Food Analytical Methods

, Volume 11, Issue 5, pp 1467–1475 | Cite as

Italian Cheeses Discrimination by Means of δ13C and δ15N Isotopic Ratio Mass Spectrometry

  • Angelo Faberi
  • Dario Compagnone
  • Fabio Fuselli
  • Alessandro La Mantia
  • Marcello Mascini
  • Camilla Montesano
  • Rachele Rocchi
  • Manuel Sergi
Article
  • 60 Downloads

Abstract

Protection of the quality products and particularly Protected Designation of Origin (PDO)/Protected Geographical Indication (PGI) foods is a strategic issue in the EU economy, in terms of protection of market competition and safety. Having reliable tools for the assessment of key parameters useful for the identification of authenticity and/or frauds is therefore of main interest. In this work, the isotope ratios of stable elements variability of four PDO cheeses (Taleggio PDO, Asiago PDO, Pecorino Toscano PDO, and Provolone Valpadana PDO) were investigated with the aim to find discrimination among different kinds of cheeses. The specificity of isotope ratios of stable elements can be profitably used when sample characteristics, conditions, or degradation strongly suggest looking directly at the atoms rather than to the molecules. We analyzed five isotopic parameters: δ13C and δ15N on casein fraction and on cheese as a whole; δ13C on the fat fraction of the cheese. The dataset was composed by 118 cheese samples coming from five different Italian regions and collected over a 3-year period. Data elaboration showed that beyond interesting differences already observed on each individual cheese on the basis of some parameters taken into account (year, season, province, altitude), the characteristic isotopic ratios of each cheese are stable within a narrow range of δ‰. Univariate analysis showed that single parameters were not enough to provide a clear discrimination between each cheese, while principal component analysis (PCA) and partial least squares regression-discriminant analysis (PLS-DA) showed a good separation between cheese classes, particularly for the Pecorino Toscano cheese type. This data suggested a positive indication to the possibility of introducing in the production disciplinary of the concerned cheeses also a range of isotopic ratios of C and N as a further tool for the protection of this four types of PDO cheeses.

Keywords

Stable isotope ratio analysis IRMS Cheese discrimination 

Notes

Compliance with Ethical Standards

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Not applicable.

Conflict of Interest

Angelo Faberi declares that he has no conflict of interest. Dario Compagnone declares that he has no conflict of interest. Fabio Fuselli declares that he has no conflict of interest. Alessandro La Mantia declares that he has no conflict of interest. Marcello Mascini declares that he has no conflict of interest. Camilla Montesano declares that she has no conflict of interest. Rachele Rocchi declares that she has no conflict of interest. Author Manuel Sergi declares that he has no conflict of interest.

