Nanometer titanium dioxide immobilized on silica gel as sorbent for preconcentration of metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

Nanometer titanium dioxide immobilized on silica gel (immobilized nanometer TiO₂) was prepared by sol-gel method and characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorptive potential of immobilized nanometer TiO₂ for the preconcentration of trace Cd, Cr, Cu and Mn was assessed in this work. The metal ions studied can be quantitative retained at a pH range of 8-9, and 0.5 mol L⁻¹ HNO₃ was sufficient for complete elution. The adsorption capacity of immobilized nanometer TiO₂ for Cd, Cr, Cu and Mn was found to be 2.93, 2.11, 6.69 and 2.47 mg g⁻¹, respectively. A new method using a microcolumn packed with immobilized nanometer TiO₂ as sorbent has been developed for the preconcentration of trace amounts of Cd, Cr, Cu and Mn prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). The method has been successfully applied for the determination of trace elements in some environmental samples with satisfactory results.     

Simultaneous on-line preconcentration and determination of trace metals in environmental samples using a modified nanometer-sized alumina packed micro-column by flow injection combined with ICP-OES

A novel organic reagent 3-(8-quinolinylazo)-4-hydroxybenzoic acid (QAHBA) was synthesized for chemically modified nanometer-sized alumina, and it was characterized with infrared spectrum and ¹H NMR spectra. By using modified nanometer-sized alumina as micro-column packing material, a new method of flow injection (FI) on-line preconcentration coupled to ICP-OES was developed for simultaneous determination of trace metals (Ag, Pd, Au, Ga, In and Nb) in geological and environmental samples. The effects of pH, sample flow rate, sample volume, elution and interfering ions on the recovery of the analytes have been investigated. Under the optimized operating conditions, the adsorption capacity of the modified nanometer-sized alumina for Ag, Pd, Au, Ga, In and Nb were found to be 5.1, 7.6, 17.7, 15.6, 8.1 and 12.3 mg g⁻¹, respectively. With 4 min preconcentration time and 24 s elution time, the enrichment factor was 10 and the sample frequency was 10 h⁻¹. The detection limits of this method for Ag, Pd, Au, Ga, In and Nb were 0.12, 0.44, 0.27, 0.19, 0.54 and 0.18 μg l⁻¹, respectively, while the R.S.D.s were 1.6, 2.3, 4.5, 1.6, 1.9 and 1.7% (n = 7, c = 50 ng ml⁻¹), respectively. The proposed method has been applied to the determination of these trace metals in geological-certified reference materials and natural water samples with satisfactory results.     

On-site preconcentration and trace metal ions determination in the Okavango Delta water system, Botswana

Microcolumns containing 8-hydroxyquinoline azo-immobilized on controlled pore glass were incorporated in a field sampler for on-site collection, isolation and preconcentration of trace metal ions in waters of the Okavango Delta, Botswana. Sequestered trace metal ions were recovered by elution with 0.5 ml of 1.5 M nitric acid, and determined by graphite furnace atomic absorption spectrometry (GFAAS). This sampling and enrichment method minimizes sample contamination, and collection of large volumes of water samples for transporting, over long distances, to analytical laboratories is avoided.Data reported comprise one of the initial surveys on trace metal ion concentrations in waters of the Okavango Delta, Botswana. In waters with more efficient mixing, dissolved metal ion concentrations found were generally low with slightly elevated levels of manganese (7-19 μg l⁻¹), zinc (2.7-4.8 μg l⁻¹), nickel (0.2-2.5 μg l⁻¹) and copper (0.3-2.1 μg l⁻¹). For each trace metal ion, concentration levels seem to reflect zones of varying water conveyance, and show no obvious temporal and spatial variations apart from a slight increment from the inlet in the upper Delta to the outlets in the lower Delta.     

Chemically-modified activated carbon with ethylenediamine for selective solid-phase extraction and preconcentration of metal ions

A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L⁻¹ HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n = 8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.     

