97 research outputs found
Report of the VthWorkshop of the Spanish National Network on Mycotoxins and Toxigenic Fungi and Their Decontamination Processes (MICOFOOD), 10–11 December 2020
Spanish Ministry of Economy, Industry and Competitiveness
AGL2017-90787-REDTFaculty of Pharmacy (University of Valencia, Spain)AIMPLAS (Plastic Technology Centre)AINIA Technology CentreIATA (Institute of Agrochemistry and Food Technology, CSIC)IMPORTAC
Application of LC–MS/MS in the Mycotoxins Studies
The editors are really grateful to all the authors who contributed their high-quality works
to this Special Issue. Special thanks go to the expert peer reviewers, whose rigorous evaluations of all of the
submitted manuscripts have, no doubt, improved this Special Issue. Last but not least, the editors really appreciate
the good organization and constant support of the MDPI editorial team and staff
An integrated targeted and untargeted approach for the analysis of ergot alkaloids in cereals using UHPLC - hybrid quadrupole time-of-flight mass spectrometry
An ultra-high performance liquid chromatography hybrid quadrupole time of flight (Q-TOF) mass spectrometry (MS) method is described for the simultaneous quantitative determination of common ergot alkaloids and the screening, detection and identification of unexpected (less studied or novel) members of this class of toxic fungal secondary metabolites. The employed analytical strategy involves an untargeted data acquisition (consisting of full scan TOF MS survey and information dependent acquisition MS/MS scans) and the processing of data using both targeted and untargeted approaches. Method performance characteristics for the quantitative analysis of 6 common ergot alkaloids i.e. ergometrine, ergosine, ergotamine, ergocornine, ergocristine, ergokryptine and their corresponding epimers in rye were comparable to those previously reported for triple-quadrupole (QqQ) MS/MS. The method limits of quantification (LOQ) were in the range from 3 to 19 mu g/kg, and good linearity was observed for the different ergot alkaloids in the range from LOQ to 1000 mu g/kg. Furthermore, the method demonstrated good precision (relative standard deviations at 50 mu g/kg not higher than 14.6 and 16.2% for the intra-day and inter-day precision, respectively), and the trueness values at different concentration levels were all between 89 and 115%. The method was applied for the analysis of a set of 17 rye samples and demonstrated the presence of these ergot alkaloids in the range from <LOQ to 2,811 mu g/kg. Further mining of the same data based on a 'non-targeted peak finding' algorithm and the use of full MS and MS/MS accurate mass data allowed the detection and identification of 19 ergot alkaloids that are commonly not included in most analytical methods using QqQ instruments. Some of these alkaloids are reported for the first time in naturally contaminated samples
Occurrence of Ergot Alkaloids in Barley and Wheat from Algeria
The natural occurrence of six major ergot alkaloids, ergometrine, ergosine, ergotamine,
ergocornine, ergokryptine and ergocristine, as well as their corresponding epimers, were investigated
in 60 cereal samples (barley and wheat) from Algeria. Ultra-high performance liquid chromatography
coupled to tandem mass spectrometry (UHPLC-MS/MS) and a QuEChERS extraction method were
used for sample analysis. The results revealed that 12 out of 60 samples (20%) were contaminated
with ergot alkaloids. Wheat was the most contaminated matrix, with an incidence of 26.7% (8 out
of 30 samples). The concentration of total ergot alkaloids ranged from 17.8 to 53.9 µg/kg for barley
and from 3.66 to 76.0 µg/kg for wheat samples. Ergosine, ergokryptine and ergocristine showed the
highest incidences in wheat, while ergometrine was the most common ergot in barley.Spanish Ministry of Science, Innovation and Universities
(Project Ref.: RTI2018-097043-B-I00
Non-aqueous capillary electrophoresis–time of flight mass spectrometry method to determine emerging mycotoxins
