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Supervised field trial was conducted to study the dissipation pattern of fluopyram in rice plant after application of fluopyram 400 g/L SC(Velum Prime) as soil drenching at the time of sowing in nursery bed at X (500 g a.i. ha -1 ) and 1.25X (625.2 g a.i. ha -1 ) doses. Samples of rice plant were collected on 0, 1, 3, 7, 10, 15, and 20 days after transplanting. QuEChERS-based extraction method was validated and adopted to determine the residues of fluopyram in rice seedlings, whole rice grains (with husk), polished rice grain, husk, straw, and soil using LC-MS/MS (liquid chromatography-tandem mass spectrometry).The initial deposit of fluopyram in rice plant recorded were 0.27 and 0.41 mg kg -1 in X and 1.25X doses, respectively. Fluopyram residues dissipated following first-order kinetics with half-life of 2.53 and 2.57 days at X and 1.25X doses, respectively. Residues were detected in seedlings up to 15 days after transplanting and were at below LOQ in whole rice grains (with husk), polished rice grain, husk, straw, and soil collected at harvest. Monitoring study revealed that application of novel nematicide fluopyram for the management of nematodes in rice does not pose any risks to consumers., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

A novel dispersive solid-phase microextraction method based on a metal-organic framework (MIL-100(Fe)) combined with a dispersive liquid-liquid microextraction technique was proposed for the extraction and enrichment of four insecticides in beverages. The qualitative and quantitative analysis of these insecticides was conducted using HPLC-MS/MS. To optimize the extraction process, several parameters were investigated, and the main variables were optimized using CCD-based RSM. The developed method displayed a wide linear range of 1.000-1000 ng/L and R 2 values >0.993 for all four calibration curves. The method demonstrated high sensitivity, with LODs and LOQs of 0.3-0.6 ng/L and 0.8-1.0 ng/L, respectively. In addition, the greenness of the proposed method was assessed using the Complex GAPI tool, and the results showed that the proposed method exhibits benefits, such as minimal usage of organic solvents and negligible matrix influence, making it a suitable method for the detection of insecticide residues in beverages., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Food safety is an important issue to protect humane health and improve the life quality. Hence, analysis of the possible contaminants in food samples is essential. A rapid and efficient vortexed-assisted dispersive µ-solid-phase extraction coupled with gas chromatography-mass spectrometry was proposed for simultaneous separation/preconcentration and determination of five commonly used organophosphorus pesticides. Reduced graphene oxide decorated NiCo 2 (OH) 6 nanoflowers as a novel nanostructure was synthetized and introduced for separation of the target pesticides from the wheat flour, rice flour, and baby food cereal samples. The characterization of the nanoflowers was accomplished by SEM-EDX, XRD, and FT-IR techniques. The main factors including pH, the amount of nanoflower, the volume of sample solution, salt concentration (ionic strength), desorption conditions (i.e. desorption solvent type and volume, and desorption time) on the pesticides extraction efficiencies were inquired using matrixed match method. Applying the optimum conditions, the linearity of 0.100-500.000 µg kg -1 , LODs and LOQs in the range of 0.03-0.04 µg kg -1 and 0.1 µg kg -1 for the studied food samples were obtained. The repeatability (intra-day precision (n = 5)) of ≤ 2.0 % and reproducibility (inter-day precision, days = 5, n = 3) of ≤3.1 % and were appraise at three concentration levels (10, 50 and 100 μg kg -1 of each analyte). High relative recoveries of 90.0-99.3 % ascertained high potential of the presented method for complex matrix analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A sensitive and accurate analysis of organochlorine pesticide (OCP) residues in dairy products poses a significant challenge. Herein, a novel covalent organic polymer, Azo-COP-1, was synthesized for the enhanced extraction of OCPs in dairy products. The solid phase microextraction fiber coated with Azo-COP-1 demonstrated excellent extraction performance for the OCPs via hydrogen bonding, halogen bonding, π-π stacking, and electrostatic interactions. Coupled with gas chromatography-electron capture detection, we developed a facile and reliable method for detecting OCPs in six types of dairy products with low limits of detection (2.0-400 pg g -1 ) and high method recoveries (82.6-113%). Azo-COP-1 coatings exhibited good stability and durability. The results verified the feasibility of using Azo-COP-1-based SPME to extract OCP residues in dairy product samples, highlighting its potential for routine monitoring of pesticide residues and food safety assessments.

