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•LC-HRMS was used for the detection of metabolites of the two co-formulants.•Three and five metabolites were found from the two co-formulants in vegetables.•Three metabolites were ...more toxic than their original molecule.•Most metabolites are persistent, detected at 21 days with high concentrations.
Plant protection products contain co-formulants that could end up in vegetables, and they can generate transformation products that can be more toxic than their original molecule, which are a potential risk to food safety. Therefore, this study evaluated the dissipation of two co-formulants, dodecylbenzenesulfonic acid and 1-ethyl-2-pyrrolidone, in courgette and tangerine samples to determine possible harmful metabolites under laboratory conditions. The analyses of these substances were performed by liquid chromatography coupled to quadrupole-Orbitrap high-resolution mass spectrometry (LC-Q-Orbitrap-HRMS). For the degradation of both compounds, a single-phase kinetic model was fitted, with R2 values greater than 0.99. In courgette and tangerine, half-lives (DT50) for dodecylbenzene sulfonic acid were 1.83 and 1.42 days, while DT50 was 6.26 and 5.04 days for 1-ethyl-2-pyrrolidone, respectively. Three metabolites of dodecylbenzenesulfonic acid and five metabolites of 1-ethyl-2-pyrrolidone were found in courgette, while the same metabolites were detected in tangerine samples, except benzoic acid and 4-aminobutanoic acid. These metabolites were identified for the first time from these compounds except for benzoic acid, observing that 5-hydroxy-N-ethylpyrrolidone was the most concentrated metabolite in tangerine 14 days after application, reaching a maximum concentration of 149 µg/kg. Furthermore, some of the detected metabolites possessed a value of LD50 lower than their original molecules. In consequence, such metabolites, derived from these co-formulants, should be controlled to prevent negative health effects, and ensure food safety.
In this study, 21 pesticides and 4 aflatoxins were monitored in baby food marketed in Brazil, applying ultra-high-performance liquid chromatography coupled to quadrupole-Orbitrap mass spectrometry ...(UHPLC-Q-Orbitrap-MS). The quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method combined with dispersive solid-phase extraction (d-SPE) clean-up was applied and primary secondary amine (PSA), octadecylsilane (C18) and C18 with silica coated with zirconium dioxide (Z-Sep+) were used during the clean-up stage. Suitable performance criteria, set by the SANTE/2020/12830 guidelines, were achieved, and therefore, all targeted analytes were successfully validated. The method was applied to the analysis of 50 baby food samples. Cypermethrin was detected at 10.3 μg kg−1 (above maximum residue level (MRL) established by the European Union (EU)). Furthermore, suspect screening analysis was performed for reliable identification of contaminants not included in this study such as other pesticides, mycotoxins, hormones, veterinary drugs and their metabolites. Finally 10 pesticides and one metabolite were detected, demonstrating the suitability of the proposed approach.
•LC-HRMS was used to determine 21 pesticides and 4 aflatoxins in baby food.•Validated method with suitable values of linearity, trueness, precision and LOQs.•68% of the samples were contaminated with at least one targeted pesticide.•Cypermethrin was detected at a level that exceeded MRL established by EU.•10 parent compounds and one metabolite were detected by suspect screening.
A method based on liquid chromatography-triple quadrupole tandem mass spectrometry was developed and validated for the analysis of acrylamide in baby foods. The sample preparation involves a simple ...extraction process using a mixture of acetonitrile:water:formic acid (69:30:1, v/v/v) in combination with dispersive solid-phase extraction (d-SPE) using alumina as sorbent. The method shown good linearity within the range 20–250 μg kg
−1
through matrix-matched and solvent calibrations. The recovery rates for acrylamide ranged from 100 to 108% with coefficients of variation below 10%, under repeatability and reproducibility conditions (within-laboratory). The obtained limit of quantification (20 μg kg
−1
) complies with the values indicated by the European Union for acrylamide analysis in baby foods. The developed and validated method was applied to 50 ready-to-eat baby foods available in the Brazilian market. Acrylamide was detected in 13% of samples primarily composed of fruits, whereas it was found in approximately 37% of baby food containing meat and/or vegetables. Additionally, in 2 samples, the detected levels exceeded the benchmark value established by the EU (40 μg kg
−1
). The study showcases the applicability of this method for routine analysis of acrylamide detection.
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•Commercial biopesticides characterization by targeted and untargeted analyses.•A home-made database was built by LC and GC-HRMS methodologies.•17 target and 101 untargeted compounds ...were detected in the tested samples.•In addition to natural compounds, BHT or diisobutyl phthalate were detected.
