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Simultaneous analysis of natural pigments and E-141i in olive oils by liquid chromatography–tandem mass spectrometry

  • Ane Arrizabalaga-Larrañaga
  • Pilar Rodríguez
  • Mireia Medina
  • F. Javier Santos
  • Encarnación MoyanoEmail author
Research Paper

Abstract

This work describes the development of an ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) method for the determination of carotenoids (β-carotene, lutein, β-criptoxanthin, neoxanthin, violaxanthin) and chlorophylls, as well as their related compounds (chlorophyll A and B, pheophytin A and B and the banned dyes Cu–pyropheophytin A, Cu–pheophytin A and B) in olive oils. For this purpose, the feasibility of electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) for the ionization of these compounds was evaluated and compared. Tandem mass spectrometry (MS/MS) fragmentation was discussed for each family of compounds, and the most characteristic and abundant product ions were selected to propose a selective and sensitive UHPLC–MS/MS method. The best results were obtained using APCI and APPI, while ESI provided the worst signal-to-noise ratio (S/N) for all compounds. For the analysis of olive oils, a simple solid-phase extraction (SPE) with silica cartridges was applied before the determination by UHPLC–MS/MS (APCI and APPI) in multiple reaction monitoring (MRM) mode. Method quality parameters were stablished, and the results demonstrate the good performance of the new methods, providing low limits of detection (0.004–0.9 mg L−1), high extraction efficiencies (62–95%) and low matrix effects (< 25%). The developed UHPLC–API–MS/MS (APCI and APPI) methods were applied to the analysis of olive oil samples, and β-carotene, pheophytin A, pheophytin B and lutein were detected and quantified in all of them at concentrations ranging from 0.1 to 9.5 mg L−1.

Graphical abstract

Keywords

Natural pigments Olive oil Atmospheric pressure chemical ionization Atmospheric pressure photoionization Ultra-high-performance liquid chromatography–tandem mass spectrometry 

Notes

Funding information

The authors gratefully acknowledge the financial support received from the Spanish Ministry of Economy and Competitiveness under the project CTQ2015-63968-C2-P and from the Agency for Management of University and Research Grants (Government of Catalonia, Spain) under the project 2017SGR-310. Ane Arrizabalaga Larrañaga also thanks the Agency for Management of University and Research Grants (Government of Catalonia) and to the European Social Fund for the PhD FI–DGR fellowship.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

216_2019_1939_MOESM1_ESM.pdf (415 kb)
ESM 1 (PDF 414 kb)

