A new, direct analytical method using LC-MS/MS for fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible oils

Abstract

A new, direct analytical method for the determination of 3-chloro-1,2-propanediol fatty acid esters (3-MCPD esters) was developed. The targeted 3-MCPD esters included five types of monoester and 25 [corrected] types of diester. Samples (oils and fats) were dissolved in a mixture of tert-butyl methyl ether and ethyl acetate (4:1), purified using two solid-phase extraction (SPE) cartridges (C(18) and silica), then analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Five monoesters and five diesters with the same fatty acid group could be separated and quantified. Pairs of 3-MCPD diesters carrying the same two different fatty acid groups, but at reversed positions (sn-1 and sn-2), could not be separated and so were expressed as a sum of both compounds. The limits of quantification (LOQs) were estimated to be between 0.02 to 0.08 mg kg(-1), depending on the types of 3-MCPD ester. Repeatability expressed as relative standard deviation (RSD(r)%) varied from 5.5% to 25.5%. The new method was shown to be applicable to various commercial edible oils and showed levels of 3-MCPD esters varying from 0.58 to 25.35 mg kg(-1). The levels of mono- and diesters ranged from 0.10 to 0.69 mg kg(-1) and from 0.06 to 16 mg kg(-1), respectively.

Ésteres de cloropropanóis e de glicidol em alimentos

“…46 Diversos estudos têm demonstrado que os níveis de diésteres são superiores aos de monoésteres e que as espécies predominantes dos compostos variam em função do tipo de amostra. 19,21,38,41,47,48 Em óleo de palma, por exemplo, Yamazaki e colaboradores 48 reportaram 12940 µg/kg de diésteres e 1460 µg/ kg de monoésteres de 3-MCPD. Os principais tipos de diésteres encontrados foram 3-MCPD-palmitato-oleato, 3-MCPD-dipalmitato e 3-MCPD-dioleato.…”

“…70 Alguns autores propõem a injeção direta da amostra após diluição em solvente apropriado enquanto outros sugerem a utilização de SPE em cartuchos de sílica, C18 e aminopropil para limpeza do extrato e separação das frações correspondentes a monoésteres e diésteres. 47,48,[76][77][78] O desempenho de métodos diretos ainda não foi avaliado em ensaios de proficiência. Entretanto, alguns autores têm comparado os resultados obtidos por estes métodos àqueles gerados pelos procedimentos indiretos.…”

Characterization of Electron Ionization Mass Spectral (EIMS) Fragmentation Patterns of Chloropropanol Esters of Palmitic Acid Using Isotope Labeling Technique

“…(11) 147 (17) 330 ( 5) 508 (35) 368 ( 34) 3-CP-13 C 3 -DP 239 (12) 43 (50) 335 (100) 138 (15) 150 (15) 333 ( 8) 511 (30) 371 ( 37) 3-CP-d 5 -DP 239 (12) 43 (45) 337 (100) 140 (13) 152 (14) 335 ( 9) 513 (30) 373 ( 42) 2-CPDP 239 (10) 43 (35) 332 ( 30) 135 ( 8) 147 (15) 330 ( 9) 508 (40) 368 (100) 2-CP-d 5 -DP 239 (15) 43 (50) 337 ( 40) 140 (11) 152 (15) 335 ( 9) 513 (40) 373 (100) 3-CP-1-P 239 (11) 43 (64) 135 ( 8) 147 (20) 3-CP-2-P 239 (12) 43 (65) 135 ( 6) 147 (24) 2-CP-P 239 (10) 43 (49) 135 (12) 147 (10) Glycidyl Palmitate 239 ( 5) Table 3 . Furthermore, the data also indicated the incorporation of a single 13 C 1 atom from palmitic acid moiety.…”

Optimization of an Indirect Enzymatic Method for the Simultaneous Analysis of 3-MCPD, 2-MCPD, and Glycidyl Esters in Edible Oils

“…Through a joint study by Japan Oil Chemists Society JOCS and American Oil Chemists Society AOCS , a direct analytical method for Gly-Es was registered as the JOCS Standard Method for the Analysis of Fats, Oils, and Related Materials 2.4.13 -2013 5, 6 . Meanwhile, a direct method for the analysis of 3-MCPD-Es has been reported by Yamazaki et al 7 and Hori et al 8 . These direct analytical techniques are suitable for the toxicological assessment of individual compounds and the elucidation of their formation mechanism; however, the preparation of numerous standard reagents is required.…”