In this study, a QuEChERS method based on citrate was developed and utilized for the analysis of twelve neonicotinoid pesticides in fresh red chilies, fresh green chilies, and dried chilies, coupled with ultra-high performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF/MS). In the sample preparation, acetonitrile containing 1% formic acid was used as the extraction solvent. Anhydrous sodium sulfate replaced the traditional anhydrous magnesium sulfate for water removal, effectively eliminating the issues of salt caking. Graphitized carbon black, octadecyl silica, and primary secondary amine were used as cleaning agents. The method showed good sensitivity, with the limits of quantification below 0.03 mg/kg for fresh chilies and below 0.15 mg/kg for dried chilies. Values of matrix effects ranged from -19.5% to 8.4%, and the recovery was 86.9% - 105.2%. The analytical method provided an effective tool for the high throughput detection of neonicotinoid pesticide residues in multiple chili matrices., Competing Interests: Declaration of competing interest The authors declared that they have no conflicts of interest to this work., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The use of pesticides has increased with the development of agriculture. However, due to the trace content and the matrix's inherent complexity in environmental water, development of rapid and sensitive detection method present significant challenges in the analysis of pesticide residues. The study synthesized magnetic graphene oxide (MGO) by combining superparamagnetic nanoparticles with the easy modification of graphene oxide (GO). Covalent organic frameworks (COFs) were then modified to have a large specific surface area. Finally, magnetic graphene oxide-based covalent organic frameworks, namely MGO-COFs, were obtained with a spherical structure and used as magnetic solid-phase extraction materials, which was successfully used to determine the seven pesticide residues in environmental samples in conjunction with high performance liquid chromatography. The method has a wide linear range for the tested pesticides, with satisfactory correlation coefficients (R ≥ 0.099) and low detection limits (0.3-1.21 μg L -1 ). The correlation coefficients for all seven pesticides were high (R 2 ≥ 0.9996). The spiked recoveries, exhibiting a range of 91.3 to 109 %, demonstrated that the developed MGO-COF-MSPE-HPLC-UV method is simple, efficient, and suitable for the analysis and detection of seven pesticide residues in environmental water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The work was based on N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)-functionalized Fe-MIL-101 and gold nanoparticles (AuNPs) as sensing materials, and an electrochemiluminescence (ECL) aptasensor was constructed for detecting acetamiprid. As a metal-organic framework (MOF) material, Fe-MIL-101, was renowned for its unique three-dimensional network structure and efficient catalytic capability. ABEI, a common ECL reagent, was widely applied. ABEI was introduced into the Fe-MIL-101 structure as a luminescence functionalization reagent to form Fe-MIL-101@ABEI. This approach avoided limitations on the loading capacity of luminescent reagents imposed by modification and encapsulation methods. With character of excellent catalytic activity and ease of bioconjugation, AuNPs offered significant advantages in biosensing. Leveraging the reductive properties of ABEI, AuNPs were reduced around Fe-MIL-101@ABEI, resulting in the modified luminescent functionalized material denoted as Fe-MIL-101@ABEI@AuNPs. An aptamer was employed as a recognition element and was modified accordingly. The aptamer was immobilized on Fe-MIL-101@ABEI@AuNPs through gold-sulfur (Au-S) bonds. After capturing acetamiprid, the aptamer induced a decrease in the ECL signal intensity within the ABEI-hydrogen peroxide (H 2 O 2 ) system, enabling the quantitative detection of acetamiprid. The aptasensor displayed remarkable stability and repeatability, featured a detection range of 1×10 -3 -1×10 2  nM, and had a limit of detection (LOD) of 0.3 pM (S/N=3), which underscored its substantial practical application potential., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A modified QuEChERS method was developed to determine multi-class pesticide and veterinary residues in aquatic products. Chitosan microspheres were conveniently synthesized and utilized as the cleanup adsorbent in the QuEChERS procedure, showcasing rapid filtration one-step pretreatment ability for the determination of drug multi-residues in aquatic products. Compared to conventional synthetic sorbents, chitosan microspheres not only have good purification performance, but also have renewable and degradable properties. This novel sorbent worked well in the simultaneous determination of 95 pesticides and veterinary drug residues in aquatic products after being combined with an improved one-step vortex oscillating cleanup method. We achieved recoveries ranging from 64.0% to 115.9% for target drugs in shrimp and fish matrix. The limits of detection and quantification were 0.5-1.0 and 1.0-2.0 μg kg -1 , respectively. Notably, hydrocortisone was detected with considerable frequency and concentration in the tested samples, underscoring the necessity for stringent monitoring of this compound in aquatic products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Residues of pesticides in milk may pose a threat to human health. This study aimed to develop a liquid-phase microextraction (LPME) method using hexafluoroisopropanol (HFIP)-based supramolecular solvent (SUPRAS) for the simultaneous extraction and purification of four pesticides (boscalid, novaluron, cypermethrin and bifenthrin) in milk. Pesticides were extracted using SUPRAS prepared with nonanol and HFIP, and the extraction efficiency was analyzed. Results showed satisfactory recoveries ranging from 80.8%-111.0%, with relative standard deviations (RSDs) of <6.4%. Additionally, satisfactory linearities were observed, with correlation coefficients >0.9952. The limits of quantification (LOQs) were in the range of 1.8 μg·L -1 -14.0 μg·L -1 . The established method demonstrated high extraction efficiency with a short operation time (15 mins) and low solvent consumption (2.7 mL). The HFIP-based SUPRAS LPME method offers a convenient and efficient approach for the extraction of pesticides from milk, presenting a promising alternative to conventional techniques., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this study, a hydrophobic covalent organic framework-functionalized magnetic composite (CoFe 2 O 4 @Ti 3 C 2 @TAPB-TFTA) with a high specific area with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,3,5,6-tetrafluoroterephthalaldehyde (TFTA) was designed and synthesized through Schiff base reaction. An efficient magnetic solid-phase extraction method was established and combined with gas chromatography-triple quadrupole mass spectrometry to sensitively determine 10 organochlorine and organophosphorus pesticides in tea samples. The established method exhibited good linearity in the range of 0.05-120 μg/L and had low limits of detection (0.013-0.018 μg/L). The method was evaluated with tea samples, and the spiked recoveries of pesticides in different tea samples reached satisfactory values of 85.7-96.8%. Moreover, the adsorption of pesticides was spontaneous and followed Redlich-Peterson isotherm and pseudo-second-order kinetic models. These results demonstrate the sensitivity, effectiveness, and reliability of the proposed method for monitoring organochlorine and organophosphorus pesticides in tea samples, providing a preliminary basis for researchers to reasonably design adsorbents for the efficient extraction of pesticides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Multi-residue methods for pesticide analysis in food are available for many compounds, but polar pesticides are not generally included due to their specific properties, which include high polarity and low molecular weight. Single residue methods are therefore needed for sample preparation, while chromatographic separation often requires derivatization, ion paring, or dedicated methods suitable for polar compounds, mostly ion chromatography and hydrophilic interaction liquid chromatography (HILIC). These challenges affect the important pesticide glyphosate and the related compounds aminomethylphosphonic acid (AMPA) and glufosinate. There are only a few methods including these compounds in large-scale analysis, mostly complex methods based on multidimensional chromatography., Results: A new method, for the global online extraction and analysis of pesticides in beer was developed and validated. The method exploited an online trapping device, with reversed-phase (RP) and anion exchange properties, that can trap small molecules from liquid samples. The ion exchange mechanism was used to retain the very polar pesticides glyphosate, AMPA, and glufosinate. The hydrophobic properties of the trapping column were also exploited to trap pesticides suitable for multi-residue investigations. The chromatographic separation was optimized by comparison of HILIC and RP C30, which could separate pesticides, including the polar ones, with modulation by the trapping column after proper selection of the mobile phase composition and basic modifier. The validation for beer provided recoveries in the range 71-112 %, with <15 % RSD, and LOD and LOQ values of 0.02-1 and 0.3-3 μg L -1 , respectively. The result was competitive with previous methods on polar pesticide analysis in beer., Significance: The method was validated for 15 pesticides, over the log K ow range from -4.4 to 4.5, using a methodology with single and fast chromatographic separation under conditions compatible with multi-residue analysis by RP-LC-MS/MS. In the case of beer, for which the method was validated, the sample preparation was also performed online, after simple degassing, and sample dilution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Given that the determination of biocides in food and feed is currently not routinely done, more information on these compounds is useful for consumer's safety. This work describes a sensitive and reliable method for quantitative analysis of a wide range of biocides in dairy products and slurry feed. The method comprises acetate-buffered QuEChERS extraction without clean-up. Analyses were performed by LC-Q-Orbitrap™-MS and a full-scan acquisition event without fragmentation was followed by five fragmentation events (data-independent acquisition-DIA). The quantitative validation was performed according to SANTE/11312/2021 at 10, 50 and 200 ng g -1 spiking levels, and the results showed that the vast majority of the compounds met the criteria for trueness and precision. The LOQ was 10 ng g -1 for the majority of biocides depending on the matrix. The method was successfully applied to quantify biocides in dairy products and feed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed., Results: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (R s ) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-R s values were significantly higher than the in vitro-R s for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days., Significance: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

