Esters of 2- and 3-monochloropropane-1,2-diol (MCPD) are significative contaminants of processed edible oils used as foods or food ingredients. The aim of this study was to develop and validate a new method by GC-MS for the simultaneous quantification of 2 and 3-MCPD esters in infant milk powder and edible vegetable oils. The developed protocol included fat fraction in infant milk powder and edible vegetable oils samples was extracted and treated with sodium methylate-methanol to cleave the ester bonds of the 2- and 3-MCPD esters, moreover, standard samples of deuterium isotope-labeled 2- and 3-MCPD palmitic acid double esters and stearic acid double esters were used as the internal standards. Furthermore, this method was validated when it was applied to food products, concrete manifestation in its good accuracy (the recovery of MCPD esters ranged from 86% to 114%), high sensitivity (the LOD of 3-MCPD and 2-MCPD esters were 0.025 and 0.020 mg/kg, LOQ were 0.075, 0.060 mg/kg, respectively) and satisfactory repeatability (RSD below 6.8%) for all analytes. In the 150 commercial edible vegetable oils and infant formula milk powder samples, we obtained a preliminary profile of MCPD ester contamination.
References
[1]
Wu, P., Zhang, L., Shen, X., Wang, L., Zou, Y., Zhang, J., Tan, Y., Tang, J., Ma, B., Pan, X. and Jiang, W. (2015) Determination of Ethyl Carbamate in Chinese Yellow Rice Wine by Diatomaceous Earth Extraction and GC/MS Method. Journal of AOAC International, 98, 834-838. https://doi.org/10.5740/jaoacint.14-231
[2]
Crews, C., Chiodini, A., Granvogl, M., Hamlet, C., Hrnčiřík, K., Kuhlmann, J., Lampen, A., Scholz, G., Weisshaar, R., Wenzl, T., Jasti, P.R. and Seefelder, W. (2013) Analytical Approaches for MCPD Esters and Glycidyl Esters in Food and Biological Samples: A Review and Future Perspectives. Food Additives & Contaminants: Part A, 30, 11-45. https://doi.org/10.1080/19440049.2012.720385
[3]
Hamlet, C.G., Sadd, P.A., Crews, C., Velíšek, J. and Baxter, D.E. (2002) Occurrence of 3-Chloro-Propane-1, 2-Diol (3-MCPD) and Related Compounds in Foods: A Review. Food Additives & Contaminants, 19, 619-631. https://doi.org/10.1080/02652030210132391
[4]
Gao, B., Li, Y., Huang, G. and Yu, L. (2019) Fatty Acid Esters of 3-Monochloropropanediol: A Review. Annual Review of Food Science and Technology, 10, 259-284. https://doi.org/10.1146/annurev-food-032818-121245
[5]
Xu, B., Zhang, P., Zhou, H., Sun, Y., Tang, J. and Fan, H. (2019) Identification of Novel Genes Associated with Anti-Phagocytic Functions in Streptococcus equi subsp. Zooepidemicus. Veterinary Microbiology, 233, 28-38. https://doi.org/10.1016/j.vetmic.2019.04.023
[6]
Beekman, J. and MacMahon, S. (2019) The Impact of Infant Formula Production on the Concentrations of 3-MCPD and Glycidyl Esters. Food Additives & Contaminants: Part A, 37, 48-60. https://doi.org/10.1080/19440049.2019.1672898
[7]
Schilter, B., Scholz, G. and Seefelder, W. (2011) Fatty Acid Esters of Chloropropanols and Related Compounds in Food: Toxicological Aspects. European Journal of Lipid Science and Technology, 113, 309-313. https://doi.org/10.1002/ejlt.201000311
[8]
Wong, Y.H., Goh, K.M., Nyam, K.L., Cheong, L.Z., Wang, Y., Nehdi, I.A., Mansour, L. and Tan, C.P. (2020) Monitoring of Heat-Induced Carcinogenic Compounds (3-Monochloropropane-1, 2-Diol Esters and Glycidyl Esters) in Fries. Scientific Reports, 10, Article No. 15110. https://doi.org/10.1038/s41598-020-72118-z
[9]
Zhang, Z., Gao, B., Zhang, X., Jiang, Y., Xu, X. and Yu, L. (2015) Formation of 3-Monochloro-1, 2-propanediol (3-MCPD) Di- and Monoesters from Tristearoylglycerol (TSG) and the Potential Catalytic Effect of Fe2+ and Fe3+. Journal of Agricultural and Food Chemistry, 63, 1839-1848. https://doi.org/10.1021/jf5061216
[10]
Zhang, H., Jin, P., Zhang, M., Cheong, L.Z., Hu, P., Zhao, Y., Yu, L., Wang, Y., Jiang, Y. and Xu, X. (2016) Mitigation of 3-Monochloro-1, 2-Propanediol Ester Formation by Radical Scavengers. Journal of Agricultural and Food Chemistry, 64, 5887-5892. https://doi.org/10.1021/acs.jafc.6b02016
