Adsorption of Pb2+ on Chitosan Cross‐Linked with Triethylene‐Tetramine

A novel triethylene‐tetramine cross‐linked chitosan (CCTS) was synthesized via the cross‐linking of triethylene‐tetramine and epichlorohydrin activated chitosan. Its structure was characterized by elemental analysis, infrared spectroscopy and X‐ray diffraction analysis, and the surface topography was determined with ESEM. The results were in agreement with expectations. The capacity of CCTS to adsorb Pb²⁺ ions from aqueous solutions was examined, and equilibrium and kinetic investigations were undertaken. The adsorption isotherms were fitted well by the Langmuir equation (R > 0.999). The maximum adsorbed amount, at pH 5.5, with an initial concentration of 3 mmol/L (621 ppm), was 378.8 mg/g. The adsorption process could be best described by a second‐order equation (R = 1). This suggests that the rate‐limiting step may be the chemical adsorption (chemisorption) step and not the mass transport. The separation factor used was 0 < R_L < 1. Therefore, it can be concluded that CCTS is an effective adsorbent for the collection of Pb²⁺.     

Application of crosslinked chitosan in the analysis of butyl tin speciation

A new method for the separation and preconcentration of butyl tin speciation with crosslinked chitosan (CCTS) and for its determination by hydride generation atomic absorption spectrometry was developed. At pHs 6.8, 4.4, and 3.0, monobutyl tin (MBT), dibutyl tin (DBT), and tributyl tin (TBT), respectively, were separated and preconcentrated with CCTS, eluted quantitatively with 10 mL of 1 mol L^?1 HCl, and determined. The method was applied to the discrimination and determination of MBT, DBT, and TBT in water and sediment samples. The detection limits of TBT, DBT, and MBT were 21.2, 25.5, and 28.5 ng L^?1, respectively. The analytical recoveries of MBT, DBT, and TBT added to the samples were 91–95% for water samples and 82–90% for sediment samples. The results were satisfactory. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1326–1328, 2004     

Removal of chromium (VI) from aqueous solutions using poly(4‐vinyl pyridine) beads

Sorption of hexavalent chromium ions from aqueous solution by poly 4‐vinyl pyridine [Poly(4‐VP)] was studied. The batch method was applied for adsorption processes. The effects of initial ion concentration, time, pH and temperature on adsorption were investigated. A treatment time of 60 min was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value for the process. The maximum adsorption performance was achieved at 86.7 mg g^?1 using 500 mg L^?1 Cr (VI) solutions. The process of adsorption of Cr (VI) was explained by Langmuir isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2865–2870, 2006     

Self-assembly of thiourea intercalated graphene oxide based dual IIP for the SPE coupled FAAS method development of Cu(II) and Pb(II) determination

A new dual-template surface imprinted polymer for Cu(II) and Pb(II) was synthesized in one pot. Magnetic graphene oxide was self-assembled with low cost and environmentally benign thiourea. Presence of sulfur and nitrogen donor atoms provide hooks for coordination and partial reduction of graphene oxide matrix. It was used as an solid-phase extraction adsorbent for extraction, preconcentration, and coupled with flame atomic absorption spectrometry to manifest performance comparable with inductively coupled plasma atomic emission spectrometry (ICPAES) both in terms of quantification limit as well as interference. The critical experimental parameters such as pH; 4.6, contact time of 15 min and initial concentration of 777 (Q_e; 227 mg g⁻¹) and 800 μg L⁻¹ (Q_e; 273 mg g⁻¹) for Cu(II) and Pb(II), respectively, were optimized using RSM-CCD and artificial neural network. The adsorption process was kinetically faster (50% adsorption in 5 min), following fractal-like-pseudo-second-order (FLPSO) kinetics and Brouers–Sotolongo isotherm model owing to the heterogenous energy landscape. The imprinting factors were in the range of 4–7 in the presence of all coexisting ions. The proposed method was robust in the determination and removal of Cu(II) and Pb(II) from food, ground water, and industry effluents with low limit of detection (Cu(II); 1.03 μg L⁻¹ & Pb(II); 1.79 μgL⁻¹). Spiking and recovery tests were used to assess the method's accuracy. Cu(II)/Pb(II) loaded dual template IIP (DIIP) was utilized to remove anionic dyes with >95% efficiency. Thorough examination of the method and material selectivity (in binary, ternary, and multielement system), multi fold applications of determination, removal of Cu(II), Pb(II), and removal of anionic dyes makes DIIP a promising candidate for environmental remediation.     

