Process Design of Groundnut Husk Waste for Pb2+ and Cd2+ Ions Mitigation in Drinking Water Purification

This present work has explored a novel application of modified Arachis hypogaea (groundnut) husk on mitigation of toxic Pb²⁺ and Cd²⁺ ions in aqueous phase. Ecotoxicological assessment of exhausted adsorbent was investigated as per standard OECD guidelines. Standard deviation, correlation coefficient, and the reduced chi square test were evaluated and compared statistically on experimental data. The results showed good sorption capacities—31.62 and 29.78 mg g^?l for Pb²⁺ and Cd²⁺ ions, respectively. Pseudo first-order rate kinetics was well correlated for Pb²⁺ and Cd²⁺ ions sorption over all kinetic models. The sorption data was in good agreement with the Freundlich isotherm for Pb²⁺ and the Sips model for Cd²⁺ ions sorption. The sorption capacity was endothermic in nature. Pb²⁺ ions desorption was three times faster than Cd²⁺ ions. The sorption mechanism was plausibly explained by spectroscopic techniques. Herein, the tailored abundant agro-waste material is a competitive sorbent and may be exploited in decontamination of metal ions in a wide range of concentrations. Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

Amidoximation of Cyano Group for Chelating Ion Exchange of Some Heavy Metal Ions from Wastewater

Ion exchange behavior of some heavy metal ions, Pb²⁺, Ni²⁺, and Cd²⁺, onto amidoximated polyacrylonitrile based Ce(IV) phosphate was investigated. Polyacrylonitrile based Ce(IV) phosphate was prepared and followed by functionalization of the cyano group to amidoxime group with hydroxylamine. The amidoximated resin was characterized using FT-IR and SEM. Removal of Pb²⁺, Ni²⁺, and Cd²⁺ ions from aqueous solution was examined by studying some factors using the batch technique such as effect of pH, contact time, initial metal ion concentration, and temperature. Some kinetic and isotherm models had been applied. The calculated amount of the sorbed values in case of the pseudo-second-order model are closer to the experimental data than that of the pseudo-first-order model, and with a correlation coefficients R² > 0.99. Therefore, the sorption of the three metal ions can be approximated more favorably by the pseudo-second-order model. The sorption process obeys the Freundlich isotherm model. The sorption has an endothermic nature which is indicated by the positive value of the enthalpy change, ΔH, the high positive values of the entropy change, and ΔS show the increased randomness at the solid/solution interface. The obtained negative values of free energy change, ΔG, indicate the feasibility and the spontaneous nature of the sorption process.     

Spectroscopic and Thermodynamic Analysis of Cd2+ Ion Sorption Kinetics by Manganese Dioxide in the Presence of Oxyanions

The present study reports the effect of contact time, nature of electrolyte, and temperature on the sorption kinetics of Cd²⁺ by manganese dioxide, which is the most active oxide in soils and sediments. The sorption kinetics of Cd²⁺ by manganese dioxide is evaluated at pH 6 in different electrolytes in the temperatures range 293-323 K. The solid samples are equilibrated in 0.45 mmol.L^?1 Cd²⁺ and different electrolytes at pH 6. The results indicate that sorption of Cd²⁺ increases with time and temperature and the system attains equilibrium within 60 min in KNO₃ as the electrolyte. However, in the presence of 0.001 M KH2PO₄ sorption of Cd²⁺ increases and the time for equilibrium shifts to 90 min. The data second-order kinetics model and the calculated rate constant k and initial sorption rate h increases with increasing temperature phosphate treatment. Among the calculated thermodynamic activation parameters the positive values of ΔH^? and ΔG^? show the sorption process to be endothermic and nonspontaneous, while the ΔS^? being negative indicates a decrease in randomness of the system during sorption process at the solid-liquid interface. The free energy of activation decreases from 15.95 kJ.mol^?1 in nitrate to 8.76 kJ.mol^?1 in phosphate. These observations suggest that the rate controlling step in Cd²⁺ sorption is diffusionally controlled, a fact that has been proved by application of Fick’s law.     