[11]
Wang, L., Ying, Y., Hu, Z., Wang, T., Shen, X. and Wu, P. (2016) Simultaneous Determination of 2- and 3-MCPD Esters in Infant Formula Milk Powder by Solid-Phase Extraction and GC-MS Analysis. Journal of AOAC International, 99, 786-791. https://doi.org/10.5740/jaoacint.15-0310
[12]
Santiago, J.K., Silva, W.C., Capristo, M.F., Ferreira, M.C., Ferrari, R.A., Vicente, E., Meirelles, A.J.A., Arisseto, A.P. and Sampaio, K.A. (2021) Organic, Conventional and Sustainable Palm Oil (RSPO): Formation of 2- and 3-MCPD Esters and Glycidyl Esters and Influence of Aqueous Washing on Their Reduction. Food Research International, 140, Article ID: 109998. https://doi.org/10.1016/j.foodres.2020.109998
[13]
Dubois, M., Empl, A.-M., Jaudzems, G., Basle, Q. and KoninGs, E. (2014) Determination of 2- and 3-MCPD as Well as 2- and 3-MCPD Esters and Glycidyl Esters (GE) in Infant and Adult/Pediatric Nutritional Formula by Gas Chromatography Coupled to Mass Spectrometry Method, First Action 2018.03. Journal of AOAC International, 97, 1397-1403. https://doi.org/10.5740/jaoacint.18-0266
[14]
Goh, K.M., Wong, Y.H., Ang, M.Y., Yeo, S.C.M., Abas, F., Lai, O.M. and Tan, C.P. (2019) Comparison Assessment between SIM and MRM Mode in the Analysis of 3-MCPD Ester, 2-MCPD Ester and Glycidyl Ester. Food Research International, 121, 553-560. https://doi.org/10.1016/j.foodres.2018.12.013
[15]
MacMahon, S. (2018) MCPD Esters and Glycidyl Esters: A Review of Analytical Methods. In: Melton, L., Shahidi, F. and Varelis, P., Eds., Encyclopedia of Food Chemistry, Elsevier, Amsterdam, 569-577. https://doi.org/10.1016/B978-0-08-100596-5.21826-X
[16]
Association of Official Agricultural Chemists (2002) AOAC Guidelines for Single Aboratory Validation of Chemical Methods for Dietary Supplements and Botanicals.
[17]
American Oil Chemists’ Society (2013) AOCS Official Method Cd 29a-13: 2- and 3-MCPD Fatty Acid Esters and Glycidol Fatty Acid Esters in Edible Oils and Fats by Acid Transesterification, Urbana (IL).
[18]
Miyazaki, K., Takagishi, Y., Sakamoto, K., Yamada, Y. and Koyama, K. (2022) Development of Indirect Quantitative Methods for 3-MCPD Fatty Acid Esters (3-MCPDEs) and Glycidyl Fatty Acid Esters (GEs) in Thermally Processed Foodstuffs. Journal of Oleo Science, 71, 15-29. https://doi.org/10.5650/jos.ess21114
[19]
Liu, Q., Han, F., Xie, K., Miao, H. and Wu, Y. (2013) Simultaneous Determination of Total Fatty Acid Esters of Chloropropanols in Edible Oils by Gas Chromatography-Mass Spectrometry with Solid-Supported Liquid-Liquid Extraction. Journal of Chromatography A, 1314, 208-215. https://doi.org/10.1016/j.chroma.2013.08.074
[20]
Ermacora, A. and Hrnčiřík, K. (2014) Development of an Analytical Method for the Simultaneous Analysis of MCPD Esters and Glycidyl Esters in Oil-Based Foodstuffs. Food Additives & Contaminants: Part A, 31, 985-994. https://doi.org/10.1080/19440049.2014.905712
[21]
Shaari, N.A., Ahmad Tarmizi, A.H. and Md Sikin, A. (2021) In-House Validation of Accelerated Solvent Extraction-Gas Chromatography-Mass Spectrometry for the Determination of Bound 3- and 2-Monochloropropanediols (MCPD) and Glycidol in Food Products. Food Additives & Contaminants: Part A, 38, 223-236. https://doi.org/10.1080/19440049.2020.1845400
[22]
Koyama, K., Miyazaki, K., Abe, K., Egawa, Y., Kido, H., Kitta, T., Miyashita, T., Nezu, T., Nohara, H., Sano, T., Takahashi, Y., Taniguchi, H., Yada, H., Yamazaki, K. and Watanabe, Y. (2016) Collaborative Study of an Indirect Enzymatic Method for the Simultaneous Analysis of 3-MCPD, 2-MCPD, and Glycidyl Esters in Edible Oils. Journal of Oleo Science, 65, 557-568. https://doi.org/10.5650/jos.ess16021
[23]
Haines, T.D., Adlaf, K.J., Pierceall, R.M., Lee, I., Venkitasubramanian, P. and Collison, M.W. (2011) Direct Determination of MCPD Fatty Acid Esters and Glycidyl Fatty Acid Esters in Vegetable Oils by LC–TOFMS. Journal of the American Oil Chemists’ Society, 88, 1-14. https://doi.org/10.1007/s11746-010-1732-5