Development of a new green non-dispersive ionic liquid microextraction method in a narrow glass column for determination of cadmium prior to couple with graphite furnace atomic absorption spectrometry.

Easy and innovative non-dispersive ionic liquid based microextraction (NDILME) has been developed for preconcentration of trace level of cadmium (Cd) in aqueous real surface water samples prior to couple with graphite furnace atomic absorption spectrometry (GFAAS). A 200 cm long narrow glass column containing aqueous solution of standard/sample was used to increase phase transfer ratio by providing more contact area between two medium (aqueous and extractive), which drastically improve the recoveries of labile hydrophobic chelate of Cd ammonium pyrrolidinedithiocarbamate (APDC), into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6]. Different aspect of the desire method have been investigated and optimized. Under the optimized key experimental variables, limit of detection (LOD) and enhancement factor (EF) were achieved to be 0.5 ng L(-1) and 150, respectively. Reliability of the model method was checked by relative standard deviation (%RSD), which was found to be <5%. Validity and accuracy of the developed method was checked by analysis of certified reference water samples (SLRS-4 Riverine water) using standard addition method. Application of the model method was productively performed by analysis of Cd in real surface water samples (tap and sea).

Arsenic in water, food and cigarettes: a cancer risk to Pakistani population.

Inorganic arsenic (iAs) in drinking water and food items has been associated with lung and bladder cancers in several countries including Pakistan. In present study water, food items were collected from Arsenic (As) endemic areas (southern part of Pakistan) during 2008-2012, to evaluate its impact on the health of local population. Exposure of As was checked by analyzing biological samples (blood and scalp hairs) of male lung and bladder cancer patients (smokers and non-smokers). For comparative purpose the healthy subjects of same age group and residential area as exposed referents (EXR) and from non-contaminated area (Hyderabad, Pakistan) as non-exposed referents (NER) were also selected. As concentration in drinking water, food and biological samples were analyzed using electrothermal atomic absorption spectrometry. The validation of technique was done by the analysis of certified reference material (CRM) of blood and hair samples. The As contents in drinking water and food were found 3-15-folds elevated than permissible limits, where as in biological samples; EXR have 2-3-folds higher than NER and cancer patients have 5-9-folds higher than NER. The significant difference was observed in smokers (P < 0.01). The outcomes of the study revealed that As levels were elevated in blood and scalp hair samples of both types of cancer subjects as compared to referents (P < 0.001). It was observed that the lung cancer patients (LCP) have 20-35% higher levels of As in both biological samples as compared to bladder cancer patients (BCP) due to smoking habit. This study has proved the correlation among As contaminated water, food and cigarette smoking between different types of cancer risks.

Separation and determination of copper in bottled water samples by combination of dispersive liquid--liquid microextraction and microsample introduction flame atomic absorption spectrometry.

A new and simple method for the determination of trace amounts of Cu(II) was developed by combination of dispersive liquid-liquid microextraction (DLLME) preconcentration and microsample introduction flame atomic absorption spectrometry. In this method, ethanol and chloroform were chosen as disperser and extraction solvents, respectively, and 1-nitroso-2-naphthol was used as the complexing agent. The factors affecting the extraction efficiency and determination of Cu(II), including extraction and disperser solvent nature and volume, concentration of the complexing agent, pH of the solution, extraction time, and matrix ions, were investigated. Under optimal conditions, the LOD for Cu(II) was 0.95 microg/L with a preconcentration factor of 70. The RSD was 1.9%. The accuracy of the developed DLLME method was verified by determination of Cu(II) in a certified reference material (NRCC-SLRS-4 river water). The relative error was -3.31%. The developed preconcentration procedure was successfully applied to the analysis of bottled drinking water samples.

Cloud point extraction of copper, lead, cadmium, and iron using 2,6-diamino-4-phenyl-1,3,5-triazine and nonionic surfactant, and their flame atomic absorption spectrometric determination in water and canned food samples.

