Skip to main content
SpringerLink
Log in

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

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • 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

    Article  CAS  Google Scholar 

  • AOAC Official Method 991.41-1996, C-4 plant sugars in honey. Internal standards

  • AOAC Official Method 2004.01-2004, Carbon stable isotope ratio of ethanol derive

  • 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

    Article  CAS  Google Scholar 

  • 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):425–467

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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 118:901–909

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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 2017:176–187

    Article  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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 10–12

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • DOOR: EU database of agricultural products and food. http://ec.europa.eu/agriculture/quality/door/list.html. Accessed 28 Nov 2017

  • EC No: IT-PDO-0217-0011-26.07.2006 Off J Eur Union, C 199 24–34

  • Eriksson I, Byrne T, Johansson E, Trygg J, Wikstrom C (2001) Multi- and megavariate data analysis. Principles and applications. Umetrics Academy, Umeå, pp 1–533

    Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Jolliffe IT (2002) Principal component analysis, 2nd edition. Springer series in statistics. New York: Springer-Verlag

  • 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

    Article  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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 15:75–84

    CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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 343:1–29

  • 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

    Article  CAS  Google Scholar 

  • 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, Germany

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. MiPAAF, Dipartimento dell’Ispettorato Centrale della tutela della Qualità e Repressione Frodi dei Prodotti Agroalimentari, Laboratorio Centrale di Roma, 00149, Rome, Italy

    Angelo Faberi, Fabio Fuselli & Alessandro La Mantia

  2. Faculty of Bioscience and Technology for Food, Agriculture and Environment, University of Teramo, 64100, Teramo, Italy

    Dario Compagnone, Marcello Mascini, Rachele Rocchi & Manuel Sergi

  3. Deparment of Chemistry, University of Rome “La Sapienza”, 00183, Rome, Italy

    Camilla Montesano

Authors
  1. Angelo Faberi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dario Compagnone
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Fabio Fuselli
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alessandro La Mantia
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Marcello Mascini
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Camilla Montesano
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Rachele Rocchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Manuel Sergi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Angelo Faberi.

Ethics declarations

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.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Faberi, A., Compagnone, D., Fuselli, F. et al. Italian Cheeses Discrimination by Means of δ13C and δ15N Isotopic Ratio Mass Spectrometry. Food Anal. Methods 11, 1467–1475 (2018). https://doi.org/10.1007/s12161-017-1110-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-017-1110-0

Keywords

Search

Navigation