Studies of adsorption behavior of crosslinked chitosan for Cr(VI), Se(VI)

In this work, it was found that crosslinked chitosan (CCTS) had strong adsorption ability for some anions under certain conditions. Cr(VI) and Se(VI) existed in anion forms in aqueous solution, and their adsorption rates by CCTS were 97% for Cr(VI) at pH 3.0 and 95% for Se(VI) at pH 4.0. In addition, the adsorption balance time and isotherm of CCTS for Cr(VI) and Se (VI) were discussed and adsorption mechanism was explained. This research will be useful for designing CCTS‐based adsorption for metallic toxin removal and preconcentrating Cr(VI) and Se(VI) in their trace analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3216–3219, 2000     

Application of crosslinked carboxymethyl konjac glucomannan in speciation of dissolved Fe(II) and Fe(III) in water samples

A new solid‐phase extraction technique has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in environmental water samples with a microcolumn packed with crosslinked carboxymethyl konjac glucomannan (CCMKGM) prior to its determination by flame atomic absorption spectrometry (FAAS). Various influencing factors on the separation and preconcentration of Fe(II) and Fe(III), such as the acidity of the aqueous solution, sample flow rate and volume, and eluent concentration and volume, have been investigated systematically and optimized. Fe(III) could be quantitatively retained by CCMKGM in the pH range of 3.0–7.0, then the retained Fe(III) on the CCMKGM was eluted with 5.0 mol L^?1 HCl after cleaning with 0.01 mol L^?1 HCl to eliminate Fe(II) and determined by FAAS. Total Fe was determined after the oxidation of Fe(II) to Fe(III) by H₂O₂, and Fe(II) concentration was calculated by subtracting Fe(III) from total iron. The adsorption capacity of CCMKGM for Fe(III) was found to be as high as 162.3 mg g^?1. The detection limit (3σ) for Fe(III) was 1.5 μg L^?1 and the RSD was 3.5% (n = 11, c = 20 μg L^?1) with an enrichment factor of 50. The proposed method has been applied to the speciation of iron in water samples with satisfactory results. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and adsorption properties for metal ions of crosslinked chitosan acetate crown ethers

Two novel chitosan derivatives—crosslinked chitosan dibenzo‐16‐c‐5 acetate crown ether (CCTS‐1) and crosslinked chitosan 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 diacetate crown ether (CCTS‐2)—were synthesized by the reaction of crosslinked chitosan with dibenzo‐16‐c‐5 chloracetate crown ether and 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 dichloracetate crown ether with the intent of forming polymers that could be used in hazardous waste remediation as toxic metal‐binding agents in aqueous environments. Their structures were confirmed with elemental analysis, infrared spectral analysis, and X‐ray diffraction analysis. In the infrared spectra of CCTS‐1 and CCTS‐2, the characteristic peaks of aromatic backbone vibration appeared at 1595 cm⁻¹ and 1500 cm⁻¹; the intensity of the N H and O H stretching vibration in the region of 3150–3200 cm⁻¹ decreased greatly. The X‐ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in CCTS‐1 and CCTS‐2. The adsorption and selectivity properties of CCTS‐1 and CCTS‐2 for Pb²⁺, Cu²⁺, Cr³⁺, and Ni²⁺ were studied. Experimental results showed that the two crosslinked chitosan derivatives had not only good adsorption capacities for Pb²⁺, Cu²⁺, but also high selectivity for Pb²⁺, Cu²⁺ in the coexistence of Ni²⁺. For aqueous systems containing Pb²⁺, Ni²⁺, or Cu²⁺, Ni²⁺, CCTS‐1 only adsorbed Pb²⁺ or Cu²⁺. For aqueous systems containing Pb²⁺, Cr²⁺ and Ni²⁺, CCTS‐2 had high adsorption and selectivity properties for Pb²⁺. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2069–2074, 1999     

