Activated carbon cloth filled pipette tip for solid phase extraction of nickel(II), lead(II), cadmium(II), copper(II) and cobalt(II) as 1,3,4-thiadiazole-2,5-dithiol chelates for ultra-trace detection by FAAS

A solid phase extraction method is established for preconcentration of nickel, lead, cadmium, copper and cobalt using pipette tip solid phase extraction. The presented process was dependent on chelation of analytes with 1,3,4-thiadiazole-2,5-dithiol, then allowing the solution to flow through an activated carbon cloth packed pipette tip. The adsorbed metal chelates on the surface of activated carbon cloth were eluted by 5 mL of 3 M HNO₃. The concentrations of nickel, lead, cadmium, copper and cobalt were detected using a flame atomic absorption spectrometer (FAAS). The pipette tip solid phase extraction exhibit a preconcentration factor of 120. The limit of detection values were 2.7, 1.7, 1.3, 2.0 and 2.9 µg L^?1 for Ni(II), Pb(II), Cd(II), Cu(II) and Co(II), respectively. Validation of the method was checked by the analysis of TMDA-53.3 and TMDA-64.2 certified reference materials. The method was successfully applied for water and fertiliser samples.     

Dithizone-modified nanoporous fructose as a novel sorbent for solid-phase extraction of ultra-trace levels of heavy metals

We are introducing nanoporous fructose (np-F) modified with dithizone as a new solid-phase for extraction of heavy metals ions including cadmium(II), copper(II), nickel(II) and lead(II). Effects of pH value, flow rates, type, concentration and volume of the eluent, breakthrough volume, and of other ions were studied. Under optimized conditions, the extraction efficiency is >97 %, and the limits of detection are 0.025, 0.15, 0.5 and 1.2 ng mL^?1 for the ions of cadmium, copper, nickel, and lead, respectively, and the adsorption capacities for these ions are 101, 81, 74 and 178 mg g^?1. The modified np-F sorbent was characterized by thermogravimetric analysis, differential thermal analysis, transmission electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction, and nitrogen adsorption surface area (BET) measurements.

Solid-Phase Extractive Preconcentration of Trace Copper as its Calmagite Anionic Chelate using a Polyaniline Column for Flame Atomic Absorption Spectrometric Determination

A new solid phase extraction method based on the application of polyaniline as the sorbent and calmagite as the anionic chelating agent is reported for selective preconcentration of trace copper, prior to its determination by microsample injection system-flame atomic absorption spectrometry. The parameters that influence the extraction and chelate formation were optimized. The copper was retained on a polyaniline minicolumn at pH 4.0 and eluted with 2.0 mL of 3.0 mol L^?1 nitric acid. Under the optimum conditions, the limit of detection, the relative standard deviation, and the preconcentration factor were 1.98 µg L^?1, less than 5.4%, and 50 to 200, respectively. The method was validated through the analysis of certified reference water samples and standard addition measurements. Quantitative recoveries between 93.4% and 103.5% were obtained. The method was successfully applied to the determination of copper in water.     

Multi‐Walled Carbon Nanotubes as Sorbent for Flow Injection On‐Line Microcolumn Preconcentration Coupled with Flame Atomic Absorption Spectrometry for Determination of Cadmium and Copper

Abstract

Multi‐walled carbon nanotubes (MWNTs) were used as sorbent for flow injection (FI) on‐line microcolumn preconcentration coupled with flame atomic absorption spectrometry (FAAS) for determination of trace cadmium and copper in environmental and biological samples. Effective preconcentration of trace cadmium and copper was achieved in a pH range of 4.5–6.5 and 5.0–7.5, respectively. The retained cadmium and copper were efficiently eluted with 0.5 mol L^?1 HCl for on‐line FAAS determination. The MWNTs packed microcolumn exhibited fairly fast kinetics for the adsorption of cadmium and copper, permitting the use of high sample flow rates up to at least 7.8 mL min^?1 for the FI on‐line microcolumn preconcentration system without loss of the retention efficiency. With a preconcentration time of 60 sec at a sample loading flow rate of 4.3 mL min^?1, the enhancement factor was 24 for cadmium and 25 for copper at a sample throughput of 45 h^?1. The detection limits (3σ) were 0.30 and 0.11 µg L^?1 for Cd and Cu, respectively. The precision (RSD) for 11 replicate measurements was 2.1% at the 10‐µg L^?1 Cd level and 2.4% at the 10‐µg L^?1 Cu level. The developed method was successfully applied to the determination of trace Cd and Cu in a variety of environmental and biological samples.     

