Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.     

Complexing of heavy metals with DNA and new bioaffinity method of their determination based on amperometric DNA-based biosensor

The immobilized single-stranded DNA (ssIDNA) has been found to be a very effective biospecific analytical reagent when used in a newly developed bioaffinity method of the determination of heavy metals based on the amperometric DNA-based biosensor. This has been concluded from the comparative study of the complexing of heavy metals with double-stranded DNA, single-stranded DNA, and ssIDNA, using Fe(III) and Cu(II) as a model (metal/nucleotide ratio and stability constants are maximum for ssIDNA), from the study of adsorption of Fe(III), Cu(II), Pb(II), and Cd(II) on nitrocellulose membranes, containing single-stranded DNA, and from the determination of their binding constants with ssIDNA. According to these data, the chosen heavy metals can be lined up in a series of binding strengths with ssIDNA: Cu(II) > Pb(II) > Fe(III) > Cd(II). The method of the determination of heavy metals is based on biospecific preconcentration of metal ions on the biosensor followed by the destruction of DNA-metal complexes with ethylenediaminetetraacetate and voltammogram recording has been proposed. The lower detection limits are 4.0 x 10(-11), 1.0 x 10(-10), 1.0 x 10(-9), and 5.0 x 10(-9) M for Cu(II), Pb(II), Cd(II), and Fe(III), respectively. The heavy metals have been assayed in multicomponent environmental and biological systems such as natural and drinking water, milk, and blood serum samples.     

Screening biochars for heavy metal retention in soil: role of oxygen functional groups

Oxygen-containing carboxyl, hydroxyl, and phenolic surface functional groups of soil organic and mineral components play central roles in binding metal ions, and biochar amendment can provide means of increasing these surface ligands in soil. In this study, positive matrix factorization (PMF) was first employed to fingerprint the principal components responsible for the stabilization of heavy metals (Cu, Ni, Cd, Pb) and the release of selected elements (Na, Ca, K, Mg, S, Al, P, Zn) and the pH change in biochar amended soils. The PMF analysis indicated that effective heavy metal stabilization occurred concurrently with the release of Na, Ca, S, K, and Mg originating from soil and biochar, resulting in as much as an order or magnitude greater equilibrium concentrations relative to the soil-only control. In weathered acidic soil, the heavy metal (especially Pb and Cu) stabilization ability of biochar directly correlated with the amount of oxygen functional groups revealed by the O/C ratio, pH(pzc), total acidity, and by the (1)H NMR analysis. Equilibrium speciation calculation showed minor influence of hydrolysis on the total soluble metal concentration, further suggesting the importance of binding by surface ligands of biochar that is likely to be promoted by biochar-induced pH increase.     

Grape bagasse as an alternative natural adsorbent of cadmium and lead for effluent treatment

This work investigated the utilization of grape bagasse as an alternative natural adsorbent to remove Cd(II) and Pb(II) ions from laboratory effluent. X-ray diffractometry, Fourier transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, thermogravimetric analyses, surface analysis, porosity and porous size were used for characterization of the material. Batch experiments were carried out to evaluate the adsorption capacity of the material. Parameters such as adsorption pH and contact time were optimized for the maximum accumulation onto the solid surface. The pH values found were 7 and 3 for Cd(II) and Pb(II), respectively, and contact time was 5 min for both metals. Adsorption capacity for metals were calculated from adsorption isotherms by applying the Langmüir model and found to be 0.774 and 0.428 mmol g(-1) for Cd(II) and Pb(II), respectively. The competition between metals for the same adsorption sites on grape bagasse was also evaluated, showing an increasing affinity for Pb(II) over Cd(II) when only these metals are present. The potential of this material was demonstrated by efficient metal removal from laboratory effluent using a glass column. The results indicate that the referred material could be employed as adsorbent for effluent treatment, especially due to its easy acquisition and low cost as well as the fast adsorption involved.     

