Preconcentration Of Cu Research Articles

Solid phase extraction on multiwalled carbon nanotubes and flame atomic absorption spectrometry combination for determination of some metal ions in environmental and food samples

In this study, a new sensitive and simple method for simultaneous separation and preconcentration of Cu2+, Zn2+, Pb2+, and Cd2+ ions from various real samples prior to their measurements by flame atomic absorption spectrometry has been developed. The proposed method is based on the utilization of multiwalled carbon nanotube in combination with (E)-N1-(4-nitro-benzylidene)-N2-(2-((E)-4-nitrobenzylideneamino)ethyl) ethane-1,2-diamine as a solid phase extractant. The separation parameters for effective adsorption of Cu2+, Zn2+, Pb2+, and Cd2+ ions, including the effects of pH, amount of ligand, sample and eluent flow rate, and common coexisting ions were examined. The optimum pH for the separation of Cu2+, Zn2+, Pb2+, and Cd2+ ions on the new sorbent was 6.0. The detection limits based on 3 sigma (n = 15) for Cu2+, Zn2+, Pb2+, and Cd2+ ions was 0.69, 0.48, 8.9, and 0.25 ng mL−1 while respective preconcentration factor for Cu2+, Zn2+ ions was 80 and for Pb2+ and Cd2+ ion was 20 and 60, respectively, with relative standard deviations between 0.7% and 5.8%. The proposed preconcentration procedure was applied to the analysis of various real samples.

On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

AbstractAn on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L−1 HNO3 solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L−1, and a relative standard deviation of 1.2% at 0.2 µg mL−1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.

Optimization of the solid phase extraction method for determination of Cu(ii) in natural waters by using response surface methodology

A solid-phase extraction method was proposed for the preconcentration of Cu(II) in different samples in a mini-column packed with functionalized multi-walled carbon nanotubes (MWCNTs-COOH) as an effective sorbent, without using any complexing reagent, prior to its determination by flame atomic absorption spectrometry using response surface methodology. The experimental optimization step was performed by both a two-level full factorial design, with a center point, and a Box-Behnken design combined with response surface methodology. Three variables (pH, amount of Cu(II), and sample volume) were regarded as factors in the optimization. It was found that pH is the most significant factor affecting the preconcentration of Cu(II). The preconcentration factor was obtained as 100. The linear range was 1-5 mg L(-1) (R(2) = 0.999). Under the optimized experimental conditions, the detection limit (3s) of the proposed method followed by FAAS was found to be 0.27 μg L(-1). The relative standard deviation for 10 replicate measurements of 50 and 100 μg L(-1) Cu(II) was 2.39% and 0.98%, respectively. The response surface methodology was successfully applied to the determination of Cu(II) in water samples and mussel samples, and in a certified standard reference material (BCR-320R, Channel sediment).

A New Thioamide Derivative for Separation and Preconcentration of Multi Elements in Aquatic Environment by Cloud Point Extraction

2-(pyridine-2-yl)-N-p-chlorohydrazinecarbothioamide (HCPTS) was synthesized, characterized and successfully applied for the preconcentration of Cu(II), Ni(II), Zn(II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II) in water, blood, and urine samples prior to graphite furnace atomic absorption determination (GFAAS); Hg was determined by cold vapor technique. Under the optimum experimental conditions (i.e. pH = 8, 10–4 M of HCPTS, 0.05% w/v of Triton X-114), calibration graphs were linear in the range of 0.02 to 200 ng?mL–1 for Co(II), Cd(II), Pb(II) and Ni(II); 0.03 to 200 ng?mL–1 for Cu(II); 0.07 to 200 ng?mL–1 for Fe(II) and Zn(II) and 0.02 to 150 ng?mL–1 for Hg(II). The enrichment factors were 43, 51, 41, 46, 54, 40, 45 and 52 for Cu(II), Ni(II),Zn (II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II), respectively. The limit of detection were found to be 0.019, 0.094, 0.0514, 0.052, 0.0165, 0.047, 0.068 and 0.041 ng?mL–1 for Cu(II), Ni(II), Zn(II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II), respectively. The developed method was applied to the determination of these metal ions in water, blood and urine samples with satisfactory results.

