Combination of hollow-fiber-supported liquid membrane and dispersive liquid-liquid microextraction as a fast and sensitive technique for the extraction of pesticides from grape juice followed by high-performance liquid chromatography.

The simultaneous use of a hollow-fiber-supported liquid membrane and dispersive liquid-liquid microextraction for the determination of pesticides directly in grape juice was investigated. The detection and quantification were performed by liquid chromatography with diode array detection. The optimum extraction condition was reached by filling the pores of the membrane wall with dodecanol and using hexane/acetone as extraction/dispersion solvents. Salt addition had a highly negative effect on the extraction efficiency and the optimum extraction time was 60 min. The volume of hexane/acetone mixture and the sample pH did not affect the signal at the levels studied. Therefore, an intermediate amount of these solvents (250 µL; 1:7.5 v/v) and pH 6 were selected. The optimum desorption condition was obtained with acetonitrile and 10 min of desorption time. The linear working range varied from 58 to 500 µg/L (parathion-methyl), 62-500 µg/L (difenoconazole) and 107-500 µg/L (chlorpyrifos), with correlation coefficients ranging from 0.9980-0.9942. The limits of detection and quantification found were, respectively, 17 and 58 µg/L for parathion-methyl, 19 and 62 µg/L for difenoconazole and 32 and 107 µg/L for chlorpyrifos. The relative standard deviation ranged between 3.5 and 11.2%.

Isolation and preconcentration of Cd(II) from environmental samples using polypropylene porous membrane in a hollow fiber renewal liquid membrane extraction procedure and determination by FAAS.

The use of polypropylene porous membrane in a hollow fiber renewal liquid membrane (HFRLM) procedure for determination of Cd(II) in water samples was assessed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex. The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the polypropylene membrane porous. The organic solvent is immobilized inside the polypropylene membrane porous, leading to an homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and Cd(II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. The optimized variables were: sample pH, DDTP concentration, stripping pH, EDTA concentration, extraction temperature and time, extractor solvent and addition of salt to saturate the sample. The sample volume used was 15 mL and the stripping volume was 165 microL. The analyte enrichment factor was 107, limit of detection 1.5 microg L(-1), relative standard deviation 4.0% (15 microg L(-1), n=7) and the working linear range 5-30 microg L(-1).

Simple hollow fiber renewal liquid membrane extraction method for pre-concentration of Cd(II) in environmental samples and detection by flame atomic absorption spectrometry.

A hollow fiber renewal liquid membrane (HFRLM) extraction method to determine cadmium (II) in water samples using Flame Atomic Absorption Spectrometry (FAAS) was developed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex (ML(2)). The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the poly(dimethylsiloxane) (PDMS) membrane, that had their walls previously filled with the same organic solvent. The organic solvent is solubilized inside the PDMS membrane, leading to a homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and cadmium (II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. A multivariate procedure was used to optimize the studied variables. The optimized variables were: sample (donor phase) pH 3.25, DDTP concentration 0.05% (m/v), stripping (acceptor phase) pH 8.75, EDTA concentration 1.5x10(-2) mol L(-1), extraction temperature 40 degrees C, extraction time 40 min, a solvent mixture N-butyl acetate and hexane (60/40%, v/v) with a volume of 100 microL, and addition of ammonium sulfate to saturate the sample. The sample volume used was 20 mL and the stripping volume was 165 microL. The analyte enrichment factor was 120, limit of detection (LOD) 1.3 microg L(-1), relative standard deviation (RSD) 5.5% and the working linear range 2-30 microg L(-1).

Application of factorial design and Doehlert matrix for determination of trace lead in environmental samples by on-line column preconcentration FAAS using silica gel chemically modified with niobium(V) oxide.

In this study a new method for Pb determination in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The sorbent used for Pb preconcentration and extraction was silica gel chemically modified with niobium(V) oxide. Flow and chemical variables of the system were optimized through a multivariate procedure. The factors selected were buffer type, eluent concentration, and sample and eluent flow rates. It was verified that the aforementioned factors as well as their interactions were statistically significant at the 95% confidence level. The effect of foreign ions was evaluated using a fractionary factorial experimental design. The detection limit was 0.35 microg L(-1) and the precision was 1.6%. Results for recovery tests using different environmental samples were between 90 and 104%. Certified reference materials were analyzed in order to check the accuracy of the proposed method.

Use of 8-hydroxyquinoline-chitosan chelating resin in an automated on-line preconcentration system for determination of zinc(II) by F AAS.

This study presents the development of an on-line preconcentration system for zinc(II) determination in aqueous samples. The analyte was trapped in a mini-column filled with a chelating resin based on a chitosan biopolymer modified with 8-hydroxyquinoline obtained by the diazotization reaction. Flow and chemical variables of the system, as well as the potential interference ions, were optimized through a multivariate procedure. The factors selected were sample pH, eluent concentration (HNO(3)), and sample and eluent flow rates. It was verified through a full factorial design that the sample pH and eluent flow rate factors were statistically significant at the 95% confidence level. A final optimization of the significant factors was carried out using a Doehlert matrix. The preconcentration system was linear between 2.5 and 75 microgL(-1), with a regression coefficient of 0.9995. The enrichment factor was 17.6. The limits of detection and quantification were 0.8 and 2.5 microgL(-1), respectively. The repeatability and the analytical frequency were, respectively, 2.7 (25.0 microgL(-1), n=8) and 18 samples per hour. Results for recovery tests using mineral water samples were between 85 and 93%. Certified reference materials were analyzed in order to check the accuracy of the proposed method.