High selectivity molecularly imprinted polymer based on short amylose as bio-based functional monomers for selective extraction of λ-cyhalothrin.

Nowadays, the development of sustainable molecularly imprinted polymers (MIPs) with high selectivity is still challenging due to the limitations of bio-based functional monomers. In this study, the highly selective and porous MIPs (LC-TMIPs) were designed and prepared on short amylose (SAM) as bio-based functional monomers, λ-cyhalothrin (LC) as a template molecule, and tetrafluoroterephthalonitrile as a rigid crosslinking agent. Static, dynamic, and selective adsorption experiments were conducted to investigate the adsorption performance. The results indicated that, compared to MIPs prepared using epichlorohydrin as flexible crosslinking agents, LC-TMIPs exhibited higher imprinting factor (3.93), selectivity (5.78), and adsorption capacity (35.79 mg g-1), as well as faster adsorption/desorption kinetics. The LC-TMIPs were used as sorbents for the selective determination of LC in both apple and cucumber samples by high-performance liquid chromatography. Under the optimal extraction conditions, the recoveries of the method reached 92.1-106.1 %, with a linear range of 1.5-30 ng g-1 and a detection limit of 0.5 ng g-1. The proposed preparation method of LC-TMIPs is expected to open a new way to prepare highly selective and sustainable MIPs for hydrophobic compounds.

A new sustainable filtration membrane extraction method based on nanoconfined liquid phase extraction: Determination of organochlorinated pesticides and pyrethroids in tea samples.

BACKGROUND: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CµS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL-1 (R2 ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 µg kg-1. The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34).

COF-SiO2@Fe3O4 Composite for Magnetic Solid-Phase Extraction of Pyrethroid Pesticides in Vegetables.

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

Consecutive high-performance removal of Cu2+ metal ions and Deltamethrin using multifunctional pyrolysis cuttlebone/cotton fabric nanocomposite.

A simple technique was developed for the modification of cotton materials that is inexpensive, environmentally friendly, and very effective. Waste Cotton fabrics (WCFs) are loaded with propolis extract (PE) for Cu2+ removal. Then, Cu2+ underwent a pyrolysis process with modified cuttlebone (CB) at 900 °C for 5 h. The surface of the prepared materials was characterized using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX), Fourier transform infrared (FTIR), BET, particle sizes, thermogravimetric analysis (TGA) and zeta potential analysis. The Cu2+ metal ions from an aqueous solution were removed using WCFs/PE, and DLM was subsequently removed using pyro WCFs/PE/Cu/CB. The as-prepared NPs exhibited the face-centered cubic structure of WCFs/PE/Cu/CB with crystallite sizes ranging from 386.70 to 653.10 nm. FTIR spectra revealed that CB was present on the surface of the resulting WCFs/PE/Cu. SEM revealed the dispersion of a uniformly flower-like morphology over a large area. Sorption studies were performed based on parameters that included pH, dose, contact time, and initial concentration. The adsorption isotherm and the kinetic studies of the DLM adsorption process were applied at a pH of 5.0 and a temperature of 25 °C using several isotherms and kinetic models. The results revealed qmax (20.51 mg/g) with R2 = 0.97, the Langmuir isotherm that best matches the experimental data. Hence, the Langmuir isotherm suggests that it is the model that best describes sorption on homogenous surfaces or surface-supporting sites with various affinities. The correlation coefficient R2, χ2, adjusted correlation coefficient, and error functions like root mean square (RMSE), normalized root mean square error (NRMES), and mean absolute error (MAE) were used to evaluate the best-fit models to the experimental adsorption data. Moreover, cost estimation for the prepared adsorbent WCFs/PE/Cu showed that it costs approximately 3 USD/g, which is a cheap adsorbent compared to other similar adsorbents reported in the literature. The examined WCFs/PE have significant applicability potential for Cu2+-laden wastewater treatment due to their superior Cu2+ metal ions adsorption capability and reusability. The cytotoxicity and safety study showed that at higher concentrations, it resulted in much less cell viability. Additionally, the removal efficiency of Cu2+ metal ions from synthetic, realistic industrial wastewater using WCFs/PE reached up to 96.29 %, demonstrating good adsorption capability. Thus, there is a huge possibility of accomplishing this and performing well. This study paves the way for the reuse and valorization of selected adsorbents following circular economy principles. Two green metrics were applied, the Analytical Eco-scale and the Analytical GREEnness Calculator (AGREE).

