•The first study applying GC-HRMS fingerprinting for authentication of thyme.•Spanish, Moroccan, and Polish thyme was distinguished by PLS-DA.•OPLS-DA allowed discriminating processing between ...non-sterilized and sterilized thyme.•PLS-DA/OPLS-DA models were validated showing an excellent predictive ability of 100%.•24 metabolites were described as markers for reliable sample discrimination.
Thyme is an aromatic herb traditionally used for food purposes due to its organoleptic characteristics and medicinal properties, which is highly susceptible to food fraud. In this study, GC-HRMS-based fingerprinting was applied for the first time to determine the geographical traceability of thyme based on different origins (Spain, Poland, and Morocco), as well as to assess its processing by comparing sterilized vs. non-sterilized thyme. Unsupervised chemometric methods (PCA and HCA) revealed a predominant influence of the geographical origin on thyme fingerprints rather than processing effects. Supervised PLS-DA and OPLS-DA were used for discrimination purposes, revealing high predictive ability for further samples (100%), and allowing the identification of differential compounds (markers). A total of 24 markers were putatively identified (13 metabolites were confirmed) belonging to different classes: monoterpenoids, diterpenoids, sesquiterpenoids, alkenylbenzenes, and other miscellaneous compounds. This study outlines the potential of combining untargeted analysis by GC-HRMS with chemometrics for thyme authenticity and traceability.
Polycyclic aromatic hydrocarbons (PAHs) are compounds widespread in the environment, many of them showing carcinogenic effects. These compounds can reach the food chain by different ways and, ...therefore, the analysis of PAHs in food is a matter of concern. This article reviews the extraction methodologies together with the separation and detection techniques which are currently applied in the determination of PAHs in food and beverages. Specific extraction conditions, performance characteristics, chromatographic and detection parameters are discussed. A review of the occurrence of these compounds in the matrixes under study is also provided.
Display omitted
•Degradation of trans-cinnamaldehyde and limonene in cucumbers was studied.•Degradation studies, in both laboratory and greenhouse, were carried out.•First and second order kinetic ...models were observed for their dissipation.•Metabolites were tentatively identified by GC and UHPLC-HRMS.
Degradation of trans-cinnamaldehyde and limonene in cucumber was evaluated under laboratory and greenhouse conditions. Two commercial biopesticides, one based on cinnamon extract and other from orange oil, were utilized. Compound degradation was monitored using gas chromatography (GC) and ultra-high-performance liquid chromatography (UHPLC) coupled to a quadrupole-high-resolution mass analyzer (Q-Orbitrap). In both studies, trans-cinnamaldehyde followed a second-order degradation kinetics, whereas limonene followed a first-order kinetics. The half-life values (DT50 or t1/2) for trans-cinnamaldehyde ranged from 2.02 to 2.49 h, while for limonene this value ranged from 0.49 to 6.17 h. Non-targeted analysis (suspect and unknown modes) allowed for the detection of trans-cinnamaldehyde and limonene metabolites. Benzyl alcohol, cinnamyl alcohol, cinnamic acid, p-tolylacetic acid and 4-hydoxycinnamic acid were tentatively identified as trans-cinnamaldehyde metabolites. While three limonene metabolites, carvone, limonene-1,2-epoxide, and perillyl alcohol, were tentatively identified. Greenhouse studies have not revealed any metabolites of these compounds because the parent compounds degrade more quickly.
Display omitted
•LC and GC-HRMS were used to detect co-formulants present in PPPs in food.•Suspect analysis allowed the tentative identification of 37 co-formulants.•Twenty one co-formulants were ...quantified in fruits, vegetables and leaves.•1-Ethyl-2-pyrrolidone was identified in all samples and at high concentrations.•Some compounds were declared as unsuitable co-formulants because their toxicity.
