Malaysian Journal of Analytical Sciences, Vol 27 No 5 (2023): 1126 - 1146

 

GLYCIDYL ESTERS: AN UPDATED MINI-REVIEW OF ANALYTICAL METHODS (2015-2022)

 

(Glisidil Ester: Suatu Tinjauan Terkini Ulasan Mini bagi Kaedah Analisis (2015-2022))

 

Nor Syuhada Mat Shukri1, Nur Syafiqah Subri1, Siti Munirah Ishak2, Nur Nadhirah Mohamad Zain2, Mazidatulakmam Miskam3, Wan Nazwanie Wan Abdullah3, Sazlinda Kamaruzaman4, Nor Suhaila Mohamad Hanapi5, Wan Nazihah Wan Ibrahim5, Muggundha Raoov6, and Noorfatimah Yahaya2*

 

1Faculty of Industrial Science & Technology, Universiti Malaysia Pahang, Lebuhraya Tun Razak,

26300 Gambang, Kuantan, Pahang, Malaysia

2Department of Toxicology, Advanced Medical and Dental Institute (AMDI), Universiti Sains Malaysia, 13200 Bertam Kepala Batas, Penang, Malaysia

3School of Chemical Sciences, Universiti Sains Malaysia, 11800, USM Pulau Pinang, Malaysia

4Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia

5Faculty of Applied Sciences, Universiti Teknologi MARA, 40450, Shah Alam, Selangor, Malaysia

6Department of Chemistry,Faculty of Science, Universiti Malaya, Kuala Lumpur 50603, Malaysia

*Corresponding author: noorfatimah@usm.my

 

 

Received: 2 September 2022; Accepted: 21 August 2023; Published:  30 October 2023

 

 

Abstract

Recent issues on the presence of glycidyl ester (GE), a potentially carcinogenic compound, in food have sparked consumer worry. Fatty acid esters of glycidol pose potential food safety concerns and have been classified by IARC as a “likely human carcinogen”. They are generated during the high-temperature deodorization step. Vegetable oils consist primarily of five fatty acids, palmitic acid, linolenic acid, linoleic acid, oleic acid, and stearic acid. Palm kernel and coconut oil also contain significant quantities of lauric acid and myristic acid. These fatty acids of edible oil undergo various reactions, producing different GE. Researchers have developed a GE quantitation method called “indirect” methodology, but this method uses hydrolysis to release glycidol from GE instead of directly targeting the intact fatty acid esters. It also requires a derivatization step before gas chromatography-mass spectrometry (GC–MS) analysis. While the early methods developed to target these contaminants exclusively utilized the ‘indirect’ approach, they were critical in bringing attention to the presence of GE in oils. The factors that are highly related to GE formations include process temperature, process duration, and the presence of precursors. This paper reviews previous studies on various methods and instruments that focused on detecting GE in different matrices from 2015 to 2022.

 

Keywords: glycidyl ester, deodorization, hydrolysis

 

Abstrak

Isu terkini mengenai kehadiran ester glisidil (GE), sebatian berpotensi karsinogenik, di dalam makanan telah mencetuskan kebimbangan dalam kalangan pengguna. Ester asid lemak glisidol menimbulkan potensi keselamatan makanan dan telah diklasifikasikan oleh IARC sebagai "kemungkinan karsinogen manusia". Ia dihasilkan semasa proses penyahbauan pada suhu tinggi. Minyak sayuran yang utama terdiri daripada lima asid lemak, asid palmitik, asid linolenat, asid linoleat, asid oleik, dan asid stearat. Biji kelapa sawit dan minyak kelapa juga mengandungi asid laurik dan asid miristik dalam jumlah yang banyak. Asid-asid lemak dalam minyak yang boleh dimakan tersebut melalui pelbagai tindak balas, menghasilkan GE yang berbeza. Para penyelidik telah membangunkan kaedah kuantitasi GE yang disebut metodologi "tidak langsung", tetapi kaedah ini menggunakan hidrolisis untuk membebaskan glisidol dari GE dan bukannya menyasarkan secara terus ester asid lemak yang utuh. Kaedah ini juga memerlukan langkah derivatisasi sebelum analisis kromatografi gas-spektrometri jisim (GC–MS). Meskipun kaedah-kaedah awal yang dibangunkan untuk mengesan bahan cemar ini menggunakan pendekatan tidak langsung secara eksklusif, kaedah-kaedah tersebut sangat penting dalam mengarah perhatian kepada kehadiran GE di dalam minyak. Antara factor-faktor yang berkait rapat dengan penghasilan GE termasuklah suhu proses, masa proses dan kehadiran pelopor. Makalah ini membentangkan resensi kajian-kajian terdahulu mengenai pelbagai kaedah dan instrumen yang tertumpu kepada pengesanan GE dalam pelbagai matriks dari tahun 2015 hingga 2022.