Residual characteristics of etofenprox in the processing stages of rice cakes and cookies.

The changes in residual amounts of an insecticide (etofenprox) in processed rice cakes and cookies were investigated in this study. Test samples were sprayed with etofenprox during rice cultivation, and brown rice samples were dipped in a pesticide solution to investigate the effects of washing and processing. A multiresidue method for multiclass pesticides was employed for etofenprox analysis using a high-performance liquid chromatography-ultraviolet detector setup. Etofenprox was not detected in polished rice that was processed into rice cakes and cookies. The etofenprox residue levels were 2.13 mg/kg in each processing stage of brown rice products that were dipped in 400 mg/kg etofenprox solutions. The residual amounts of etofenprox in washed/polished rice and rice flour obtained by grinding were 1.25 and 0.77 mg/kg, respectively. The residual levels were 0.38 mg/kg in rice cakes prepared by cooking rice flour in a steamer for 20 min (a decrease of 82.1% compared to that in polished rice), 0.47 mg/kg in rice cookies baked in an oven for 20 min (a decrease of 78.0%), and 0.21 mg/kg in fried rice cookies (a decrease of 90.2%). Overall, the residual levels of etofenprox decreased in a range of 40-100% during the processing of rice cakes and cookies.

Automated Solid-Phase Microextraction and Negative Chemical Ionization GC-MS for the Measurement of Synthetic Pyrethroids.

Synthetic pyrethroids are frequently detected as trace contaminants in sediment and natural waters. Because of the importance of measuring both total and freely available concentrations for ecotoxicity evaluations, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry using negative chemical ionization (NCI-GC-MS) was investigated as an analytical technique. Automated SPME-NCI-GC-MS quantification of freely dissolved (and thus potentially bioavailable) pyrethroids in aqueous samples containing dissolved organic matter (DOM) was successfully applied. The introduction of stable isotope-labeled pyrethroid calibration standards into the water sample allows for the simultaneous determination of total concentrations. Because pyrethroids adsorb rapidly to container walls (especially in calibration standard solutions without DOM) it was necessary to develop a technique to minimize the resulting time-dependent losses from calibration standard solutions in autosampler vials as they await analysis. A staggered preparation of these analytical calibration standards immediately prior to analysis was shown to ameliorate this problem. The developed method provides accurate and reproducible results for aqueous samples containing a range of dissolved organic matter concentrations (e.g., sediment pore water or sediment/water mixtures) and yields practical benefits in comparison to conventional analysis methods, such as reduced sample volume requirements, reduced solvent consumption, and fewer sample manipulations, and makes simultaneous measurements of freely dissolved/bioavailable pyrethroids and total pyrethroids possible.

Use of 1-octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine as sorbent for the extraction of pyrethroid insecticides from tea infusion.

Magnetic hyperbranched polyamideamine was carboxylated using succinic anhydride and modified further with 1-octyl-3-methylimidazole hexafluorophosphate successively. The morphology and chemical composition of the prepared material was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement, X-ray photoelectron spectroscopy, etc. 1-Octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine was used as sorbent in the magnetic solid-phase extraction for the separation and enrichment of five pyrethroid insecticides from tea infusion. The magnetic solid-phase extraction method proposed in this article has low method detection limits (0.53-0.71 ng/mL), acceptable coefficient of determination (0.9992-0.9998), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 1.2-6.3%; interday: 1.6-5.4%). In the detection of five pyrethroid insecticides in tea infusion, relative recoveries were in the range from 87.7 to 114.7% with satisfactory relative standard deviations (0.2-7.4%). With the aid of quantum chemistry calculations, the interaction energy between the sorbent and five pyrethroid insecticides was calculated, which proved the necessity of the modification of 1-octyl-3-methylimidazole hexafluorophosphate.

Determination of organophosphorus and synthetic pyrethroid pesticide residues and their variability in large size fruit crops.

