Simultaneous Determination of Multiclass Pesticides and Antibiotics in Honey Samples Based on Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

A simple, fast, and efficient method was developed for simultaneous determination of 79 pesticides and 13 antibiotics compounds of different chemical classes of pesticides and antibiotics in honey samples by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). The sample preparation procedure includes homogenization with McIlvaine buffer 0.1 mol L^?1 (pH 4), followed by extraction with acetonitrile and cleanup with florisil, using dispersive solid phase extraction (d-SPE). The proposed method was validated with good results, such as linearity (r ²?>?0.9901), normality, and independence of the evaluated data, as well as recoveries between 70 and 120 % with relative standard deviation (RSD) <20 % for most of the compounds spiked from 0.1 to 200 μg kg^?1. The experimental method limits of detection and quantification were from 0.03 to 1.51 μg kg^?1 and from 0.1 to 5 μg kg^?1, respectively, for the pesticides. For the antibiotics, the decision limits (0.1 to 2 μg g^?1) and the detection capacity (0.12 to 2.81 μg g^?1) were below the maximum residue limits (MRLs) established for honey by the Brazilian and European legislation. The method was successfully applied to real samples from different botanical and geographic origins. From them, 44 % presented residues from 0.12 to 10 μg kg^?1 of one or more analytes. The proposed method combines the advantages of a quick sample preparation step with the selectivity and sensitivity of the UHPLC-MS/MS and proved to be suitable for routine analyses.     

Dispersive Liquid-Liquid Microextraction for the Determination of Emerging <Emphasis Type="Italic">Fusarium</Emphasis> Mycotoxins in Water

A new method was optimized for the determination of emerging Fusarium mycotoxins enniatins (ENs) and beauvericin (BEA) in different types of water. Mycotoxin analysis was performed by dispersive liquid-liquid microextraction (DLLME) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Mycotoxins were efficiently extracted from water into carbon tetrachloride by DLLME technique using acetonitrile as disperser solvent. Detection limits were in the range of 0.06–0.17 μg L^?1. Quantification was performed using matrix-matched calibration curves over a linear range from limit of quantification (LOQ) to 200 μg L^?1. Acceptable recoveries were obtained between 78.5 and 100.1 % with relative standard deviations of <14 %. The proposed method may be advised as an easy, sensitive, and accurate method for determining emerging Fusarium mycotoxins in water. The method was successfully applied to the analysis of different kinds of water. No detectable levels were achieved in surface, ground, tap, and bottled water. Concentration levels up to 50 μg L^?1 were detected in cooking water related to the pasta cooking process.     

Determination of Pesticide Residues in Soy-Based Beverages Using a QuEChERS Method (with Clean-Up Optimized by Central Composite Design) and Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry

Soybean production is responsible for a great amount of pesticides applied in Brazil. In the last years, an increase of soy-based beverage consumption and a higher concern about pesticide residues in food occurred. A simple, fast, and efficient multiresidue method based on the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed for simultaneous determination of 39 pesticides and two plant growth regulators in soy-based beverages by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The clean-up procedure was established based on central composite design (CCD), using response surface methodology (RSM). For the optimization of the clean-up step, different amounts of sorbents in dispersive solid phase extraction (d-SPE) were evaluated. Validation results were satisfactory, considering that the optimized method presented recoveries between 70 and 112 %, with RSD lower than 19 % for spike levels between 10 and 50 μg L^?1. The method limit of detection (LOD) and quantification (LOQ) ranged from 3 to 8 and 10 to 25 μg L^?1, respectively. The proposed method combines the advantages of QuEChERS and UHPLC-MS/MS and proved to be suitable for the pesticide multiresidue determination in soy-based beverages in routine laboratory analyses.     

Optimization of QuEChERS Procedure Coupled to GC-ECD for Organochlorine Pesticide Determination in Carrot Samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO₄) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EU maximum residue limits (MRLs) for carrots, 10–50 μg kg^?1, while the limit of quantification did exceed 10 μg kg^?1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg^?1), ranged from 66 to 111 % with relative standard deviations in the range of 2–15 % (n?=?3) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg^?1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg^?1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.     

