Etched stainless steel wire modified with conjugated microporous polymers-F6 for jacket-free stir bar sorptive extraction of benzoylureas in juice sample.

Benzoylurea (BU) insecticides have been widely used for pest control as third-generation insecticides. Considering that their residues in food may cause adverse effects on human health, the upper limits of BUs remaining in food have been set by the administration. Therefore, it is essential to develop a sensitive and efficient analytical method to determine the residues of BUs in food. Stir bar sorptive extraction (SBSE) is a novel sample preparation technique, and stainless steel wire (SSW) is an ideal substrate for an SBSE device. In this work, a novel SBSE device of SSW jacket-free stir bar with a dumbbell shape was designed and prepared. The conjugated microporous polymer CMP-F6, which possesses a porous structure, high hydrophobicity and rich fluorine-containing functional groups, was immobilized on the surface of SSW by the method of polyacrylonitrile glue adhesion. Compared with previous studies, which used SSW as a substrate, the method of etching partial SSW with hydrochloric acid, on the one hand, made the surface of SSW rough and easy to modify the extraction coating, and on the other hand, converted itself into a dumbbell-shaped structure, which is conducive to improving the extraction efficiency and stability of the SBSE device. The method of SBSE-HPLC-UV was established for determining five BUs. Owing to the hydrophobic interaction and F-F interaction between CMP-F6 and analytes, this method showed good extraction efficiency and had good linearity (R2 ≥ 0.9945) and high sensitivity (LODs in the range of 0.1-0.2 ng mL-1). It was used for the analysis of benzoylurea in an apple juice sample, and the recoveries were 74.3-117.9%.

Magnetic metal-organic framework MIL-100 (Fe)/polyethyleneimine composite as an adsorbent for the magnetic solid-phase extraction of fungicides and their determination using HPLC-UV.

Fe3O4@MIL-100 (Fe)/PEI are used for the first time as an adsorbent material for the extraction of pesticide residues (epoxiconazole, flusilazole, tebuconazole, and triadimefon) from food matrices. The adsorbent proposed (Fe3O4@MIL-100(Fe)/PEI) was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), thermogravimetric (TG) analysis, and vibrating sample magnetometer (VSM) techniques to evaluate the properties of the sorbent. Then, the Fe3O4@MIL-100 (Fe)/PEI was employed for the quantification of the four triazole fungicides in fruits and vegetables (apple, orange, tomato, cabbage, and cucumber) using HPLC-UV for separation and detection. During the extraction process, the main parameters such as amount of adsorbent, extraction time, pH value, ionic strength, eluting solvent, and eluting volume were optimized. Under the optimum conditions, good linearity of this method was observed for all analytes, with correlation coefficients (R2) ≥ 0.9908. The limits of detection (LODs) ranged from 0.021-3.04 µg kg-1. The extraction recoveries of the four triazole fungicides varied from 73.9 to 109.4% with relative standard deviations (RSD) in the range 0.5 to 6.2%. Compared with other MOFs, the modification of Fe3O4@MIL-100 (Fe) with PEI shows high efficient adsorption due to the combined benefits of MIL-100 (Fe) and PEI. The material is easily synthesized, has good stability, and is of low cost.  Graphical abstract.

Magnetic solid-phase extraction of benzoylurea insecticides in tea samples with Fe3 O4 -hyperbranched polyester magnetic composite as sorbent.

In this work, a method for the analysis of benzoylurea insecticides, including hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron, in tea samples by high-performance liquid chromatography with Fe3 O4 -hyperbranched polyester nanocomposite as the adsorbent for magnetic solid-phase extraction was developed. The magnetic nanocomposite was prepared and characterized by infrared spectroscopy, vibrating sample magnetometry, and scanning electron microscopy. The as-prepared nanocomposite was used as a sorbent for the extraction and preconcentration of pesticide residues in tea samples. The extraction and desorption conditions, including mass ratios of raw materials, amount of sorbent, pH value, extraction time, and desorption time, were investigated. Under the final conditions chosen for the analysis, good linearity was obtained for all the tested compounds, with R2 values of at least 0.9979. The limits of detection were determined in the range of 0.15-0.3 µg/L. The recovery obtained from the analysis of tea samples with various spiked concentrations was between 90.7 and 98.4%, with relative standard deviations (n = 4) lower than 4.1%. Furthermore, the present approach was successfully applied to the quantitative determination of residues of benzoylurea insecticides in real samples.

