Chemically modified multiwalled carbon nanotubes as efficient and selective sorbent for separation and preconcentration of trace amount of Co(II), Cd(II), Pb(II), and Pd(II)

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized by glutaric dihydrazide (GDH) and characterized with FT-IR technique. This new sorbent was used for enrichment and preconcentration of Co(II), Cd(II), Pb(II), and Pd(II) ions. The adsorption was achieved quantitatively on MWCNTs at pH 4.0, and then the retained metal ions on the adsorbent were eluted with 1.5 mol L^?1 HNO₃. The effects of analytical parameters including pH of the solution, eluent type, sample volume, and matrix ions were investigated for optimization of the presented procedure. The adsorption capacity of the adsorbent at optimum conditions was found to be 33.6, 29.2, 22.1, and 36.0 mg g^?1 for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The LOD values of the method were 0.16, 0.19, 0.17, and 0.12 ng mL^?1 (3Sb, n = 10) for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The RSDs values of the method were 0.75, 0.85, 1.16, and 1.30 ng mL^?1 for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The method was applied for the determination of analytes in soil, well water, and wastewater samples with satisfactory results.     

Novel modified carbon nanotubes as a selective sorbent for preconcentration and determination of trace copper ions in fruit samples

In this work, multiwalled carbon nanotubes were reacted with N‐[3‐(triet‐hoxysilyl)propyl]isonicotinamide to prepare pyridine‐functionalized carbon nanotubes. This novel sorbent was characterized by infrared spectroscopy, thermal and elemental analysis, and scanning electron microscopy. Functionalized carbon nanotubes were applied for the preconcentration and determination of copper ions using flame atomic absorption spectrometry. Various parameters such as sample pH, flow rate, eluent type and concentration, and its volume were optimized. Under optimal experimental conditions, the limit of detection, the relative standard deviation, and the recovery of the method were 0.65 ng/mL, 3.2% and 99.4%, respectively. After validating the method using standard reference materials, the new sorbent was applied for the extraction and determination of trace copper(II) ions in fruit samples.     

Extraction and preconcentration of ultra trace amounts of beryllium from aqueous samples by nanometer mesoporous silica functionalized by 2,4-dihydroxybenzaldehyde prior to ICP OES determination

A new functionalized nanometer mesoporous silica (MCM-41) using 2,4-dihydroxybenzaldehyde (4-OHsal) was applied as an effective sorbent for solid phase extraction (SPE) of beryllium ions from aqueous solution followed by inductively coupled plasma optical emission spectrometric detection (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ion were investigated in batch method. In order to perform the batch mode of SPE, known amount of sorbent was added to a test tube containing sample solution buffered at pH 7.2. After manual shaking and centrifugation the aqueous phase was decanted and beryllium was desorbed by adding 1.0 mL of 1.0 mol L^?1 HNO₃ to the sedimented sorbent. The sorbent was separated by centrifugation and the concentration of beryllium in the supernatant was determined by ICP OES. The maximum sorption capacity of the modified MCM-41 was found to be 34 mg g^?1. The sorbent exhibited good stability, reusability and fast rate of equilibrium for sorption/desorption of beryllium ions. The present method was used for preconcentration and determination of beryllium for water samples. Under optimal conditions, the limit of detection (LOD) obtained was 0.3 ng L^?1. The accuracy of the procedure was evaluated by analysis of the certified reference material (NIST 1640).     

Multiwalled carbon nanotubes modified with 2-aminobenzothiazole modified for uniquely selective solid-phase extraction and determination of Pb(II) ion in water samples

A solid phase extraction method is presented for the selective preconcentration and/or separation of trace Pb(II) on multiwalled carbon nanotubes modified with 2-aminobenzothiazole. Inductively coupled plasma optical emission spectrometry was used for detection. The effects of pH, shaking time, sample flow rate and volume, elution condition and interfering ions were examined using batch and column procedures. An enrichment factor of 100 was accomplished. Common other ions do not interfere in both the separation and determination. The maximum adsorption capacity of the sorbent at optimum conditions is 60.3?mg?g^?1 of Pb(II), the detection limit (3??) is 0.27?ng?mL^?1, and the relative standard deviation is 1.6% (n?=?8). The method was validated using a certified reference material, and has been applied to the determination of trace Pb(II) in water samples with satisfactory results.

