Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: Significance in the formation of 3-MCPD

Quality and Safety Assurance Department, Nestlé Research Center, Nestec Ltd, CH-1000 Lausanne 26, Switzerland.
Food Additives and Contaminants - Part A Chemistry, Analysis, Control, Exposure and Risk Assessment (Impact Factor: 1.8). 05/2008; 25(4):391-400. DOI: 10.1080/02652030701385241
Source: PubMed


3-Mono-chloropropane-1,2-diol (3-MCPD) is a contaminant that occurs in food in its free (diol) form as well as in an esterified (with fatty acids) form. Using a simple intestinal model, it was demonstrated that 3-MCPD monoesters and 3-MCPD diesters are accepted by intestinal lipase as substrates in vitro. Under the chosen conditions, the yield of 3-MCPD from a 3-MCPD monoester was greater than 95% in approximately 1 min. Release from the diesters was slower, reaching about 45, 65 and 95% of 3-MCPD after 1, 5 and 90 min of incubation, respectively. However, in human, the hydrolysis of 3-MCPD esters is unlikely to release 100% as 3-MCPD, as triglycerides and phospholipids are hydrolysed in the intestine liberating 2-monoglycerides. Assuming a similar metabolism for 3-MCPD esters as that known for acylglycerols in humans in vivo, the de-esterification in positions 1 and 3 would thus be favoured by pancreatic lipases. Therefore, 3-MCPD, and 3-MCPD-2 monoesters would be released, respectively, from the 1-/3-monoesters, and the diesters potentially present in food. Hence, information on the exact amounts of the partial fatty acid chloroesters, i.e. 3-MCPD mono- and diesters, is important to assess the contribution of foods to the bioavailability of 3-MCPD. Therefore, a rapid method for the determination of the ratio of 3-MCPD monoesters to diesters in fats and oils was developed using gas chromatography-mass spectrometry (GC-MS) and isotopically labelled 3-MCPD esters as internal standards. The analysis of 11 different samples of fat mixes typically employed in food manufacturing demonstrated that a maximum of about 15% of the total amount of 3-MCPD bound in esters is present in the monoesterified form. The potentially slower release of 3-MCPD from 3-MCPD diesters, and the mono- to diesters ratio suggest that 3-MCPD esters may in fact contribute only marginally to the overall dietary exposure to 3-MCPD. Further work on the bioavailability, metabolism and possible toxicity of chloroesters per se is warranted.

