A Highly Sensitive Method for the Determination of Thiophanate Methyl,Cyromazine, and Their Metabolites in Edible Fungi by Ultra-Performance Liquid Chromatography Using Accelerated Solvent Extraction and Cleanup with Solid-Phase Extraction

A highly sensitive ultra-performance liquid chromatographic method with diode-array detection was developed for residue determination of thiophanate methyl (TM), cyromazine (CYR), and their metabolites, carbendazim (MBC) and melamine (MEL). Edible fungi samples were treated using accelerated solvent extraction (ASE) followed by cleanup with solid-phase extraction (SPE). Under optimized conditions, good linearity was achieved with a correlation coefficient (r ²) of ≥0.9998. The limit of quantification was 0.36, 0.24, 0.4, and 0.5 μg kg^?1 for MEL, CYR, MBC, and TM, respectively. The intra- and interday precisions (in terms of the relative standard deviation (RSD)) of the four analytes were in the range of 2.3–4.5 and 3.1–6.3 %, respectively. The recoveries for TM, MBC, CYR, and MEL in four edible fungi samples at three spiked levels of 0.6, 6, and 20 μg kg^?1 for TM and MBC and 0.4, 4, and 20 μg kg^?1 for CYR and MEL were in the range of 82–105 % with RSDs below 5.6 %. The proposed method can be used for the routine determination of CYR and MEL in edible fungi with high sensitivity and accuracy as well as low consumption of reagents.     

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.     

Simultaneous Determination of Nine Quinolones in Food by Liquid Chromatography with Fluorescence Detection

A confirmatory analytical method for simultaneous determination of nine regulated quinolones (Council Regulation 2377/90/ECC) in six matrices of animal origin is proposed. The sample pretreatment involves double step liquid extraction with acetonitrile and purification by solid-phase extraction on Oasis HLB cartridges. The quinolones were separated by liquid chromatography on C18 Zorbax column with gradient elution program. Aqueous formic acid, methanol, and acetonitrile were used as a mobile phase. A multi-wavelength excitation/emission program was used for sensitive fluorescence detection of quinolones. The proposed sample pretreatment protocol was applied to each of the six studied matrices without any modification. The method was validated according to Commission Decision 2002/657 EC. Residues were quantified down to 15 μg kg^?1 with limits of detection and quantification ranging from 3 to 50 μg kg^?1 and from 7.5 to 100 μg kg^?1, respectively. The recoveries at the maximum residual limits (MRLs) were between 77 and 120 % with RSD values lower than 30 %. For quinolones without established MRL or maximum required performance limit, the accuracy and precision of the method were estimated at concentration levels corresponding to the lowest linear calibration point and recoveries between 70 and 130 % were achieved. Decision limits, detection capability, and linear range in eggs, milk, fish, ovine muscle, chicken muscle, and porcine kidney are also reported.     

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.     

Optimization and Validation of a Method Without Alkaline Clean-Up for Patulin Analysis on Apple Puree Agar Medium (APAM) and Apple Products

A sensitive high-performance liquid chromatography-UV (HPLC-UV) method, based on the Association of Analytical Communities (AOAC) Official method 2000.02, was developed and validated for the high-throughput analysis of patulin in in vitro experiments on apple puree agar medium (APAM). The importance of repeating the ethyl acetate extraction step at liquid-liquid extraction (LLE) was examined, as well as the extent of patulin degradation during the sodium carbonate clean-up. In addition to this alkaline clean-up, the efficiency of using an Oasis HLB or C₁₈ cartridge as solid-phase extraction (SPE) clean-up was compared. This resulted in a two-step ethyl acetate LLE, followed by an Oasis HLB SPE clean-up, without alkaline clean-up conditions. The method was fully validated for APAM, cloudy apple juice, and apple puree. Average patulin recoveries at levels of 100, 500, and 1000 μg kg^?1 of APAM varied between 95 and 113 % over 3 independent days, with an interday precision (RSD_R) of 5 to 10 %. Recovery experiments carried out with the spiked apple juice (at 50 μg kg^?1) and apple puree (10 μg kg^?1) showed average recovery rates laying between 80–101 % (RSD_R?=?12 %) and 77–100 % (RSD_R?=?9 %), respectively. This method offered a detection limit of 3–4 μg kg^?1 and a quantification limit of 5–8 μg kg^?1 for APAM, apple juice, and puree.     