Development of One-Step Derivatization and Preconcentration Technique Using Weak Anion-Exchange Resin Modified with Sodium Diethyldithiocarbamate for Determination of Trace Amount of Copper(II) in Water

A new method was developed using weak anion exchange resin modified with sodium diethyldithiocarbamate (DDTC) for the derivatization and preconcentration of copper(II) in water prior to spectrophotometric determination. Several conditions affecting the extraction efficiency were investigated. Under the optimum conditions, an enrichment factor of 50 was achieved. The reaction mechanism of copper(II) and DDTC on the resin and binding experiment was studied. The detection limit is 0.6 μ g L^?1. The relative standard deviations of intra- and inter-day ranging from 2.1 to 3.6% and from 1.3 to 4.0% were obtained, respectively, and the recoveries were in the range of 95.3–99.6%.     

Determination of silver in sea water by coprecipitation with cobalt pyrrolidinedithiocarbamate and Zeeman graphite-furnace atomic absorption spectrometry

A preconcentration technique is described for silver, which allows the precise and accurate determination of silver in sea water at nanogram per liter levels. Silver is co-precipitated with cobalt(II) pyrrolidinedithiocarbamate from 200-ml samples. The precipitate is dissolved in concentrated nitric acid and silver is quantified by Zeeman graphite-furnace atomic absorption spectrometry, with acid phosphate matrix modification. The detection limit is 0.1 ng l^?. The method is simple and rapid, and also allows the simultaneous extraction of lead, copper, cadmium, and nickel.     

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.     

Graphene oxide-packed micro-column solid-phase extraction combined with flame atomic absorption spectrometry for determination of lead (II) and nickel (II) in water samples

A sensitive and simple method has been established for simultaneous preconcentration of trace amounts of Pb (II) and Ni (II) ions in water samples prior to their determination by flame atomic absorption spectrometry. This method was based on the using of a micro-column filled with graphene oxide as an adsorbent. The influences of various analytical parameters such as solution pH, adsorbent amount, eluent type and volume, flow rates of sample and eluent, and matrix ions on the recoveries of the metal ions were investigated. Using the optimum conditions, the calibration graphs were linear in the range of 7–260 and 5–85 μg L^?1 with detection limits (3S_b) of 2.1 and 1.4 μg L^?1 for lead and nickel ions, respectively. The relative standard deviation for 10 replicate determinations of 50 μg L^?1 of lead and nickel ions were 4.1% and 3.8%, respectively. The preconcentration factors were 102.5 and 95 for lead and nickel ions, respectively. The adsorption capacity of the adsorbent was also determined. The method was successfully applied to determine the trace amounts of Pb (II) and Ni (II) ions in real water samples. The validation of the method was also performed by the standard reference material.     

Preconcentration of Trace Cadmium (II) and Copper (II) in Environmental Water Using a Column Packed with Modified Silica Gel-Chitosan Prior to Flame Atomic Absorption Spectrometry Determination

A new column loaded with modified silica gel-chitosan is proposed as a preconcentration system for adsorption of trace cadmium (II) and copper (II). The optimization steps were performed under dynamic conditions, involving pH, sample flow rate, eluent selection, concentration, volume, and flow rate. Trace Cd(II) and Cu(II) were quantitatively adsorbed by the modified silica gel-chitosan. The metal ions adsorbed on the separation column were eluted with 0.1 M HNO₃ and determined by flame atomic absorption spectrometry. Under the optimum conditions, this method allowed the determination of cadmium and copper with limits of detection (LOD) of 20 ng L^?1 and 38 ng L^?1, respectively. The relative standard deviation values (RSDs) for 1.0 mg L^?1 of cadmium and 1.0 mg L^?1 of copper were 2.62% and 2.85%, respectively.     

Trace Enrichment and Atomic Absorption Spectrometric Determination of Lead,Copper, Cadmium and Nickel in Drinking Water Samples by Use of an Activated Carbon Column

Abstract

A simple method for atomic absorption spectrometric determination of lead, copper, cadmium and nickel in drinking water samples after preconcentration by sorbing 1-(2-pyridylazo) 2-naphthol (PAN) complex of these metals on an activated carbon column has been established. The metal/PAN complexes were quantitatively retained on the activated carbon in the pH range 6-8. Metals retained on the activated carbon column were completely eluted with 2M HCl in acetone. This method was applied to the determination of lead, copper, cadmium and nickel in drinking water samples and good results were obtained (Recoveries >95%, relative standard deviations <7%, relative error <3%).     

Starch coated titanium dioxide nanoparticles as a challenging sorbent to separate and preconcentrate some heavy metals using graphite furnace atomic absorption spectrometry

In this study, a challenging nanosorbent was described for preconcentration/separation method based on the sorption of cadmium, cobalt, copper, nickel, lead on starch coated titanium dioxide nanoparticles and its analysis by graphite furnace atomic absorption spectrometry. Optimum conditions were investigated for quantitative sorption. By using the proposed technique, the analyte elements were determined in spiked tap-water samples in the range of 95% confidence level. Limit of detection (3δ) was 0.05, 0.28, 1.90, 3.10 and 0.11 µg/L (3σ, N = 10) for cadmium, cobalt, copper, nickel and lead, respectively. The optimised technique is fast, easy handled, simple and environmental friendly.     

