aqueous solution onto clay admixed with various mix ratios of quarry fines was investigated. The amount of Cu(II) adsorption increases with increase in contact time. The copper removal efficiencies of the composite mixture gradually decrease from 94.53 % (raw clay) to 85.59 % (20 % of quarry fines with clay), and appreciable decrease in percent removal 75.61 % was found with 25 % of quarry fines with clay. The kinetic adsorption data were analyzed by pseudo-first-order, pseudo-second-order, Bhattacharya–Venkobachar and Natarajan–Khalaf kinetic models to classify adsorption process mechanisms. Kinetic experimental data were good agreement with pseudo-second-order kinetic model with the degree of fitness of the data (R ²) 0.9999 for the adsorption of Cu(II). The results revealed that quarry fines can be used with optimum of 20 % replacement of natural clay for removal of Cu(II) as a liner material in landfills.     

Predominant hosting lead(II) in ternary mixtures of heavy metal ions by a novel of diethylaminomethyl-calix[4]resorcinarene

Heavy metal ions from single and ternary systems of Pb(II), Cu(II), and Ni(II) adsorbed by calix[4]resorcinarenes in water–chloroform extraction were studied. Comparison was made of calix[4]resorcinarenes, 2,8,14,20-tetraundecyl calix[4]resorcinarene-4,6,10,12,16,18,22,24-octol, and diethylaminomethyl-calix[4]resorcinarene, 5,11,17,23-tetra(diethylaminomethyl)-2,8,14,20- tetraundecylcalix[4]resorcinarene-4,6,10,12,16,18,22,24-octol, for predominant extraction of their ions from the ternary mixture of aqueous solution at different pH in a water layer. The hosting of Pb(II) by the diethylaminomethyl-calix[4]resorcinarene occurred efficiently at pH 6–7. The hosting of Pb(II), Cu(II), and Ni(II) ions for the ternary aqueous mixture was applied to the Langmuir isotherm. Adsorption was studied using nuclear magnetic resonance spectroscopy in a water–deuterium chloroform extraction system. Results showed that as the heavy metal ions were included into the host cavity, the observation of shifted peaks of water molecules from downfield to higher field was visible in the nuclear magnetic resonance spectra, meaning that water molecules were included with heavy metal ion into the host cavity. The spectra also showed that the diethylamino group expressed formation of the coordination complex between the diethylaminomethyl-calix[4]resorcinarene and Pb(II) for the purpose of predominant hosting of Pb(II).     

Lead(II) complexation by fulvic acid: how it differs from fulvic acid complexation of copper(II) and cadmium(II)

Pb²⁺, like Cu²⁺, forms strong complexes with fulvic acids (Cd²⁺-fulvate complexes are much weaker), but Pb-fulvate precipitates at a much lower mole ratio of metal ion to fulvic acid than either Cu-fulvate or Cd-fulvate does. Physical association of Pb²⁺ with Pb-fulvate solids as well as complexation by sites still available in the precipitates probably causes the increased removal of free Pb²⁺ from solution after precipitation begins.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Biosorption of Cu(II) and Pb(II) from aqueous solutions by chemically modified spent coffee grains

In this research, spent coffee grains were modified with citric acid solutions (0.1 and 0.6 M) to increase the quantity of carboxylic groups improving its metal adsorption capacity. Added functional groups on modified and non-modified spent coffee grains were identified and quantified by attenuated total reflection Fourier transform infrared analyses and potentiometric titrations, respectively. These adsorbents were used for the removal of lead (II) and copper (II) from aqueous solutions at 30 °C and different pH in batch systems. In addition, adsorption–desorption experiments were conducted to evaluate the possibility of re-using the modified adsorbent. Potentiometric titrations data reveal that the quantity of carboxylic groups was increased from 0.47 to 2.2 mmol/g when spent coffee grains were modified with 0.1 and 0.6 M citric acid. Spent coffee grains treated with 0.6 M citric acid, achieved a maximum adsorption capacity of 0.77 and 1.53 mmol/g for lead (II) and copper (II), respectively, whereas non-modified spent coffee grains only reached 0.24 and 0.19 mmol/g for lead (II) and copper (II), respectively. Desorption of lead (II) and copper (II) achieved around 70 % using 0.1 N HCl for non-modified and modified spent coffee grains with 0.6 M citric acid. It is suggested that lead (II) and copper (II) species were adsorbed mainly on the carboxylic groups of modified spent coffee grains and these metals may be exchanged for hydrogen and calcium (II) ions during adsorption on non-modified spent coffee grains. Finally, the adsorption equilibrium was reached after 400 min for modified spent coffee grains with 0.6 M citric acid. Modified spent coffee grains are a promising option for removing metal cations from aqueous solutions due to its low cost and high adsorption capacity (about 10 times higher than the activated carbons).     