Determination of Benzalkonium Homologues and Didecyldimethylammonium in Powdered and Liquid Milk for Infants by Hydrophilic Interaction Liquid Chromatography–Mass Spectrometry

In this study, a hydrophilic interaction liquid chromatography–mass spectrometry (HILIC-MS/MS) method for the determination of benzalkonium (BAC) homologues and didecyldimethylammonium (DDAC) was developed. A satisfactory chromatographic separation of BAC homologues and DDAC was achieved using, as mobile phase, acetonitrile–aqueous 50 mM ammonium formate (pH 3.2) (93?+?7 v/v) at 0.3 mL min^?1. The elution order of BAC homologues was from benzyldimethylhexadecylammonium chloride (C₁₆-BAC) to benzyldimethyldecylammonium chloride (C₁₀-BAC), the exact opposite with respect to separation using reversed liquid chromatography. The instrumental method was successfully applied to powdered and liquid milk for infants (about 50 samples). From powdered milk samples, BAC and DDAC were extracted using 5 % formic acid in methanol for 60 min at 60 °C in an ultrasonic bath; after dilution with water and 5 % NH₄OH solution, a purification step using a weak cationic exchange column was performed. Satisfactory limit of detections (LODs) were achieved, below 1.0 μg kg^?1 and 0.05 μg L^?1 for powdered and liquid milk for infants, respectively. No sample was free of BAC homologues and DDAC, and in one powdered milk sample, the contamination level exceeded 500 μg kg^?1, the maximum level recommended by the Standing Committee on the Food Chain and Animal Health for food and feed.     

Simultaneous Determination of Eight Tranquilizers in Pork by Ultra-Performance Liquid Chromatography Coupled with Electrospray Tandem Mass Spectrometry

An ultra-performance liquid chromatography/electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) method was developed and validated for quantification of eight tranquillizers (chlorpromazine, imipramine hydrochloride, diazepam, nitrazepam, nordazepam, oxazepam, flurazepam, and haloperidol) in pork. Sample pretreatment consisted of extraction by acetonitrile, defatted by n-hexane, and further solid phase extraction by hydrophilic-lipophilic balance (HLB) extraction cartridges. The triple quadrupole mass spectrometer was operated in positive ion mode, and multiple reaction monitoring was used for drug quantification. The method was validated over the concentration ranges of 1.0 ～ 250 μg kg^?1 for the eight tranquillizers. The calibrations were performed in sample matrices, and the interference effect of sample matrices on the ionization was effectively eliminated. Good linear relationship (R ² > 0.99) was observed within the concentration range of 1.0–250 μg kg^?1. The average recoveries of the eight tranquillizers spiked at three levels ranged from 63.7 to103.2 % with the relative standard deviation below 11.8 %. The limits of detection were between 0.06 and 0.30 μg kg^?1, and the limits of quantification were between 0.2 and1.0 μg kg^?1 for all analytes in pork. This validated method has been successfully used to quantify the concentration of the eight tranquillizers in pork samples.     

Quantitative determination of sodium monofluoroacetate “1080” in infant formulas and dairy products by isotope dilution LC-MS/MS

A fast and easy-to-use confirmatory liquid-chromatography tandem mass-spectrometry (LC-MS/MS) based-method was developed for the analysis of the pesticide sodium monofluoroacetate (MFA, also called “1080”) in infant formulas and related dairy products. Extraction of the compound encompassed sample reconstitution and liquid–liquid extraction under acidic conditions. Time-consuming solid-phase extraction steps for clean-up and enrichment and tedious derivatisation were thus avoided. Resulting sample extracts were analysed by electrospray ionisation (ESI) in negative mode. Quantification was performed by the isotopic dilution approach using ¹³C-labelled MFA as internal standard. The procedure was validated according to the European document SANCO/12571/2013 and performance parameters such as linearity (r² > 0.99), precision (RSD(r) ≤ 9%, RSD(iR) ≤ 11%) and recovery (96–117%) fulfilled its requirements. Limit of quantifications (LOQ) was 1 µg kg^?1 for infant formulas and related dairy products except for whey proteins powders with a LOQ of 5 µg kg^?1. Method ruggedness was further assessed in another laboratory devoted to routine testing for quality control.     