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 ( R 2 ≥ 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%.

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-SiO 2 @Fe 3 O 4 as an adsorbent. COF-SiO 2 @Fe 3 O 4 was prepared by a straightforward solvothermal method, using Fe 3 O 4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO 2 @Fe 3 O 4 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-SiO 2 @Fe 3 O 4 , NH 2 -SiO 2 @Fe 3 O 4 and Fe 3 O 4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO 2 @Fe 3 O 4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

In multiresidue analysis, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) is one of the most popular techniques routinely used by researchers during pesticide analysis of food and vegetable samples. Originally, the QuEChERS method was developed for analysis of pesticide residues from fruits and vegetables, but rapidly gained popularity in the extraction of analytes from different matrices. This analytical approach shows several advantages over traditional extraction techniques: it requires lower sample and solvent amounts while shortening the time of sample preparation. However, it presents some limitations for complex matrices such as those containing high amounts of chlorophyll. To overcome the problem of strong matrix effect and influence of interferences, different approaches are applied. Most are concerning modifications of the cleanup step, that is, sorbent type and its amount. Optimization of other parameters, such as sample size, hydration level, extraction solvent, and buffering, also has an impact on overall performance. Combining proper sample preparation with modern highly sensitive and selective detection techniques enables receiving desired limits of quantification. This article presents an overview of strategies employed by researchers for analysis of green, high chlorophyll content commodities and results obtained in their studies., (© 2021 Wiley-VCH GmbH.)

In this study, a new fluorinated methacrylamide (MACF) was synthesized and evaluated as an adsorbent in the dispersive solid-phase extraction for the effective determination and extraction of 20 organophosphorus pesticides (OPPs) from ginseng samples using the QuEChERS (quick, easy, cheap, effective, rugged, safe) method coupled with GC-MS/MS. The properties of MACF were characterized using Fourier-transform infrared spectroscopy, elemental analysis, and high-resolution 19 F NMR. MACF, chitosan, primary and secondary amine, octadecylsilane, graphitized carbon black, Z-Sep, Z-Sep + , and EMR-Lipid were compared in terms of extraction efficiency. The best results were obtained when MACF was used. Matrix-matched calibration was employed for quantification. All the OPPs exhibited good linearity (r 2  > 0.9969) with the concentration at their respective concentration ranges. The limits of detection were 1.5-3.0 μg/kg, and the limits of quantification were 5.0-10.0 μg/kg. The trueness of the 20 pesticides at four spiked levels ranged from 86.1 to 111.1%, and the relative standard deviation was less than 11.3%. The modified QuEChERS method using MACF as the adsorbent was sensitive, reliable, and cost-effective and could be used for the determination of 20 OPP residues in ginseng., (© 2021 John Wiley & Sons, Ltd.)

In order to achieve rapid detection of thiamethoxam residues in mango, cowpea and water, this study modified the screen printed carbon electrode (SPCE) to make a specific molecular imprinting sensor (Thiamethoxam-MIP/Au/rGO/SPCE) for thiamethoxam. An integrated smartphone platform was also built for thiamethoxam residue analysis. The performance of the complete system was analyzed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The system was then applied for the rapid determination of thiamethoxam residues in water, mango and cowpea samples. The results showed that the molecular sensor showed good linearity in the range 0.5-3.0 μmol/L of thiamethoxam. The detection limit of thiamethoxam was 0.5 μmol/L. Moreover, the sensor had good reproducibility and anti-interference performance. The average recovery rates of the pesticide residues in water, mango and cowpea samples were in the range of 90-110% with relative standard deviations < 5%. The rapid detection system for thiamethoxam residue constructed in this study was simple, reliable, reproducible and had strong anti-interference. It has broad application prospects in the field detection of thiamethoxam residue, and serves as a valuable reference for the further development of rapid detection technology of pesticide residues in the field of environment and food safety., Competing Interests: The authors have declared that no competing interests exist.

Extensive use of organophosphorus pesticides in agriculture leads to adverse effects to the environment and human health. Sample preparation is compulsory to enrich target analytes prior to detection as they often exist at trace levels and this step is critical as it determines the concentration of pollutants present in samples. The selection of a suitable extraction method is of great importance. The analytical performance of the extraction methods is influenced by the selection of sorbents as sorbents play a vital role in the sensitivity and selectivity of an analytical method. To date, numerous sorbent materials have been developed to cater to the needs of selective and sensitive pesticides' detection. Comprehensive details pertaining to extraction methods, developed sorbents, and analytical performance are provided. This review intended to provide a general overview on different extraction techniques and sorbents that have been developed in the last 10 years for organophosphorus pesticides' determinations in food and water samples.