Determination of trace metals by ICP-OES in plant materials after preconcentration of 1,10-phenanthroline complexes on activated carbon

In this work, 1,10-phenanthroline was used as a complexing agent for the separation and preconcentration of Cd(II), Co(II), Ni(II), Cu(II) and Pb(II) on activated carbon. The metals were adsorbed on activated carbon by two methods: static (1) and dynamic (2). The optimal condition for separation and quantitative preconcentration of metal ions with activated carbon for the proposed methods was for (1) in the static methods in the pH range 7-9. The desorption was found quantitative with 8 mol dm⁻³ HNO₃ for Cd(II) (92.6%), Co(II) (95.6%), Pb(II) (91.0%), and with 3 mol dm⁻³ HNO₃ for Cd(II) (95.4%), Pb(II) (100.2%). The preconcentration factor was 100 with R.S.D. values between 1.0 and 2.9%. For (2), the dynamic method (SPE), the pH range for the quantitative sorption was 7-9. The desorption was found quantitative with 8 mol dm⁻³ HNO₃ for Cd(II) (100.6%), Pb(II) (94.4%), and reasonably high recovery for Co(II) (83%), Cu(II) (88%). The optimum flow rate of metal ions solution for quantitative sorption of metals with 1,10-phenanthroline was 1-2 cm³ min⁻¹ whereas for desorption it was 1 cm³ min⁻¹. The preconcentration factor was 50 for all the ions of the metals with R.S.D. values between 2.9 and 9.8%.The samples of the activated carbon with the adsorbed trace metals can be determined by ICP-OES after mineralization by means of a high-pressure microwave mineralizer. The proposed method provides recovery for Cd (100.8%), Co (97.2%), Cu (94.6%), Ni (99.6%) and Pb (100.0%) with R.S.D. values between 1.2 and 3.2%.The preconcentration procedure showed a linear calibration curve within the concentration range 0.1-1.5 μg cm⁻³. The limits of detection values (defined as “blank + 3s” where s is standard deviation of the blank determination) are 5.8, 70.8, 6.7, 24.6, and 10.8 μg dm⁻³ for Cd(II), Pb(II), Co(II), Ni(II) and Cu(II), respectively, and corresponding limit of quantification (blank + 10s) values were 13.5, 151.3, 20.0, 58.9 and 33.2 μg dm⁻³, respectively.As a result, these simple methods were applied for the determination of the above-mentioned metals in reference materials and in samples of plant material.     

Sulphoxine immobilized onto chitosan microspheres by spray drying: application for metal ions preconcentration by flow injection analysis

A new chelating resin based on chitosan biopolymer modified with 5-sulphonic acid 8-hydroxyquinoline using the spray drying technique for immobilization is proposed. The chelating resin was characterized by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) and surface area by nitrogen sorption. The efficiency of the chelating resin was evaluated by the preconcentration of metal ions Cu(II) and Cd(II) present in aqueous samples in trace amounts. The metal ions were previously enriched in a minicolumn and the concentrations of the analytes were determined on-line by flame atomic absorption spectrometry (FAAS). The maximum retention for Cu(II) occurred in the pH range 8-10, and for Cd(II) at pH 7. The optimum flow rate for sorption was found to be 7.2 ml min⁻¹ for the preconcentration of the metal ions. The analytes gave relative standard deviations (R.S.D.) of 0.7 and 0.6% for solutions containing 20 μg l⁻¹ of Cu(II) and 15 μg l⁻¹ of Cd (II), respectively (n=7). The enrichment factors for Cu(II) and Cd (II) were 19.1 and 13.9, respectively, and the limits of detection (LOD) were 0.2 μg l⁻¹ for Cd(II) and 0.3 μg l⁻¹ for Cu(II), using a preconcentration time of 90 s (n=11). The accuracy of the proposed method was evaluated by the metal ion recovery technique, in the analysis of potable water and water from a lake, with recoveries being between 97.2 and 107.3%.     

Synthesis of amidinothioureido-silica gel and its application to flame atomic absorption spectrometric determination of silver, gold and palladium with on-line preconcentration and separation

A simple and highly selective flow injection (FI) on-line preconcentration and separation flame atomic absorption spectrometric (FAAS) method was developed for the determinations of trace amounts of silver, gold and palladium. The selective preconcentration of the noble metals was achieved in a wide range of sample acidity (0.1-6 M HNO₃ or HCl) on a microcolumn packed with amidinothioureido-silica gel (ATuSG). The analytes retained on the column were effectively eluted with 5.0% thiourea solution. The analytical procedure was optimized for sample acidity, elution, interferences, flow rate of sampling and eluting, and concentration of sample. Common co-existing cations and anions did not interfere with the preconcentration and determination of the three metals. At a sample loading flow rate of 4.5 ml min⁻¹ with 60 s preconcentration, detection limits (3σ) of 1.1 ng ml⁻¹ Ag, 13 ng ml⁻¹ Au and 17 ng ml⁻¹ Pd were obtained. The precisions (R.S.D., n=11) were 1.2% for Ag, 1.2% for Au and 1.7% for Pd, respectively. The detection limits can be further improved by increasing sample volume. The analytical results obtained by the proposed method for a number of standard reference materials were in good agreement with the certified values.     

