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Compositional Information Useful for Authentication of Krill Oil and the Detection of Adulterants

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Abstract

Nuclear magnetic resonance (NMR) spectroscopy and chromatography, particularly thin layer chromatography with flame ionisation detector (TLC-FID), were used to investigate fish oil adulteration of krill oil with ethyl esters and triacylglycerol. Natural krill oil has higher levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in phospholipid than in triacylglycerol and so high levels of these omega-3 fatty acids in krill oil triacylglycerol was indicative of adulteration. Carbon (13C) NMR detected adulteration of krill oil with 10% or more anchovy oil, while TLC-FID detected levels as low as 1% adulteration with EPA ethyl esters. However, positional distribution of EPA and DHA, as determined using 13C NMR, was similar for both fish oil and krill oil, indicating that positional distribution cannot be used to show adulteration. Phosphorous (31P) NMR spectroscopy can show adulteration with low cost sources of phospholipid but was not useful for determining adulteration of krill oil with fish oil.

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References

  • Ackman RG (2002) The gas chromatograph in practical analyses of common and uncommon fatty acids for the 21st century. Anal Chim Acta 465:175–192

    Article  CAS  Google Scholar 

  • Ahmad MU, Xu X (2015) Polar lipids: biology, chemistry, and technology. Elsevier

  • Akanbi TO, Barrow CJ (2015a) Lipase-catalysed incorporation of EPA into emu oil: formation and characterisation of new structured lipids. J Funct Foods 19:801–809

    Article  CAS  Google Scholar 

  • Akanbi TO, Barrow CJ (2015b) Lipid profiles, in vitro digestion and oxidative stability of mutton bird oil. J Food Sci Technol:1–8

  • Akanbi TO, Adcock JL, Barrow CJ (2013) Selective concentration of EPA and DHA using Thermomyces lanuginosus lipase is due to fatty acid selectivity and not regioselectivity. Food Chem 138:615–620

    Article  CAS  Google Scholar 

  • Akanbi TO, Sinclair AJ, Barrow CJ (2014) Pancreatic lipase selectively hydrolyses DPA over EPA and DHA due to location of double bonds in the fatty acid rather than regioselectivity. Food Chem 160:61–66

    Article  CAS  Google Scholar 

  • Araujo P, Zhu H, Breivik JF, Hjelle JI, Zeng Y (2014) Determination and structural elucidation of triacylglycerols in krill oil by chromatographic techniques. Lipids 49:163–172

    Article  CAS  Google Scholar 

  • Aursand M, Standal IB, Prael A, McEvoy L, Irvine J, Axelson DE (2009) 13C NMR pattern recognition techniques for the classification of Atlantic salmon (Salmo salar L.) according to their wild, farmed, and geographical origin. J Agric Food Chem 57:3444–3451

    Article  CAS  Google Scholar 

  • Azadmard-Damirchi S (2010) Review of the use of phytosterols as a detection tool for adulteration of olive oil with hazelnut oil. Food Addit Contam 27:1–10

    Article  CAS  Google Scholar 

  • Bottino NR (1975) Lipid composition of two species of Antarctic krill: Euphausia superba and E. crystallorophias. Comp Biochem Physiol B Comp Biochem 50:479–484

    Article  CAS  Google Scholar 

  • Bruheim I, Griinari M, Tilseth S, Banni S, Stuart CJ, Mancinelli D (2008) Bioeffective krill oil compositions. US patent application number 20080274203

  • Castro-Gómez MP, Holgado F, Rodríguez-Alcalá LM, Montero O, Fontecha J (2015) Comprehensive study of the lipid classes of krill oil by fractionation and identification of triacylglycerols, diacylglycerols, and phospholipid molecular species by using UPLC/QToF-MS. Food Anal Methods 8:2568–2580

    Article  Google Scholar 

  • De Kock J (1993) The European analytical subgroup of ILPS-A. Joint effort to clarify lecithin and phospholipid analysis. Lipid/Fett 95:352–355