Adsorption behaviour of Cu and Cd onto natural bentonite

The adsorption behaviour of Cu²⁺ and Cd²⁺ onto bentonite was studied as a function of temperature under optimized conditions of amount of adsorbent, particle size, pH, concentration of metals, and shaking time. The adsorption patterns of metal ions onto followed the Langmuir, Freundlich and Dubinin-Radushkevich isotherms. This included adsorption isotherms of single-metal solutions at 298-333 K by batch experiments. The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnK_o vs. 1 / T plots. The adsorptions were endothermic reactions. The results suggested that natural bentonite was suitable as sorbent material for the recovery and adsorption of metal ions from aqueous solutions.     

Removal of cadmium from aqueous solution by organic-inorganic hybrid sorbent combining sol-gel processing and imprinting technique

An organic-inorganic hybrid sorbent with high adsorption capacity was prepared by surface imprinting technique combined with sol-gel processing with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane as a functional precursor and silica as the support for the removal of Cd(II) ion from aqueous solution, and was characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, nitrogen gas sorption and thermogravimetric analysis. The influences of different adsorption parameters, such as pH value of solution, contact time and the initial concentrations of Cd(II) ions on the adsorption amount of Cd(II), were examined. The optimum pH for adsorption was found to be in the range of 4–8. The adsorption rate of Cd(II) on the imprinted hybrid sorbent was rapid. The relative selectivity coefficients of the imprinted hybrid sorbent were higher than those of the non-imprinted sorbent. Ho’s pseudosecond-order model best described the kinetics of the adsorption reaction. The adsorption process of metals followed Redlich-Peterson and Langmuir isotherms models, and the experimental value of maximum adsorption capacity for Cd(II) was 77.2mg·g^?1. The positive values of ΔH ^○ suggested endothermic nature of Cd(II) adsorption on the imprinted hybrid sorbent. Increase in entropy of adsorption reaction was shown by the positive values of ΔS ^○ and the negative values of ΔG ^○ indicating that the adsorption was spontaneous.     

Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

Kinetics of the sorption of heavy-metal ions by a sorbent obtained from boric acid production waste

The results of studies of kinetic regularities of sorption of heavy-metals ions (Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Mn²⁺) by a sorbent based on calcium hydrosilicate (hereinafter referred to as silicate sorbent) produced from manmade waste formed during the processing of the boron-containing mineral raw materials (boron–gypsum) have been presented.     

Congo red attached poly(EGDMA–HEMA) microspheres as specific sorbents for removal of cadmium ions

Poly[ethyleneglycoldimethacrylate (EGDMA)–hydroxyethylmethacrylate (HEMA)] microspheres (150–200 μm in diameter) were produced by suspension copolymerization of EGDMA and HEMA in an aqueous medium. Toluene was included in the formulations in order to produce water-swellable microspheres. Poly(vinyl alcohol) and benzoyl peroxide were used as stabilizer and initiator, respectively. Congo red was chemically attached to the microspheres as a metal chelating ligand for specific adsorption of heavy metal ions. These sorbents were characterized by an optical microscopy and a FTIR. Adsorption/desorption of cadmium (Cd²⁺) ions from aqueous solutions on these sorbents were investigated in batch equilibrium experiments by using an atomic absorption spectroscopy with a graphite furnace atomizer. The maximum cadmium adsorption on to the dye-attached microspheres (i.e., by complex formation) was about 18.3 mg Cd²⁺ ions/g polymer, which was observed at pH 6.8. While adsorption onto the plain poly(EGDMA–HEMA) microspheres (i.e., nonspecific adsorption) was about 0.93 mg Cd²⁺ ions/g polymer at the same conditions. More than 90% of the adsorbed cadmium was desorbed in 1 h by using 2M NaCl as an eluant. The resorption capacity of the sorbent did not significantly decrease during repeated sorption–desorption cycling. © 1996 John Wiley & Sons, Inc.     

Application of a carbon sorbent for the removal of cadmium and other heavy metal ions from aqueous solution

Treatment of flax shive with sulfuric acid produces a carbonaceous material that has been used to remove metal ions from aqueous solution. Metal ions including Cd(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II) and Pb(II) have been investigated for kinetic behaviour and sorption capacities. These metal ions show fast sorption kinetics following a first order rate equation. Cadmium was chosen as representative of these metal ions and a detailed study was carried out. The effect of pH on sorption was studied and it was found that maximum uptake occurred above pH 3–7, sorption was accompanied by release of protons into the solution and a ratio of [H⁺] released to [Cd²⁺] sorbed of approximately 2 was found. The sorption capacity showed no significant increase with increase of temperature. The presence of other metal ions such as K⁺, Na⁺, Mg²⁺ and Ca²⁺ decreases the Cd(II) capacity, indicating competition for the ion exchange sites. Successive sorption of Cd(II) shows that the capacity exceeds the monolayer capacity calculated from the Langmuir equation. Column studies showed good performance over a total of seven cycles of loading/stripping. These studies indicate that the sorption mechanism for these metal ions is related to a reversible ion exchange process on the carbon surface. © 2002 Society of Chemical Industry     