Chemically modified attapulgite with asparagine for selective solid-phase extraction and preconcentration of Fe(III) from environmental samples

A new method that utilizes asparagine modified attapulgite as a solid phase extractant has been developed for preconcentration of trace Fe(III) prior to the measurement by inductively coupled plasma optical emission spectrometry. Characterization of the surface modification was performed on the basis of Fourier transform infrared spectra. The separation/preconcentration conditions of the analyte were investigated, including the pH value, the shaking time, the sample ?ow rate and volume, the elution condition and the interfering ions. At pH 4, the new adsorbent had relatively high capacity and enrichment factor compared to other methods reported so far. The adsorbed Fe(III) was quantitatively eluted by 2 mL of 0.5 mol L⁻¹ HCl. Common coexisting ions did not interfere with the separation. The detection limit of the method was 0.19 μg L⁻¹. The relative standard deviation was 3.4% (n = 8) which indicated that the method had good precision for the analysis of trace Fe(III) in solution samples. The method was validated using two certified reference materials and has been applied for the determination of trace Fe(III) in biological and natural water samples with satisfactory results.     

Micro-column preconcentration/separation using thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO2 as packing materials on-line coupled to inductively coupled plasma optical emission spectrometry for the determination of trace heavy metals in environmental water samples

A novel adsorbent of thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO₂ was prepared and was used as a packing material for flow injection (FI) micro-column (20 mm × 4.0 mm i.d.) separation/preconcentration on-line coupled to inductively coupled plasma optical emission spectrometry (ICP-OES) simultaneous determination of trace metals (V, Cu, Pb, Cr) in environmental water samples. The experimental conditions for modified mesoporous TiO₂ packed micro-column separation/preconcentration of the target metals were optimized and the interference of commonly coexisting ions was examined. The adsorption capacities of thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO₂ for V, Cu, Pb and Cr were found to be 14.0, 11.7, 17.7 and 14.5 mg g^− 1, respectively. The detection limits of the method were 0.09, 0.23, 0.50 and 0.15 µg L^− 1 for V, Cu, Pb and Cr, respectively, with a preconcentration factor of 20. The precision of this method were 1.7% (V), 3.9% (Cu), 4.6% (Pb) and 2.9% (Cr) (n = 7, C = 5 µg L^− 1), respectively. The developed method was applied to the determination of trace heavy metals in real samples and the recoveries for spiked samples were found to be in the range of 88.7-107.1%. For validation, a certified reference material of GSBZ50009-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values.     

Chitosan modified ordered mesoporous silica as micro-column packing materials for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples

A novel adsorbent of chitosan chemically modified ordered mesoporous silica was synthesized and employed as a solid phase extraction (SPE) material for flow injection (FI) micro-column preconcentration on-line coupled with inductively coupled plasma optical emission spectrometry (ICP-OES) determination of trace heavy metals V, Cu, Pb, Cd and Hg in environmental water samples. The factors affecting separation and preconcentration of target heavy metals such as pH, sample flow rate and volume, eluent concentration and volume, interfering ions were investigated. Under the optimized experimental conditions, an enrichment factor of 20 and sampling frequency of 10 h⁻¹ were obtained. The detection limits of the method for V, Cu, Pb, Cd and Hg were 0.33, 0.30, 0.96, 0.05 and 0.93 ng mL⁻¹, and the relative standard deviations (RSDs) were 2.8%, 6.7%, 1.8%, 4.0% and 5.3% (n = 7, C = 10 ng mL⁻¹), respectively. The adsorption capacities of chitosan modified ordered mesoporous silica for V, Cu, Pb, Cd, and Hg were found to be 16.3, 21.7, 22.9, 12.2 and 13.5 mg g⁻¹, respectively. In order to validate the developed method, a certified reference material of GSBZ50009-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values. The proposed method has also been applied to the determination of trace heavy metals in natural water samples with satisfactory results.     

