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1.
Poly-L-histidine immobilized poly(glycidyl methacrylate) (PGMA) cryogel discs were used for the removal of heavy metal ions [Pb(II), Cd(II), Zn(II) and Cu(II)] from aqueous solutions. In the first step, PGMA cryogel discs were synthesized using glycidyl methacrylate (GMA) as a basic monomer and methylene bisacrylamide (MBAAm) as a cross linker in order to introduce active epoxy groups through the polymeric backbone. Then, the metal chelating groups are incorporated to cryogel discs by immobilizing poly-L-histidine (mol wt ≥ 5000) having poly-imidazole ring. The swelling test, fourier transform infrared spectroscopy and scanning electron microscopy were performed to characterize both the PGMA and poly-L-histidine immobilized PGMA [P-His@PGMA] cryogel discs. The effects of the metal ion concentration and pH on the adsorption capacity were studied. These parameters were varied between 3.0–6.0 and 10–800 mg/L for pH and metal ion concentration, respectively. The maximum adsorption capacity of heavy metal ions of P-His@PGMA cryogel discs were 6.9 mg/g for Pb(II), 6.4 mg/g for Cd(II), 5.6 mg/g for Cu(II) and 4.3 mg/g for > Zn(II). Desorption of heavy metal ions was studied with 0.1 M HNO3 solution. It was observed that cryogel discs could be recurrently used without important loss in the adsorption amount after five repetitive adsorption/desorption processes. Adsorption isotherms were fitted to Langmuir model and adsorption kinetics were suited to pseudo-second order model. Thermodynamic parameters (i.e. ΔH° ΔS°, ΔG°) were also calculated at different temperatures.  相似文献   

2.
A method using commercially available sputtered bismuth screen‐printed electrodes (BispSPE), as substitute to mercury electrodes, for the determination of trace Pb(II) and Cd(II) ions in drinking well water samples collected in a contaminated area in The Republic of El Salvador by means of differential pulse anodic stripping voltammetry (DPASV) has been proposed. The comparable detection and quantification limits obtained for both BispSPE and hanging mercury drop electrode (HMDE), together with the similar results with a high reproducibility obtained in these water samples analyses recommend the applicability of BispSPE for the determination of low level of metal concentrations in natural samples.  相似文献   

3.
《中国化学快报》2020,31(10):2752-2756
Electrochemical analysis is a promising technique for detecting biotoxic and non-biodegradable heavy metals. This article proposes a novel composite electrode based on a polyaniline (PANi) framework doped with bismuth nanoparticle@graphene oxide multi-walled carbon nanotubes (Bi NPs@GO-MWCNTs) for the simultaneous detection of multiple heavy metal ions. Composite electrodes are prepared on screen-printed electrodes (SPCEs) using an efficient dispensing technique. We used a SM200SX-3A dispenser to load a laboratory-specific ink with optimized viscosity and adhesion to draw a pattern on the work area. The SPCE was used as substrate to facilitate cost-effective and more convenient real-time detection technology. Electrochemical techniques, such as cyclic voltammetry and differential pulse voltammetry, were used to demonstrate the sensing capabilities of the proposed sensor. The sensitivity, limit of detection, and linear range of the PANi-Bi NPs@GO-MWCNT electrode are 2.57 × 102 μA L μmol−1 cm−2, 0.01 nmol/L, and 0.01 nmol/L–5 mmol/L and 0.15 × 10−1 μA L μmol−1 cm−2, 0.5 nmol/L, and 0.5 nmol/L–5 mmol/L for mercury ion (Hg(II)) and copper ion (Cu(II)) detection, respectively. In addition, the electrode exhibits a good selectivity and repeatability for Hg(II) and Cu(II) sensing when tested in a complex heavy metal ion solution. The constructed electrode system exhibits a detection performance superior to similar methods and also increases the types of heavy metal ions that can be detected. Therefore, the proposed device can be used as an efficient sensor for the detection of multiple heavy metal ions in complex environments.  相似文献   

4.
The suitability of mercury films on commercial screen‐printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)‐ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L?1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen‐printed devices.  相似文献   

5.
《Electroanalysis》2006,18(10):955-964
The effects of the proximity of the signals of two heavy metal ions in stripping voltammetry (SV) and constant‐current stripping chronopotentiometry (SCP) is studied at mercury drop (HMDE) and mercury film (MFE) electrodes. For this purpose, the Cd(II)‐Pb(II)‐phthalate system is used, taking advantage of the approaching of the signals corresponding to Cd(II)‐phthalate and Pb(II)‐phthalate labile complexes as phthalate is added to mixtures of Cd(II) and Pb(II)‐ions. The results are compared with those obtained by differential pulse polarography (DPP) and by stripping measurements on the Pb(II)‐phthalate system alone, showing discrepancies in SCP data under nondepletive conditions and negligible differences in the other cases.  相似文献   