Ethylenediamine tetraacetic acid modification of crosslinked chitosan designed for a novel metal‐ion adsorbent

Novel chitosan‐based adsorbent materials were synthesized with a higher fatty diacid diglycidyl as a crosslinking agent, and the adsorption ability of the resulting polymers for several metal ions was evaluated. Selective adsorption for Cu²⁺ in comparison with other divalent metal ions, such as Ni²⁺, Pb²⁺, Cd²⁺, and Ca²⁺, was observed with the crosslinked chitosan sorbent at pH 6; however, the adsorption power decreased abruptly as the pH value of the solution decreased. The addition of ethylenediamine tetraacetic acid (EDTA) residues to crosslinked chitosan significantly enhanced the adsorption power for metal ions, especially for Ca²⁺. The adsorptivity of Ca²⁺ was dramatically improved with the introduction of EDTA residues, and the value was greater than that obtained with a commercial chelate resin (CR11). Although the adsorption power of the EDTA‐derivatized sorbent for other metal ions was just comparable to that of the CR11 material, the newly synthesized adsorbent could be used for the recovery of metal ions from industrial waste solutions with a relatively wide range of pHs, from 4.0 to 6.0. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2758–2764, 2004     

Removal of Lead from Water Samples by Sorption onto Powdered Limestone

Abstract

Bench scale batch adsorption experiments were performed, aiming at the removal of the Pb²⁺ ions from aqueous solutions and water samples by fine powdered Limestone (LS) as an effective inorganic sorbent, which is inexpensive, widespread, and cheap. The main parameters (i.e., solution pH, sorbent and lead concentrations, stirring times, and temperature) influencing the sorption process, in addition to the effect of some foreign ions, were investigated. The results obtained stated that the sorption of Pb²⁺ ions onto LS is well described by Freundlich model and deviated from that of Langmuir over the concentration range studied. Under the optimum experimental conditions employed, the removal of ca. 100% of Pb²⁺ ions was attained. The procedure was successfully applied to the removal of lead from aqueous and different natural water samples. Moreover, the adsorption mechanism is suggested.     

Surface chemistry and adsorption mechanism of cadmium ion on activated carbon derived from Garcinia mangostana shell

A detailed surface characterizations and adsorption mechanism of Cd²⁺ on chemical activated carbon (CAC) prepared from Garnicia mangostana shell were investigated. The activation is accomplished in self-generating atmosphere using phosphoric acid as activating agent. The characterizations performed are elemental analysis, functional group identification, N₂ adsorption isotherm and surface charges. Adsorption mechanism of metal ion was tested using Cd²⁺ as model ion. CAC achieved BET surface area of 1,498 m²/g with a mixture of micro and mesopores. The point of zero charge is observed to be at pH 2.8 and the optimum pH for Cd²⁺ adsorption on CAC is 12. The adsorption isotherm followed the Freundlich model, and the adsorption kinetics was explained by pseudo-second order kinetic model. From thermodynamic studies, the adsorption was found to be physical adsorption. X-ray photoelectron spectroscopy (XPS) confirmed the adsorption of Cd²⁺ onto CAC as +2 oxidation state.     

Competitive adsorption of Pb, Cu and Cd ions from aqueous solutions by multiwalled carbon nanotubes

The individual and competitive adsorption capacities of Pb²⁺, Cu²⁺ and Cd²⁺ by nitric acid treated multiwalled carbon nanotubes (CNTs) were studied. The maximum sorption capacities calculated by applying the Langmuir equation to single ion adsorption isotherms were 97.08 mg/g for Pb²⁺, 24.49 mg/g for Cu²⁺ and 10.86 mg/g for Cd²⁺ at an equilibrium concentration of 10 mg/l. The competitive adsorption studies showed that the affinity order of three metal ions adsorbed by CNTs is Pb²⁺>Cu²⁺>Cd²⁺. The Langmuir adsorption model can represent experimental data of Pb²⁺ and Cu²⁺ well, but does not provide a good fit for Cd²⁺ adsorption data. The effects of solution pH, ionic strength and CNT dosage on the competitive adsorption of Pb²⁺, Cu²⁺ and Cd²⁺ ions were investigated. The comparison of CNTs with other adsorbents suggests that CNTs have great potential applications in environmental protection regardless of their higher cost at present.     