15 commercial biopesticides (CBs), based on vegetable extracts and oils, were characterized. Ultra-high-performance liquid chromatography (UHPLC) and gas chromatography (GC) coupled to a hybrid high-resolution mass spectrometry (HRMS) analyser, such as quadrupole (Q)-Orbitrap, were used. Both targeted and untargeted (suspect and unknown modes) analyses were carried out. For the targeted analysis, a database was built, encompassing volatile and non-volatile compounds commonly found in vegetable extracts and oils. This database comprised 27 LC-amenable compounds and 31 GC-amenable compounds. 17 targeted compounds were quantified, and 101 compounds were tentatively identified by untargeted analysis. CBs based on essential oils, such as orange oil or cinnamon extract contained the highest number of detected compounds. Monoterpenes (limonene or linalool), and sesquiterpenes (δ-cadinene or γ-elemene) were mainly found. Moreover, some co-formulants such as dibutyl phthalate or butylated hydroxytoluene (BHT) were also detected. The concentration of targeted natural compounds ranged from 2 mg/L (linalool) to 450 g/L (trans-cinnamaldehyde).
This study compared four extraction methods for the simultaneous determination of tetracyclines, macrolides, quinolones, sulphonamides and anthelmintics (including benzimidazoles and avermectins) in ...eggs by ultra-high pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS). Solvent extraction, solid-phase extraction (SPE), matrix solid-phase dispersion (MSPD) and modified QuEChERS procedure were compared in terms of recovery and number of veterinary drugs extracted. The solvent extraction procedure with a clean-up step provided better results than the other tested procedures. The QuEChERS procedure was simpler and faster, but extracted fewer compounds than solvent extraction. MSPD did not extract tetracyclines and quinolones, whereas macrolides and tetracyclines were not extracted when SPE was applied. The solvent extraction procedure was validated, obtaining recoveries ranging from 60% (sulfaquinoxaline) to 119% (levamisole) with repeatability values (expressed as relative standard deviations, RSDs) lower than 20% at two concentration levels (10 and 100
μg
kg
−1), except for erythromycin, emamectin and ivermectin that showed RSD values close to 25% at 10
μg
kg
−1. Limits of quantification (LOQs) were always equal or lower than 5
μg
kg
−1. Finally the method was applied to egg samples, and erythromycin, enrofloxacin, difloxacin, thiabendazole, emamectin and fenbendazole were detected in four samples.
A rapid, reliable and sensitive method was developed to determine 12 mycotoxins (deoxynivalenol, aflatoxins B1, B2, G1, G2 and M1, fumonisins B1 and B2, ochratoxin A, HT-2 and T-2 toxin and ...zearalenone) simultaneously in maize, walnuts, biscuits and breakfast cereals. The method is based on a single extraction step using acetonitrile/water mixture (80/20
v/v) followed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC–MS/MS). The selectivity of the MS/MS detection allowed the elimination of further clean up steps. Extraction, chromatographic and detection conditions were optimised in order to increase sample throughput and sensitivity. Matrix-matched calibration was used for quantification and recoveries of the extraction process ranged from 70.0% and 108.4%, with relative standard deviations lower than 25% in all the cases, when samples were fortified at 5 and 50
μg/kg. Limits of detection ranged from 0.01 to 2.1
μg/kg and limits of quantification ranged from 0.03 to 6.30
μg/kg, which were always below the tolerance levels of mycotoxins set by European Union in the matrices evaluated. Several samples were analysed and aflatoxins B1, B2, G1, G2 and T-2 toxin were detected in one maize sample, with concentrations lower than 6.0
μg/kg and deoxynivalenol was detected in a breakfast cereal at 42.1
μg/kg.
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•Novel workflow for black pepper classification using LC-HRMS fingerprinting.•OPLS-DA successfully distinguished geographical origin and processing of samples.•Eight markers were ...putatively identified using OPLS-DA followed by VIP analysis.•High predictive power and clustering were offered by the proposed untargeted approach.•LC-MS, GC–MS and 1H NMR data fusion was assessed in black pepper for the first time.
