Multiple Assignment Recovered Analysis (MARA) NMR for a Direct Food Labeling: the Case Study of Olive Oils

  • Archimede RotondoEmail author
  • Luisa Mannina
  • Andrea Salvo


The multiple assignment recovered analysis (MARA) on nuclear magnetic resonance (NMR) spectra is here presented with the aim to provide the quantitative label of chemical mixtures such as foodstuff. The method takes advantage from the multiple NMR signals generated by any chemical; these will be all proportional to the concentration of the parent compound. In a well-known system, the selection of many integration regions enables the development of simple relationships fulfilled just by specific quantitative values of the expected components. As long as the number of equations is bigger than the known quantitative variables, MARA-NMR best-fitting algorithm will be suitably designed to output trustworthy and robust results. This is definitely demonstrated for the extra-virgin olive oil (EVOO) taken as case study: MARA-NMR showed consistency with traditional analytical measurements over 30 specimens recording satisfactory repeatability. The minimization procedure is applied by tuning the quantitative variables; these are affecting the function ρ which represents the experimental lapse from the corresponding theoretical dataset. MARA-NMR is an effective, innovative, and quick method for food labeling; unlike other analytical techniques, it is self-consistent smoothing out random instrumental outliers or unpredictable anomalies. MARA is customized in order to be versatile paving the way for new updated, extended, and refined labeling protocols and also for the extension of this approach on the study of whichever matrix.


Multiple integration Quantitative analysis NMR Food chemical label Olive oil 


Compliance and Ethical Standards

Conflict of Interest

Archimede Rotondo declares that he has no conflict of interest; Luisa Mannina declares that she has no conflict of interest; Andrea Salvo declares that he has no conflict of interest.

Ethical Approval

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

Informed Consent

Not applicable.