Simultaneous determination of 30 hormones illegally added to anti-ageing functional foods using UPLC-MS/MS coupled with SPE clean-up

A novel analytical method employing solid-phase extraction (SPE) coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 30 hormones in anti-ageing functional foods (capsules, powders and tablets). The analytes were extracted with acetic acid–acetonitrile (1–99 v/v), methanol and acetone, respectively. The extract was purified using a combined column, followed by analyte detection with electrospray ionisation in positive- or negative-ion modes. The results indicated that the 30 compounds had good linear correlations in the range of 1–1000 μg kg^–1, and the correlation coefficients were above 0.99. The limits of detection (LOD) and limits of quantification (LOQ) were 0.03–2 and 0.1–5 μg kg^–1, respectively. The average recovery of 30 compounds at the three spiked levels varied from 74.7% to 124.1%, and the relative standard deviation (RSD) was 2.4–15.0%. This method was applied to the analysis of hormones in 14 real samples of which seven hormones (such as estrone, dienestrol) were detected in four samples, but the remainder of the hormones were not detected. The developed method is sensitive, efficient, reliable and applicable to real samples.     

Determination of Polycyclic Aromatic Hydrocarbons (PAH4) in the Traditional Lebanese Grilled Chicken: Implementation of New,Rapid and Economic Analysis Method

Polycyclic aromatic hydrocarbons (PAH4) (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) are evaluated in a traditional and widely consumed staple in Lebanon “Lebanese Grilled Chicken.” Forty samples with different local additives grilled by charcoal were purchased from different restaurants located in different regions in Lebanon. For this purpose, a simple and a reliable analytical method based on sonication technique and gas chromatography coupled to mass spectrometer (GC-MS) has been developed and validated. Several parameters affecting the extraction efficiency, such as the nature and the volume of the extract solvent, as well as other factors were investigated and optimized. The developed method is environmentally and economically friendly with a minimized consuming time, consisting of a single sonication step for 15 min using 12 mL of non-carcinogenic solvent acetonitrile (ACN) and without any further concentration prior to analysis. Following extraction, the cleanup step was based on freezing and d-SPE by C18 addition. Under optimized conditions, the method performances were evaluated; the limits of quantification (LOQs) achieved were lower than 0.689 μg kg^?1, and these values fit the performance criteria for the method given by the EC that defined the LOQ values of PAH lower than 0.9 μg kg^?1. In addition, the recovery values of the analyzed PAHs ranged from 88.9 to 119.3% with relative standard deviations (RSDs) less than 8% (n = 15). The levels of PAH4 were in the range from 1.52 to 49.9 μg kg^?1, where about 40% of the Lebanese grilled chicken exceeded the EU commission MRLs of 12 μg kg^?1.     

Gas Purge Microsyringe Extraction Coupled with Dispersive Liquid-Liquid Microextraction for the Determination of Acidic Compounds in Food Packaging Materials

A green, simple and sensitive method was developed for the analysis of volatile carboxylic acids (VFAs) and perfluorocarboxylic acids (PFCAs) in food packaging materials. The acidic compounds in food packaging materials were first extracted by gas purge microsyringe extraction (GP–MSE) with 1.0 mL 0.1 mol·L^?1 NaOH solution, then the analytes were dispersive liquid-liquid microextracted (DLLME) by 50 μL chloroform as extraction solvent and 200 μL acetonitrile as dispersive solvent. The 2-(5-Benzoacridine) ethyl-p-toluenesulfonate (BAETS) with excellent fluorescence property was applied to enhance the high performance liquid chromatography (HPLC) sensitivity. The obtained recoveries for the VFAs ranged from 92.0 to 101 %. The method LODs calculated at a signal-to-noise ratio (S/N) of 3 were in the range of 0.80–3.40 μg·kg^?1, while the LOQs calculated at S/N of 10 were in the range of 2.5–10.2 μg·kg^?1. All compounds were in good linearity with concentration coefficients of higher than 0.997. Perfluorooctanoic acid (PFOA) was found in all of the 15 kinds of samples analyzed with concentrations ranging from 4.86–7.56 μg·kg^?1. Acetic acid, butyric acid, and caprylic acid were found in half of the samples analyzed. The other analytes were also found in more than 30 % samples with concentrations varied between 3.96 and 293 μg·kg^?1.     