In this paper, a method for the separation of triadimenol stereoisomers using ultra-performance convergence chromatography and an analytical method for the determination of triadimenol stereoisomer residues in pumpkin puree, apple puree, and tomato puree as a supplement for infants are established. Test samples were extracted with acetonitrile and successively purified with graphitized carbon black and Florisil column. Afterward, Acquity Trefoil AMY1 column was adopted for chiral separation of chromatographic column, and gradient elute was carried out with supercritical carbon dioxide-methanol as the mobile phase and with external standard method for quantitation. Results showed that the linearly dependent coefficient of the four kinds of triadimenol stereoisomers within 1.0 and 50 mg/L was greater than 0.9997, and the limit of quantitation of the four kinds of triadimenol stereoisomers was 0.05 mg/kg. Recovery experiment was carried out within 0.05 and 1.0 mg/kg scope, the recoveries were 81.0-107％, and the relative standard deviation was 2.3-7.6%. This method implemented the separation of triadimenol stereoisomers and its residue test in pumpkin puree, apple puree, and tomato puree as a supplement for infants, and it can provide reliable technical support for the analysis of pesticide residue and assessment of product quality., (© 2021 Wiley-VCH GmbH.)

A method for simultaneous determination of carbendazim and tebuconazole residues in cabbage was developed and validated in LC-MS/MS. Samples were extracted and purified following the modified QuEChERS procedure, which enabled the elution of carbendazim and tebuconazole at 0.96 and 5.31 min, respectively. LOD and LOQ were 0.0005 and 0.0015 mg kg -1 , respectively. Mean recovery was in the range of 78.94 to 104.89% for carbendazim and 76.07 to 98.62% for tebuconazole. The field samples recorded residues of 0.274 and 0.481 mg kg -1 ; and 0.194 and 0.392 mg kg -1 at single and double dose for carbendazim and tebuconazole, respectively. Half-life values were 2.17 and 2.99 for carbendazim and 2.74 and 2.81 for tebuconazole at single and double dose, respectively. Decontamination with saltwater wash followed by cooking and lemon water wash found superior in the removal of residues more than 90%., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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 (RSD r ) ≤ 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., (© 2021 Society of Chemical Industry.)

Pesticide residues are one of the most important issues affecting food safety. In this review, the general situation of pesticide residues in fruits and vegetables based on the background of the Chinese fruit and vegetable industry is first described. On the basis of primary processing of agricultural products, the effects of processing methods on the removal and metabolism of pesticide residues are reviewed in this paper. In addition, the transformation mechanism of pesticides in crops and in the environment is discussed. Finally, this study summarizes the development trend of pesticide-residue monitoring methods. With the prohibition of a large number of pesticides in China, the risk of pesticide residues is gradually reduced. However, some highly toxic pesticides can still be detected. Furthermore, the development of high-resolution mass spectrometry screening methods and rapid and intelligent detection instruments is the development trend for pesticide monitoring in the future., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Food analysis is a tremendously broad field that is constantly evolving. New methods have emerged to increase productivity, such as modern miniaturized and robotic analytical techniques. In this paper, a micro-solid-phase extraction system (µ-SPE) for clean-up was combined with a robotic autosampler to yield ready-to-analyze extracts. The system was evaluated for its applicability in routine laboratories. The new, automated, high-throughput µ-SPE clean-up method was applied to acetonitrile extracts and was developed for the analysis of pesticide residues in cereals by gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap-MS). The µ-SPE clean-up efficiency was demonstrated in the removal of matrix-interfering components and in the recovery of pesticides. The sorbent bed mixture consisted of magnesium sulfate, primary-secondary amine, C 18 , and CarbonX, and effectively retained matrix components without loss of target analytes. Analysis of five types of cereals (barley, oat, rice, rye, and wheat) by GC-Orbitrap-MS showed that the method removed more than 70% of matrix components. The clean-up method was validated for 170 pesticides in rye, 159 pesticides in wheat, 142 pesticides in barley, 130 pesticides in oat, and 127 pesticides in rice. Spike recovery values were 70-120% for all pesticides and the repeatability, calculated as the relative standard deviation, was less than 20%. The limits of quantitation achieved were 0.005 mg kg -1 for almost all analytes, ensuring compliance with the maximum residue limits., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

Propolis is a resinous natural product collected by honeybees ( Apis mellifera and others) from tree exudates that has been widely used in folk medicine. The present study was carried out to investigate the fatty acid composition, chemical constituents, antioxidant, and xanthine oxidase (XO) inhibitory activity of Jordanian propolis, collected from Al-Ghour, Jordan. The hexane extract of Jordanian propolis contained different fatty acids, which are reported for the first time by using GC-FID. The HPLC was carried out to identify important chemical constituents such as fatty acids, polyphenols and α-tocopherol. The antioxidant and xanthine oxidase inhibitory activities were also monitored. The major fatty acid identified were palmitic acid (44.6%), oleic acid (18:1∆ 9 cis , 24.6%), arachidic acid (7.4%), stearic acid (5.4%), linoleic acid (18:2∆ 9-12 cis , 3.1%), caprylic acid (2.9%), lignoceric acid (2.6%), cis -11,14-eicosaldienoic acid (20:2∆ 11-14 cis , 2.4%), palmitoleic acid (1.5%), cis -11-eicosenoic acid (1.2%), α-linolenic acid (18:3∆ 9-12-15 cis , 1.1%), cis -13,16-docosadienoic acid (22:2∆ 13-16 cis , 1.0%), along with other fatty acids. The major chemical constituents identified using gradient HPLC-PDA analysis were pinocembrin (2.82%), chrysin (1.83%), luteolin-7- O -glucoside (1.23%), caffeic acid (1.12%), caffeic acid phenethyl ester (CAPE, 0.79%), apigenin (0.54%), galangin (0.46%), and luteolin (0.30%); while the minor constituents were hesperidin, quercetin, rutin, and vanillic acid. The percentage of α-tocopherol was 2.01 µg/g of the lipid fraction of propolis. Antioxidant properties of the extracts were determined via DPPH radical scavenging. The DPPH radical scavenging activities (IC 50 ) of different extracts ranged from 6.13 to 60.5 µg/mL compared to ascorbic acid (1.21 µg/mL). The xanthine oxidase inhibition (IC 50 ) ranged from 75.11 to 250.74 µg/mL compared to allopurinol (0.38 µg/mL). The results indicate that the various flavonoids, phenolic compounds, α-tocopherol, and other constituents which are present in propolis are responsible for the antioxidant and xanthine oxidation inhibition activity. To evaluate the safety studies of propolis, the pesticide residues were also monitored by LC-MS-MS 4500 Q-Trap. Trace amounts of pesticide residue (ng/mL) were detected in the samples, which are far below the permissible limit as per international guidelines.