Antioxidant Activity and Determination of Phenolic Compounds from <Emphasis Type="Italic">Eugenia involucrata</Emphasis> DC. Fruits by UHPLC-MS/MS

Fruits have been the focus of several studies aimed at finding new antioxidant sources for protection against the damage caused by reactive species. In this study, the antioxidant activity and the presence of phenolic compounds in all parts (peel, pulp, and seeds) of Eugenia involucrata DC. fruits were evaluated. DPPH^·, ABTS^·+, and ORAC methods were used to determine the antioxidant activity, and an UHPLC-MS/MS method was developed for determining the phenolic compounds (gallic, chlorogenic, ferulic, p-coumaric and ellagic acids, quercetin, and myricetin). In the determination of both antioxidant activity and phenolic composition, the efficiency of solvents with different polarities—methanol/H₂O (80:20, v/v), ethanol/H₂O (80:20, v/v), methanol/acidified water with phosphoric acid pH 3.00 (80:20, v/v), and ethyl acetate—for the extraction of the phenolic compounds, was also evaluated. All parts of E. involucrata fruits showed antioxidant activity, in the range of 36.68 ± 1.44 to 873.87 ± 18.24 μmol TE g^?1, being the highest values found in the seeds and peel when more polar extraction solvents were used. Six, five, and three phenolic compounds were identified and quantified in the pulp, peel, and seeds, respectively, with the highest abundance as p-coumaric acid (14 ± 2 mg kg^?1) in the pulp, quercetin (47 ± 5 mg kg^?1) in the peel, and gallic acid (74 ± 4 mg kg^?1) in the seeds, also when more polar solvents were used. Although antioxidant activity methods suggested that the peel and seeds have more antioxidant potential, a wider variety of compounds were determined in the pulp.     

Characterization and transformation of the <Emphasis Type="Italic">Opuntia ficus indica</Emphasis> fruits

Opuntia ficus indica fruits have been associated with health effects, due to their protective actions against oxidation. Nevertheless, few studies about processing of Opuntia fruits are available’; therefore, we studied the pulp characteristics and processing of a local variety, for producing beverage nectars. The pulp had an average pH of 5.64, 13.47 °Brix, with total sugars (106 g L^?1), K (1180 mg L^?1), 503.3 µg L^?1 of β carotene, 120 mg L^?1 of total phenolic compounds, 4.9 mg and 46.9 mg L^?1 respectively for betacyanins and betaxanthins and 243.4 mg L^?1 of vitamin C. The formulated nectars with 35% of pulp (N35) and 45% of pulp (N45) had respectively 14 and 15 °Brix. Minor components represent 1109 and 1112 mg L^?1 of K for N35 and N45 respectively, β carotene (318.6 µg and 362.8 µg L^?1), and vitamin C 227 and 231 mg L^?1. We confirmed the stability and acceptability of these beverages after a month of storage, after stability and panel tests. Therefore, we suggest that the pulp processing can be used as a new form of agro industrial utilization of this underutilized fruit.     

Rapid Quantification Method of Three <Emphasis Type="Italic">Alternaria</Emphasis> Mycotoxins in Strawberries

Validation of simple and rapid method for three Alternaria mycotoxins determination including alternariol (AOH), alternariol methyl ether (AME) and tentoxin (TEN) in strawberries is described. The extraction procedure was based on a simple liquid–liquid extraction with ethyl acetate, which provided the highest recoveries and the lowest matrix effect. Analytes were determinated by liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS). The obtained relative recoveries were higher than 63 % for the studied mycotoxins in strawberries at the limit of quantification (LQ). Good linearity (r ²?>?0.993) and quantification limits (3–14 ng/g) were obtained. Repeatability, expressed as relative standard deviation, was always lower than 6 %, whereas interday precision was lower than 13 % for the developed method. The method was applied to analyse 24 strawberry samples commercialized in markets of the Valencia city (Spain). Analysed samples were only contaminated with AOH and AME.     