Magnetite-doped eggshell membrane as a magnetic sorbent for extraction of aluminum(III) ions prior to their fluorometric determination

We have explored the feasibility of using a magnetite-doped eggshell membrane as a magnetic solid phase extraction sorbent for the separation of aluminum ion from aqueous solutions. The sorbent was characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. A fast, simple and non-expensive method was then developed for the determination of trace quantities of Al(III) in water and food samples by combining magnetic solid phase extraction with fluorometric quantitation via its highly fluorescent complex with 8-hydroxyquinoline. The effects of pH value, amount of sorbent, sample volume, elution conditions and interfering ions on extraction were optimized. Under optimum conditions, the calibration graph extends from 0.5 to 65.0 μg L^?1, the limit of detection is 0.2 μg L^?1, and the enrichment factor is 84. The method was validated by the successful analysis of a standard reference material (NIST SRM 1549; nonfat milk powder) and applied to the determination of Al(III) in several waters, black tea, tomato paste and cocoa powder samples. Figure

Synthesis and application of magnetite-doped eggshell membrane for the separation of aluminum(III) ions from aqueous solutions is shown. After extraction for 5 min, the sorbent was gathered under an external magnetic field and the clear supernatant was directly decanted. The enriched analyte was then eluted from the sorbent prior to determination.     

Solid phase extraction and flame atomic absorption spectrometric determination of trace amounts of cadmium and lead in water and biological samples using modified TiO2 nanoparticles

A solid phase extraction procedure for the separation and preconcentration of trace amounts of Cd(II) and Pb(II) using the alizarin red S modified TiO₂ nanoparticles prior to their determination by flame atomic absorption spectrometry has been proposed. The influences of some analytical parameters such as pH, flow rates of sample and eluent, type and concentration of the eluent, and interfering ions on the recovery of Cd(II) and Pb(II) by the sorbent were investigated. The analytes were quantitatively sorbed from the aqueous solution at pH 5.5 onto a microcolumn packed with the sorbent and recovered with 2.0?mL of 1.5?mol?L^?1 hydrochloric acid. Under the optimum experimental conditions, the detection limits for Cd(II) and Pb(II) were 0.11 and 0.30?ng?mL^?1 and the relative standard deviations for ten replicate measurements of 5.0 and 50.0?ng?mL^?1 of Cd(II) and Pb(II) were 2.1 and 1.9%, respectively. A sample volume of 200?mL resulted in a preconcentration factor of 100. The method was successfully applied to the determination of Cd(II) and Pb(II) in water and biological samples, and accuracy was examined by the recovery experiments, independent analysis using electrothermal atomic absorption spectrometry, and analysis of a water standard reference material (SRM 1643e).     

Triazine-modified magnetite nanoparticles as a novel sorbent for preconcentration of lead and cadmium ions

We report on a new sorbent for preconcentration of cadmium and lead ions that is based on triazine-functionalized magnetite nanoparticles that were prepared by direct silylation of magnetic nanoparticles with 3-aminopropyltriethoxysilane-2,4-bis(3,5-dimethylpyrazol)-triazine. The sorbent was characterized by IR spectroscopy, X-ray powder diffraction, scanning electron microscopy, thermal and elemental analysis. The sorbent was applied to the preconcentration of lead and cadmium ions which then were quantified by FAAS. The effects of sample pH value, extraction time, of type, concentration and volume of eluent, and of elution time were optimized. The limits of detection are 0.7 ng mL⁻¹ for Pb(II) ion and 0.01 ng mL⁻¹ for Cd(II). The effects of potentially interfering ions often found in real samples on the recovery in the determination of cadmium and lead ions in real samples were also investigated. The accuracy of the method was confirmed by analyzing the certified reference materials NIST 1571 (orchard leaves) and NIST 1572 (citrus leaves). Finally, the method was successfully applied to the determination of cadmium and lead ions in some fruit samples.