References

  1. 1.
    International Olive Oil Council, RES-2/91-IV-04, trade standard applying to table olives, 2004.Google Scholar
  2. 2.
    Roca M, Gallardo-Guerrero L, Mínguez-Mosquera MI, Rojas BG. Control of olive oil adulteration with copper-chlorophyll derivatives. J Agric Food Chem. 2010;58:51–6.CrossRefGoogle Scholar
  3. 3.
    Fang M, Tsai CF, Wu GY, Tseng SH, Cheng HF, Kuo CH, et al. Identification and quantification of Cu-chlorophyll adulteration of edible oils. Food Addit Contam Part B. 2015;8:157–62.CrossRefGoogle Scholar
  4. 4.
    Luaces P, Pérez AG, García JM, Sanz C. Effects of heat-treatments of olive fruit on pigment composition of virgin olive oil. Food Chem. 2015;90:169–74.CrossRefGoogle Scholar
  5. 5.
    Buckle KA, Edwards RA. Chlorophyll, colour and pH changes H.T.S.T. processed green pea puree. J Food Technol. 1970;5:173–86.CrossRefGoogle Scholar
  6. 6.
    Demmig-Adams B, Gilmore AM, Adams WW. In vivo functions of carotenoids in higher plants. FASEB J. 1996;10:403–12.CrossRefGoogle Scholar
  7. 7.
    Mangos TJ, Berger RG. Determination of major chlorophyll degradation products. Z Leb Unters Forsch A. 1997;204:345–50.CrossRefGoogle Scholar
  8. 8.
    Weemaes CA, Ooms V, Van Loey AM, Hendrickx ME. Kinetics of chlorophyll degradation and color loss in heated broccoli juice. J Agric Food Chem. 1999;47:2404–9.CrossRefGoogle Scholar
  9. 9.
    Jones ID, White RC, Gibbs E, Butler LS, Nelson LA. Experimental formation of zinc and copper complexes of chlorophyll derivatives in vegetable tissue by thermal processing. J Agric Food Chem. 1977;25:149–53.CrossRefGoogle Scholar
  10. 10.
    Council decision (EU) 1333/2008 of 16 December 2008 on food additives. Off J Eur Communities L 354, 2008, 1–342.Google Scholar
  11. 11.
    Mínguez-Mosquera MI, Gandul-Rojas B, Gallardo-Guerrero ML. Rapid method of quantification of chlorophylls and carotenoids in virgin olive oil by high-performance liquid chromatography. J Agric Food Chem. 1992;40:60–3.CrossRefGoogle Scholar
  12. 12.
    Mateos R, García-Mesa JA. Rapid and quantitative extraction method for the determination of chlorophylls and carotenoids in olive oil by high-performance liquid chromatography. Anal Bioanal Chem. 2006;385:1247–54.CrossRefGoogle Scholar
  13. 13.
    Giuffrida D, Salvo F, Salvo A, La Pera L, Dugo G. Pigments composition in monovarietal virgin olive oils from various sicilian olive varieties. Food Chem. 2007;101:833–7.CrossRefGoogle Scholar
  14. 14.
    Criado MN, Romero MP, Motilva MJ. Effect of the technological and agronomical factors on pigment transfer during olive oil extraction. J Agric Food Chem. 2007;55:5681–8.CrossRefGoogle Scholar
  15. 15.
    Kao TH, Huang SC, Inbaraj BS, Chen BH. Determination of flavonoids and saponins in Gynostemma pentaphyllum (Thunb.) Makino by liquid chromatography-mass spectrometry. Anal Chim Acta. 2008;626:200–11.CrossRefGoogle Scholar
  16. 16.
    Mendes-Pinto MM, Silva Ferreira AC, Caris-Veyrat C, De Pinho PG. Carotenoid, chlorophyll, and chlorophyll-derived compounds in grapes and port wines. J Agric Food Chem. 2005;53:10034–41.CrossRefGoogle Scholar
  17. 17.
    De Rosso VV, Mercadante AZ. Identification and quantification of carotenoids, by HPLC-PDA-MS/MS, from Amazonian fruits. J Agric Food Chem. 2007;55:5062–72.CrossRefGoogle Scholar
  18. 18.
    Aparicio-Ruiz R, Riedl KM, Schwartz SJ. Identification and quantification of metallo-chlorophyll complexes in bright green table olives by high-performance liquid chromatography-mass spectrometry quadrupole/time-of-flight. J Agric Food Chem. 2011;59:11100–8.CrossRefGoogle Scholar
  19. 19.
    Zvezdanovic JB, Petrovic SM, Markovic DZ, Andjelkovic TD, Andjelkovic DH. Electrospray ionization mass spectrometry combined with ultra high performance liquid chromatography in the analysis of in vitro formation of chlorophyll complexes with copper and zinc. J Serb Chem Soc. 2014;79:689–706.CrossRefGoogle Scholar
  20. 20.
    Rivera SM, Christou P, Canela-Garayoa R. Identification of carotenoids using mass spectrometry. Mass Spectrom Rev. 2014;33:353–72.CrossRefGoogle Scholar
  21. 21.
    Schwartz SJ, Woo SL, von Elbe JH. High-performance liquid chromatography of chlorophylls and their derivatives in fresh and processed spinach. J Agric Food Chem. 1981;29:533–5.CrossRefGoogle Scholar
  22. 22.
    Kuronen P, Hyvärinen K, Hynninen PH, Kilpeläinen I. High-performance liquid chromatographic separation and isolation of the methanolic allomerization products of chlorophyll a. J Chromatogr A. 1993;654:93–104.CrossRefGoogle Scholar
  23. 23.
    Gross JH, Eckert A, Sierbert W. Negative-ion electrospray mass spectrometry of carbon dioxide-protected N-heterocyclic anions. J Mass Spectrom. 2002;37:541–643.CrossRefGoogle Scholar
  24. 24.
    Liu D, Gao Y, Kispert LD. Electrochemical properties of natural carotenoids. J Electroanal Chem. 2000;488:140–50.CrossRefGoogle Scholar
  25. 25.
    Cole RB, editor. Electrospray and MALDI mass spectrometry: fundamentals, instrumentation, practicalities, and biological applications. second ed. New York: Wiley; 2010.Google Scholar
  26. 26.
    Nakato Y, Chiyoda T, Tsubomura H. Experimental determination of ionization potentials of organic amines, b-carotene and chlorophyll a. Bull Chem Soc Jpn. 1974;47:3001–5.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Ane Arrizabalaga-Larrañaga
    • 1
  • Pilar Rodríguez
    • 2
  • Mireia Medina
    • 2
  • F. Javier Santos
    • 1
  • Encarnación Moyano
    • 1
    Email author
  1. 1.Department of Chemical Engineering and Analytical ChemistryUniversity of BarcelonaBarcelonaSpain
  2. 2.Laboratori AgroalimentariGeneralitat de CatalunyaCabrilsSpain

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