Chloropropanole, chloropropanodiole i ich estry w żywności

• Autorzy: Kowalska D. , Gruczynska E. , Kowalska M. , Kozlowska M. , Kowalski B.

Warianty tytułu

EN

Chloropropanols, chloropropandiols and their esters in food - formation, occurrence, determination, reduction of content

• Języki publikacji: PL

Abstrakty

PL

Związki: 3-monochloropropano-1,2-diol (3-MCPD), 2-monochloropropano-1,3-diol (2-MCPD), 1,3- i 2,3-dichloropropanole (1,3-DCP i 2,3-DCP) oraz ich estry należą do grupy tzw. zanieczyszczeń procesowych żywności. 3-MCPD wykryto jako pierwszy, w 1978 roku w produktach kwasowej hydrolizy białek roślinnych, a jego estry zidentyfikowano w 1980 r. W 2006 roku stwierdzono obecność dużych ilości estrów 3-MCPD w rafinowanych olejach roślinnych. Od ponad 35 lat prowadzone są badania nad mechanizmami powstawania wymienionych związków w żywności bogatej w tłuszcz, ogrzewanej do wysokiej temperatury. Do produktów narażonych na zanieczyszczenie związkami 3-MCPD i jego estrami w trakcie procesu technologicznego należą m.in. oleje rafinowane, frytki, chipsy, pieczywo, produkty wędzone. W pracy przedstawiono stan badań dotyczący powstawania 3-MCPD i jego estrów, występowania w żywności, aspektów analitycznych i toksykologicznych oraz uregulowań prawnych. Opisano także sposoby redukcji zawartości 3-MCPD i jego estrów w żywności.

EN

3-MCPD, 2-MCPD, 1,2- and 2,3-DCP and their esters belong to the group of well known process-induced contaminants. The 3-MCPD was first identified in 1978 in acid-hydrolyzed vegetable proteins and its corresponding esters in 1980. Since their discovery more than 35 years later the exact mechanisms of their formation in foods is still studied. 3-MCPD and its esters occur in fat rich food that was thermally processed. In 2006 the huge quantities of 3-MCPD esters were detected in refined vegetable oils. The presented paper contains information on 3-MCPD and its esters formation, occurrence in foods, and on analytical and toxicological aspects. The strategies for the reduction of content of 3-MCPD and 3-MCPD-esters in foods are also briefly discussed.

• Wydawca: -
• Czasopismo: Żywność Nauka Technologia Jakość
• Rocznik: 2015
• Tom: 22
• Numer: 4
• Opis fizyczny: s.5-20,rys.,bibliogr.

Twórcy

autor

Kowalska D.

• Katedra Chemii, Wydział Nauk o Żywności, Szkoła Główna Gospodarstwa Wiejskiego, ul.Nowoursynowska 159C, 02-776 Warszawa

autor

Gruczynska E.

• Katedra Chemii, Wydział Nauk o Żywności, Szkoła Główna Gospodarstwa Wiejskiego, ul.Nowoursynowska 159C, 02-776 Warszawa

autor

Kowalska M.

• Katedra Chemii, Wydział Materiałoznawstwa, Technologii i Wzornictwa, Uniwersytet Techniczno-Humanistyczny, ul.Chrobrego 27, 26-600 Radom

autor

Kozlowska M.

• Katedra Chemii, Wydział Nauk o Żywności, Szkoła Główna Gospodarstwa Wiejskiego, ul.Nowoursynowska 159C, 02-776 Warszawa

autor

Kowalski B.