We report on a new sorbent for preconcentration of cadmium and lead ions that is based on triazine-functionalized magnetite nanoparticles. After optimization of the preconcentration step the method was successfully applied to the determination of cadmium and lead ions in some fruit samples

     

Solid-phase extraction using multiwalled carbon nanotubes and quinalizarin for preconcentration and determination of trace amounts of some heavy metals in food,water and environmental samples

A solid phase extraction procedure has been developed using multiwalled carbon nanotubes (MWCNTs) as a solid sorbent and quinalizarin [1,2,5,8-tetrahydroxyanthracene-9,10-dione] as a chelating agent for separation and preconcentration of trace amounts of some heavy metal ions, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) before their determination by flame atomic absorption spectroscopy (FAAS). The influences of the analytical parameters, including pH, amounts of quinalizarin and adsorbent, sample volume, elution conditions such as volume and concentration of eluent, flow rates of solution and matrix ions, were investigated for the optimum recoveries of the analyte ions. No interference effects were observed from the foreign metal ions. The preconcentration factor was 100. The detection limit (LOD) for the investigated metals at the optimal conditions were observed in the range of 0.30–0.65 μg L^?1. The relative standard deviation (RSDs), and the recoveries of standard addition for this method were lower than 5.0% and 96–102%, respectively. The new procedure was successfully applied to the determination of analytes in food, water and environmental samples with satisfactory results.     

Preparation and evaluation of an ion imprinted sol–gel material for selective solid-phase extraction of Ni(II)

An ion imprinted silica sorbent was prepared using a sol–gel process for selective extraction of Ni(II) ions from water samples. Bis(dibenzoylmethanto)nickel(II) complex was used as template; phenyltrimethoxysilane and 3-aminopropyltriethoxysilane as functional monomers and tetraethylorthosilicate as reticulating agent. The material was packed in solid-phase extraction (SPE) column. The effect of sampling volume, elution conditions, sample pH and sample flow rate on the extraction of Ni ions from water samples were studied. The relative selectivity coefficients of imprinted sorbent for Ni(II)/Co(II), Ni(II)/Cu(II) and Ni(II)/Cd(II) were 23.7, 30.3 and 24.4, times greater than non-imprinted sorbent, respectively. The relative standard deviation of the eight replicate determinations of Ni(II) was 4.2%. The detection limit was 0.9 µg L^?1 using flame atomic absorption spectrometry. The developed method was successfully applied to the determination of trace nickel in water samples.     

Use of pyrocatechol violet modified sodium dodecyl sulfate coated on alumina for separation and preconcentration of uranium(VI)

A sensitive and selective solid phase extraction procedure for the determination of trace of uranium(VI) has been developed. An alumina-sodium dodecyl sulfate coated on with pyrocatechol violet was used for preconcentration and determination of uranyl ions by spectrophotometry method using Arsenazo III reagent. Sorbed ions were quantitatively eluted using 5 mL of 0.25 mol L⁻¹ HNO₃. The effects of parameters such as pH, amount of alumina, amount of ligand, flow rate, type and concentration of elution agent were examined. The capacity of the sorbent for U(VI) was found to be 0.92 mmol g⁻¹. The relative standard deviation was 1.28% for 10 replicate determinations of U(VI) ion in a solution with a concentration of 1.0 μg mL⁻¹. The practical applicability of the developed sorbent was examined using synthetic and real samples such as standard reference material 2709 (San Joaquin Soil) and 2711 (Montana Soil).     

