Determination of pesticides of different chemical classes in drinking water of the state of Santa Catarina (Brazil) using solid-phase microextraction coupled to chromatographic determinations.

The evaluation of the concentration of pesticides in drinking water presents a real concern. In this study, a simple and rapid method based on solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry and electron capture detectors was developed aiming at multiclass determination of 23 pesticides regulated by the Brazilian legislation. The extraction was carried out by direct immersion mode (DI-SPME) using DVB/Car/PDMS fiber coating. In order to improve the extraction efficiency, parameters such as temperature, salting-out effect, and extraction time were optimized. The method was evaluated using drinking water samples spiked with the analytes at different concentrations, and it showed good linearity in the range studied. The values obtained for limits of quantification (LOQ) were below the limits established by Brazilian regulations. Accuracy and precision of the method exhibited satisfactory results, providing relative recoveries from 70 to 123.34% at three spiked levels, and the relative standard deviations ranged from 0.53 to 24.8%. The method was applied in 20 drinking water samples from 13 cities in the State of Santa Catarina, Brazil.

Bract as a novel extraction phase in thin-film SPME combined with 96-well plate system for the high-throughput determination of estrogens in human urine by liquid chromatography coupled to fluorescence detection.

In this study, an environmentally friendly and high-throughput method was developed for the determination of estrone (E1), 17ß-estradiol (E2), 17α-ethinylestradiol (EE2) and estriol (E3) in human urine by liquid chromatography-fluorescence detector (HPLC-FLD). A biosorbent (bract) was proposed as extraction phase for Thin-Film SPME combined with 96-well system. The characterization of the biosorbent was performed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The optimizations were carried out through univariate and multivariate approaches with optimal conditions comprised of urine samples diluted 40-fold, liquid desorption performed in methanol and addition of 20% (w/v) of NaCl in the sample. Considering an extraction/desorption cycle using the 96-well plate system, the sample preparation time was 1.7 min per sample, which contributes to the high-throughput of the method proposed. The analytical parameters of merit were determined and satisfactory results were achieved, including limits of detection ranging from 0.3 µg L-1 for estradiol to 3 µg L-1 for estrone, while limits of quantification varied from 1 µg L-1 for estradiol to 10 µg L-1 for estrone. The correlation coefficients ranged from 0.9947 for estrone to 0.9999 for estriol. The accuracy and intra-assay and intermediate precisions (RSD) were evaluated through extractions in diluted urine samples (40-fold) spiked with each analyte (1, 200 and 400 µg L-1 for E3; 0.1, 200 and 400 µg L-1 for E2; 0.5, 200 and 400 µg L-1 for EE2 and 10, 200 and 400 µg L-1 for E1). The relative recoveries (n = 3) ranged from 71 to 105%, intra-assay precision (n = 3) varied from 1 to 17% and intermediate precision (n = 9) ranged from 2 to 19%. The method developed can be successfully used for the quantification of estrogens in human urine samples.

A low-cost biosorbent-based coating for the highly sensitive determination of organochlorine pesticides by solid-phase microextraction and gas chromatography-electron capture detection.

In this study, an environmentally friendly and low-cost biosorbent coating was evaluated, for the first time, as the extraction phase for solid-phase microextraction (SPME) supported on a nitinol alloy. The characterization of the new fiber was performed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The applicability of the biosorbent-based fiber in the determination of δ-hexachlorocyclohexane, aldrin, heptachlor epoxide, α-endosulfan, endrin and 4,4'-DDD in water samples was verified, with separation/detection by gas chromatography coupled to electron capture detection (GC-ECD). The influencing parameters (temperature, extraction time and ionic strength) were optimized simultaneously using a central composite design. The optimum conditions were: extraction time of 80min at 80°C and sodium chloride concentration of 15% (w/v). Satisfactory analytical performance was achieved with limits of detection (LOD) between 0.19 and 0.71ngL-1 and limits of quantification (LOQ) between 0.65 and 2.38ngL-1. The relative recoveries for the analytes were determined using river and lake water samples spiked at different concentrations and ranged from 60% for α-endosulfan to 113% for δ-hexachlorocyclohexane, with relative standard deviations (RSD) lower than 21%. The fiber-to-fiber reproducibility (n=3) was also evaluated and the RSD was lower than 14%. The extraction efficiency obtained for the proposed biosorbent coating was compared to a commercially available DVB/Car/PDMS coating. The proposed fiber provided very promising results, including LODs at the level of parts per trillion and highly satisfactory thermal and mechanical stability.