BACKGROUND: Variability of pesticide residues in food item plays a key role for the evaluation of consumer food safety. However, variability factors (VFs) derived from the large size fruit crops are still scarce. Therefore, the present work was aimed to quantify pesticide residues and to estimate VFs in large size fruit crops of mango and guava. RESULTS: A total of 140 mango and 130 guava samples from different marketplaces in Bangladesh were collected to estimate the variability of pesticide residues (acephate, diazinon, malathion, fenitrothion, chlorpyrifos, quinalphos, dimethoate and cypermethrin) by in-house validated methods based on modified QuEChERS extraction and gas chromatography coupled with electron capture detector (ECD) and flame thermionic detector (FTD). The method was validated at three fortification levels (0.01, 0.10 and 0.30 mg kg-1 ) and satisfactory recoveries (80-111%) with relative standard deviation (RSDr ) ≤ 13% were achieved. A wide variation of residues was found in the analyzed samples. In the case of mango, the ranges of residues were 0.011-0.314, 0.015-0.04, and 0.05-0.291 mg kg-1 , respectively, for cypermethrin, chlorpyrifos, and dimethoate, while in the case of guava, the ranges were 0.04-0.113, and 0.03-0.290 mg kg-1 , respectively, for cypermethrin and acephate. The average VF for mango was 4.06 and it was 5.70 for guava. CONCLUSION: VFs originating from the marketed samples of mango and guava are reported in this study for the first time. The estimated VFs were higher than the default value of 3, therefore, the default VFs should be reconsidered when more data are obtained regarding large size crops. © 2021 Society of Chemical Industry.

Screening of lactic acid bacteria for their capacity to bind cypermethrin in vitro and the binding characteristics and its application.

In this study, the cypermethrin binding characteristics of lactic acid bacteria were investigated for the first time. Two strains, Lactobacillus plantarum RS60 and Pediococcus acidilactici D15, possessed the highest cypermethrin removal capacity and good tolerance to simulated digestive juices. They were employed for further studies on cypermethrin binding characteristics. 55.06% and 56.46% of cypermethrin were removed within 0.25 h by strains RS60 and D15, respectively. The effect of pH on binding capacity was negligible. Heat treatment enhanced cypermethrin binding rate. Moreover, inactive cells were capable of removing cypermethrin from fruit and vegetable juices, with over 60% cypermethrin reduction within 2 h. No adverse effect was found on the quality of juice during the biosorption process. Besides, these two strains also could bind other several pyrethroids and 3-phenoxybenzoic acid. These findings indicated that L. plantarum RS60 and P. acidilactici D15 may be useful to reduce cypermethrin in contaminated foods.

Overcoming matrix effects in the analysis of pyrethroids in honey by a fully automated direct immersion solid-phase microextraction method using a matrix-compatible fiber.

Pyrethroids insecticides may constitute a major hazard to honeybees, leading to colony collapse disorder. However, the determination of pyrethroids in honey has remained a challenging undertaking for analysts to date due to the high complexity of this matrix as well as the MRLs. This paper presents a fully automated method to overcome matrix influences using matrix-compatible overcoated SPME fiber for quantitative analysis of pyrethroids in diluted honey by GC-MS. The developed method was optimized using a multivariate approach providing LOQ values much lower than the stablished MRL (0.10-10 ng/g), while granting satisfactory linearity (R2 > 0.998) in a wide linear range of 0.1-2000 ng/g, repeatability with RSDs < 10%, reproducibility RSDs < 20%, and accuracy ranging from 75 to 118% and from 82 to 120 % for inter-day and intra-day assays, respectively by using five replicates. The method herein proposed overcomes challenges presented by complex matrices while minimizing sample handling and the overall complexity of the procedure.

Rapid Quantitative Detection of Deltamethrin in Corydalis yanhusuo by SERS Coupled with Multi-Walled Carbon Nanotubes.

With the increase in demand, artificially planting Chinese medicinal materials (CHMs) has also increased, and the ensuing pesticide residue problems have attracted more and more attention. An optimized quick, easy, cheap, effective, rugged and safe (QuEChERS) method with multi-walled carbon nanotubes as dispersive solid-phase extraction sorbents coupled with surface-enhanced Raman spectroscopy (SERS) was first proposed for the detection of deltamethrin in complex matrix Corydalis yanhusuo. Our results demonstrate that using the optimized QuEChERS method could effectively extract the analyte and reduce background interference from Corydalis. Facile synthesized gold nanoparticles with a large diameter of 75 nm had a strong SERS enhancement for deltamethrin determination. The best prediction model was established with partial least squares regression of the SERS spectra ranges of 545~573 cm-1 and 987~1011 cm-1 with a coefficient of determination (R2) of 0.9306, a detection limit of 0.484 mg/L and a residual predictive deviation of 3.046. In summary, this article provides a new rapid and effective method for the detection of pesticide residues in CHMs.