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    • "Minyak goreng telah diteliti mengandung senyawa 3-monokloro-1,2-propanadiol (3-MCPD) dalam bentuk ester yang merupakan senyawa kontaminan (Seefelder et al. 2008). Analisis 3-MCPD ester pada minyak sawit yang dominan dikonsumsi masyarakat Indonesia sangat penting untuk dilakukan mengingat senyawa ini merupakan prekursor pembentukan 3- MCPD yang telah terbukti sebagai senyawa karsinogen pada hewan percobaan (Cho et al. 2008). "
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    ABSTRACT: A group of components called as 3-monochloropropane-1,2-diol (3-MCPD) esters has been found in some vegetable oils, particularly palm oil. Analysis of these components needs GC-MS instrument to reach a low level detection, parts per billion or ppb level. An effort to validate the 3-MCPD esters analysis by GC-MS method (Weiβhaar method) using phenyl boronic acid (PBA) as a derivatizing agent and isotopic internal standard (IS) 3-MCPD-D5 followed by the determination of 3-MCPD in commercial palm oils has been conducted. The analytical results showed the instrumental performance as follows: instrument linearity for the analysis of 3-MCPD standard solutions containing IS 2.0 μg/mL was obtained at a concentration range of 0.257.50 μg/mL test solution with R 2 higher than 0.990, precision of 3-MCPD as well as IS retention time was less than 2.0 which was acceptable according to JECFA guidance. Instrument detection limit (LOD) and limit of quantitation (LOQ) were read from GC-MS based on the linearity experiment, i.e. 0.17 and 0.59 μg/mL solution, respectively. Method linearity by using palm oil as a matrix also showed R 2 higher than 0.990. Recovery test result at 40 μg/g gave an accuracy at 83.29 ± 7.12 which is in the range of AOAC standard (80110) and precision at 5.38 (less than RSDHORWITZ). Analysis of 14 palm oils from local market showed 100 of the sampels were positive to contain 3-MCPD esters. 3-MCPD esters in palm oil were found at a concentration range of 8.1558.14 µg 3-MCPD/g sample.
    Full-text · Article · Aug 2015
    • "Accordingly, 3- MCPD is frequently detected in refined vegetable oils or in vegetable fat-containing products (Seefelder et al., 2008; Svejkovska et al., 2004; Zelinkova et al., 2006). 3-MCPD occurs in foodstuff not only in its free form, but also esterified in the form of mono-and diesters with different higher fatty acids (Seefelder et al., 2008). Orally ingested 3-MCPD esters are hydrolyzed to 3-MCPD in the gastrointestinal tract. "
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    ABSTRACT: Thermal treatment of foodstuff containing fats and salt promotes the formation of 3-chloropropane-1,2-diol (3-MCPD) and its fatty acid esters. 3-MCPD-exposed rats develop testicular lesions and Leydig cell tumors. 3-MCPD and 3-MCPD ester toxicity is thought to be caused by 3-MCPD and its metabolites, since 3-MCPD esters are hydrolyzed in the gut. Inhibition of glycolysis is one of the few known molecular mechanisms of 3-MCPD toxicity. To obtain deeper insight into this process, a comparative proteomic approach was chosen, based on a 28-days repeated-dose feeding study with male Wistar rats. Animals received equimolar doses of 3-MCPD or 3-MCPD dipalmitate. A lower dose of 3-MCPD dipalmitate was also administered. Absence of histopathological changes supported an analysis of early cellular disturbance. Testes were analyzed by two-dimensional gel electrophoresis followed by mass-spectrometric protein identification. Data provide a comprehensive overview of proteomic changes induced by 3-MCPD and 3-MCPD dipalmitate in rat testis in an early phase of organ impairment. Results are compatible with known 3-MCPD effects on reproductive function, substantially extend our knowledge about cellular responses to 3-MCPD and support the hypothesis that toxicity of 3-MCPD and 3-MCPD esters is mediated via common effectors. DJ-1 was identified as a candidate marker for 3-MCPD exposure. Copyright © 2015 Elsevier Ltd. All rights reserved.
    No preview · Article · Jun 2015 · Food and chemical toxicology: an international journal published for the British Industrial Biological Research Association
    • "refined oils and fats also as mono-or di-esters of fatty acids [3] [4]. Further identified analogous compounds that are supposed to be generated during the deodorization of edible oils are glycidyl esters [5] and 2-monochloropropane- 1,3-diol (2-MCPD) esters [6]. "
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    ABSTRACT: In the present study existing official methods for oils were modified in order to analyse free and bound MCPD and bound glycidol in fish. Free 3-MCPD was determined in aqueous extracts of fishery products. DGF standard methods C-VI-17(10) and C-VI-18(10) and the “3 in 1” method were modified and tested to quantify ester-bound 2- and 3-MCPD and glycidyl esters. The different methods were validated using spiked fish mince and a “naturally contaminanted” reference material consisting of homogenized smoked sprat and fish sticks. The methods showed good agreement. Assay B of the modified DGF method C-VI-18(10) and the adapted “3 in 1“ method allows a quantitative determination of bound 2- and 3-MCPD in fishery products. In addition glycidyl esters can be quantified applying the “3 in 1” method. The screening of various fishery products showed that smoked fish may contain considerable amounts of free 3-MCPD. Concentrations ranged between 8-388 μg/kg wet weight (ww). Only traces of free 3-MCPD were found in all other fishery products. Fish sticks and fried fish products are potential sources of 3- and 2-MCPD esters, but large variation were observed. Bound 3-MCPD ranged between 45-377 μg/kg ww, bound 2-MCPD between 9-116 μg/kg ww.Practical applicationsThe European Food Safety Authority (EFSA) is calling for occurrence data of 2-MCPD, 3-MCPD, 2-MCPD ester, 3-MCPD ester and glycidyl ester in foods including fishery products. At present, there is no official method for the determination of these food processing contaminants in fish and fishery products. Therefore, the approach of this study was to establish analytical methods for the quantification of free and bound MCPD and bound glycidol in fish, based on the modification of existing methods for edible oils. The adapted methods allow a sensitive quantitative determination of the target analytes in various fishery products.
    No preview · Article · May 2015 · European Journal of Lipid Science and Technology
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