Modelling Individual and Competitive Adsorption of Cadmium(II) and Zinc(II) Metal Ions from Aqueous Solution onto Bagasse Fly Ash

Abstract

The present study deals with the competitive adsorption of cadmium (Cd(II)) and zinc (Zn(II)) ions onto bagasse fly ash (BFA) from binary systems. BFA is a waste obtained from the bagasse‐fired boilers of sugar mills. The initial pH≈6.0 is found to be the optimum for the individual removal of Cd(II) and Zn(II) ions by BFA. The equilibrium adsorption data were obtained at different initial concentrations (C ₀ = 10–100 mg/l), 5 h contact time, 30°C temperature, BFA dosage of 10 mg/l at pH ₀ = 6. The Redlich–Peterson (R–P) and the Freundlich models represent the single ion equilibrium adsorption data better than the Langmuir model. The adsorption capacities in the binary‐metal mixtures are in the order Zn(II)>Cd(II) and is in agreement with the single‐component adsorption data. The equilibrium metal removal decreases with increasing concentrations of the other metal ion and the combined action of Cd(II) and Zn(II) ions on BFA is found to be antagonistic. Equilibrium isotherms for the binary adsorption of Cd(II) and Zn(II) ions on BFA have been analyzed by non‐modified Langmuir, modified Langmuir, extended‐Langmuir, Sheindorf–Rebuhn–Sheintuch (SRS), non‐modified R–P and modified R–P adsorption models. The isotherm model fitting has been done by minimizing the Marquardt's percent standard deviation (MPSD) error function using MS Excel. The SRS model satisfactory fits for most of the adsorption equilibrium data of Cd(II) and Zn(II) ions onto BFA.     

Kinetic and Equilibrium Modeling of Pb(II) and Co(II) Sorption onto Rose Waste Biomass

Abstract

An attempt was made to assess the biosorption potential of rose waste biomass for the removal of Pb(II) and Co(II) ions from synthetic effluents. Biosorption of heavy metal ions (>90%) reached equilibrium in 30 min. Maximum removal of Pb(II) and Co(II) occurred at pH 5 and 6 respectively. The biosorbent dose for efficient uptake of Pb(II) and Co(II) was 0.5 g/L for both metals. The biosorbent size affected the Pb(II) and Co(II) biosorption rate and capacity. Rose waste biomass was found effective for Pb(II) and Co(II) removal from synthetic effluents in the concentration range 10–640 mg/L. Equilibrium sorption studies showed that the extent of Pb(II) and Co(II) uptake by the rose waste biomass was better described by the Langmuir isotherm in comparison to the Freundlich model. The uptake capacities of the two metal ions were 156 and 27.15 mg/g for Pb(II) and Co(II) respectively.     

Removal of Cu(II) and Zn(II) Using Lignocellulosic Fiber Derived from Citrus reticulata (Kinnow) Waste Biomass

Abstract

The biosorption of Cu(II) and Zn(II) using dried untreated and pretreated Citrus reticulata waste biomass were evaluated. The Cu(II) and Zn(II) sorption were found to be dependent on the solution pH, the biosorbent dose, the biosorbent particle size, the shaking speed, the temperature, the initial metal ions (800 mg/L), and the contact time. Twenty-eight physical and chemical pretreatments of Citrus reticulata waste biomass were evaluated for the sorption of Cu(II) and Zn(II) from aqueous solutions. The results indicated that biomass pretreated with sulphuric acid and EDTA had maximum Cu(II) and Zn(II) uptake capacity of 87.14 mg/g and 86.4 mg/g respectively. Moreover, the Langmuir isotherm model fitted well than the Freundlich model with R ² > 0.95 for both metal ions. The sorption of Cu(II) and Zn(II) occurred rapidly in the first 120 min and the equilibrium was reached in 240 min. FTIR and SEM studies were also carried out to investigate functional groups present in the biomass and the surface morphological changes of biomass.     

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.     

Pb(II) biosorption using DAP/EDTA-modified biopolymer (Chitosan)

Abstract

In this study, chitosan was chemically modified with only diammonium phosphate (DAP) and DAP/EDTA (ethylenediaminetetraacetic acid) mixture for the removal of Pb(II) ions from aqueous solution. Modified chitosan forms were analyzed using thermo-gravimetric analyzer (TGA), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) to investigate the thermal degradation behavior, structural modifications, and the surface texture of the cross-linked chitosan adsorbents, respectively. The adsorption results were analyzed by well-known kinetic and isotherm models. The kinetics of metal adsorption followed the pseudo-second-order model. The maximum sorption capacities obtained from the Langmuir isotherm model were 126?mg/g for diammonium phosphate-modified Chitosan (DMC) and 137?mg/g for DAP/EDTA-modified chitosan (EDMC). The thermodynamic analysis showed that the metal removal process was endothermic in nature.     