Adsorption of chromium (VI) on functionalized and non-functionalized carbon nanotubes

We did a comparative study on the adsorption capacity of Cr (VI) between functionalized carbon nanotubes (CNTs) and non-functionalized CNTs. The statistical analysis reveals that the optimum conditions for the highest removal of Cr (VI) are at pH 9, with dosage 0.1 gram, agitation speed and time of 120 rpm and 120 minutes, respectively. For the initial concentration of 1.0 mg/l, the removal efficiency of Cr (VI) using functionalized CNTs was 87.6% and 83% of non-functionalized CNTs. The maximum adsorption capacities of functionalized and non-functionalized CNTs were 2.517 and 2.49 mg/g, respectively. Langmuir and Freundlich models were adopted to study the adsorption isotherm, which provided a K _L and K _F value of 1.217 L/mg and 18.14 mg^1?n L ⁿ /g functionalized CNT, while 2.365 L/mg and 2.307 mg^1?n L ⁿ /g for non-functionalized CNTs. This result proves that functionalized CNTs are a better adsorbent with a higher adsorption capacity compared with the non-functionalized CNTs.     

Magnetic molecularly imprinted polymer nanoparticles coupled with high performance liquid chromatography for solid‐phase extraction of carvedilol in serum samples

Herein, we report a magnetic molecularly imprinted polymers (m‐MIPs) using Fe₃O₄ as a magnetic component, carvedilol as a template molecule for the solid‐phase extraction (MISPE) as the sample clean‐up technique combined with high‐performance liquid chromatography (HPLC) and for the controlled release of carvedilol at different pH values of 1.0 (simulated gastric fluid), 6.8 (simulated intestinal fluid), and 7.4 (simulated biological fluid). The adsorption kinetics was modeled with the pseudo‐first‐order and pseudo‐second‐order kinetics, and the adsorption isotherms were fitted with Langmuir and Freundlich models. The performance of the m‐MIPs for the controlled release of carvedilol was assessed and results indicated that the magnetic MIPs also have potential applications in controlled drug release. Furthermore, the m‐MIPs were applied to the extraction of carvedilol from human blood plasma samples. Carvedilol can be quantified by this method in the 2–350 μg L^?1 concentration range. The limit of detection and limit of quantification in plasma samples are 0.13 and 0.45 μg L^?1. The results from HPLC showed good precision (3.5% for 50.0 μg L^?1) and recoveries (between 85 and 93) using m‐MIP from human plasma samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41209.     

Adsorption of chromate and molybdate by cetylpyridinium bentonite

Bentonite was modified with cetylpyridinium bromide (CPBr) and investigated by elemental analysis, IR, X-ray diffraction, thermogravimetric analysis, specific surface area (BET) and electrokinetic mobility measurements. The surfactant was adsorbed on the montmorillonite in a bilayer structure. The organo-bentonite removed the oxyanions of Cr(VI) and Mo(VI) from aqueous solutions. The adsorption followed a pseudo-second-order kinetics and adsorption capacities of 0.7 and 1.4 mmol/g for Cr(VI) and Mo(VI) were recorded. E_a = 5.34 and 14.50 kJ/mol for the adsorption of Cr(VI) and Mo(VI) indicated an ion exchange mechanism. The standard free energy values (ΔG°) of − 2.11 and − 3.40 kJ/mol for Cr(VI) and Mo(VI) indicated a spontaneous adsorption process. Column studies showed the suitability of the organo-bentonite for operation in continuous flow systems.     