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., Competing Interests: The authors have declared that no competing interests exist.

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%., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

A novel magnetic covalent organic framework (NH 2 -Fe 3 O 4 @COF) was prepared using a simple room-temperature synthesis in this study. These magnetic particles exhibited high adsorption performance with short adsorption time (10 min) for six benzoylurea insecticides (BUs) as magnetic solid-phase extraction (MSPE) adsorbents. Quantum chemistry calculation demonstrated that adsorption mechanism was primarily attributed to strong halogen bonds between electronegative O atoms of COF and electropositive F atoms of BUs as well as potential hydrophobic effect. Wide linearities (10-1000 ng·L -1 ) and low limits of detection (0.06-1.65 ng·L -1 ) for six analytes were obtained via liquid chromatography-tandem mass spectrometry. Applicability of the proposed method was further evaluated by analyzing four kinds of original tea beverages. Recoveries of six BUs in spiked samples ranged from 80.1% to 108.4%., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

A novel in-syringe temperature-controlled liquid-liquid microextraction based on solidified floating ionic liquid (in-syringe TC-LLME-SFIL) combined with high performance liquid chromatography was developed for the simultaneous determination of monuron, chlorotoluron, atrazine, monolinuron, propazine and prometryn in commercial vegetable protein drinks. The samples were deproteinized by trichloroacetic acid and further cleaned up by solid phase extraction column. The ionic liquid tributyldodecylphosphonium tetrafluoroborate ([P 4 4 4 12 ]BF 4 ) was used as extraction solvent and dispersed into the depurated sample solution to form fine droplets with the assistance of heating and vortex. With the help of an ice bath, the ionic liquid phase solidified and floated on the surface of aqueous phase. After separation from the aqueous phase, the solidified ionic liquids were dissolved with acetonitrile and the resulting solution was analyzed by high performance liquid chromatography. Some extraction parameters, including type and amount of adsorbent, type and amount of ionic liquids, amount of NaCl, melting temperature and time of ionic liquid, vortex time, pH of sample solution, ice bath temperature and time, were investigated and optimized by single-factor experiment, Plackett-Burman design and Box-Behnken design. The results showed that good linearities (r ≥ 0.9994) were obtained in the concentration range of 7.8-1000.0 μg/L. The limits of detection and quantification were in the range of 0.25-2.59 μg/L and 0.82-8.63 μg/L, respectively. The spiked recoveries were 81.26-118.42% with the relative standard deviation (RSD, n = 3) lower than 8.17%. The present method was successfully applied to the simultaneous determination of triazine and phenylurea herbicides in vegetable protein drinks., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The development of sensitive method for analysis ofpesticide residue is of great significance to ensure food safety and promote globalization of food trade. An original method was proposed for analysis of phenoxy carboxylic acids (PCAs) pesticide in plant-derived food. To concentrate trace PCAs, the TAPT-DHTA-COF was fabricated by a facile room-temperature method and utilized as the solid phase extraction cartridge packing. The TAPT-DHTA-COF exhibited excellent adsorption capacity and recyclability towards PCAs. Theoretical simulation indicated that the adsorption of PCAs onto the TAPT-DHTA-COF was driven by hydrogen bond, halogen bond and π-π interaction. Using liquid chromatography tandem mass spectrometry for detection, good linearity ranged from 0.10 to 40 ng·g -1 and low limits of detection varied from 0.007 to 0.030 ng·g -1 were achieved for PCAs in rice, apple and greengrocery. The recoveries of PCAs from the spiked samples ranged from 81.2% to 107%. The reliability was verified by the accurate determination of certified reference materials., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

An efficient dispersive solid-phase extraction method was developed to trace pesticide residues in commonly consumed vegetables. In this method, UiO-66 with uniform micropores was used as sorbent, and gas chromatography-mass spectrometry was applied to detect the pesticides. Thanks to the size sieving action of uniform micropores, UiO-66 directly extracted the target pesticides from vegetable matrices and excluded the relatively large matrix compounds. This well eliminated the matrix effect. The important experimental conditions were evaluated by orthogonal array experimental design. In optimized conditions, good linearity (R 2  ≥ 0.99), detection limits (0.4-2.0 ng/g), recoveries (60.9-117.5%) and precision (relativestandarddeviations < 14.6%) were achieved. Moreover, the sorbent UiO-66 can be reused more than 20 times. These demonstrate a simple, reliable and robust method to screen the pesticide residues in vegetables. Furthermore, the validated method was applied to detect the pesticides in various organic and conventional vegetables., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

A composite built with aminated zeolitic imidazolate framework and gold nanoparticles (AuNPs) for solid-phase extraction (SPE) of neonicotinoids in agricultural samples is presented. The composite was prepared through the assembly of AuNPs onto the surface of metal-organic framework based on the strong interaction between the amino group and AuNP. These metallic surfaces provided additional interactions based on the affinity of amino and cyano groups present in the target compounds. The composite was characterized by scanning electron microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, and surface area measurements. Regarding the SPE protocol, several parameters that can influence the extraction performance were optimized, such as sample volume or composition of elution solvent, among others. After elution, the analytes were determined via HPLC with diode-array detection. Under the selected conditions, satisfactory recoveries of five pesticides (thiamethoxan, clothianidin, imidacloprid, acetamiprid, and thiacloprid) were obtained (between 80 and 110%) in real samples, whereas the limits of detection ranged from 0.019 to 0.041 μg L -1 in aqueous samples and 0.3 to 0.8 μg g -1 in solid samples.

