Determination of Copper in Water Samples after Solid‐phase Extraction Using Dimethylglyoxime‐modified Silica

This work describes the modification of silica gel with dimethylglyoxime, in order to prepare an effective sorbent for the preconcentration and determination of copper. The sorption capacity of dimethylglyoxime‐modified silica‐gel (DMGMS) was 71.37 mg g^–1 and the optimum pH for the quantitative recovery of copper was found to be 5.0. The optimum flow rate, sorbent amount, and sample volume were 1 mL min^–1, 300 mg, and 50 mL, respectively. 10 mL of 0.1 mol L^–1 HCl was the most suitable eluent. The detection limit of copper was 6.0 ng mL^–1. The recommended method, for the determination of copper, is simple and reliable, without any notable matrix effect and can be successfully applied to environmental water samples. Copper recovery in the range from 99–100% was obtained from seawater and thermal spring water using this method. The method was applied to standard reference materials, NIST‐1515 (apple leaves) and NIST‐1643e (simulated fresh water), for the determination of copper and the results were in good agreement with certified values.     

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.     

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.     

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.     

Determination of Selected Endocrine Disrupter Compounds at Trace Levels in Sewage Sludge Samples

Simultaneous determination of endocrine disrupter compounds (EDCs), namely diltiazem, progesterone, benzylbutylphthalate (BBP), estrone, and carbamazepine (Cbz) were performed by using high performance LC–electrospray tandem MS. The ultrasound‐aided sequential extraction of sludge samples was optimized to increase extraction efficiencies of the analytes; ranging between 93.0–98.3% recovery. The limit of detection values for diltiazem, progesterone, BBP, estrone, and Cbz were found as 0.78, 0.72, 0.24, 0.75, and 0.72 µg/kg, respectively. Sludge samples taken from Ankara Tatlar; Hurma, Lara and Kemer of Antalya, and Middle East Technical University‐vacuum rotating membrane wastewater treatment plant (WWTP) aeration tanks were analyzed for their EDCs contents under optimized conditions. Diltiazem was found in all the samples in the range between 116.4–180.8 ng/g while progesterone and estrone were not detected in any of the samples analyzed with the exception of Tatlar WWTP. The BBP concentration was between beyond detection and 9195.5 ng/g. In addition, Cbz was found in all the samples ranging from 25.6 to 118.8 ng/g.     

Regeneration and Reuse of a Seaweed‐Based Biosorbent in Single and Multi‐Metal Systems

A seaweed‐waste material resulting from the processing of Ascophyllum nodosum was previously shown to be very efficient at removing Zn(II), Ni(II) and Al(III) both in single and multi‐metal waste streams. In this study, the regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Maximum desorption efficiencies (DE) of 183, 122 and 91% were achieved for Zn(II), Ni(II) and Al(III), respectively, for subsequent metal loading cycles, significantly exceeding the desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency (RE) for both single and multi‐metal systems. Values of 92, 96 and 94% RE were achieved for Zn(II), Ni(II) and Al(III), respectively, for the 5^th sorption cycle in single metal aqueous solutions. A slight decrease was observed for the same metals in multi‐metal systems with maximum REs of 85, 82 and 82% for Zn(II), Ni(II) and Al(III), respectively. This study showed that the novel sorbent derived from a seaweed industrial waste would be suitable for multiple metal sorption cycles without any significant loss in RE.     

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.     

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.     

