Czech J. Food Sci., 2011, 29(4):448-456 | DOI: 10.17221/212/2011-CJFS

Formation of acylglycerol chloro derivatives in vegetable oils and mitigation strategy

Jan Šmidrkal1, Vojtěch Ilko2, Vladimír Filip1, Marek Doležal2, Zuzana Zelinková2, Jan Kyselka1, Iveta Hrádková1, Jan Velíšek2
1 Department of Dairy and Fat Technology and
2 Department of Food Chemistry and Analysis, Faculty of Food and Biochemical Technology, Institute of Chemical Technology, Prague, Prague, Czech Republic

The most important acylglycerol chloroderivatives identified in foods are 3-chlorpropane-1,2-diol fatty acid esters (3-CPD esters) that are accompanied by epoxypropanol fatty acid esters formed in processed foods and, particularly, during the deodorisation of vegetable oils. Their content in refined vegetable oils is influenced by the oil composition, refining process conditions and process conditions of hydrogenation. Described and discussed here are the main pathways that lead to the formation of acylglycerols chloroderivatives and epoxypropanol fatty acid esters. The article offers detailed explanation of the reaction mechanisms using the well-known chemical principals based on experimental data. The conditions suitable for removing the unwanted products from the refined vegetable oils were studied in models containing variable proportions of agents (bicarbonates or carbonates) causing the decomposition of 3-CPD fatty acid esters.

Keywords: 3-chloropropane-1,2-diol; 3-CPD, 3-MCPD; 3-chloropropane-1,2-diol esters; bound 3-CPD; processing contaminants; mitigation strategy

Published: August 31, 2011  Show citation

ACS AIP APA ASA Harvard Chicago Chicago Notes IEEE ISO690 MLA NLM Turabian Vancouver
Šmidrkal J, Ilko V, Filip V, Doležal M, Zelinková Z, Kyselka J, et al.. Formation of acylglycerol chloro derivatives in vegetable oils and mitigation strategy. Czech J. Food Sci. 2011;29(4):448-456. doi: 10.17221/212/2011-CJFS.
Download citation