Adsorption of copper from aqueous solution on Brassica cumpestris (mustard oil cake)

The adsorption behavior of various heavy metals on mustard oil cake (MOC) was studied. The maximum adsorption of Cu(II) was observed followed by Zn(II), Cr(VI), Mn(II), Cd(II), Ni(II) and Pb(II). The adsorption of Cu(II) was found to be dependent on initial concentration of solution, pH, adsorbent dose, temperature and contact time. The adsorption followed pseudo-first-order and second-order kinetics but pseudo-second-order kinetic model was better obeyed since experimental data agreed well with theoretical data. Thermodynamic parameters were also evaluated. The adsorption process was found to be endothermic and spontaneous in nature. Attempts were also made to desorb Cu(II) from the adsorbent and regeneration of the spent adsorbent. The breakthrough and exhaustive capacities were found to be 5 and 10 mg g(-1), respectively.     

Adsorption of metal ions on lignin

This study investigated the adsorption of the heavy metal ions Pb(II), Cu(II), Cd(II), Zn(II), and Ni(II) on a lignin isolated from black liquor, a waste product of the paper industry. Lignin has affinity with metal ions in the following order: Pb(II)>Cu(II)>Cd(II)>Zn(II)>Ni(II). The adsorption kinetic data can be described well with a pseudosecond-order model and the equilibrium data can be fitted well to the Langmuir isotherm. Metal ion adsorption was strongly dependent on pH and ionic strength. Surface complexation modelling was performed to elucidate the adsorption mechanism involved. This shows that lignin surfaces contain two main types of acid sites attributed to carboxylic- and phenolic-type surface groups and the phenolic sites have a higher affinity for metal ions than the carboxylic sites.     

Removal of copper ions by modified Unye clay, Turkey

This paper presents the adsorption of Cu(II) from aqueous solution on modified Unye bentonite. Adsorption of Cu(II) by manganase oxide modified bentonite (MMB) sample was investigated as a function of the initial Cu(II) concentration, solution pH, ionic strength, temperature and inorganic ligands (Cl(-), SO(4)(2-), HPO(4)(2-)). Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, N(2) gas adsorption and potentiometric titration data. The adsorption properties of raw bentonite (RB) were further improved by modification with manganese oxide. Langmuir monolayer adsorption capacity of the MMB (105.38 mg/g) was found greater than that of the raw bentonite (42.41 mg/g). The spontaneity of the adsorption process is established by decrease in DeltaG which varied from -4.68 to -5.10 kJ mol(-1) in temperature range 303-313 K. The high performance exhibited by MMB was attributed to increased surface area and higher negative surface charge after modification.     

Heavy metals binding properties of esterified lemon

Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.     

Characterization of the biosorption of cadmium, lead and copper with the brown alga Fucus vesiculosus

The recovery of cadmium, lead and copper with the brown alga Fucus vesiculosus was characterized and quantified. The biosorption data fitted the pseudo-second order and Langmuir isotherm models, but did not adjust to the intraparticle diffusion model. The metal uptakes deduced from the pseudo-second order kinetic model and the Langmuir isotherm model followed a similar sequence: Cu>Cd approximately Pb. The Langmuir maximum metal uptakes were: 0.9626mmol/g, Pb 1.02mmol/g, and Cu 1.66mmol/g. According to the equilibrium constants of this isotherm model, the affinity of metals for the biomass followed this order: Pb>Cu>Cd. Biosorption was accomplished by ion exchange between metals in solution and algal protons, calcium and other light metals, and by complexation of the adsorbed metals with algal carboxyl groups. FTIR spectra showed a shift in the bands of carboxyl, hydroxyl and sulfonate groups.     