Deep eutectic solvents are versatile, green and new generation solvents that can be used during dispersive liquid-liquid micro-extraction techniques for pesticides. They have tunable physico-chemical properties that can be easily changed by varying the ratios of hydrogen bond donors and hydrogen bond acceptors in their structures. Deep eutectic solvents are non-flammable, chemically and thermally stable solvents with low vapour pressure. Thus, they have characteristics that are similar to those of ionic liquids. However, they have simpler synthetic procedures, less expensive and are more biodegradable than ionic liquids. One of the limitations of deep eutectic solvents is their toxicity to the environment but they are less toxic than ionic liquids. This paper gives a focused and comprehensive recent review on the applications of deep eutectic solvents during dispersive liquid-liquid micro-extraction of pesticides in food samples for the period starting from 2016 to 2020. Emphasis was placed on the modifications done to the deep eutectic solvent-based dispersive liquid-liquid micro-extraction techniques in order to enhance their greenness during pesticide pre-concentration in food samples. In addition, hyphenated dispersive liquid-liquid micro-extraction techniques were also reviewed and lastly, the paper outlined the challenges associated with the use of DESs during the DLLME techniques., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Ginseng extracts are rich in a variety of ginseng monomer saponins, which have pharmacological functions of retarding aging, enhancing immunity, stimulating blood circulation, and lowering blood pressure. Ginseng is widely used in health products and dietary supplements in the domestic and foreign market. However, the amount of pesticide residues is an important index for measuring the quality of ginseng and ginseng extracts. Therefore, studies focused on methods for the removal of pesticide residues in ginseng extract are of great significance. Hydrophilic interaction liquid chromatography (HILIC) is used to improve the retention and separation selectivity of strongly polar substances, and it is widely employed in drug analysis, metabolomics, proteomics, etc. In this study, a method for the removal of pesticide residues was developed based on the difference in the retention behavior of pesticide residues and ginsenosides on the HILIC column. Using commercially available ginsenoside extracts, the retention behaviors of pesticide residues and ginsenosides on reverse chromatography and hydrophilic chromatographic columns were evaluated by high performance liquid chromatography. The results proved that on the reversed-phase liquid chromatography (RPLC) stationary phase, in addition to the strong retentions of quintozene and pentachloroaniline, which could be clearly separated from the saponins, the retentions of the other five pesticide residues including carbendazim, azoxystrobin, procymidone, iprodione and propiconazole were similar to total ginsenosides. The seven ginsenosides showed strong retention due to the formation of hydrogen bonds between the hydroxyl groups on the sugar chain and the carboxyl groups on the HILIC stationary phase. However, the pesticide residues were not well retained because of their poor hydrophilicity and small molecular weights. For this reason, the pesticide residues and ginsenosides could be completely separated on the HILIC column. Thus, enrichment of the seven ginsenosides and removal of the 14 pesticide residues was realized in one step on the HILIC column. In addition, the effects of loading amount, loading volume, and washing volume on the removal of pesticide residues in ginsenosides were investigated using the Click XIon SPE column. Then, taking the ginsenoside recoveries and pesticide residue removal rates into account, we confirmed the following: the ratio of the maximum sample loading mass to the filler mass was 1∶10; the optimal elution volume was twice the column volume; and the optimal loading volume was twice the column volume. The ginseng extracts were solvated with a 95% ethanol solution and loaded onto an HILIC column. The sample was subjected to pesticide residue removal, and ginsenoside purification and enrichment under the optimum removal conditions. Gradient elution was carried out using ethanol and water as the mobile phases. The total ginsenoside content in the final extracts was increased to 69.61%. The recovery of the total ginsenosides was 94.4%. The pesticide residues in the samples were quantitatively detected by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) in the multiple reaction monitoring (MRM) mode. The 14 pesticide residues in the original ginsenoside extracts were effectively removed. The amounts of five residues were reduced to below 0.05 mg/kg, while the other nine residues were completely eliminated. This study demonstrates the application of HILIC to pesticide residue removal in traditional Chinese medicine extracts and reveals a new technique for the purification of natural products. The proposed method shows a high removal rate of pesticide residues and a high recovery of total ginsenosides. It is safe, efficient, and environment-friendly, and can aid the development of high-quality ginsenoside extracts.

An analytical method was developed for the quantification of spinosad (sum of spinosyns A and D) in five animal-derived products (chicken breast, pork, beef, egg, and milk) using LC-MS/MS. The sample was extracted using acetonitrile/1% acetic acid and a combination of magnesium sulfate and sodium acetate salts. The sample was purified using multiwalled carbon nanotubes as sorbent via a dispersive-solid-phase extraction procedure. Matrix-matched calibration (seven-point) provided good linearity with coefficient of determination (R 2 ) ≥0.99 for each product. The limits of detection and quantification (LOQs) ranged between 0.0003-0.03 and 0.001-0.1 mg/kg, respectively. Method validation was carried out after spiking the target standard to blank matrices at the concentration levels of LOQ, 2 × LOQ, and 10 × LOQ with three replicates for each. The average recoveries were between 74 and 104%, with relative standard deviations ≤9.68, which were within the acceptable range designated by the international organizations. The developed method was successfully applied for monitoring market samples collected throughout the Korean Peninsula, and none of the samples tested positive for the target analytes. It has therefore been shown that dehydration and acidification were effective to extract spinosad from animal-derived products., (© 2020 John Wiley & Sons, Ltd.)