• Katedra Chemii, Wydział Nauk o Żywności, Szkoła Główna Gospodarstwa Wiejskiego, ul.Nowoursynowska 159C, 02-776 Warszawa

Bibliografia

• [1] Baer I., Calle B., Taylor P.: 3-MCPD in food other than soy sauce hydrolised vegetable protein (HVP). Anal. Bioanal. Chem. 2010, 396, 443-456.
• [2] Bertoli C., Cauville F.: 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 20110098 A1, 20110127.
• [3] Bornscheuer U.T., Hesseler M.: Enzymatic removal of 3-monochloro-1,2-propanediol (3-MCPD) and its esters from oils. Eur. J. Lipid Sci. Technol., 2010, 112, 552-556.
• [4] Brereton P., Kelly J., Crews C., Honour S., Wood R., Davies A.: Determination of 3-chloro-1,2- propanediol in foods and food ingredients by GC/MS detection. J. AOAC Int 2001, 84, 455-465.
• [5] Burke T., Weisshaar R., Lampen A.: Absorption and metabolism of the food contaminant 3-MCPD) and its fatty acid esters by human intestinal Caco-2 cells. Arch. Toxicol., 2011, 85, 1201-1208.
• [6] Cerbulis J., Parks O.W., Liu R., Piotrowski G., Farrell H.: Occurence of diesters of 3-chloro-1,2- propanediol in the neutral lipid fraction of goats' milk. J. Agric. Food Chem., 1984, 32, 474-476.
• [7] Chung S.W.C., Kwong K.P., Yau J.C.W., Wong A.M.C., Xiao Y.: Chloropropanols levels in foodstuffs marketed in Hong Kong. J. Food Composition Anal., 2008, 21, 569-573.
• [8] Chung S.W.C., Chan B.T.P.: Simultaneous determination of 2- and 3-MCPD esters in foods by enzymatic hydrolysis and GC-MS detection. Chromatographia, 2012, 75, 1049-1056.
• [9] Craft B.D., Nagy K., Sandoz L., Destaillats F.: Factors impacting the formation of monochloropropanediol (MCPD) fatty acid diesters during palm (Elaeis guineesis) oil production. Food Addit. Contamin., 2012, 29, 354-361.
• [10] Craft B.D., Chiodini A., Garst J., Granvogl M.: Fatty acid esters of monochloropropandiol (MCPD) and glycidol in refined edible oils. Food Addit. Contamin. Part A, 2013, 30, 46-51.
• [11] Crews C., Brereton P., Davies A.: The effects of domestic cooking on the levels of 3-monochloropropandiol in foods. Food Addit. Contamin. Part A, 2001, 18, 271-280.
• [12] Crews C., Chiodini A., Granvogl M., Hamlet C., Hrncirik K., Kuhlman J., Lampen A., Scholtz G., Weiβhaar R., Wenzl T., Jasti P.R., Seefelder W.: Analytical approaches for MCPD esters and glycidyl esters in food and biological samples: a review and future perspectives. Food Addit. Contamin. Part A., 2013, 30, 11- 45.
• [13] Davidek J., Velisek J., Kubelka V., Janicek G., Simicowa Z.: Glycerol chlorohydrins and their esters as products of the hydrolysis of tripalmitin, tristearin and triolein with hydrochloric acid. Z. Lebensm. Unters. Forsch., 1980, 171, 14-17.
• [14] Destaillats F., Craft B.D., Sandoz L., Nagy K.: Formation mechanism of MCPD fatty acid diesters in refined palm (Elaeis guineensis) oil and related fractions. Food Addit. Contamin. Part A, 2012, 29, 29-37.
• [15] DGF Standard Method C III 18 (2009). Determination of ester bound 3-MCPD esters and 3-MCPD forming substances in fats and oils by means of GC/MS. Stuttgard, 2009.
• [16] DGF Standard Method C VI 18/2011. Fatty-acid-bound 3 chloropropane-1,2-diol (3-MCPD) and 2,3-epoxipropane-1-ol (glycidol). Determination in oils and fats by GC/MS. Federal Institute for Risk Assessment, Berlin, 2011.
