Targeted analysis for detection the adulteration in extra virgin olive oil’s using LC-DAD/ESI–MS/MS and combined with chemometrics tools

Abstract

The hand-held LC-DAD/ESI–MS/MS approach was employed, for the first time, for the quantification of extra virgin olive oil (EVOO) adulteration with refined pomace olive oil (RPOO). The total polyphenols (TP) and sterols were quantified according to their chemical methods, with more reliable methods required in this field to avoid undue dependence on chlorophylls, carotenoids contents and antioxidant activity (DPPH assays), which were evaluated by spectrophotometric methods. Some differences concerning the antioxidant activity and the TP content were observed. Actually, Chemlali EVOO activity was the most pronounced (13.84 ± 0.21%) and it contained the highest TP content (284.54 ± 4.27 mg/kg). Indeed, a correlation between antioxidant activity, TP and oxidative stability was established herewith. The metabolomics data were elaborated with the help of chemometric tools i.e. principal component analysis (PCA) and hierarchical cluster analysis (HCA). This approach allowed the estimation of the best discrimination markers for EVOO authenticity evaluation (i.e. Hydroxytyrosol quinone, oxidized hydroxytyrosol, 3,4-DHPEA-EA, p-HPEA (tyrosol), p-coumaric acid, luteolin, decarboxymethyl 10-hydroxyoleuropein aglycon, β-sitosterol apparently; campesterol, stigmasterol, ∆-7-stigmastenol and ∆-7-avenasterol).

Graphic abstract

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Abbreviations

EVOO:

Extra virgin olive oil

RPOO:

Refined pomace olive oil

TP:

Total Polyphenols

PCA:

Principal component analysis

HCA:

Hierarchical cluster analysis

IOC:

International olive Council

FID:

Flame ionization detector

FAEEs:

Fatty acid ethyl ester

DPPH radical:

Free radical 2,2-diphenyl-1- picrylhydrazyl

References

  1. 1.

    Romani A, Ieri F, Urciuoli S et al (2019) Health effects of phenolic compounds found in extra-virgin olive oil, by-products, and leaf of Olea europaea L. Nutrients. https://doi.org/10.3390/nu11081776

    Article  PubMed  PubMed Central  Google Scholar 

  2. 2.

    Tuberoso CIG, Jerković I, Maldini M, Serreli G (2016) Phenolic compounds, antioxidant activity, and other characteristics of extra virgin olive oils from Italian autochthonous varieties Tonda di Villacidro, Tonda di Cagliari, Semidana, and Bosana. In: J. Chem. https://www.hindawi.com/journals/jchem/2016/8462741/. Accessed 27 Apr 2020

  3. 3.

    Bendini A, Cerretani L, Di Virgilio F et al (2007) Preliminary evaluation of the application of the ftir spectroscopy to control the geographic origin and quality of virgin olive oils. J Food Qual 30:424–437. https://doi.org/10.1111/j.1745-4557.2007.00132.x

    CAS  Article  Google Scholar 

  4. 4.

    García-Villalba R, Carrasco-Pancorbo A, Oliveras-Ferraros C et al (2010) Characterization and quantification of phenolic compounds of extra-virgin olive oils with anticancer properties by a rapid and resolutive LC-ESI-TOF MS method. J Pharm Biomed Anal 51:416–429. https://doi.org/10.1016/j.jpba.2009.06.021

    CAS  Article  PubMed  Google Scholar 

  5. 5.

    Becerra-Herrera M, Sanchez-Astudillo M, Beltran R, Sayago A (2014) Determination of phenolic compounds in olive oil: new method based on liquid-liquid micro extraction and ultra high performance liquid chromatography-triple-quadrupole mass spectrometry. FOOD Sci Technol -ZURICH- 57:49–57

    CAS  Google Scholar 

  6. 6.

    Saba A, Mazzini F, Raffaelli A et al (2005) Identification of 9(E),11(E)-18:2 fatty acid methyl ester at trace level in thermal stressed olive oils by GC coupled to acetonitrile CI-MS and CI-MS/MS, a possible marker for adulteration by addition of deodorized olive oil. J Agric Food Chem 53:4867–4872. https://doi.org/10.1021/jf050274b

    CAS  Article  PubMed  Google Scholar 

  7. 7.

    Al-Ismail KM, Alsaed AK, Ahmad R, Al-Dabbas M (2010) Detection of olive oil adulteration with some plant oils by GLC analysis of sterols using polar column. Food Chem 121:1255–1259. https://doi.org/10.1016/j.foodchem.2010.01.016

    CAS  Article  Google Scholar 

  8. 8.