Inexpensive, effective novel activated carbon fibers for sample cleanup: application to multipesticide residue analysis in food commodities using a QuEChERS method.

Phenolic resin based activated carbon fibers (ACFs) were applied for the first time as a reversed-dispersive solid-phase extraction (r-DSPE) sorbent. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied to determine 26 pesticides (organophosphates, organochlorines, synthetic pyrethroids, and herbicides) in different complex matrices, including cauliflower, cucumber, banana, apple, wheat, and black gram. Different physicochemical characterization techniques were used to investigate the engineering and structural properties of the r-DSPE sorbent. All the chromatographic analyses were performed with a gas chromatograph equipped with an electron capture detector. The recoveries of all 26 pesticides were acceptable (70-120%), with relative standard deviations of less than 15%. The limit of detection and the limit of quantification were 1.13-5.48 ng/g and 3.42-16.60 ng/g, respectively. In the original QuEChERS method, primary secondary amine is extensively used as the r-DSPE sorbent in the cleanup process, but it is eightfold more expensive than the ACFs used in this study. Therefore, the modified QuEChERS method using ACFs during the cleanup process is more efficient, cheaper, and more robust to determine pesticides from different types of matrices, including vegetables, grains, and fruits, and ACFs could be used as a cost-effective alternative to primary secondary amine. Graphical Abstract Sample clean-up using PSA and ACF as r-DSPE sorbent in QuEChERS method.

Residue investigation of some phenylureas and tebuthiuron herbicides in vegetables by ultra-performance liquid chromatography coupled with integrated selective accelerated solvent extraction-clean up in situ.

BACKGROUND: Some trace amounts of urea herbicide residues can be transferred to humans via the food chain, thereby being potentially harmful to human health. The development of a robust analytical methodology for effective sample preparation and simultaneous determination of herbicide residues in vegetable samples is required for achieving food safety. RESULTS: The diuron-molecularly imprinted polymers (MIPs) synthesized have excellent affinity and high selectivity to phenylureas (monolinuron, isoproturon, diuron and linuron) and tebuthiuron. A novel automated procedure with better selectivity for vegetable sample treatment was developed by integrated matrix solid-phase dispersion-accelerated solvent extraction clean-up in situ. Five herbicides can be baseline separated with runtime down to 5 min by ultra-performance liquid chromatography, and good linearity was obtained with a correlation coefficient (r) of 0.9999. The limit of quantification of the method was in the range of 0.8-2.3 µg kg-1 . Diuron residue in cherry tomato sample was found to be 40 µg kg-1 . CONCLUSION: The developed method has satisfactory selectivity, good linearity, high sensitivity and accuracy as well as speediness, and can ensure rapid selective extraction and sensitive multi-residue analysis at low microgram per kilogram levels of the herbicides in vegetable food. © 2018 Society of Chemical Industry.

Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine.

The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol-water partition coefficient (log Kow) 2.7-6.3 and water solubility 0.0002-142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log Kow, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.

Novel metal-ion-mediated, complex-imprinted solid-phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples.

A novel metal-ion-mediated complex-imprinted-polymer-coated solid-phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex-imprinted polymer was introduced as a novel SPME coating using a "complex template" constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex-imprinted-polymer-coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0-150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0-86.9% and RSDs of 2.0-8.1%. This research provides an example to prepare a desirable water-compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator.

Application of the molecularly imprinted solid-phase extraction to the organophosphate residues determination in strawberries.

