Development of a polyurethane-coated thin film solid phase microextraction device for multi-residue monitoring of pesticides in fruit and tea beverages.

A novel solid-phase microextraction device coated with an efficient and cheap thin film of polyurethane was developed for trace determination of 13 widely used pesticides in fruit and tea beverages. A round-shaped polyurethane film covering the bottom of a glass vial was fabricated as the sorbent to exhibit a superior capacity for preconcentrating target compounds and reducing matrix interferences. After optimization of the key parameters including the film type, extraction time, solution pH, ionic strength, desorption solvent, and conditions, this device allowed an efficient adsorption-desorption cycle for the pesticides accomplished in one vial. Coupled with gas chromatography-electron capture detection, the polyurethane-coated thin film microextraction method was successfully established and applied for the analysis of real fruit and tea drinks, showing low limits of detection (0.001-0.015 µg/L), wide linear ranges (1.0-500.0 µg/L, r2  > 0.9931), good relative recoveries (77.2%-106.3%) and negligible matrix effects (86.1%-107.5%) for the target pesticides. The proposed approach revealed strong potential of extending its application by flexibly modifying the type or size of the coating film. This study provides insights into the enrichment of contaminants from complex samples using inexpensive and reusable microextraction devices that can limit the environmental and health impact of the sample preparation protocol.

Target and suspect screening of pesticide residues in soil samples from peach orchards using liquid chromatography quadrupole time-of-flight mass spectrometry.

Agricultural soil contamination by pesticide residues has become a serious issue of increasing concern due to their high persistence and toxicity to non-target species. However, as the world's largest peach producer, national scale surveys on pesticide residues in peach orchard soils are scarce in China. In this study, a target and suspect screening method covering over 200 pesticides commonly used in peach orchards was developed using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry in MSE. An identification strategy using different data processing parameters was developed to identify the pesticide occurrence in soil. The method was applied to soil samples from typical peach orchards in 12 regions across China. The present work also discusses in detail the frequency of occurrence, concentration of pesticides, spatial distribution of multiresidues, and relationship between pesticide occurrence and soil properties. In the tested soil samples, 21 herbicides (level 1), 31 fungicides (level 2a), 24 insecticides (level 2a), and 3 growth regulators (level 2a) were identified. The total concentrations of quantifiable herbicides in the soil samples ranged from 1.05 to 327 ng/g. Only in 5.4% of the soil samples, no pesticide residues were present. By contrast, more than 86% of the total contained multiple residues. This study represents the first large-scale survey of pesticides in soil from peach orchards and provides comprehensive and accurate information on the pesticide residue status for risk assessment.

Multi-Residue Detection of Eight Glucocorticoids by Nano-Au/Fluticasone Propionate Electrochemical Immunosensor.

Based on an indirect competitive method, a novel nano-Au/fluticasone propionate electrochemical immunosensor was successfully fabricated by combining the nanoscale effect, superior conductivity of nano-Au, stable Au-S chemical bond as well as strong interaction between glucocorticoid and the receptor, which was used to simultaneously detect eight kinds of glucocorticoids. The modified immunosensors' electrochemical properties were explored by means of a cyclic voltammetry (CV) method and electrochemical impedance spectroscopy (EIS) measurements. Two factors (glucocorticoid receptor concentration, incubation time) were studied in order to obtain the optimal results. The immunosensor presents attractive electrochemical performance with a wide linear range (between 0.1 and 1500 ng⋅mL-1) and low detection limit (between 0.057 and 0.357 ng⋅mL-1), realizing the rapid multi-residue detection of a large class of glucocorticoids. Two glucocorticoids (hydrocortisone, triamcinolone) were detected in actual skincare samples, which obtained satisfactory detection results.

Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 µg g-1 dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 µg g-1 d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements.

Critical Evaluation of Two Qualitative Analytical Approaches for Multiclass Determination of Veterinary Drugs in Bovine Muscle Using UHPLC-Q-Orbitrap: The Wind of Change in Brazilian Monitoring.

