0000000000125258
AUTHOR
Nuria León
Target analysis and retrospective screening of veterinary drugs, ergot alkaloids, plant toxins and other undesirable substances in feed using liquid chromatography-high resolution mass spectrometry.
A comprehensive strategy combining a quantitative method for 77 banned veterinary drugs, mycotoxins, ergot alkaloids and plant toxins, and a post-target screening for 425 substances including pesticides and environmental contaminants in feed were developed using a QuEChERS-based extraction and an ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS). The quantitative method was validated after previous statistical optimisation of the main parameters governing ionisation, and presented recoveries ranging, in general, from 80 to 120%, with a precision in terms of Relative Standard Deviation (RSD) lower than 20%. The full-scan accurate mass data…
Comprehensive analytical strategy for biomonitoring of pesticides in urine by liquid chromatography–orbitrap high resolution mass spectrometry
In this study we propose an analytical strategy that combines a target approach for the quantitative analysis of contemporary pesticide metabolites with a comprehensive post-target screening for the identification of biomarkers of exposure to environmental contaminants in urine using liquid chromatography coupled to high-resolution mass spectrometry (LC–HRMS). The quantitative method for the target analysis of 29 urinary metabolites of organophosphate (OP) insecticides, synthetic pyrethroids, herbicides and fungicides was validated after a previous statistical optimization of the main factors governing the ion source ionization and a fragmentation study using the high energy collision disso…
Determination of 3-MCPD by GC-MS/MS with PTV-LV injector used for a survey of Spanish foodstuffs
3-Monochloropropane-1,2-diol (3-MCPD) is the most common chemical contaminant of the group of chloropropanols. It can occur in foods and food ingredients at low levels as a result of processing, migration from packaging materials during storage and domestic cooking. A sensitive method for determination of 3-MCPD in foodstuffs using programmable temperature vaporization (PTV) with large-volume injection (LVI) gas chromatography (GC) with tandem mass spectrometry detection (MS/MS) has been developed and optimized. The optimization of the injection and detection parameters was carried out using statistical experimental design. A Plackett-Burman design was used to estimate the influence of reso…
Risk assessment of exposure to phthalates in breastfeeding women using human biomonitoring
In this study, we assessed the presence of 14 phthalate metabolites in the urine of 104 lactating mothers from Valencia (Spain) who took part in the human biomonitoring project BETTERMILK. Nine of the metabolites studied showed detection frequencies >80%, whereas the rest of the metabolites presented low detection frequencies (<5%). The concentrations ranged from <LoQ to 1291 ng/mL with monoethyl phthalate showing the highest concentration, with a geometric mean of 34.90 ng/mL. In general, the phthalate metabolite levels quantified in the present study were lower than the urinary levels found in previous studies that involved lactating mothers. The consumption of packaged juices and the fre…
Determination of bisphenol diglycidyl ether residues in canned foods by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry
Abstract A new confirmatory method for simultaneous determination of bisphenol diglycidyl ether residues (BADGE, BADGE·H2O, BADGE·2H2O, BADGE·H2O·HCl, BADGE·HCl, BADGE·2HCl, BFDGE and BFDGE·2HCl) from canned food has been developed. The proposed method includes extraction by pressurized liquid extraction (PLE) followed by liquid–liquid partition and purification by solid phase extraction (SPE). Several solvent systems and different operating conditions (time, temperature) have been investigated for PLE optimization. A reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to atmospheric pressure chemical ionisation tandem mass spectrometry (APCI-MS–MS) method was developed …
Combined target and post-run target strategy for a comprehensive analysis of pesticides in ambient air using liquid chromatography-Orbitrap high resolution mass spectrometry
Abstract A comprehensive strategy for the analysis of current airborne pesticides has been developed using liquid chromatography coupled to high resolution mass spectrometry. The methodology includes both quantitative target analysis and post-run target screening analysis. The quantitative method was validated after a previous statistical optimisation of the main factors governing the ion source ionization and a study of the single-stage Orbitrap fragmentation through the HCD cell. The quantitative method presented recoveries ranging from 73 to 116%, with precision (RSD) lower than 20%, for the 35 substances in the scope of the target method. The full-scan accurate mass data were acquired w…
Biomonitoring of Phthalates, Bisphenols and Parabens in Children: Exposure, Predictors and Risk Assessment
Exposure to emerging contaminants, such as phthalates, bisphenols and parabens in children has been associated with possible neurodevelopment and endocrine alterations. In the present study, the biomonitoring of biomarkers in children (5–12 years old) from the Valencia Region (Spain) have been implemented using urines from the BIOVAL program. More than 75% of the children studied (n = 562) were internally exposed (>
Development of a pressurised liquid extraction and liquid chromatography with electrospray ionization-tandem mass spectrometry method for the determination of domoic acid in shellfish.
