Synthesis, characterization and application of allyl phenol modified amberlite XAD-4 resin for preconcentration and determination of copper in water samples

A new chelating resin was prepared by coupling Amberlite XAD-4 with phenol through an azo spacer, then modified by allyl bromide and characterized (by elemental analysis and IR) and studied for preconcentration of Cu(II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The optimum pH value for sorption of the above mentioned metal ion was 4.5. The resin was subjected to chemical evaluation through batch binding and column chromatography of Cu(II). The chelating resin can be reused for 15 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 98% was obtained for the metal ion with 0.5 M HNO₃ as eluting agent. The equilibrium adsorption data of Cu(II) on modified resin were analyzed by Langmuir, Freundlich and Temkin models. Based on equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined to be 0.061, 0.193 and 0.045 at pH 4.5 and 25 °C. The method was applied for the copper determination from industrial waste water sample.     

Synthesis,characterization, and application of amberlite XAD‐2‐ salicylic acid‐ iminodiacetic acid for lead removal from human plasma and environmental samples

A new chelating resin is prepared by coup‐ling Amberlite XAD‐2 with salicylic acid (SAL) through an azo spacer. Then the polymer support was coupled with iminodiacetic acid (IDA). The resulting sorbent has been characterized by FT‐IR, elemental analysis, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) and studied for the preconcentration and determination of trace Pb (II) ion from human biological fluid and environmental water samples. The optimum pH value for sorption of the metal ion was 5. The sorption capacity of functionalized resin is 67 mg g⁻¹. The chelating sorbent can be reused for 20 cycles of sorption–desorption without any significant change in sorption capacity. A recovery of 95% was obtained for the metal ion with 0.5M nitric acid as eluting agent. The profile of lead uptake on this sorbent reflects good accessibility of the chelating sites in the Amberlite XAD‐2‐SAL/IDA. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Pb (II) on modified resin were analyzed by Langmuir, Freundlich, Temkin, and Redlich‐Peterson models. Based on equili‐brium adsorption data the Langmuir, Freundlich, and Temkin constants were determined 0.428, 20.99, and 7 × 10⁻¹² at pH 5 and 20°C. The method was successfully applied for determination of lead ions in human plasma and sea water sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification and characterization of amberlite XAD-2 with calcein blue for preconcentration and determination of copper(II) from environmental samples by atomic absorption spectroscopy

A chelating resin is produced by coupling a dye calcein blue to Amberlite XAD-2 through an azo spacer. The resulting resin has been characterized by FT-IR, elemental analysis, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) studied for the preconcentration and determination of trace Cu(II) from solution samples. The optimum pH for adsorption of copper ions was 6. The sorption capacity of functionalized resin is 27 mg·g⁻¹. The chelating resin can be reused for 10 cycles without any significant changes in sorption capacity. A recovery of 100% was obtained for Cu(II) when eluted with 0.5 M nitric acid. Scatchard analysis revealed that homogeneous binding sites were formed in the resin. The equilibrium adsorption data of Cu(II) on modified resin were analyzed by Langmuir, Freundlich and Temkin models. Based on equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined 0.036, 2.196 and 0.348 at pH 6 and 20 °C, respectively. The method was applied for Cu(II) assay in environmental samples.     

Modification and characterization of poly (ethylene terephthalate)‐grafted‐acrylic acid/acryl amide fiber for removal of lead from human plasma and environmental samples

A new fibrous adsorbent was prepared by grafting acrylic acid/acryl amide (AA/AAm) comonomers onto poly (ethylene terephthalate) (PET) fibers. The resulting sorbent has been characterized by Fourier transform infrared (FT‐IR), elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy (SEM) and studied for the preconcentration and determination of trace Pb (II) ion from human biological fluid and environmental water samples. The optimum pH value for sorption of the metal ion was 8. The sorption capacity of functionalized resin is 44.1 mg g^?1. The chelating sorbent can be reused for 20 cycles of sorption–desorption without any significant change in sorption capacity. A recovery of 100.2% was obtained for the metal ion with 0.5M nitric acid as eluting agent. Effect of grafting yield, shaking time, shape of sorbent, and pH of the medium on adsorption of the metal ion were investigated. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Pb (II) on modified fiber were analyzed by Langmuir, Freundlich, Temkin, and Redlich‐Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.236, 10.544, and 9.497 at pH 8 and 20°C, respectively. The method was applied for lead ions determination from human plasma and sea water sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Iminodiacetic acid‐containing polymer brushes grafted onto silica gel for preconcentration and determination of copper(II) in environmental samples

