Abstract
Spectroscopic non-targeted methods are gaining ever-growing importance in quality control and authenticity assessment of food products because of their strong potential for identification of specific features of the products by data-driven classifiers. One of the factors hampering the diffusion of spectroscopic non-targeted methods and data-driven classifiers is the lack of harmonized guidelines for their development and validation. In particular, to date, neither conditions to directly compare spectra recorded by different spectrometers nor studies demonstrating the statistical equivalence of the spectra are available. Among the spectroscopic analytical techniques suitable for the development of non-targeted methods, nuclear magnetic resonance (NMR) offers the unique opportunity to generate statistically equivalent signals. In this paper, the feasibility of NMR spectroscopy to generate statistically equivalent NMR signals from a number of different spectrometers was demonstrated for complex mixtures (aqueous extracts of wheat and flour) by organizing an inter-laboratory comparison involving 36 NMR spectrometers. Univariate statistics along with multivariate analysis were exploited to establish unbiased criteria for assessing the statistical equivalence of the NMR signals. The aspects affecting the signal equivalence were investigated, and possible solutions to reduce the extent of the human error were proposed and applied with satisfactory results. This study furnishes the scientific community with an appropriate and easy procedure to validate non-targeted NMR methods and provides error values to be used as a reference for future studies.
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Acknowledgments
The authors acknowledge Norell for the generous loan of NMR tubes, Eurisotop for the generous supplying of the deuterated solvents, Professor Ana M. Gil for assistance in spectral analysis at CICECO-Aveiro Institute of Materials, the team of the NMR department at CVUA Karlsruhe (Kuballa, T., Ackermann, S.; Boehm, M.; Geisser, J.; Siebler, B.; Scharinger, A.), and Dr. Ileana Menegazzo for the acquisition of the spectra at the University of Padova.
Funding
This study was funded by: (a) Regione Puglia and Distretto Agroalimentare Regionale (Project “Apulian Wheat Fingerprint” in the framework of “Avviso Pubblico relativo alla selezione di Progetti Integrati di Filiera - BURP n. 102 - 10/06/2010 - Misura 124 - Cooperazione per lo sviluppo di nuovi prodotti, processi e tecnologie nei settori agricolo e alimentare, e in quello forestale”); (b) the European Union’s Seventh Framework Program for research, technological development and demonstration (Grant no. 613688, FOODINTEGRITY); (c) CICECO-Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019, financed by national funds through the FCT/MCTES, the Portuguese National NMR (PTNMR) Network.
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Vito Gallo, Rosa Ragone, Biagia Musio, Stefano Todisco, Antonino Rizzuti, Piero Mastrorilli, Stefania Pontrelli, Nicola Intini, Pasquale Scapicchio, Maurizio Triggiani, Antonello Pascazio, Carlos Cobas, Silvia Mari, Cristiano Garino, Marco Arlorio, Domenico Acquotti, Cristina Airoldi, Fabio Arnesano, Michael Assfalg, Andersson Barison, Francesca Benevelli, Anna Borioni, Laura Ruth Cagliani, Luca Casadei, Flaminia Cesare Marincola, Kim Colson, Roberto Consonni, Gabriele Costantino, Mauro Andrea Cremonini, Silvia Davalli, Iola Duarte, Sophie Guyader, Erwann Hamon, Maren Hegmanns, Raffaele Lamanna, Francesco Longobardi, Domenico Mallamace, Stefano Mammi, Michelle Markus, Leociley Rocha Alencar Menezes, Salvatore Milone, Dolores Molero-Vilchez, Adele Mucci, Claudia Napoli, Maria Cecilia Rossi, Elena Sáez-Barajas, Francesco Savorani, Elisabetta Schievano, Fabio Sciubba, Anatoly Sobolev, Panteleimon G. Takis, Freddy Thomas, Palmira Villa-Valverde and Mario Latronico declare that they have no conflict of interest.
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Gallo, V., Ragone, R., Musio, B. et al. A Contribution to the Harmonization of Non-targeted NMR Methods for Data-Driven Food Authenticity Assessment. Food Anal. Methods 13, 530–541 (2020). https://doi.org/10.1007/s12161-019-01664-8
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DOI: https://doi.org/10.1007/s12161-019-01664-8