On-line solid phase extraction system using 1,10-phenanthroline immobilized on surfactant coated alumina for the flame atomic absorption spectrometric determination of copper and cadmium

An on-line solid phase extraction (SPE) preconcentration system coupled to flame atomic absorption spectrometer (FAAS) was developed for determination of copper and cadmium at μg L⁻¹ level. The method is based on the on-line retention of copper and cadmium on a microcolumn of alumina modified with sodium dodecyl sulfate (SDS) and 1,10-phenanthroline and subsequent elution with ethanol and determination by FAAS. The effect of chemical and flow variables that could affect the performance of the system was investigated. The relative standard deviation (n = 6) at 20 μg L⁻¹ level for copper and cadmium were 1.4 and 2.2% and the corresponding limits of detection (based on 3σ) were 0.04 and 0.14 μg L⁻¹, respectively. The method was successfully applied to determination of copper and cadmium in human hair and water samples.     

Determination of trace vanadium in sea cucumbers by ultrasound-assisted cloud point extraction and graphite furnace atomic absorption spectrometry

An ultrasound-assisted cloud point extraction (CPE) procedure was used for preconcentration and determination of vanadium by graphite furnace atomic absorption spectrometry. The vanadyl(IV) complex with ascorbic acid form a hydrophobic complex with 4-(2-pyridylazo) resorcinol (PAR) in a micelle medium, which is stable under our working conditions, and followed by its extraction into Triton X-100 surfactant-rich phase. The main factors affecting CPE efficiency, such as pH, concentrations of PAR, ascorbic acid and Triton X-100, incubation temperature, frequency and equilibration time of ultrasonic bath were investigated in detail. Under the optimum conditions, preconcentration of 10 mL sample gave a preconcentration factor of 36.4 and a detection limit of 4.0 µg kg^?1. The proposed method was successfully applied to determination of vanadium in sea cucumbers with satisfactory results.     

Synthesis and application of polythiophene-coated Fe3O4 nanoparticles for preconcentration of ultra-trace levels of cadmium in different real samples followed by electrothermal atomic absorption spectrometry

In this research, magnetic Fe₃O₄ nanoparticles were synthesised by co-precipitation method and modified with polythiophene (PT) to produce Fe₃O₄-PT nanoparticles for preconcentration and determination of cadmium (??) ion followed by electrothermal atomic absorption spectrometry. The results of FT-IR spectroscopy, EDX analysis and SEM images show that Fe₃O₄-PT nanoparticles were synthesised successfully. Different parameters such as sample pH, amounts of adsorbent, sample volume, extraction time, type and concentration of eluent and desorption time were completely investigated and optimum conditions were selected.

Under the optimum conditions, the calibration curve was linear in the range of 0.01–0.25 µg L^?1 of cadmium (??). The relative standard deviation was 4.7% (n = 7, 0.10 µg L^?1 Cd²⁺) and limit of detection was 3.30 ng L^?1. The accuracy of the proposed method was verified by the analysis of a certified reference material and spike method. Finally, the proposed method was applied for the determination of ultra-trace levels of cadmium (??) in different water and food samples.     

Use of Nb(2)O(5)-SiO(2) in an automated on-line preconcentration system for determination of copper and cadmium by FAAS

A procedure for the determination of trace level of copper(II) and cadmium(II) by FAAS using an on-line preconcentration system has been proposed. In this system, copper and cadmium ions were adsorbed onto a minicolumn packed with silica gel modified with niobium(V) oxide (Nb₂O₅-SiO₂), followed by nitric acid elution in reverse mode and determination on-line by flame atomic absorption spectrometry (AAS) without interference of the matrix. Chemical and flow variables as well as concomitant ions were studied in the developed procedure. The enrichment factor for copper(II) and cadmium(II) was 34.2 and 33.0, respectively, using a preconcentration time of 2 min. The limit of detection for copper(II) and cadmium(II) was 0.4, and 0.1 μg l⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation in solutions containing 15 μg l⁻¹ of copper and 10 μg l⁻¹ of cadmium, by analyzing a series of seven replicates, was 1.8 and 1.6%, respectively. The accuracy was assessed through recovery experiments of certified material and water samples.     

The uses of 1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin on the solid phase extraction of traces heavy metal ions and their determinations by atomic absorption spectrometry

1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin was used as solid phase extractor of copper, nickel, cadmium, lead, chromium and cobalt ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The parameters including pH, sample volume, matrix effects were also investigated. The relative standard deviation (R.S.D.) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was between 0.21 and 1.4 μg l⁻¹. The results were used for preconcentration of analyte ions from natural water samples. The method was also applied to a stream sediment standard reference material (GBW7309) for the determination of Cu, Ni, Cd, Pb, Cr and Co.     

