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Assessing fish authenticity by direct analysis in real time-high resolution mass spectrometry and multivariate analysis: discrimination between wild-type and farmed salmon

Fiorino, Giuseppina M., Losito, Ilario, De Angelis, Elisabetta, Arlorio, Marco, Logrieco, Antonio F., Monaci, Linda
Food research international 2019 v.116 pp. 1258-1265
Salmo salar, aquaculture, carbon, commercialization, data collection, discriminant analysis, farmed fish, fatty acids, fish fillets, markets, mass spectrometry, multivariate analysis, oxidation, principal component analysis, provenance, salmon, seafood consumption, seafoods, Canada, Chile, Norway
The constant increase in seafood consumption worldwide has led to a parallel growth of the incidence of products obtained by aquaculture on the market, but also of the fraudulent commercialization of farmed products as wild-type ones. A careful characterization of the lipid component of seafood products based on chromatography-mass spectrometry techniques has been reported as a promising approach to reliably differentiate farmed from wild-type products. In this context, a fast method based on Direct Analysis in Real Time (DART) coupled to High Resolution Mass Spectrometry (HRMS) based on a single stage Orbitrap mass analyzer, integrated by Principal Component Analysis (PCA), was developed in the present study and applied to scout for spectral features useful to discriminate wild-type from farmed salmon of Salmo salar species. In particular, normalized intensities obtained for the 30 most intense signals (all referred to fatty acids, FA) detected in negative ion DART-HRMS spectra of the lipid extracts of salmon fillets [26 wild-type from Canada, 74 farmed from Canada (25), Norway (25) and Chile (24)] were considered as the variables for PCA. The scatterplot referred to the first two principal components showed a clear distinction between wild-type and farmed salmon, which gathered as a unique cluster, despite the remarkable differences in their geographical origin. In accordance with previous studies based on more complex and time-demanding analytical approaches, three saturated (14:0, 16:0 and 18:0) FA, along with unsaturated ones having 20 or 22 carbon atoms, were found as the main discriminating variables for wild-type salmons, whereas FA with compositions 18:1, 18:2, 18:3 and several oxidized forms arising from them were found to have a significantly higher incidence in farmed salmon. The method was further validated by Discriminant Analysis (DA) performed on the same dataset used for PCA integrated by data obtained from 6 commercial samples, putatively referred to farmed Norwegian salmon. Results showed that 100% of the latter were correctly classified as farmed type. Relative abundances of DART-HRMS signals related to specific FA appear then very promising for the differentiation of wild-type salmon from farmed ones, a very relevant issue in the context of consumers' protection from seafood frauds.