Las eniatinas (ENN) y la beauvericina (BEA) son micotoxinas emergentes que tradicionalmente se han determinado mediante cromatografĂa lĂquida acoplada a espectrometrĂa de masas en tándem (LC-MS/MS). Sin embargo, hasta donde sabemos, hasta el momento no se han publicado mĂ©todos analĂticos basados ​​en electroforesis capilar (CE)-MS/MS. Debido a su naturaleza no polar, en este trabajo se propone por primera vez un mĂ©todo de CE no acuosa (NACE) acoplada a MS de cuadrupolo-tiempo de vuelo para identificar y cuantificar estas micotoxinas. La determinaciĂłn se logrĂł en 4 min en condiciones Ăłptimas: acetato de amonio 40 mM en acetonitrilo-metanol 80:20 (v/v) (tampĂłn), 30 kV (voltaje), 80 cm (longitud del capilar), 20 °C (temperatura del capilar) y 50 mbar Ă— 30 s (inyecciĂłn). Se puede lograr una mayor selectividad en comparaciĂłn con LC debido a la formaciĂłn de aductos CE exclusivos como [M + CH3CH2NH3]+. Se seleccionĂł el modo de adquisiciĂłn “All Ions” ya que permite la cuantificaciĂłn de los ENN habituales, asĂ como la identificaciĂłn de las ENN menos comunes. El mĂ©todo fue validado para muestras de trigo, obteniendo lĂmites de cuantificaciĂłn de 4,0 a 8,3 ÎĽg/kg dependiendo de la micotoxina emergente, valores de recuperaciĂłn superiores al 87,4 % y valores de precisiĂłn intra e interdiarios (RSD) inferiores al 15,1 % en todos los casos. Finalmente, se analizaron 29 muestras de trigo, encontrando 26 muestras con concentraciones de eniatina B superiores al lĂmite de cuantificaciĂłn (7,5-1480 ÎĽg/kg), 20 de eniatina B1 (5,2-550 ÎĽg/kg), 7 de eniatina A (10 –55 ÎĽg/kg), 4 para eniatina A1 (12,6-77 ÎĽg/kg) y 5 para BEA (9,2-16,4 ÎĽg/kg). Además, se identificaron tentativamente otras dos ENN.
Enniatins (ENN) and beauvericin (BEA) are emerging mycotoxins that have been traditionally determined by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). However, to the best of our knowledge, no analytical methods based on capillary electrophoresis (CE)–MS/MS have been reported so far. Due to their non-polar nature, in this work, a non-aqueous CE (NACE) method coupled to quadrupole time-of-flight–MS is proposed for the first time to identify and quantify these mycotoxins. Determination was achieved in 4 min under optimum conditions: 40 mM ammonium acetate in 80:20 (v/v) acetonitrile-methanol (buffer), 30 kV (voltage), 80 cm (capillary length), 20 °C (capillary temperature) and 50 mbar Ă— 30 s (injection). Higher selectivity can be achieved when compared with LC due to the formation of exclusive CE adducts such as [M + CH3CH2NH3]+. “All Ions” acquisition mode was selected as it allows the quantification of the usual ENNs, as well as the identity confirmation of less common ENNs. The method was validated for wheat samples, obtaining limits of quantification from 4.0 to 8.3 ÎĽg/kg depending on the emerging mycotoxin, recovery values higher than 87.4%, and intra- and inter-day precision values (RSDs) lower than 15.1% in all cases. Finally, 29 wheat samples were analyzed, finding 26 samples with concentrations of enniatin B higher than the limit of quantification (7.5–1480 ÎĽg/kg), 20 for enniatin B1 (5.2–550 ÎĽg/kg), 7 for enniatin A (10–55 ÎĽg/kg), 4 for enniatin A1 (12.6–77 ÎĽg/kg) and 5 for BEA (9.2–16.4 ÎĽg/kg). Moreover, two other ENNs were tentatively identified.Proyectos Ref.: RTI2018-097043-B-I00 y EQC2018-004453-P financiados por MCIN/AEI/10.13039/501100011033/FEDER “Una manera de hacer Europa” y Junta de AndalucĂa - Programa Operativo FEDER [B-AGR-202-UGR20]. M.M.D.P. agradece un contrato posdoctoral a la Junta de AndalucĂa (DOC_00230). Los autores agradecen al Dr. Choukri Khelifa por suministrar la muestras de cereales. FinanciaciĂłn para publicaciĂłn en acceso abierto a cargo de Universidad de Granada/CBUA
Occurrence of Mycotoxins in Swine Feeding from Spain
A survey including 228 pig feed samples from Spain has been developed, exploring the
occurrence of 19 mycotoxins (aflatoxins B1, B2, G1 and G2, ochratoxin A, fumonisins B1 and B2,
citrinin, zearalenone, deoxynivalenol, fusarenon X, sterigmatocystin, T-2 toxin, HT-2 toxin, enniatins
A, A1, B and B2, and beauvericin). The samples were analysed by solid-liquid extraction followed by
liquid chromatography coupled with fluorescence or mass spectrometry detection. Enniatin B was
found in 100% of the samples (up to 1200 ug/kg) and beauvericin in more than 90%. Moreover, 40% of
samples were contaminated with more than five mycotoxins. This high occurrence is insurmountable
