A metabolomics approach using LC TOF-MS to evaluate oxidation levels of edible oils

  • Katsuhito Hori
  • Fook Hee Koh
  • Kazunobu TsumuraEmail author


Accurate and reliable techniques to analyze oxidation levels of lipids are essential for the refining process and quality control in the edible oil industry. In the present study, we demonstrate a metabolomics approach for the determination of lipid oxidation levels, by photo-oxidation, using liquid chromatography time-of-flight mass spectrometry (LC TOF-MS) and multivariate analysis. Edible oils with different oxidation levels were used to prove the effectiveness of the developed technique. Critical markers, such as oxidized triacylglycerols, responsible for such variations, were detected through the corresponding loading weights, and the tentative identification of the compounds was supported by the accurate mass identification using the TOF-MS. The results revealed that the LC TOF-MS, coupled with a partial least squares model, can be successfully used to estimate the peroxide value of edible oils for effective quality control.


Edible oils LC TOF-MS Metabolomics Peroxide value 


Compliance with Ethical Standards

Conflict of Interest

Katsuhito Hori declares that he has no conflict of interest. Fook Hee Koh declares that he has no conflict of interest. Kazunobu Tsumura 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.


  1. Cañabate-Díaz B, Carretero AS, Fernández-Gutiérrez A, Vega AB, Frenich AG, Vidal JM, Martos JD (2007) Separation and determination of sterols in olive oil by HPLC-MS. Food Chem 102(3):593–598CrossRefGoogle Scholar
  2. Choe E, Min DB (2006) Mechanisms and factors for edible oil oxidation. Compr Rev Food Sci Food Saf 5(4):169–186CrossRefGoogle Scholar
  3. Cvaliere B, De Nino A, Hayet F, Lazez A, Macchione B, Moncef C, Perri E, Sindona G, Tagarelli A (2007) A metabolomic approach to the evaluation of the origin of extra virgin olive oil: a convenient statistical treatment of mass spectrometric analytical data. J Agric Food Chem 55(4):1454–1462CrossRefGoogle Scholar
  4. Gray JI (1978) Measurement of lipid oxidation: a review. J Am Oil Chem Soc 55(6):539–546CrossRefGoogle Scholar
  5. Herrera LC, Ramaley L, Potvin MA, Melanson JE (2013) A method for determining regioisomer abundances of polyunsaturated triacylglycerols in omega-3 enriched fish oils using reversed-phase liquid chromatography and triple-stage mass spectrometry. Food Chem 139(1-4):655–662CrossRefGoogle Scholar
  6. Hori K, Koriyama N, Omori H, Kuriyama M, Arishima T, Tsumura K (2012) Simultaneous determination of 3-MCPD fatty acid esters and glycidol fatty acid esters in edible oils using liquid chromatography time-of-flight mass spectrometry. LWT 48(2):204–208CrossRefGoogle Scholar
  7. Hori K, Kiriyama T, Tsumura K (2016) A liquid chromatography time-of-flight mass spectrometry-based metabolomics approach for the discrimination of cocoa beans from different growing regions. Food Anal Methods 9(3):738–743CrossRefGoogle Scholar
  8. Ito J, Mizuochi S, Nakagawa K, Kato S, Miyazawa T (2015) Tandem mass spectrometry analysis of linoleic and arachidonic acid hydroperoxides via promotion of alkali metal adduct formation. Anal Chem 87(9):4980–4987CrossRefGoogle Scholar
  9. Ito J, Shimizu N, Kobayashi E, Hanzawa Y, Otoki Y, Kato S, Hirokawa T, Kuwahara S, Miyazawa T, Nakagawa K (2017) A novel chiral stationary phase LC-MS/MS method to evaluate oxidation mechanisms of edible oils. Sci Rep 7(1):10026CrossRefGoogle Scholar
  10. Japan Oil Chemists’ Society 2018 Standard Methods for the Analysis of Fats, Oils and Related Materials (The JOCS Standard Methods, Tokyo, JapanGoogle Scholar
  11. Jumhawan U, Putri SP, Yusianto Y, Marwanni E, Bamba T, Fukusaki E (2013) Selection of discriminant marker for authentication of Asian palm civet coffee (Kopi Luwak): a metabolomics approach. J Agric Food Chem 61(33):7994–8001CrossRefGoogle Scholar