Silica gel modified with 1-(2-aminoethyl)-3-phenylurea for selective solid-phase extraction and preconcentration of Sc(III) from environmental samples

A new method that utilizes 1-(2-aminoethyl)-3-phenylurea-modified silica gel as a solid-phase extractant has been developed for preconcentration of trace Sc(III) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace level of Sc(III) were optimized using batch and column procedures in detail. The optimum pH value for the separation of Sc(III) on the new sorbent was 4 and complete elution of Sc(III) from the sorbent surface was carried out using 1.0 mL of 0.1 mol L⁻¹ HCl. Common coexisting ions did not interfere with the separation and determination of the analyte. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 32.5 mg g⁻¹ while the time of 95% adsorption was less than 2 min. The detection limit of present method was found to be 0.091 μg g⁻¹, and the relative standard deviation (RSD) was lower than 3.0% (n = 8). The method was successfully applied for the preconcentration of trace Sc(III) in the environmental samples with satisfactory results.     

ICP-AES determination of trace elements after preconcentrated with p-dimethylaminobenzaldehyde-modified nanometer SiO2 from sample solution

A new method that utilizes p-dimethylaminobenzaldehyde-modified nanometer SiO₂ (SiO₂-p-DMABD) as a solid phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The preconcentration conditions of analytes were investigated, including the pH value, the shaking time, the mass of sorbent, the sample flow rate and volume, the elution condition and the interfering ions. The adsorption capacity of nanometer SiO₂-p-DMABD was found to be (mg g^− 1) Cr(III): 6.2, Cu(II): 18.6, Fe(III): 4.7 and Pb(II): 6.0 at pH 4. The adsorbed metals were quantitatively eluted with 4 mL of 1.0 mol L^− 1 HCl. According to the definition of IUPAC, the detection limits (3σ) of this method for Cr(III), Cu(II), Fe(III) and Pb(II) were 0.79, 1.27, 0.40 and 1.79 ng mL^− 1, respectively. The proposed method achieved satisfied results when it was applied to the determination of trace Cr(III), Cu(II), Fe(III) and Pb(II) in biological and water samples.     

On-line preconcentration and separation of Co, Ni and Cd via capillary microextraction on ordered mesoporous alumina coating and determination by inductively plasma mass spectrometry (ICP-MS)

In this paper, an ordered mesoporous alumina coating was prepared and applied to capillary microextraction (CME) of trace Co, Ni and Cd for the first time. The coated capillary was used for on-line coupling CME with inductively plasma mass spectrometry (ICP-MS) for the determination of trace metals of Co, Ni and Cd. The porous structure of Al₂O₃ coating was examined by SEM and TEM. The effects of the extraction parameters including pH, sample flow rate and volume, elution solution and interfering ions on the recovery of analytes have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.33, 1.5 and 1.4 ng L⁻¹ for Co, Ni and Cd, respectively, with a preconcentration factor of 10 times. The precisions for all investigated elements were 2.7, 4.1 and 2.5% (c = 0.05 ng L⁻¹, n = 7), for Co, Ni and Cd, respectively, and the sample frequency was 8 h⁻¹.The proposed method was successfully applied for the analysis of trace metals in water, rice and urine samples with the recovery of 94-105%. In order to validate the proposed method, two certified reference materials of GBW 0913 human urine and NIES No.10-b rice flour were analyzed, and the determination values are in good agreement with the certified values. The ordered mesoporous Al₂O₃ coated capillary can be used more than 20 times without decreasing the extraction efficiency.     

On-line sorptive preconcentration platform incorporating a readily exchangeable Oasis HLB extraction micro-cartridge for trace cadmium and lead determination by flow injection-flame atomic absorption spectrometry

A simple, sensitive and inexpensive flow injection solid phase extraction (SPE) system was developed for automatic determination of trace level concentrations of metals. The potentials of this novel scheme, coupled to flame atomic absorption spectrometry (FAAS), were demonstrated for trace cadmium and lead determination in environmental water samples. The method was based on on-line chelate complex formation of target species with ammonium diethyldithiophosphate (DDTP), retention onto the surface of reversed-phase poly(divinylbenzene-N-vinylpyrrolidone) co-polymeric beads (Oasis HLB) and elution with methanol prior to atomization. A special PVC adapter was designed for easy and rapid replacement of the commercially available SPE cartridge. All main chemical and hydrodynamic parameters affecting the complex formation, sorption and elution of the analyte were optimized thoroughly. Moreover, the effect of potential interfering species occurring in environmental samples was also explored.For 90 s preconcentration time, enhancement factors of 155 and 180, detection limits (3s) of 0.09 μg L^− 1 and 0.9 μg L^− 1 and relative standard deviations (R.S.D.) of 2.9% (at 4.0 μg L^− 1) and 2.6% (at 20.0 μg L^− 1) were obtained for cadmium and lead, respectively, with a sample throughput of 24 h^− 1. The measurement trueness of the developed method was evaluated by analyzing a certified reference material and spiked environmental water samples. The proposed method is well suited to detect the target elements at concentration levels below the maximum allowed concentrations endorsed by the European Framework Directive (2008/105/EC) in inland and coastal waters.     