Adsorption of Lead and Cadmium on Ca-Deficient Hydroxyapatite

A Ca-deficient hydroxyapatite(d-HAp) has been used to remove lead and cadmium from their mixed ions solution. The effect of pH, coexistent calcium and magnesium ions, and humic acid on the adsorption efficiency were investigated. The results showed that this d-HAp adsorbed both Cd²⁺ and Pb²⁺ efficiently within a wide pH range. The existence of humic acid reduced the removal efficiency of Cd²⁺ and Pb²⁺. The addition of Ca²⁺ and Mg²⁺ with a concentration of 500 mg/L only slightly reduced the removal efficiency. The adsorption kinetics was described by pseudo-second-order reaction model and the adsorption isotherm followed the Langmuir model.     

Synthesis of chelating resins with iminodiacetic acid and its wastewater treatment application

The chelating resins have high potential applications for the selective removal and recovery of metal ions from industrial waste solutions. The hydrophilic acrylate monomer with the iminodiacetic acid chelating group was prepared from glycidyl methacrylate and iminodiacetic acid at 60°C. The microbeads, prepared from acrylate monomer with the iminodiacetic acid chelating group, were employed by inversion suspension polymerization. In the pH range of 2–6, a reasonably good equilibrium sorption capacity is maintained for Cr³⁺ (ca. 2.7 mmol/g) and Cu²⁺ (ca. 1.8 mmol/g) in the chelating resins. The adsorption of Cd²⁺ and Pb²⁺ on microbeads is clearly affected by the pH of the solution, such that these ions' adsorption capacity increased with the pH of the aqueous solution. The adsorption of Cd²⁺ (ca. 1.25–1.87 mmol/g) and Pb²⁺ (ca. 0.99–1.89 mmol/g) showed a maximum at approximately pH = 5 and 6, respectively. The adsorption isotherms of Cr³⁺ and Cu²⁺ adsorbed on microbeads were following the Langmuir isotherm, but the adsorption behavior of Cd²⁺ and Pb²⁺ were not. The concentration of alkaline earth–metal cations on the range of 0–200 ppm had no influence on metal ions adsorbed capacity of chelating resins. Additionally, NTA (nitrilotriacetic acid) had no significant influence on metal ion adsorption by chelating resins. Furthermore, phenol pollutant can be adsorbed effectively by metal ions chelated microbeads; therefore, the microbeads were useful not only in recovering metal ions but also in the treating phenol pollutants in wastewater. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1353–1362, 2002; DOI 10.1002/app.10243     

Adsorption of copper on specifically modified polyamide sorbent

A novel, specific sorbent based on polyamide covalently immobilized with dead yeast cells by glutaraldehyde was prepared and characterized. This sorbent exhibits a high capacity for metal complexation based on multifunctional groups of dead cells, as well as a good stability for reuse based on the crosslinking agent, glutaraldehyde. The Cu²⁺ sorption characteristics of the polyamide modified with immobilized dead cells were studied and compared to those of the polyamide chemically modified without cells. The adsorption capacity of specifically modified polyamide was about 19‐fold higher than the chemically modified polymer. The adsorption isotherms of Langmuir and Freundlich for the new specific sorbent were determined. The effect of pH, temperature and co‐ions (Zn²⁺, Pb²⁺, Co²⁺, Ca²⁺ and Mg²⁺) on the Cu²⁺ sorption capacity were studied. The effectiveness of heavy metal desorption and the coefficient of recovery of sorption ability were determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 80–85, 2003     

Investigation of α‐iron oxide‐coated polymeric nanocomposites capacity for efficient heavy metal removal from aqueous solution