Detection of low levels of triazole fungicides in agricultural product matrices is important. Although several detection methods have been developed, all have some drawbacks, such as being time-consuming, requiring complex sample pretreatment, and consuming large volumes of organic solvents. There is an urgent need for a simple and rapid detection method for triazole fungicides. In this study, the adsorbent composite material magnetic MOFs based on Fe 3 O 4 -MWCNT was synthesized by in-situ polymerization at room temperature, and was applied to extract triazole pesticides from fruits and vegetables. High-performance liquid chromatography-tandem mass spectrometry was used for quantification. Under optimized conditions, the constructed detection method showed a low detection (LOD) of 0.52-1.83 μg/L (S/N = 3) and wide linear range of 5.00-500.00 μg/L for triazole fungicides in the fruit and vegetable samples. The method recovery for spiked fungicides (10, 50, and 100 μg/L) in cabbage, spinach, orange juice, and apple juice ranged from 62.80% to 94.20%. The constructed detection method has a lower detection limit than previously reported methods and has a higher sensitivity for triazole pesticide residues in complex matrices., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Herein we report the first example of Fe 3 O 4 nanoparticles (FNPs) being used as single-matrix solid-phase dispersion (MSPD) adsorbents for the extraction of 30 representative pesticides from vegetables. This study was aimed at analyzing the extracted samples using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Various condition parameters, such as the eluent, volume of the eluent, and amount of FNPs were optimized to achieve good sensitivity and precision for the elution and extraction of the analytes. The developed method was validated using matrices consisting of eight vegetables (lettuce, cucumber, carrot, tomato, pepper, shallot, Chinese flowering cabbage, and cabbage) spiked with 30 pesticides at concentrations of 0.01, 0.1, and 1.0 mg/kg. The recoveries of the 30 pesticides (organophosphorus, triazole, carbamate, nicotine, amide, and other different structures of pesticides) were in the range 71.0-110.8% (n = 5) (except those of prothioconazole and dinotefuran), with relative standard deviations lower than 13.5% in all the matrices under optimal conditions. The matrix effects were observed by comparing the slope of the matrix-matched standard calibration curve with that of the solvent. However, the matrix effects of the eight vegetables did not show evident regularities. For pepper, tomato, and shallot, a sizable number of pesticides (24, 21, and 21, respectively) showed suppressive matrix effects. On the other hand, for cucumber, Chinese flowering cabbage, and cabbage, a good number of pesticides (19, 18, and 15, respectively) showed negligible matrix effects. Furthermore, for carrot matrices, 21 pesticides showed a matrix enhancement effect. Excellent linearity was achieved at pesticide concentrations of 0.01-1.0 mg/L, and the limits of quantification (LOQ) for the developed method reached 0.01 mg/kg (except that for dinotefuran, which was 0.1 mg/kg), based on the spiked test. The developed method was successfully employed in the analysis of real samples in Nanning, China, and three pesticide residues (halosulfuron methyl, tebuconazole, and azoxystrobin) were commonly detected in vegetable samples. In the present study, a reliable method-validation performance and excellent cleanup effects were observed by using the modified MSPD method consisting of the FNPs in the cleanup step., (Copyright © 2021. Published by Elsevier B.V.)

In this work, a new mega-method of sample preparation called "QuEChERSER" (more than QuEChERS) is being presented for the first time. Fast, efficient, and cost-effective analysis of chemical contaminants in meat is useful for international trade, domestic monitoring, risk assessment, and other purposes. The goal of this study was to develop and validate a simple high-throughput mega-method for residual analysis of 161 pesticides, 63 veterinary drugs, 24 metabolites, and 14 legacy environmental contaminants (polychlorinated biphenyls) in bovine muscle for implementation in routine laboratory analyses. Sample preparation of 2 g test portions entailed QuEChERS-based extraction with 10 mL of 4:1 (v/v) acetonitrile/water, and then 204 μL was taken, diluted, and ultracentrifuged prior to analysis of veterinary drugs and pesticides by ultra-high-performance liquid chromatography-tandem mass spectrometry. The remaining extract was salted out with 4:1 (w/w) anhydrous MgSO 4 /NaCl, and 1 mL was transferred to an autosampler vial for automated mini-cartridge solid-phase extraction (Instrument Top Sample Preparation) cleanup with immediate injection using fast low-pressure gas chromatography-tandem mass spectrometry analysis. The automated cleanup and both instruments were all operated in parallel in 13-15 min cycle times per sample. Method validation according to United States Department of Agriculture requirements demonstrated that 221 (85%) of the 259 analytes gave average recovery between 70 and 120% and interday relative standard deviation of ≤25%. Analysis of a certified reference material for veterinary drugs in freeze-dried bovine muscle was also very accurate, further demonstrating that the QuEChERSER mega-method can be implemented to save time, labor, and resources compared to current practices to use multiple methods to cover the same analytical scope.

Since the beginning of the widespread use of pesticides, their removal from food has become a serious concern. In this study, the removal of residual pesticides (malathion and carbosulfan) from pak choi via treatment with ozonated water was investigated. Under the optimal treatment conditions, i.e., 2.0 mg/L ozonated water and a treatment duration of 15 min, malathion and carbosulfan were degraded by 53.0 and 33.0%, respectively, without any significant changes in color. Even though there was a slight decrease in vitamin C content (~7.9 mg/100 g) following the treatments, a significant decrease in the microbial colonies on the vegetables was observed. Additionally, the pesticide degradation mechanism showed good fitting with a "first + first"-order kinetic model (R 2  > 0.9), and the slope (k) indicated that ozone had a more prominent degradation effect on malathion than on carbosulfan. Therefore, this study provides a theoretical basis for controlling agricultural pesticide residues in household applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Fe 3 O 4 @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 (Fe 3 O 4 @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 Fe 3 O 4 @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 (R 2 ) ≥ 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 Fe 3 O 4 @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.

The objective of this study consists of being able to develop a precise, reliable, easy, cheap and quick method to identify and quantify the presence of pesticide metabolites and their parents in human urine. In order to reach our purpose we selected the pesticides and their metabolites with intended uses on permanent crops such as orchards and vineyard. The activity planning started with the identification of the target list carried out by UHPLC-MS/MS and GC-MS/MS, succeeded by several tests oriented to determine the best sample treatment having recourse to instrumental analysis in the range 5-100 ng/mL. Several purifications were also investigated combining different adsorbents (PSA, EMR-lipid and final polish pouch). The use of formic acid during the extraction step has no impact on the recoveries, whereas the PSA adsorbent in the cleanup step negatively affects the results for all investigated metabolites. Any substantial differences were not observed in urine matrix for parent compounds achieving recoveries higher than 80% and RSD less than 20%. The final polish in combination or not with Enhanced Matrix Removal EMR-lipid did not show statistically significant difference in term of trueness and precision for both metabolites and parents, as evaluated by one-way ANOVA. The 3-OH THPI was the most critical compound with not acceptable results for linearity, trueness and precision.

Neonicotinoid pesticides are widely applied for controlling pests in a variety of agriculture crops. Due to the systemic distribution in plants, neonicotinoid pesticides have been found in nectar and pollen, which are the main source of food for the important pollinator honeybee. The risk of neonicotinoid residues in honeybee products and honeybee has caused great attention since their impacts on the environment, ecology, and food safety issues. These concerns require the accurate and sensitive determination of neonicotinoids and their metabolites in the honeybee products and honeybee. Since the trace residue level of neonicotinoid and the complexity of the samples, analysis of neonicotinoid targets in these important matrices is still a great challenge. The present review provides general overview of analytical methods for the determination of neonicotinoid pesticides and their metabolites in honeybee products and honeybee.