1-(2-Formamidoethyl)-3-phenylurea functionalized activated carbon for selective solid-phase extraction and preconcentration of metal ions

A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L⁻¹ HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g⁻¹ for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL⁻¹ for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n = 8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.     

Synthesis of salicylaldehyde-modified mesoporous silica and its application as a new sorbent for separation, preconcentration and determination of uranium by inductively coupled plasma atomic emission spectrometry

A new functionalized mesoporous silica (MCM-41) using salicylaldehyde was utilized for the separation, preconcentration and determination of uranium in natural water by inductively coupled plasma atomic emission spectrometry (ICP-AES).Experimental conditions for effective adsorption of trace levels of U(VI) were optimized. The preconcentration factor was 100 (1.0 mL of elution for a 100 mL sample volume). The analytical curve was linear in the range 2-1000 μg L⁻¹ and the detection limit was 0.5 ng mL⁻¹. The relative standard deviation (R.S.D.) under optimum conditions was 2.5% (n = 10). Common coexisting ions did not interfere with the separation and determination of uranium at pH 5. The sorbent exhibited excellent stability and its sorption capacity under optimum conditions has been found to be 10 mg of uranium per gram of sorbent. The method was applied for the recovery and determination of uranium in different water samples.     

Ultrasensitive and simultaneous detection of heavy metal ions based on three-dimensional graphene-carbon nanotubes hybrid electrode materials

A green and facile method was developed to prepare a novel hybrid nanocomposite that consisted of one-dimensional multi-walled carbon nanotubes (MWCNTs) and two-dimensional graphene oxide (GO) sheets. The as-prepared three-dimensional GO–MWCNTs hybrid nanocomposites exhibit excellent water-solubility owing to the high hydrophilicity of GO components; meanwhile, a certain amount of MWCNTs loaded on the surface of GO sheets through π–π interaction seem to be “dissolved” in water. Moreover, the graphene(G)-MWCNTs nanocomposites with excellent conductivity were obtained conveniently by the direct electrochemical reduction of GO–MWCNTs nanocomposites. Seeing that there is a good synergistic effect between MWCNTs and graphene components in enhancing preconcentration efficiency of metal ions and accelerating electron transfer rate at G-MWCNTs/electrolyte interface, the G-MWCNTs nanocomposites possess fast, simultaneous and sensitive detection performance for trace amounts of heavy metal ions. The electrochemical results demonstrate that the G-MWCNTs nanocomposites can act as a kind of practical sensing material to simultaneously determine Pb²⁺ and Cd²⁺ ions in terms of anodic stripping voltammetry (ASV). The linear calibration plots for Pb²⁺ and Cd²⁺ ranged from 0.5 μg L⁻¹ to 30 μg L⁻¹. The detection limits were determined to be 0.2 μg L⁻¹ (S/N = 3) for Pb²⁺ and 0.1 μg L⁻¹ (S/N = 3) for Cd²⁺ in the case of a deposition time of 180 s. It is worth mentioning that the G-MWCNTs modified electrodes were successfully applied to the simultaneous detection of Cd²⁺ and Pb²⁺ ions in real electroplating effluent samples containing lots of surface active impurities, showing a good application prospect in the determination of trace amounts of heavy metals.     