Silica gel has been modified by silylation with 3‐mercaptopropyltrimethoxysilane followed by graft polymerization of dimethylacrylamide and (N,N‐bis‐carboxymethyl)amino‐3‐allylglycerol‐co‐dimethylacrylamide, synthesized via the reaction of allyl glycidyl ether with iminodiacetic acid. The sorbent, poly(AGE/IDA‐co‐DMAA)‐grafted silica gel, has been characterized by FTIR, elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy and studied for the preconcentration and determination of trace amounts of Cu(II) ion in environmental water samples. The optimum pH value for quantitative sorption of Cu(II) in batch mode was 5.5 and desorption was achieved, using 0.5 mol L^?1 nitric acid. The sorption capacity of functionalized sorbent is 32.3 mg g^?1. The chelating sorbent was reused for 15 sorption–desorption cycles without any significant change in sorption capacity. The profile of copper uptake by the sorbent reflected good accessibility of the chelating sites in the poly(AGE/IDA‐co‐DMAA)‐grafted silica gel. Scatchard analysis demonstrated homogeneous nature of binding sites. The equilibrium adsorption data of Cu(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.0665, 4.26, and 8.34, respectively, at pH 5.5 and 20°C. Adsorption isotherms were analyzed at different temperatures to obtain free energy, enthalpy, and entropy of adsorption. The method was applied for Cu(II) determination in sea water samples. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Adsorption of Cr(III), Ni(II), Zn(II), Co(II) ions onto phenolated wood resin

In this study, phenolated wood resin was used an adsorbent for the removal of Cr(III), Ni(II), Zn(II), Co(II) ions by adsorption from aqueous solution. The adsorption of metal ions from solution was carried at different contact times, concentrations and pHs at room temperature (25°C). For individual metal ion, the amount of metal ions adsorbed per unit weight of phenolated wood resin at equilibrium time increased with increasing concentration and pH. Also, when the amounts of metal ions adsorbed are compared to each other, it was seen that this increase was order of Cr(III) > Ni(II) > Zn(II) > Co(II). This increase was order of Cr(III) > Ni(II) > Co(II) > Zn(II) for commercial phenol–formaldehyde resin. Kinetic studies showed that the adsorption process obeyed the intraparticle diffusion model. It was also determined that adsorption isotherm followed Langmuir and Freundlich models. Adsorption isotherm obtained for commercial phenol–formaldehyde resin was consistent with Freundlich model well. Adsorption capacities from Langmuir isotherm for commercial phenol–formaldehyde resin were higher than those of phenolated wood resin, in the case of individual metal ions. Original adsorption isotherm demonstrated the monolayer coverage of the surface of phenolated wood resin. Adsorption kinetic followed the intraparticle diffusion model. The positive values of ΔG° determined using the equilibrium constants showed that the adsorption was not of spontaneous nature. It was seen that values of distribution coefficient (K_D) decreasing with metal ion concentration in solution at equilibrium (C_e) indicated that the occupation of active surface sites of adsorbent increased with metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2838–2846, 2006     

Synthesis and analytical application of a chelating resin based on a crosslinked styrene/maleic acid copolymer for the extraction of trace‐metal ions

A new chelating polymer sorbent was synthesized through the copolymerization of styrene and maleic anhydride in the presence of divinyl benzene as the crosslinking agent, followed by hydrolysis. This polymeric resin, bearing O donor groups, had the advantage of being stable in basic and saline media, unlike its linear analogue. This newly developed chelating matrix has a high resin capacity for metal ions such as Cr, Fe, Ni, Cu, and Pb. Various physicochemical parameters, such as the pH, volume, and flow rate, and the interference effect on metal uptake were studied. The sorption capacities of the crosslinked resin for Cr(III), Fe(III), Ni(II), Cu(II), and Pb(II) were 10.2, 14.3, 14.2, 15.4, and 8.8 mg/g, respectively. A high recovery of 98% was obtained for all the metal ions with 2N HCl as the eluting agent. The chelating resin was characterized by swelling studies, Fourier transform infrared, elemental analysis, X‐ray studies, and thermal analysis. The Langmuir and Freundlich adsorption isotherms were used to validate the metal‐uptake data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1771–1779, 2004     