Simultaneous Determination of Cyadox and Its Metabolites in Chicken Tissues by LC-MS/MS

A specific and sensitive LC-MS/MS method was firstly established for the simultaneous extraction and determination of cyadox and its three main metabolites—1,4-bisdesoxycyadox, 4-desoxycyadox, and quinoxaline-2-carboxylic acid—in chicken muscle, liver, kidney, and fat tissues. Samples were subjected to extraction using ethyl acetate and followed by acetonitrile–chloroform (1:4, v/v) and further purified by Oasis mixed mode anion exchange SPE cartridge. Analysis was performed on a C₁₈ column by detection with MS in multiple-reaction monitoring mode. A gradient elution program with 0.1 % formic acid solution, acetonitrile, and 1 % formic acid (adjusted to pH 8 with ammonia) was performed at a flow rate of 0.2 mL min^?1. The correlation coefficients (r) for each calibration curve are higher than 0.99 within the experimental concentration range. The recoveries of the four target analytes at three spiking levels of 2.5, 25 and 250 μg kg^?1 were between 74.5 and 93.8 %, with relative standard deviations less than 12 %. The decision limits (CCαs) of the four analytes in chicken edible tissues ranged from 0.3 to 1.5 μg kg^?1, and the detection capabilities (CCβs) were below 2.3 μg kg^?1. The developed method demonstrated a satisfactory applicability in incurred chicken tissue samples.     

Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Olive and Refined Pomace Olive Oils with Modified Low Temperature and Ultrasound-Assisted Liquid–Liquid Extraction Method Followed by the HPLC/FLD

The cleanup method of modified low temperature was compared with the standardized method of modified ultrasound-assisted liquid–liquid (UALL) extraction for the analysis of 15 polycyclic aromatic hydrocarbons (PAHs) in olive oil and refined pomace olive oil. The modified UALL extraction consisted in purification on C₁₈ reversed-phase, Florisil-bonded-phase and NH₂ cartridges, and modified low-temperature extraction was followed by alumina-N and NH₂ solid-phase extraction (SPE) cartridges. Both methods are followed by reversed-phase high-performance liquid chromatography with fluorescence detection. The chromatograms of the final extracts showed lower interferences in both of the methods. The solvent consumption and cost for the modified UALL method were higher than those of the modified low temperature, and also, it needed more equipment, but its analysis time was less. The limit of detection and limit of quantitation of the modified UALL method were 0.16–0.97 and 0.57–2.93 μg kg^?1, respectively, and for the modified low temperature, they were 0.09–1.97 and 0.29–5.99 μg kg^?1, respectively. The PAH recoveries for the modified UALL extraction method ranged from 75.0 to 111.0 % (RSD?=?3–8 %), and for the modified low temperature, they ranged from 81.5 to 113.8 % (RSD?=?3–10 %).     