Adsorption of Ni(II) and Co(II) Using Microballoons Containing Mg-Silicate and CYANEX923 Prepared by the Emulsion Liquid Membrane System

Abstract

The Mg-silicate microballoons containing CYANEX923 were prepared by W/O/W emulsion. The diameter of obtained micro-sphere particles was ～10 µm and shell thickness was 2 µm. The adsorption of Co(II) and Ni(II) from aqueous solutions using prepared micro-sphere particles was investigated. Experiments were carried out as a function of solute concentration and temperature (25–60°C). Several kinetic models were used to test the experimental rate data and to examine the controlling mechanism of the adsorption process. Equilibrium adsorption data were analyzed using Langmuir isotherm model. The results indicated that prepared micro-sphere particles can be used as an efficient adsorbent for the removal of Ni(II) and Co(II) from aqueous solution.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Biosorption of cadmium(II) and lead(II) from aqueous solutions using Pleurotus ostreatus immobilized on bentonite

The purpose of this work was to evaluate the potential of a white rot fungi (P. ostreatus) immobilized on bentonite, in a continuous flow removal of trace heavy metals. The procedure is based on the biosorption of Cd(II) and Pb(II) ions on a column of bentonite loaded with dried, dead fungi components prior to their determination by atomic absorption spectroscopy (AAS). Cd(II) and Pb(II) were determined with a relative error of less than 5%. Various parameters such as “pH, amount of adsorbent, eluent type and volume, flow rate of the solution and matrix interference effect” on the retention of the metal ions were investigated. This procedure was applied to Cd(II) and Pb(II) determination in aqueous solutions, including tap water system. The optimum experimental parameters were determined to be pH 5, concentration of 10 mg/L, contact time of 30 min and 0.2 g of adsorbent for a quantitative adsorption of the metals. The optimum flow rate was found to be 2.5 mL/min for all metal ions. Each column can be used up to 20 successive analyses without considerable change in recoveries of metal ions.

The proposed method is excellent as regards simplicity, sensitivity, selectivity, precision, accuracy and column stability.     

Adsorption of Divalent Cobalt from Aqueous Solution onto Chitosan–Coated Perlite Beads as Biosorbent

Abstract

Chitosan coated perlite beads are prepared by drop‐wise addition of a liquid slurry containing chitosan and perlite to an alkaline bath. The resulting beads are characterized using FTIR, SEM, EDXRF, and Surface area analysis and the chitosan content of the beads is 23% as determined by a pyrolysis method. Adsorption of Co (II) metal ions from aqueous solution on chitosan coated perlite beads is studied under both equilibrium and dynamic conditions. In the present investigation, a first order reversible rate equation is used to understand the kinetics of metal removal and to calculate the rate constants at different initial concentrations. The equilibrium characteristics of metal ion on newly developed biosorbent are studied and the experimental adsorption data are well fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters are evaluated. The effect of pH, agitation time, concentration of adsorbate, and amount of adsorbent on the extent of the adsorption are investigated. The sorbent loaded with metal is regenerated with 0.10 mol dm^?3 sodium hydroxide solution. The adsorption desorption cycles indicated that the chitosan coated perlite could be regenerated and reused to remove Co (II) from waste water.     

Removal of Mercury (II) from Aqueous Solution using Chitosan-graft-Polyacrylamide Semi-IPN Hydrogels

Chitosan-graft-polyacrylamide semi-interpenetrating polymer network (IPN) superabsorbent hydrogel was prepared via UV irradiation and N, N′-methylene-bis-acrylamide was used as crosslinker. The product was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM). The hydrogels were observed to exhibit as much as 2580.2% swelling under optimum reaction conditions. The hydrogel is an efficient selective sorbent for the removal of mercuric ions (Hg(II)) from aqueous solutions. The mercury sorption capacity under non-buffered conditions is achieved around 9.98 mmol · g^?1 (or 2001.8 mg (mercury)/g (hydrogel)) via the colorimetric method. The kinetic data were fitted to the pseudo second order model. Furthermore, the influence of pH, hydrogel dose, and initial mercury concentration on adsorption capacity of the semi-IPN hydrogel was evaluated. Also, the isothermal adsorption equilibrium data was described using the Langmuir model. Finally, the mercury loaded hydrogel was regenerated without losing its original activity and stability.     