Poly(L-cysteine) as an electrochemically modifiable ligand for trace metal chelation

The short-chain (n approximately equal to 50) homopolymer poly(L-cysteine) (PLC) has been previously studied for use as a novel metal chelator. PLC exhibits reversible oxidation-reduction chemistry involving the thiol groups of the cysteine (Cys) residues. Previously, chemical oxidation of the PLC immobilized on silica showed that metal binding capacity was minimal in the oxidized state. In this study, Cys and PLC are immobilized on a glassy carbon disk electrode (GCE) to study these redox processes and how they impact metal binding and release. Voltammetric and chronoamperometric methods were employed to demonstrate nearly monolayer coverage of both immobilized Cys monomer and immobilized PLC on GCE. The PLC-GCE exhibited a maximum metal binding capacity for Cd2+ of approximately 11 Cd2+ ions/chain. No detectable metal binding capacity was observed for oxidized PLC. The bound metals were capable of being efficiently released through disulfide bond formation and tertiary structure changes by means of repetitive oxidative pulses. The Cys-modified electrode exhibited a metal binding capacity for Cd2+ of approximately 1 Cd2+/Cys. Oxidized Cys did retain a significant capacity following oxidation, likely as a result of complexation with the terminal carboxylate site and unoxidized thiols. A glycine (Gly)-modified electrode was also evaluated as an amino acid control. Minimal Cd2+ binding was observed. Further metal binding studies were conducted using PLC-GCE with single metal solutions of Co2+, Cu2+, Ni2+, and Pb2+, as well as a multimetal solution composed of equal concentrations of all five target metals. The observed metal binding trend was as follows: Cu2+ > Cd2+ > Ni2+ > Pb2+ > Co2+. All metals were quantitatively released upon oxidation of PLC using the same anodic potential, 600 mV vs Ag/AgCl.     

Removal of heavy metal ions by iron oxide coated sewage sludge

The municipal sewage sludge was modified with iron oxide employed in metal ions removal. The surface modification method was proposed and the effect of parameters in the preparation was studied. The iron oxide coated sludge had higher surface area, pore volume and iron content, compared to uncoated sludge. The suitable conditions for removal of Cu(II), Cd(II), Ni(II) and Pb(II) ions from solutions were investigated using batch method. The suitable pH value in the extraction was 7 for adsorption of Cd(II) and Ni(II), 6 for Cu(II) and 5 for Pb(II) ions. The presence of NaNO(3), Ca(NO(3))(2) and Na(2)SO(4) in metal solution in the concentration of 0.01 M and 0.50 M could reduce the removal efficiency. The adsorption isotherms for the adsorption of the metal ions were defined by Langmuir relation. The maximum adsorption capacity of the iron oxide coated sludge for Cu(II), Cd(II), Ni(II) and Pb(II) was 17.3, 14.7, 7.8 and 42.4 mg g(-1), respectively. The adsorption kinetics for every metal ions followed pseudo-second order model. The metal removal from wastewater by iron oxide coated sludge was also demonstrated.     

Physical Studies of Some Hydrazinobenzoic Acid Complexes

The stability constants of complexes of 2-hydrazinobenzoic acid and 4-hydrazinobenzoic acid with Ni (Ⅱ), Cu (Ⅱ),Zn (Ⅱ), Cd (Ⅱ), and Hg (Ⅱ) were determined potentiometrically at different temperatures. The thermodynamic parameters,△AG°,△AH°, and △S° were calculated and proved that the complexation process is spontaneous and endothermic. The thermodynamic functions were analyzed in terms of electrostatic and non-electrostatic components and the results reveal that ionic bonds are formed between the studied ligands and metal ions. Conductometric titration was shown that the stoichiometry of the formed complexes are M:L and M:2L. The structure of the prepared solid complexes was characterized using IR, 1H NMR, 13C NMR spectroscopies as well as X-ray diffraction technique.Finally electrical conductivity of the ligands and their copper complexes was measured and shown that the ligands have a semiconductor behaviour.     

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.     