References

  1. Afzal MI, Ariceaga CCG, Boulahya KA, Jacquot M, Delaunay S, Cailliez-Grimal C (2017) Biosynthesis and role of 3-methylbutanal in cheese by lactic acid bacteria: major metabolic pathways, enzymes involved, and strategies for control. Crit Rev Food Sci Nutr 57(2):399–406.  https://doi.org/10.1080/10408398.2014.893502 CrossRefGoogle Scholar
  2. AOAC Official Method 991.41-1996, C-4 plant sugars in honey. Internal standardsGoogle Scholar
  3. AOAC Official Method 2004.01-2004, Carbon stable isotope ratio of ethanol deriveGoogle Scholar
  4. Bontempo L, Lombardi G, Paoletti R, Ziller L, Camin F (2012) H, C, N and O stable isotope characteristics of alpine forage, milk and cheese. Int Dairy J 23(2):99–104.  https://doi.org/10.1016/j.idairyj.2011.10.005 CrossRefGoogle Scholar
  5. Brand WA, Coplen TB, Vogl J, Rosner M, Prohaska T (2014) Assessment of international reference materials for isotope-ratio analysis (IUPAC technical report). Pure Appl Chem 86(3):425–467CrossRefGoogle Scholar
  6. Brescia MA, Monfreda M, Buccolieri A, Carrino C (2005) Characterisation of the geographical origin of buffalo milk and mozzarella cheese by means of analytical and spectroscopic determinations. Food Chem 89(1):139–147.  https://doi.org/10.1016/j.foodchem.2004.02.016 CrossRefGoogle Scholar
  7. Camin F, Wietzerbin K, Cortes AB, Gaberhauer H, Lees M, Versini G (2004) Application of multielement stable isotope ratio analysis to the characterization of French, Italian, and Spanish cheeses. J Agri Food Chem 52(21):6592–6601.  https://doi.org/10.1021/jf040062z CrossRefGoogle Scholar
  8. Camin F, Larcher R, Perini M, Bontempo L, Bertoldi D, Gagliano G, Nicolini G, Versini G (2010) Characterisation of authentic Italian extra-virgin olive oils by stable isotope ratios of C, O and H and mineral composition. Food Chem 118:901–909CrossRefGoogle Scholar
  9. Camin F, Wehrens R, Bertoldi D, Bontempo L, Ziller L, Perini M, Nicolini G, Nocetti M, Larcher R (2012) H, C, N, and S stable isotopes and mineral profiles to objectively guarantee the authenticity of grated hard cheeses. Anal Chimi Acta 711:54–595.  https://doi.org/10.1016/j.aca.2011.10.047 CrossRefGoogle Scholar
  10. Camin F, Bertoldi D, Santato A, Bontempo L, Perini M, Ziller L, Stroppa A, Larcher R (2015) Validation of methods for H, C, N and S stable isotopes and elemental analysis of cheese: results of an international collaborative study. Rapid Commun Mass Spectrom 29(5):415–423.  https://doi.org/10.1002/rcm.7117 CrossRefGoogle Scholar
  11. Camin F, Pavone A, Bontempo L, Wehrens R, Paolini M, Faberi A, Marianella RM, Capitani D, Vista S, Mannina L (2016) The use of IRMS, 1H NMR and chemical analysis to characterise Italian and imported Tunisian olive oils. Food Chem 196:98–105.  https://doi.org/10.1016/j.foodchem.2015.08.132 CrossRefGoogle Scholar
  12. Camin F, Boner M, Bontempo L, Fauhl-Hassek C, Kelly S, Riedl J, Rossmanne A (2017) Stable isotope techniques for verifying the declared geographical origin of food in legal cases. Trends Food Sci Technol 2017:176–187CrossRefGoogle Scholar
  13. Capici C, Mimmo T, Kerschbaumer L, Cesco S, Scampicchio M (2015) Determination of cheese authenticity by carbon and nitrogen isotope analysis: Stelvio cheese as a case study. Food Anal Meth 8(8):2157–2162.  https://doi.org/10.1007/s12161-015-0113-y CrossRefGoogle Scholar
  14. Commission Regulation (EC) No 822/97 of 6 May 1997 amending Regulation (EEC) No 2676/90 determining Community methods for the analysis of wines. Official Journal of the European Union, L 117 10–12Google Scholar
  15. Craig H (1957) Isotopic standards for carbon and oxygen and correction factors for mass spectrometric analysis of carbon dioxide. Geochim Cosmochim Acta 12(1-2):133–149.  https://doi.org/10.1016/0016-7037(57)90024-8 CrossRefGoogle Scholar