8-羟基喹哪啶螯合树脂对Cr~（6＋）的吸附性能研究

研究了8-羟基喹哪啶螯合树脂（PS-HQD）在HAc-NaAc体系中对铬离子的吸附性能。结果表明,该树脂吸附Cr6＋的最佳pH为5.0,树脂吸附的平衡时间为8 h,吸附容量9.68 mg/g。表观速率常数k298=1.87×10^-4s^-1,一次洗脱回收率达94.3%。吸附过程符合Langmuir和Freundlich模型。     

Insights into the Sorption Mechanisms of Cr(III) by Chemically Modified Pine Bark

The mechanisms of Cr(III) sorption by pine bark treated chemically (MPB) with NaOH were investigated. The removal of Cr(III) was found to be strongly dependent on the initial pH. Thus, a model was developed for describing the adsorption as a function of this variable. The removal efficiencies as a function of the adsorbent dosage for different pH values were predicted. The equilibrium data were well fitted by the modified Langmuir isotherm. Ion exchange at equilibrium suggested chromium uptake and Ca²⁺ release occurs approximately according to the stoichiometry of the equilibrium reactions. Cr(III) desorption from MPB with chelating agents was not very effective while high efficiencies were achieved with HNO₃ solutions.     

Ghezeljeh nanoclay as a new natural adsorbent for the removal of copper and mercury ions:Equilibrium,kinetics and thermodynamics studies

Heavy metal determination was carried out by applying the solid phase extraction (SPE) method in batch mode followed by atomic absorption spectroscopy (AAS) and inductively coupled plasma atomic emission spectrosco-py (ICP-AES) from aqueous solutions using Ghezeljeh montmoril onite nanoclay as a new natural adsorbent. The Ghezeljeh clay is characterized by using Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Mi-croscopy–Energy Dispersive Spectrometry (SEM–EDS) and X-ray Diffractometry (XRD) and X-ray Fluorescence (XRF). The results of XRD and FT-IR of nanoclay confirm that montmoril onite is the dominant mineral phase. Based on SEM images of Ghezeljeh clay, it can be seen that the distance between the plates is Nano. The effects of varying parameters such as initial concentration of metal ions, pH and type of buffer solutions, amount of ad-sorbent, contact time, and temperature on the adsorption process were examined. The effect of various interfer-ing ions was studied. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Langmuir and Freundlich isotherms showed the best fit to the equilibrium data for Hg(I ), but the equilibrium nature of Cu(II) adsorption has been described by the Langmuir isotherm. The kinetic data were described with pseudo-first-order, pseudo-second-order and double-exponential models. The adsorp-tion process follows a pseudo-second-order reaction scheme. Calculation ofΔG0,ΔH0 andΔS0 showed that the nature of Hg(II) ion sorption onto the Ghezeljeh nanoclay was endothermic and was favored at higher temper-ature, and the nature of Cu(II) ion sorption was exothermic and was favored at lower temperature.     

Comparison of Cr(VI) Adsorption Using Synthetic Schwertmannite Obtained by Fe3+ Hydrolysis and Fe2+ Oxidation: Kinetics,Isotherms and Adsorption Mechanism

Good sorption properties and simple synthesis route make schwertmannite an increasingly popular adsorbent. In this work, the adsorption properties of synthetic schwertmannite towards Cr(VI) were investigated. This study aimed to compare the properties and sorption performance of adsorbents obtained by two methods: Fe³⁺ hydrolysis (SCH_A) and Fe²⁺ oxidation (SCH_B). To characterise the sorbents before and after Cr(VI) adsorption, specific surface area, particle size distribution, density, and zeta potential were determined. Additionally, optical micrographs, SEM, and FTIR analyses were performed. Adsorption experiments were performed in varying process conditions: pH, adsorbent dosage, contact time, and initial concentration. Adsorption isotherms were fitted by Freundlich, Langmuir, and Temkin models. Pseudo-first-order, pseudo-second-order, intraparticle diffusion, and liquid film diffusion models were used to fit the kinetics data. Linear regression was used to estimate the parameters of isotherm and kinetic models. The maximum adsorption capacity resulting from the fitted Langmuir isotherm is 42.97 and 17.54 mg·g⁻¹ for SCH_A and SCH_B. Results show that the adsorption kinetics follows the pseudo-second-order kinetic model. Both iron-based adsorbents are suitable for removing Cr(VI) ions from aqueous solutions. Characterisation of the adsorbents after adsorption suggests that Cr(VI) adsorption can be mainly attributed to ion exchange with SO₄²⁻ groups.     

Poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] brushes grafted onto siliceous support for preconcentration and determination of cobalt (II) in human plasma and environmental samples

A chelating matrix prepared by surface grafting of polymer containing a functional monomer, poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-methylacrylamide] (poly(AGE/IDA-co-DMAA) onto a modified silica. The silica surface was modified by silylation with 3-mercaptopropyltrimethoxysilane followed by graft polymerization. Monomer of allyl glycidyl ether-iminodiacetic acid was synthesized by reaction of allyl glycidyl ether with iminodiacetic acid. The chelating sorbent can be reused for 15 cycles of sorption-desorption without any significant change in sorption capacity. The profile of cobalt uptake on the sorbent reflects good accessibility of chelating sites in poly(AGE/IDA-co-DMAA)-grafted silica gel. The equilibrium adsorption data of Co(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin and Redlich-Peterson models. The method was applied for cobalt ions determination in human plasma and sea water sample with satisfactory results.     

Adsorption of Cr(III) ions by Turkish brown coals

The equilibrium and kinetic properties of Cr(III) ion adsorption by two brown coals from Anatolia, Turkey, have been investigated in batch stirred-tank experiments. The effects of adsorbent dose, initial sorbate concentration and contact time on the adsorption of Cr(III) by Isparta-Yalvaç-Yarikkaya (YK) and Kasikara (KK) brown coals were evaluated. The Cr(III) ions are able to form complex compounds with carboxylic and phenolic groups of brown coals and they were also bounded with phenolic groups even at low pH reaction of the solution (<3). Mechanisms including ion exchange, complexation and adsorption to the surface are possible in the sorption process. Our batch adsorption studies show the equilibrium adsorption data fit the linear Langmuir adsorption isotherm. Adsorption equilibrium was achieved in about 15–20 min for chromium(III). The Langmuir adsorption isotherm was used to describe the observed sorption phenomena. The maximum equilibrium uptake was 0.05 mmol of Cr(III)/g for KK, and 0.26 mmol of Cr(III)/g for YK, respectively, at a pH of 4.5. More than 90% of chromium(III) was removed by KK and YK from an aqueous solution after 60 min. In every experiment, the maximum Cr(III) was sequestered from the solution within 60 min. It is proposed that KK and YK brown coals can be used as potential sorbents for Cr(III) removal from aqueous solutions.     

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.     

Microwave-assisted urea-modified sorghum biomass for Cr (III) elimination from aqueous solutions

The present study concentrated on the use of an agro-waste biodegradable sorghum biomass in its simple and modified forms for the binding of Cr (III) ions. A relatively new method of modification was adopted using urea under microwave irradiation. FTIR analysis showed the presence of oxygen and nitrogen bearing functional groups in unmodified (UMS) and modified (MS) sorghum biomass. The appearance of new bands and shifts in the peaks confirmed the modification. The influence of different process parameters such as the adsorbent dose, solution pH, contact time, agitation speed and initial metal ion concentration was studied thoroughly to evaluate optimum conditions for adsorption. Maximum adsorption for Cr (III) ions occurred at pH 5.0–6.0 using UMS and MS. Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models in a non-linear fashion were used to explain the phenomenon. Maximum adsorption capacity was 7.03 and 16.36 mg of Cr (III) per gram of UMS and MS, respectively. Adsorption mechanism was explored by pseudo-first- and pseudo-second-order kinetic models, and it was found that the process followed pseudo-second-order kinetics. Thermodynamic study indicated the process favorability. The study concluded that urea modification under microwave irradiation produces a non-toxic and more effective adsorbent for Cr (III) remediation by inducing new nitrogen bearing functional groups to sorghum biomass.     

Factors Affecting on the Sorption/Desorption of Eu (III) using Activated Carbon

Abstract

The sorption and desorption of Eu (III) on H‐APC activated carbon using a batch technique has been studied as a function of carbon type, shaking time, initial pH solution, temperature, particle size of carbon, and concentration of the adsorbent and the adsorbate. The influence of different anions and cations on adsorption has been examined. The experimental data have been analyzed by Langmuir, Freundlich, and Temkin sorption isotherm models and the adsorption data for Eu (III) onto activated carbon were better correlated to the Temkin isotherm and the maximum absorption capacities obtained was 46.5 mg g^?1. Anions of phosphate, carbonate, oxalate, and acetate were found to increase the adsorption of Eu (III), whereas nitrate, chloride and all studied cations, potassium, sodium, calcium, magnesium, and aluminum have a negative effect on the adsorption capacity. More than 99% europium adsorbed on H‐APC eluted with 0.5 M HCl solution. The activated carbon prepared from apricot stone using 70% H₃PO₄ could be considered as an adsorbent that has a commercial potential for Eu (III) treatment.     