  12. Jumtee K, Bamba T, Fukusaki E (2009) Fast GC-FID based metabolic fingerprinting of Japanese green tea leaf for its quality ranking prediction. J Sep Sci 32(13):2296–2304CrossRefGoogle Scholar
  13. Jung Y, Lee J, Kwon J, Lee KS, Ryu DH, Hwang GH (2010) Discrimination of the geographical origin of beef by 1H NMR-based metabolomics. J Agric Food Chem 58(19):10458–10466CrossRefGoogle Scholar
  14. Keszler Á, Héberger K, Gude M (1998) Identification of volatile compounds in sunflower oil by headspace SPME and ion-trap GC/MS. J High Resolut Chromatogr 21(6):368–370CrossRefGoogle Scholar
  15. Lipp EM, Anklam E (1998) Review of cocoa butter and alternative fats for use in chocolate—part A. Compositional data. Food Chem 62(1):73–97CrossRefGoogle Scholar
  16. Lísa M, Holčapek M (2008) Triacylglycerols profiling in plant oils important in food industry, dietetics and cosmetics using high-performance liquid chromatography–atmospheric pressure chemical ionization mass spectrometry. J Chromatogr A 1198:115–130CrossRefGoogle Scholar
  17. Ochi H, Naito H, Iwatsuki K, Bamba T, Fukusaki E (2012) Metabolomics-based component profiling of hard and semi-hard natural cheeses with gas chromatography/time-of-flight-mass spectrometry, and its application to sensory predictive modeling. J Biosci Bioeng 113(6):751–758CrossRefGoogle Scholar
  18. Ono D, Bamba T, Oku Y, Yonetani T, Fukusaki E (2011) Application of Fourier transform near-infrared spectroscopy to optimization of green tea steaming process conditions. J Biosci Bioeng 112(3):247–251CrossRefGoogle Scholar
  19. Schwartz H, Ollilainen V, Piironen V, Lampi AM (2008) Tocopherol, tocotrienol and plant sterol contents of vegetable oils and industrial fats. J Food Compos Anal 21(2):152–161CrossRefGoogle Scholar
  20. Strohschein S, Rentel C, Lacker T, Bayer E, Albert K (1999) Separation and identification of tocotrienol isomers by HPLC− MS and HPLC− NMR coupling. Anal Chem 71(9):1780–1785CrossRefGoogle Scholar
  21. Stuffins CB, Weatherall H (1945) Determination of the peroxide value of oils and fats. Analyst 70(836):403–409CrossRefGoogle Scholar
  22. Suomela JP, Ahotupa M, Sjovall O, Kurvinen JP, Kallio H (2004) Diet and lipoprotein oxidation:analysis of oxidized triacylglycerols in pig lipoproteins. Lipids 39(7):639–647CrossRefGoogle Scholar
  23. Suomela JP, Ahotupa M, Kallio H (2005) Triacylglycerol hydroperoxides not detected in pig small intestinal epithelial cell after a diet rich in oxidized triacylglycerols. Lipids 40(4):349–353CrossRefGoogle Scholar
  24. Tan CP, Man YC (2000) Differential scanning calorimetric analysis of edible oils: comparison of thermal properties and chemical composition. J Am Oil Chem Soc 77(2):143–155CrossRefGoogle Scholar
  25. Tarvainen M, Phuphusit A, Suomela JP, Kuksis A, Kallio H (2012) Effects of antioxidants on rapeseed oil oxidation in an artificial digestion model analyzed by UHPLC–ESI–MS. J Agric Food Chem 60(14):3564–3579CrossRefGoogle Scholar
  26. Waraho T, McClements DJ, Decker EA (2011) Mechanisms of lipid oxidation in food dispersions. Trends Food Sci Technol 22(1):3–13CrossRefGoogle Scholar
  27. Yamamoto S, Bamba T, Sano A, Kodama Y, Imamura M, Obata A, Fukusaki E (2012) Metabolite profiling of soy sauce using gas chromatography with time-of-flight mass spectrometry and analysis of correlation with quantitative descriptive analysis. J Biosci Bioeng 114(2):170–175CrossRefGoogle Scholar
  28. Yin H, Xu L, Porter NA (2011) Free radical lipid peroxidation: mechanisms and analysis. Chem Rev 111(10):5944–5972CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Oil DepartmentFuji Oil Co., LtdOsakaJapan
  2. 2.Fuji Oil Holdings IncResearch Institute for Creating the FutureOsakaJapan

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