An investigation of Cu(II) adsorption by raw and acid-activated bentonite: a combined potentiometric, thermodynamic, XRD, IR, DTA study

Adsorption of Cu(II) by raw bentonite (RB) and acid-activated bentonite (AAB) samples was investigated as a function of the initial Cu(II) concentration, solution pH, ionic strength, temperature, the competitive and complexation effects of ligands (Cl-, SO4(2-), PO4(3-)). Langmuir monolayer adsorption capacity of the RB (42.41 mg g(-1)) was found greater than that of the AAB (32.17 mg g(-1)). The effect of structural charges on the reactivity of the edge groups was evidenced by the particular proton adsorption behaviour of the bentonite samples. The spontaneity of the adsorption process is established by decrease in DeltaG which varied from -0.34 to -0.71 kJ mol(-1) (RB), -1.13 to -1.49 kJ mol(-1) (AAB) in temperature range 303-313 K. Infrared (IR) spectra of the bentonite samples showed that the positions and shapes of the fundamental vibrations of the OH and Si-O groups were influenced by the adsorbed Cu(II) cations. Differential thermal analysis (DTA) results showed that adsorbed Cu(II) cations have a great effect on the thermal behaviour of the bentonite samples. The X-ray diffraction (XRD) spectra indicated that the Cu(II) adsorption onto the bentonite samples led to changes in unit cell dimensions and symmetry of the parent bentonites.     

Nanodiamond as the pH‐Responsive Vehicle for an Anticancer Drug

Cis‐dichlorodiammineplatinum(II) (CDDP, cisplatin), a widely used anticancer drug, is successfully loaded onto nanodiamond (ND) by adsorption and complexation. The CDDP–ND composite is characterized by IR spectroscopy, atomic absorption spectroscopy, thermogravimetric analysis, energy‐dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy. CDDP is released from the composite in phosphate‐buffered saline (PBS) of pH 6.0 at a rate higher than in PBS of pH 7.4. Therefore, it is predicted that the ND vehicle would deliver low concentrations of CDDP in the blood, but release much more drug after integration into the acidic cytoplasm, thereby reducing toxic side effects. The complexation between CDDP and the carboxyl groups on the ND surface is responsible for the pH‐responsive release property. The drug released from the composite retains the same cytotoxicity as free CDDP against human cervical cancer cells.     

Cystine-modified biomass for Cd(II) and Pb(II) biosorption

The surface of dried biomass of baker's yeast was modified by crosslinking cystine with glutaraldehyde. X-ray photoelectron spectroscopy and microscope were used to characterize the modified biomass. The adsorption capacity of the modified biomass for Cd(2+) and Pb(2+) showed an increase compared with the pristine biomass due to the presence of cystine on the biomass surface. Experimental data showed that the adsorption of the two metal ions increased with time until equilibrium was achieved. The adsorption capacities for Cd(2+) and Pb(2+) were 11.63 and 45.87 mg g(-1), respectively, which were determined from the Langmuir isotherm. The loaded biosorbent was regenerated using HCl solution and could be used repeatedly at six times with little loss of uptake capacity. FTIR spectroscopy revealed that carboxyl, amide, and hydroxyl groups on the biomass surface were involved in the adsorption of Cd(2+) and Pb(2+).     

Reuse of waste silica as adsorbent for metal removal by iron oxide modification

Silica gel is widely used in research laboratories, especially for the purification of organic compounds. Consequently, waste silica gel is generated in increasing amounts. In this work, waste silica was modified by coating its surface with iron oxide aiming to obtain an effective adsorbent for metal removal from wastewater. In the preparation of the adsorbent, the optimal pretreatment temperature and iron concentration were investigated. The coated waste silica was characterized for BET surface area, pore size, specific pore volume and iron content. Iron oxide-coated waste silica was tested for the adsorption of Pb(II), Cu(II), Cd(II) and Ni(II) from solutions in a batch system. The effect of contact time, pH and salt concentration on metal adsorption was investigated. It was found that the adsorption of metals occurred rapidly and reached equilibrium within 30 min. The pH suitable for metal adsorption was between 6 and 7 and leaching of iron from the coating was observed only at pH 3 or lower. The presence of salt reduced the adsorption efficiency of the adsorbent. The adsorption behavior followed both Langmuir and Freundlich isotherms (25 degrees C). Finally, the efficacy of the adsorbents was investigated using aqueous lab waste where removal efficiencies ranging from 62 to 89% were achieved when the initial metal concentrations ranged from 13 to 42 mg L(-1).     

