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A rapid environmental pollution screening and monitoring workflow based on fabric phase sorptive extraction-gas chromatography-tandem mass spectrometry (FPSE-GC-MS/MS) is proposed for the first time for the analysis of 17 widespread used fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) in environmental waters. The most critical parameters affecting FPSE, such as sample volume, matrix pH, desorption solvent and time, and ionic strength were optimized by statistical design of experiment to obtain the highest extraction efficiency. Under the optimized conditions, the proposed FPSE-GC-MS/MS method was validated in terms of linearity, repeatability, reproducibility, accuracy and precision. To assess matrix effects, recovery studies were performed employing different water matrices including ultrapure, fountain, river, spring, and tap water at 4 different concentration levels (0.1, 0.5, 1 and 5 µg/L). Recoveries were quantitative with values ranging between 70-115%, and relative standard deviation values lower than 14%. Limits of quantification were at the low ng/L for all the target fungicides. Finally, the validated FPSE-GC-MS/MS method was applied to real water samples, revealing the presence of 11 out of the 17 target fungicides.

The metal-organic framework [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ was synthetized and characterized by X-ray diffractometry, differential thermogravimetric analysis, and infrared spectroscopy. The material was tested for the development and validation of a matrix solid-phase dispersion procedure for extraction of atrazine, bifenthrin, bromuconazole, clofentezine, fenbuconazole, flumetralin, procymidone, and pirimicarb, from peppers, with analysis using gas chromatography with mass spectrometry in the selected ion monitoring mode. The method developed was linear over the range tested (50.0-1000.0 μg/kg for procymidone and 200.0-1000.0 μg/kg for all other pesticides), with correlation coefficients ranging from 0.9930 to 0.9992. Experiments were carried out at 250.0, 500.0, and 1000.0 μg/kg fortification levels, and resulted in recoveries in the range of 52.7-135.0%, with coefficient of variation values between 5.2 and 5.4%, respectively, for [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ sorbent. Detection and quantification limits ranged from 16.0 to 67.0 μg/kg and from 50.0 to 200.0 μg/kg, respectively, for the different pesticides studied. The results were compared with literature data. The developed and validated method was applied to real samples. The analysis detected the presence of residues of pesticides procymidone, fenbuconazole, flumetralin, clofentezine, atrazine, and bifenthrin.

A robust solid-phase microextraction fiber was fabricated by electropolymerization of thiophene on a stainless steel wire. This fiber was applied for the determination of endocrine-disruptor pesticides, namely, chlorpyrifos, penconazole, procymidone, bromopropylate, and λ-cyhalothrin in well waters by a headspace solid-phase microextraction procedure. Operational parameters, namely, pH, sample volume, adsorption temperature and time, desorption temperature, stirring rate, and salt amount were optimized as 7.0, 8 mL, 70°C and 20 min, 250°C, 600 rpm, and 0.3 g/mL, respectively. The separation power of GC was coupled with the excellent sensitivity of the developed fiber enabling us to determine pesticide mixtures simultaneously in a ng/mL range. The LOD was in the range of 0.02-0.64 ng/mL. The method was successfully applied for the selective and sensitive determination of target pesticides in well water samples with acceptable recovery values (92-110%). The polythiophene fiber gives satisfactory results compared with commercial fibers. Commonly used pesticides with different polarities were chosen as representative compounds to search the applicability of the fiber for well water analysis collected from vineyards.

In multiresidue pesticide analysis using gas chromatography, it has long been recognized that an increase in the number of pesticides present in a standard solution can result in an enhancement of the peak responses of certain pesticides. Despite being widely acknowledged, this phenomenon has been rarely studied and is poorly understood. In this study, the authors have tentatively called this phenomenon the "matrix-like effect" and demonstrated it clearly using gas chromatography with tandem mass spectrometry. Five selected pesticides, namely, omethoate, terbufos, malathion, procymidone, and permethrin, and four internal standard candidates, namely, triphenyl phosphate, naphthalene-d8 , phenanthrene-d10 , and fluoranthene-d10 , were used to evaluate the matrix-like effect following the addition of 58, 108, and 166 other pesticides. With the exception of naphthalene-d8 , the responses of all evaluated pesticides and internal standard candidates were dramatically enhanced by the addition of up to 166 coexisting pesticides. The relative response factors of the five pesticides to each internal standard candidate were not constant under the conditions studied, meaning that these internal standard candidates did not adequately compensate for the matrix-like effect, at least for the five evaluated pesticides. The results revealed that the presence of various mixtures of pesticides in standard solutions might act as an unintentional analyte protectant, that is, some sort of troublesome "quasi-matrix."

