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Determination of the Phenol and Tocopherol Content in Italian High-Quality Extra-Virgin Olive Oils by Using LC-MS and Multivariate Data Analysis

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Abstract

Italian extra-virgin olive oil market presents several kinds of products, some of which are of higher quality compared to others. Italian high-quality extra-virgin olive oils can have Protected Designation of Origin, Protected Geographical Identification and organic farming denominations. Each high-quality olive oil produced shows peculiar chemical composition and organoleptic characteristics. The present work was aimed to endorse the use of Italian high-quality extra-virgin olive oils and to promote the “Italian quality olive oil culture” to the consumers. To obtain this, task two analytical methods were developed in order to investigate the phenol and tocopherol contents in one hundred eighty-six high-quality extra-virgin olive oils by using HPLC coupled to mass spectrometry and fluorimetric detection, respectively. Olives milled to obtain these samples belong to forty-seven different cultivars. Furthermore, four different assays were used in order to evaluate antioxidant activity of all samples: TEAC, ORAC, FRAP, and DPPH, while the total phenols content was assessed by the Folin-Ciocalteu method. Finally, all these information were used to make a principal component analysis (PCA) in order to verify a possible correlation between oils belonging to the same region, or to the same cultivar, or to denomination. To the best of our knowledge, this is the first research article that reports the bioactive molecule content and a PCA statistical correlation between total phenol content, antioxidant activity (TEAC, FRAP, DPPH and ORAC), tocopherols and phenols in a large array of Italian high-quality extra-virgin olive oils (174) produced in different regions; in addition a number of 12 samples came from foreign countries (Portugal, Spain and Croatia). The gathered information attained could be useful for the generation of a database of a qualitative and quantitative profile of antioxidant molecules in extra-virgin olive.

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References

  • Alves FCGBS, Coqueiro A, Março PH, Valderrama P (2019) Evaluation of olive oils from the Mediterranean region by UV–Vis spectroscopy and independent component analysis. Food Chem 273:124–129

    Article  CAS  Google Scholar 

  • Belitz HD, Grosch W, Schieberle P (2009) Lipids. In: Food chemistry, 4th revised and extended edition. Springer-Verlag Berlin Heidelberg, Berlin, pp 158–247

  • Bendini A, Bonoli M, Cerretani L, Biguzzi B, Lercker G, Gallina Toschi T (2003) Liquid-liquid and solid-phase extractions of phenols from virgin olive oil and their separation by chromatographic and electrophoretic methods. J Chromatogr A 985:425–433

    Article  CAS  Google Scholar 

  • Bendini A, Cerretani L, Carrasco-Pancorbo A, Gómez-Caravaca AM, Segura-Carretero A, Fernández-Gutiérrez A, Lercker G (2007) Phenolic molecules in virgin olive oils: a survey of their sensory properties, health effects, antioxidant activity and analytical methods. An overview of the last decade. Molecules 12:1679–1719

    Article  CAS  Google Scholar 

  • Brigelius-Flohé R, Kelly FJ, Salonen JT, Neuzil J, Zingg JM, Azzi A (2002) The European perspective on vitamin E: current knowledge and future research. Am J Clin Nutr 76:703–716

    Article  Google Scholar 

  • Buettner GR (1993) The pecking order of free radicals and antioxidants: lipid peroxidation, alpha-tocopherol, and ascorbate. Arch Biochem Bioph 300:535–543

    Article  CAS  Google Scholar 

  • Capriotti AL, Cavaliere C, Crescenzi C, Foglia P, Nescatelli R, Samperi R, Laganà A (2014) Comparison of extraction methods for the identification and quantification of polyphenols in virgin olive oil by ultra-HPLC-QToF mass spectrometry. Food Chem 158:392–400

    Article  CAS  Google Scholar 

  • Cardoso SM, Guyot S, Marnet N, Lopes-da-Silva JA, Renard CMGC, Coimbra MA (2005) Characterisation of phenolic extracts from olive pulp and olive pomace by electrospray mass spectrometry. J Sci Food Agric 85:21–32

