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.

Expanding the applicability of magnetic ionic liquids for multiclass determination in biological matrices based on dispersive liquid-liquid microextraction and HPLC with diode array detector analysis.

Monitoring biological samples at trace levels of chemicals from anthropogenic actions such as pesticides, pharmaceuticals, and hormones has become a very important subject. This work describes a method for the determination of eight compounds of different chemical classes in human urine samples. Dispersive liquid-liquid microextraction based on magnetic ionic liquids was used as the sample preparation procedure. The main parameters of the method, such as sample dilution, type, and volume of disperser solvent, amount of magnetic ionic liquids, extraction time, and pH were optimized by univariate and multivariate procedures. Validation was performed using a urine sample of a male volunteer in order to obtain a calibration curve and the main analytical parameters of merit such as limits of detection and quantification. Values varied from 3.0 to 7.5 µg/L and from 10 to 25 µg/L, respectively. Satisfactory precisions of 21% for intraday (n = 3) and 16% for interday (n = 9) were achieved. Accuracy was evaluated by relative recovery assays using different urine samples and ranged from 75 to 130%. Robustness was assured by the Lenth method. The validated procedure was applied to five urine samples from different volunteers and the hormone estrone was found in one sample.

Magnetic ionic liquids as versatile extraction phases for the rapid determination of estrogens in human urine by dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography-diode array detection.

In this study, a rapid and straightforward approach based on magnetic ionic liquids (MIL) as extraction phases and dispersive liquid-liquid microextraction (DLLME) was developed to analyze the hormones estriol, 17-ß-estradiol, 17-α-ethynylestradiol, and estrone in human urine samples. This is the first report of an application of manganese-based MILs compatible with HPLC to extract compounds of biological interest from urine samples. The hydrophobic MILs trihexyltetradecylphosphonium tetrachloromanganate (II) ([P6,6,6,14+]2[MnCl42-]) and aliquat tetrachloromanganate (II) ([Aliquat+]2[MnCl42-]) were employed and the optimized extraction conditions were comprised of 5 mg of MIL ([P6,6,6,14+]2[MnCl42-]), 5 µL of methanol (MeOH) as disperser solvent, and an extraction time of 90 s at sample pH 6. The analytical parameters of merit were determined under optimized conditions and very satisfactory results were achieved, with LODs of 2 ng mL-1 for all analytes, determination coefficients (R2) ranging from 0.9949 for 17-ß-estradiol to 0.9998 for estrone. In addition, good results of method precision were achieved with the intraday (n = 3) varying from 4.7% for 17-ß-estradiol to 19.5% for estriol (both at 5 ng mL-1) and interday precision (evaluated at 100 ng mL-1) ranging from 11.4% for estrone to 17.7% for 17-α-ethynylestradiol and analyte relative recovery evaluated in three real samples ranged from 67.5 to 115.6%. The proposed DLLME/MIL-based approach allowed for a reliable, environmentally friendly and high-throughput methodology with no need for a centrifugation step. Graphical abstract An overview of the rapid and straightforward extraction procedure using DLLME/MIL-based approach.

A hybrid material as a sorbent phase for the disposable pipette extraction technique enhances efficiency in the determination of phenolic endocrine-disrupting compounds.

In this study, the hybrid material 3-n-propyl(3-methylpyridinium) silsesquioxane chloride (Si3Py+Cl-) was synthesized and investigated as a novel sorbent phase for the disposable pipette extraction (DPX) technique coupled to high-performance liquid chromatography-florescence detection. This sorbent phase was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Aqueous samples containing the phenolic endocrine-disrupting compounds bisphenol A (BPA), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) were subjected to DPX procedures and a series of optimizations was performed to determine the ideal extraction conditions using this approach. The proposed sorbent phase exhibited higher extraction efficiency than DPX-RP (reversed phase tips containing styrene-divinylbenzene), commonly used for the determination of the phenolic endocrine- disrupting-compounds under study. Satisfactory analytical performance was achieved with linear ranges from 2 to 100µgL-1 for 4-t-OP and 1-100µgL-1 for the other analytes. Limits of detection of 0.60µgL-1 for 4-t-OP and 0.30µgL-1 for other analytes, RSDs ranging from 1 to 20% and relative recoveries of 83-116% were obtained. Based on these satisfactory results, this sorbent phase represents a valuable alternative for the extraction of compounds with polar moieties in their structure.