In the present study, PS@α‐Fe₂O₃ nanocomposites were prepared by chemical microemulsion polymerization approach and the ability of magnetic beads to remove Cu(II) ions from aqueous solutions in a batch media was investigated. Various physico‐chemical parameters such as pH, initial metal ion concentration, temperature, and equilibrium contact time were also studied. Adsorption mechanism of Cu²⁺ ions onto magnetic polymeric adsorbents has been investigated using Langmuir, Freundlich, Sips and Redlich–Petersen isotherms. The results demonstrated that the PS@α‐Fe₂O₃ nanocomposite is an effective adsorbent for Cu²⁺ ions removal. The Sips adsorption isotherm model (R² > 0.99) was more in consistence with the adsorption isotherm data of Cu(II) ions compared to other models and the maximum adsorbed amount of copper was 34.25 mg/g. The adsorption kinetics well fitted to a pseudo second‐order kinetic model. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the temperature dependent sorption isotherms, and the results suggested that copper adsorption was a spontaneous and exothermic process. POLYM. ENG. SCI., 55:2735–2742, 2015. © 2015 Society of Plastics Engineers     

Removal of Cd2+ ions from aqueous solution using cassava starch–based superabsorbent polymers

A comprehensive feasibility study on the adsorption of Cd²⁺ ions by cassava starch–based superabsorbent polymers (CST‐SAPs) as the biosorbent was investigated as a function of adsorbent dosage, pH, initial concentration, contact time, and temperature. An orthogonal experiment and range analysis were applied to optimize the adsorption conditions. Adsorbent dosage and initial concentration were the most sensitive variables for adsorption capacity. The maximum adsorption value of Cd²⁺ ions was determined as 347.46 mg/g at pH 6.0, initial concentration of 200 mg/L, and contact temperature and time of 323 K and 6 h, respectively, with 0.1 g adsorbent dosage. The equilibrium data were well described by a Langmuir model, and the adsorption process was well fitted by pseudo‐second‐order kinetics. The Fourier transform infrared spectroscopy (FTIR) data confirmed that acrylic acid and acrylic amide grafted onto the cassava starch. The X‐ray diffraction and FTIR results for the Cd²⁺‐absorbed CST‐SAP (CST‐SAP‐Cd²⁺) samples showed that the CST‐SAP could effectively adsorb Cd²⁺ ions and that the characteristic groups were translocated by chelation. The scanning electron microscopy results for the CST‐SAP revealed that the surface of the polymer was rough, and the layered structure that was full of folds caused an enhanced specific surface; such conditions were beneficial to Cd²⁺ ion adsorption. It was concluded that the CST‐SAP was an excellent adsorbent for Cd²⁺ ion removal from aqueous solution. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44758.     

Equilibrium and kinetic modelling of the adsorption of Cd ions onto chestnut shell

A study on the removal of Cd²⁺ ions from aqueous solutions by acid formaldehyde pretreated chestnut (Castanea sativa) shell was conducted in batch conditions. The influence of different parameters: adsorption time, temperature (15, 25 and 35 °C) and initial concentration of Cd²⁺ ions (15.3, 50.5 and 87.3 mg L^− 1), on cadmium uptake was analysed. Cadmium free and cadmium loaded chestnut shell were characterized by FTIR spectroscopy, which evidenced the functional groups involved in cadmium uptake. Cadmium adsorption equilibrium could be described by the Freundlich adsorption model at all the temperatures essayed, which predicted shell heterogeneity. The Cd²⁺ adsorption process by chestnut shell followed the pseudo second order kinetic model. Cadmium sorption capacity increased with decreasing temperature at an initial concentration of 15.3 mg L^− 1 and with increasing initial cadmium concentration at a temperature of 25 °C. The second order kinetic constant, which increased with increasing temperature, was used to calculate the energy of adsorption as equal to 19.2 kJ mol^− 1.     

Use of chitosan complex with aminophosphonic groups and cobalt for the removal of Sr2+ ions

We briefly describe the adsorbent performance of the chitosan complex with aminophosphonic groups and cobalt in the removal process of Sr²⁺ ions from aqueous solutions. The strontium adsorption was studied as a function of pH, contact time, and initial strontium concentration. Adsorption isotherms such as Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin were used to analyze the equilibrium data at different concentrations. The kinetics of the Sr²⁺ sorption was analyzed using the pseudo-first-order and pseudo-second-order kinetic models. The results clearly indicate that the chitosan complex with aminophosphonic groups and cobalt is an efficient adsorbent with respect to its capacity to absorb Sr²⁺ ions from aqueous solutions.