Equilibrium Studies in Adsorption of Hg(II) from Aqueous Solutions using Biocompatible Polymeric Polypyrrole-Chitosan Nanocomposite

This article deals with the adsorption of Hg(II) ions from aqueous solution on biocompatible polymeric polypyrrole-chitosan (PPy/CTN) nanocomposite. The Hg(II) uptake of PPy/CTN was quantitatively evaluated using sorption isotherms. In order to describe the isotherm mathematically, the experimental data of the removal equilibrium were correlated by either the Langmuir, Freundlich and Temkin equations. Results indicated that the Langmuir model gave a better fit to the experimental data than the other two equations. The adsorption capacity (q_max) of PPy/CTN for Hg(II) ions in terms of monolayer adsorption was 40 mg/g.     

Selective Competitive Biosorption of Au(III) and Cu(II) in Binary Systems by Magnetospirillum gryphiswaldense

The biosorption of Au(III) and Cu(II) ions in both single and binary systems by Magnetospirillum gryphiswaldense (MSR-1) was investigated. For comparison with the selective reinforced competitive biosorption process in a binary system, the experimental research first explored the biosorption of Au(III) and Cu(II) in a single system under various conditions. The biomass exhibited the highest single Au(III) and Cu(II) ion adsorption yields at room temperature (25°C), pH values of 2.5 and 5.0, respectively, and a biomass concentration of 10 g · L^?1 (3.83 g · L^?1, dry basis). The experimental data from the single component system for the two metallic ions fitted well to a Langmuir isotherm and a pseudo second-order kinetic models. In the Au(III)-Cu(II) binary system, the coexistence of Cu(II) cations promoted the adsorption of Au(III) within a certain range of ratios. A new sigmoidal Cu(II) biosorption isotherm was determined specifically to reveal the Cu(II) adsorption behavior in this case.     

Comparison of Biosorption of Nickel (II) and Copper (II) Ions from Aqueous Solution by Sphaeroplea Algae and Acid Treated Sphaeroplea Algae

Abstract

Biosorption of nickel (II) and copper (II) ions from aqueous solution by dead sphaeroplea algae in natural and acid treated forms were studied as a function of concentration, pH, and adsorbent dose. The optimum pH for nickel (II) and copper (II) biosorption was found to be 6.0 and 4.0 respectively. The metal ion uptake increased with initial metal ion concentration studied up to 500 mg/L. Both the Freundlich and Langmuir adsorption models could fit the equilibrium data. The adsorption reasonably fitted the Lagergren kinetic model. Further the biomass was characterized by FTIR spectra. Surface area values are measured to be 0.9 and 2.1 m²/g for natural and acid treated forms respectively. The maximum adsorption capacity was found to be 3.40, 4.15 mmol/g for nickel (II) and 2.21, 3.41 mmol/g for copper (II) in natural and acid treated forms respectively.     

Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads

The adsorption of Cu(II) ions onto chitosan and cross-linked chitosan beads has been investigated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. Batch adsorption experiments were carried out as a function of pH, agitation period, agitation rate and concentration of Cu(II) ions. A pH of 6.0 was found to be a optimum for Cu(II) adsorption on chitosan and cross-linked chitosan beads. Isotherm studies indicate Cu(II) can be effectively removed by chitosan and cross-linked chitosan beads. Adsorption isothermal data could be well interpreted by the Langmuir equation. Langmuir constants have been determined for chitosan and cross-linked chitosan beads. The experimental data of the adsorption equilibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu(II) ions on chitosan beads were 80.71 mg Cu(II)/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II)/g chitosan-GLA, on chitosan-ECH beads were 62.47 mg Cu(II)/g chitosan-ECH and on chitosan-EGDE beads were 45.94 mg Cu(II)/g chitosan-EGDE. The Cu(II) ions can be removed from the chitosan and cross-linked chitosan beads rapidly by treatment with an aqueous EDTA solution and at the same time the chitosan and cross-linked chitosan beads can be regenerated and also can be used again to adsorb heavy metal ions.     