Supplementary material

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  1. Alonso-Salces RM, Moreno-Rojas JM, Holland MV, Reniero F, Guillou C, Héberger C (2010) Virgin olive oil authentication by multivariate analyses of 1H NMR fingerprints and δ13C and δ2H data. J Agric Food Chem 58:5586–5596CrossRefGoogle Scholar
  2. Barison A, Pereira da Silva CW, Ramos Campos F, Simonelli F, Lenz CA, Ferreira AG (2010) A simple methodology for the determination of fatty acid composition in edible oils through 1H NMR spectroscopy. Magn Reson Chem 48:642–650Google Scholar
  3. Carvalho MS, Mendonça MA, Pinho DMM, Resckc IS, Suarez PAZ (2012) Chromatographic analyses of fatty acid methyl esters by HPLC-UV and GC-FID. J Braz Chem Soc 23(4):763–769CrossRefGoogle Scholar
  4. Castejón D, Mateos-Aparicio I, Molero MD, Cambero MI, Herrera A (2014) Evaluation and optimization of the analysis of fatty acid types in edible oils by 1H-NMR. Food Anal Methods 7:1285–1297CrossRefGoogle Scholar
  5. Castejón D, Fricke P, Cambero MI, Herrera A (2016) Automatic 1H-NMR screening of fatty acid composition in edible oils. Nutrients 8:93. CrossRefGoogle Scholar
  6. Cevallos-Cevallos JM, Reyes-De-Corcueraa JI, Etxeberria E, Danyluka MD, Rodrick GE (2009) Metabolomic analysis in food science: a review. Trends Food Sci Technol 20:557–566CrossRefGoogle Scholar
  7. Dugo G, Rotondo A, Mallamace D, Cicero N, Salvo A, Rotondo E, Corsaro C (2015) Enhanced detection of aldehydes in Extra-Virgin Olive Oil by means of band selective NMR spectroscopy. Physica A 420:258–264CrossRefGoogle Scholar
  8. EU No. 29/2012 Commission Implementing Regulation. Available online: (accessed on 27 July 2018)Google Scholar
  9. EU No. 1833/2015 (2015) European Union Commission. Off. Regulation EU no. 1833/2015 on the characteristics of olive oil and olive-residue oil and on the relevant methods of analysis. Off J Eur Communities L266:29–52Google Scholar
  10. Jiang B, Xiao M, Liu HL, Zhou ZM, Mao XA, Liu ML (2008) Optimized quantitative DEPT and quantitative POMMIE experiments for C-13 NMR. Anal Chem 80:8293–8298. CrossRefGoogle Scholar
  11. Laghi L, Picone G, Capozzi F (2014) Nuclear magnetic resonance for foodomics beyond food analysis. Trends Anal Chem 59:93–102CrossRefGoogle Scholar
  12. Laincer F, Iaccarino N, Amato J, Pagano B, Pagano A, Tenore G, Tamendjari A, Rovellini P, Venturini S, Bellan G, Ritieni A, Mannina L, Novellino E, Randazzo A (2016) Characterization of monovarietal extra virgin olive oils from the province of Béjaïa (Algeria). Food Res Int 89:1123–1133CrossRefGoogle Scholar
  13. Liland KH (2011) Multivariate methods in metabolomics – from pre-processing to dimension reduction and statistical analysis. Tr Anal Chem 30(6):827–841CrossRefGoogle Scholar
  14. Mannina L, Sobolev AP (2011) High resolution NMR characterization of olive oils in terms of quality, authenticity and geographical origin. Magn Reson Chem 49:S3–S11CrossRefGoogle Scholar
  15. Mannina L, Luchinat C, Patumi M, Emanuele MC, Rossi E, Segre A (2000) Concentration dependence of 13C NMR spectra of triglycerides: implications for the NMR analysis of olive oils. Magn Reson Chem 38:886–890CrossRefGoogle Scholar
  16. Marcone MF, Wang S, Albabish W, Nie S, Somnarain D, Hill A (2013) Diverse food-based applications of nuclear magnetic resonance (NMR) technology. Food Res Int 51:729–747CrossRefGoogle Scholar
  17. Monakhova YB, Kuballa T, Lachenmeier DW (2013) Chemometric methods in NMR spectroscopic analysis of food products. J Anal Chem 68(9):755–766CrossRefGoogle Scholar
  18. Monakhova YB, Tsikin AM, Kuballa T, Lachenmeier DW, Mushtakova SP (2014) Independent component analysis (ICA) algorithms for improved spectral deconvolution of overlapped signals in 1H NMR analysis: application to foods and related products. Magn Reson Chem 52:231–240CrossRefGoogle Scholar
  19. Naccari C, Rando R, Salvo A, Donato D, Bartolomeo G, Mangano V, Lo Turco V, Dugo G (2017) Study on the composition and quality of several Sicilian EVOOs (harvesting year 2015). Riv Ital Sostanze Gr 94:231–237Google Scholar
  20. Pauli GF, Jaki BU, Lankin DC (2005) Quantitative 1H NMR: development and potential of a method for natural products analysis. J Nat Prod 68:133–149CrossRefGoogle Scholar
  21. Rongai D, Sabatini N, Del Coco L, Perri E, Del Re P, Simone N, Marchegiani D, Fanizzi FP (2017) 1H NMR and multivariate analysis for geographic characterization of commercial extra virgin olive oil: a possible correlation with climate data. Foods 6:96. CrossRefGoogle Scholar
  22. Retief L, McKenzie JM, Koch KR (2009) A novel approach to the rapid assignment of 13C NMR spectra of major components of vegetable oils such as avocado, mango kernel and macadamia nut oils. Magn Reson Chem 47:771–781CrossRefGoogle Scholar
  23. Rotondo A, Salvo A, Gallo V, Rastrelli L, Dugo G (2017) Quick unreferenced NMR quantification of squalene in vegetable oils. Eur J Lipid Sci Technol 119(11):1–6. CrossRefGoogle Scholar
  24. Rotondo A, Salvo A, Giuffrida D, Dugo G., Rotondo E. (2011) NMR analysis of aldehydes in sicilian extra-virgin olive oils by DPFGSE techniques. Atti Accademia Peloritana dei Pericolanti ISSN: 1825–1242, 89(C1A8901002):1–7;
  25. Ruiz-Aracama A, Goicoechea E, Guillén MD (2017) Direct study of minor extra-virgin olive oil components without any sample modification. 1H NMR multisupression experiment: a powerful tool. Food Chem 228:301–314CrossRefGoogle Scholar
  26. Salvo A, Rotondo A, La Torre GL, Cicero N, Dugo G (2017) Determination of 1,2/1,3-diglycerides in Sicilian extra-virgin olive oils by 1H-NMR over a one-year storage period. Nat Prod Res 31:822–828CrossRefGoogle Scholar
  27. Simmler C, Napolitano JG, McAlpine JB, Chen S-N, Pauli GF (2014) Universal quantitative NMR analysis of complex natural samples. Curr Opin Biotechnol 25:51–59CrossRefGoogle Scholar
  28. Vlahov G, Schiavone C, Simone N (2001) Quantitative 13C NMR method using the DEPT pulse sequence for the determination of the geographical origin (DOP) of olive oils. Magn Reson Chem 39:689–695CrossRefGoogle Scholar
  29. Zhang H, Wang Z, Liu O (2015) Development and validation of a GC–FID method for quantitative analysis of oleic acid and related fatty acids. J Pharm Analysis 5:223–230CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Department of Biomedical and Dental Sciences and Morphofunctional ImagingUniversity of MessinaMessinaItaly
  2. 2.Department of Chemistry and Drug TechnologyUniversity of Roma “La Sapienza”RomeItaly

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