This study describe an analytical method employing gas chromatography (GC) using flame photometric detection that has been developed for the simultaneous determination of organophosphate pesticides (diazinon, disulfoton, parathion, chlorpyrifos and malathion) in strawberry samples. For this purpose, molecularly imprinted solid-phase extraction was applied as a sample preparation technique. The method was linear in the ranges from 0.10 to 1.00 µg g(-1), for diazinon, disulfoton, parathion and chlorpyrifos, and 0.10 to 2.00 µg g(-1) for malathion with r > 0.99. The detection limits (LD) ranged from 0.02 to 0.05 µg g(-1). Recovery studies yielded average recoveries in the range of 65.25 to 87.70 %. These results showed the potential of this technique for organophosphate residue monitoring in strawberry samples.

Enantioselective degradation of indoxacarb in cabbage and soil under field conditions.

The enantioselective degradation of indoxacarb in cabbage and soil has been investigated in Beijing and Anhui under open conditions. Indoxacarb enantiomers in samples were extracted with acetonitrile, cleaned up by florisil SPE column, separated on high performance liquid chromatography with a cellulose-tris-(3, 5-dimethylphenylcarbamate)-based chiral stationary phase (CDMPC-CSP), and determined by a photodiode array detector. The validation of the developed method by fortification rac-indoxcarb in cabbage and soil showed good accuracy and precision. The results of field trials indicated that the dissipation of indoxacarb enantiomers followed pseudo-first-order kinetics or first-order kinetics in cabbage and soil at two locations. The half-lives of two enantiomers in cabbage ranged from 2.8 to 4.6 d which were shorter than those in soil ranging from 23 to 35 d. The changes of enantiomeric fraction values proved that enantioselective degradation of indoxacarb happened in cabbage and soil. The (-)-indoxacarb showed faster degradation in the Beijing cabbage, whereas in the Anhui cabbage, (+)-indoxacarb preferentially degraded. In soil, preferential degradation of (+)-indoxacarb was observed at two locations.

Synthesis of core-shell molecularly imprinted polymer microspheres by precipitation polymerization for the inline molecularly imprinted solid-phase extraction of thiabendazole from citrus fruits and orange juice samples.

In this work, the synthesis of molecularly imprinted polymer microspheres with narrow particle size distributions and core-shell morphology by a two-step precipitation polymerization procedure is described. Polydivinylbenzene (poly DVB-80) core particles were used as seed particles in the production of molecularly imprinted polymer shells by copolymerization of divinylbenzene-80 with methacrylic acid in the presence of thiabendazole (TBZ) and an appropriate porogen. Thereafter, polymer particles were packed into refillable stainless steel HPLC columns used in the development of an inline molecularly imprinted SPE method for the determination of TBZ in citrus fruits and orange juice samples. Under optimized chromatographic conditions, recoveries of TBZ within the range 81.1-106.4%, depending upon the sample, were obtained, with RSDs lower than 10%. This novel method permits the unequivocal determination of TBZ in the samples under study, according to the maximum residue levels allowed within Europe, in less than 20 min and without any need for a clean-up step in the analytical protocol.

Cloud point extraction with Triton X-114 for separation of metsulfuron-methyl, chlorsulfuron, and bensulfuron-methyl from water, soil, and rice and analysis by high-performance liquid chromatography.