Selective solid phase extraction and preconcentration of trace mercury(II) with poly-allylthiourea packed columns

A new method for selective solid-phase extraction and preconcentration of trace mercury(II) from aqueous solution was developed by using poly-allylthiourea as a new extractant. The procedure is based on the retention of analyte in the form of thiourea complex on a mini column of polymer resin. The effects of pH, eluent type, eluent concentration, sample volume, sample flow rate, and foreign ions on the recovery of the analyte were investigated using model solutions. At optimal pH value, the extraction capacity of the new sorbent was 1.13 mmol g^?1. The adsorption behavior of mercury(II) on the sorbent can be described by a Langmuir adsorption isotherm equation. The method was validated by analyzing a certified reference material with the results being in agreement with those quoted by manufacturers. The method was applied to the determination of trace inorganic mercury(II) in natural water samples and vegetables with satisfactory results.     

Preconcentration of trace amounts of cobalt (II) ions in water and agricultural products samples using of 5-(4-dimethylaminobenzylidene) rhodanin modified SBA-15 sorbent prior to FAAS determination

In the present study, the ?5-(4-dimethylaminobenzylidene)rhodanin-modified SBA-15? was applied as stable solid sorbent for the separation and preconcentration of trace amounts of cobalt ions in aqueous solution. SBA-15 was modified by ?5-(4-dimethylaminobenzylidene)rhodanin reagent. The sorption of Co²⁺ ions was done onto modified sorbent in the pH range of 6.8–7.9 and desorption occurred in 5.0 mL of 3.0 mol L^?1 HNO₃. The results exhibit a linear dynamic range from 0.01 to 6.0 mg L^?1 for cobalt. Intra-day (repeatability) and inter-day (reproducibility) for 10 replicated determination of 0.06 mg L^?1 of cobalt was ±1.82% and ?±1.97%?. Detection limit was 4.2 µg L^?1 (3S_b, n = 5) and preconcentration factor was 80. The effects of the experimental parameters, including the sample pH, flow rates of sample and eluent solution, eluent type and interference ions were studied for the preconcentration of Co²⁺. The proposed method was applied for the determination of cobalt in standard samples, water samples and agricultural products.     

Improvements in the electrochemical generation of arsine at gold electrodes as a sample introduction strategy for arsenic determination in well-water samples by atomic absorption spectrometry

The development and evaluation of a cathode consisting of a gold electrode covered by a polyaniline film, PANI/Au modified electrode, for electrochemical generation of arsine is described. The efficiency of arsine production using the new electrode was ascertained by comparison with corresponding hydride generation atomic absorption spectroscopy determinations of arsenic (As) in aqueous standards. The PANI/Au modified electrodes provide better sensitivity, accuracy and precision than the pure Au cathodes. The PANI/Au cathodes were prepared by controlled electrodeposition cycles of polyaniline films on top of Au electrodes. Cathodes obtained after 10 electrodeposition cycles showed the best performance, while the ones obtained after five voltammetry cycles produced films too thin and those obtained after 20 voltammetry cycles produced films too thick for the purpose of this work. Under optimised conditions, the As limit of detection in aqueous solutions, according to the (3σ) criterion, was 2.48 µg L^?1. For accuracy determination, the modified electrode was applied to quantification of As(III) in acidified aqueous solutions of the certified standard reference material, NIST SRM 1643d, and in well-water samples containing possible interfering ions. Application of the Student’s t-test showed no significant difference between the expected and obtained results of the NIST SRM standard analysis at the 95% confidence level. Values for six replicate determinations of As(III) in the well-water samples showed close agreement with values obtained by analyses using hydride generation atomic absorption. Recoveries were in the range of 95–105% at test for acceptable accuracy in the analysis of real samples.     