Removal of heavy metal ions from aqueous solutions using carbon aerogel as an adsorbent

The removal of Cd(II), Pb(II), Hg(II), Cu(II), Ni(II), Mn(II) and Zn(II) by carbon aerogel has been found to be concentration, pH, contact time, adsorbent dose and temperature dependent. The adsorption parameters were determined using both Langmuir and Freundlich isotherm models. Surface complexation and ion exchange are the major removal mechanisms involved. The adsorption isotherm studies clearly indicated that the adsorptive behaviour of metal ions on carbon aerogel satisfies not only the Langmuir assumptions but also the Freundlich assumptions, i.e. multilayer formation on the surface of the adsorbent with an exponential distribution of site energy. The applicability of the Lagergren kinetic model has also been investigated. Thermodynamic constant (K(ad)), standard free energy (DeltaG(0)), enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were calculated for predicting the nature of adsorption. The results indicate the potential application of this method for effluent treatment in industries and also provide strong evidence to support the adsorption mechanism proposed.     

Removal of lead(II) and cadmium(II) from aqueous solutions using grape stalk waste

The sorption of lead and cadmium from aqueous solutions by grape stalk waste (a by-product of wine production) was investigated. The effects of the contact time, pH of the solution, ionic medium, initial metal concentration, other metal ions present and ligands were studied in batch experiments at 20 degrees C. Maximum sorption for both metals was found to occur at an initial pH of around 5.5. The equilibrium process was described well by the Langmuir isotherm model, with maximum grape stalk sorption capacities of 0.241 and 0.248 mmol g(-1) for Pb(II) and Cd(II), respectively, at pH around 5.5. Kinetic studies showed good correlation coefficients for a pseudo-second-order kinetic model. The presence of NaCl and NaClO(4) in the solution caused a reduction in Pb and Cd sorption, the latter being more strongly suppressed. The presence of other metals in the uptake process did not affect the removal of Pb, while the Cd uptake was much reduced. HCl or EDTA solutions were able to desorb lead from the grape stalks completely, while an approximately 65% desorption yield was obtained for cadmium. From the results obtained it seems that other mechanisms, such as surface complexation and electrostatic interactions, must be involved in the metal sorption in addition to ion exchange.     

Evaluation of iron-based hybrid materials for heavy metal ions removal

The article presents in detail the results of the sorption of heavy metal ions such as Cu(II), Zn(II), Cd(II), and Zn(II) in the presence of ethylenediamine-N,N′-disuccinic acid as well as chromium(VI) on Purolite Arsen X^np and Lewatit FO36. Factors affecting the sorption equilibrium (sorbent dose, contact time, temperature, pH, and the presence of interfering ions) were studied. To compare the surface morphologies of the studied ion exchangers, scans using atomic force microscope were also recorded, and attenuated total reflectance infrared spectroscopy was applied to establish the adsorption mechanism. The main parameters affecting sorption are initial concentration of the solution, pH, and phase contact time. Temperature has only a slight influence. The kinetic data were fitted using the pseudo-first-order and pseudo-second-order models. In the case of Cr(VI) adsorption, the equilibriums on Purolite Arsen X^np and Lewatit FO36 were established within 60 min, in the case of Cu(II) and Zn(II) within 30–40 min and for Cd(II) and Pb(II) even less than 30 min. Moreover, it was found that the effectiveness of adsorption in the case of Cr(VI), Cu(II), Zn(II), Cd(II), and Pb(II) on Purolite ArsenX^np was higher than that on Lewatit FO36.