    Drira M, Jabeur H, Marrakchi F, Bouaziz M (2018) Delta-7-stigmastenol: quantification and isomeric formation during chemical refining of olive pomace oil and optimization of the neutralization step. Eur Food Res Technol. https://doi.org/10.1007/s00217-018-3132-2

    Article  Google Scholar 

  9. 9.

    Jabeur H, Drira M, Rebai A, Bouaziz M (2017) Putative markers of adulteration of higher-grade olive oil with less expensive pomace olive oil by GC Combined with chemometrics. J Agric Food Chem. https://doi.org/10.1021/acs.jafc.7b00687

    Article  PubMed  Google Scholar 

  10. 10.

    Lukić M, Lukić I, Krapac M et al (2013) Sterols and triterpene diols in olive oil as indicators of variety and degree of ripening. Food Chem 136:251–258. https://doi.org/10.1016/j.foodchem.2012.08.005

    CAS  Article  PubMed  Google Scholar 

  11. 11.

    Guillaume C, Ravetti L, Ray DL, Johnson J (2012) Technological factors affecting sterols in Australian olive oils. J Am Oil Chem Soc 89:29–39. https://doi.org/10.1007/s11746-011-1883-z

    CAS  Article  Google Scholar 

  12. 12.

    Rivera del Álamo RM, Fregapane G, Aranda F et al (2004) Sterol and alcohol composition of Cornicabra virgin olive oil: the campesterol content exceeds the upper limit of 4% established by EU regulations. Food Chem 84:533–537. https://doi.org/10.1016/S0308-8146(03)00275-9

    CAS  Article  Google Scholar 

  13. 13.

    Fragaki G, Spyros A, Siragakis G et al (2005) Detection of extra virgin olive oil adulteration with lampante olive oil and refined olive oil using nuclear magnetic resonance spectroscopy and multivariate statistical analysis. J Agric Food Chem 53:2810–2816. https://doi.org/10.1021/jf040279t

    CAS  Article  PubMed  Google Scholar 

  14. 14.

    Mannina L, D’Imperio M, Capitani D et al (2009) 1H NMR-based protocol for the detection of adulterations of refined olive oil with refined hazelnut oil. J Agric Food Chem 57:11550–11556. https://doi.org/10.1021/jf902426b

    CAS  Article  PubMed  Google Scholar 

  15. 15.

    Torrecilla JS, García J, García S, Rodríguez F (2011) Quantification of adulterant agents in extra virgin olive oil by models based on its thermophysical properties. J Food Eng 103:211–218. https://doi.org/10.1016/j.jfoodeng.2010.10.017

    CAS  Article  Google Scholar 

  16. 16.

    Drira M, Jabeur H, Bouaziz M (2018) Chemometric characterization of chemlali extra-virgin olive oil adulteration mixed with soybean oil, corn oil and sunflower oil. Proc MOL2NET 2018 Int Conf Multidiscip Sci 4th Ed 1. https://doi.org/10.3390/mol2net-04-06074

  17. 17.

    Selli S, Kelebek H, Kesen S, Sonmezdag AS (2018) GC-MS olfactometric and LC-DAD-ESI-MS/MS characterization of key odorants and phenolic compounds in black dry-salted olives. J Sci Food Agric 98:4104–4111. https://doi.org/10.1002/jsfa.8927

    CAS  Article  PubMed  Google Scholar 

  18. 18.

    COI/T.20/Doc.No28/ Rev.2 (2017) Determination of the content of waxes fatty acid methyl esters and fatty acid ethyl esters by capillary gas chromatography

  19. 19.

    COI/T.20/Doc. No. 30/Rev.2 (2017) Determination of the composition and content of sterols and triterpene dialcohols by capillary column gas chromatography.

  20. 20.

    Gargouri B, Ammar S, Zribi A et al (2013) Effect of growing region on quality characteristics and phenolic compounds of chemlali extra-virgin olive oils. Acta Physiol Plant 35:2801–2812. https://doi.org/10.1007/s11738-013-1312-z

    CAS  Article  Google Scholar 

  21. 21.

    Bouaziz M, Feki I, Ayadi M et al (2010) Stability of refined olive oil and olive-pomace oil added by phenolic compounds from olive leaves. Eur J Lipid Sci Technol 112:894–905. https://doi.org/10.1002/ejlt.200900166

    CAS  Article  Google Scholar 

  22. 22.