A cloud point extraction procedure was optimized for the separation and preconcentration of lead(II), cadmium(II), copper(II), and iron(III) ions in various water and canned food samples. The metal ions formed complexes with 2,6-diamino-4-phenyl-1,3,5-triazine that were extracted by surfactant-rich phases in the nonionic surfactant Triton X-114. The surfactant-rich phase was diluted with 1 M HNO3 in methanol prior to its analysis by flame atomic absorption spectrometry. The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, surfactant concentration, temperature, and incubation time, were optimized. LOD values based on three times the SD of the blank (3Sb) were 0.38, 0.48, 1.33, and 1.85 microg/L for cadmium(II), copper(II), lead(II), and iron(III) ions, respectively. The precision (RSD) of the method was in the 1.86-3.06% range (n=7). Validation of the procedure was carried out by analysis of National Institute of Standards and Technology Standard Reference Material (NIST-SRM) 1568a Rice Flour and GBW 07605 Tea. The method was applied to water and canned food samples for determination of metal ions.

Determination of copper, lead and iron in water and food samples after column solid phase extraction using 1-phenylthiosemicarbazide on Dowex Optipore L-493 resin.

A novel solid phase extraction procedure for determination of copper, lead and iron in natural water and food samples has been established in the presented work. 1-Phenylthiosemicarbazide (1-PTSC) as ligand and Dowex Optipore L-493 resin as adsorbent were used in a mini chromatographic column. Various analytical conditions for the quantitative recoveries of analyte ions including pH, amounts of adsorbent, eluent, sample volume, etc. were investigated. The recovery values for analyte ions were higher than 95%. The determination of copper, lead and iron was performed by flame atomic absorption spectrometry. The influences of some alkali, alkali earth and transition metals on the recoveries of analyte ions were investigated. The preconcentration factor was 62.5. The limit of detections of the understudied analytes (k=3, N=21) were 0.64 µg L(-1) for copper, 0.55 µg L(-1) for lead and 0.82 µg L(-1) for iron. The relative standard deviation was found to be lower than 6%. The accuracy of the method was confirmed with certified reference material (GBW 07605 Tea). The method was successively applied for the determination of copper, lead and iron in water and some food samples including cheese, bread, baby food, pekmez, honey, milk and red wine after microwave digestion.

A novel preconcentration procedure using cloud point extraction for determination of lead, cobalt and copper in water and food samples using flame atomic absorption spectrometry.

In this work, a new cloud point extraction (CPE) procedure was developed for the separation and preconcentration of lead(II), cobalt(II), and copper(II) in various water and food samples. Complexes of metal ions with 1-Phenylthiosemicarbazide (1-PTSC) were extracted into the surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114) from samples. After phase separation, the enriched analytes were determined by flame atomic absorption spectrometry (FAAS). Factors affecting cloud point extraction, such as pH, reagent and surfactant concentrations, temperature, and incubation time were evaluated and optimized. The interference effect of some cations and anions was also studied. After optimization of the CPE conditions, the preconcentration factor of 25 and the limits of detection (L.O.D.) obtained for lead(II), cobalt(II), and copper(II) based on three sigma (n=20) were 3.42, 1.00, and 0.67 microg L(-1), respectively. The method presented precision (R.S.D.) between 1.7% and 4.8% (n=7). The presented preconcentration procedure was applied to the determination of metal ions in reference standard materials (SRM 1515 Apple leaves and GBW 07605 Tea) and some real samples including tap water, spring water, sea water, canned fish, black tea, green tea, tomato sauce and honey.

Speciation of Mn(II), Mn(VII) and total manganese in water and food samples by coprecipitation-atomic absorption spectrometry combination.