Food safety is recognized as a main requirement for consumers, food industries, and official laboratories. Here, we present the optimization and screening qualitative validation of two multianalyte methods in bovine muscle tissues by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry with an Orbitrap-type analyzer, operated with a heated ionization source in positive and negative mode. This aims for not only the simultaneous detection of veterinary drugs regulated in Brazil but also the prospection of antimicrobials not yet monitored. Two different sample preparation procedures were applied: method A-generic solid-liquid extraction with 0.1% formic acid (v/v) in an aqueous solution of EDTA 0.1% (w/v)-acetonitrile-methanol (1:1:1, v/v/v), followed by an additional ultrasound-assisted extraction and method B-QuEChERS. In both procedures, selectivity showed satisfactory conformity. From a detection capability (CCß) equivalent to ½ the maximum residue limit, >34% of the analyte resulted in a false positive rate of <5%, preponderant by the QuEChERS method, which exhibited a higher yield of the sample. The results showed the potential application of both procedures in the routine analysis of foods by official laboratories, enabling the expansion of this methodological portfolio as well as its analytical scopes, thus optimizing the control of residues of veterinary drugs in the country.

Multi-residue analysis of 206 pesticides in grass forage by the one-step quick, easy, cheap, effective, rugged, and safe method combined with ultrahigh-performance liquid chromatography quadrupole orbitrap mass spectrometry.

A novel method for detecting pesticide multi-residue in grass forage (alfalfa and oat) was established based on the one-step automatic extraction and purification technology of quick, easy, cheap, effective, rugged, and safe combined with ultrahigh-performance liquid chromatography quadrupole Orbitrap high-resolution mass spectrometry. The crushed sample was extracted with acetonitrile with 1% acetate, followed by a cleanup step with a primary-secondary amine, octadecylsilane, and graphitized carbon black. The extraction and purification were carried out using the one-step automatic pretreatment equipment. The target pesticides were acquired in positive ion electrospray ionization mode and full scan/data dependent secondary scan mode. The calibration curve shows good linearity over the corresponding concentration range, with the coefficient of determination greater than 0.99. The screening detection limits were 0.5-50 µg/kg, and the limit of quantification for the 206 pesticides was set at 1-50 µg/kg. At the spiking levels of one, two, and 10 times of limit of quantification, more than 95% of pesticides had recovery between 70-120%, with a relative standard deviation ≤20%. The method was proved to be simple, rapid, high-sensitivity, and could be routinely used for the high throughput screening and quantitative analysis of pesticide residues in alfalfa and oat.

Analysis of Pesticide Residues by QuEChERS Method and LC-MS/MS for a New Extrapolation of Maximum Residue Levels in Persimmon Minor Crop.

According to EU guidance SANCO/7525/VI/95 Rev. 10.3, residue data extrapolation from a surrogate major crop to a minor crop can be used for setting maximum residue levels (MRLs) with a reduced number of residue trials and representative selected pesticides. In this work, a QuEChERS method (citrate-buffered version and PSA with MgSO4 clean-up) and LC-ESI-MS/MS for the determination of boscalid, pyraclostrobin, fludioxonil, fluopyram and tebuconazole in persimmon was developed and validated according to EU Commission guidelines and afterwards used for the determination of residues in four field trials. Residue levels at harvest for each pesticide ranged between 0.347 and 0.028 mg/kg. After comparing EFSA residue data on apples, as the surrogate major crop, and conducting a consumer risk assessment, a proposal of residue data extrapolation to set MRLs in persimmons was performed. The results showed that pesticide residues in persimmons at harvest were consistently lower than residues in apples when substances were applied according to the same critical GAP. MRLs were set at 0.5 mg/kg for fludioxonil, 0.6 mg/kg for boscalid, 0.3 mg/kg for tebuconazole, 0.4 mg/kg for fluopyran and 0.3 mg/kg for pyraclostrobin. The ratio of the MRLs for apple/persimmon varied between 2.5 for boscalid and 1.25 for fluopyram, suggesting that residue extrapolation can be feasible, promoting the process of pesticide registration for minor crops and the settlement of MRL.

Multi-residue analysis of 20 mycotoxins including major metabolites and emerging mycotoxins in freshwater using UHPLC-MS/MS and application to freshwater ponds in flanders, Belgium.