A new approach to calibration and determination of selected trace elements in food contact polymers by LA-ICP-MS.

A calibration strategy using porous nylon disks and reference solutions is proposed for the first time for matrix matching and determination of As, Ba, Cd, Cr, Pb, Sr and Zn in polymers by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). Polymer samples commonly used in contact with food were analyzed. The procedure consists on the use of porous nylon disks as support for a dried droplet reference solution. Calibration in the range of 0.50-190µgg-1 for Ba, Cd, Cr, Pb, Sr and Zn and from 0.30-9.0µgg-1 for As was used. Laser and ICP-MS instrument conditions were evaluated in order to achieve the best signal-to-background ratio. The radiofrequency power and carrier gas flow rate were fixed at 1300W and 1.25Lmin-1, respectively. Spot size, repetition rate, scan line speed and laser fluency were set to 100µm, 20Hz, 100µms-1 and 17.9Jcm-2, respectively, as the established conditions for analysis of standards and samples. By using these conditions, limits of detection, estimated considering B+3s (where B is the value of the blank and s is the standard deviation of 10 measurements of the blank), ranged from 0.09µgg-1 (208Pb) to 1.09 (53Cr) and 0.05µgg-1 (208Pb) to 2.10 (53Cr) for calibration with and without 13C as internal standard (IS). In spite to the use of nylon for matrix matching of different polymeric matrices, the normalization with 13C as IS was also evaluated. The precision of the method is relatively good (RSD<20%), and the accuracy of the method, evaluated by analysis of certified reference materials (CRM) and by comparison with results obtained from solution analysis by ICP-MS after sample decomposition by microwave induced combustion (MIC) is relatively good. The suitability of the proposed method resulted in direct and reliable analyses of polymer samples with a simplified or unnecessary sample preparation step. In addition, the calibration with dried droplet reference solutions may be considered a promising procedure in view of its advantages to other forms of calibration, as the use of CRM or the preparation of synthetic standards. The use of porous nylon disks spiked with reference solutions for calibration is the main advantage of the present work.

External calibration strategy for trace element quantification in botanical samples by LA-ICP-MS using filter paper.

The use of reference solutions dispersed on filter paper discs is proposed for the first time as an external calibration strategy for matrix matching and determination of As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn in plants by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The procedure is based on the use of filter paper discs as support for aqueous reference solutions, which are further evaporated, resulting in solid standards with concentrations up to 250 µg g(-1) of each element. The use of filter paper for calibration is proposed as matrix matched standards due to the similarities of this material with botanical samples, regarding to carbon concentration and its distribution through both matrices. These characteristics allowed the use of (13)C as internal standard (IS) during the analysis by LA-ICP-MS. In this way, parameters as analyte signal normalization with (13)C, carrier gas flow rate, laser energy, spot size, and calibration range were monitored. The calibration procedure using solution deposition on filter paper discs resulted in precision improvement when (13)C was used as IS. The method precision was calculated by the analysis of a certified reference material (CRM) of botanical matrix, considering the RSD obtained for 5 line scans and was lower than 20%. Accuracy of LA-ICP-MS determinations were evaluated by analysis of four CRM pellets of botanical composition, as well as by comparison with results obtained by ICP-MS using solution nebulization after microwave assisted digestion. Plant samples of unknown elemental composition were analyzed by the proposed LA method and good agreement were obtained with results of solution analysis. Limits of detection (LOD) established for LA-ICP-MS were obtained by the ablation of 10 lines on the filter paper disc containing 40 µL of 5% HNO3 (v v(-1)) as calibration blank. Values ranged from 0.05 to 0.81  µg g(-1). Overall, the use of filter paper as support for dried aqueous standards showed to be a useful strategy for calibration and plant analysis by LA-ICP-MS.