Skip to main content
Log in

Oxidation of a functional, CLA-rich oil: determination of volatile and non-volatile compounds

  • Original Paper
  • Published:
European Food Research and Technology Aims and scope Submit manuscript

Abstract

The objective of this work was to monitor and compare formation of non-volatile and volatile oxidation compounds in a conjugated linoleic acid (CLA)-rich oil, Tonalin® oil (TO) and a linoleic acid (LA)-rich oil, safflower oil (SO) at 40 °C in the dark. In the TO, formation of hydroperoxides was negligible and the first and major compounds formed were polymerization products. When tocopherols were exhausted, the SO showed 152 meq O2/kg oil and 3 % polymers, values which are consistent with the expected progress of oxidation in unsaturated oils under these conditions, while the TO showed only 19 meq O2/kg oil of peroxide value and as much as 15 % polymers. In relation to the composition of volatile compounds, that found in the SO was close to that expected from the cleavage of the alkoxyl radicals formed from the LA-derived hydroperoxides, where hexanal is the main compound. However, the composition of volatile compounds of the TO was characterized by the occurrence of heptanal and t-2-nonenal, which were absent in the SO. An alternative route of formation for these distinct volatile oxidation compounds in TO could be scission of dioxoethanes coming from 1,2 cycloadditions of CLA with oxygen. Overall, the results obtained in this study, both on non-volatile and on volatile compounds, support that oxidation kinetics of CLA-rich oils differ substantially from that expected according to the hydroperoxide theory. Oxidation of CLA seems to proceed preferentially by the addition of the peroxyl radical to a double bond during propagation reactions, thus supporting the formation of oligomeric peroxides from the early events of lipid degradation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Özer BH, Kirmazi HA (2010) Functional milks and dairy beverages. Int J Dairy Technol 63:1–15

    Article  Google Scholar 

  2. Koba K, Yanagita T (2014) Health benefits of conjugated linoleic acid. Obes Res Clin Pract 8:525–532

    Article  Google Scholar 

  3. Yang B, Chen H, Stanton C, Ross RP, Zhang H, Chen YQ, Chen W (2015) Review of the roles of conjugated linoleic acid in health and disease. J Funct Foods 15:314–325

    Article  CAS  Google Scholar 

  4. Saebo A (2003) Commercial synthesis of conjugated linoleate. In: Sebedio JL, Christie WW, Adlof R (eds) Advances in CLA research, vol 2., AOCS PressChampaign, IL, pp 71–81

    Google Scholar 

  5. Dobarganes MC, Márquez-Ruiz G (2003) Oxidized fats in foods. Curr Opin Clin Nutr Metab Care 6:157–163

    Article  CAS  Google Scholar 

  6. García-Martínez MC, Márquez-Ruiz G (2009) Lipid oxidation in functional dairy products. Curr Nutr Food Sci 5:209–216

    Article  Google Scholar 

  7. Eulitz K, Yurawecz MP, Ku Y (1999) The oxidation of conjugated linoleic acid. In: Yurawecz MP, Mossoba MM, Kramer JKG, Pariza MW, Nelso GJ (eds) Advances in CLA research, vol 1. AOCS Press, Champaign, pp 55–63

    Google Scholar 

  8. Brimberg UI, Kamal-Eldin A (2003) On the kinetics of the autoxidation of fats: substrates with conjugated double bonds. Eur J Lipid Sci Technol 105:17–22

    Article  CAS  Google Scholar 

  9. Yurawecz MP, Delmonte P, Vogel T, Kramer JKG (2003) Oxidation of conjugated linoleic acid: Initiators and simultaneous reactions: theory and practice. In: Sebedio JL, Christie WW, Adlof R (eds) Advances in CLA research, vol 2., AOCS PressChampaign, IL, pp 56–70

    Google Scholar 

  10. Yurawecz MP, Sehat N, Mossoba MM, Roach JAG, Ku Y (1997) Oxidation products of conjugated linoleic acid and furan fatty acids. In: McDonald RE, Mossoba MM (eds) New techniques and applications in lipid analysis. AOCS Press, Champaign, pp 183–215