Amnesic shellfish poisoning (ASP) is a potentially lethal human toxic syndrome which is caused by domoic acid (DA) that originates in marine phytoplankton belonging to the Pseudonitzschia genus. A confirmatory and sensitive procedure has been developed and validated for the determination of DA in shellfish. The proposed method includes pressurised liquid extraction (PLE) with methanol/acetone (9:1), florisil ® cleanup purification inside the PLE extraction cell and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS–MS). Comparison of ionization sources (ESI, atmospheric pressure ionization (APCI) atmospheric pressure …
Wide-range screening of banned veterinary drugs in urine by ultra high liquid chromatography coupled to high-resolution mass spectrometry
In this work, an ultra high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS) methodology is proposed for the multi-class multi-residue screening of banned and unauthorized veterinary drugs in bovine urine, using an Orbitrap Exactive™ analyzer working at a resolving power of 50,000 FWHM in full scan, both in positive and negative mode. The method currently covers 87 analytes belonging to different families such as steroid hormones, β-agonists, resorcylic acid lactones (RAL), stilbens, tranquillizers, nitroimidazoles, corticosteroids, NSAIDs, amphenicoles, thyreostatics and other substances such as dapsone. A database including the elemental composition, the po…
Protein Biomarkers of Bovine Defective Meats at a Glance: Gel-Free Hybrid Quadrupole-Orbitrap Analysis for Rapid Screening
An understanding of biological mechanisms that could be involved in the stress response of animal cattle prior to slaughter is critical to create effective strategies aiming at the production of high-quality meat. The sarcoplasmic proteome of directly extracted samples from normal and high ultimate pH (pHu) meat groups was studied through a straightforward gel-free strategy supported by liquid chromatography hybrid quadrupole-Orbitrap high-resolution mass spectrometry (LC-HRMS) analysis. A stepped proteomic pipeline combining rapid biomarker hunting supported by qualitative protein Mascot scores followed by targeted label-free peptide quantification revealed 26 descriptors that characterize…
Determination of acrylamide in coffee and chocolate by pressurised fluid extraction and liquid chromatography-tandem mass spectrometry.
A selective and sensitive procedure has been developed and validated for the determination of acrylamide in difficult matrices, such as coffee and chocolate. The proposed method includes pressurised fluid extraction (PFE) with acetonitrile, florisil clean-up purification inside the PFE extraction cell and detection by liquid chromatography (LC) coupled to atmospheric pressure ionisation in positive mode tandem mass spectrometry (APCI-MS-MS). Comparison of ionisation sources (atmospheric pressure chemical ionisation (APCI), atmospheric pressure photoionization (APPI) and the combined APCI/APPI) and clean-up procedures were carried out to improve the analytical signal. The main parameters aff…
Development and validation of a liquid chromatography tandem mass spectrometry method for the analysis of beta-agonists in animal feed and drinking water.
A reproducible, sensitive and selective multiresidue analytical method for seven beta-agonists: clenbuterol (CBT), clenpenterol (CPT), ractopamine (RTP), brombuterol (BBT), mabuterol (MBT), mapenterol (MPT), and hydroxymethylclenbuterol (HMCBT) was developed and validated by using liquid chromatography tandem mass spectrometry (LC-MS/MS) in feed and drinking water samples. The validation was achieved according to the criteria laid down in the Commission Decision 2002/657/EC, however it was necessary to use minimum required performance limits (MRPLs) proposed by the Community Reference Laboratories (CRLs) due to the lack of maximum residue limits (MRLs) for beta-agonists. By setting up these…
Qualitative screening of 116 veterinary drugs in feed by liquid chromatography-high resolution mass spectrometry: potential application to quantitative analysis.
Abstract Veterinarian and human pharmaceuticals may be intentionally added to animal feed to enhance animal production. Monitoring these substances is necessary for protecting the consumers. In this work, a screening method covering 116 human and veterinary drugs has been developed and validated in five types of animal feed at 0.02 and 0.2 mg kg−1. After a simple extraction and dilution, the samples were analysed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS). Nearly all compounds tested were detected at 0.02 mg kg−1, based on the presence of the accurate-mass (de)protonated molecule. However, the identification using a…
Evaluation of mycotoxins and their metabolites in human breast milk using liquid chromatography coupled to high resolution mass spectrometry
Humans can be exposed to mycotoxins through the food chain. Mycotoxins are mainly found as contaminants in food and could be subsequently excreted via biological fluids such as urine or human breast milk in native or metabolised form. Since breast milk is usually supposed as the only food for new-borns, the occurrence of mycotoxins in thirty-five human milk samples was evaluated by a newly developed method based on QuEChERS extraction and UHPLC-HRMS detection. The method described here allows the detection of target mycotoxins in order to determine the quality of this initial feeding. The method has been fully validated, with recoveries ranging from 64% to 93% and relative standard deviatio…
Development of a method for the analysis of seven banned azo-dyes in chilli and hot chilli food samples by pressurised liquid extraction and liquid chromatography with electrospray ionization-tandem mass spectrometry
An automated, confirmatory and sensitive procedure has been developed and validated for the determination of Sudan (I-IV), Sudan Orange G, Sudan Red 7B and Para Red in hot chilli food samples. The proposed method includes pressurised liquid extraction (PLE) with acetone, gel permeation chromatography (GPC) clean-up and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS-MS). The main parameters affecting the performance of the different ionization sources and PLE parameters were previously optimised using statistical design of experiments (DOE). The method was in-house validated on chilli powder and chilli meat. Linear…