Solid-phase extraction with C30 bonded silica for analysis of polycyclic aromatic hydrocarbons in airborne particulate matters by gas chromatography-mass spectrometry

A solid-phase extraction (SPE) method using triacontyl bonded silica (C30) as sorbent was developed for the determination of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matters quantitatively by gas chromatography-mass spectrometry (GC-MS). Optimization experiments were conducted using spiked standard aqueous solution of PAHs and real airborne particulates samples aiming to obtain highest SPE recoveries and extraction efficiency. Factors were studied in SPE procedures including the concentration of organic modifier, flow rate of sample loading and elution solvents. The ultrasonication time and solvents were also investigated. Recoveries were in the range of 68-107% for standard PAHs aqueous solution and 61-116% for real spiked sample. Limits of detection (LODs) and limits of quantification (LOQs) with standard solution were in the range of 0.0070-0.21 microgL(-1) and 0.022-0.67 microgL(-1), respectively. The optimized method was successfully applied to the determination of 16 PAHs in real airborne particulate matters.     

Ion-imprinted interpenetrating network gels for solid-phase extraction of heavy metal ions

In the present work, ion-imprinted interpenetrating polymer network (IPN) gels were prepared by free radical/cationic hybrid polymerisation of acrylamide (AAm) and 1,4-butanediol vinyl ether (BVE). These gels were respectively used for separation of Cu²⁺, Ni²⁺ and Zn²⁺ ions in natural water samples. Experimental conditions for effective adsorption of metal ions were optimised with respect to different experimental parameters by column procedures in detail. The optimum pH value for the adsorption of Cu²⁺, Ni²⁺ and Zn²⁺ ions on these sorbents was 6.0. Complete elution of the adsorbed metal ions from the sorbent was carried out using 1.0 mol/L of HCl solution. The optimum sample flow rate and eluent flow rate were, respectively, 1.0 and 0.3 mL/min. Common coexisting ions did not interfere with the separation and determination of the target ions. The accuracy of the proposed method was validated by analysis of the standard reference material (GBW 08301, river sediment). The measured contents of metal ions in the reference material were in good agreement with the certified values. The presented method was successfully applied for the determination of Cu²⁺, Ni²⁺ and Zn²⁺ ions in three different water samples (well water, seawater and waste water).     

Potential of Modified Multiwalled Carbon Nanotubes with 1-(2-Pyridylazo)-2-naphtol as a New Solid Sorbent for the Preconcentration of Trace Amounts of Cobalt(II) Ion

The present paper reports on the application of modified multiwalled carbon nanotubes (MMWCNTs) as a new, easily prepared and stable solid sorbent for the preconcentration of trace Co(II) in aqueous solution. Multiwalled carbon nanotubes (MWCNTs) were oxidized with concentrated HNO(3) and modified with 1-(2-pyridylazo)-2-naphtol (PAN), and were then used as a solid phase for the preconcentration of Co(II). Factors influencing the sorption and desorption of Co(II) were investigated. Elution was carried out with 0.5 mol L(-1) HNO(3). The amount of eluted Co(II) was measured using flame atomic absorption spectrometry. The effects of the experimental parameters, including the sample pH, sample flow rate, eluent flow rate and eluent concentration, were investigated. The effect of coexisting ions showed no interference from most ions tested. The proposed method permitted a large enrichment factor (about 300). The precision of the method was 1.63% (for eight replicate determination of 0.5 microg mL(-1) of Co(II)) and the limit of detection was 0.55 ng mL(-1). The method was applied to the determination of Co(II) in water, biological and standard samples.     

Development of a flow system for the determination of low concentrations of silver using Moringa oleifera seeds as biosorbent and flame atomic absorption spectrometry