6.
The removal of Hg(II) ions from aqueous solution by adsorption onto cross-linked polymeric beads of carboxymethyl cellulose (CMC) and sodium alginate was studied at fixed pH (6) and room temperature 28 ± 0.2°C. The cross-linked polymeric beads were characterized by FTIR spectra. Sorption capacity of the polymer for the mercury ions was investigated in aqueous media consisting different amounts of mercury ions (2.5 to 100 mg dm?3) and at different pH values (2 to 8). Adsorption behavior of Hg(II) ions could be modeled using both the Langmuir and Freundlich isotherms. The dynamic nature of adsorption was quantified in terms of several kinetic constants such as rate constants for adsorption (k1) and Lagergreen rate constant (Kad). The influence of various experimental parameters such as effect of pH, contact time, solid-to-liquid ratio, salt effect, and temperature effect etc. were investigated on the adsorption of Hg(II) ions.  相似文献   

7.
Carboxylated multi-walled carbon nanotubes (MWCNTs-COOH) were chemically modified with 3-aminopyrazole (MWCNTs-f) and applied as an efficient adsorbent to mercury and arsenic adsorption from aqueous solutions. The adsorbents were characterized by FT-IR, EDX, FE-SEM, TGA, and BET. The effects of pH, adsorbent dose, and initial ions concentration on the adsorption efficiency and the optimum conditions were investigated by central composite design. The optimum conditions were obtained at pH 7.6–7.9, adsorbent dose 20 mg, and initial ions concentration 20 ppm. So the maximum adsorption efficiencies in these conditions were 80.5 and 72.4% for the removal of Hg(II) and As(III) by MWCNTs-f, respectively. The quadratic model was used for the analysis of variance and indicated that adsorption of metal ions strongly depends on pH. Also, the pseudo-second-order model has been achieved from the adsorption kinetic studies. Furthermore, the experimental data were well fitted to the Langmuir isotherm and the maximum adsorption capacities obtained were 112 and 133 mg g?1 for the adsorption of Hg(II) and As(III) by MWCNTs-f, respectively. Moreover, a thermodynamic study revealed that the adsorption reactions were spontaneous and endothermic with the increase in randomness. In addition, a desorption study showed the favorable regeneration ability of MWCNTs-f even after three adsorption–desorption cycles. Therefore, the MWCNTs-f adsorbent has good potential for the removal of Hg(II) and As(III) pollutants from aqueous solutions.  相似文献   

8.
Various carbon nanomaterials for use in anodic stripping voltammetric analysis of Hg(II), Cu(II), Pb(II) and Cd(II) are screened. Graphene, carbon nanotubes, carbon nanofibers and fullerene (C60), dispersed in chitosan (Chit) aqueous solution, are used to modify a glassy carbon electrode (GCE). The fullerene-chitosan modified GCE (C60-Chit/GCE) displays superior performance in terms of simultaneous determination of the above ions. The electrodes and materials are characterized by electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The excellent performance of C60-Chit/GCE is attributed to the good electrical conductivity, large surface area, strong adsorption affinity and unique crystalline structure of C60. Using differential pulse anodic stripping voltammetry, the assay has the following features for Hg(II), Cu(II), Pb(II) and Cd(II), respectively: (a) Peak voltages of +0.14, ?0.11, ?0.58 and???0.82 V (vs SCE); (b) linear ranges extending from 0.01–6.0 μM, 0.05–6.0 μM, 0.005–6.0 μM and 0.5–9.0 μM; and (c), detection limits (3σ method) of 3 nM (0.6 ppb), 14 nM (0.9 ppb), 1 nM (0.2 ppb) and 21 nM (2.4 ppb). Moreover, the modified GCE is well reproducible and suitable for long-term usage. The method was successfully applied to the simultaneous determination of these ions in spiked foodstuff.
Graphical abstract Compared with graphene, carbon nanotubes and carbon nanofibers, an electrode modified with fullerene in chitosan electrode displays superior performance for the simultaneous anodic stripping voltammetric detection of Hg(II), Cu(II), Pb(II) and Cd(II).
  相似文献   