Mycotoxins are known for their negative impact on human and animal health as they frequently contaminate food and feed products from crop origin that are consumed by humans and animals. Furthermore, mycotoxins can leach out of plant tissue, to be transported through runoff water into nearby ponds where they can exert negative effects on aquatic organisms, such as fish, amphibians and zooplankton. The overall goal of this study was to develop a SPE-UHPLC-MS/MS method for the detection and quantification of multiple mycotoxins in amphibian breeding ponds. The method was validated and yielded acceptable within-run and between-run apparent recoveries and precision, as well as good linearity. Matrix effects (i.e. 75.7-109.6%, ≤ 17.8% RSD) were evaluated using water from 20 different ponds in Flanders, Belgium. By incorporating internal standards, overall results improved and adequate precision values (i.e. ≤ 15%) were obtained according to the EMA guideline. Additionally, extraction recovery (n = 3) was evaluated, yielding good results for all mycotoxins (i.e. 75.3-109.1%, ≤15% RSD), except for AME (i.e. 6.7 ± 0.7%), which implied the need for a matrix-matched calibration curve. Detection sensitivity was in the low nanograms per liter range. Storage stability experiments indicated that sample storage at 4 °C in amber glass bottles and analysis performed within 96 h after sampling was sufficient to avoid loss by degradation for all compounds, excluding ß-ZAL and ß-ZEL, for which analysis within 24 h is more indicated. The method was successfully applied to water samples originating from 18 amphibian breeding ponds situated across Flanders. Overall, enniatins B, B1 and A1 were most commonly detected at maximum concentrations of 6.9, 3.3 and 2.6 ng L-1, respectively, followed by detection of beauvericin (1.1 ng L-1 and < 1 ng L-1), alternariol monomethyl ether (< 10 ng L-1), HT2-toxin (< 40 ng L-1), zearalenone (< 25 ng L-1) and α-zearalanol (< 10 ng L-1). We believe that this method will boost further research into the dynamics and ecotoxicological impact of mycotoxins in aquatic environments.

Comparative evaluation of multi-residue methods for analysis of pesticide residues in black pepper by gas chromatography tandem mass spectrometry: critical evaluation of matrix co-extractives and method validation.

A gas chromatography tandem mass spectrometry method was developed for simultaneous determination of 133 pesticides in Black pepper (Piper nigrum). QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) sample preparation method is preferred over multistep methods. Extraction was done by using acetonitrile followed by clean up using graphitized carbon, primary secondary amine and octadecyl silica (C18). Even after the cleanup, non-volatile co-extractives stick to the liner and column which results in affecting the performance of the instrument and volatile co-extractives impact the analysis by enhancing the analyte concentration. So we evaluated a dilution procedure to overcome the drawbacks. The limit of quantification of 0.01 mg kg-1 was achieved for fifty times diluted sample extract with S/N ≥ 10. The recovery was between 70 and 120% for 0.01, 0.025 and 0.05 mg kg-1 for fortified samples and corresponding precision was between 3 and 16% RSD. The seven-level calibration curve shows a regression co-efficient of 0.99.

Amphiphilic block copolymer-grafted magnetic multi-walled carbon nanotubes as QuEChERS adsorbent for simultaneous determination of mycotoxins and pesticides in grains via liquid chromatography tandem mass spectrometry.

An amphiphilic block copolymer consisting of poly(N-acryloyl-glucosamine) (PAGA) and poly(tert-butyl methacrylate) (PtBMA) was designed and grafted on magnetic multi-walled carbon nanotubes (Fe3O4MWCNTs). The resultant Fe3O4MWCNTs@copolymer was proposed as QuEChERS adsorbent for determination of 15 mycotoxins and 25 pesticides in grains via liquid chromatography tandem mass spectrometry. The adsorbent was characterized by a transmission electron microscope, scanning electron microscope, elemental analysis, and other techniques. The common matrix interferences were efficiently removed by the proposed adsorbent, such as pigment, fatty acids, and the saccharide. PAGA segment played an important role in removing the hydrophilic interferences through hydrogen bonding due to the high density of hydroxyl groups. PtBMA segment removed the fatty residues through its strong hydrophobic carbon moiety. In comparison with the commercially available QuEChERS adsorbents, the proposed adsorbent had higher adsorption capacities towards the typical matrix interferences. To achieve satisfactory recoveries of analytes, various parameters in the QuEChERS procedure were comprehensively investigated. Under the optimal conditions, 95.0% of the analytes showed satisfactory recoveries in the range 70.0-120% as well as negligible matrix effects. The limits of detection (LOD) were in the range 0.00015-1.3 µg kg-1. Compared with previously reported QuEChERS methods, the proposed method had improved sensitivity and benefited from low matrix effects. The recoveries of analytes in various grains were in the range 60.8-108% with relative standard deviations (RSD) less than 13%. Moreover, the Fe3O4MWCNTs@copolymer exhibited good synthetic reproducibility and rapid magnetic separation (less than 10 s). The research provides a versatile platform to develop multi-functional QuEChERS adsorbents based on the amphiphilic block copolymer.