Several methods used for the multiresidue analysis of pesticides from the environment and drinking water have been reported. However, most of these reports dealt with a small number of targeted pesticides or some special groups. A method that is simple, faster, and more cost-effective than the environmental protection agency (EPA) method has been developed for the analysis of 82 frequently used pesticides in water samples obtained from Yeongsan and Sumjin rivers, as well as rice fields located in various locations around the two rivers. The samples were extracted by dichloromethane, and the pesticides were analyzed using a GC-electron capture detector (ECD), followed by confirmation with GC-MS. Recoveries were found to be between 82 and 120.1% for most of the tested pesticides, which were in agreement with the standard values dictated by the EPA. The method was potentially applied to 66 water samples for human consumption and 90 water samples from the rice fields and irrigation ditches that were collected from June to September 2007. Oxadiazon, butachlor, and alachlor were detected in some of the river water samples collected in June, iprobenfos (IBP) was detected in samples collected in August, and no pesticide was detected in September. On the other hand, chlorpyrifos-methyl, IBP, hexaconazole, diazinon, oxadiazon, butachlor, and isoprothiolane were detected at relatively high concentrations in 48 rice paddy field water samples collected between June and September 2007. Alachlor in one sample and procymidone in some of the rice paddy field water samples were also detected in trace amounts. The results were consistent with the temporal pattern of pesticide application in Korean rice fields.

In this work, the determination of 11 pesticides (pirimicarb, metalaxyl, pyrimethanil, procymidone, nuarimol, azoxystrobin, tebufenozide, fenarimol, benalaxyl, penconazole, and tetradifon) in rose wines by micellar EKC (MEKC) using reversed electrode polarity stacking mode (REPSM) as online preconcentration strategy is described. The MEKC buffer consisted of 100 mM sodium tetraborate and 30 mM SDS at pH 8.5 with 6% v/v 1-propanol. A solid-phase microextraction (SPME) procedure using PDMS/divinylbenzene (PDMS/DVB) fibers was applied to extract the selected pesticides from the rose wine samples. The comparison between the calibration curves obtained from hydroalcoholic solutions (12% v/v ethanol) and from rose wines (matrix matched calibration) showed the existence of a strong matrix effect. Furthermore, a comparison with calibration curves obtained with white wine samples also showed significant differences for most of the analyzed pesticides. As a result, a matrix matched calibration was developed. Quantitative extraction from spiked wine samples was carried out in triplicate at two levels of concentration (range 0.18-6.00 mg/L). LODs between 0.040 and 0.929 mg/L were achieved, which are below the maximum residue limits (MRLs) established for wine grapes (except for pirimicarb) by the EU and Spain legislation as well as by the Codex Alimentarius. The established method - which is solvent free, cost effective, and fast - was also applied to the analysis of several homemade rose wine samples and a commercial one. Two of the selected pesticides were found in some of the analyzed samples.

A new material for matrix solid phase dispersion (MSPD) was synthesized -- p-nitro-N-propylaniline/silica (pNNPASi) by grafting reactions, characterized by elemental analysis and N(2)-adsorption-desorption isotherms, and tested for multiclass multiresidue analysis of pesticides in wet and freeze-dried carrots. Results obtained applying this new solid phase sorbent to MSPD extraction of ten pesticides (trichlorphon, trifluralin, dicloran, chlorothalonil, prometryn, linuron, captan, procymidone, prochloraz, and deltametrin) in wet carrots showed better results than the ones obtained for freeze-dried samples. Recoveries were in the range of 48-106% and precisions varied from 6 to 20% when wet samples were employed. Comparison between pNNPASi sorbent and C(18) showed better performance of pNNPASi for eight out of ten pesticides tested. The LOQs show that the developed method can be used to detect the pesticides investigated in carrots at concentrations below the maximum residue levels (MRL) established by EU, USEPA, and National Sanitary Surveillance Agency (ANVISA). Linuron, captan, prochloraz, and deltamethrin were found in at least one of the two commercial samples studied in concentrations above the LOQ of this method. Concentrations of the last three pesticides were above the European MRL in one of the commercial samples.

The metal-organic framework (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] was tested for extraction of pyrimicarb, procymidone, malathion, methyl parathion and α- and β-endosulfan from lettuce, with analysis using GC/MS in SIM mode. Experiments were carried out in triplicate at two fortification levels (0.1 and 0.5 mg/kg), and resulted in recoveries in the range of 78-107%, with RSD values between 1.6 and 8.0% for (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] sorbent. Detection and quantification limits ranged from 0.02 to 0.05 mg/kg and from 0.05 to 0.10 mg/kg, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.05-10.0 μg/mL), with correlation coefficients ranging from 0.9990 to 0.9997. Comparison between (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] and conventional sorbent (silica gel) showed better performance of the (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] polymeric sorbent for all pesticides tested.