    Article  CAS  Google Scholar 

  • Carrasco-Pancorbo A, Cerretani L, Bendini A, Segura-Carretero A, Gallina-Toschi T, Fernàndez-Gutirrez A (2005) Analytical determination of polyphenols in olive oils. J Sep Sci 28:837–858

    Article  CAS  Google Scholar 

  • Cioffi G, Pesca MS, De Caprariis P, Braca A, Severino L, De Tommasi N (2010) Phenolic compounds in olive oil and olive pomace from Cilento (Campania, Italy) and their antioxidant activity. Food Chem 121:105–111

    Article  CAS  Google Scholar 

  • De La Torre-Carbot K, Jauregui O, Gimeno E, Castellote AI, Lamuela-Raventos RM, Lopez-Sabater MC (2005) Characterization and quantification of phenolic compounds in olive oils by solid-phase extraction, HPLC-DA, and HPLC-MS/MS. J Agric Food Chem 53:4331–4340

    Article  Google Scholar 

  • Di Serio MD, Di Giacinto L, Di Loreto G, Giansante L, Pellegrino M, Vito R, Perri E (2016) Chemical and sensory characteristics of Italian virgin olive oils from Grossa di Gerace cv. European Journal of Lipid Science and Technology 118(2):288–298

  • EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA); Scientific Opinion on the substantiation of health claims related to polyphenols in olive and protection of LDL particles from oxidative damage (ID 1333, 1638, 1639, 1696, 2865), maintenance of normal blood HDL-cholesterol concentrations (ID 1639), maintenance of normal blood pressure (ID 3781), “anti-inflammatory properties” (ID 1882), “contributes to the upper respiratory tract health” (ID 3468), “can help to maintain a normal function of gastrointestinal tract” (3779), and “contributes to body defences against external agents” (ID 3467) pursuant to Article 13(1) of Regulation (EC) No 1924/2006. EFSA Journal 2011; 9(4):2033, 25 pp. doi:https://doi.org/10.2903/j.efsa.2011.2033. Available online: www.efsa.europa.eu/efsajournal

  • EFSA NDA Panel (EFSA Panel on Dietetic Products, Nutrition and Allergies), 2015. Scientific Opinion on Dietary Reference Values for vitamin E as α-tocopherol. EFSA Journal 2015; 13(7):4149, 72 pp. doi:https://doi.org/10.2903/j.efsa.2015.4149. Available online: www.efsa.europa.eu/efsajournal

  • EU Regulation n. 1151/2012 of European Parliament and Council (2012) “Elenco delle denominazioni italiane, iscritte nel Registro delle denominazioni di origine protette, delle indicazioni geografiche protette e delle specialità tradizionali garantite”. Updated to November 7, 2019

  • Fanali C, Della Posta S, Vilmercati A, Dugo L, Russo M, Petitti T, Mondello L, De Gara L (2018) Extraction, analysis, and antioxidant activity evaluation of phenolic compounds in different Italian extra-virgin olive oils. Molecules 23:3249

    Article  Google Scholar 

  • Fiorini D, Boarelli MC, Conti P, Alfei B, Caprioli G, Ricciutelli M, Sagratini G, Fedeli D, Gabbianelli R, Pacetti D (2018) Chemical and sensory differences between high price and low price extra virgin olive oils. Food Res Int 105:65–75

    Article  CAS  Google Scholar 

  • Gimeno E, Castellote AI, Lamuela-Raventos RM, de la Torre MC, Lopez-Sabater MC (2000) Rapid determination of vitamin E in vegetable oils by reversed phase high-performance liquid chromatography. J Chromatogr A 881:251–254

    Article  CAS  Google Scholar 

  • Gómez-Rico A, Fregapane G, Desamparados Salvador M (2008) Effect of cultivar and ripening on minor components in Spanish olive fruits and their corresponding virgin olive oils. Food Res Int 41:433–440