Novel Polymeric Resin for Solid Phase Extraction and Determination of Lead in Waters

Interest in preconcentration techniques for the determination of metals at ultratrace levels still continues increasingly because of some disadvantages of flameless atomic absorption spectrometry and the high costs of other sensitive methods in compared to flame atomic absorption spectrometry (FAAS). Among preconcentration techniques, solid‐phase extraction is the most popular because of a number of advantages. In this work, thiol‐containing sulfonamide resin was synthesized, characterized, and applied as a new sorption material for solid phase extraction and determination of lead in natural water samples. The optimization of experimental conditions was performed using the parameters including pH, contact time, and volumes of initial and elution solutions. After preconcentration procedure, FAAS was used for determinations. The synthesized resin exhibits the superiority in compared to the other adsorption reagents because of the fact that there is no necessity of any complexing reagent as well as high sorption capacity. Consequently, 280‐fold improvement in the sensitivity of analytical scheme was achieved by combining the slotted tube atom trap‐atomic absorption spectrometry (STAT‐FAAS) and the developed preconcentration method. The limit of detection was found to be 0.15 ng mL^?1. The Pb²⁺ concentrations in the studied water samples were found to be in the range of 0.9–6.7 ng mL^?1.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Ultrasound‐Assisted Emulsification–Microextraction Combined with Graphite Furnace Atomic Absorption Spectrometry for the Determination of Trace Lead in Water

The ultrasound‐assisted emulsification–microextraction (USAEME) method was combined with graphite furnace atomic absorption spectrometry (GFAAS) for the determination of trace Pb using dithizone (H²DZ) as chelating reagent. Some effective parameters influenced the detection and microextraction, such as ashing temperature and atomization temperature, pH, extraction solvent, sample volume, extraction time, and extraction temperature were selected and optimized. After extraction, the calibration curves for Pb was in the concentration range of 0.1–10 ng mL^?1, and the linear equation was y = 0.097 x + 0.023 (R = 0.99). Under the optimized conditions, the detection limit of the method was 20 pg mL^?1 with an enrichment factor of 70 and the relative standards deviation (RSD) for seven determinations of 1 ng mL^?1 Pb was 11%. The proposed method was successfully applied to determine trace Pb in Yueya Lake water, pond water, and spiked samples. Furthermore, a certified reference material of Environment Water (GBW08607) was analyzed and the determined value was in good agreement with the certified value, which showed the accuracy, recovery, and applicability of the reported method.     

Cloud Point Extraction for the Preconcentration of Silver and Palladium in Real Samples and Determination by Atomic Absorption Spectrometry

A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag⁺ and Pd²⁺ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10^–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag⁺ and Pd²⁺, respectively. The enrichment factors were 35.0 and 28.0 for Ag⁺ and Pd²⁺, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.     

Simultaneous and Sensitive HPLC Determination of Mono‐ and Disaccharides,Uronic Acids,and Amino Sugars after Derivatization by Reductive Amination

The reductive amination of low‐molecular‐weight saccharides, uronic acids, and amino sugars, followed by a separation of the derivates by means of ion‐pair chromatography or RP‐HPLC, offers an interesting alternative to HPAEC‐PAD for the environmental analysis of these compounds. Under this aspect various potential amination reagents, i.e., p‐amino‐benzoic acid (p‐AMBA), p‐AMBA propyl ester, 1‐aminopyrene, 2‐(2‐aminophenyl)indole, and 4‐aminoazobenzene, were tested with regard to the formation of derivates and to the chromatographic properties of the formed derivates. p‐AMBA, p‐AMBA propyl ester and 4‐aminoazobenzene proved to be especially suited, because they facilitate the amination of all carbohydrate reference components together with a complete separation and sensible detection (detection limits < 0.5 mg/L) of the derivates. Mainly the following elution sequence was ascertained: amino sugars (hexosamines) / disaccharide(s) / monosaccharides (hexoses) / hexuronic acid(s) / N‐acetyl‐D‐glucosamine. Detection limits down to 0.1 μmol/L were realized using p‐AMBA as reagent, facilitating the determination of the target compounds in landfill leachates and lysimeter percolates. Applying the p‐AMBA propyl ester for derivatization, chromatographic interferences with weakly retained derivates and the coelution of the reagent with its galactosamine derivate can be avoided, since the ester elutes after its derivates unlike p‐AMBA itself.