A speciation procedure based on the coprecipitation of manganese(II) with zirconium(IV) hydroxide has been developed for the investigation of levels of manganese species. The determination of manganese levels was performed by flame atomic absorption spectrometry (FAAS). Total manganese was determined after the reduction of Mn(VII) to Mn(II) by ascorbic acid. The analytical parameters including pH, amount of zirconium(IV), sample volume, etc., were investigated for the quantitative recoveries of manganese(II). The effects of matrix ions were also examined. The recoveries for manganese(II) were in the range of 95-98%. Preconcentration factor was calculated as 50. The detection limit for the analyte ions based on 3 sigma (n=21) was 0.75 microg L(-1) for Mn(II). The relative standard deviation was found to be lower than 7%. The validation of the presented procedure was performed by analysis of certified reference material having different matrices, NIST SRM 1515 (Apple Leaves) and NIST SRM 1568a (Rice Flour). The procedure was successfully applied to natural waters and food samples.

Simultaneous coprecipitation of lead, cobalt, copper, cadmium, iron and nickel in food samples with zirconium(IV) hydroxide prior to their flame atomic absorption spectrometric determination.

A simple and new coprecipitation procedure is developed for the determination of trace quantities of heavy metals (lead, cobalt, copper, cadmium, iron and nickel) in natural water and food samples. Analyte ions were coprecipitated by using zirconium(IV) hydroxide. The determination of metal levels was performed by flame atomic absorption spectrometry (FAAS). The influences of analytical parameters including pH, amount of zirconium(IV), sample volume, etc. were investigated on the recoveries of analyte ions. The effects of possible matrix ions were also examined. The recoveries of the analyte ions were in the range of 95-100%. Preconcentration factor was calculated as 25. The detection limits for the analyte ions based on 3 sigma (n=21) were in the range of 0.27-2.50 microgL(-1). Relative standard deviation was found to be lower than 8%. The validation of the presented coprecipitation procedure was performed by the analysis certified reference materials (GBW 07605 Tea and LGC 6010 Hard drinking water). The procedure was successfully applied to natural waters and food samples like coffee, fish, tobacco, black and green tea.

Mercury(II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination.

A method has been developed for mercury(II) and methyl mercury speciation on Staphylococcus aureus loaded Dowex Optipore V-493 micro-column in the presented work, by using cold vapour atomic absorption spectrometry. Selective and sequential elution with 0.1 molL(-1) HCl for methyl mercury and 2 molL(-1) HCl for mercury(II) were performed at the pH range of 2-6. Optimal analytical conditions including pH, amounts of biosorbent, sample volumes were investigated. The detection limits of the analytes were 2.5 ngL(-1) for Hg(II) and 1.7 ngL(-1) for methyl mercury. The capacity of biosorbent for mercury(II) and methyl mercury was 6.5 and 5.4 mgg(-1), respectively. The validation of the presented procedure is performed by the analysis of standard reference material. The speciation procedure established was successfully applied to the speciation of mercury(II) and methyl mercury in natural water and microwave digested fish samples.

Arsenic speciation in natural water samples by coprecipitation-hydride generation atomic absorption spectrometry combination.

A speciation procedure for As(III) and As(V) ions in environmental samples has been presented. As(V) was quantitatively recovered on aluminum hydroxide precipitate. After oxidation of As(III) by using dilute KMnO(4), the developed coprecipitation was applied to determination of total arsenic. Arsenic(III) was calculated as the difference between the total arsenic content and As(V) content. The determination of arsenic levels was performed by hydride generation atomic absorption spectrometry (HG-AAS). The analytical conditions for the quantitative recoveries of As(V) including pH, amount of aluminum as carrier element and sample volume, etc. on the presented coprecipitation system were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was calculated as 25. The detection limits (LOD) based on three times sigma of the blank (N: 21) for As(V) was 0.012 microg L(-1). The satisfactory results for the analysis of arsenic in NIST SRM 2711 Montana soil and LGC 6010 Hard drinking water certified reference materials for the validation of the method was obtained. The presented procedure was successfully applied to real samples including natural waters for arsenic speciation.

A preconcentration system for determination of copper and nickel in water and food samples employing flame atomic absorption spectrometry.