Multi-residual Pesticide Monitoring in Commercial Chinese Herbal Medicines by Gas Chromatography–Triple Quadrupole Tandem Mass Spectrometry

To investigate multi-residual pesticide monitoring data in commercial Chinese herbal medicines on major markets, an easy, rapid, and selective gas chromatography with mass spectrometry (GC/MS/MS) method was established for simultaneously determining multi-residual pesticides including organochlorine, pyrethroid, carbamate, and organophosphorus pesticides in Chinese herbal medicines. The analytical method was based on an efficient extraction procedure and further cleanup steps by solid-phase extraction columns, yielding recovery rates in the range of 70.0–120.0 % for the majority of pesticides, except for hexachlorobenze, diazinon, β-HCH, δ-HCH, and omethoate, with precision values expressed as relative standard deviation of 0.1–14.7 %. The limits of detection of the established GC/MS/MS method for all investigated pesticides ranged from 0.01 to 3.6 μg kg^?1 and limits of quantification from 0.03 to 11.88 μg kg^?1. With this validated method, multi-residual pesticides of 132 Chinese herbal medicine samples were analyzed. The monitoring results indicated that pesticide residue was found in 74 samples. In total, 51 pesticides were found with detection rate ranging from 0.76 to 18.94 %. An 82.3 % of positive pesticides were found in less than 6 % of samples. Hexachlorobenzene was found in 25 samples, quintozene in 15 samples, and acephate and simazine in 13 samples. Concentrations of pesticide residue from monitoring data obtained ranged from 0.5 to 203.5 μg kg^?1. The simple and rapid method can be used as routine analysis method in multi-residual pesticide monitoring of Chinese herbal medicines.     

<Emphasis Type="Italic">Spirulina</Emphasis> sp. biomass dried/disrupted by different methods and their application in biofilms production

Arthrospira Spirulina biomass is a source of intracellular compounds with great commercial interest, such as phycocyanin and phenolic compounds. In this work, different cell disruption methods of the microalgae biomass dried in spouted bed and in conventional tray were performed, aiming lead to the better extraction yields of these compounds. The samples of both drying techniques with the most suitable cell disruption were used to biofilms production. FTIR, DSC, and SEM for all samples were performed. The samples dried in spouted bed with cell disruption by milling and by microwave showed the best results for the powder products, with phycocyanin contents of 75.0 and 85.4 mg g^?1, and total phenolic compounds of 41.6 and 41.9 mg g^?1, respectively. However, the tray drying/milling produced the biofilms with the best characteristics (tensile strength of 3.69 MPa and water vapor permeability of 1.67?×?10^?11 g m s^?1 m^?2 Pa^?1) and the highest thermal stability.     

Development of Advance Extraction Methods for the Extraction of Myristicin from <Emphasis Type="Italic">Myristica fragrans</Emphasis>

Myristicin in a psychoactive, hallucinogenic substance and as a constituent of nutmeg and mace (Myristica fragrans nut and its aril, respectively) is widely available for people seeking so-called legal highs of natural origin. In this work, we present three methods for determination of myristicin from plant material. The methods consist of optimized extraction procedures: microwave-assisted extraction, ultrasound-assisted extraction utilizing ultrasound bath or sonotrode and gas chromatography-mass spectrometry (GC-MS) analysis method. The methods were validated: repeatability and intermediate were below 10 % and recovery ranged from 97 to 109 %. The developed methods were then used for determination of myristicin in commercially available nutmeg and mace samples. The concentration ranged from 0.58 to 12.94 μg mg^?1, and the highest concentration of myristicin was observed in samples of those producers, which are often recommended by individuals experimenting with nutmeg. The microwave-assisted extraction (MAE) method has been proven to be the most effective one for the extraction of myristicin from plant material, as it also generates deeper changes in sample structure than UAE techniques. The MAE/GC-MS method was successfully used for nutmeg residue analysis, allowing identification of five characteristic violate constituents of nutmeg.     