A new and efficient analytic methodology based on cloud point extraction (CPE) was developed for determination of pesticide residues of metsulfuron-methyl (MSM), chlorsulfuron (CS), and bensulfuron-methyl (BSM) in water, soil, and rice grain by high-performance liquid chromatography (HPLC). Multiple experimental conditions that affected CPE efficiency-including surfactant type and concentration, equilibration temperature and duration, ionic strength, and solution pH were identified. CPE conditions were optimized as follows: 1.5% Triton X-114 (w/v), 12% Na(2)SO(4) (w/v) solution (pH 2.0), and heat-assisted at 50 °C for 15 min. The calibration curves for all analytes were linear, ranging from 0.05 to 4.0 mg L(-1), with the correlation coefficients >0.9995 by HPLC-ultraviolet detector and were linear, ranging from 0.004 to 2.0 mg L(-1), with correlation coefficients >0.9983 by CPE-HPLC. The average recoveries at the three spiked levels using CPE ranged from 86.0% to 94.5% for water samples with relative SDs (RSDs) of 0.4% to approximately 7.8%; from 85.6% to 94.8% for soil samples with RSDs of 1.2% to approximately 9.5%; and from 81.9% to 91.3% for rice samples with RSDs of 1.7% to approximately 5.8%. The proposed CPE-HPLC method can be successfully used to analyze MSM, CS, and BSM residues from contaminated water, soil, and rice grain samples.

Partially carbonized cellulose filter paper as a green adsorbent for the extraction of pesticides from fruit juices.

In this study, a new solid phase extraction method based on the use of a low-cost funnel-shaped partially carbonized cellulose filter paper as a sorbent has been developed. The sorbent is easily prepared by heating the folded filter paper wetted with sulfuric acid solution and can be reused for several times. It is combined with dispersive liquid-liquid microextraction and used for the extraction of some pesticide residues from fruit juice samples prior to their analysis by gas chromatography-flame ionization detection. In this work, limits of detection and quantification were in the ranges of 0.30-0.61 and 1.0-2.0 µg L-1, respectively, and relative standard deviations ranged between 3 and 6% for intra- (n=5) and inter-day (n=5) precisions at a concentration of 25 µg L-1 of each pesticide. The enrichment factors of 452-751 were achieved. Extraction recoveries were in the range of 45-75%. The calibration curves had wide linear ranges with a good linearity (coefficient of determination ≥ 0.994). Finally, efficiency of the method was apprised by determining the analytes in fruit juice samples and relative recoveries were found to be in the range of 85-101%.

Mesoporous molecularly imprinted polymer core@shell hybrid silica nanoparticles as adsorbent in microextraction by packed sorbent for multiresidue determination of pesticides in apple juice.

In this work, we report the synthesis of a mesoporous molecularly imprinted polymer on the surface of silica nanoparticles (core@mMIP) to be applied as adsorbent in microextraction by packed sorbent (MEPS) for selective determination of pesticides in apple juice. The core@mMIP was properly characterized, showing good adhesion of the polymer to the silica core. The best extraction conditions were: 200 µL of ultrapure water as washing solvent, 150 µL of acetonitrile as eluent, 100 µL of sample at pH 2.5, five draw-eject cycles and 8 mg of adsorbent. Thereby, recoveries of 96.12 ± 1.05%, 76.88 ± 6.18% and 76.18 ± 5.57% were obtained for pyriproxyfen (PPX), deltamethrin (DTM) and etofenprox (ETF), respectively. After validation, the method presented linearity in the range of 0.02-10 µg mL-1 (r > 0.99), limit of detection of 0.005 µg mL-1, satisfactory selectivity, and proper precision and accuracy. The method was successfully applied real samples of processed and fresh apple juice.

PEG-modified magnetic Schiff base network-1 materials for the magnetic solid phase extraction of benzoylurea pesticides from environmental water samples.

It is necessary to establish a rapid, simple and environmentally friendly detection method for benzoylurea pesticides (BUs) in environmental water samples because of their toxicity in environmental circulation. Herein, a novel polyethylene glycol (PEG) modified magnetic covalent organic framework material based on the Schiff base reaction was prepared (PEG/Fe3O4@SNW-1). This material was used as a sorbent for enriching five BUs by magnetic solid phase extraction prior to detection via high-performance liquid chromatography. After the optimization of several parameters (such as the salinity, extraction time, amount of sorbent, desorption time, etc.) that influenced the recovery of the magnetic solid phase extraction process, the limits of detection (S/N = 3) were defined as less than 1.0 µg L-1, and the limits of quantitation (S/N = 10) were calculated as being lower than 3.4 µg L-1. A satisfactory linear range of 5-1000 µg L-1 was achieved. Finally, the proposed method was applied to analyze benzoylurea pesticides in three environmental water samples. These results indicated that the proposed method was feasible and demonstrated the potential application of the PEG/Fe3O4@SNW-1 material for detecting similar pesticide residues in environmental water samples.