Characterization of a chelating resin functionalized via azo spacer and its analytical applicability for the determination of trace metal ions in real matrices

A selective flame atomic absorption spectrometric method has been developed for the determination of trace amount of metal ions after preconcentration on salicylic acid (SA) loaded Amberlite XAD‐4 resin (AXAD‐4) at suitable pH. The chelating resin AXAD‐4‐SA was characterized based on FTIR, thermal and chemical stability, and hydrogen ion capacity. The sorption capacity was found to be 245.0, 156.2, 155.0, 145.0, 125.0, 122.5, and 70 μmol g^?1 for Cu(II), Cr(III), Zn(II), Cd(II), Mn(II), Ni(II), and Co(II), respectively with t_1/2 <15 min. All the metals could be eluted by 5 mL of 4 mol L^?1 HCl/HNO₃ resulting in high preconcentration factor of 200–360 up to a low preconcentration limit of 5.5–10 μg L^?1. The accuracy and precision of the developed method was checked by analyzing standard reference materials. The experimental values were not statistically significant from the certified values with <5% RSD. The detection limits were found to be 0.42, 0.57, 0.63, 0.77, 0.94, 0.96, and 1.41 μg L^?1, respectively. The analytical utility of the AXAD‐4‐SA for preconcentration and determination of metal ions was explored by analyzing river, canal, sewage, and tap water by direct as well as standard addition method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Separation of Simulated Mixed Mo(VI) and V(V) From HNO3 and HCl Solutions by Selective Extraction and Stripping with Tri-N-Butyl Phosphate as Extractant

Equilibrium study was carried out to determine the optimum conditions required for Mo(VI) extraction from HNO₃ solutions and subsequently, simulated mixed Mo(VI), and V(V) were extracted from HNO₃ (pH = 1.0) and 6.0 mol L^?1 HCl solutions with TBP dissolved in n-hexane. The variation of pH (selective extraction) and selective stripping were investigated as methods of separation of Mo(VI) and V(V). The latter method was found inefficient for separations from HNO₃ solutions (pH = 1.0) except supplemented with selective stripping (back-extraction with 2.0 mol L^?1 H₂SO₄/14.5 mol L^?1 NH₄OH). While from 6.0 mol L^?1 HCl, selective stripping was adequate to quantitatively strip in turns the Mo(VI) and V(V) co-extracted into the TBP phase. About 100% of the co-extracted V(V) from the HCl medium was stripped in a two-stage process, in contrast to a single-stage required for Mo(VI) of the same result. The selective stripping method was found to be better because an initial appreciable co-extraction had occurred prior to stripping separation. Based on analytical and spectra data, the extracted complexes from HNO₃ and HCl media were formulated as ((MoO₂)_7–8n(VO₂)_2n · (NO₃)₁₆) ^(16–18)n- · m TBP (where n>m) and (MoO₂Cl₂ · VO₂ Cl) · xTBP, respectively.     

Surface complexation modeling of soluble molybdenum adsorption by Mn3O4

BACKGROUND: Mo is a harmful element that should strictly be limited in electrolytic manganese dioxide but can readily be removed by Mn₃O₄. However, as its adsorption mechanism is not yet clear the aims of this work are to clarify the absorption phenomena and specific reaction processes of Mo onto Mn₃O₄. RESULTS: Some theoretical parameters have been obtained: the total surface site density and protonation constants (N_T = 6.84 × 10^?3 mol g^?1, , ) were obtained by non‐linear data fitting of acid‐base titrations. Distribution of soluble Mo species derived from thermodynamic calculations showed that the concentration of poly‐molybdenum acid ion was extraordinarily low and could be ignored when the concentration of soluble Mo was 1 mg L^?1. The adsorption isotherm followed the Freundlich adsorption equation. Under the conditions V = 0.15 L, W = 2 g L^?1, [Mo]_T = 1.12 mg L^?1, T = 80 °C, P = 1.013 × 10⁵ Pa, 1.0 mol L^?1 MnSO₄ and pH range 1–6.5, the non‐electrostatic model (NEM) was used to quantify Mo adsorption. CONCLUSION: The surface adsorption complexation modeling of Mo onto Mn₃O₄ can be successfully applied to predict adsorption rates of Mo onto Mn₃O₄ at different pH values, with an absolute error less than 6%. Copyright © 2009 Society of Chemical Industry     