Development and validation of an UHPLC-MS/MS method for the determination of mycotoxins in grass silages

An ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) multi-mycotoxin analytical method was developed to simultaneously identify and quantify 20 mycotoxins in grass silages, inclusive of mycotoxins that are currently regulated in European Union feeds. Extraction of mycotoxins from dried grass silages was performed using of a modified QuEChERS extraction employing an acidified aqueous extraction (0.1 N HCl) with no further clean-up. Following chromatographic separation, analytes were detected using a fast polarity-switching MS/MS method that allowed both positive and negative ions to be analysed from a single injection, thus the reducing time and cost of analysis. The limits of detection and quantification ranged between 3 µg kg^–1 DM (aflatoxin B₁, beauvericin and enniatin A and A₁) and 200 µg kg^–1 DM (deoxynivalenol), and between 10 µg kg^–1 DM (aflatoxin B₁, beauvericin and enniatin A₁) and 500 µg kg^–1 DM (deoxynivalenol), respectively. Inter-assay accuracy and precision ranged between 90% and 107% and between 3.9% and 15.0% CV, respectively. The accuracy of the method was assessed through the application to a range of incurred samples in an inter-laboratory study.     

Application of Ionic Liquid-Based Ultrasound-Assisted Extraction of Five Phenolic Compounds from Fig (<Emphasis Type="Italic">Ficus carica</Emphasis> L.) for HPLC-UV

Ionic liquid-based ultrasonic-assisted extraction (IL-UAE) was successfully developed to extract the known phenolics gallic acid, chlorogenic acid, rutin, psoralen, and bergapten present in the leaves, pulps, and peels of Ficus carica L. In this work, the proposed method was evaluated in comparison with regular ultrasonic-assisted extraction in which methanol was the extractant and exhibited higher efficiency. Moreover, ionic liquids with different cations were investigated and 1-butyl-3-methylimidazole hexafluorophosphate solution was selected as the optimal extractant at concentration of 1.0 mol L^?1. The corresponding extraction parameters including extraction solvent, the concentration of [BMIM][PF₆], solid–liquid ratio (g mL^?1), ultrasonic extraction time, and extraction temperature were optimized. The phenolics were then determined by high-performance liquid chromatography (HPLC). Under the optimized conditions, the content of gallic acid, chlorogenic acid, rutin, psoralen, and bergapten in leaves, pulps, and peels of F. carica L. was 12.67–37.16, 14.75–90.07, 107.91–222.37, 2.59–67.83, and 1.99–20.21 μg/0.1 g, respectively. This study suggests that IL-UAE is a rapid, simple, and green preparation technique.     

A Simple and Fast Method for the Determination of 20 Veterinary Drug Residues in Bovine Kidney and Liver by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

A simple and rapid sample preparation method was developed and validated for multi-class analysis of veterinary drug residues in bovine kidney and liver. Sample preparation procedure was performed using acetonitrile and trichloroacetic acid for protein precipitation followed by ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis. The proposed method was validated according to the criteria of the Commission Decision 2002/657/EC evaluating linearity, selectivity, accuracy and precision, determination limit (CCα), and detection capacity (CCβ). Linearity presented r ² ≥ 0.99 for all the target compounds, and recoveries ranged from 80 to 110 % with RSD ≤17 % for intra- and inter-day assay. Values of CCα and CCβ ranged from 11 to 1096 and from 12 to 1191 μg kg^?1, respectively. The proposed sample preparation followed by UHPLC-MS/MS analysis was suitable for the determination of 20 veterinary drug residues in bovine kidney and liver in routine analysis. Method applicability was evaluated using commercial samples.     

Rapid Detection of <Emphasis Type="Italic">Vibrio parahaemolyticus</Emphasis> in Shellfish by Real-Time Recombinase Polymerase Amplification

Vibrio parahaemolyticus (V. parahaemolyticus) is a zoonotic pathogen generally found in seafood. To detect the foodborne pathogen rapidly and accurately for food safety measures, we developed a real-time recombinase polymerase amplification (RPA) method. An evaluation of the specificity and sensitivity of the method is discussed here. A set of primers and probe was specially designed to target the tlh gene, which is usually regarded as a marker of total V. parahaemolyticus strains. During the reaction, target DNA was amplified and tagged with specific fluorophore within 10 min and at an incubation temperature of 40 °C. In addition to fast amplification and low temperature, the fluorescence signal was synchronized with the amplification of products for the generation of real-time data. The detection limit of this assay was 0.4 pg/μL of DNA, which is comparable to assays that use the bacterial culture as template, 4?×?10³ cfu/mL. The real-time RPA method had a stable performance when testing the spiking shellfish samples at the same level of contamination by the pathogen in different kinds of shellfish. Thus, the real-time RPA method shows great potential for on-site detection of V. parahaemolyticus, especially in low-resource settings.     

