Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Preparation and Characterization of the Newly Synthesized Metal‐Complexing‐Ligand N‐Methacryloylhistidine Having PHEMA Beads for Heavy Metal Removal from Aqueous Solutions

The aim of this study was to investigate in detail the performance for removal of heavy metal ions of beads composed of poly(2‐hydroxyethyl methacrylate) (pHEMA) to which N‐methacryloylhistidine (MAH) was copolymerized. The metal‐complexing ligand MAH was synthesized by using methacryloyl chloride and histidine. Spherical beads with an average size of 150–200 μm were obtained by the radical suspension polymerization of MAH and HEMA conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, p(HEMA‐MAH) beads had a specific surface area of 17.6 m²/g. The synthesized MAH monomer was characterized by NMR; p(HEMA‐MAH) beads were characterized by swelling studies, FTIR and elemental analysis. The p(HEMA‐MAH) beads with a swelling ratio of 65%, and containing 1.6 mmol MAH/g, were used in the adsorption/desorption experiments. Adsorption capacity of the beads for the selected metal ions, i. e., Cu(II), Cd(II), Cr(III), Hg(II) and Pb(II), were investigated in aqueous media containing different amounts of these ions (10–750 mg/L) and at different pH values (3.0–7.0). Adsorption equilibria were established in about 20 min. The maximum adsorption capacities of the p(HEMA‐MAH) beads were 122.7 mg/g for Cu(II), 468.8 mg/g for Cr(III), 639.4 mg/g for Cd(II), 714.1 mg/g for Pb(II) and 1 234.4 mg/g for Hg(II). pH significantly affected the adsorption capacity of MAH incorporated beads. The chelating beads can be easily regenerated by 0.1 M HNO₃ with high effectiveness. These features make p(HEMA‐MAH) beads a potential candidate for heavy metal removal at high capacity.     

Poly(2‐hydroxyethylmethacrylate)/chitosan dye and different metal‐ion‐immobilized interpenetrating network membranes: Preparation and application in metal affinity chromatography

Composite membranes were synthesized with 2‐hydroxyethylmethacrylate and chitosan (pHEMA/chitosan) via an ultraviolet‐initiated photopolymerization technique in the presence of an initiator (α,α′‐azobisisobutyronitrile). The interpenetrating network (IPN) membranes were improved by the immobilization of dye molecules via hydroxyl and amino groups on the membrane surfaces from the IPNs. A triazidine dye (Procion Green H‐4G) was covalently immobilized as a ligand onto the IPN membranes. The protein showed various affinities to different chelated metal ions on the membrane surfaces that best matched its own distribution of functional sites, resulting in a distribution of binding energies. In support of this interpretation, two different metal ions, Zn(II) and Fe(III), were chelated with the immobilized dye molecules. The adsorption and binding characteristics of the different metal‐ion‐chelated dye‐immobilized IPN membranes for the lysozyme were investigated with aqueous solutions in magnetically stirred cells. The experimental data were analyzed with two adsorption kinetic models, pseudo‐first‐order and pseudo‐second‐order, to determine the best fit equation for the adsorption of lysozyme onto IPN membranes. The second‐order equation for the lysozyme–dye–metal‐chelated IPN membrane systems was the most appropriate equation for predicting the adsorption capacity for all the tested adsorbents. The reversible lysozyme adsorption on the dye‐immobilized and metal‐ion‐chelated membranes obeyed the Temkin isotherm. The lysozyme adsorption capacity of the pHEMA/chitosan dye, pHEMA/chitosan dye–Zn(II), and pHEMA/chitosan dye–Fe(III) membranes were 2.54, 2.85, and 3.64 mg cm^?2, respectively. The nonspecific adsorption of the lysozyme on the plain pHEMA/chitosan membrane was about 0.18 mg cm^?2. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1843–1853, 2003     

Metal‐chelating properties of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) membranes