Application of Three Agarose Based Chelating Adsorbents for Preconcentration of Some Metal Ions in Water

Properties of two agarose based Chelating ion exchangers with, respectively, dipicolyl amine (DPA) and tris (2-aminoethyl) amine (TREN) as functional groups are investigated and compared to those of a previously studied adsorbent functionalized using iminodiacetic acid (IDA), with the same matrix, for preconcentration of Cu2+, A13+ and Mo3+ in water. Binding capacities, adsorption rates and column recoveries of the metal ions are carefully investigated. An inductively coupled plasma atomic emission spectroscopy (ICPAES) instrument is used for measurements.The capacity of all adsorbents for Cu ions at different pH was similar while, for other metal ions was more variable and pH dependent. The highest capacity of the DPA and TREN sorbents was obtained for copper, which is averaged to 18.3 (±0.3) and 120.0 (±6.0) μmol /mL, respectively. Kinetic studies indicated relatively high adsorption rates of Cu2+ on all the sorbents. Al and Mo, on the other hand, showed relatively high rates on the DPA and TREN chelators. High column recoveries were obtained for Cu and Al ions on the IDA adsorbent and only very low recovery of Mo ion was observed at the studied pHs. The column recoveries for the DPA sorbent, on the other hand, were quite low for Cu and Mo. It indicated high recoveries only for Al, which rose up to 77.9 (±0.6)% at pH 7.3. Copper also was almost quantitatively recovered on the TREN sorbent, with pH dependent recoveries for Al and Mo ions. The method was evaluated by preconcentration of spiked river water samples. Good agreement was obtained between the results obtained for natural samples and standard solutions. In general, more selectivities, slower adsorption rates and lower and more pH dependent recoveries were identified for the DPA and TREN sorbents compared to that with the IDA groups.

Preconcentration of Cu(II), Cd(II) and Pb(II) on Amberlite XAD-4 Resin Functionalized with N,N'-Bis(o-vanillinidene)-ethylenediamine and Their Determination by FAAs in Water samples

A new polystyrene divinylbenzene-based chelating resin was synthesized by functionalizing Amberlite XAD-4 with N,N'-bis(o-vanillinidene)ethylenediamine. This resin was capable of preconcentrating Cu(II), Cd(II) and Pb(II) in water samples prior to FAAS determination. Various parameters, such as the pH, eluent type and concentration, volume of the eluent and the sample, and diverse ion effects have been studied. The recoveries for the analytes under the optimum working conditions were higher than 95%. The accuracy of the method was tested with standard reference materials (MBH-C31XB20, GBW-02703 and CRM BCR-32) and Cd(II), Cu(II) and Pb(II) standard solutions. The method was successfully applied to water samples.

Preconcentration and determination of copper and cadmium ions with 1,6-bis(2-carboxy aldehyde phenoxy)butane functionalized Amberlite XAD-16 by flame atomic absorption spectrometry

A new chelating resin, covalently linked 1,6-bis(2-carboxy aldehyde phenoxy)butane with the Amberlite XAD-16 was synthesized and used for preconcentration of Cu(II) and Cd(II) prior to their determination by flame atomic absorption spectrometry (FAAS). It was characterized by elemental analyses and Fourier Transform Infrared Spectroscopy (FT-IR). Cu(II) and Cd(II) ions were quantitatively preconcentrated on minicolumn loaded with synthesised resin at pH 4.00 and 6.00, respectively. They were eluated with 5mL of 0.5molL−1 HCl. Recoveries of Cu(II) and Cd(II) were found to be 100±2.15, 100±1.40 (N=5), the limits of detection of Cu(II) and Cd(II) in the determination by FAAS (3s, N=20) were found to be 0.33 and 1.19μgL−1, respectively. The effect of foreign ions on the recovery has been investigated. The proposed method has been applied for the determination of Cu(II) and Cd(II) ions to the real samples collected from Tigris river water in Diyarbakır and Elazığ cities in Turkey. Standard addition method and analysis of the certified reference material (NCS-DC 73350) was employed to check the accuracy of the method.