9.
《Analytical letters》2012,45(6):912-922
An amine-Fe3O4 modified glassy carbon (GC) electrode was constructed for detecting Pb(II) ions in wastewater. The electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Square wave anodic stripping voltammetry (SWASV) was used to detect the Pb(II), and the detection limit of Pb(II) was 0.15 µM. The sensitivity of the electrode to detect Pb(II) was about 10.07 µA/µM, with a correlation coefficient of 0.991, which was approximately 10 times bigger than that of a pure Fe3O4 modified electrode. The electrode also showed good selectivity and stability. This results indicated that the amine-magnetite material could have some potential applications in heavy metal ions detection in wastewater.  相似文献   

10.
Salih B  Denizli A  Kavaklı C  Say R  Pişkin E 《Talanta》1998,46(5):1205-1213
The dithizone-anchored poly (EGDMA-HEMA) microbeads were prepared for the removal of heavy metal ions (i.e. cadmium, mercury, chromium and lead) from aqueous media containing different amounts of these ions (25-500 ppm) and at different pH values (2.0-8.0). The maximum adsorptions of heavy metal ions onto the dithizone-anchored microbeads from their solutions was 18.3, Cd(II); 43.1, Hg(II); 62.2, Cr(III) and 155.2 mg g(-1) for Pb(II). Competition between heavy metal ions (in the case of adsorption from mixture) yielded adsorption capacities of 9.7, Cd(II); 28.7, Hg(II); 17.6, Cr(III) and 38.3 mg g(-1) for Pb(II). The same affinity order was observed under non-competitive and competitive adsorption, i.e. Cr(III)>Pb(II)>Hg(II)>Cd(II). The adsorption of heavy metal ions increased with increasing pH and reached a plateaue value at around pH 5.0. Heavy metal ion adsorption from artificial wastewater was also studied. The adsorption capacities are 4.3, Cd(II); 13.2, Hg(II); 7.2, Cr(III) and 16.4 mg g(-1) for Pb(II). Desorption of heavy metal ions was achieved using 0.1 M HNO(3). The dithizone-anchored microbeads are suitable for repeated use (for more than five cycles) without noticeable loss of capacity.  相似文献   

11.
A series of granular pH-sensitive semi-interpenetrating polymer network (semi-IPN) hydrogels based on chitosan (CTS), acrylic acid (AA) and gelatine (GE) were utilized for the adsorption and recycle of Pb(II) from aqueous solutions. The composite hydrogels have been characterized by FT-IR and TGA. The effects of contact time, pH value and initial Pb(II) concentration on the adsorption were investigated. Results indicated that the adsorption capacity of the hydrogel increased with increasing pH value and initial Pb(II) concentration, and a pH-sensitive adsorption characteristic was presented. The adsorption rate of the semi-IPN hydrogels on Pb(II) is fast with an adsorption rate constant of 14.9790 mg/(g·s), and adsorption equilibrium could be reached within 10 min. The adsorption isotherms of the hydrogels for Pb(II) could be described well by the Langmuir equation, rather than the Freundlich equation. The as-prepared hydrogels showed good reusability with 0.05 mol/l HNO3 solutions as the desorbing agent and 0.1 mol/l NaOH solutions as the regeneration agent, respectively. After five consecutive adsorption-desorption processes, the semi-IPN hydrogel with 20 wt% GE may reach 85.26% of its initial adsorption capacity. In addition, the adsorbed Pb(II) can be quantitatively recovered by simply eluting the hydrogel with dilute HNO3 solution, and a recovery ratio of 89.27% was reached for the semi-IPN hydrogel. The satisfactory adsorption amount is mainly derived from the chelating of functional groups (i.e. –COO? and –NH2) with Pb(II) ions. The hydrogel adsorbents exhibited excellent affinity for Pb(II), and can be applied to treat wastewater containing heavy metal ion and simultaneously recover the valuable metal sources.  相似文献   

12.
Silica gel modified with 3-aminopropyltrimethoxysilane was anchored with nicotinaldehyde to prepare a new chelating surface (or matrix). It was synthesized and characterized by elemental analysis, cross-polarization magic-angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy, diffuse reflectance infrared Fourier-transform spectroscopy, nitrogen adsorption–desorption isotherm, Brunauer–Emmett–Teller surface area, and Barrett–Joyner–Halenda pore sizes. The new surface exhibits good chemical and thermal stability as determined by thermogravimetry curves. This new organic–inorganic material was used for preconcentration of Hg(II), Pb(II), Zn(II), and Cd(II) from water prior to their determination by inductively coupled plasma atomic emission spectrometry. The optimum pH for quantitative sorption of these metal ions is in the range of 6–8, and the sorption capacity is in range of 486–1,449 μmol/g. By batch method, 95 % extraction takes ≤30 min. All the metals could be desorbed with a solution of hydrochloric acid (6 N) without loss of the expensive ligand. Solutions of the metal ions were prepared by dissolution of the nitrate solution.  相似文献   