Removal of hexavalent chromium in wastewater by polyacrylamide modified iron oxide nanoparticle

Iron oxide nanoparticle has been successfully modified by polyacrylamide and the polyacrylamide modified magnetic nanoparticles (PMMNs) were applied to remove Cr(VI) in wastewater. The vibrating sample magnetometer (VSM) spectra indicated the large saturation magnetization and superparamagnetic property of the PMMNs. This made the polyacrylamide modified iron oxide easily separate with liquid phase. Scanning electron microscope (SEM) results showed that both the synthesized iron oxide and the PMMNs were nanoscale. Batch adsorption studies had been carried out to determine the effect of pH, contact time, Cr(VI) initial concentration, and coexisting salts on the adsorption of Cr(VI). Maximum removal (98.30%) was observed from an initial concentration of 100 mg L^?1 Cr(VI) at pH 3.0, 30°C. This process followed pseudo‐second‐order kinetics model and the equilibrium time was 40 min. The experimental data fitted the Langmuir isotherm better than Freundlich. Maximum adsorption amount of Cr(VI) by PMMN was 35.186 mg g^?1. The effect of coexisting salts on Cr(VI) removal was not apparent even the concentration of salt was 10 times as big as the low concentration, 0.01M. It had been proposed that the mechanism of Cr(VI) uptake onto PMMN was adsorption‐coupled reduction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40945.     

Preconcentration and Determination of Metal Ions in Commercial Ethanol Used as Fuel for Automotive Engines

Abstract

The present investigation reports the synthesis, characterization, and adsorption properties of a new nanomaterial based on organomodified silsesquioxane nanocages. The adsorption isotherms for CuCl₂, CoCl₂, ZnCl₂, NiCl₂, and FeCl₃ from ethanol solutions were performed by using the batchwise method. The equilibrium condition is reached very quickly (3 min), indicating that the adsorption sites are well exposed. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of the nanomaterial, using 5 mL of 1.0 mol L^?1 HCl solution as eluent. The sorption‐desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2, and 3 indicated an amount of copper of 51, 60, and 78 µg L^?1, and of iron of 2, 15, and 13 µg L^?1, respectively. These values are very close to those determined by conventional analytical methods. Thus, these similar values demonstrated the accuracy of the determination by recommended method.     

Synthesis,characterization, and application of a new chelating resin functionalized with dithiooxamide

Chloromethylated polystyrene‐divinylbenzene has been functionalized with dithiooxamide. The resulting chelating resin (DTOA) has been characterized by elemental analyses, infrared spectroscopy, thermogravimetric analysis, and metal ion sorption capacities. It has been used for the preconcentration and separation of Cu(II), Zn(II), Cd(II), and Pb(II) prior to their determination by FAAS. Parameters such as the amount of the resin, effect of pH, equilibration rate, sorption and desorption of metal ions, and effect of diverse ions have been studied. The maximum sorption capacities found are 0.97, 0.12, 0.08, and 0.12 mmol g^?1 for Cu(II), Zn(II), Cd(II), and Pb(II) at pH 6.0, 5.5, 1.0, and 5.5, respectively. The preconcentration factors are 100, 100, 50, and 50 for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. Recoveries of the metal ions were 96 ± 5, 97 ± 6, 96 ± 5, and 96 ± 5 at 95% confidence level, whereas the limits of detection are 2.0, 1.3, 2.5, and 25.0 μg L^?1 for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The calibration curves were linear up to 12 μg mL^?1 (R² = 1.000), 2 μg mL^?1 (R² = 0.998), 2 μg ml^?1 (R² = 1.000), and 5 μg mL^?1 (R² = 0.979) for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The reliability of the method has been tested by analyzing certified samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2281–2285, 2007     