Comparison of Sample Preparation and Determination of 60 Veterinary Drug Residues in Flatfish Using Liquid Chromatography-Tandem Mass Spectrometry.

This study was performed to optimize the analytical method for multi-residues of 60 compounds in flatfish samples. Three sample preparation methods were tested to identify the optimal recovery conditions for target analytes. As a result, 10 mL of water/acetonitrile (1:4, v/v) was used to extract analytes from fish samples. For purification, C18 and 10 mL of acetonitrile saturated hexane were used to treat the samples. After evaporation and reconstitution, the fish samples were analyzed by ultra-performance liquid chromatography-tandem mass spectrometry. The proposed method was validated according to the CODEX guidelines (CAC/GL-71). Our results showed the recoveries of 73.2%-115% and coefficients of variation of 1.6%-22.1%. The limit of quantification was 0.0005-0.005 mg/kg in the fishery products. In analysis of real samples, no samples exceeded the limit of quantification. This analytical method can be used for multi-residue screening and confirmation of the residues of veterinary drugs in fishery products.

Rapid Multi-Residue Detection Methods for Pesticides and Veterinary Drugs.

The excessive use or abuse of pesticides and veterinary drugs leads to residues in food, which can threaten human health. Therefore, there is an extremely urgent need for multi-analyte analysis techniques for the detection of pesticide and veterinary drug residues, which can be applied as screening techniques for food safety monitoring and detection. Recent developments related to rapid multi-residue detection methods for pesticide and veterinary drug residues are reviewed herein. Methods based on different recognition elements or the inherent characteristics of pesticides and veterinary drugs are described in detail. The preparation and application of three broadly specific recognition elements-antibodies, aptamers, and molecular imprinted polymers-are summarized. Furthermore, enzymatic inhibition-based sensors, near-infrared spectroscopy, and SERS spectroscopy based on the inherent characteristics are also discussed. The aim of this review is to provide a useful reference for the further development of rapid multi-analyte analysis of pesticide and veterinary drug residues.

Multivariate optimization of a new LC-MS/MS method for the determination of 156 pesticide residues in milk and dairy products.

BACKGROUND: Pesticides are widely utilized worldwide to control undesirable life forms during the planting procedure in agriculture. But they can pollute the nature and jeopardize human wellbeing. Additionally, on account of high resistance and biological activity; pesticides are able to accumulate in living organs and lead to acute and long-term negative effects along with toxicity. Milk and dairy products constitute an important part of a humans' diet since they contain fundamental supplements and nutrients, however they may also be the source of unhealthy components including pesticides. Therefore efficient, accurate and sensitive determination methods must be improved to quantify pesticide residues in these food samples. RESULTS: Multivariate optimization strategy was employed to optimize an efficient and robust liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method for the determination of 156 pesticide residues in milk and dairy products. Three independent variables considered and their levels in the Box-Behnken design were as follows: initial percentage of eluent A in mobile phase (30, 40, 50%), flow rate of the mobile phase (0.1, 0.2, 0.3 mL min-1 ), and ammonium formate concentration in mobile phase (0.0, 0.5, 1.0 mmol L-1 ). Under optimized conditions, average recoveries of target analytes were obtained in the range of 70.38% to 119.04%. Detection and quantification limits ranged from 0.06 to 2.70 µg kg-1 and from 0.22 to 8.10 µg kg-1 , respectively. CONCLUSION: The validated method was successfully implemented to the analysis of 20 milk and dairy products including cream, cheese and yogurt. This method could be applied in many laboratories to reduce analysis time and cost. © 2020 Society of Chemical Industry.

Multi-residue analysis of plant growth regulators and pesticides in traditional Chinese medicines by high-performance liquid chromatography coupled with tandem mass spectrometry.