13.
Fine powder of Typha latifolia L. root was used for adsorption of copper and zinc ions from buffered and nonbuffered aqueous solutions. The adsorption reached equilibrium in 60 min. During this time, more than 90 % of the adsorption process was completed. The effect of initial pH, initial concentration of metal ion, and contact time was investigated in a batch system at room temperature. The optimum adsorption performance was observed at pH 5.00 and 4.25 for nonbuffered solutions of Cu(II) and Zn(II), respectively, while for buffered solutions it occurred at pH 6.00. The total metal uptake decreased on application of ammonium acetate buffer, from 37.35 to 17.00 mg g?1 and 28.80 to 9.90 mg g?1 for Cu(II) and Zn(II) solutions, respectively, with 100 mg L?1 initial concentration. The pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models were used to describe the adsorption kinetics. The experimental data followed the pseudo-second-order kinetic model. The biosorption equilibrium was well described by Langmuir and Freundlich isotherm models.  相似文献   

14.
Dias Filho NL  do Carmo DR 《Talanta》2006,68(3):919-927
In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexadecyltrimethylammonium ions (HDTA), with the formulae of [(CH3)3N(C16H33)]+ ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded on the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination.  相似文献   

15.
In this work, a new method has been proposed to simultaneously determine V(V), Co(II) and Cu(II) ions from aqueous solution by spectrophotometry after cloud point extraction using partial least squares regression (PLS). The metal ions in 10 ml of aqueous solution (containing 0.2 M sodium acetate buffer solution, pH 3.5) were formed complexes with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). Then, Triton X-114 (2 %, v/v) was added to the solution. By increasing the temperature of the solution up to 55 °C, a phase separation occurred. After centrifugation at 3,000 rpm for 10 min, the surfactant-rich phase was dissolved and diluted to 0.5 mL with ethanol. The metal ions were then determined using spectrophotometry. At these optimal extraction and operating conditions, linearity was obeyed in the range 7–300, 3–100 and 15–700 ng mL?1 of V(V), Co(II) and Cu(II), with the detection limit of 2.2, 1.0 and 4.5 ng mL?1, respectively. The relative predictive error for the simultaneous determination of 15 test samples of different concentrations of V(V), Co(II) and Cu(II) was 3.28, 3.64 and 4.04 %, respectively. The root mean square error of prediction for applying the PLS method to 15 synthetic samples in the linear ranges of these metal ions was 3.4, 1.6 and 18.1 ng mL?1. The interference effect of some anions and cations was also tested. The proposed method has been applied successfully to the simultaneous determination of V(V), Co(II) and Cu(II) ions in real matrix samples with the recoveries of 96.75–104.80 %.  相似文献   

16.
A novel approach to the electrochemical determination of heavy metals in tap water using anodic stripping voltammetry was developed using screen-printed electrodes modified with gold films. After optimisation of the experimental conditions, the screen-printed electrodes modified with gold films displayed excellent linear behaviour in the examined concentration range from 2 to 16 µg L-1 mercury and lead in 50 mM HCl with a detection limit of 1.5 µg L-1 and 0.5 µg L-1 for mercury and lead, respectively. In order to decrease the working range down to less than 1 µg L-1, a preconcentration step based on the use of magnetic particles modified with thiols was introduced into the protocol. Applying optimum binding conditions, the assay using screen-printed electrodes modified with gold films displayed excellent linear behaviour in the concentration range 0.1 to 0.8 µg L-1 in 50 mM HCl. The detection limit after a 120 s deposition time for mercury and lead were 0.08 µg L-1 and 0.02 µg L-1, respectively. The method has been applied to the determination of mercury and lead traces in tap water  相似文献   

17.
The system Cu(II)Cu(I)Cu(0) in acidified thiocyanate medium was investigated at carbon, mercury, and copper amalgam electrodes using cyclic voltammetry, normal, differential and reverse pulse voltammetry, double potential step chronocoulometry, and exhaustive coulometry. Reduction of Cu(II) to Cu(I) on carbon electrodes proceeds quasireversibly. At moderate concentrations of Cu(II) and SCN? the reduction of Cu(II) leads to three-dimensional precipitation of CuSCN which can be deposited at the electrode surface. At high concentration of SCN? complexation dominates over precipitation and only soluble species are formed. At mercury and copper amalgam electrodes the situation is more complicated. The three- dimensional precipitation is preceded by strong thiocyanate-induced adsorption of Cu(I) which results in formation of a mono layer at potential well-separated from those where diffusing product is formed.  相似文献   