Simultaneous preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using a chelating calix[4]arene anchored chloromethylated polystyrene solid phase

A new chelating polymeric sorbent is developed using Merrifield chloromethylated resin anchored with calix[4]arene-o-vanillinsemicarbazone for simultaneous separation and solid phase extractive preconcentration of U(VI) and Th(IV). The “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone was covalently linked to Merrifield resin and characterized by FT-IR and elemental analysis. The synthesized chelating polymeric sorbent shows superior binding affinity towards U(VI) and Th(IV) under selective pH conditions. Various physico-chemical parameters that influence the quantitative extraction of metal ions were optimized. The optimum pH range and flow rates for U(VI) and Th(IV) were 6.0-7.0 and 1.0-4.0 ml min⁻¹ and 3.5-4.5 and 1.5-4.0 ml min⁻¹, respectively. The total sorption capacity found for U(VI) and Th(IV) was 48734 and 41175 μg g⁻¹, respectively. Interference studies carried out in the presence of diverse ions and electrolyte species showed quantitative analyte recovery (98-98.5%) with lower limits of detection, 6.14 and 4.29 μg l⁻¹ and high preconcentration factors, 143 and 153 for U(VI) and Th(IV), respectively. The uptake and stripping of these metal ions on the resin were fast, indicating a better accessibility of the metal ions towards the chelating sites. The analytical applicability of the synthesized polymeric sorbent was tested with some synthetic mixtures for the separation of U(VI) and Th(IV) from each other and also from La(III), Cu(II) and Pb(II) by varying the pH and sequential acidic elution. The validity of the proposed method was checked by analyzing these metal ions in natural water samples, monazite sand and standard geological materials.     

Solid-phase extraction system for Pb (II) ions enrichment based on multiwall carbon nanotubes coupled on-line to flame atomic absorption spectrometry

The present paper proposes the application of multiwall carbon nanotubes (MWCNTs) as a solid sorbent for lead preconcentration using a flow system coupled to flame atomic absorption spectrometry. The method comprises the preconcentration of Pb (II) ions at a buffered solution (pH 4.7) onto 30 mg of MWCNTs previously oxidized with concentrated HNO₃. The elution step is carried out with 1.0 mol L⁻¹ HNO₃. The effect of the experimental parameters, including sample pH, sampling flow rate, buffer and eluent concentrations were investigated by means of a 2⁴ full factorial design, while for the final optimization a Doehlert design was employed. Under the best experimental conditions the preconcentration system provided detection and quantification limits of 2.6 and 8.6 μg L⁻¹, respectively. A wide linear range varying from 8.6 up to 775 μg L⁻¹ (r > 0.999) and the respective precision (relative standard deviation) of 7.7 and 1.4% for the 15 and 200 μg L⁻¹ levels were obtained. The characteristics obtained for the performance of the flow preconcentration system were a preconcentration factor of 44.2, preconcentration efficiency of 11 min⁻¹, consumptive index of 0.45 mL and sampling frequency estimated as 14 h⁻¹. Preconcentration studies of Pb (II) ions in the presence of the majority foreign ions tested did not show interference, attesting the good performance of MWCNTs. The accuracy of the method was assessed from analysis of water samples (tap, mineral, physiological serum and synthetic seawater) and common medicinal herbs submitted to the acid decomposition (garlic and Ginkgo Biloba). The satisfactory recovery values obtained without using analyte addition method confirms the feasibility of this method for Pb (II) ions determination in different type of samples.     

Silica-coated magnetic nanoparticles modified with γ-mercaptopropyltrimethoxysilane for fast and selective solid phase extraction of trace amounts of Cd,Cu, Hg,and Pb in environmental and biological samples prior to their determination by inductively coupled plasma mass spectrometry

We report here the synthesis of a new sorbent comprising silica-coated magnetic nanoparticles (SCMNPs) modified with γ-mercaptopropyltrimethoxysilane (γ-MPTMS) for solid phase extraction of trace amounts of Cd, Cu, Hg, and Pb from biological and environmental samples. The prepared nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, and static adsorption-desorption experiments. These magnetic nanoparticles carrying the target metals could be easily separated from the aqueous solution simply by applying an external magnetic field; no filtration or centrifugation was necessary. Using this novel magnetic material, we have developed an efficient and cost-effective two-step method for detecting trace amounts of Cd, Cu, Hg, and Pb in environmental and biological samples. The first step of the method is a separation/preconcentration step, in which metals are adsorbed onto γ-MPTMS-SCMNPs. In the second step, inductively coupled plasma mass spectrometry is used to study the adsorbed metals. The effects of pH, sample volume, eluent, and interfering ions have been investigated. Under the optimized conditions, the limits of detection for Cd, Cu, Hg, and Pb were as low as 24, 92, 107, and 56 pg L^− 1, respectively. Relative standard deviations (RSDs, C = 2 ng L^− 1, n = 7) were 6.7%, 9.6%, 8.3%, and 3.7%, respectively.The proposed method has been validated using three certified reference materials, and it has been applied successfully in the determination of trace metals in biological and environmental samples.