Metal‐chelating membranes have advantages as adsorbents in comparison with conventional beads because they are not compressible and they eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) [poly(HEMA–MAH)] membranes for the removal of three toxic heavy‐metal ions—Cd(II), Pb(II), and Hg(II)—from aquatic systems. The poly(HEMA–MAH) membranes were characterized with scanning electron microscopy and ¹H‐NMR spectroscopy. The adsorption capacity of the poly(HEMA–MAH) membranes for the selected heavy‐metal ions from aqueous media containing different amounts of these ions (30–500 mg/L) and at different pH values (3.0–7.0) was investigated. The adsorption capacity of the membranes increased with time during the first 60 min and then leveled off toward the equilibrium adsorption. The maximum amounts of the heavy‐metal ions adsorbed were 8.2, 31.5, and 23.2 mg/g for Cd(II), Pb(II), and Hg(II), respectively. The competitive adsorption of the metal ions was also studied. When the metal ions competed, the adsorbed amounts were 2.9 mg of Cd(II)/g, 14.8 mg of Pb(II)/g, and 9.4 mg of Hg(II)/g. The poly(HEMA–MAH) membranes could be regenerated via washing with a solution of nitric acid (0.01M). The desorption ratio was as high as 97%. These membranes were suitable for repeated use for more than three adsorption/desorption cycles with negligible loss in the adsorption capacity. The stability constants for the metal‐ion/2‐methacryloylamidohistidine complexes were calculated to be 3.47 × 10⁶, 7.75 × 10⁷, and 2.01 × 10⁷ L/mol for Cd(II), Pb(II), and Hg(II) ions, respectively, with the Ruzic method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1213–1219, 2005     

Adsorption characterization of lead(II) and cadmium(II) on crosslinked carboxymethyl starch

The adsorption of Pb(II) and Cd(II) ions with crosslinked carboxymethyl starch (CCS) was investigated as function of the solution pH, contact time, initial metal‐ion concentration, and temperature. Isotherm studies revealed that the adsorption of metal ions onto CCS better followed the Langmuir isotherm and the Dubinin–Radushkevich isotherm with adsorption maximum capacities of about 80.0 and 47.0 mg/g for Pb(II) and Cd(II) ions, respectively. The mean free energies of adsorption were found to be between 8 and 16 kJ/mol for Pb(II) and Cd(II) ions; this suggested that the adsorption of Pb(II) and Cd(II) ions onto CCS occurred with an ion‐exchange process. For two‐target heavy‐metal ion adsorption, a pseudo‐second‐order model and intraparticle diffusion seem significant in the rate‐controlling step, but the pseudo‐second‐order chemical reaction kinetics provide the best correlation for the experimental data. The enthalpy change for the process was found to be exothermic, and the ΔS^θ values were calculated to be negative for the adsorption of Pb(II) and Cd(II) ions onto CCS. Negative free enthalpy change values indicated that the adsorption process was feasible. The studies of the kinetics, isotherm, and thermodynamics indicated that the adsorption of CCS was more effective for Pb(II) ions than for Cd(II) ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption of heavy‐metal ions on poly(ethylene imine)‐immobilized poly(methyl methacrylate) microspheres

Poly(methyl methacrylate) (PMMA) microspheres carrying poly(ethylene imine) (PEI) were prepared for the removal of heavy‐metal ions (copper, cadmium, and lead) from aqueous solutions with different amounts of these ions (50–600 mg/L) and different pH values (3.0–7.0). Ester groups in the PMMA structures were converted to imine groups in a reaction with PEI as a metal‐chelating ligand in the presence of NaH. The adsorption of heavy‐metal ions on the unmodified PMMA microspheres was very low [3.6 μmol/g for Cu(II), 4.6 μmol/g for Cd(II), and 4.2 μmol/g for Pb(II)]. PEI immobilization significantly increased the heavy‐metal adsorption [0.224 mmol/g for Cu(II), 0.276 mmol/g for Cd(II), and 0.126 mmol/g for Pb(II)]. The affinity order of adsorption (in moles) was Cd(II) > Cu(II) > Pb(II). The adsorption of heavy‐metal ions increased with increasing pH and reached a plateau value around pH 5.5. Their adsorption behavior was approximately described with the Langmuir equation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 197–205, 2001     

Mono- and multi-component biosorption of lead(II), cadmium(II), copper(II) and nickel(II) ions onto coco-peat biomass

The potential of using coco-peat biomass (CPB) has been assessed for the removal of Pb(II), Cd(II), Cu(II) and Ni(II) ions from single and quaternary solutions. According to Langmuir isotherm, the maximum biosorption capacity of CPB was 0.484, 0.151, 0.383 and 0.181 mmol/g for Pb(II), Cd(II), Cu(II) and Ni(II) ions, respectively. Scanning electron microscopy along with energy-dispersive X-ray spectroscopy and Fourier-transform IR spectroscopy confirmed changes in the biosorbent functionality after metal sorption. Through quaternary isotherm experiments, 16.1%, 48.2%, 32.3% and 46.5% decrease in experimental uptakes were observed for Pb(II), Cd(II), Cu(II) and Ni(II), respectively, in the presence of other metal ions.     