18.
Activated carbons from watermelon shell (GACW) and walnut shell (GACN) were synthesized through chemical activation with phosphoric acid 40 % w/w, as an alternative low-cost adsorbent for the removal of lead(II) and zinc(II) ions from aqueous solutions. The yield of production was 85 and 80 % for GACW and GACN respectively. To compare the differences and similarities between the two activated carbons the following tests were performed: surface and pore width with SEM, nitrogen adsorption isotherms at ?196 °C (77 K), IR spectroscopy, TGA, point of zero charge (PZC) and Boehm titration. The GACN has 10 % more surface area (789 m2 g?1 for GACN and 710 m2 g?1 for GACW) and 13 % more pore volume than GACW. Also, GACN has a better resistance to high temperatures than GACW (the loss of mass at 900 °C was 20 % for GACN, while for GACW was 31 %). The effect of the initial concentration of lead(II) and zinc(II) ions on the adsorption process was studied in a batch process mode. To quantify the adsorption of lead and zinc adsorption isotherms of both metals in aqueous solution were performed for each carbon using analytic technique of atomic absorption. The adsorption isotherm data were better fitted by Langmuir model. Experimental results suggests that one gram of GACW adsorbs more milligrams of lead(II) and zinc(II) than one gram of GACN; it is suggest that the pore distribution is a significant variable in the adsorption process because GACW present mesopores and micropores, while GACN has only micropores. Also, the surface chemistry is an important variable in the adsorption process because GACW presents a lower pHPZC than GACN (3.05 for GACW and 4.5 for GACN) and the solution’s pH of each metal was adjusted in 4.5, for that it could be suggested that the electrostatic interactions were increased between the ion and the carbon surface.  相似文献   

19.
《Analytical letters》2012,45(6):1209-1226
Abstract

A sensitive method for the simultaneous spectrophotometric determination of Fe(II), Cu(II), Zn(II), and Mn(II) in mixtures has been developed with the aid of multivariate calibration methods, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). The method is based on the spectral differences of the analytes in their complexation reaction with 4‐(2‐pyridylazo)‐resorcinol (PAR) and the use of full spectra with wavelengths in the range of 300–600 nm. It was found that both the spectral positive and negative bands obtained against the PAR blank, are proportional to the concentration for each metal complex. The obtained linear calibration concentration ranges are 0.025–0.6, 0.05–0.8, 0.025–0.8, and 0.05–0.8 µg ml?1 for Fe(II), Cu(II), Zn(II), and Mn(II), respectively, and the LODs for the four metal ions were found to be approximately 1–3×10?2 µg ml?1. The proposed method was applied to a verification set of synthetic mixtures of these four metal ions, with models built in three different wavelength ranges, i.e., 300–450, 450–600, and 300–600 nm, corresponding to the positive, negative bands and their combinations, respectively. It was shown that the PLS model for the 300–600 nm range gave the best results (RPET=6.9% and average recovery ~100%; cf. PCR: RPET=9.5% and average Recovery ~110%). This method was also successfully applied for the determination of the four metal ions in pharmaceutical preparations, chicken feedstuff, and water samples.  相似文献   

20.
Three types of agricultural waste, citrus maxima peel (CM), passion fruit shell (PF) and sugarcane bagasse (SB), were used to produce biosorbents for removing the heavy metal ions of copper(II), cadmium(II), nickel(II) and lead(II) from a pH 5.0 solution. The properties of biosorbents were characterized using scanning electron microscopy (SEM), zeta potential analyzer, Fourier transform infrared (FTIR) spectroscopy, elemental analyzer and tests of cation exchange capacity (CEC). The result indicated that the selected biosorbents possess rich carboxyl (COOH) and hydroxyl (OH) groups to produce a complexation with the heavy metals. Moreover, the negative surface charge of the biosorbent might adsorb the metal ions through the ion exchange. All of the adsorption isotherms indicated that L-type characters represented complexation and ion exchanges that were the adsorption mechanisms of biosorbents toward heavy metals. Biosorbents with higher oxygen content might generate high adsorption capacities. The adsorption capacities of CM and PF, estimated from the fitting to the Langmuir isotherm, are similar to those reported by others regarding biosorbents.  相似文献   

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