Optimization of a Simplified and Effective Analytical Method of Pesticide Residues in Mealworms (Tenebrio molitor Larvae) Combined with GC-MS/MS and LC-MS/MS.

An effective analytical method was optimized for residues including chlorpyrifos-methyl, deltamethrin, fenoxanil, thiobencarb and fludioxonil in mealworms, the larval form of Tenebrio molitor. They are listed for pest control during wheat cultivation and can be found in wheat-bran feed for growing mealworms in South Korea. Analytes were extracted using acetonitrile and salt packet. Four clean-up methods ((1) MgSO4 + 25 mg PSA + 25 mg C18; (2) MgSO4 + 50 mg PSA + 50 mg C18; (3) EMR-lipidTM tube; and (4) 10 mL n-hexane) were investigated and the method (1) was selected due to its robustness. Low-temperature precipitation of fat and proteins improved the recoveries. Recoveries from the Method (1) were satisfying with 70-120% with <20% relative SD at a spiking level of 0.01 mg/kg. With the simultaneous sample preparation, fenoxanil, thiobencarb and fludioxonil were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and chlorpyrifos-methyl and deltamethrin by gas chromatography tandem mass spectrometry (GC-MS/MS). Quantification limits for LC-MS/MS and GC-MS/MS were 0.5 and 2.5 µg/L, respectively. No pesticides of interest were detected in 30 real samples collected across the nation. However, the data can be provided for establishing maximum residue limits for the pesticides in mealworms in response to the positive list system.

Effective preparation of magnetic molecularly imprinted polymer nanoparticle for the rapid and selective extraction of cyfluthrin from honeysuckle.

Cyfluthrin is a widely used pesticide. In this study, a sensitive and efficient magnetic molecularly imprinted polymer (MMIP) was prepared by surface molecular imprinting, which used functionalized Fe3O4 particles as magnetic cores. Cyfluthrin was extracted and enriched using magnetic molecularly polymer for analyzing pesticide residue of Chinese herbal medicines. The crystal type, microstructure, particle size, saturation magnetization, and characteristic functional groups of the synthesized MMIPs were analyzed by analysis equipment. The results of isothermal adsorption and kinetic adsorption indicated that MMIPs reached adsorption equilibrium at 30 min, with a maximum capacity of 4.9 mg g-1, which had good adsorption performance, while selective adsorption experiments showed that MMIPs had higher affinity for cyfluthrin. Under the optimized conditions, the limit of detection (LOD) and the limit of quantification (LOQ) were 32.987 ng ml-1 and 109.955 ng ml-1, respectively. And linear range (30-3000ng ml-1) of cyfluthrin with correlation coefficient R2=0.9979, and MMIPs were used in honeysuckle, the recoveries were 91.5%∼97.2%, and RSD was 5.35%∼8.32% (n = 3). It is indicated that the magnetic molecularly imprinted polymer can be used as an effective material for the specific separation of cyfluthrin from honeysuckle.

Sequential extraction and enrichment of pesticide residues in Longan fruit by ultrasonic-assisted aqueous two-phase extraction linked to vortex-assisted dispersive liquid-liquid microextraction prior to high performance liquid chromatography analysis.

A simple, green and efficient method for extraction, purification and enrichment of pesticide residues of triazoles and pyrethroids in Longan fruit was developed by ultrasonic-assisted aqueous two-phase extraction (UAATPE) coupled to vortex-assisted dispersive liquid-liquid microextraction (VADLLME). Using an aqueous two-phase system (ATPS) of ethanol/K2HPO4 as extraction solvent, the composition of the ATPS, extraction temperature and time were investigated, respectively. Then VADLLME process also was optimized by investigating type and volume of extracting and dispersive solvents, vortex-assisted time and salt addition. The optimum conditions were as follows: the ATPS composition of ethanol concentration 30.0% (w/w) and K2HPO4 concentration 25% (w/w), extraction temperature 70 °C and extraction time 15 min for UAATPE; 1-dodecanol 200 µL as extraction solvent, ethanol 1.25 mL as dispersive solvent, vortex-assisted time 1.5 min and addition of NaCl 4% (w/v) for VADLLME. Ethanol as extraction solvent and dispersive solvent could directly connect UAATPE with VADLLME without extra steps. By means of HPLC-DAD detection, nine pesticides had good linearity ranged from 0.0200 to 13.59 µg/mL (R2 ≥ 0.9957). LODs and LOQs were in the range of 0.005576-0.01740 µg/mL and 0.01859-0.05010 µg/mL, respectively. UAATPE-VADLLME coupled to HPLC was successfully applied to simultaneous determination of multiple pesticides in Longan fruit, and mean recoveries and RSDs were between 76.95% and 98.63%, 1.2% and 9.8%, respectively. Furthermore, myclobutanil, fenpropathrin and deltamethrin were detected in pericarp and pulp of Longan samples from different districts, respectively.