 

Kata kunci: glisidil ester, penyahbauan, hidrolisis

 

References

1.       Albuquerque, T. G., Costa, H. S., Silva, M. A., and Oliveira, M. B. P. P. (2020). Are chloropropanols and glycidyl fatty acid esters a matter of concern in palm oil? Trends in Food Science and Technology, 105: 494-514.

2.       Arisseto, A. P., Silva, W. C., Scaranelo, G. R., and Vicente, E. (2017). 3-MCPD and glycidyl esters in infant formulas from the Brazilian market: Occurrence and risk assessment. Food Control, 77: 76-81.

3.       Aniołowska, M., and Kita, A. (2016). The effect of frying on glicydyl esters content in palm oil. Food Chemistry, 203: 95-103.

4.       Stadler, R. H. (2015). Monochloropropane-1,2-diol esters (MCPDEs) and glycidyl esters (GEs): An update. Current Opinion in Food Science, 6: 12-18.

5.       Becalski, A., Feng, S., Lau, B. P. Y., and Zhao, T. (2015). A pilot survey of 2- and 3-monochloropropanediol and glycidol fatty acid esters in foods on the Canadian market 2011-2013. Journal of Food Composition and Analysis, 37: 58-66.

6.       Bognár, E., Hellner, G., Radnóti, A., Somogyi, L., and Kemény, Z. (2019). Formation of glycidyl esters during the deodorization of vegetable oils. Hungarian Journal of Industry and Chemistry, 46(2): 67-71.

7.       Arisseto, A. P., Silva, W. C., Tivanello, R. G., Sampaio, K. A., and Vicente, E. (2018). Recent advances in toxicity and analytical methods of monochloropropanediols and glycidyl fatty acid esters in foods. Current Opinion in Food Science, 24: 36-42.

8.       MacMahon, S. (2019). MCPD esters and glycidyl esters: A review of analytical methods. In Encyclopedia of Food Chemistry: pp. 569-577.

9.       Kalkan, O., Topkafa, M., and Kara, H. (2021). Determination of effect of some parameters on formation of 2-monochloropropanediol, 3-monochloropropanediol and glycidyl esters in the frying process with sunflower oil, by using central composite design. Journal of Food Composition and Analysis, 96(7): 103681.

10.    Nguyen, K. H., and Fromberg, A. (2020). Monochloropropanediol and glycidyl esters in infant formula and baby food products on the Danish market: Occurrence and preliminary risk assessment. Food Control, 110(11): 106980.

11.    Zelinkova, Z., Giri, A., and Wenzl, T. (2017). Assessment of critical steps of a GC/MS based indirect analytical method for the determination of fatty acid esters of monochloropropanediols (MCPDEs) and of glycidol (GEs). Food Control, 77: 65-75.

12.    Stadler, R. H., and Seefelder, W. (2016). An update on processing-derived food contaminants: acrylamide, monochloropropane-1,2-diol (MCPD) esters, and glycidyl esters. In Reference Module in Food Science. Elsevier.

13.    Wang, S., Liu, G., and Cheng, W. (2021). Chloride-mediated co-formation of 3-monochloropropanediol esters and glycidyl esters in both model vegetable oils and chemical model systems. Food Research International, 140(381): 109879.

14.    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(12): 109998.

15.    Hew, K. S., Khor, Y. P., Tan, T. B., Yusoff, M. M., Lai, O. M., Asis, A. J., Alharthi, F. A., Nehdi, I. A., and Tan, C. P. (2021). Mitigation of 3-monochloropropane-1,2-diol esters and glycidyl esters in refined palm oil: A new and optimized approach. LWT, 139: 110612.

16.    Wu, P. Y., Chen, H., Su, N. W., Chiou, T. Y., and Lee, W. J. (2021). First determination of glycidyl ester species in edible oils by reverse-phase ultra-performance liquid chromatography coupled with an evaporative light-scattering detector. Molecules, 26(9): 2702.

17.    Hidalgo-Ruiz, J. L., Romero-González, R., Martínez Vidal, J. L., and Garrido Frenich, A. (2021). Determination of 3-monochloropropanediol esters and glycidyl esters in fatty matrices by ultra-high performance liquid chromatography-tandem mass spectrometry. Journal of Chromatography A, 1639: 461940.

