Analysis of Processing Contaminants in Edible Oils. Part 1. Liquid Chromatography–Tandem Mass Spectrometry Method for the Direct Detection of 3-Monochloropropanediol Monoesters and Glycidyl Esters

Abstract

A new analytical method has been developed and validated for the detection of glycidyl esters (GEs) and 3-monochloropropanediol (3-MCPD) monoesters in edible oils. The target compounds represent two classes of potentially carcinogenic chemical contaminants formed during the processing of edible oils. Target analytes are separated from edible oil matrices using a two-step solid-phase extraction (SPE) procedure. The extracts are then analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). Chromatographic conditions that separate sn-1 and sn-2 monoesters of 3-MCPD have been developed for the first time. The method has been validated for GEs, sn-1 3-MCPD monoesters of lauric, myristic, linolenic, linoleic, oleic, and stearic acids, and sn-2 3-MCPD monoesters of oleic and palmitic acids in coconut, olive, and palm oils using an external calibration curve. The range of average recoveries and relative standard deviations (RSDs) across the three oil matrices at three spiking concentrations are 84-115% (3-16% RSD) for the GEs, 95-113% (1-10% RSD) for the sn-1 3-MCPD monoesters, and 76.8-103% (5.1-11.2% RSD) for the sn-2 3-MCPD monoesters, with limits of quantitation at or below 30 ng/g for the GEs, 60 ng/g for sn-1 3-MCPD monoesters, and 180 ng/g for sn-2 3-MCPD monoesters.

Direct determination of fatty acid esters of 3-chloro-1, 2-propanediol in edible vegetable oils by isotope dilution - ultra high performance liquid chromatography - triple quadrupole mass spectrometry

“…to previously reported methods [31,[33][34][35]39,40,44,46], lower LODs were obtained in the present method (Table 4). For the extraction and cleanup of 3-MCPD esters in edible oil samples, the matrix interferences of MSPD cleanup in this study should be lower than that of the "Direct dilution and injection" method [36,47].…”

“…Analysis of monoester and diester fractions can clearly provide detailed information on the individual esters, which is important for the toxicological studies or the understanding of the pollution profile of different 3-MCPD esters. However, the direct methods for 3-MCPD esters have not taken into the separation of 3-MCPD esters and 2-MCPD esters with the exception of the study by MacMahon [39][40][41], which has separated three pairs of monoester isomers and eleven pairs of diester isomers.…”

Occurrence of fatty acid esters of 3-MCPD, 2-MCPD and glycidol in infant formula

“…The esters are detected by means of LC-MS, LC-MS/MS, LCToF-MS, GC-MS or LC-high-resolution-MS (Moravcova et al 2012;MacMahon et al 2013b andDubois et al 2011;Haines et al 2011). For glycidyl-esters different direct methods were developed (Dubois et al 2011;Haines et al 2011;Becalski et al 2012;Steenbergen et al 2013) and one direct LC-MS method developed by Masukawa et al (2011) and Shiro et al (2011) was validated in a collaborative trial and adopted by the American Oil Chemists' Society (AOCS) (Blumhorst et al 2013;AOAC 2012).…”

Chloropropanols, Chloropropandiols and Their Esters in Food – Formation, Occurrence, Determination, Reduction of Content

“…MacMahon i wsp. [47 -49] opublikowali serię prac dotyczących bezpośredniego oznaczania estrów MCPD, w tym: zasady oznaczania monoestrów 3-MCPD oraz estrów glicydolu w olejach rafinowanych [49]. Autorzy opracowali metodę (z walidacją) bezpośredniego oznaczania diestrów 3-MCPD.…”