Adsorption of Cd(II), Pb(II), and Ag(I) in aqueous solution on hollow chitosan microspheres

Cross‐linked chitosans synthesized by the inverse emulsion cross‐link method were used to investigate adsorption of three metal ions [Cd(II), Pb(II), and Ag(I)] in an aqueous solution. The chitosan microsphere, was characterized by FTIR and SEM, and adsorption of Cd(II), Pb(II), and Ag(I) ions onto a cross‐linked chitosan was examined through analysis of pH, agitation time, temperature, and initial concentration of the metal. The order of adsorption capacity for the three metal ions was Cd²⁺ > Pb²⁺ > Ag⁺. This method showed that adsorption of the three metal ions in an aqueous solution followed the monolayer coverage of the adsorbents through physical adsorption phenomena and coordination because the amino (? NH₂) and/or hydroxy (? OH) groups on chitosan chains serve as coordination sites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads have been studied. Poly(EGDMA‐HEMA) microbeads were prepared by suspension copolymerization of ethylene glycol dimethacrylate (EGDMA) and hydroxy‐ethyl methacrylate (HEMA) by using poly(vinyl alcohol), benzoyl peroxide, and toluene as the stabilizer, the initiator, and the pore‐former, respectively. Cibacron Blue F3GA was covalently attached to the microbeads via the nucleophilic substitution reaction between the chloride of its triazine ring and the hydroxyl groups of the HEMA, under alkaline conditions. Microbeads (150–200 μm in diameter) with a swelling ratio of 55%, and carrying 16.5 μmol Cibacron Blue F3GA/g polymer were used in the adsorption/desorption studies. Adsorption capacity of the microbeads for the selected metal ions, i.e., Cu(II), Zn(II), Cd(II), Fe(III), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–200 ppm) and at different pH values (2.0–7.0). The maximum adsorptions of metal ions onto the Cibacron Blue F3GA‐derived microbeads were 0.19 mmol/g for Cu(II), 0.34 mmol/g for Zn(II), 0.40 mmol/g for Cd(II), 0.91 mmol/g for Fe(III), and 1.05 mmol/g for Pb(II). Desorption of metal ions were studied by using 0.1 M HNO₃. High desorption ratios (up to 97%) were observed in all cases. Repeated adsorption/desorption operations showed the feasibility of repeated use of this novel sorbent system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1397–1403, 1999     

Synthesis and characterization of poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) copolymer beads for heavy‐metal removal

We prepared poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads (average diameter = 150–200 μm) by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer composition was characterized by elemental analysis and found to contain five EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads had a specific surface area of 65.8 m²/g. Poly(EGDMA–VTAZ) beads were characterized by Fourier transform infrared spectroscopy, elemental analysis, surface area measurements, swelling studies, and scanning electron microscopy. Poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used for the heavy‐metal removal studies. The adsorption capacities of the beads for Cd(II), Hg(II), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(EGDMA–VTAZ) beads were 85.7 mg/g (0.76 mmol/g) for Cd(II), 134.9 mg/g (0.65 mmol/g) for Pb(II), and 186.5 mg/g (0.93 mmol/g) for Hg(II). The affinity order toward triazole groups on a molar basis was observed as follows: Hg(II) > Cd(II) > Pb(II). pH significantly affected the adsorption capacity of the VTAZ‐incorporated beads. The equilibrium data were well fitted to the Redlich–Peterson isotherm. Consideration of the kinetic data suggested that chemisorption processes could have been the rate‐limiting step in the adsorption process. Regeneration of the chelating‐beads was easily performed with 0.1M HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4276–4283, 2006     

Studies on uptake behavior of Hg(II) and Pb(II) by amine modified glycidyl methacrylate–styrene–N,N′-methylenebisacrylamide terpolymer

The removal of mercury and lead ions from aqueous solutions investigated by ethylenediamine, diethylenetriamine and tetraethylenepentamine functionalized polymeric adsorbent. The adsorbent was prepared by amination of terpolymer synthesized from glycidylmethacrylate, styrene and N,N′-methylenebisacrylamide. In the single metal species system (only mercury or lead ions are present) poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA), and poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA) were found to adsorb lead or mercury ions with a slightly higher adsorption uptake capacity for lead than mercury ions. Among the three functionalized polymers poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA) shows faster and higher adsorption capacity than poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA). The natural pH of both the metal ions was found to be most suitable for uptake. The uptake of Hg(II) and Pb(II) ions was investigated by using batch technique. The maximum adsorption capacities of Pb ions were predicted to be 4.74, 4.76 and 4.73 mmol/g and the maximum Hg(II) ion uptakes were found to be 4.76, 4.80 and 4.21 mmol/g respectively for PGMA–EDA, PGMA–DETA and PGMA–TEPA resins at their natural pH. The uptakes of Hg(II) and Pb(II) ions on the resins were found to follow Langmuir adsorption isotherm and pseudosecond order kinetics.     