18.    FEDIOL (2015). MCPD esters and glycidyl esters. Review of mitigation measures revision 2015. 15SAF108: pp. 1-17.

19.    Aniołowska, M., and Kita, A. (2015). The effect of type of oil and degree of degradation on glycidyl esters content during the frying of french fries. Journal of the American Oil Chemists’ Society, 92(11–12): 1621-1631.

20.    Wenzl, T., Samaras, V., Giri, A., Buttinger, G., Karasek, L., and Zelinkova, Z. (2015). Development and validation of analytical methods for the analysis of 3- MCPD (both in free and ester form) and glycidyl esters in various food matrices and performance of an ad-hoc survey on specific food groups. EFSA Supporting Publication 2015: EN-779, 12(3): 78.

21.    Dingel, A., and Matissek, R. (2015). Esters of 3-monochloropropane-1,2-diol and glycidol: no formation by deep frying during large-scale production of potato crisps. European Food Research and Technology, 241(5): 719-723.

22.    Aniołowska, M., and Kita, A. (2016a). Monitoring of glycidyl fatty acid esters in refined vegetable oils from retail outlets by LC–MS. Journal of the Science of Food and Agriculture, 96(12): 4056-4061.

23.    Samaras, V. G., Giri, A., Zelinkova, Z., Karasek, L., Buttinger, G., and Wenzl, T. (2016). Analytical method for the trace determination of esterified 3- and 2-monochloropropanediol and glycidyl fatty acid esters in various food matrices. Journal of Chromatography A, 1466: 136-147.

24.    Wöhrlin, F., Fry, H., Lahrssen-Wiederholt, M., and Preiß-Weigert, A. (2015). Occurrence of fatty acid esters of 3-MCPD, 2-MCPD and glycidol in infant formula. Food Additives and Contaminants - Part A Chemistry, Analysis, Control, Exposure and Risk Assessment, 32(11): 1810-1822.

25.    Marc, C., Drouard-Pascarel, V., Retho, C., Janvion, P., and Saltron, F. (2016). Determination of MCDP esters and glycidyl esters by microwave extraction in different foodstuffs. Journal of Agricultural and Food Chemistry, 1(1): 1-15.

26.    Leigh, J. K., and MacMahon, S. (2016). Extraction and liquid chromatography-tandem mass spectrometry detection of 3-monochloropropanediol esters and glycidyl esters in infant formula. Journal of Agricultural and Food Chemistry, 64(49): 9442-9451.

27.    Cheng, W., Liu, G., and Liu, X. (2016). Formation of glycidyl fatty acid esters both in real edible oils during laboratory-scale refining and in chemical model during high temperature exposure. Journal of Agricultural and Food Chemistry, 64(29): 5919-5927.

28.    Garballo-Rubio, A., Soto-Chinchilla, J., Moreno, A., and Zafra-Gómez, A. (2017). A novel method for the determination of glycidyl and 3-monochloropropanediol esters in fish oil by gas chromatography tandem mass spectrometry. Talanta, 165: 267-273.

29.    Xu, M., Jin, Z., Yang, Z., Rao, J., and Chen, B. (2020). Optimization and validation of in-situ derivatization and headspace solid-phase microextraction for gas chromatography–mass spectrometry analysis of 3-MCPD esters, 2-MCPD esters and glycidyl esters in edible oils via central composite design. Food Chemistry, 307(5): 125542.

30.    Goh, K. M., Maulidiani, M., Rudiyanto, R., Abas, F., Lai, O. M., Nyam, K. L., Alharthi, F. A., Nehdi, I. A., and Tan, C. P. (2021). The detection of glycidyl ester in edible palm-based cooking oil using FTIR-chemometrics and 1H NMR analysis. Food Control, 125(1): 108018.

31.    Jana, B., Hepner, R., Sellers, K., Majer, H., and Konschnik, J. (n.d.). Optimizing GC-MS and GC-MS/MS analysis of 3-mcpd and glycidyl esters in edible oils. Technical Literature Library, Restek Pure Chromatography: pp 1-10.

32.    Ioime, P., Piva, E., Pozzebon, M., and Pascali, J. P. (2021). Automated sample preparation and analysis by gas chromatography tandem mass spectrometry (GC–MS/MS) for the determination of 3- and 2-monochloropropanediol (MCPD) esters and glycidol esters in edible oils. Journal of Chromatography A, 1650: 462253.