A multi-residue method was developed for the simultaneous determination of 24 plant growth regulators (PGRs) and 11 representative pesticides that were widely applied in plants used in traditional Chinese medicines (TCMs) by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The method was validated taking into consideration EU guidelines; calibration curves for all of the targeted analytes showed correlation coefficients (γ2) higher than 0.9901. The limits of detection (LOD) ranged from 0.2 to 8 µg/kg. The average recovery for all analytes in spiked samples ranged from 63.18 to 127.23%, with a relative standard deviation of ≤ 15%. The proposed method has been applied to 480 batches of TCM samples, including 34 species of medicinal plants, from the TCM market. The results showed that 14 PGRs and 5 pesticides were detected, including choline chloride, chlormequat, paclobutrazol, uniconazole, phoxim, etc. Among them, there were high detection rates for chlormequat (40%), choline chloride (100%), atonik (73.75%), abscisic acid (80.83%), and indole-3-acetic acid (41.25%). The residual level of paclobutrazol in Ophiopogonis radix exceeded the recommended maximum residue limits (MRLs) according to GB 2763-2016. In addition, 14 agrochemicals used in TCM planting were collected and detected; the result showed various PGRs were detected in samples registered as fertilizer. These results indicate that PGRs and pesticides were widely used in the cultivation of medicinal plants, especially for radix and rhizome herbs. The residue of targeted PGRs and pesticides in TCM samples from this study have a high frequency and high level. Graphical abstract.

A simple, fast method for the analysis of 20 contaminants of emerging concern in river water using large-volume direct injection liquid chromatography-tandem mass spectrometry.

A fast and sensitive method for the determination of a structurally and physico-chemically diverse group of contaminants of emerging concern (CEC) based on large-volume direct injection liquid chromatography-tandem mass spectrometry was developed. The method can be used to determine 20 CECs belonging to different pollutant families (pharmaceuticals, personal care products, and pesticides) in river water at nanogram per liter. A single analytical run is required and the positive and negative ionization modes can be used simultaneously. Because of the large-volume injections of samples and the high sensitivity of the current mass spectrometers, the method has no need of a preconcentration step. The analytes are quantitated with matrix-matched calibration curves. The estimated limits of detection were in the range 0.1-5 ng L-1. The accuracy of the method was in the range 86-114%, and the precision, expressed as a relative standard deviation (RSD %), was below 18% for all the analytes (n = 5, at 5, 10, and 25 ng L-1). The method was applied to water samples taken from different points along the lower course of the Ebro River, Spain. A total of 12 out of the 20 target analytes were detected, and the ones at higher concentrations were caffeine and the pharmaceuticals paracetamol and ibuprofen (184.8 ng L-1, 63.3 ng L-1, and 23.3 ng L-1, respectively).

Fabric phase sorptive extraction/GC-MS method for rapid determination of broad polarity spectrum multi-class emerging pollutants in various aqueous samples.

A rapid extraction and cleanup method using selective fabric phase sorptive extraction combined with gas chromatography and mass spectrometry has been developed and validated for the determination of broad polarity spectrum emerging pollutants, ethyl paraben, butyl paraben, diethyl phthalate, dibutyl phthalate, lidocaine, prilocaine, triclosan, and bisphenol A in various aqueous samples. Some important parameters of fabric phase sorptive extraction such as extraction time, matrix pH, stirring speed, type and volume of desorption solvent were investigated and optimized. Calibration curves were obtained in the concentration range 0.05-500 ng/mL. Under the optimum conditions, the limits of detection were in the range 0.009 -0.021 ng/mL. This method was validated by analyzing the compounds in spiked aqueous samples at different levels with recoveries of 93 to 99% and relative standard deviations of <6%. The developed method was applied for the determination of the emerging contaminants in tap water, municipal water, ground water, sewage water, and sludge water samples. The results demonstrate that fabric phase sorptive extraction has great potential in the preconcentration of trace analytes in complex matrix.

A magnetic graphene-like MoS2 nanocomposite for simultaneous preconcentration of multi-residue herbicides prior to UHPLC with ion trap mass spectrometric detection.

A magnetic graphene-like molybdenum disulfide nanocomposite was prepared by liquid-phase exfoliation and hydrothermal synthesis. The morphology, structure, and magnetic behavior of the nanocomposite were characterized by X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, scanning electron microscopy and transmission electron microscopy. The nanocomposite was employed as a sorbent for magnetic solid-phase extraction (MSPE) of eight triazine and ten sulfonylurea herbicides from environmental water and corn samples. Specifically, this was studied with cyanazine, simetryn, atrazine, methoprotryne, ametryn, prometryn, terbutryn, dipropetryn, metsulfuron-methyl, sulfometuron-methyl, amidosulfuron, rimsulfuron, nicosulfuron, bensulfuron-methyl, halosulfuron-methyl, pyrazosulfuron-ethyl, chlorimuron-ethyl, and cyclosulfamuron. The parameters affecting extraction efficiency (sorbent amount, pH value of the sample, extraction and elution conditions) were studied and optimized. Following MSPE, the multi-residue herbicides were quantified by ultra-high performance liquid chromatography combined with ion trap mass spectrometry and electrospray ionization. The limits of detection range between 20 and 170 ng·L-1. The extraction recoveries of eighteen herbicides from corn samples were in the range between of 64.7% and 103.1%, with RSDs of <17.6%. Graphical abstract Schematic presentation of magnetic graphene-like MoS2 nanocomposite as an absorbent for simultaneous preconcentration of eight triazine and ten sulfonylurea herbicides in corn and water prior to ultra-high performance liquid chromatography (UHPLC) with ion trap mass spectrometry detection.