References

  1. Bertoli C., Cauville F. (2011): A deodorized edible oil or fat with low levels of bound mcpd and process of making using an inert gas (Nestec S.A., Switzerland). PCT Int. Appl. (2011), CODEN: PIXXD2 WO 2011009843 A1 20110127, Application: WO 2010-EP60450 20100720.
  2. Bertoli C., Cauville F., Schoonman A.J.H. (2011): A deodorized edible oil or fat with low levels of bound mcpd and process of making by carboxymethyl cellulose and/or resin purification (Nestec S.A., Switzerland). PCT Int. Appl. (2011), CODEN: PIXXD2 WO 2011009841 A1 20110127. Application: WO 2010-EP60448 20100719.
  3. BfR (2007): Infant formula and follow-up formula may contain harmful 3-MCPD fatty acid esters, BfR Opinion No. 047/2007, 11 December 2007. Available at http://www.bfr.bund.de/cm/245/infant_formula_and_follow_up_formula_may_contain_harmful_3_mcpd_fatty_acid_esters.pdf (accessed January 2011)
  4. Bornscheuer U.T., Hesseler M. (2010): Enzymatic removal of 3-monochloro-1,2-propanediol (3-MCPD) and its esters from oils. European Journal of Lipid Science and Technology, 112: 552-556. Go to original source...
  5. Collier P.D., Cromie D.D.O., Davies A.P. (1991): Mechanism of formation of chloropropanols present in protein hydrolysates. Journal of the American Oil Chemists' Society, 68: 785-790. Go to original source...
  6. Collison M.W. (2010): Direct determination of MCPD esters and glycidylesters by LC/MS. OVID Meeting - Association of the oilseed crushing and oil refining industry in Germany, Berlin, 25 January 2010. Available at http://www.ovid-verband.de/fileadmin/user_upload/ovid-verband.de/downloads/ADM_Collison.pdf (accessed September 2010)
  7. Divinová V., Svejkovská B., Doležal M., Velíšek J. (2004). Determination of free and bound 3-chloropropane-1,2-diol by gas chromatography with mass spectrometric detection using deuterated 3-chloropropane-1,2-diol as internal standard. Czech Journal of Food Sciences, 22: 182-189. Go to original source...
  8. EFSA (2008): Statement of the scientific panel on contaminants in the food chain (CONTAM) on a request from the European Commission related to 3-MCPD esters. Question number: EFSA-Q-2008-258, Adopted: 28 March 2008. Available at http://www.efsa.europa.eu/en/scdocs/scdoc/1048.htm (accessed September 2010)
  9. Ernest I., Heřmánek S., Hudlický M. (1959): Preparativní reakce v organické chemii. díl IV. Nakladatelství ČSAV, Praha.
  10. European Commission (2001a): Opinion of the scientific committee on food on 3-monochloro-propane-1,2-diol (3-MCPD) updating the SCF opinion of 1994 (adopted on 30 May 2001). SCF/CS/CNTM/OTH/17 Final. Brussels: European Commission.
  11. European Commission (2001b): Commission Regulation (EC) No. 466/2001 of 8 March 2001 setting maximum levels for certain contaminants in foodstuffs. Oj No. L77, 16. 3. 2001: 1-13.
  12. Franke K., Strijowski U., Fleck G., Pudel F. (2009): Influence of chemical refining process and oil type on bound 3-chloro-1,2-propanediol contents in palm oil and rapeseed oil. Food Science and Technology, 42: 1751-1754. Go to original source...
  13. Hamlet C.G., Sadd P.A. (2009): Chloropropanols and chloroesters. In: Stadler R.H., Lineback D.R. (eds): Process-induced Food Toxicants: Occurrence, Formation, Mitigation, and Health Risks. John Wiley & Sons, Inc., New Jersey: 175-214. Go to original source...
  14. Hamlet, C.G., Sadd, P.A., Crews, C., Velisek, J., Baxter, D.E. (2002): Occurrence of 3-chloropropane-1,2-diol (3MCPD) and related compounds in foods: a review. Food Additives and Contaminants, 19: 619-631. Go to original source... Go to PubMed...
  15. Hamlet C.G., Asuncion L., Velíšek J., Doležal M., Zelinková Z., Crews C. (2011): Esters of 3-chloro1,2-propanediol (3-CPD) in foods: What we know and what we assume. European Journal of Lipid Science and Technology, 113: 279-303. Go to original source...
  16. Ilko V., Zelinková Z., Doležal M., Velíšek J. (2011): 3-Chloropropane-1,2-diol fatty acid esters in potato products. Czech Journal of Food Sciences, 29: 411-419. Go to original source...
  17. Karšulínová L., Folprechtová B., Doležal M., Dostálová J., Velíšek J. (2007): Analysis of the lipid fraction of coffee creamers, cream aerosols and bouillon cubes for their health risk associated constituents. Czech Journal of Food Sciences, 25: 257-264. Go to original source...
  18. Kraft R., Brachwitz H., Etyold G., Langen P., Zöpel H.-J. (1979): Massenspektrometrische Strukturuntersuchung stellungsisomerer Fettsäureester der Halogenpropandiole (Desoxyhalogen-glyceride). Journal für praktische Chemie, 321: 756-768. Go to original source...
  19. Langen P., Brachwitz H., Schildt J. (1979): Inhibition of proliferation of Ehrlich ascites carcinoma cells in vitro and in vivo by halogeno analogues of long chain acyl- and alkylglycerols. Acta Biologica et Medica Germanica, 38: 965-974.
  20. Lin S.W., Ibrahim N.I., Ramli M.R., Kuntom A., Razak R.A.A., Nesaretnam K.: Formation of 3-MCPD esters upon refining of oils. In: 8 th Euro Fed Lipid Congress, Munich, November 2010.