    Chtourou M, Gargouri B, Jaber H et al (2013) Comparative study of olive oil quality from Chemlali Sfax versus Arbequina cultivated in Tunisia. Eur J Lipid Sci Technol 115:631–640. https://doi.org/10.1002/ejlt.201200234

    CAS  Article  Google Scholar 

  23. 23.

    International Olive Council (2018) Trade standard applying to olive oils and olive-pomace oils. COIT15NC No 3Rev12

  24. 24.

    Jabeur H, Zribi A, Makni J et al (2014) Detection of Chemlali extra-virgin olive oil adulteration mixed with soybean oil, corn oil, and sunflower oil by using GC and HPLC. J Agric Food Chem 62:4893–4904. https://doi.org/10.1021/jf500571n

    CAS  Article  PubMed  Google Scholar 

  25. 25.

    COI/T, 20/Doc. No. 30 (2013) Determination of the composition and content of sterols and triterpene dialcohols by capillary column gas chromatography

  26. 26.

    European Union Commission Regulation EEC/2568/91 (2013) Characteristics of olive and olive pomace oils and their analytical methods and subsequent amendments (latest: EU Commission Implementing Regulation 1348/2013 of the Commission of 16 December. EU J L 338:31–67

    Google Scholar 

  27. 27.

    COI/T, 20/Doc. No. 28 (2009) Determination of the content of waxes fatty acid methyl esters and fatty acid ethyl esters by capillary gas chromatography

  28. 28.

    Vekiari SA, Oreopoulou V, Kourkoutas Y, et al Characterization and seasonal variation of the quality of virgin olive oil of the Throumbolia and Koroneiki varieties from southern Greece. Grasas Aceites 61:221–231

  29. 29.

    Aparicio-Ruiz R, Harwood J (2013) Handbook of olive oil, Texte d’origine: analysis and properties, 2nd edn. Springer, US

    Google Scholar 

  30. 30.

    Lazzez A, Perri E, Caravita MA et al (2008) Influence of olive maturity stage and geographical origin on some minor components in virgin olive oil of the chemlali variety. J Agric Food Chem 56:982–988. https://doi.org/10.1021/jf0722147

    CAS  Article  PubMed  Google Scholar 

  31. 31.

    Boulkroune H, Lazzez A, Guissous M et al (2017) Characterization of sterolic and alcoholic fractions of some Algerian olive oils according to the variety and ripening stage. OCL 24:A502. https://doi.org/10.1051/ocl/2017026

    Article  Google Scholar 

  32. 32.

    Costa R, Bartolomeo G, Saija E, et al (2017) Determination of alkyl esters content in PDO Extra virgin olive oils from Sicily. J Food Qual. https://www.hindawi.com/journals/jfq/2017/3078105/. Accessed 4 May 2020

  33. 33.

    Jabeur H, Zribi A, Abdelhedi R, Bouaziz M (2015) Effect of olive storage conditions on Chemlali olive oil quality and the effective role of fatty acids alkyl esters in checking olive oils authenticity. Food Chem 169:289–296. https://doi.org/10.1016/j.foodchem.2014.07.118

    CAS  Article  PubMed  Google Scholar 

  34. 34.

    Mansour AB, Gargouri B, Flamini G, Bouaziz M (2015) Effect of agricultural sites on differentiation between Chemlali and Neb Jmel olive oils. J Oleo Sci 64:381–392. https://doi.org/10.5650/jos.ess14204

    CAS  Article  PubMed  Google Scholar 

  35. 35.

    Servili M, Selvaggini R, Esposto S et al (2004) Health and sensory properties of virgin olive oil hydrophilic phenols: agronomic and technological aspects of production that affect their occurrence in the oil. J Chromatogr A 1054:113–127. https://doi.org/10.1016/j.chroma.2004.08.070

    CAS  Article  PubMed  Google Scholar 

  36. 36.

    Krishna AGG, Khatoon S, Shiela PM et al (2001) Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil. J Am Oil Chem Soc 78:127–131. https://doi.org/10.1007/s11746-001-0232-0

    CAS  Article  Google Scholar 

  37. 37.

    Nergíz C (1993) The effect of refining processes on the total polyphenol and 1,2-diphenol content of olive oil. Int J Food Sci Technol 28:461–464. https://doi.org/10.1111/j.1365-2621.1993.tb01295.x

    Article  Google Scholar 

  38. 38.

    Cortesi N, Ponziani A, Fedeli E (1981) Caratterizzazione degli oli vergini e raffinati mediante HPLC dei componenti polari. Nota preliminare, Riv Ital Delle Sostanze Grasse

    Google Scholar 

  39. 39.