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

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

Preconcentration of Cu (II) from seawater using a novel and stable phenol–formaldehyde resin

Preconcentration of Cu (II) from seawater using a novel phenol-formaldehyde (P-F) resin was investigated. 1,2-dihydroxybenzene-4-azo-3-hydroxybenzene-formaldehyde resin (DAHBF) was prepared by condensing 1,2-dihydroxybenzene-4-azo-3-hydroxybenzene with formaldehyde (1:2 mole ratio) in the presence of oxalic acid as catalyst. Polychelates were obtained when the DAHBF was treated with the aqueous solution of Cu (II) ions. The polymeric resin and polymer-metal complexes were characterized with thermal analysis and spectral studies. The IR spectra of polychelates suggest that the metal was coordinated through the oxygen atoms of the dihydroxybenzene moiety. The TGA data revealed the thermal stability of the resin and the polychelates. X-ray diffraction study revealed the incorporation of the metal ion significantly enhanced the degree of crystallinity. The sorption properties of the chelate forming resin towards divalent metal ion [Cu(II)] was studied as a function of pH, preconcentration time, metal concentration, amount of resin, aqueous phase volume and presence of electrolyte. This procedure was validated for recovery of copper from seawater samples. The method has adequate accuracy and it can be used for determination of copper in sea water samples.

Solid phase extraction and preconcentration of Cu(II), Pb(II), and Ni(II) in environmental samples on chemically modified Amberlite XAD-4 with a proper Schiff base

A new chelating resin, Amberlite XAD-4 loaded with N,N-bis(salicylidene)cyclohexanediamine (SCHD), was synthesized and characterized. The resin Amberlite XAD-4-SCHD was used for selective separation, preconcentration, and determination of Cu(II), Pb(II), and Ni(II) ions in water samples by flame atomic absorption spectrometry (FAAS). Effects of pH, concentration, and volume of elution solution; flow rate of elution; and sample solution, sample volume, and interfering ions for the recovery of the analytes were investigated. These metal ions can be desorbed with 0.5-M HNO3 (recovery, 98%-101%). The sorption capacity was found between 1.38×10(-1) and 3.58×10(-1) mmol/g. In order to evaluate the accuracy of the proposed procedure, the certified reference materials, BCR-032 (Moroccan phosphate rock) and BCR-715 (industrial effluent wastewater), were analyzed. The detection limits of the method were found to be 0.11, 1.91, and 0.43 μg/L for Cu(II), Pb(II), and Ni(II), respectively. The method was applied to the extraction and the recovery of copper, lead, and nickel in wastewater and other water samples.

Simultaneous and selective preconcentration of trace Cu and Ag by one-step displacement cloud point extraction for FAAS determination

A simple, rapid and selective one-step displacement cloud point extraction (D-CPE) procedure was developed for the simultaneous preconcentration of trace Cu and Ag followed by flame atomic absorption spectrometric (FAAS) measurement. In this proposed procedure, Ni-DDTC complex instead of DDTC was used to achieve one-step extraction. Since the stability of Cu-DDTC and Ag-DDTC is higher than that of Ni-DDTC, simultaneous preconcentration of Cu and Ag can be achieved in a single step. Up to 15,000 mg L(-1) Co(2+), 10,000 mg L(-1) Zn(2+), 5000 mg L(-1) Cd(2+) and 5000 mg L(-1) Al(3+) did not cause significant interferences for the determination of 50 microg L(-1) Cu by FAAS, while 8000 mg L(-1) Zn(2+), 4000 mg L(-1) Co(2+), 4000 mg L(-1) Cd(2+) and 5000 mg L(-1) Al(3+) had no distinct effect on the determination of 80 microg L(-1) Ag. The limits of detection (LODs) of 0.5 microg L(-1) for Cu and 1.0 microg L(-1) for Ag, respectively, were obtained by FAAS detection. The accuracy of the proposed method is validated by analyzing certified reference materials (GBW 07405, GBW 07311 and GBW 07260) with satisfactory results. Furthermore, the one-step D-CPE was also applied for the preconcentration/separation of Cu and Ag in high-purity salts and artificial seawater, followed by FAAS or inductively coupled plasma-mass spectrometry (ICP-MS) determination.