Intermittent and Continuous Microwave-Convective Air-Drying Characteristics of Sage (<Emphasis Type="Italic">Salvia officinalis</Emphasis>) Leaves

The effect of microwave-convective air-drying (continuous and intermittent) and convective air-drying of sage (Salvia officinalis) on color and essential oil content were studied. For microwave-convective air-drying, four pulse ratio levels (PR1, PR2, PR3, and PR4) at 25 °C drying air temperature were used and the average drying rates were 0.404, 0.158, 0.114, and 0.085 kg H₂O kg^?1 DM min^?1 for PR1, PR2, PR3, and PR4, respectively. For convective air-drying, two drying temperatures of 40 and 50 °C were examined and the average drying rates were 0.005 and 0.006 kg H₂O kg^?1 DM min^?1 for 40 and 50 °C, respectively. The experimental data were fitted to 11 different moisture ratio models to describe the drying kinetics under various drying conditions. Page model was found satisfactory to describe the drying curves of sage leaves. Comparing with the fresh sage, lightness (L*), greenness, and yellowness decreased for all drying applications. Lightness, greenness, and yellowness of the convective air-dried sage leaves were higher than those of microwave-convective air-dried sage leaves. The deviation from fresh product color (ΔE*) increased as the pulse ratio or the drying air temperature increased. The total quantity of essential oils of sage decreased considerably during microwave-convective air-drying whereas the loss of essential oils was limited during air-drying.     

Simultaneous Determination of Five Neonicotinoid Insecticides in Edible Fungi Using Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry (UHPLC-MS/MS)

A robust analytical method for simultaneously determining five neonicotinoid insecticides (clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam) in commonly consumed edible fungi (Agaricus bisporus, Flammulina velutipes, Hypsizygus marmoreus, Lentinus edodes, and Pleurotus eryngii) was provided in the present study. Samples were pretreated using a modified QuEChERS (quick, easy, cheap, efficient, rugged, and safe) method with the detection of neonicotinoids by ultrahigh-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). A number of optimizations performed to sample pretreatment and detection conditions were discussed. Limits of detection (LODs) for all analytes in edible fungi were between 0.03 and 0.7 μg kg^?1, while limits of quantitation (LOQs) ranged from 0.1 to 2 μg kg^?1. Mean recoveries for clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam were in the range of 100.5–118.0, 73.9–89.5, 88.6–117.8, 72.9–121.8, and 98.9–117.2%, respectively, with RSDs less than 8.1%. This method could be used for fast screen of the five neonicotinoid insecticides in edible fungi for risk assessing aims.     

Determination of seven pyrethroid pesticide residues in vegetables by gas chromatography using carboxylated multi-walled carbon nanotubes as dispersion solid phase extraction sorbent

ABSTRACT

A novel carboxylated multi-walled carbon nanotubes (MWCNTs-COOH) dispersive solid phase extraction (d-SPE) method combined with gas chromatography (GC) with an electron capture detector (ECD) was developed for the determination of seven pyrethroid pesticides in cucumber, spinach, eggplant, tomato and carrot. We optimised d-SPE conditions including the type and volume of the extractant, the type and amount of the sorbent, and shaking time. Under the optimal conditions, the linear range was from 2.0 to 2000 μg kg^?1. The recoveries were from 88.5% to 108.2%, with the corresponding RSDs <6%, correlation coefficients 0.9987–0.9998, LOD 0.5–2.9 μg kg^?1 and LOQ 1.5–9.7 μg kg^?1. The proposed method is simple, fast, and safe, with high recovery and sensitivity, and is applicable to analysis of pyrethroid pesticides in vegetable samples.     