  16. Crittenden RG, Andrew AS, LeFournour M, Young MD, Middleton H, Stockmann R (2007) Determining the geographic origin of milk in Australasia using multi-element stable isotope ratio analysis. Int Dairy J 17(5):421–428.  https://doi.org/10.1016/j.idairyj.2006.05.012 CrossRefGoogle Scholar
  17. DOOR: EU database of agricultural products and food. http://ec.europa.eu/agriculture/quality/door/list.html. Accessed 28 Nov 2017
  18. EC No: IT-PDO-0217-0011-26.07.2006 Off J Eur Union, C 199 24–34Google Scholar
  19. Eriksson I, Byrne T, Johansson E, Trygg J, Wikstrom C (2001) Multi- and megavariate data analysis. Principles and applications. Umetrics Academy, Umeå, pp 1–533Google Scholar
  20. Faberi A, Marianella RS, Fuselli F, La Mantia A, Ciardiello F, Montesano C, Mascini M, Sergi M, Compagnone D (2014) Fatty acid composition and delta13 C of bulk and individual fatty acids as marker for authenticating Italian PDO/PGI extra virgin olive oils by means of isotopic ratio mass spectrometry. J Mass Spectrom 49(9):840–849.  https://doi.org/10.1002/jms.3399 CrossRefGoogle Scholar
  21. Gan HH, Yan B, Linforth RST, Fisk ID (2016) Development and validation of an APCI-MS/GC–MS approach for the classification and prediction of cheddar cheese maturity. Food Chem 190:442–447.  https://doi.org/10.1016/j.foodchem.2015.05.096 CrossRefGoogle Scholar
  22. Gromski PS, Muhamadali H, Ellis DI, Xu Y, Correa E, Turner ML, Goodacre R (2015) A tutorial review: metabolomics and partial least squares-discriminant analysis—a marriage of convenience or a shotgun wedding. Anal Chim Acta 879:10–23.  https://doi.org/10.1016/j.aca.2015.02.012 CrossRefGoogle Scholar
  23. Jolliffe IT (2002) Principal component analysis, 2nd edition. Springer series in statistics. New York: Springer-VerlagGoogle Scholar
  24. Maltas DC, Kwok K, Wang P, Taylor LS, Ben-Amotz D (2013) Rapid classification of pharmaceutical ingredients with Raman spectroscopy using compressive detection strategy with PLS-DA multivariate filters. J Pharm Biomed Anal 80:63–68.  https://doi.org/10.1016/j.jpba.2013.02.029 CrossRefGoogle Scholar
  25. Manca G, Camin F, Coloru GC, Del Caro A, Depentori D, Franco MA, Versin G (2001) Characterization of the geographical origin of Pecorino Sardo cheese by casein stable isotope (13C/12C and 15N/14N) ratios and free amino acid ratios. J Agri Food Chem 49(3):1404–1409.  https://doi.org/10.1021/jf000706c CrossRefGoogle Scholar
  26. Nečemer M, Potocnik D, Ogrinc N (2016) Discrimination between Slovenian cow, goat and sheep milk and cheese according to geographical origin using a combination of elemental content and stable isotope data. J Food Comp Anal 52:16–23.  https://doi.org/10.1016/j.jfca.2016.07.002 CrossRefGoogle Scholar
  27. Pierna JAF, Abbas O, Dardenne P, Baeten V (2011) Discrimination of Corsican honey by FT-Raman spectroscopy and chemometrics. Biotechnologie, Agronomie, Sociy by FT-Raman spectro 15:75–84Google Scholar
  28. Pillonel L, Badertscher R, Froidevaux P, Haberhauer G, Holzld S, Horn P, Jakob A, Pfammatter E, Piantini U, Rossmann A, Tabacchi R, Bosset JO (2003) Stable isotope ratios, major, trace and radioactive elements in emmental cheeses of different origins. LWT-Food Science and Technology 36(6):615–623.  https://doi.org/10.1016/S0023-6438(03)00081-1 CrossRefGoogle Scholar
  29. Piras C, Marincola FC, Savorani F, Engelser SB, Cosentino S, Viale S, Pisano MB (2013) A NMR metabolomics study of the ripening process of the Fiore Sardo cheese produced with autochthonous adjunct cultures. Food Chem 141(3):2137–2147.  https://doi.org/10.1016/j.foodchem.2013.04.108 CrossRefGoogle Scholar
  30. Pisano MB, Scano P, Murgia A, Cosentino S, Caboni P (2016) Metabolomics and microbiological profile of Italian mozzarella cheese produced with buffalo and cow milk. Food Chem 192:618–624.  https://doi.org/10.1016/j.foodchem.2015.07.061 CrossRefGoogle Scholar