• [17] Divinova V., Svejkovska B., Dolezal M., Velisek J.: Determination of free and bound chloropropane-1,2-diol by gas chromatography with mass spectrometric detection using deuterated 3-chloropropane-1,2-diol as internal standard. Czech J. Food Sci., 2004, 22, 182-189.
• [18] Divinova V., Dolezal M., Velisek J.: Free and bound 3-chloropropane-1,2-diol in coffee surrogates and malts. Czech J. Food Sci., 2007, 25, 39-47.
• [19] Doleżal M., Chaloupska M., Divinova V., Svejkovska B., Velisek J.: Occurrence of 3-chloropropane-1,2-diol and its esters in coffee. Eur. Food Res. Technol., 2005, 221, 221-225.
• [20] Doleżal M., Kortisova J., Zelinkova Z., Velisek J.: Analysis of bread lipids for 3-MCPD esters. Czech J. Food Sci., 2009, 27, S417-S419. Czech J. Food Sci., 2009, 27, S417-S419
• [21] Ermacora A., Hrncirik K.: Evaluation of an improved indirect method for the analysis of 3-MCPD esters based on acid trans- esterification. J. Am. Oil Chem. Soc., 2012, 89, 211-217.
• [22] Ermacora A., Hrncirik K.: A novel method for simultaneous monitoring of 2-MCPD, 3-MCPD and glicidyl esters in oils and fats. J. Am. Oil Chem. Soc., 2013, 90, 1-8.
• [23] Ermacora A., Hrncirik K.: Development of an analytical method for the simultaneous analysis of MCPD and glycidyl esters in oil-based foodstuffs. Food Addit. Contamin. Part A. 2014, 31, 985-994.
• [24] Ermacora A., Hrncirik K.: Study on the thermal degradation of 3-MCPD esters in model systems simulating deodorization of vegetable oils. Food Chem., 2014, 150, 158-163.
• [25] Freudenstein A., Weking J., Matthäus B.: Influence of precursors on the formation of 3-MCPD and glycidyl esters in a model oil under simulated deodorization conditions. Eur. J. Lipid Sci. Technol., 2013, 115, 286-294.
• [26] Gawarska H., Sawilska-Rautenstrauch D., Starski A., Karłowski K.: Występowanie 3-MCPD) w produktach spożywczych. Roczniki PZH., 2009, 60, 213-216.
• [27] Gromadzka J., Biernacka P., Namieśnik J.: 3-monochloro-1,2-propandiol w produktach żywnościowych. Problemy i wyzwania analityczne. Analityka, 2013, 3 (14), 44-50.
• [28] Haines T.D., Adlaf K.J., Pierceal R.M., Lee I., Venkitasubramanian P., Collison M.W.: Direct determination of MCPD fatty acid esters and glycidyl fatty acid esters in vegetable oils by LCTOFMS. J. Am. Oil Chem. Soc., 2011, 88, 1-14.
• [29] Hamlet C.G., Saad P.A., Crews C., Velisek J., Baxter D.E.: Occurence of 3-chloropropane-1,2- diol (3-MCPD) and related compounds in foods. Food Addit. Contamin. Part A., 2002, 17, 619-631.
• [30] Hamlet C.G., Saad P.A., Gray D.A.: Influence of composition, moisture, pH and temperature on the formation and decay kinetics of monochloropropanediols in wheat flour dough. Eur. Food Res. Technol., 2003, 216, 122-128.
• [31] Hamlet C.G., Saad P.A., Gray D.A.: Generation of monochloropropandiols (MCPDs) in model dough systems. Leavened doughts. J. Agric. Food Chem., 2004, 52, 2059-2066.
• [32] Hamlet C.G., Saad P.A., Gray D.A.: Generation of monochloropropandiols (MCPDs) in model dough systems. Unleavened doughts. J. Agric. Food Chem., 2004, 52, 2067-2072.
• [33] Hamlet C.G., Saad P.A.: Chloropropanols and their esters in cereal products. Czech J. Food Sci., 2004, 22, 259-262.
• [34] Hamlet C.G., Asuncion L., Velisek J., Doleżal M., Zelinkowa Z., Crews C.: Formation and occurrence of esters of 3-chloro-propane -1,2-diol (3-CPD) in foods: What we know and what we assume. Eur. J. Lipid Sci. Technol., 2011, 113, 279-303.