Preconcentration and Quantitative Determination of Esomeprazole Magnesium Present in Water

A simple, accurate, and sensitive preconcentration method for determination of esomeprazole magnesium in treated sewage water was developed based on HPLC. A preconcentration method was developed for aqueous solution containing pure drug using solid phase extraction. Macroporous beads of polystyrene divinyl benzene (PSDVB) polymer were used for preconcentration followed by chromatographic determination. Experimental parameters were optimized. This optimized method can detect esomeprazole magnesium concentration up to 0.003 mg L^?1 after preconcentration. This method was used for determination of esomeprazole magnesium in water collected from a sewage treatment facility. Esomeprazole magnesium could not be detected in the treated sewage water sample collected for the study.     

Synthesis of magnetically modified mesoporous nanoparticles and their application in simultaneous determination of Pb(II), Cd(II) and Cu(II)

In this study, a novel adsorbent from a mesoporous family (MCM-41) coating with CoFe₂O₄ and piperazine was synthesized by a simple and easy route. Its application for simultaneous preconcentration of three heavy metals including lead, cadmium and copper in real samples followed by a flame atomic absorption spectroscopy was investigated. The central composite design was employed for investigating the most effective factors of pH, amount of adsorbent, the equilibrium time and their interactions. Under the optimum conditions, the detection limits for lead, cadmium and copper were 0.50, 0.30 and 0.25 μg L^?1, respectively, and the preconcentration factor (PF) was 33. The presented method was successfully employed for the simultaneous determination of the three mentioned heavy metals in real samples with recoveries of 90%–105%. The accuracy of the suggested methods was also investigated through spiking samples and a reasonable range for recoveries from 90.3% to 107% was acquired. The isotherm models and thermodynamic parameters have also been studied. The new adsorbent showed fast adsorption kinetics within 10 min and maximum Langmuir monolayer capacities of 238.09, 178.57 and 208.33 mg g^?1 for lead, cadmium and copper, respectively.     

Cadmium Preconcentration from Aqueous Environmental Samples Using Microcrystalline Phenolphthalein Modified by Crystal Violet

Abstract

The present work describes a novel method for cadmium preconcentration and separation with microcrystalline phenolphthalein. Phenolphthalein as an extractant modified by crystal violet was originally applied to cadmium extraction from aqueous solution. Cadmium(II) as CdI₃ ^? and CdI₄ ^2? can associate with the cationic crystal violet (CV⁺) forming water‐insoluble ion‐association complexes (CdI₃ ^?) · (CV⁺) and (CdI₄ ^2?) · (CV⁺)₂, which are quantitatively adsorbed on microcrystalline phenolphthalein over the pH range from 1.0 to 6.0. All experimental parameters necessary for successful preconcentration and separation have been investigated and optimized. The study shows that common metal ions, such as Zn(II), Fe(II), Co(II), Ni(II), Mn(II), Cr(III) and Al(III), cannot interfere with cadmium extraction in this microcrystalline system by controlling acidity. The extraction can be accomplished in 15 min. The interaction between CdI₃ ^?and CdI₄ ^2? and CV⁺ plays an important role in the extraction process. The reported method was successfully applied to the preconcentration and separation of cadmium in synthetic samples and real samples with satisfactory results. The results proved that it is an efficient and attractive technique for cadmium preconcentration and separation at trace level.     

Synthesis of 2-mercaptobenzothiazole/magnetic nanoparticles modified multi-walled carbon nanotubes for simultaneous solid-phase microextraction of cadmium and lead

This study describes the successful sequential modification of multi-walled carbon nanotube (MWCNT) by Fe₃O₄ magnetic nanoparticles and 2-mercaptobenzothiazole (MBT) followed by its application as a novel sorbent for simultaneous magnetic solid phase microextraction of lead and cadmium. Fourier transform infrared spectroscopy and scanning electron microscopy were employed to confirm the chemical surface modification of the MWCNT. The ions retained on the 2-MBT/magnetic nanoparticles modified MWCNTs were eluted with 1.0 mL of nitric acid (0.8 mol L^?1) in methanol solution and determined by the flame atomic absorption spectrometry. All parameters affecting the extraction condition were thoroughly investigated and optimised. Under the optimised condition preconcentration factor of 150.0, enhancement factors of 149.0 and 149.2 and limits of detection of 0.21 and 0.01 µg L^?1 were achieved for lead and cadmium, respectively. Using the prepared magnetic nanocomposite, the possible interference of other common ions associated with lead and cadmium determination was effectively avoided and the method was successfully applied to the simultaneous determination of the target ions in various environmental water samples.