A separation/preconcentration procedure using solid phase extraction has been proposed for the flame atomic absorption spectrometric determination of copper and nickel at trace level in food samples. The solid phase is Dowex Optipore SD-2 resin contained on a minicolumn, where analyte ions are sorbed as 5-methyl-4-(2-thiazolylazo) resorcinol chelates. After elution using 1 mol L(-1) nitric acid solution, the analytes are determinate employing flame atomic absorption spectrometry. The optimization step was performed using a full two-level factorial design and the variables studied were: pH, reagent concentration (RC) and amount of resin on the column (AR). Under the experimental conditions established in the optimization step, the procedure allows the determination of copper and nickel with limit of detection of 1.03 and 1.90 microg L(-1), respectively and precision of 7 and 8%, for concentrations of copper and nickel of 200 microg L(-1). The effect of matrix ions was also evaluated. The accuracy was confirmed by analyzing of the followings certified reference materials: NIST SRM 1515 Apple leaves and GBW 07603 Aquatic and Terrestrial Biological Products. The developed method was successfully applied for the determination of copper and nickel in real samples including human hair, chicken meat, black tea and canned fish.

5-Chloro-2-hydroxyaniline-copper(II) coprecipitation system for preconcentration and separation of lead(II) and chromium(III) at trace levels.

A separation-preconcentration procedure based on the coprecipitation of lead(II) and chromium(III) ions with copper(II)-5-chloro-2-hydroxyaniline system has been developed. Effects of pH, sample volume and interferences on the recovery of the metal ions were investigated. The detection limits corresponding to three times the standard deviation of the blank were found to be 2.72 microg L(-1) for lead and 1.20 microg L(-1) for chromium. The preconcentration factor is 50. The effectiveness of the present method was assessed by determining analyte metals in GBW 07309 stream sediment and NIST SRM 1633b coal fly ash certified reference materials. The method was successfully applied to the determination of trace lead and chromium in environmental samples.

Equilibrium, kinetic and thermodynamic studies of adsorption of Pb(II) from aqueous solution onto Turkish kaolinite clay.

The adsorption of Pb(II) onto Turkish (Bandirma region) kaolinite clay was examined in aqueous solution with respect to the pH, adsorbent dosage, contact time, and temperature. The linear Langmuir and Freundlich models were applied to describe equilibrium isotherms and both models fitted well. The monolayer adsorption capacity was found as 31.75 mg/g at pH 5 and 20 degrees C. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (13.78 kJ/mol) indicated that the adsorption of Pb(II) onto kaolinite clay may be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, free energy (deltaG degrees ), enthalpy (deltaH degrees ) and entropy (deltaS degrees ) of adsorption were also calculated. These parameters showed that the adsorption of Pb(II) onto kaolinite clay was feasible, spontaneous and exothermic process in nature. Furthermore, the Lagergren-first-order, pseudo-second-order and the intraparticle diffusion models were used to describe the kinetic data. The experimental data fitted well the pseudo-second-order kinetics.

Adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite from aqueous solution.

The adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite (EP) from aqueous solution were investigated with respect to the changes in pH of solution, adsorbent dosage, contact time and temperature of solution. For the adsorption of both metal ions, the Langmuir isotherm model fitted to equilibrium data better than the Freundlich isotherm model. Using the Langmuir model equation, the monolayer adsorption capacity of EP was found to be 8.62 and 13.39 mg/g for Cu(II) and Pb(II) ions, respectively. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data and the mean free energies of adsorption were found as 10.82 kJ/mol for Cu(II) and 9.12 kJ/mol for Pb(II) indicating that the adsorption of both metal ions onto EP was taken place by chemical ion-exchange. Thermodynamic functions, the change of free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) of adsorption were also calculated for each metal ions. These parameters showed that the adsorption of Cu(II) and Pb(II) ions onto EP was feasible, spontaneous and exothermic at 20-50 degrees C. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that adsorption process for both metal ions followed well pseudo-second-order kinetics.