Adsorption Thermodynamics and Kinetics of Mercury (II), Cadmium (II) and Lead (II) on Lignite

This study examines the adsorption thermodynamics and kinetics of heavy metal ions [(Hg (II), Cd (II), Pb (II)] on a demineralized lignite coal. The study also investigates the effects of process parameters like contact time, pH, concentration of metal ion, temperature and adsorbent mass on the extent of metal-ion adsorption from solution.The results of the kinetic studies show that the adsorption reaction is first order with respect to the metal cation solution concentration, with activation energies of 4.9, 8.2 and 9.1 kJ mol^–1 for Hg (II), Cd (II) and Pb (II), respectively. These low activation energy values indicate that the adsorption reaction is diffusion-controlled. The results of the thermodynamic investigations indicate that the adsorption reactions are spontaneous (ΔG°< 0), slightly exothermic (ΔH°< 0) and irreversible (ΔS°> 0).The results of the study further show that the adsorption process is pH, adsorbent mass and metal-ion concentration dependent. Adsorption increases with increase in these variables. Temperature has only a marginal effect on adsorption. The reasons for these observations have been suggested.     

Removal of Ni(II), Cd(II), and Pb(II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica

In the present study, the application for the removal of Ni(II), Cd(II) and Pb(II) ions from aqueous solution by using mesoporous silica materials, namely, MCM-41, nanoparticle of MCM-41, NH₂-MCM-41 (amino functionalized MCM-41) and nano NH₂-MCM-41 was investigated. Suitable adsorbents preparation techniques were developed in the laboratory. The effects of the solution pH, metal ion concentrations, adsorbent dosages, and contact time were studied. It was found that NH₂-MCM-41 showed the highest uptake for metal ions in aqueous solution. The results indicated that the adsorption of Ni(II), Cd(II) and Pb(II) ions on the surface of the adsorbent was increased with increasing solution pH. The experimental data were analyzed using the Langmuir and Freundlich equations. Correlation coefficients were determined by analyzing each isotherm. It was found that the Langmuir equation showed better correlation with the experimental data than the Freundlich. According to the parameters of the Langmuir isotherm, the maximum adsorption capacity of NH₂-MCM-41 for Ni(II), Cd(II) and Pb(II) was found to be 12.36, 18.25 and 57.74 mg/g, respectively. The kinetic data of adsorption reactions and the evaluation of adsorption equilibrium parameters were described by pseudo-first-order and pseudo-second-order equations. The synthesized solid sorbents were characterized by Fourier transform infrared (FT-IR) spectrometry, X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen sorption measurements.     

Preparation and Characterization of Poly(2,2-dimethyl-1,3-propylene oxalate) Polymer and the Study of its Metal Uptake Behavior Toward Pb(II), Cd(II), and Hg(II) Ions

Abstract

Poly(2,2-dimethyl-1,3-propylene oxalate) was synthesized from oxalyl chloride and 2,2-dimethyl-1,3-propane diol. The polymer was characterized by inherent viscosity, FT-IR, XRD, SEM, ¹H-NMR, ¹³C-NMR, DSC, and TGA. The polymer uptake behavior towards Pb(II), Cd(II), and Hg(II) ions was studied by the batch equilibrium technique as a function of pH and contact time. The adsorption isotherms of metal ions were also investigated. Column experiments were used to determine the loading capacity and study desorption of metal ions. The polymer showed high metal-ion uptake capacity towards Pb(II), but moderate capacity towards Cd(II) and Hg(II) ions. Interestingly, the polymer was found to be highly selective for Pb(II) ions at pH 5 and 25°C. The metal ion uptake properties of the polymer show fittings for both Langmuir's and Freundlich equations. The metal-bound polymer was regenerated by treatment with 1 M HNO₃. Therefore, it may be employed for the removal of heavy metal pollutants in environmental and industrial applications.     

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.     

Removal Characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) by Natural Mongolian Zeolite through Batch and Column Experiments

The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.     