Vegetables can contain co-formulants derived from the use of plant protection products (PPPs) in crops. Thus, in the current study co-formulants were determined in different fruits and vegetables and their leaves by gas and liquid chromatography coupled to Q-Orbitrap high-resolution mass spectrometry (GC-Q-Orbitrap and LC-Q-Orbitrap-MS). A total of 37 co-formulants were tentatively identified, and among them, 12 compounds were quantified by LC-Q-Orbitrap-MS and 9 by GC-Q-Orbitrap-MS. The mean co-formulant levels in fruit and vegetable samples was 92% lower than in leaf samples. Selected samples showed a high concentration of 1-ethyl-2-pyrrolidone among the co-formulants detected. This compound ranged from 22 µg/kg (strawberry) to 722 µg/kg (red grape), whereas in the case of leaves, its concentration was up to 6513 µg/kg in cucumber leaf. In addition, it has an LD50 equal to 1.440 g/kg. Therefore, this type of PPP co-formulants should be controlled in fruits and vegetables to avoid adverse health effects.
A reliable and rapid method has been developed for the determination of 10 mycotoxins (beauvericin, enniatin A, A1, B1, citrinin, aflatoxin B1, B2, G1, G2 and ochratoxin A) in eggs at trace levels. ...Ultra-high-pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS) has been used for the analysis of these compounds in less than 7
min. Mycotoxins have been extracted from egg samples using a QuEChERS-based extraction procedure (Quick, Easy, Cheap, Effective, Rugged and Safe) without applying any further clean-up step. Extraction, chromatographic and detection conditions were optimised in order to increase sample throughput and sensitivity. Matrix-matched calibration was used for quantification. Blank samples were fortified at 10, 25, 50 and 100
μg
kg
−1, and recoveries ranged from 70% to 110%, except for ochratoxin A and aflatoxin G1 at 10
μg
kg
−1, and aflatoxin G2 at 50
μg
kg
−1. Relative standard deviations were lower than 25% in all the cases. Limits of detection ranged from 0.5
μg
kg
−1 (for aflatoxins B1, B2 and G1) to 5
μg
kg
−1 (for enniatin A, citrinin and ochratoxin A) and limits of quantification ranged from 1
μg
kg
−1 (for aflatoxins B1, B2 and G1) to 10
μg
kg
−1 (for enniatin A, citrinin and ochratoxin A). Seven samples were analyzed and aflatoxins B1, B2, G1, G2, and beauvericin were detected at trace levels.
Display omitted
•Thyme origin and processing were traced by comprehensive fingerprint analysis.•Signature differences were observed in thyme fingerprint due to the “terroir”.•Overall higher ...metabolite levels were observed as a result of thyme sterilization.•Amino acid derivatives and flavonoids were prevalent among discriminant compounds.
The metabolic composition of thyme, one of the most used aromatic herbs, is influenced by environmental and post-harvest processing factors, presenting the possibility of exploiting thyme fingerprint to assess its authenticity. In this study, a comprehensive UHPLC-QTOF-HRMS fingerprinting approach was applied with a dual objective: (1) tracing thyme from three regions of production (Spain, Morocco, and Poland) and (2) evaluating the metabolic differences in response to processing, considering sterilized thyme samples. Multivariate statistics reveal 37 and 33 key origin and processing differentiation compounds, respectively. The findings highlighted the remarkable “terroir” influence on thyme fingerprint, noticing flavonoids, amino acids, and peptides among the most discriminant chemical classes. Thyme sterilization led to an overall metabolite enrichment, most likely due to the facilitated compound accessibility as a result of processing. The findings provide a comprehensive metabolomics insight into the origin and processing effect on thyme composition for product traceability and quality assessment.
•We review UHPLC-MS methods for determination of contaminants and residues.•We focus on analyses of pesticides, veterinary drugs and mycotoxins in food.•We describe multi-class and multi-residue ...methods of UHPLC-MS.•We discuss generic extraction methods for UHPLC-MS.•UHPLC with high-resolution MS is a valuable tool for comprehensive analysis.
This review provides an overview of current methods, based on ultra-high-performance liquid chromatography coupled to mass-spectrometry analyzers (UHPLC-MS), for the determination of organic contaminants and residues in food. Although most of the methods mainly focus on the analysis of one type of compound (e.g., pesticides, veterinary drugs or mycotoxins), current methods are aimed at the simultaneous determination of several families of contaminants and/or residues. These methods increase sample throughput and the capabilities of routine laboratories, because of the advantages provided by the UHPLC technique. For UHPLC-MS, generic extraction procedures can be applied, allowing the simultaneous extraction of compounds with different physicochemical properties.