Use of Factorial Design in the Development of Multiresidue Method for Determination of Pesticide Residues in Wheat by Liquid Chromatography-Tandem Mass Spectrometry

The evaluation of analytical methods for determining the level of residues and contaminants in food samples is a continuing need. To improve this evaluation, it is necessary to investigate different extraction procedures and conditions. A 2³ factorial design was applied to establish an analytical method for determining pesticide residues in wheat by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Factors that influence the recovery of compounds, such as agitation and different processes of partition and cleanup, were investigated. Extracts were analyzed by LC-MS/MS with electrospray ionization in a triple quadrupole system. The use of ultrasonic agitation in the extraction step, deep freezing for the partition step, and C18 cleanup provided significantly better recoveries for most of the compounds evaluated. Assessment of each factor as well as interactions between factors allowed for a more effective evaluation of the parameters involved in the development of analytical methods. The validation results were satisfactory, since the method presented linearity (r ²) >0.99 for all compounds, the matrix effect ranged from 3 to 97 % and was corrected by matrix-matched standards, and recoveries ranged from 70 to 120 % with RSD ≤20 % for the spike levels of 10 and 100 μg kg^?1. The method limit of detection and limit of quantification ranged from 3.3 to 6.7 μg kg^?1 and from 10 to 20 μg kg^?1, respectively, and the expanded uncertainty ranged from 15 to 32 %. The proposed method met the criteria for determination of 42 pesticides in wheat samples and was successfully tested in real samples.     

Ionic Liquid-Based Dispersive Liquid–Liquid Microextraction Following High-Performance Liquid Chromatography for the Determination of Fungicides in Fruit Juices

This paper described an ionic liquid-based dispersive liquid–liquid microextraction (IL-DLLME) combined with high-performance liquid chromatography (HPLC) method to determine fungicides in fruit juices. In this method, 1-hexyl-3-methyli-midazolium hexafluorophosphate (HMIMPF₆) was used as extraction solvent, which dispersed into the fruit juices under vigorously shaking with the vortex. The effects of experimental parameters, such as extraction solvent volume, disperser solvent and its volume, vortex time, centrifugation time, sample pH, on the extraction efficiency were investigated. Under the optimum conditions, the linear correlation coefficients ranged from 0.9902 to 0.9979 for concentration levels of 0.02–2 mg l^?1, the extraction recoveries were ranged 66.2–92.9 % except pyrimethanil (39.5–44.6 %), The relative standard deviations (RSDs; n?=?6) ranged from 2.2 % to 11.6 %, and the limits of detection (LODs) for the fungicides were between 3.1 and 10.2 μg l^?1. Two real samples including apple and grape juices, spiked at two concentration levels were analyzed and yielded recoveries ranging from 71.3–93.1 % and 65.4–87.7 %, respectively.     

Occurrence of 15 + 1 EU priority polycyclic aromatic hydrocarbons (PAH) in various types of tea (Camellia sinensis) and herbal infusions

For the analysis of 15 + 1 EU priority PAH in tea and herbal infusions, an online-SPE-LVI-GC-MS method was developed. This method includes sample extraction of the tea and herbal infusions with saponification followed by an automated SPE clean-up step. For brews a liquid–liquid extraction with cyclohexane was performed before an automated SPE clean-up. Gas chromatographic separation was done using an Agilent J&W Select PAH (15 m × 0.15 mm × 0.10 µm) column, which allows the separation of the three benzofluoranthenes as well as triphenylene from chrysene. Method performance criteria such as method linearity, limit of quantitation (LOQ) and repeatability were determined and demonstrated that the method was fit for purpose. The method was used to analyse 15 + 1 EU priority PAH in 91 tea and herbal infusion samples. The levels of PAHs ranged from below 0.5 (LOQ) to 460 µg kg^?1, with a median of 4.7 µg kg^?1 and a mean of 39 µg kg^?1 for BaP, and from below 1.0 (LOQ) to 2700 µg kg^?1, with a median of 39 µg kg^?1 and a mean of 250 µg kg^?1 for total PAH, which were in good agreement with other studies reported in the literature. For the brews prepared under normal house preparation (20 g material in 2 L boiling tap water for 10 min), no total 15 + 1 PAH could be detected above the LOQ. With an extended brewing time of 30 min, a transfer rate between 0.25% and 0.52% could be determined, which results in no exceeding of the maximum limits given by the European Union directive for drinking water (EU Council Directive 98/83/EC).     