and surpasses all previous studies, probably due to the inclusion of emerging mycotoxins, scarcely
explored. The majority of the samples (96.9%) were in accordance with EU regulations, which do not
address emerging mycotoxins or co-occurrence. These results show that in order to ensure mycotoxin
absence, emerging mycotoxins should always be considered.This research was funded by SPANISH MINISTRY OF ECONOMY AND COMPETITIVENESS and
EUROPEAN REGIONAL DEVELOPMENT FUND (MINECO/FEDER, UE), grant number AGL2015-70708-R
Ion mobility-mass spectrometry to extend analytical performance in the determination of ergot alkaloids in cereal samples
This work evaluates the potential of ion mobility spectrometry (IMS) to improve the analytical perfor- mance of current liquid chromatography-mass spectrometry (LC-MS) workflows applied to the determi- nation of ergot alkaloids (EAs) in cereal samples. Collision cross section (CCS) values for EA epimers are reported for the first time to contribute to their unambiguous identification. Additionally, CCS values have been inter-laboratory cross-validated and compared with CCS values predicted by machine-learning mod- els. Slight differences were observed in terms of CCS values for ergotamine, ergosine and ergocristine and their corresponding epimers (from 3.3 to 4%), being sufficient to achieve a satisfactory peak-to-peak res- olution for their unequivocal identification. A LC-travelling wave ion mobility (TWIM)-MS method has been developed for the analysis of EAs in barley and wheat samples. Signal-to-noise ratio (S/N) was im- proved between 2.5 and 4-fold compared to the analog LC-TOF-MS method. The quality of the extracted ion chromatograms was also improved by using IMS.European Commission 795946MCIN/AEI (European Regional Development Fund-ERDF, a way to build Europe) PID2021-127804OB-I0
Assessing human exposure to pesticides and mycotoxins: optimization and validation of a method for multianalyte determination in urine samples
Humans are exposed to an increasing number of contaminants, with diet being one of the most important exposure routes. In
this framework, human biomonitoring is considered the gold standard for evaluating human exposure to chemicals. Pesticides
and mycotoxins are chemicals of special concern due to their health implications. They constitute the predominant border
rejection notifications for food and feed in Europe and the USA. However, current biomonitoring studies are focused on a
limited number of compounds and do not evaluate mycotoxins and pesticides together. In this study, an analytical method
has been developed for the determination of 30 pesticides and 23 mycotoxins of concern in urine samples. A salting-out
liquid–liquid extraction (SALLE) procedure was optimized achieving recoveries between 70 and 120% for almost all the
compounds and limits as lower as when QuEChERS was applied. The compounds were then determined by liquid chromatography
coupled to triple quadrupole mass spectrometry. Different chromatographic conditions and analytical columns
were tested, selecting a Hypersild gold aQ column as the best option. Finally, the method was applied to the analysis of 45
urine samples, in which organophosphate and pyrethroid pesticides (detection rates (DR) of 82% and 42%, respectively)
and ochratoxin A and deoxynivalenol (DR of 51% and 33%, respectively) were the most detected compounds. The proposed
analytical method involves the simultaneous determination of a diverse set of pesticides and mycotoxins, including their
most relevant metabolites, in human urine. It serves as an essential tool for biomonitoring the presence of highly prevalent
contaminants in modern society.Funding for open access publishing: Universidad de AlmerĂa/
CBUA.Andalusian Government (Project
ref. PROYEXCEL_00195) and PID2021-127804OB-I00 funded
by Spanish MCIN/AEI/ 10.13039/501100011033 and by “ERDF A
way of making Europe”University of AlmerĂa for “Convocatoria de RecualificaciĂłn do Sistema Universitario Español-Margarita Salas” postdoc grant under the “Plan de RecuperaciĂłn TransformaciĂłn” programme funded by the Spanish Ministry of Universities with European Union’s NextGenerationEU fundsGrant IJC2019-040989-I funded by MCIN/AEI/
10.13039/50110001103
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