    Article  Google Scholar 

  • Hokanson GC (1994) A life cycle approach to the validation of analytical methods during pharmaceutical product development, part I. the initial validation process. Pharm Technol 18:118–130

    CAS  Google Scholar 

  • Hosomi A, Arita M, Sato Y, Kiyose C, Ueda T, Igarashi O, Arai H, Inoue K (1997) Affinity for alpha-tocopherol transfer protein as a determinant of the biological activities of vitamin E analogs. FEBS Lett 409:105–108

    Article  CAS  Google Scholar 

  • Iqdiam BM, Mostafa H, Goodrich-Schneider R, Baker GL, Welt B, Marshall MR (2018) High power ultrasound: impact on olive paste temperature, malaxation time, extraction efficiency, and characteristics of extra virgin olive oil. Food Bioprocess Tech 11:634–644

    Article  CAS  Google Scholar 

  • Kalogeropoulos N, Tsimidou M (2014) Antioxidants in Greek Virgin Olive Oils. Antioxidants 3(2):387–413

  • Klikarová J, Rotondo A, Cacciola F, Česlová L, Dugo P, Mondello L, Rigano F (2019) The phenolic fraction of Italian extra virgin olive oils: elucidation through combined liquid chromatography and NMR approaches. Food Anal Methods 12:1759–1770

    Article  Google Scholar 

  • Massart DL, Vandeginste BGM, Buydens LMC, De Jong S, Lewi PJ, Smeyers-Verbeke J (eds) (1998) Handbook of Chemometrics and Qualimetrics. In: Data Handling in Science and Technology, So2, vol20. Elsevier, Amsterdam

  • Motilva MJ, Serra A, Macià A (2013) Analysis of food polyphenols by ultra high-performance liquid chromatography coupled to mass spectrometry: an overview. J Chromatogr A 1292:66–82

    Article  CAS  Google Scholar 

  • Niki E (2014) Role of vitamin E as a lipid-soluble peroxyl radical scavenger: in vitro and in vivo evidence. Free Radic Bio Med 66:3–12

    Article  CAS  Google Scholar 

  • Olmo-García L, Polari JJ, Li X, Bajoub A, Fernández-Gutiérrez A, Wang SC, Carrasco-Pancorbo A (2018) Deep insight into the minor fraction of virgin olive oil by using LC-MS and GC-MS multi-class methodologies. Food Chem 261:184–193

    Article  Google Scholar 

  • Pascale R, Bianco G, Cataldi TRI, Buchicchio A, Losito I, Altieri G, Genovese F, Tauriello A, Di Renzo GC, Lafiosca MC (2018) Investigation of the effects of virgin olive oil cleaning systems on the secoiridoid aglycone content using high performance liquid chromatography–mass spectrometry. J Am Chem Soc 95:665–671

    CAS  Google Scholar 

  • Pinheiro-Sant’Ana HM, Guinazi M, Oliveira DDS, Della Lucia CM, Reis BDL, Brandao SCC (2011) Method for simultaneous analysis of eight vitamin E isomers in various foods by high performance liquid chromatography and fluorescence detection. J Chromatogr A 1218:8496–8502

    Article  Google Scholar 

  • Pirisi FM, Angioni A, Cabras P, Garau VL, Sanjust di Teulada MT, Karim dos Santos M, Bandino G (1997) Phenolic compounds in virgin olive oils I. Low-wavelength quantitative determination of complex phenols by high-performance liquid chromatography under isocratic elution. J Chromatogr A 768:207–213

    Article  CAS  Google Scholar 

  • Piscopo A, Zappia A, De Bruno A, Poiana M (2018) Effect of the harvesting time on the quality of olive oils produced in Calabria. Eur J Lipid Sci Technol 120:1700304

    Article  Google Scholar 

  • Ricciutelli M, Marconi SM, Boarelli C, Caprioli G, Sagratini G, Ballini R, Fiorini D (2017) Olive oil polyphenols: a quantitative method by high-performance liquid-chromatography-diode-array detection for their determination and the assessment of the related health claim. J Chromatogr A 1481:53–63