    Vazquez-Roncero A, Janer del Valle C, Janer del Valle ML (1973) Determinacion de los polifenoles totales del aceite de oliva. Grasas Aceites

  40. 40.

    García A, Ruiz-Méndez MV, Romero C, Brenes M (2006) Effect of refining on the phenolic composition of crude olive oils. J Am Oil Chem Soc 83:159–164. https://doi.org/10.1007/s11746-006-1189-8

    Article  Google Scholar 

  41. 41.

    El-Gharbi S, Tekaya M, Bendini A et al (2018) Effects of geographical location on chemical properties of Zarazi virgin olive oil produced in the South of Tunisia. Am J Food Sci Technol 6:228–236. https://doi.org/10.12691/ajfst-6-6-1

    CAS  Article  Google Scholar 

  42. 42.

    Sánchez de Medina V, Priego-Capote F, de Castro MDL (2015) Characterization of monovarietal virgin olive oils by phenols profiling. Talanta 132:424–432. https://doi.org/10.1016/j.talanta.2014.09.039

    CAS  Article  PubMed  Google Scholar 

  43. 43.

    Suárez M, Romero M-P, Ramo T et al (2009) Methods for preparing phenolic extracts from olive cake for potential application as food antioxidants. J Agric Food Chem 57:1463–1472. https://doi.org/10.1021/jf8032254

    CAS  Article  PubMed  Google Scholar 

  44. 44.

    Kelebek H, Selli S, Kola O (2017) Quantitative determination of phenolic compounds using LC-DAD-ESI-MS/MS in cv. Ayvalik olive oils as affected by harvest time. J Food Meas Charact 11:226–235. https://doi.org/10.1007/s11694-016-9389-x

    Article  Google Scholar 

  45. 45.

    Gianfrancesco M, Maurizio S, Maura B, Enrico M (1992) Simple and hydrolyzable phenolic compounds in virgin olive oil. 2. Initial characterization of the hydrolyzable fraction. J Agric Food Chem 40:1577–1580. https://doi.org/10.1021/jf00021a020

    Article  Google Scholar 

  46. 46.

    Drira M, Rekik O, Bouaziz M (2017) Tunisian olive oil: quality, composition and antioxidant properties. In: Olive Oil: Sensory Characteristics, Composition and Importance in Human Health, Nova Science Publishers. Thore Fritjof et Bertil Henning, pp 75–108

  47. 47.

    Bulotta S, Celano M, Lepore SM et al (2014) Beneficial effects of the olive oil phenolic components oleuropein and hydroxytyrosol: focus on protection against cardiovascular and metabolic diseases. J Transl Med 12:219. https://doi.org/10.1186/s12967-014-0219-9

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  48. 48.

    Ben Brahim S, Kelebek H, Ammar S et al (2017) LC–MS phenolic profiling combined with multivariate analysis as an approach for the characterization of extra virgin olive oils of four rare Tunisian cultivars during ripening. Food Chem 229:9–19. https://doi.org/10.1016/j.foodchem.2017.02.025

    CAS  Article  PubMed  Google Scholar 

  49. 49.

    Bouaziz M, Chamkha M, Sayadi S (2004) Comparative study on phenolic content and antioxidant activity during maturation of the olive cultivar Chemlali from Tunisia. J Agric Food Chem 52:5476–5481. https://doi.org/10.1021/jf0497004

    CAS  Article  PubMed  Google Scholar 

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Acknowledgements

The authors would like to thank the "Ministère de l’Enseingement Supérieur et de la Recherche Scientifique, Tunisia LR14ES08" and the National Funds through Ministry of Higher Education-Tunisia for financing MedOOmics Project—“Mediterranean Extra Virgin Olive Oil Omics: profiling and fingerprinting”—“Arimnet2/0001/2015”, They are also thankful to Mme. Mariem DRIRA for proofreading and polishing the language of the manuscript.

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Correspondence to Mohamed Bouaziz.

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Drira, M., Kelebek, H., Guclu, G. et al. Targeted analysis for detection the adulteration in extra virgin olive oil’s using LC-DAD/ESI–MS/MS and combined with chemometrics tools. Eur Food Res Technol 246, 1661–1677 (2020). https://doi.org/10.1007/s00217-020-03522-y

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Keywords

  • Extra virgin olive oil adulteration
  • Refined pomace olive oil
  • Correlation analysis
  • Phenolic compounds
  • LC-DAD-ESI–MS/MS
  • Chemometrics