A rapid determination method of residual penicillin G and its two metabolites in citrus was developed and validated by dispersive solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry (DSPE/UPLC-MS/MS). The samples were extracted with 80% acetonitrile and purified with octadecylsilane. High linearity was obtained with correlation coefficients (r 2 ) >0.9981. The limits of quantification were 0.005-0.01 mg/kg. The recoveries of penicillin G and its metabolites spiked in blank citrus were within 76.7-107%, with relative standard deviations of 1.3-9.6%. The dissipation dynamics and distribution of penicillin G in citrus followed first-order kinetics, with half-life of 1.7-2.7 days. Penicillin G degraded easily in citrus and the metabolite was mainly penilloic acid, which can exist stably for long time. The terminal residues of penicillin G in pulp, whole citrus and peels were 0.015-0.701, 0.047-7.653 and 0.162-13.376 mg/kg, respectively. The hazard indexes for risk assessment of citrus were significantly <1, suggesting that the health risks to humans after consumption of citrus were insignificant and negligible. These results could provide necessary data for evaluating the safe and proper use of penicillin G in citrus., (© 2020 John Wiley & Sons, Ltd.)

Biopurification systems are useful in the management of pesticide residues and provide an option to dispose wastewaters of agricultural origin derived from pesticide application practices. The analysis of pesticide residues in the biopurification system biomixture is necessary to determine whether the removal of the target compounds occurs with reliable results. In this study, the pesticide extraction methodology was optimized and validated in a biomixture composed of coconut fiber, compost and soil, to determine a total of 43 molecules, distributed among triazines (10), triazoles (13) and organophosphates (20) using liquid chromatography coupled to a triple quadrupole mass spectrometer. For the validation, the parameters of linearity, matrix effect, limit of determination (LOD), specificity, selectivity, precision, trueness and robustness in the proposed biomixture were evaluated. The analyses of those parameters revealed satisfactory results of the method for most of the compounds, with the exception of diclorvos and ciromazine, for which the development of an alternative method is recommended. Once the extraction methodology was validated, the removal of eight molecules was assayed in a biopurification system used for the simultaneous treatment of a mixture of pesticide commercial formulations. Although most of the compounds were at least partially removed, none of them was eliminated at levels below the LOD. The removal pattern of ametryn, atrazine, chlorpyrifos, malathion and terbutryn was comparable to those obtained in other efficient biomixtures, and the highly recalcitrant triadimenol was eliminated; nonetheless, tebuconazole and diazinon were not significantly removed., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The application and evaluation of highly efficient chromatographic techniques with tandem mass spectrometry for the detection and quantitation of 108 pesticides and metabolites, some considered persistent organic pollutants, was performed in muscle samples obtained from 25 birds of prey belonging to the families Accipitridae, Falconidae, and Strigidae presented dead in 2013 to Grupo de Rehabilitación de la Fauna Autóctona y su Hábitat, in Madrid, Spain. Pesticides with prohibited use were detected at high concentrations in the muscle samples analyzed. Based on its high sensitivity to detect pesticides in muscle, the described chromatographic techniques with tandem mass spectrometry should be considered an alternative testing methodology to those commonly used for routine application in ecotoxicological forensic research.

A novel, ecofriendly, and easy extraction and preconcentration method named as vortex-assisted spraying-based fine droplet formation liquid-phase microextraction was proposed for the determination of prochloraz at trace levels in orange juice samples by gas chromatography-mass spectrometry (GC-MS). In this novel system, extraction solvent is dispersed by the help of spraying apparatus instead of dispersive solvent. Various parameters of the method were carefully optimized to increase signal-to-noise ratio of the analyte. Under the optimum chromatographic and extraction conditions, limit of detection and limit of quantification were calculated as 3.2 and 10.8 μg/kg, respectively. Moreover, enhancement in quantification power for the GC-MS system was determined as 372 folds based on LOQ comparison. Relative recovery results for orange juice samples were found to be between 95.0-107.7% by utilizing matrix matching calibration. Furthermore, the developed method may be used to efficiently and simply extract other organic compounds for their determinations in several matrices., (© 2020 John Wiley & Sons, Ltd.)

Maximum residue limits (MRLs) for pesticides have been established in teas for quality control and protection of consumer health in many countries and regions, including Europe. It is, however, challenging to quantify multi-pesticide residues at low concentrations in complex matrices, such as tea. In this study, highly sensitive, efficient, and rugged analytical methods were adapted for simultaneous determination of 400 pesticide residues in green tea products using ultra performance liquid and gas chromatography coupled to tandem mass spectroscopy (UPLC-MS/MS and GC-MS/MS). Matrix effects were minimized by combining QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction and mixed-mode SPE clean-up with different sorbents in sample preparation. A C18 SPE cartridge paired with SPE GCB/PSA proved to be the most effective clean-up method and enabled 225 pesticide residues to be quantified, based on solvent calibration curves (154 residues using UPLC-MS/MS and 71 residues using GC-MS/MS). The analytical methods were validated fully in accordance with the SANTE/11945/2015. LOQs for most pesticides (386/400 or 96.5%) were below 10 µg/kg, i.e., less than the EU MRL (5-70 mg/kg). Thus, these approaches can be applied for routine analysis of multi-pesticide residues in green tea., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Baijiu, a conventional fermented beverage with thousands history, plays a crucial part in physical health of people and social culture in China. The application of high-throughput screening and confirmation of flavor components in the field of authenticity identification and potential function has attracted more and more attention and interest of researchers. With more attention to health, pesticides residues, phthalates, biogenic amines and other hazardous substances remained in Baijiu have also become the quality parameters concerned by consumers. This review aims to present updated and critical overview on the substances analysis of Baijiu by means of hyphenated chromatographic techniques based on various pretreatment approaches in recent years. Subsequently, the advance and main direction of Baijiu composition analysis were evaluated and prospected., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)