    Article  Google Scholar 

  • Deutsch L (2007) Evaluation of the effect of Neptune krill oil on chronic inflammation and arthritic symptoms. J Am Coll Nutr 26:39–48

    Article  CAS  Google Scholar 

  • Diehl BW (2001) High resolution NMR spectroscopy. Eur J Lipid Sci Technol 103:830–834

    Article  CAS  Google Scholar 

  • Fragaki G, Spyros A, Siragakis G, Salivaras E, Dais P (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

    Article  CAS  Google Scholar 

  • Fricke H, Gercken G, Schreiber W, Oehlenschläger J (1984) Lipid, sterol and fatty acid composition of Antarctic krill (Euphausia superba Dana). Lipids 19:821–827

    Article  CAS  Google Scholar 

  • García-González DL, Mannina L, D’Imperio M, Segre AL, Aparicio R (2004) Using 1H and 13C NMR techniques and artificial neural networks to detect the adulteration of olive oil with hazelnut oil. Eur Food Res Technol 219:545–548

    Article  Google Scholar 

  • Gigliotti JC, Davenport MP, Beamer SK, Tou JC, Jaczynski J (2011) Extraction and characterisation of lipids from Antarctic krill (Euphausia superba). Food Chem 125:1028–1036

    Article  CAS  Google Scholar 

  • Hatziantoniou S, Demetzos C (2006) Qualitative and quantitative one-step analysis of lipids and encapsulated bioactive molecules in liposome preparations by HPTLC/FID (Iatroscan). J Liposome Res 16:321–330

    Article  CAS  Google Scholar 

  • Ju S-J, Kang H-K, Kim WS, Harvey HR (2009) Comparative lipid dynamics of euphausiids from the Antarctic and Northeast Pacific Oceans. Mar Biol 156:1459–1473

    Article  CAS  Google Scholar 

  • Karlsson AÅ, Michelsen P, Larsen Å, Odham G (1996) Normal-phase liquid chromatography class separation and species determination of phospholipids utilizing electrospray mass spectrometry/tandem mass spectrometry. Rapid Commun Mass Spectrom 10:775–780

    Article  CAS  Google Scholar 

  • Kim J, Hoppel CL (2013) Comprehensive approach to the quantitative analysis of mitochondrial phospholipids by HPLC–MS. J Chromatogr B 912:105–114

    Article  CAS  Google Scholar 

  • Köhler A, Sarkkinen E, Tapola N, Niskanen T, Bruheim I (2015) Bioavailability of fatty acids from krill oil, krill meal and fish oil in healthy subjects—a randomized, single-dose, cross-over trial. Lipids Health Dis 14:19

    Article  Google Scholar 

  • Küllenberg D, Taylor LA, Schneider M, Massing U (2012) Health effects of dietary phospholipids. Lipids Health Dis 11:1

    Article  Google Scholar 

  • Le Grandois J, Marchioni E, Zhao M, Giuffrida F, Sd E, Bindler F (2009) Investigation of natural phosphatidylcholine sources: separation and identification by liquid chromatography− electrospray ionization− tandem mass spectrometry (LC− ESI− MS2) of molecular species. J Agric Food Chem 57:6014–6020

    Article  Google Scholar 

  • Lerna M, Kerr A, Scales H, Berge K, Griinari M (2010) Supplementation of diet with krill oil protects against experimental rheumatoid arthritis. BMC Musculoskelet Disord 11:1

    Article  Google Scholar 

  • Massrieh W (2008) Health benefits of omega-3 fatty acids from Neptune krill oil. Lipid Technol 20:108–111

    Article  CAS  Google Scholar 

  • Paradies G, Ruggiero FM, Petrosillo G, Quagliariello E (1993) Age-dependent decrease in the cytochrome c oxidase activity and changes in phospholipids in rat-heart mitochondria. Arch Gerontol Geriatr 16:263–272