• [35] Hori K., Koriyama N., Omori H., Kuriyama M., Arishima T., Tsumura K.: 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 – Food Sci. Technol., 2012, 48, 204-208.
• [36] Hrncirik K., Zelinkowa Z., Ermacora A.: Critical factors of indirect determination of 3-chloropropane-1,2-diol esters. Eur. J. Lipid Sci. Technol., 2011, 113, 361-367.
• [37] IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Some chemicals present in industrial and consumer products, food and drinking-water. Vol. 101 pp. 349-374. Published by IARC, Lyon 2012. Distributed by WHO Press, Geneva.
• [38] Ilko V., Zelinkova Z., Doleżal M., Velisek J.: 3-Chloropropane-1,2-diol fatty acid esters in potato products. Czech J. Food Sci., 2011, 29, 411-419.
• [39] Jędrkiewicz R., Kupska M., Głowacz A., Gromadzka J., Namieśnik J.: 3-MCPD: A world wide problem of food chem. Crit. Rev. Food Sci. Nutr., 2015, 4, DOI: 10.1080/10408398.2013.829414.
• [40] Karasek L., Wenzl T., Ulberth F.: Determination of 3-MCPD esters in edible oil – methods of analysis and comparability of results. Eur. J. Lipid Sci. Technol., 2011, 113, 1433-1442.
• [41] Karsulinova L., Folprechtova B., Dolezal M., Dostalova J., Velisek J.: Analysis of the lipid fraction of coffee creamers, cream aerosols, and boulion cubes for their health risk associated constituents. Czech J. Food Sci., 2007, 25, 257-264.
• [42] Kaze N., Sato H., Yamamoto H., Watanabe Y.: Improvement of accuracy in quantification of 3-monochloropropane-1,2-diol by Deutsche Gesellschaft fur Fettwissenschaft standard methods C-III 18. Eur. J. Lipid Sci. Technol., 2011, 113, 1168-1171.
• [43] Kaze N., Sato H., Yamamoto H., Watanabe Y.: Bidirectional conversion between 3-MCPD and 1,2-MCPD and glycidol in the Procedure of DGF Standard. J. Am. Oil Chem. Soc., 2011, 88, 1143-1151.
• [44] Kuhlman J.: Determination of bound 2,3-epoxy-1-propanol (glycidol) and bound monochloropropanediol (MCPD) in refined oils. Eur. J. Lipid Sci. Technol., 2011, 113, 335-344.
• [45] Kuntzler J., Weisshaar R.: The smoking process – A potent source of 3-chloropropane-1,2-diol (3-MCPD) in meat products. Deutsche Lebensmittel Rundschau, 2006, 102, 397-400.
• [46] Küsters M., Bimber U., Ossenbrüggen A., Reeser S., Gallitzendörfer, Gerhartz M.: Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs. J. Agric. Food Chem., 2010, 58, 6570-6577.
• [47] MacMahon S., Begley T.H., Diachenko G.W.: Occurence of 3-MCPD and glycidyl esters in edible oils in the United States. Food Addit. Contamin. Part A., 2013, 30, 2081-2092.
• [48] MacMahon S., Begley T.H., Diachenko G.W.: Analysis of processing contaminants in edible oils. Part 2. Liquid chromatography – tandem mass spectrometry method for the direct etection of 3- and 2-Monochloropropandiols diesters. J. Agric. Food Chem., 2013, 61, 4748-4757.
• [49] MacMahon S., Mazola E., Begley T.H., Diachenko G.W.: Analysis of processing contaminants in edible oils. Part 1. Liquid Chromatography – Tandem Mass Spectrometry Method for the direct detection of 3-Monochloropropandiol monoesters and glycidyl esters. J. Agric. Food Chem., 2013, 61, 4737-4747.