Impedimetric microbial biosensor based on single wall carbon nanotube modified microelectrodes for trichloroethylene detection

Contamination of soils and groundwaters with persistent organic pollutants is a matter of increasing concern. The most common organic pollutants are chlorinated hydrocarbons such as perchloroethylene and trichloroethylene (TCE). In this study, we developed a bacterial impedimetric biosensor for TCE detection, based on the immobilization of Pseudomonas putida F1 strain on gold microelectrodes functionalized with single wall carbon nanotubes covalently linked to anti-Pseudomonas antibodies. The different steps of microelectrodes functionalization were characterized by electrochemical impedance and atomic force spectroscopies, and analytical performances of the developed microbial biosensor were determined. The impedimetric biosensor response was linear with TCE concentration up to 150 μg L⁻¹ and a low limit of detection (20 μg L⁻¹) was achieved. No significant loss of signal was observed after 4 weeks of storage at 4 °C in phosphate buffer saline pH 7 (three to four measurements a week). After 5 weeks, 90% of the initial value still remained. cis-1,2-Dichloroethylene and vinylchloride, the main TCE degradation products, did not significantly interfere with TCE. The microbial sensor was finally applied to the determination of TCE in natural water samples spiked at the 30, 50 and 75 μg L⁻¹ levels. Recoveries were very good, ranging from 100 to 103%.     

Studies of adsorption properties of crosslinked chitosan for vanadium(V), tungsten(VI)

In this article, the adsorption properties of crosslinked chitosan (CCTS) for V(V) and W(VI) were studied. Experimental results showed the adsorption rates of CCTS for V(V) and W(VI) were closely related to the acidity of solution. The adsorption rates were 97% for V(V) at pH 4.0 and 96% for W(VI) at pH 4.5. The adsorption balance times, adsorption capacities, and adsorption mechanism were explored. This research is of significance for removal of V(V) and W(VI) in industrial wastewater and their preconcentration in trace analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1584–1588, 2004     

Determination of hexavalent chromium in South African cements and cement-related materials with electrothermal atomic absorption spectrometry

The selective extraction of Cr(VI) in a cement matrix, based on treatment with 0.1 M Na₂CO₃ solution and subsequent determination of chromium by electrothermal atomic absorption spectrometry has been proposed. The proposed method has been applied to South African cement clinkers, natural gypsum, limestone and certified reference materials. The limit of detection of chromium determination in cement samples was found to be 0.14 μg g⁻¹. Between 30% and 80% of the total chromium in South African cement clinkers are Cr(VI) compounds and 8-26% of the total amount of Cr(VI) species is water soluble. The analytical performance of the proposed method has been verified by the analysis of BCS-CRM, a sulphate-resisting Portland cement, and the results obtained were in good agreement with the certified values.     

Single step modification of micrometer-sized polystyrene particles by electromagnetic polyaniline and sorption of chromium(VI) metal ions from water

This article describes a single-step reproducible approach for the surface modification of micrometer-sized polystyrene (PS) core particles to prepare electromagnetic PS/polyaniline–Fe₃O₄ (PS/PANi–Fe₃O₄) composite particles. The electromagnetic PANi–Fe₃O₄ shell was formed by simultaneous seeded chemical oxidative polymerization of aniline and precipitation of Fe₃O₄ nanoparticles. The weight ratio of PS to aniline was optimized to produce core–shell structure. PS/PANi–Fe₃O₄ composite particles were used as adsorbent for the removal of Cr(VI) via anion-exchange mechanism. The composite particles possessed enough magnetic property for magnetic separation. The adsorption was highly pH dependent. Adsorption efficiency reached 100% at pH 2 in 120 min when 0.05 g of composite particles was mixed with 30 mL 5 mg L⁻¹ Cr(VI) solution. The adsorption isotherm fitted best with Freundlich model and maximum adsorption capacity approached 20.289 mg g⁻¹ at 323 K. The prepared composite was found to be an useful adsorbent for the removal of soluble Cr(VI) ions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47524.