    Google Scholar 

  11. Luna P, De la Fuente MA, Salvador D, Márquez-Ruiz G (2007) Differences in oxidation kinetics between conjugated and non-conjugated methyl linoleate. Lipids 42:1085–1092

    Article  CAS  Google Scholar 

  12. Pajunen TI, Kamal-Eldin A (2008) Oxidation of conjugated linoleic acid. In: Kamal-Eldin A, Min DB (eds) Lipid oxidation pathways, vol 2., AOCS PressChampaign, IL, pp 77–110

    Google Scholar 

  13. Márquez-Ruiz G, García-Martínez MC, Holgado F, Velasco J (2014) Effectiveness of α-, γ- and δ-tocopherol in a CLA-rich oil. Antioxidants 3:176–188

    Article  Google Scholar 

  14. Suzuki R, Abe M, Miyashita K (2004) Comparative study of the autoxidation of TAG containing conjugated and nonconjugated C18 PUFA. J Am Oil Chem Soc 81:563–569

    Article  CAS  Google Scholar 

  15. Lee J, Lee S-M, Kim I-H, Jeong J-H, Rhee C, Lee K-W (2003) Oxidative instability of CLA concentrate and its avoidance with antioxidants. J Am Oil Chem Soc 80:807–810

    Article  CAS  Google Scholar 

  16. Minemoto Y, Adachi S, Shimada Y, Nagao T, Iwata T, Yamauchi-Sato Y, Yamamoto T, Kometani T, Matsuno R (2003) Oxidation kinetics for cis-9, trans-11 and trans-10, cis-12 isomers of CLA. J Am Oil Chem Soc 80:675–678

    Article  CAS  Google Scholar 

  17. Tsuzuki T, Igarashi M, Iwata T, Yamauchi-Sato Y, Yamamoto T, Ogita K, Suzuki T, Miyazawa T (2004) Oxidation rate of conjugated linoleic acid and conjugated linolenic acid is slowed by triacylglycerol esterification and α-tocopherol. Lipids 39:475–480

    Article  CAS  Google Scholar 

  18. Yetella RR, Castrodale C, Proctor A (2011) Oxidative stability of conjugated linoleic acid rich soy oil. J Am Oil Chem Soc 89:685–693

    Article  Google Scholar 

  19. Lele SR, Proctor A, Ruan CM (2014) Oxidative stability of conjugated linoleic acid rich soy oil obtained by heterogeneous catalysis. J Am Oil Chem Soc 91:2043–2052

    Article  CAS  Google Scholar 

  20. García-Martínez MC, Márquez-Ruiz G, Fontecha J, Gordon MH (2009) Volatile oxidation compounds in a conjugated linoleic acid-rich oil. Food Chem 113:926–931

    Article  Google Scholar 

  21. Giua L, Blasi F, Simonetti MS, Cossignani L (2013) Oxidative modifications of conjugated and unconjugated linoleic acid during heating. Food Chem 140:680–685

    Article  CAS  Google Scholar 

  22. Cossignani L, Giua L, Simonetti S, Blasi F (2014) Volatile compounds as indicators of conjugated and unconjugated linoleic acid thermal oxidation. Eur J Lipid Sci Technol 116:407–412

    Article  CAS  Google Scholar 

  23. Martínez-Monteagudo SI, Leal-Dávila M, Curtis JM (2015) Oxidative stability of ultra high temperature milk enriched in conjugated linoleic acid and trans-vaccenic acid. Int Dairy J 43:70–77

    Article  Google Scholar 

  24. IUPAC (1992) Standard methods for the analysis of oils, fats and derivatives, 7th edn. International Union of Pure and Applied Chemistry, Blackwell Scientific, Oxford

  25. Márquez-Ruiz G, Dobarganes MC (2007) High-performance size-exclusion chromatography for lipid analysis in organic media. In: Mossoba MM, Kramer JKG, Brenna JT, McDonald RE (eds) Lipid analysis and lipidomics. New techniques and applications. AOCS Press, Champaign, pp 205–238