  21. Matthäus B. (2009): Potential ways of reduction of 3-MCPD esters in vegetable oils/data on mitigation. ILSI Workshop on 3-MCPD esters, Brussels, Belgium, February 5-6., 2009. Available at http://www.ilsi.org/Europe/Documents/E2009MCPD-11.pdf (accessed September 2010)
  22. Matthäus B., Vosmann K. (2009): Potential ways of reduction of 3-MCPD esters in vegetable oils/data on mitigation. In: 7th Euro Fed Lipid Congress, Graz, October 2009.
  23. Matthäus B., Freudenstein A., Pudel F., Fehling P. (2010): Possibilities to reduce 3-MCPD esters and related compounds during the refining process - results from the German FEI research project. In: 8th Euro Fed Lipid Congress, Munich, November 2010.
  24. Schurz K. (2010a): Method for reducing 3-MCPD content in refined vegetable oils (Sued-Chemie AG, Germany). PCT Int. Appl. (2010), Chemical Indexing Equivalent to 153:39716 (DE). CODEN: PIXXD2 WO 2010063450 A1 20100610. Application: WO 2009-EP8557 20091201.
  25. Schurz K. (2010b): Method for reducing 3-MCPD content in refined vegetable oils (Sued-Chemie AG, Germany). Ger. Offen. Chemical Indexing Equivalent to 153:39720 (WO). CODEN: GWXXBX DE 102008060059 A1 20100610. Application: DE 2008-102008060059 20081202.
  26. Seefelder W., Varga N., Studer A., Williamson G., Scanlan F.P., Stadler R.H. (2008). Esters of 3-chloro1,2-propanediol (3-MCPD) in vegetable oils: Significance in the formation of 3-MCPD. Food Additives and Contaminants, 25: 391-400. Go to original source... Go to PubMed...
  27. Šilhánková L., Šmíd F., Černá M., Davídek J., Velíšek J. (1982). Mutagenicity of glycerol chlorohydrins and of their esters with higher fatty acids present in protein hydrolysates. Mutation Research, 103: 77-81. Go to original source... Go to PubMed...
  28. Stamatov S.D., Stawinski J. (2006). Regioselective and stereospecific cleavage of a terminal oxirane system: A novel synthetic approach to lipid mediator congeners- 1,2(2,3)-diacyl-3(1)-halo-sn-glycerols. Bioorganic and Medicinal Chemistry Letters, 16: 3388-3391. Go to original source... Go to PubMed...
  29. Svejkovská B., Novotný O., Divinová M., Réblová Z., Doležal M., Velíšek J. (2004): Esters of 3-chloropropane-1,2-diol in foodstuffs. Czech Journal of Food Sciences, 22: 190-196. Go to original source...
  30. Strijowski U., Franke K (2010): Surface adsorption reduce 3-monochlorpropanol-forming substances vegetable oils. In: 8th Euro Fed Lipid Congress, Munich, November 2010.
  31. Velíšek J. (2009): Chloropropanols, in process-induced food toxicants: In: Stadler R.H., Lineback D.R. (eds): Process-induced Food Toxicants: Occurrence, Formation, Mitigation, and Health Risks. John Wiley & Sons, Inc., New Jersey: 539-562. Go to original source...
  32. Velíšek J., Calta P., Crews C., Hasnip S., Doležal M. (2003): 3-Chloropropane-1,2-diol in models simulating processed foods: precursors and agents causing its decomposition. Czech Journal of Food Sciences, 21: 153-161. Go to original source...
  33. Weisshaar R. (2011): Fatty acid esters of 3-MCPD: Overview of occurrence and exposure estimates. European Journal of Lipid Science and Technology, 113: 304-308. Go to original source...
  34. Weisshaar R., Perz R. (2010): Fatty acid esters of glycidol in refined fats and oils. European Journal of Lipid Science and Technology, 112: 158-165. Go to original source...
  35. Yaylayan V.A. (2009): Molecular mechanism of 3-MCPD ester formation: Facts and hypothesis. ILSI Workshop on 3-MCPD esters, February 5-6, 2009, Brussels, Belgium. Available at http://www.ilsi.org/Europe/Documents/E2009MCPD-6.pdf (accessed September 2010)
  36. Zelinková, Z., Svejkovská, B., Velíšek, J., Doležal, M. (2006): Fatty acid esters of 3-chloropropane-1,2-diol in edible oils. Food Additives and Contaminants: Part A, 23, 1290-1298. Go to original source... Go to PubMed...
  37. Zelinková, Z., Doležal, M., Velíšek, J. (2009): Occurrence of 3-chloropropane-1,2-diol fatty acid esters in infant and baby foods. European Food Research and Technology, 228: 571-578. Go to original source...
  38. Zieverink M.M.P., De Ruiter, G.A., Berg H.E. (2011a): Process for removing unwanted propanol components from unused triglyceride oil (Sime Darby Malaysia Berhad, Malaysia). PCT Int. Appl. (2011), CODEN: PIXXD2 WO 2011005081 A1 0110113. Application: WO 2010NL50411 20100630.
  39. Zieverink M.M.P., De Ruiter G.A., Lapit R.B.A., Al Krishnan A., Bin Hashim K. (2011b): Process for manufacturing palm oil fractions containing virtually no 3-monochloropropanediol fatty acid esters (Sime Darby Malaysia Berhad, Malaysia). PCT Int. Appl. (2011), CODEN: PIXXD2 WO 2011002275 A1 20110106.

This is an open access article distributed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY NC 4.0), which permits non-comercial use, distribution, and reproduction in any medium, provided the original publication is properly cited. No use, distribution or reproduction is permitted which does not comply with these terms.