An untargeted metabolomics approach based on ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) fingerprinting was applied to investigate the metabolic differences of black pepper among three geographical origins (Sri Lanka, Vietnam, and Brazil) and two post-harvest processing (sterilized and non-sterilized spice). Principal component analysis (PCA) was employed to assess the overall clustering of samples, whereas supervised orthogonal partial least squares discriminant analysis (OPLS-DA) was effectively used for discrimination purposes. OPLS-DA models were fully validated (R2Y and Q2 values > 0.5) and the variable importance in projection (VIP) approach was employed to provide valuable data about differential metabolites with high discrimination potential (8 markers were putatively identified). For origin differentiation, three markers were highlighted with VIP values > 1.5 (i.e. reynosin, artabsinolide D, and tatridin B). Fatty acid derivates were the most frequent markers within the metabolites annotated for processing discrimination (e.g. 10,16-dihydroxyhexadecanoic acid and 9-hydroperoxy-10E-octadecenoic acid). Additionally, different combinations of mid-level data fusion of chromatographic-mass spectrometric techniques (UHPLC and gas chromatography coupled to HRMS) and proton nuclear magnetic resonance spectroscopy (1H NMR) were evaluated for the first time for geographical and processing discrimination of black pepper. The NMR-UHPLC-GC mid-level fused model was preferred among the tested fusion approaches since good sample clustering and no misclassification were achieved. Enhanced correct classification rate was achieved by mid-level data fusion compared with the findings obtained for one of the individual techniques (1H NMR fingerprinting) (from 92% to 100% of samples correctly classified). This study opens the path to new metabolomics approaches for black pepper authentication and quality control.
Edible and highly demanded plant-derived products such as herbs, spices, and tea may be subjected to exogenous contamination of well-known chemical hazards such as persistent organic pollutants ...(POPs), and emerging ones such as plasticizers, affecting negatively the safety of these food commodities. This fact has led to the increasing analysis of exogenous compounds including priority POPs such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs), as well as highly persistent polycyclic aromatic hydrocarbons (PAHs). Currently, plasticizer residues are also considered an emerging issue because of the extensive use in food packaging and potential migration into foodstuffs. In this review, the studies published from 2010 to 2020 were discussed, including the main extraction methods applied for these contaminants from herbs, spices, and tea, and it was revealed the trend toward the use of less solvent-consuming and time-effective methods. Chromatographic methods were also described, which were mainly combined with detection techniques such as classical or mass spectrometry (MS) detection. Finally, a comprehensive overview of the occurrence of these selected exogenous compounds was presented in the studied matrices, showing that their monitoring should be further investigated to ensure food safety of highly consumed condiments and tea.
A simple, selective and fast multi-residue method was developed to determine 18 veterinary drugs in milk by ultra-high-pressure liquid chromatography coupled to tandem quadrupole mass spectrometry. ...The selected antibiotics include quinolones, sulphonamides, macrolides, anthelmintics and one tetracycline. An extraction procedure based on QuEChERS methodology (quick, easy, cheap, effective, rugged and safe), consisting of a liquid extraction of the milk samples with acetonitrile without sample clean up was performed. The extract was centrifuged and the supernatant was filtered prior to chromatographic analysis. Several chromatographic conditions were optimized in order to obtain a fast separation (less than 10
min). The antibiotics were detected by electrospray ionization in positive ion mode with multiple reaction monitoring (MRM) and mass spectrometric conditions were optimized in order to increase selectivity and sensitivity. The developed method was validated in terms of linearity, trueness, precision, limits of detection (LODs) and quantification. Mean recoveries ranged from 70% to 110% and interday precision was lower than 21%. LODs ranged from 1 to 4
μg/kg. Finally, the method was applied to real samples and only traces of tylosin and fenbendezol were detected in two samples.
•Pesticides have been determined in nutraceutical products from green tea.•More than 90 polar pesticides have been analyzed by UHPLC–QqQ-MS/MS.•American and European QuEChERS methods were tested to ...extract the compounds.•No clean-up steps are needed.•Acetamiprid and carbendazim were detected in the analyzed samples.
A QuEChERS (quick, easy, cheap, effective, rugged, and safe) based method has been evaluated and validated for the determination and quantification of approximately 100 LC-amenable pesticides in nutraceutical products obtained from green tea (Camellia sinensis). Extraction was performed with acidified acetonitrile (acetic acid 1% (v/v)), and additional clean-up steps were not necessary. Pesticides determination was achieved using ultra high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC–QqQ-MS/MS). Total running time was 11min. Pesticides were quantified using matrix-matched calibration. Recoveries ranged from 70% to 117% and relative standard deviation (RSD) was lower than 20% at concentration levels of 25, 50 and 100μg/kg for intra-day precision and equal or lower than 25% for inter-day precision. Limits of quantification (LOQ) were equal or lower than 25μg/kg. The validated method was applied to commercial nutraceutical products, detecting acetamiprid (56μg/kg) and carbendazim (13μg/kg) in two samples.
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