Purification of pyrethrins from flowers of Chrysanthemum cineraraeflium by high-speed counter-current chromatography based on coordination reaction with silver nitrate.

Pyrethrum extract is a natural insecticide that has been used worldwide for centuries, with pyrethrins being considered active ingredients. Their purification is difficult due to their chemical structural similarity and instability to light. In the present study, a coordination complex high-speed counter-current chromatography was used to separate pyrethrins from pyrethrum extract. The two-phase solvent system composed of petroleum ether-ethyl acetate-methanol-water (10:2:10:2, v/v/v/v) with 0.30 mol/L silver nitrate was selected for separation. As a result, five pyrethrins including cinerin II (31.2 mg), pyrethrin II (43.9 mg), jasmalin II (39.1 mg), pyrethrin I (32.4 mg), and jasmalin I (16.0 mg) were obtained from 400 mg crude extract in 6 h by one-step HSCCC separation, with purities over 95%. The isolated compounds were identified by MS, 1H-NMR and 13C-NMR spectroscopy. The results demonstrated that the addition of silver nitrate in the two-phase solvent system of HSCCC significantly increased the HSCCC separation factor of pyrethrins. HSCCC is a rapid method for purification of pyrenthrins from pyrethrum extract. The established method may also be applied to separate analogous compounds from natural products in which the chemical structure differs in the position or numbers of alkenes.

Analysis of organophosphorus and pyrethroid pesticides in organic and conventional vegetables using QuEChERS combined with dispersive liquid-liquid microextraction based on the solidification of floating organic droplet.

A simple, sensitive and environmentally-friendly method for determining organophosphorus and pyrethroid pesticides in vegetables was developed to better evaluate the risk of consuming them. The pesticides in vegetables were extracted, purified and concentrated by using the QuEChERS (quick, easy, cheap, effective, rugged and safe method) combined DLLME-SFO (dispersive liquid-liquid microextraction based on solidification of floating organic droplet) techniques. The key parameters were optimized through orthogonal array experimental design and statistical analysis. The linearity of the calibration curves was satisfied in matrix-matched standard solution with R2 ≥ 0.99. The limits of detection and limits of quantification were 0.3-1.5 and 0.9-4.7 µg/kg, respectively. The average recoveries of pesticides were 61.6-119.4% with relative standard deviations <16.1%. Furthermore, the method was applied successfully to analyse the pesticides in 15 pairs of organic and conventional vegetables. These results reflect the efficiency, reliability and robustness of the developed method.

Magnetic Solid-Phase Extraction of Pyrethroid Pesticides from Environmental Water Samples Using Deep Eutectic Solvent-type Surfactant Modified Magnetic Zeolitic Imidazolate Framework-8.

A simple, sensitive and effective magnetic solid-phase extraction (MSPE) technique was developed for the extraction of pyrethroid pesticides from environmental water samples, followed by gas chromatography tandem triple quadrupole mass spectrometry determination. An adsorbent of magnetic zeolitic imidazolate framework-8@deep eutectic solvent (M-ZIF-8@DES) was prepared using deep eutectic solvent coated on the surface of M-ZIF-8. The features of M-ZIF-8@DES were confirmed by material characterizations, and the results indicated that M-ZIF-8@DES has a good magnetism (61.3 emu g-1), a decent surface area (96.83 m2 g-1) and pore volume (0.292 mL g-1). Single factor experiments were carried out to investigate the effect of different conditions on the performance of MSPE. Under the optimal conditions, the developed method performs good linearity (R2 ≥ 0.9916) in the concentration range of 1-500 µg L-1. The limits of detection were in the range of 0.05-0.21 µg L-1 (signal/noise = 3/1). The intraday relative standard deviation (RSD) and interday RSD were less than 9.40%. Finally, the proposed technique was applied for the determination of pyrethroid pesticides in environmental water samples. This work shows the potential of DES-modified metal-organic frameworks for different sample pretreatment techniques.