Direct-immersion SPME in soy milk for pesticide analysis at trace levels by means of a matrix-compatible coating.

This study demonstrates a newly developed PDMS/DVB/PDMS fiber's suitability for the determination of pesticides in soy milk via direct-immersion solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry, eliminating the need for extensive sample pre-treatment procedures. Fouling accumulation on the coating surface was further minimized by implementing rapid and effective pre- and post-desorption cleaning steps. Under optimum conditions, the fiber was used to perform over 120 extractions while maintaining RSD values of less than 24.5% for 10 extracted pesticides. By comparison, the RSD values ranged from 8.4% to 42.8% over 80 extractions using a commercial PDMS/DVB fiber. The optimized conditions were used to fully validate a quantitative method for the targeted analytes by matrix-matched calibration and isotopically labeled internal standard correction. Significantly, the proposed method was able to achieve limits of quantitation (1-2.5 µg/kg) for the targeted analytes that were below the Maximum Residue Levels mandated for soy-based products. Accuracy, intra- and inter-day repeatability were also satisfactory. The proposed PDMS/DVB/PDMS fiber dramatically improved repeatability and suitability for direct-immersion SPME in soy milk, and represents a good alternative to other extraction methods for high-throughput quantitative analysis of pesticide residues in soy-based products.

Polyethyleneimine as weak anionic exchanger adsorbent for clean-up in pesticide residue analysis of fruits and vegetables.

Pesticide residue analysis in fruits and vegetables is generally performed with the QuEChERS method, when clean-up is mainly achieved with primary secondary amine (PSA) by dispersive solid phase extraction (dSPE). In this work, we present a rapid and efficient method for the clean-up of fruit and vegetable extracts with polyethyleneimine (PEI) as alternative to PSA. Clean-up of QuEChERS extracts with a mixture of branched PEI adsorbed on magnesium sulfate and silica gel was realized in 10 min, when several polar matrix components were clearly reduced. The success of the clean-up for representative matrices was visualized by both high-performance thin-layer chromatography with different detection options and total ion current chromatograms of liquid chromatography-mass spectrometry analyses. Generally, dSPE clean-up with PEI was at least equally effective as dSPE with PSA, but PEI clearly superimposed PSA in terms of adsorption capabilities towards fatty acids. After clean-up of fatty acid mixtures with 150 and 300 mg/L, total fatty acids were reduced by 98% and 99%, respectively, while PSA left two- and three-fold quantities. Additionally, the susceptibility of base-labile pesticides towards PEI as compared to PSA generally was negligible, further supporting the high suitability of PEI for clean-up in pesticide residue analysis. Thus, clean-up with PEI enables a clear reduction of various matrix compounds in fruit and vegetable extracts and provides a rapid, convenient and low-cost alternative to the existing dSPE methods with PSA.

Assessment of magnetic core-shell mesoporous molecularly imprinted polymers for selective recognition of triazoles residual levels in cucumber.

Functional magnetic nanomaterials based on molecular imprinting technique were successfully prepared on the surface of modified Fe3O4. Transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffractometer, and vibrating sample magnetometry were applied for characterization of the synthesized magnetic nanoparticles. The magnetic molecularly imprinted polymers (MMIPs) exhibited satisfactory magnetic response, specific recognition, and excellent adsorption capacity toward triazoles (maximum adsorption capacity of 9202.9 µg g-1 for triadimefon). The obtained MMIPs were further used as magnetic dispersive solid-phase extraction (MDSPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for detection of 20 triazoles in cucumber spiked at different levels. The mean recoveries were ranged from 79.9% to 110.3% and relative standard deviations (RSDs) were <11.2% (n = 5). Herein, we report a simple, rapid, environmentally friendly, and magnetic stuff recyclable approach for triazoles residual analysis in complicated agricultural products.