In vitro cadmium removal from human serum by Cibacron Blue F3GA–thionein‐complex conjugated affinity membranes

A new membrane affinity biosorbent carrying thionein has been developed for selective removal of cadmium ions from human serum. Microporous poly(2‐hydroxyethyl methacrylate) (pHEMA) membranes were prepared by photopolymerization of HEMA. The pseudo dye ligand Cibacron Blue F3GA (CB) was covalently immobilized on the pHEMA membranes. Then, the cysteine‐rich metallopeptide thionein was conjugated onto the CB‐immobilized membrane. The maximum amounts of CB immobilized and thionein conjugated on the membranes were 1.07 µmol cm⁻² and 0.92 µmol cm⁻², respectively. The hydrophilic pHEMA membrane had a swelling ratio of 58% (w/w) with a contact angle of 45.8 °. CB‐immobilized and CB‐immobilized–thionein‐conjugated membranes were used in the Cd(II) removal studies. Cd(II) ion adsorption appeared to reach equilibrium within 30 min and to follow a typical Langmuir adsorption isotherm. The maximum capacity (q _m) of the CB‐immobilized membranes was 0.203 (µmol Cd(II)) cm⁻² membrane and increased to 1.48 (µmol Cd(II)) cm⁻² upon CB–thionein‐complex conjugation. The pHEMA membranes retained their cadmium adsorption capacity even after 10 cycles of repeated use. © 2000 Society of Chemical Industry     

Removal of Pb(II) from Aqueous Solution by Cross-linked Starch Phosphate Carbamate

The adsorption process of Pb(II) ions from aqueous solution by water-insoluble starch phosphate carbamates was investigated. The influences of adsorption conditions, such as adsorption time, adsorbent dose, pH, content of the substituent groups, initial Pb(II) concentration, and temperature, were thoroughly studied. It was shown that an adsorption time of 20 min is sufficient to reach the adsorption equilibrium, the adsorption equilibrium data follow well the Langmuir isotherm model, and the adsorption of Pb(II) ions on cross-linked starch phosphate carbamate is endothermic in nature. For the cross-linked starch phosphate carbamate (CSPC3) with a phosphate group content of 3.10 mmol/g and a carbamate group content of 1.40 mmol/g, the maximum adsorption capacity evaluated from the Langmuir isotherm towards Pb(II) is 2.01 mmol/g. In addition, repeated adsorption/desorption cycles were performed to examine the reusability of adsorbents and the recovery efficiency of Pb(II) ions. The adsorption capacity of Pb(II) ions by CSPC3 decreased from 1.85 to 1.47 mmol/g for three cycles.     

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.     

Cysteine-metal affinity chromatography: determination of heavy metal adsorption properties

Various adsorbent materials have been reported in the literature for heavy metal removal. We have developed a novel approach to obtain high metal sorption capacity utilising cysteine containing adsorbent. Metal complexing aminoacid-ligand cysteine was immobilised onto poly(hydroxyethylmethacrylate) (PHEMA) microbeads. PHEMA-cysteine affinity microbeads containing 0.318 mmol cysteine/g were used in the removal of heavy metal ions (i.e. copper, lead and cadmium) from aqueous media containing different amounts of these ions (50–400 mg/l for Pb(II) and Cd(II), 25–60 mg/l for Cu(II)) and at different pH values (4.0–7.0). The maximum adsorption capacity of heavy metal ions onto the cysteine-containing microbeads under non-competitive conditions were 0.259 mmol/g for Pb(II), 0.330 mmol/g for Cd(II) and 0.229 mmol/g for Cu(II). The affinity order was observed as follows: Cd(II)>Pb(II)>Cu(II). The competitive adsorption capacities of the heavy metals were 0.260 mmol/g for Cd(II) and 0.120 mmol/g for Cu(II). Pb(II) adsorption onto cysteine-immobilised microbeads was zero under competitive conditions. The affinity order was as follows: Cd(II)>Cu(II)>Pb(II). The formation constants of cysteine–metal ion complexes have been investigated applying the method of Ruzic. The calculated value of stability constants were 1.75×10⁴ l/mol for Pb(II)–cysteine complex and 4.35×10⁴ l/mol for Cd(II)–cysteine complex and 1.39×10⁴ l/mol for Cu(II)–cysteine complex. PHEMA microbeads carrying cysteine can be regenerated by washing with a solution of hydrochloric acid (0.05 M). The maximum desorption ratio was greater than 99%. These PHEMA microbeads are suitable for repeated use for more than three adsorption–desorption cycles without considerable loss in adsorption capacity.