• [50] Matthäus B., Pudel F., Fehling P., Vosmann K., Freudenstein A.: Strategies for the reduction of 3-MCPD esters and related compounds in oils. Eur. J. Lipid Sci. Technol., 2011, 113, 380-386.
• [51] Matthäus B., Freudenstein A., Pudel P., Fehling P.: Final results of the German FEI research project concerning 3-MCPD esters and related compounds – mitigation strategies. Paper presented at: 9th Eurofed Lipid Congress, 18-21 September 2011, Rotterdam, the Nederlands.
• [52] Matthäus B., Freudenstein A., Vosmann K., Pudel F., Rudolph T., Franke K., Strijowski U.: Mitigation of 3-MCPD esters in refined vegetable oils. Sweet Baking 2012, 1, 12-15.
• [53] Matthäus B.: Organic or not organic – that is the question: How the knowledge about the origin of chlorinated compounds can help to reduce formation of 3-MCPD esters. Eur. J. Lipid Sci. Technol., 2012, 114, 1333-1334.
• [54] Miyazaki K., Koyama K., Sasako K., Hirao T. Indirect method for simultaneous determination of 3-chloro-1,2-propandiol and glycidol fatty acid esters. J. Am. Oil Chem. Soc., 2012, 89, 1403-1407.
• [55] Nagy K., Sandoz L., Craft B.D., Destaillats F.: Massdefect filtering of isotope signatures to reveal the source of chlorinated palm oil contaminants. Food Addit. Contamin. Part A, 2011, 28, 1492-1500.
• [56] PN-EN 14573:2005. Artykuły żywnościowe. Oznaczanie 3-MCPD metodą GC/MS.
• [57] Pudel F., Benecke P., Fehling P., Freudenstein A., Matthaus B., Schwar A.: On the necessity of edible oil refining and possible sources of 3-MCPD and glycidyl esters. Eur. J. Lipid Sci. Technol., 2011, 113, 368-373.
• [58] Rahn A.K.K., Yaylayan V.A.: Thermal degradation of sucralose and its potential in generating chloropropanols in the presence of glycerol. Food Chem., 2010, 118, 56-61.
• [59] Rahn A.K.K., Yaylayan V.A., What do we know about the molecular mechanism of 3-MCPD esters formation. Eur. J. Lipid Sci. Technol., 2011, 113, 323-329.
• [60] Rahn A.K.K., Yaylayan V.A.: Monitoring cycling acyloxonium ion formation in palmitin systems using IR spectroscopy and isotope labeling. Eur. J. Lipid Sci. Technol., 2011, 113, 330-334.
• [61] Ramli M.R., Siew W.L., Ibrahim N.A., Hussein R., Kuntom A., Raazak R.A.A., Nesaratnam K.: Effects of degumming and bleaching on 3-MCPD esters formation during physical refining. J. Am. Oil Chem. Soc., 2011, 88, 1839-1844.
• [62] Rozporządzenie Ministra Zdrowia z dnia 13.01.2003 w sprawie maksymalnych poziomów zanieczyszczeń chemicznych i biologicznych. Dz. U. nr 37, poz. 326. Załącznik nr 5.
• [63] Rozporządzenie Komisji UE nr 1881/2006 z dnia 19 grudnia 2006 ustalające najwyższe dopuszczalne poziomy niektórych zanieczyszczeń w środkach spożywczych. Dz. U. L 364 z 20.12.2006 s. 5.
• [64] Schilter B., Scholtz G., Seefelder W.: Fatty acid esters of chloropropanols and related compound in food: Toxicological aspects. Eur. J. Lipid Sci. Technol., 2011, 113, 309-313.
• [65] Seefelder W., Varga N., Studer A., Williamson G., Scanlan F.P., Stadler R.H.: Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: significance in the formation of 3-MCPD. Food Addit. Contamin., 2008, 25, 391-400.
• [66] Seefelder W., Scholz G., Schilter B.: Structural diversity of dietary fatty esters of chloropropanols and related substances. Eur. J. Lipid Sci. Technol., 2011, 113, 319-322.