Determination of Hormones Residues in Milk by Gas Chromatography-Mass Spectrometry

The article presents the use of gas chromatography-mass spectrometry (GC-MS) technique in a method for the determination of 18 anabolic hormones from synthetic stilbenes, steroids and resorcylic acid lactones (RALs) groups in raw milk and milk powder. Sample preparation consisted of liquid-liquid extraction with diethyl ether and purification by solid phase extraction (SPE). Prior to instrumental analysis, the reaction of derivatisation with the heptafluorobutyric anhydride or N-methyl-N-trimethylsilyltrifluoroacetamide was performed. Method validation was carried out according to the required performance criteria of the Commission Decision 2002/657/EC. The apparent recovery of all analytes at 1 μg L^?1 (kg^?1) level was ranged between 70.4 and 119.4 % with the coefficients of variation values less than 30 %. The decision limits (CCα) and the detection capabilities (CCβ) were in the range of from 0.11 to 0.44 μg L^?1 (kg^?1) and from 0.19 to 0.75 μg L^?1 (kg^?1), respectively. The procedure has been accredited and successfully applied as a screening method for the presence of hormone residues in the study of commercial samples of milk.     

Determination of Melamine in Liquid Milk and Milk Powder by Titania-Based Ligand-Exchange Hydrophilic Interaction Liquid Chromatography

A simple and rapid high-performance liquid chromatography (HPLC) procedure for the analysis of melamine in liquid milk and milk powder has been developed. Decrease of acetonitrile percentage and phosphate buffer concentration in mobile phase, and lowering of buffer pH and column temperature would benefit the retention of melamine on titania. Taking advantage of the ligand-exchange and hydrophilic interaction mixed retention mode on bare titania column, neither complex pretreatment nor ion-pair reagent was required. The whole analysis for one sample including sample pretreatment and HPLC analysis could be accomplished within 30 min. The method presented good linearity (R ² = 0.9998) in a wide range of 0.02–10 μg mL⁻¹. The limit of detection (3σ) and limit of quantification (10σ) of the method were 6 and 20 μg L⁻¹, respectively, which were equivalent to 15 and 50 μg kg⁻¹ melamine in liquid milk, 60 and 200 μg kg⁻¹ melamine in milk powder, respectively. Such sensitivity could be compared with those obtained by HPLC with solid-phase extraction or HPLC coupled with tandem mass spectrometry and was adequate for the screening of melamine in tainted dairy products. The repeatability (RSDs) of the retention times and peak areas of 11 replicate detections of 1.0 μg mL⁻¹ melamine were 0.32% and 2.5%, respectively. The intermediate precision on three consecutive days (RSDs, n = 6) of the retention times and peak areas were 1.1% and 2.3%, respectively. The recovery of spiked melamine in dairy samples ranged from 95.2% to 105%. The simplicity, sensitivity and rapidity of the proposed method make it an effective alternative detecting technique for melamine.     

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.     

Determination of Eugenol in Aquatic Products by Dispersive Solid-Phase Extraction and Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry

A novel procedure, dispersive solid-phase extraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), was developed for the determination of eugenol in aquatic products (shrimp, crab, and carp). Aquatic products were extracted with acetonitrile and primarily purified by dispersive solid-phase extraction with graphitized carbon black as absorbent. The pretreated acetonitrile extract was detected by UHPLC-MS/MS. UHPLC was carried out on Dikma Endeavorsil C₁₈ (30 mm × 2.1 mm, 1.8 μm) column eluted by methanol and water (80:20 v/v) at a rate of 0.30 mL min^?1. Tandem mass spectrometry was performed by electrospray ionization in negative ion mode to identify and quantify eugenol during multiple reaction monitoring. Under optimized analytical conditions, the matrix-matched spiked calibration sample demonstrates good linearity between 5.0 and 500.0 μg kg^?1 with a linear regression coefficient of 0.9996. The average recovery of eugenol from aquatic products is 95.3–103.4% at spiked levels between 5 and 50 μg kg^?1 with a relative standard deviation (n = 6) less than 5.4%. The limits of detection and quantification for eugenol were calculated to be 1.47 and 4.91 μg kg^?1, respectively. In comparison with those reported, the proposed method has advantages in low detection limit, high recovery, and short analysis time, meeting the requirements for the determination of trace eugenol residue in aquatic products.