Conventional and Microwave-Assisted Extraction of Mucilage from <Emphasis Type="Italic">Opuntia ficus-indica</Emphasis> Cladodes: Physico-Chemical and Rheological Properties

Cactus pear cladodes processing has potential value for mainstream industries and is equally important for marginal rural communities in arid regions. This work is focused on physico-chemical and rheological properties of Opuntia ficus-indica (OFI) peeled cladodes extracted by conventional method “CE” and using microwave-assisted extraction “MAE.” MAE gave the highest yield extraction (8.13 %, w/w) within the lowest extraction time (500 W/7 min) and provided more protein (×1.03) and carbohydrates (×1.51) than CE. The monosaccharides detected by gas chromatography were arabinose, galactose, rhamnose, xylose, and galacturonic acid. The dialyzed mucilage solution characterized by SEC/MALS/VD/DRI (size-exclusion chromatography coupled with online multi-angle light scattering, viscometer detectors, and differential refractive index) revealed fractions with molecular weight (M _w ) ranging from 15.3–15.7?×?10⁶ g mol^?1 for the CE extracts and about 16.7–17.5?×?10⁶ g mol^?1 for the MAE extracts. Dynamic oscillatory testing has been used to study the rheological properties of mucilage solution within the concentration of 0.50–3.00 % (w/v) at 25 °C. The rheological profiles of CE and MAE showed similar behavior. At low frequency and low mucilage concentration (<2.00 %), the viscous component (G") predominated over the elastic component (G'), while for higher frequencies, the behavior is reversed (G'?>?G"). If safely controlled, alternative energies like microwaves could extract soluble polymers with comparable properties to commercial ones, conventionally extracted.     

Determination of Pydiflumetofen Residues in Some Foods of Plant and Animal Origin by QuEChERS Extraction Combined with Ultra-Performance Liquid Chromatography–Tandem Mass

A rapid and effective analytical method for determination of pydiflumetofen residues in some foods of plant and animal origin (grapes, tomatoes, wheat, pork, milk, and eggs) was developed using a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation procedure followed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC–MS/MS). Acetonitrile was served as the extraction solvent, and an octadecylsilane-dispersive solid-phase extraction (C18-dSPE) was used to cleanup the analyte, and then detected by UPLC–MS/MS. Pydiflumetofen was eluted within 3.0 min from the HSS T3 chromatography column connected to an electrospray ionization source in positive mode. The linearity of the method was excellent (R²?≥?0.992) in the pydiflumetofen concentration range of 10–1000 μg kg^?1. The recoveries of spiked pydiflumetofen (10, 100, and 1000 μg kg^?1) from the matrices were satisfactory, being between 72.0 and 110.3%, and all with relative standard deviation values of <?15.1%. The limit of quantification for pydiflumetofen was 10 μg kg^?1. This study provides a method for the routine monitoring of pydiflumetofen.     

A Modified QuEChERS Sample Preparation Method for the Analysis of 70 Pesticide Residues in Tea Using Gas Chromatography-Tandem Mass Spectrometry

A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the simultaneous determination of 70 pesticides in tea was developed using gas chromatography-tandem mass spectrometry. Prior to acetonitrile extraction of the target compounds from tea matrix, samples were soaked in distilled water to improve the extraction efficiency. A mixture of adsorbents containing primary–secondary amine, octadecylsilane, graphite carbon black, and multiwalled carbon nanotubes was applied for the cleanup. Additional steps of concentration and solvent exchange were performed to reduce the amount of co-extracts and to decrease the limit of detection of the method. For all pesticides, good linear calibrations with coefficients (R ²) ≥0.99 were obtained at the concentration levels of 10, or 50 to 1,000 μg ml^?1. The limits of quantifications (LOQs) were 5–25 μg ml^?1, respectively. The recovery rates of samples spiked with 20, 100, and 200 μg kg^?1 of analytes ranged from 71 % to 105 %. In addition, the relative standard deviations were lower than 20 %. A total of 331 tea samples were analyzed using this method, and the levels of five pesticide residues in nine tea samples exceeded the strictest maximum residual limits (MRLs).