    Article  CAS  Google Scholar 

  • Phleger CF, Nichols PD, Virtue P (1998) Lipids and trophodynamics of Antarctic zooplankton. Comp Biochem Physiol B Biochemi Mol Biol 120:311–323

    Article  Google Scholar 

  • Phleger CF, Nelson MM, Mooney BD, Nichols PD (2002) Interannual and between species comparison of the lipids, fatty acids and sterols of Antarctic krill from the US AMLR Elephant Island survey area. Comp Biochem Physiol B: Biochem Mol Biol 131:733–747

    Article  Google Scholar 

  • Sacchi R, Medina I, Aubourg SP, Giudicianni I, Paolillo L, Addeo F (1993) Quantitative high-resolution carbon-13 NMR analysis of lipids extracted from the white muscle of Atlantic tuna (Thunnus alalunga). J Agric Food Chem 41:1247–1253

    Article  CAS  Google Scholar 

  • Sato Y, Nakamura T, Aoshima K, Oda Y (2010) Quantitative and wide-ranging profiling of phospholipids in human plasma by two-dimensional liquid chromatography/mass spectrometry. Anal Chem 82:9858–9864

    Article  CAS  Google Scholar 

  • Sinanoglou VJ, Strati IF, Bratakos SM, Proestos C, Zoumpoulakis P, Miniadis-Meimaroglou S (2013) On the combined application of Iatroscan TLC-FID and GC-FID to identify total, neutral, and polar lipids and their fatty acids extracted from foods ISRN Chromatography 2013

  • Sullivan JC, Budge SM, St-Onge M (2009) Determining ethyl esters in fish oil with solid phase microextraction and GC–MS. J Am Oil Chem Soc 86:743–748

    Article  CAS  Google Scholar 

  • Tandy S, Chung RW, Wat E, Kamili A, Berge K, Griinari M, Cohn JS (2009) Dietary krill oil supplementation reduces hepatic steatosis, glycemia, and hypercholesterolemia in high-fat-fed mice. J Agric Food Chem 57:9339–9345

    Article  CAS  Google Scholar 

  • United States Pharmacopeial Convention, USP (2012) Food Chemicals Codex. 8th ed. United States Pharmacopeial Convention, Board of of Trustees, Rockville

  • Vigli G, Philippidis A, Spyros A, Dais P (2003) Classification of edible oils by employing 31P and 1H NMR spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils. J Agric Food Chem 51:5715–5722

    Article  CAS  Google Scholar 

  • Werner A, Havinga R, Kuipers F, Verkade HJ (2004) Treatment of EFA deficiency with dietary triglycerides or phospholipids in a murine model of extrahepatic cholestasis. Am J Physiol Gastrointest Liver Physiol 286:G822–G832

    Article  CAS  Google Scholar 

  • Winther B, Hoem N, Berge K, Reubsaet L (2011) Elucidation of phosphatidylcholine composition in krill oil extracted from Euphausia superba. Lipids 46:25–36

  • Yao L, Jung S (2010) 31P NMR phospholipid profiling of soybean emulsion recovered from aqueous extraction. J Agric Food Chem 58:4866–4872

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge Photonz Corporation, Auckland, New Zealand, for providing the EPA-EE used in this study. Also, the authors acknowledge the Centre for Chemistry and Biotechnology for funding.

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Correspondence to Colin J. Barrow.

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Taiwo O Akanbi declares that he has no conflict of interest. Colin J Barrow declares that he has no conflict of interest.

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This article does not contain any studies with human participants or animals performed by any of the authors.

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Akanbi, T.O., Barrow, C.J. Compositional Information Useful for Authentication of Krill Oil and the Detection of Adulterants. Food Anal. Methods 11, 178–187 (2018). https://doi.org/10.1007/s12161-017-0988-x

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  • DOI: https://doi.org/10.1007/s12161-017-0988-x

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