  31. Pogačić T, Maillard MB, Leclerc A, Hervé C, Chuat V, Yee AL, Valence F, Thierry A (2015) A methodological approach to screen diverse cheese-related bacteria for their ability to produce aroma compounds. Food Microbiol 46:145–153.  https://doi.org/10.1016/j.fm.2014.07.018 CrossRefGoogle Scholar
  32. Pogačić T, Maillard MB, Leclerc A, Hervé C, Chuat V, Yee AL, Valence F, Thierry A (2016) Lactobacillus and Leuconostoc volatilomes in cheese conditions. Appl Microbiol Biot 100(5):2335–2346.  https://doi.org/10.1007/s00253-015-7227-4 CrossRefGoogle Scholar
  33. Portarena S, Baldacchini C, Brugnoli E (2017) Geographical discrimination of extra-virgin olive oils from the Italian coasts by combining stable isotope data and carotenoid content within a multivariate analysis. Food Chem 215:1–6.  https://doi.org/10.1016/j.foodchem.2016.07.135 CrossRefGoogle Scholar
  34. Regulation (EU) No 1151/2012 of the European Parliament and of the Council of 21 November 2012 on quality schemes for agricultural products and foodstuff. Off J Eur Union, L 343:1–29Google Scholar
  35. Renou JP, Deponge C, Gachon P, Bonnefoy JC, Coulon JB, Garel JP, Vérité R, Ritz P (2004) Characterization of animal products according to geographic origin and feeding diet using nuclear magnetic resonance and isotope ratio mass spectrometry: cow milk. Food Chem 85(1):63–66.  https://doi.org/10.1016/j.foodchem.2003.06.003 CrossRefGoogle Scholar
  36. Rossmann A (2007) Stable isotope databases for European food products. In: Proceedings of the international workshop “Fingerprinting methods for the identification of timber origins”. Bonn, GermanyGoogle Scholar
  37. Silva AV, Helié JF, Caxito FA, Monardes H, Mustafa AF, Stevenson R (2014) Multi-stable isotope analysis as a tool for assessing the geographic provenance of dairy products: a case study using buffalo’s milk and cheese samples from the Amazon basin, Brazil. Int Dairy J 35(2):107–110.  https://doi.org/10.1016/j.idairyj.2013.10.019 CrossRefGoogle Scholar
  38. Sliwinska M, Wisniewska P, Dymerski T, Namiesnik J, Wardencki W (2014) Food analysis using artificial senses. J Agric Food Chem 62(7):1423–1448.  https://doi.org/10.1021/jf403215y CrossRefGoogle Scholar
  39. Solieri L, Bianchi A, Mottolese G, Lemmetti F, Giudici P (2014) Tailoring the probiotic potential of non-starter Lactobacillus strains from ripened Parmigiano Reggiano cheese by in vitro screening and principal component analysis. Food Microbiol 38:240–249.  https://doi.org/10.1016/j.fm.2013.10.003 CrossRefGoogle Scholar
  40. Speranza B, Bevilacqua A, Corbo MR, Altieri C, Sinigaglia M (2015) Selection of autochthonous strains as promising starter cultures for Fior di Latte, a traditional cheese of southern Italy. J Sci Food Agric 95(1):88–97.  https://doi.org/10.1002/jsfa.6686 CrossRefGoogle Scholar
  41. Stanimirova I, Daszykowski M, Walczak B (2007) Dealing with missing values and outliers in principal component analysis. Talanta 72(1):172–178.  https://doi.org/10.1016/j.talanta.2006.10.011 CrossRefGoogle Scholar
  42. Stevenson R, Desrochers S, Helie JF (2015) Stable and radiogenic isotopes as indicators of agri-food provenance: insights from artisanal cheeses from Quebec. Canada Int Dairy J 49:37–45.  https://doi.org/10.1016/j.idairyj.2015.04.003 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  1. 1.MiPAAF, Dipartimento dell’Ispettorato Centrale della tutela della Qualità e Repressione Frodi dei Prodotti AgroalimentariLaboratorio Centrale di RomaRomeItaly
  2. 2.Faculty of Bioscience and Technology for Food, Agriculture and EnvironmentUniversity of TeramoTeramoItaly
  3. 3.Deparment of ChemistryUniversity of Rome “La Sapienza”RomeItaly

Personalised recommendations