Comparative adsorption isotherms and modeling of nickel and cobalt citrate complexes onto chelating resins

The sorption characteristics of nickel and cobalt-organic acid complexes on two commercial chelating resins (Purolite S930 and S950) were compared. Purolite S390 is based on an iminodiacetic funtional group and S950 is an aminophosphonic acid resin. Batch equilibrium adsorption tests of these resins were examined and compared using various metal citrate concentrations (15–2000 mg/L) and solution pH. The solution pH of complex solutions was varied by preparing metal solutions in 0.01, 0.1, 0.5 and 1.0 M of citric acid. Equilibrium adsorption data were fitted to empirical isotherm models; linear, Langmuir, Freundlich and Redlich–Peterson (R–P) equations to establish the mechanism for the uptake of the metal complexes onto the resins. Our study showed that nickel-citrate complex adsorption exhibited both monolayer and multilayer adsorption; the mechanism on both resins varying with acid concentration, whereas cobalt complex adsorption was independent of acid concentration but the mechanism of metal loading was found to be influenced by the nature of the resins.     

Application of multicomponent adsorption isotherms to simultaneous biosorption of iron(iii) and chromium(vi) on C. vulgaris

Although the biosorption of single metal ions to various microorganisms has been extensively studied and adsorption isotherms have been developed for single metal ion situations, very little attention has been given to the bioremoval and the expression of the adsorption isotherms of multi-metal ions systems. In this study, the competitive biosorption of iron(III) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single and dual metal ion concentrations on the biosorption rates and equilibrium uptakes were investigated. The optimum biosorption pH for both metal ions was determined as 2·0. Multi-metal ion biosorption studies were also performed at this pH value. It was observed that the biosorption rates and yields and equilibrium uptakes of iron(III) or chromium(VI) ions were reduced by the presence of increasing concentrations of the other metal ion. Adsorption isotherms developed for both single and dual metal ion systems at the optimum pH were expressed by the non-competitive and competitive Langmuir and Freundlich adsorption models, and model parameters were determined by computer. It was seen that the adsorption equilibrium data fitted very well to both of the models in the concentration ranges studied. ©1997 SCI     

Removal of Toxic/Heavy Metal Ions Using Ion-Imprinted Aminofunctionalized Silica Gel

Abstract

The investigation reports the preparation and evaluation of Cr(III) and Fe(III)-imprinted amino-functionalized silica gel adsorbents (APTS-Cr(III)-Si and APTS-Fe(III)-Si) for selective solid-phase extraction of Cr(III) and Fe(III), respectively, from aqueous solutions. The adsorbent materials were prepared by a surface imprinting technique using 3-aminopropyltrimethoxysilane as the surface modifying ligand. The effects of solution pH, sorption time, temperature, and initial metal ion concentration upon adsorption characteristics were investigated. The adsorption isotherms for Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) were evaluated and the thermodynamics of the adsorption processes were correlated. By optimizing the parameters, the synthesized materials could be used successfully for selective removal of trivalent cations from a mixture of cations in dilute aqueous solution.     

单宁基酚胺型螯合树脂的制备及对Cr(VI)的吸附

杨梅单宁先与氯化亚砜反应制得氯代单宁,再与聚乙烯亚胺交联合成单宁基酚胺型螯合树脂。通过FTIR、SEM、EDS和XPS对单宁基酚胺型螯合树脂的结构进行表征,并考察了螯合树脂对Cr(VI)的吸附性能。在单宁的分子结构侧链引入氨基,能有效改善单宁基螯合树脂对Cr(VI)的吸附性能,螯合树脂对Cr(VI)的吸附主要为还原吸附,铬主要以Cr(III)的形式吸附到树脂上;在温度为318 K、pH为2.0、Cr(VI)初始质量浓度为500 mg/L时,单宁基酚胺型螯合树脂对Cr(VI)的最大吸附量达到364.46 mg/g;当Cr(VI)初始质量浓度低于20 mg/L时,树脂对铬的吸附率达到95%以上;单宁基酚胺型螯合树脂对Cr(VI)的吸附过程符合Langmuir等温吸附模型和准二级吸附动力学方程。该树脂在含铬废水处理方面具有潜在的应用前景。