Non-phthalate plasticizers (NPPs) are a suitable alternative to phthalates, which are harmful compounds for human, animal health, and the environment. In this study, 28 commercial non-phthalate ...plasticizers (NPPs) from different families, including adipates, citrates, phosphates, sebacates, trimellitates, benzoates and cyclohexanoates, were determined. Two novel methods for determining these alternative compounds in soil were developed using gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS-Q-Orbitrap) and liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS-Q-Orbitrap). Solid-liquid extraction (SLE) with ethyl acetate or acetonitrile, along with water as extraction solvents, were employed. In most cases, the GC method exhibited recoveries ranging from 84.9 % to 110.8 % at 20, 40 and 200 μg/kg, while the LC method achieved recoveries between 73.1 % and 115.4 % at 10, 20, 40 and 200 μg/kg. Most of the relative standard deviation (RSD) values were below 20 % for both methods. The validated methods were then applied to analyse soil samples collected from four different areas in Almeria. The results indicated that the compounds detected most frequently at high concentrations were 1-hydroxycyclohexyl phenyl ketone (HCPK) using GC, in the range 29.1–67.4 μg/kg and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) using LC, in the range 39.9–51.5 μg/kg. Additionally, suspect and unknown analysis were carried out, and other plasticizers as phthalates, were also detected, in addition to other substances present in the analysed samples. All the soils exhibited the presence of a few plasticizers, either phthalic and/or non-phthalic.
Display omitted
•First study that comprehensively analysed non-phthalate plasticizers (NPP) in soils•Two methods based on GC and LC-HRMS were developed for the analysis of 28 NPPs.•Twelve NPPs were detected in soil samples above their LOQs.•TBC, ATBC and EHDP are less toxic than conventional phthalates.•Identification of phthalates was carried out when non-targeted analysis was applied.
Additives present in plant protection products (PPPs) are normally not monitored after sample treatments. In this study, the fate of additives detected by targeted and nontargeted analysis in tomato ...samples treated with two PPPs was carried out. The study was carried out in a greenhouse for 12 days, in which two applications with each PPP were made. Compounds were extracted by applying a headspace solid phase microextraction (HS-SPME) and analyzed by gas chromatography coupled to high resolution mass spectrometry (GC-HRMS), performing targeted and suspect approaches. Three targeted and 15 nontargeted compounds were identified at concentration levels of up to 150 μg/kg. Compounds detected encompassed benzene, toluene, indene, and naphthalene derivatives, as well as conservatives and flavouring compounds. Most of them degraded in less than 7 days after the second application, following first-order kinetic. This study aims to reduce knowledge gaps regarding additives and their fate under real climatic conditions of greenhouses cultivations.
A rapid and reliable multiclass method was developed for the simultaneous analysis of 21 antibiotics (beta-lactams, aminoglycosides, penicillins, cephalosporins, carbapenems or quinolones) in urine, ...serum, cerebrospinal fluid (CSF) and bronchial aspirations by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Prior to chromatographic determination, the analytes were extracted from human biological fluids by simple sample treatments, which imply dilution, liquefaction, or protein precipitation. Several chromatographic conditions were optimized in order to obtain a fast separation (<6min for each chromatographic run). MS/MS conditions were evaluated in order to increase selectivity and sensitivity and all compounds were detected in electrospray (ESI) positive ion mode, except clavulanic acid and sulbactam, which were monitored in negative ion mode. The developed method was validated in terms of linearity, selectivity, limits of detection (LODs) and quantification (LOQs), trueness, repeatability and interday precision. The LOQs ranged from 0.01 to 1.00mg/L for urine, serum and CSF. In case of bronchial aspirations, the LOQs were between 0.02 and 0.67mg/kg. In all matrices the recovery results were in the range 70-120% and interday precision was lower than 25%. Finally, the optimized method was applied to the analysis of biological samples from 10 patients in the intensive care unit (ICU) of a hospital located in Almeria (Spain). Several antibiotics (e.g., amoxicillin, tobramycin, levofloxacin, or linezolid) were found in the studied samples, observing that the highest concentrations were obtained in urine samples.