The selective removal of Co(II) from Ni(II) by coprecipitation with manganese in ammoniacal solutions

The coprecipitation of cobalt(II) and nickel(II) with manganese in ammoniacal solutions has been studied. It was found that cobalt and nickel were precipitated with the aid of manganese at pH 9.3–10.2. However, the rate of precipitation of manganese was about five times that of cobalt. The recovery of these divalent ions by precipitation increased as the pH of the solution increased, while the selectivity of cobalt against nickel decreased with the increase of pH. The partial pressure of oxygen had also an important role in the precipitation of manganese and cobalt but little effect on the up-take of nickel. As the oxygen pressure increased, manganese and cobalt oxidized at a fast rate and the rate of coprecipitation of cobalt with manganese increased. Typically, more than 90% of cobalt was recovered readily by coprecipitation with manganese, while very little nickel was removed from the solution.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Comparison of linear and nonlinear forms of isotherm models for Zn(II) and Cu(II) sorption on a kaolinite

The most appropriate method in designing the adsorption systems and assessing the performance of the adsorption systems is to have an idea on adsorption isotherms. Comparison analysis of linear least square method and nonlinear method for estimating the isotherm parameters was made using the experimental equilibrium data of Zn(II) and Cu(II) onto kaolinite. Equilibrium data were fitted to Freundlich, Langmuir, and Redlich–Peterson isotherm equations. In order to confirm the best-fit isotherms for the adsorption system, the data set using the chi-square (χ ²), combined with the values of the determined coefficient (r ²) was analyzed. Nonlinear method was found to be a more appropriate method for estimating the isotherm parameters. The best fitting isotherm was the Langmuir and Redlich–Peterson isotherm. The Redlich–Peterson is a special case of Langmuir when the Redlich–Peterson isotherm constant g was unity. The sorption capacity of kaolinite to uptake metal ions in the increasing order was given by Cu (4.2721 mg/g)?<?Zn (4.6710 mg/g).     

Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) adsorption onto kaolinite

Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO₃ and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X⁻). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K_(X2Me) and log K_(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.     

Biosorption of mercury(II), cadmium(II) and lead(II) ions from aqueous system by microalgae Chlamydomonas reinhardtii immobilized in alginate beads

The potential use of the immobilized microalgae (in Ca-alginate) of Chlamydomonas reinhardtii to remove Hg(II), Cd(II) and Pb(II) ions from aqueous solutions was evaluated using bare Ca-alginate bead as a control system. Ca-alginate beads containing immobilized microalgae were incubated for the uniform growth at 22 °C for 5 days. Effects of pH, temperature, initial concentration of metal ions and biosorbent dosages on the adsorption of Hg(II), Cd(II) and Pb(II) ions were studied. Adsorption of Hg(II), Cd(II) and Pb(II) ions on the immobilized microalgae showed highest values at around pH 5.0 to 6.0. The adsorption equilibrium was represented with Langmuir and Freundlich adsorption isotherms. The adsorption of these ions on the immobilized microalgae followed second-order kinetics and equilibrium was established in about 60 min. The temperature change in the range of 5–40 °C did not affect the adsorption capacities of the immobilized microalgae. The immobilized-algal systems can be regenerated using 2 M NaCl for Hg(II), Cd(II) and Pb(II) ions.     

Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface

A laboratory study was undertaken to ascertain the role of surface catalysis in Mn(II) oxidative removal. γ-FeOOH, a ferric oxyhydroxide formed by O₂ oxidation of ferrous iron in solution, was studied in the following ways: surface charge characteristics by acid base titration, adsorption of Mn(II) and surface oxidation of Mn(II). A rate law was formulated to account for the effects of pH and the amount of surface on the surface oxidation rate of Mn(II). The presence of milli-molar levels of γ-FeOOH was shown to reduce significantly the half-life of Mn(II) in 0.7 M NaCl from hundreds of hours to hours. The numerical values of the surface rate constants for the γ-FeOOH and that reported for colloidal MnO₂ are comparable in order of magnitude.