Solid phase extraction of copper, nickel, and cobalt in water samples after extraction using surfactant coated alumina modified with indane-1,2,3-trione 1,2-dioxime and determination by flame atomic absorption spectrometry

A simple method for simultaneous pre-concentration of Cu, Ni, and Co metal ions prior to their determination by flame atomic absorption spectrometry is reported. The method is based on the extraction of target ions via complexation with indane-1,2,3-trione 1,2-dioxime immobilized on sodium dodecyl sulfate (SDS) coated alumina. The metal content on the adsorbent was eluted with 4.5 mL of 2 mol L^{-1} nitric acid. The influences of the analytical parameters including pH, sample volume and flow rate, and eluent type and flow rate were investigated. The effect of matrix ions on the retentions of the analytes was also examined. The recoveries of analytes were generally higher than 96% with a low relative standard deviation (R.S.D. < 3%). The presented method was successfully applied for determination of these metals in water samples.

Selective homogeneous liquid-liquid extraction and preconcentration of copper(II) into a micro droplet using a benzo-substituted macrocyclic diamide, and its determination by electrothermal atomic absorption spectrometry

A fast and reliable method was developed for the selective separation and preconcentration of Cu2+ ions using homogeneous liquid-liquid extraction using a novel benzo-substituted macrocyclic diamide, 5,6,7,8,9,10-hexahydro-2H-1,13,4,7,10-benzodioatriazacyclo-pentadecine-3,11(4 H,12 H)-dione, as a selective complexing agent. An aqueous solution of Zonyl FSA (FSA) was used as a phase-separation agent at pH 4.5. Electrothermal atomic absorption spectrometry was used for Cu2+ determination after preconcentration. The influences of pH, type and volume of the water-miscible organic solvent, concentration of FSA, concentration of the ligand and the effect of diverse ions were investigated. Factorial design and response surface methods were used for the optimization purposes. Under the optimum experimental conditions, 50 ng of Cu2+ in 5 mL aqueous sample could be extracted quantitatively into 76 µL of the sediment phase. The maximum preconcentration factor was 65. The calibration curve was linear in the concentration range 0.2 to 4.0 µg L−1. The detection limit and relative standard deviation were 4 ng L−1 and 4.6%, respectively. The method was successfully applied to the extraction and determination of Cu2+ in natural water samples.

Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L−1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.

Utilization of membrane filtration for preconcentration and determination of Cu(II) and Pb(II) in food, water and geological samples by atomic absorption spectrometry

A method for separation–preconcentration of Cu(II) and Pb(III) ions by membrane filtration has been presented. The analyte ions were collected on acetate membrane filter as their 1-2-pyridylazo 2-naphthol (PAN) complexes. The analytes were determined by flame atomic absorption spectrometry. The analytical parameters including pH, eluent type, sample volume, amount of PAN, etc. were examined in order to gain quantitative recoveries of analyte ions. The effects of foreign ions on the recoveries of analyte ions were also investigated. The detection limits by three sigma were found to be 1.2 and 3.5 μg L −1 for Cu(II) and Pb(II), respectively. The preconcentration factor was 60 for Cu(II) and 20 for Pb(II). The validation of the presented procedure was checked by the analysis of certified reference materials. The optimized method was successfully applied to food, water and geological samples with good results.

Determination trace amounts of copper, nickel, cobalt and manganese ions in water samples after simultaneous separation and preconcentration

In the present article, a simple, rapid, sensitive and economical method has been developed for the simultaneous separation and preconcentration of the trace amounts of copper, nickel, cobalt and manganese in water samples by using modified XAD-4 resins. The sorption was quantitative in the pH range 6.0–9.0, whereas quantitative desorption occurred instantaneously with 5.0 mL of 2 M HNO3, and selected elements have been determined by using flame atomic absorption spectrometry. Dynamic ranges were 0.04–3.5, 0.1–6.0, 0.04–4.5 and 0.04–4.0 μg/mL for copper, nickel, cobalt and manganese, respectively. The detection limits were 9.2, 28.6, 12.3 and 5.7 ng/mL for Cu(II), Ni(II), Co(II) and Mn(II), respectively. The effects of the experimental parameters, including the sample pH, eluent type, interference ions and breakthrough volume, were studied for separation and preconcentration of Cu(II), Ni(II), Co(II) and Mn(II) ions. Determination of these ions in standard samples confirmed that the proposed method has good accuracy. The proposed method was used for the determination of these ions in water samples.