• [67] Smidrkal J., Ilko V., Filip V., Doleżal M., Zelinkova Z., Kyselka J., Hradkova I., Velisek J.: Formation of acylglycerol chloro-derivatives in vegetable oils and mitigation strategy. Czech J. Food Sci., 2011, 29, 449-456.
• [68] Starski A., Jędra M., Gawarska H., Postupolski J.: Assessing exposure to 3-MCPD of bakery products based on studies undertaken throughout Poland. Rocz. PZH, 2013, 64, 277-283.
• [69] Strijowski U., Heinz V., Franke K.: Removal of 3-MCPD esters and related substances after refining by adsorbent material. Eur. J. Lipid Sci. Technol., 2011, 113, 387-392.
• [70] Svejkowska B., Novotny O., Divinova V., Reblova Z., Doleżal M., Velisek J.: Esters of 3-chloropropane-1,2-diol in foodstuffs. Czech J. Food Sci., 2004, 22, 190-196.
• [71] Svejkowska B., Doleżal M., Velisek J.: Formation and decomposition o 3-chloropropane-1,2-diol esters in models simulating processed foods. Czech J. Food Sci., 2006, 24, 172-179.
• [72] Tomar R.S., Tsai F.C., Sandy M.S.: Evidence on the carcinogenicity of 3-monochloropropane-1,2-diol (3-MCPD). Reproductive and Cancer Hazard Assessment Branch. Office of Environmental Health Hazard Assessment (OEHHA). California Environ. Protection Agency. Sept. 2010, pp. 1-38.
• [73] Velisek J., Davidek J., Haislova J., Kubelka V., Janicek G., Mankova G.: Chlorohydrins in protein hydrolyzates. Z. Lebensmittel Unters. Forsch., 1978, 167, 241-244.
• [74] Velisek J., Calta P., Crews C., Hasnip S., Doleżal M.: 3-Chloropropane-1,2-diol in models simulating processed foods: Precursors causing its decomposition. Czech J. Food Sci., 2003, 21, 153-161.
• [75] Weiβhaar R.: Determination of total 3-chloropropane-1,2-diol (3-MCPD) in edible oils by cleavage of 3-MCPD esters with sodium methoxide. Eur. J. Lipid Sci. Technol., 2008, 110, 183-186.
• [76] Weiβhaar R.: Fatty acid esters of 3-MCPD: overview of occurrence and exposure estimates. Eur. J. Lipid Sci. Technol., 2011, 113, 304-308.
• [77] Wenzl T., Lachenmeier D.W., Gökmen V.: Analysis of heat-induced contaminants (acrylamide,chloropropanols and furan) in carbohydrate-rich food. Anal. Bioanal. Chem., 2007, 389,119-137.
• [78] Xu X.-M., Wu H.-W., He H.-L., Huang B.-F., Han J.-L., Ren Y.-P.: Study of chloropropanols in soy sauce by gas chromatography-triple quadrupole mass spectrometry with coupled column separation without derivatisation. Food Addit. Contamin. Part A., 2013, 30, 421-429.
• [79] Zalecenie Komisji UE z dnia 10.09.2014 w sprawie monitorowania występowania w żywności 2 i 3-monochloropropano-1,2-diolu (2 i 3-MCPD), estrów kwasów tłuszczowych 2 i 3-MCPD oraz estrów glicydowych kwasów tłuszczowych. Dz. U. L 271/93 z 12.09.2014.
• [80] Zelinkova Z., Svejkovska B., Velisek J., Doleżal M.: Fatty acid esters of 3-chloropropane-1,2-diol in edible oils. Food Addit. Contamin., 2006, 23, 1290-1298.
• [81] Zelinkowa Z., Novotny O., Schurek J., Velisek J., Hajslova J., Doleżal M.: Occurrence of 3-MCPD fatty acid esters in human breast milk. Food Addit. Contamin. Part A., 2008, 25, 669-678.
• [82] Zelinkowa Z., Dolezal M., Velisek J.: 3-Chloropropane-1,2-diol fatty acid esters in potato products. Czech. J. Food Sci., 2009, 27, S421-S424.
• [83] Zelinkova Z., Doleżal M., Velisek J.: Occurrence of 3-chloropropane-1,2-diol fatty acid esters in infant and baby formulas. Eur. Food Res. Technol., 2009, 228, 571-578.

Identyfikatory

DOI

10.15193/ZNTJ/2015/101/052