A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

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

An 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.     

Separation and Preconcentration of Cobalt Using a New Schiff Base Derivative on Amberlite XAD‐7

In this study, a new solid‐phase extraction procedure has been developed for preconcentration and determination of Co ions in different water samples by flame atomic absorption spectrometry (FAAS). Cobalt was preconcentrated as N,N′‐bis(pyridine‐2‐yl‐methyl)benzene‐1,4‐diamine (Co‐BPMBDA) from sample solutions using a column containing Amberlite XAD‐7 and was determined. In order to achieve the best performance for the method, effects of several parameters such as pH, concentrations of ligand, sample flow rate, eluent, and matrix ions on the method efficiency were investigated. Under optimum conditions, the preconcentration factor was found to be 200 for 1000 mL waters samples. Detection limit based on the 3S_b criterion was calculated as 0.24 µg/L for 100 mL of sample solution and relative standard deviation was found to be 1.8%. The method was applied to determine the trace amounts of cobalt in water samples.     

Solid‐Phase Removal of Dissolved Organic Species from Water and Identification by GC–MS

A method is described for the detection and identification of dissolved organic compounds (DOCs) in various water samples. Acid treated active silica gel sorbent (pH 3) was packed into a micro‐column and used as a solid‐phase extraction medium for adsorption of DOCs. Silica particles‐adsorbed‐organic species were then divided into equal portions followed by suspension into various organic solvents of different polarities such as methanol, acetone, ethyl acetate, and toluene. Suspended silica‐adsorbed‐organic species were shaken for 1 h at room temperature and the organic extracts were subjected to GC–MS analysis under temperature programming conditions for qualitative detection and identification of these species. Blank solvents and silica samples were also subjected to the same extraction procedures and GC–MS analysis for comparison. The mass spectrum of each eluted chromatographic peak was library searched or manually interpreted to identify the compound.     

Flame Atomic Absorption Spectrometry Determination of Trace Amounts of Cadmium and Zinc in Water Samples after Preconcentration onto Modified Amberlite XAD‐4 Resin

In the present article, a procedure for the simultaneous separation and preconcentration of trace amounts of cadmium and zinc is proposed. It is based on the adsorption of cadmium and zinc ions onto a column of Amberlite XAD‐4 resin loaded with aluminon reagent. Cadmium and zinc ions are quantitatively retained on the column in the pH range from 6.5–7.5, at a flow rate of 2 mL min^–1. The cadmium and zinc ions are eluted with 5.0 mL of 5 mol L^–1 HNO₃ solution. Cadmium and zinc are measured by flame atomic absorption spectrometry (FAAS). In the present case, 0.1 μg of cadmium and 0.5 μg of zinc can be concentrated in the column from 1000 mL of aqueous sample, where their concentrations are as low as 0.1 and 0.5 ng mL^–1, respectively. The relative standard deviations, for seven replicated determinations of 1.0 μg mL^–1 of cadmium and zinc, are 1.2 and 1.1%, respectively. The detection limits for cadmium and zinc in the original solution are 0.02 and 0.11 ng mL^–1, respectively. The interference of a large number of anions and cations has been studied and the optimized conditions are utilized for the determination of trace amounts of cadmium and zinc in different environmental and standard samples.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

Dispersive Liquid–Liquid Microextraction for Preconcentration and Determination of Nickel in Water

A method for the determination of nickel in water was developed. The procedure involves preconcentration of nickel by using dispersive liquid–liquid microextraction. The Ni(II) ions were extracted in chloroform in the form of complex with the reagent 2‐(2′‐benzothiazolylazo)‐p‐cresol. Ethanol was used as the disperser solvent. After injection of the extracting mixture in a solution of nickel, a cloudy mixture was observed. A quick centrifugation induces phase separation and thus the settling of rich phase. The nickel content in the rich phase is measured by flame atomic absorption spectrometry. Under optimal conditions, the limit of detection and quantification obtained were 1.4 and 4.7 µg L^?1, respectively. Some parameters used to characterize preconcentration systems, such as enrichment factor and consumption index were calculated and resulted in 29 and 0.34 mL, respectively. After optimization of variables and determination of analytical characteristics, the method was used for the analysis of certified reference materials (BCR‐713: wastewater, effluent and BCR‐414: plankton) and real water samples.     

Online Preconcentration and Determination of Trace Levels Cadmium in Water Samples Using Flow Injection Systems Coupled with Flame AAS

A rapid and sensitive method for the determination of trace levels cadmium in water samples by flame atomic absorption spectrometry was developed. It is based on the online sorption of Cd(II) ions on a microcolumn packed with HCl treated bamboo charcoal. In a pH range of 5.0–7.5, Cd(II) ions were effectively retained on the microcolumn, which exhibited fast kinetics, permitting the use of high sample flow rates up to at least 12.8 mL/min without the loss of retention efficiency. The retained Cd(II) ions were quantitatively eluted with HCl (2.0 mol/L) for an online determination. With a preconcentration time of 80 s at a sample loading flow rate of 8.6 mL/min, a sensitivity enhancement factor of 63 was obtained compared with the slope of the linear portion of the calibration curves before and after preconcentration. The calibration graph using the preconcentration system for cadmium was linear with a correlation coefficient of 0.9997, at levels from 1–40 ng/mL. The precision (RSD) for 11 replicate measurements were 3.2% for the determination of 5 ng/mL Cd(II) and 1.8% for 20 ng/mL Cd(II), respectively, and the detection limit (3s) was 0.36 ng/mL. The accuracy was assessed through the determination of a certified reference material, and also through recovery experiments.     

Removal of Bromate from Water Using De‐Acidite FF‐IP Resin and Determination by Ultra‐Performance Liquid Chromatography‐Tandem Mass Spectrometry

Contamination of water due to bromate is a severe health hazard. The aim of the present study was to remove bromate from water using a crosslinked polystyrene based strongly basic anion exchange resin De‐Acidite FF‐IP. Batch experiments were performed to study the influence of various experimental parameters such as effect of pH, contact time, temperature, and effect of competing anions on bromate removal by De‐Acidite FF‐IP resin. At optimum parameters, the removal rate of bromate was very fast and 90% removal took place in 5 min and equilibrium was established within 10 min. The presence of competitive anions reduced the bromate adsorption in the order of Cl^? > F^? > CO > SO > NO > PO. The practical utility of this resin has been demonstrated by removing bromate in some of the commercial bottled water from Saudi Arabia. The level of bromate was determined using a very sensitive, precise and rapid method based on ultra‐performance liquid chromatography‐tendem mass spectrometry (UPLC‐MS/MS).     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

A Simplified Analytical Procedure for the Determination of Organically Bound Halogens in Salt‐containing Water Samples

A method was developed for the determination of organic halogens in water samples with the aim of minimizing matrix effects and simplifying the sample preparation technique commonly used. The method is based on the adsorption of organic halogens in modified hydrophilic divinylbenzene polymer columns and their elution with methanol. The adsorbent used enables rapid adsorption and desorption due to comparatively high operating flow rates and minimized solvent amounts. Furthermore, no additional reconcentration steps are needed. The methanol extract obtained is combusted with a standard EOX (extractable organic halogen) analyzer and the concentration of organically bound halogens is determined by microcoulometric analysis. The matrix effects are considerably reduced compared to the standard procedure (EN 1485) commonly used. A detection limit of 13 μg/L was established.