Synthesis of a New Cu(II)-Ion Imprinted Polymer for Solid Phase Extraction and Preconcentration of Cu(II)

A new Cu(II)-ion imprinted polymer (IIP) has been synthesized by copolymerizing salicylic acid and formaldehyde as a monomer and crosslinker, respectively in the presence of Cu(II)-4-(2-pyridylazo) resorcinol complex. The imprinted Cu(II) ions were completely removed by leaching the IIP with 0.05 M EDTA. The maximum adsorption capacity for Cu(II) ions was 310 μg g−1 at pH 6. The IIP was repeatedly used in adsorption–desorption experiments for seven times with recoveries ~95%. The relative selectivity factor (α r) values of Cu(II)/Zn(II), Cu(II)/Cd(II), Cu(II)/Ni(II) and Cu(II)/Co(II) are 3.17, 2.90, 2.47 and 3.37, respectively. The detection limit corresponding to three times the standard deviation of the blank was found to be 3.0 μg L−1. The developed IIP has also been tested for preconcentration and recovery of Cu(II) ions from water samples.

Preconcentration of Cu(II), Fe(III) and Pb(II) with 2-((2-aminoethylamino)methyl)phenol-functionalized activated carbon followed by ICP-OES determination

A procedure for separation and preconcentration trace amount of Cu(II), Fe(III) and Pb(II) by 2-((2-aminoethylamino)methyl)phenol-functionalized activated carbon (AC-AMP) packed column has been proposed. Under the optimized conditions (pH 4, flow rate 2.0 mL min(-1)), Cu(II), Fe(III) and Pb(II) were retained on the column, then quantitatively eluted by 2 mL 1 mol L(-1) nitric acid solution and determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). The tolerance limits of electrolytes were very high. The adsorption capacity of AC-AMP was found to be 12.1, 67.1, and 16.2 mg g(-1) for Cu(II), Fe(III), and Pb(II), respectively. According to the definition of International Union of Pure and Applied Chemistry, the detection limits (3 sigma) of this method for Cu(II), Fe(III) and Pb(II) were 0.27, 0.41 and 0.16 microg L(-1), respectively. The relative standard deviation under optimum conditions is less than 3.0% (n=11). The proposed method has been validated by analyzing a certified reference material and successfully applied to the preconcentration and determination of Cu(II), Fe(III), and Pb(II) in actual samples with satisfactory results.

Solid phase selective separation and green preconcentration of Cu, Zn, Pb and Cd in drinking water by using novel functionalized resin

Abstract A new solid — phase extraction sorbent was developed based on stepwise anchoring of two ligand molecules for the determination of copper, zinc, lead and cadmium in drinking water by flame AAS. Amberlite XAD-2 functionalized with 4′-(2-hydroxyphenylazo)-3′-methyl-1′-phenyl-2′-pyrazolin-5′-one (HPAPyr) was utilized for preconcentration/separation of these elements. The sorbent was prepared by two successive azo coupling reactions. First, 2-aminophenol was anchored to the amino groups in the resin resulted from nitration followed by reduction. Then, the resulted 2-aminophenol functionalized resin was further diazotized and coupled to the pyrazolone compound and the final product HPAPyr-XAD-2 was characterized by IR and elemental analysis. The optimum pH range for sorption, shaking time, exchange capacity, sample flow rate, preconcentration factor and interference from co-existing ions were investigated. All metal ions were quantitatively desorbed from the resin by 4.5 mol L−1 nitric acid solution. The sorbent provides limit of detection within the range 0.9–3.3 µg L−1 and concentration factor up to 250. The procedure was validated by analysis of certified material NIST-SRM 1577b. Application to drinking water showed satisfactory results with relative standard deviation RSD ≤ 8.5%.

Preconcentration of ultra-trace copper in water samples with nanometer-size TiO2 colloid and determination by GFAAS with slurry sampling

A method is presented for the preconcentration of Cu(II) ions using a nanometer-sized TiO2 colloid, and for their determination in environmental water using graphite furnace atomic adsorption spectrometry (GFAAS) with slurry sampling. The adsorption efficiency is above 97% and is reached within short time at pH values between 5.5 and 6.0. Cu(II) was determined by GFAAS without elution. Conditions such as colloid dosage and effects of other ions were studied. The detection limit (3 σ) and the relative standard deviation are 290 ng L-1 and 9.8% (n = 6), respectively. This simple and rapid method was successfully applied to spiked environmental samples with recoveries ranging from 97% – 104%.