    Google Scholar 

  26. Hashizume M, Gordon MH, Mottram DS (2007) Light-induced off-flavor development in cloudy apple juice. J Agric Food Chem 55:9177–9182

    Article  CAS  Google Scholar 

  27. Márquez-Ruiz G, Martín-Polvillo M, Dobarganes MC (1996) Quantitation of oxidized triglyceride monomers and dimers as an useful measurement for early and advanced stages of oxidation. Grasas Aceites 47:48–53

    Article  Google Scholar 

  28. Márquez-Ruiz G, Martín-Polvillo M, Dobarganes MC (2003) Effect of temperature and addition of α-tocopherol on the oxidation of trilinolein model systems. Lipids 38:233–240

    Article  Google Scholar 

  29. Martín-Polvillo M, Márquez-Ruiz G, Dobarganes MC (2004) Oxidative stability of sunflower oils differing in unsaturation degree during long term storage at room temperature. J Am Oil Chem Soc 81:577–583

    Article  Google Scholar 

  30. Frankel EN (2005) Lipid oxidation. The Oily Press, Dundee

    Book  Google Scholar 

  31. Miller AB, Claxton E (1928) Atmospheric oxidation of methyl and glycol esters of beta-eleostearic acid. Ind Eng Chem 20:43–48

    Article  CAS  Google Scholar 

  32. Allen RR, Jackson A, Kummerow FA (1949) Factors which affect the stability of highly unsaturated fatty acids. 1. Difference in the oxidation of conjugated and nonconjugated linoleic acid. J Am Oil Chem Soc 26:395–399

    Article  CAS  Google Scholar 

  33. Jackson AH, Kummerow FA (1949) Factors which affect the stability of highly unsaturated fatty acids. 2. The autoxidation of linoleic and alkali conjugated acid in the presence of metallic naphthenates. J Am Oil Chem Soc 26:460–465

    Article  CAS  Google Scholar 

  34. Muizebelt WJ, Nielen MWF (1996) Oxidative crosslinking of unsaturated fatty acids studied with mass spectrometry. J Mass Spectrom 31:545–554

    Article  CAS  Google Scholar 

  35. Oyman ZO, Ming W, van der Linde R (2005) Oxidation of drying oils containing non-conjugated and conjugated double bonds catalyzed by a cobalt catalyst. Prog Org Coat 54:198–204

    Article  CAS  Google Scholar 

  36. Hämäläinen TI, Sundberg S, Hase T, Hopia A (2002) Stereochemistry of the hydroperoxides formed during autoxidation of CLA methyl ester in the presence of α-tocopherol. Lipids 37:533–540

    Article  Google Scholar 

  37. Tallman KA, Pratt DA, Porter NA (2001) Kinetic products of linoleate peroxidation: rapid β-fragmentation of nonconjugated peroxyls. J Am Chem Soc 123:11827–11828

    Article  CAS  Google Scholar 

  38. Tallman KA, Roschek JB, Porter NA (2004) Factors influencing the autoxidation of fatty acids: effect of olefin geometry of the nonconjugated diene. J Am Chem Soc 126:9240–9247

    Article  CAS  Google Scholar 

  39. Jones EL, Shingfield KJ, Kohen C, Jones AK, Lupoli B, Grandison AS, Beever DE, Williams CM, Calder PC, Yaqoob P (2005) Chemical, physical and sensory properties of dairy products enriched with conjugated linoleic acid. J Dairy Sci 88:2923–2937

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This research was financially supported by Projects AGL2010-18307 and AGL2013-45110-R of the Spanish Ministry of Economy and Competitiveness (MINECO).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Gloria Márquez-Ruiz.

Ethics declarations

Conflict of interest

None.

Compliance with Ethics Requirements

This article does not contain any studies with human or animal subjects.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Márquez-Ruiz, G., Holgado, F., Ruiz-Méndez, M.V. et al. Oxidation of a functional, CLA-rich oil: determination of volatile and non-volatile compounds. Eur Food Res Technol 242, 1993–2000 (2016). https://doi.org/10.1007/s00217-016-2698-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00217-016-2698-9

Keywords

Navigation