Determination of 107 Pesticide Residues in Wolfberry with Acetate-buffered Salt Extraction and Sin-QuEChERS Nano Column Purification Coupled with Ultra Performance Liquid Chromatography Tandem Mass Spectrometry.

A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.

Fast, sensitive and reliable multi-residue method for routine determination of 34 pesticides from various chemical groups in water samples by using dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

A simple and efficient dispersive liquid-liquid microextraction technique (DLLME) was developed by using a mixture of two solvents: 40 µL of tetrachlorethylene (extraction solvent) and 1.0 mL of methanol (disperser solvent), which was rapidly injected with a syringe into 10 mL of water sample. Some important parameters affecting the extraction efficiency, such as type and volume of solvents, water sample volume, extraction time, temperature, pH adjustment and salt addition effect were investigated. Simultaneous determination of 34 commonly used pesticides was performed by using gas chromatography coupled with mass spectrometry (GC-MS). The procedure has been validated in order to obtain the highest efficiency at the lowest concentration levels of analytes to fulfill the requirements of regulations on maximum residue limits. Under the optimum conditions, the linearity range was within 0.0096-100 µg L-1. The limits of detection (LODs) of the developed DLLME-GC-MS methodology for all investigated pesticides were in the range of 0.0032 (endrin)-0.0174 (diazinon) µg L-1 and limits of quantification (LOQs) from 0.0096 to 0.052 µg L-1. At lower concentration of 1 µg L-1 for each pesticide, recoveries ranged between 84% (tebufenpyrad) and 108% (deltamethrin) with relative standard deviations (RSDs) (n = 7) from 1.1% (metconazole) to 11% (parathion-mehtyl). This methodology was successfully applied to check contamination of environmental samples. The procedure has proved to be selective, sensitive and precise for the simultaneous determination of various pesticides. The optimized analytical method is very simple and rapid (less than 5 min). Graphical abstract Analytical procedure for testing water samples consists of dispersive liquid-liquid microextraction (DLLME) and gas chromatography coupled with mass spectrometry (GC-MS).

Evaluation of MS2 workflows in LC-Q-Orbitrap for pesticide multi-residue methods in fruits and vegetables.

LC-Q-Orbitrap efficiency was evaluated for pesticide multi-residue analysis by using three workflows involving simultaneous MS and MS2 analysis. They were as follows: data-dependent MS2 (dd-MS2), all-ion fragmentation (AIF) and variable data-independent analysis (vDIA). These MS2 workflows were tested for the main method validation parameters such as detection and identification capabilities, repeatability, linear range and quantitation. QuEChER acetonitrile extracts (blanks and spiked with 166 pesticides) of 11 different fruits and vegetables were used for this evaluation. Blank extracts were analysed to evaluate isobaric compounds and potential false identification. Spiked extracts (at 0.01 and 0.1 mg kg-1) were analysed to evaluate the false negatives potentially produced (considering a retention mass window of 0.2 min). At 0.01 mg kg-1, dd-MS2 had the highest identification rate (96-100%, depending on the matrix). In vDIA, it was 86-100% and in AIF 81-100%. But these two last workflows offered more possibilities for applying screening analysis. It was observed that application of the ion ratio criterion established in the SANTE Guidelines for identification can generate some artificial false negative results. It could be overcome by considering a mass error threshold (i.e. 5 ppm) as a selected criterion. Detection and quantitation were carried out in full-scan MS. MS2 data were used for identification. Dd-MS2 provided the highest number of points per chromatographic peak, and by that peak area, repeatability was the best (typically <10%). AIF and vDIA were characterised by longer cycle times; thus, the obtained peak area repeatability was slightly worse, but acceptable (<20%). All workflows showed very good linearity in the range 0.01-0.5 mg kg-1. The three MS2 workflows were applied to real samples with good results. Graphical abstract LC-Q-Orbitrap was used for pesticide residues analysis in fruit and vegetables. Three approaches to MS2 identificaton were evaluated.