    Article  CAS  Google Scholar 

  • Rupérez FJ, Martın D, Herrera E, Barbas C (2001) Chromatographic analysis of α-tocopherol and related compounds in various matrices. J Chromatogr A 935:45–69

    Article  Google Scholar 

  • Savarese M, De Marco E, Sacchi R (2007) Characterization of phenolic extracts from olives (Olea europaea cv. Pisciottana) by electrospray ionization mass spectrometry. Food Chem 105:761–770

    Article  CAS  Google Scholar 

  • Sordini B, Veneziani G, Servili M, Esposto S, Selvaggini R, Lorefice A, Taticchi A (2019) A quanti-qualitative study of a phenolic extract as a natural antioxidant in the frying processes. Food Chem 279:426–434

    Article  CAS  Google Scholar 

  • Špika JM, Kraljić K and Škevin D (2016) Tocopherols: Chemical Structure, Bioactivity, and Variability in Croatian Virgin Olive Oils. In: Boskou D, Clodoveo M L (eds) Products from Olive Tree. IntechOpen. https://doi.org/10.5772/64658

  • Suárez M, Macià A, Romero MP, Motilva MJ (2008) Improved liquid chromatography tandem mass spectrometry method for the determination of phenolic compounds in virgin olive oil. J Chromatogr A 1214:90–99

    Article  Google Scholar 

  • Traber MG, Atkinson J (2007) Vitamin E, antioxidant and nothing more. Free Radical Bio Med 43:4–15

    Article  CAS  Google Scholar 

  • Tsimidou MZ, Nenadis N, Mastralexi A, Servili M, Butinar B, Vichi S, Winkelmann O, García-González DL, Gallina Toschi T (2019) Toward a harmonized and standardized protocol for the determination of total hydroxytyrosol and tyrosol content in virgin olive oil (VOO). The pros of a fit for the purpose ultra high performance liquid chromatography (UHPLC) procedure. Molecules 24:2429

    Article  CAS  Google Scholar 

  • Wang X, Quinn PJ (1999) Vitamin E and its function in membranes. Prog Lipid Res 38:309–336

    Article  CAS  Google Scholar 

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Acknowledgments

Authors wish to thank Shimadzu Corporation for constantly supporting their research work.

Funding

The study was funded by Cariplo Foundation within the “Agroalimentare e Ricerca” (AGER) program. Project AGER2-Rif.2016–0169, “Valorizzazione dei prodotti italiani derivanti dall’oliva attraverso Tecniche Analitiche Innovative-VIOLIN”.

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All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by Filippo Mandolfino, Fabio Salafia, and Alessandra Vilmercati. Conceptualization: Marina Russo, Chiara Fanali, and Francesco Cacciola; Statistical analysis: Monica Casale; Writing – original draft preparation – review and editing: Marina Russo, Francesco Cacciola, Laura Dugo, Francesca Rigano, and Monica Casale; Supervision: Laura De Gara, Paola Dugo, and Luigi Mondello. The first draft of the manuscript was written by Marina Russo and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Marina Russo.

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Marina Russo declares that she has no conflict of interest. Francesco Cacciola declares that he has no conflict of interest. Filippo Mandolfino declares that he has no conflict of interest. Fabio Salafia declares that he has no conflict of interest. Alessandra Vilmercati declares that she has no conflict of interest. Chiara Fanali declares that she has no conflict of interest. Monica Casale declares that she has no conflict of interest. Laura De Gara declares that she has no conflict of interest. Paola Dugo declares that she has no conflict of interest. Luigi Mondello declares that he has no conflict of interest. Francesca Rigano declares that she has no conflict of interest.

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Dugo, L., Russo, M., Cacciola, F. et al. Determination of the Phenol and Tocopherol Content in Italian High-Quality Extra-Virgin Olive Oils by Using LC-MS and Multivariate Data Analysis. Food Anal. Methods 13, 1027–1041 (2020). https://doi.org/10.1007/s12161-020-01721-7

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