Stereoselective Analysis of Chiral Pyrethroid Insecticides Tetramethrin and α-Cypermethrin in Fruits, Vegetables, and Cereals.

This manuscript presents an effective and robust method for simultaneous stereoselective determination of two pyrethroid insecticides, tetramethrin and α-cypermethrin in different food products by high-performance liquid chromatography. Enantioseparation was carried out using reversed-phase chromatography, and the influences of four polysaccharide-based chiral columns, mobile phase composition, and column temperature on retention were fully investigated. Satisfactory separation was obtained on Chiralpak IG column using acetonitrile-water (75:25, v/v) under isocratic conditions. To extract and purify the target analytes from food matrices, matrix solid-phase dispersion was employed with C18 as dispersant and primary secondary amine as well as graphitized carbon black as cleanup sorbents. Response surface method based on Box-Behnken design was implemented to assist optimization of the extraction variables. Then, method validation was done in real samples including specificity, linearity, sensitivity, trueness, precision, as well as stability, and its analytical performance fulfills the criteria recommended by the European Union SANTE/11945/2015, demonstrating its applicability in studying the stereochemistry of chiral tetramethrin and α-cypermethrin in food products.

Development and validation of a method for the analysis of pyrethroid residues in fish using GC-MS.

The presence of the pyrethroids residues in different samples and the impact on human health is an increasing concern due to their widespread use. So, a method to determine eighteen pyrethroids in fish samples using a modified QuEChERS was developed. The clean-up procedure was performed by freezing samples overnight followed by dispersive solid phase extraction. The combination of C18, PSA and Z-Sep+ was optimized using a mixture design approach and samples were analysed using gas chromatography mass spectrometry. The method was validated using trahira samples and a scope extension was performed for tilapia and tainha. Recoveries were within 63-129%, relative standard deviation was ≤21.5% and the quantification limits were 5 µg kg-1 or 10 µg kg-1. The applicability of the method was assessed by analysis of fourteen real samples, in which residues were detected in four samples. Such detections demonstrate the importance of this sensitive method.

Monitoring of organophosphate and pyrethroid metabolites in human urine samples by an automated method (TurboFlow™) coupled to ultra-high performance liquid chromatography-Orbitrap mass spectrometry.

There is a growing concern to pesticide exposure in humans, being the organophosphate (OP), carbamate and pyrethroid the most commonly used insecticides. Therefore, a fast, simple and automated screening method based on ultra-high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry (UHPLC-Orbitrap-MS) has been developed to determine six OPs metabolites (3,5,6-trichloro-2-pyridinol "TCPy", 2-isopropyl-6-methyl-4-pyrimidinol "IMPY", 4-nitrophenol "PNP", 4-nitrophenol-d4 "PNP-d4″, 3-chloro-7-hydroxy-4-methylcoumarin "CMHC" and 2-diethylamino-6-methylpyrimidin-4ol "DEAMPY") and three pyrethroid metabolites (3-phenoxybenzoic acid "3-PBA", 4-fluoro-3-phenoxybenzoic acid "4-F-3-PBA" and 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid "cis/trans-DCCA") in human urine samples. Off-line solid phase extraction (SPE), on-line SPE and turbulent flow chromatography (TurboFlow™) extraction methodologies were compared, obtaining better results when TurboFlow™ was applied, achieving a total analysis time of 13.83 min. Several validation parameters were tested, obtaining suitable results for all studied compounds. Recoveries ranged from 70 to 116%, meanwhile repeatability and reproducibility were lower than or equal to 7% and 13%, respectively. The limits of quantification (LOQs) were set in the range from 1 µg/L to 5 µg/L (except for DCCA at 10 µg/L). Finally, thirty seven urine samples from women and men living near the agricultural areas of Almeria (Spain) were analyzed to know and control the contamination on the human health. PNP, DEAMPY and IMPY were detected in six urine samples at trace levels except IMPY, which was detected at 3.44 µg/L in one of the samples. Additionally, a post-targeted and untargeted analysis were carried out in the samples, identifying eleven insecticides such as bensulide or cinerin II, one insecticide metabolite, fipronil sulfone, one drug metabolite, carboxyibuprofen and two nicotine metabolites, cotinine and 2-(1-pyrrolidinyl)isonicotinic acid, in several samples.