Rapid Quantitative Profiling of Lipid Oxidation Products in a Food Emulsion by 1H NMR.

Lipid oxidation is one of the most important reasons for the compromised shelf life of food emulsions. A major bottleneck in unravelling the underlying mechanisms is the lack of methods that provide a rapid, quantitative, and comprehensive molecular view on lipid oxidation in these heterogeneous systems. In this study, the unbiased and quantitative nature of 1H NMR was exploited to assess lipid oxidation products in mayonnaise, a particularly oxidation-prone food emulsion. An efficient and robust procedure was implemented to produce samples where the 1H NMR signals of oxidation products could be observed in a well resolved and reproducible manner. 1H NMR signals of hydroperoxides were assigned in a fatty acid and isomer specific way. Band-selective 1H NMR pulse excitation allowed immediate and precise (RSDR = 5.9%) quantification of both hydroperoxides and aldehydes with high throughput and large dynamic range at levels of 0.03 mmol/kg. Explorative multivariate data modeling of the quantitative 1H NMR profiles revealed that shelf life temperature has a significant impact on lipid oxidation mechanisms.

Influence of oil composition on the formation of fatty acid esters of 2-chloropropane-1,3-diol (2-MCPD) and 3-chloropropane-1,2-diol (3-MCPD) under conditions simulating oil refining.

The toxicological relevance and widespread occurrence of fatty acid esters of 2-chloropropane-1,3-diol (2-MCPD) and 3-chloropropane-1,2-diol (3-MCPD) in refined oils and fats have recently triggered an interest in the mechanism of formation and decomposition of these contaminants during oil processing. In this work, the effect of the main precursors, namely acylglycerols and chlorinated compounds, on the formation yield of MCPD esters was investigated in model systems simulating oil deodorization. The composition of the oils was modified by enzymatic hydrolysis, silica gel purification and application of various refining steps prior to deodorization (namely degumming, neutralization, bleaching). Partial acylglycerols showed greater ability, than did triacylglycerols, to form MCPD esters. However, no direct correlation was found between these two parameters, since the availability of chloride ions was the main limiting factor in the formation reaction. Polar chlorinated compounds were found to be the main chloride donors, although the presence of reactive non-polar chloride-donating species was also observed.

Development of an analytical method for the simultaneous analysis of MCPD esters and glycidyl esters in oil-based foodstuffs.

Substantial progress has been recently made in the development and optimisation of analytical methods for the quantification of 2-MCPD, 3-MCPD and glycidyl esters in oils and fats, and there are a few methods currently available that allow a reliable quantification of these contaminants in bulk oils and fats. On the other hand, no standard method for the analysis of foodstuffs has yet been established. The aim of this study was the development and validation of a new method for the simultaneous quantification of 2-MCPD, 3-MCPD and glycidyl esters in oil-based food products. The developed protocol includes a first step of liquid-liquid extraction and purification of the lipophilic substances of the sample, followed by the application of a previously developed procedure based on acid transesterification, for the indirect quantification of these contaminants in oils and fats. The method validation was carried out on food products (fat-based spreads, creams, margarine, mayonnaise) manufactured in-house, in order to control the manufacturing process and account for any food matrix-analyte interactions (the sample spiking was carried out on the single components used for the formulations rather than the final products). The method showed good accuracy (the recoveries ranged from 97% to 106% for bound 3-MCPD and 2-MCPD and from 88% to 115% for bound glycidol) and sensitivity (the LOD was 0.04 and 0.05 mg kg(-1) for bound MCPD and glycidol, respectively). Repeatability and reproducibility were satisfactory (RSD below 2% and 5%, respectively) for all analytes. The levels of salts and surface-active compounds in the formulation were found to have no impact on the accuracy and the other parameters of the method.

Study on the thermal degradation of 3-MCPD esters in model systems simulating deodorization of vegetable oils.

The establishment of effective strategies for the mitigation of 3-MCPD esters in refined vegetable oils is restricted by limited knowledge of their mechanisms of formation and decomposition. In order to gain better understanding on the thermal stability of these compounds, a model system for mimicking oil refining conditions was developed. Pure 3-MCPD esters (3-MCPD dipalmitate and 3-MCPD dilaurate) were subjected to thermal treatment (180-260°C) and the degradation products where monitored over time (0-24h). After 24h of treatment, both 3-MCPD esters showed a significant degradation (ranging from 30% to 70%), correlating with the temperature applied. The degradation pathway, similar for both compounds, was found to involve isomerisation (very rapid, equilibrium was reached within 2h at 260°C), dechlorination and deacylation reactions. The higher relative abundance of non-chlorinated compounds, namely acylglycerols, in the first stages of the treatment suggested that dechlorination is preferred over deacylation with the conditions applied in this study.

Direct analysis of intact glycidyl fatty acid esters in edible oils using gas chromatography-mass spectrometry.

Glycidyl esters (GE), fatty acid esters of glycidol, are process contaminants formed during edible oil processing. A novel direct method for the determination of intact GE in oils and fats based on gas chromatography-mass spectrometry (GC-MS) is presented. The method consists of a simple extraction step of GE from the lipid matrix, purification of the extract and isolation of GE by normal phase liquid chromatography (NPLC). Individual GE in the final fraction are separated and quantified by standard GC-MS operated in selected ion monitoring (SIM) mode. The setup and conditions of the GC-MS were optimized in such a way that thermal degradation of GE and artifact formation were prevented. The method exhibits very good performance parameters: the limit of detection was approximately 0.01 mg/kg for the individual GE (corresponding to 0.002-0.003 mg/kg of free glycidol), the repeatability was in the range of 5-12% for individual GE at levels above 0.1mg/kg, and recovery values ranged from 85 to 115% depending on the level and the chain identity of the GE. The comparison of experimental values with spiked levels and with the results obtained by other methods confirmed a good trueness. Over a period of several months of extensive use the method was found to be very reliable and rugged.