In this study a method for the determination of low concentrations of silver in waters using solid-phase extraction with a flow injection analysis system and detection by flame atomic absorption spectrometry (FAAS) was developed. Moringa oleifera seeds were used as a biosorbent material. Chemical and flow variables of the on-line preconcentration system such as sample pH and flow rate, preconcentration time, eluent concentration and sorbent mass were studied. The optimum preconcentration conditions were obtained using sample pH in the range of 6.0-8.0, preconcentration time of 4 min at a flow rate of 3.5 mL min^− 1, 0.5 mol L^− 1 HNO₃ eluent at a flow rate of 4.5 mL min^− 1 and 35 mg of sorbent mass. With the optimized conditions, the preconcentration factor, precision, detection limit and sample throughput were estimated as 35 (for preconcentration of 14 mL sample), 3.8% (5.0 μg L^− 1, n = 7), 0.22 μg L^− 1 and 12 samples per hour, respectively. The developed method was successfully applied to mineral water and tap water, and accuracy was assessed through analysis of a certified reference material for water (APS-1071 NIST) and recovery tests, with recovery ranging from 94 to 101%.     

On-line solid phase extraction coupled to ICP-OES for simultaneous preconcentration and determination of some transition elements

An on-line solid phase extraction method coupled to ICP-OES was developed for the simultaneous determination of Ce(III), La(III), Sm(III), Y(III), Yb(III), Dy(III), Hf(IV), Zr(IV) and Th(IV) ions in aqueous samples. The ions forming hydrophobic complexes with 3,5,7,2?,4?-pentahydroxy flavone (morin) and were retained on an octadecyl silica (C₁₈) minicolumn. The adsorbed chelates were subsequently eluted from the column and directly transferred into the plasma with 80% (v/v) propanol:H₂O solution for the simultaneous determination of the metal ions. Different parameters affecting the ICP-OES signal intensities and extraction efficiency including pH of the solution, concentration of the chelating agent, flow rate and type of the eluent, loading rate and ionic strength were evaluated and optimized. The calibration graphs were linear in the range of 0.2–100 μg L^?1 and limit of detections for the extraction and determination of the ions in the aqueous sample (25 mL) were in the range 0.10–0.46 μg L^?1. The enhancement factors of the method for the metal ions obtained were in the range of 23 to 242 (V _Sample?=?25 mL) and the precision expressed as relative standard deviations (RSD %) was below 6.9%. Finally, the method was successfully applied to determine the target analytes in natural water samples.     

Determination of Hg in water and wastewater samples by CV-AAS following on-line preconcentration with silver trap

An online mercury preconcentration and determination system consisting of cold vapor atomic absorption spectrometry (CV-AAS) coupled to a flow injection (FI) method was studied. The method was developed involving the determination of ng/L levels of mercury retained on the silver wool solid sorbent. Experimental conditions such as sample volume, flow rate, stability of the column and effect of foreign ions on the determination of trace amounts of mercury were optimized. The detection limit is 3 ng/L and dynamic range 10–250 ng/L require only 50 mL of sample. The relative standard deviations (RSD) of the determinations are below 4%. The presence of common metal ions, such as K+, Na⁺, Cu²⁺, Pb²⁺, Fe³⁺, Ni²⁺, and Mn²⁺, does not interfere with the measurement of mercury by this method. The method was successfully applied to the determination of mercury in water and wastewater samples.     

Application of organo-nanoclay as a solid sorbent for rhodium complex separation and preconcentration

An organo-nanoclay is used as a new, easily accessible, and stable solid sorbent for the preconcentration of trace amounts of rhodium ions from aqueous solution, this followed by its determination by flame atomic absorption spectrometry (FAAS). Rh(III) ion was first complexed with 2,3,5,6-tetra(2-pyridyl) pyrazine (TPPZ) at pH values between 3.0 and 4.7, and then the complex was then adsorbed onto the nanoclay. The rhodium ions were eluted from the sorbent with HCl. The rhodium in the effluent was determined by FAAS. The linear analytical range is between 0.14 ng mL^?1 and 20.0 μg mL^?1 in the initial solution, the relative standard deviation at 2.0 μg mL^?1 of rhodium is 2.6% (n?=?8), the detection limit is 0.03 ng mL^?1, and the preconcentration factor is 140. Experimental parameters including the pH, eluent type, interference by other ions and breakthrough volume were optimized. The method was applied to the determination of rhodium in water, road dust and synthetic samples.