Removal of pesticides from white wine by the use of fining agents and filtration.

The effects of four clarification agents (bentonite, charcoal, PVPP and potassium caseinate) on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked white wine, elaborated from Airen variety grapes from the D.O. Region of Jumilla (Murcia, Spain) are studied. The clarified wines were filtered with 0.45 microm nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Hydro-alcoholic solutions with the three fungicides at concentrations of 1 and 2 ppm were then added through intense stirring to each of the containers. Two hours later, the corresponding clarifying agent was added with intense stirring for some minutes. The containers were then sealed and left to settle for five days. Once the clean wines had been racked, they were filtered through nylon 0.45 microm pore filters. All assays were performed three times. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with an electron captor detector (ECD), while that of famoxadone was made using an HPLC-DAD. For the three fungicides, the highest elimination is produced with the clarification by charcoal, reaching Levels of removal of 100% in all cases. For the four clarifying agents, the highest elimination is produced for the fluquinconazole residues. The fungicide which is retained most in the lees is famoxadone, since it has the lowest solubility of the three pesticides studied. The highest percentage of residues in the lees is obtained for the assay with charcoal. The filtration process of the clarified wines using the four agents studied is not effective, since the elimination percentage is generally lower than 10% of the initial residues in the non-clarified wines.

Evaluation of an alternative fluorinated sorbent for dispersive solid-phase extraction clean-up of the quick, easy, cheap, effective, rugged, and safe method for pesticide residues analysis.

In this study, the efficiency of a new fluorinated sorbent for dispersive solid-phase extraction (d-SPE) clean-up in extracts provided by the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) acetate method from tomato and sweet pepper samples was evaluated by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Clean-up using d-SPE technique has been widely used associated with the QuEChERS method. The most commonly sorbents used in d-SPE are primary secondary amine (PSA), octadecylsilane (C18) and graphitized carbon black (GCB), which are indicated to remove sugars, fatty acids, pigments, among others. The performance of an alternative fluorinated sorbent was compared with PSA and C18 sorbents for representative pesticides and better results were obtained when the fluorinated sorbent was used. Validation presented acceptable results for trueness and precision, with method limit of detection between 0.9 and 1.8µgkg-1 and limit of quantification from 2.6 to 5.4µgkg-1. Most of the compounds presented low matrix effect. Results showed that the fluorinated sorbent contribute to the clean-up of the tomato extract and is an effective alternative, with lower costs and greater efficiency. Commercial tomato samples were analyzed using the proposed method and residues of dimethoate, tetraconazole and thiamethoxam were detected.

Application of acid modified polyurethane foam surface for detection and removing of organochlorine pesticides from wastewater.

The commercial polyurethane foam was acid modified to get an inexpensive adsorbent (AM-PUF) has highly surface polarity and sorption capacity. The elemental analysis, scanning electron microscopy, thermal analysis, ultraviolet/visible/infrared spectroscopies and X-ray diffraction were used for characterization of AM-PUF. The surface of AM-PUF has amorphous character (broadband at 2θ, 21.75°) and contains several active sites e.g. NH, OH, CO, CC and COC groups. The electrical conductivity (σ), iodine value and methylene blue index of AM-PUF are 1.7×10-5Ω-1m-1, 208mg/g and 107mg/g. The AM-PUF has a high efficiency for completely removing (99-100%) of Aldrin, DDT, Endrin, Heptachlor, Heptachlor epoxide and Lindane pesticides in both acidic and alkaline solutions. The removing rates of the organochlorine pesticides from wastewater are very rapid (t1/2=22s). The negative value of ΔG (-10.9kJ/mol) for removing of OCPs using AM-PUF showed that the feasibility of the removing process and its spontaneous nature.