Physicochemical Parameters of Cu(II) Ions Adsorption from Aqueous Solution by Magnetic-Poly(divinylbenzene-n-vinylimidazole) Microbeads

This study is aimed at the synthesis and characterization of the mesoporous magnetic-poly(divinylbenzene-1-vinylimidazole)[m-poly(DVB-VIM))microbeads(average diameter = 53–212 µm); their application as adsorbent in the removal of Cu(II) ions from aqueous solutions was investigated. The mesoporous m-poly(DVB-VIM) microbeads were prepared by copolymerizing of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The mesoporous m-poly(DVB-VIM) microbeads were characterized by N₂ adsorption/desorption isotherms, ESR, elemental analysis, scanning electron microscope (SEM), and swelling studies. At fixed solid/solution ratio the various factors affecting adsorption of Cu(II) ions from aqueous solutions such as pH, initial concentration, amount of mesoporousm-poly(DVB-VIM)) microbeads, contact time, and temperature were analyzed. Langmuir, Freundlich, and Dubinin-Radushkvich isotherms were used the model adsorption equilibrium data. The Langmuir isotherm model was the most adequate. The pseudo first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The experimental data fitted to pseudo second-order kinetic. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy changes. Morever, after the use in adsorption, the mesoporous m-poly(DVB-VIM) microbeads with paramagnetic property was separated via the applied magnetic force. These features make the mesoporous m-poly(DVB-VIM) microbeads a potential candidate for support of Cu(II) ions removal under magnetic field.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Adsorption of Pb(II) Ions Using Humic Acid Coated Chitosan-Tripolyphosphate (HA-CTPP) Beads

A new humic acid (HA) based adsorbent was prepared by coating humic acid on chitosan tripolyphosphate (CTPP) beads. Humic acid-chitosan tripolyphosphate (HA-CTPP) beads thus obtained were characterized using Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Swelling capacity studies of CTPP and HA-CTPP beads conducted in the pH range, pH = 1–10 showed that HA-CTPP beads are more stable against swelling than CTPP beads. Equilibration of HA-CTPP beads in water for different pH showed that leaching of HA from the beads is negligible and the beads are stable for adsorption applications. Adsorption of Pb(II) ions onto HA-CTPP beads were studied as a function of various operational parameters such as initial pH, metal ion concentration, and contact time. The results showed that HA-CTPP beads are suitable for Pb(II) ions adsorption and the kinetics of sorption very well fit into pseudo-second order model. The Langmuir model was found to be more suitable for explaining the observed adsorption data, giving a theoretical maximum adsorption capacity of 223.7 mg/g. HA-CTPP beads could possibly find application in the treatment of waste water contaminated with other toxic and/or heavy metals.     

Removal of Zinc (II) Ions from Aqueous Solutions Using Surfactant Modified Bamboo Sawdust

The present study explores the ability of surfactant modified bamboo sawdust in removing zinc (II) ions from aqueous solutions. The modified bamboo sawdust is characterized by surface area analysis, Scanning Electron Microscope, and Fourier Transform Infrared and X-ray fluorescence analysis. Adsorption isotherm and kinetic models were used to study the adsorption characteristics of zinc (II) ions onto modified bamboo sawdust. The equilibrium adsorption isotherm data were fitted into the Langmuir and Freundlich adsorption isotherms. It was found that modified bamboo sawdust yielded maximum adsorption capacity of 111.12 mg/g at 50°C for zinc (II) ions. The kinetic data obtained at different initial concentrations were analyzed using first-order-reversible reaction, pseudo-first-order, and pseudo-second-order models. The results provide strong evidence to support the hypothesis of adsorption mechanism.     

EQUILIBRIUM,KINETICS, AND BREAKTHROUGH STUDIES FOR ADSORPTION OF Cr(VI) ON CHITOSAN

Wastewater containing low levels of pollutants can be effectively treated by the adsorption technique. In the present work, an adsorption study was carried out using chitosan as adsorbent in a fixed-bed column for the removal of Cr(VI) from wastewater solutions. The column performance of Cr(VI) adsorption onto chitosan was studied at different bed heights (3–9 cm), flow rates (50–200 mL/min), initial metal concentrations (2–10 mg/L), pH values (2–7), and temperatures (30°–60°C). The equilibrium data for the batch adsorption of Cr(VI) on chitosan were tested using the Langmuir, Freundlich, and BET isotherm models. The Langmuir model was found to be the most suitable, with a maximum adsorption capacity of 35.7 mg/g and a correlation coefficient (R ²) = 0.952. The experimental data were found to fit well with the pseudo-second-order kinetic model, with R ² = 0.999. The dynamics of the adsorption process was modeled using the Adams-Bohart, Thomas, and mass transfer models. The models were used to predict the breakthrough curves of adsorption systems and to determine the characteristic design parameters of the column. The adsorption data were observed to fit well with all three models. The model parameters were derived using MATLAB software. In order to compare quantitatively the applicability of adsorption dynamic models in fitting to experimental data, the percentage relative deviation (P) was calculated and found to be less than 5, confirming that the fit is good for all three models.