Development of a QuEChERS method for simultaneous analysis of 3-Monochloropropane-1,2-diol monoesters and Glycidyl esters in edible oils and margarine by LC-APCI-MS/MS.

A simple, fast and effective direct method based on HPLC-APCI-QqQ-MS/MS has been developed to simultaneously determine four 3-monochloropropane-1,2-diol monoesters (3-MCPDE) esterified with palmitic, linoleic, stearic, and oleic acid, and two glycidyl esters (GE) with palmitic and oleic acid in margarine and olive oil using a QuEChERS approach. Factors affecting the efficiency of the extraction process were assessed, including type and amount of salt, extraction solvent, test portion amount, and clean-up sorbent. The analytical method was validated according to Food and Drug Administration (FDA) guidelines using matrix-matched calibration with internal standards and showed good results in terms of linearity (r2 > 0.9992), accuracy (80

Fractionated palm oils: emerging roles in the food industry and possible cardiovascular effects.

The public health debate about fats and human health has been ongoing for a long time. Specifically, the fat types commonly used in the food industry and the techniques used in extracting them are remarkable in terms of human health. Among these, palm oil, which is mainly associated with cardiovascular disease (CVD), is a vegetable oil type that is widely used in the food industry. Moreover, the fractionation of palm oil has become quite common in the food industry when compared to other culinary oils and fats. Fractional crystallization, which has been recently regarded as an alternative to hydrogenization and interesterification methods, has become more popular in edible oil technology, even though it is an ancient method. The main fractions of palm oil are palm olein and palm stearin. Palm oil fractions, which have some pros and cons, are used in edible oils, such as margarine/shortening, as well as bread and cake-like pastry production. Since the fatty acid composition of palm oil, palm kernel oil, and their fractions is different, each type of oil needs to be evaluated separately with regards to their CVD effects and food preparation applications. However, the effects of the fractionation method and the fractional palm oil produced on health are controversial in the literature. In this review, the use of palm oil produced via the fractional crystallization method in the food industry and its potential CVD effects were evaluated.

Non-targeted detection of butter adulteration using pointwise UHPLC-ELSD and UHPLC-UV fingerprints with chemometrics.

A non-targeted chemometric method was devised to detect possible butter adulteration without prior knowledge of the adulterant and marker compounds. Nine common edible oils including vegetable oils, animal fats and margarines were selected as potential adulterants to build a unified classification model. The samples were analyzed using the high-performance liquid chromatography hyphenated with an evaporative light scattering detector (UHPLC-ELSD) and an ultraviolet detector (UHPLC-UV), with the pointwise chromatograms instead of individual peaks for modelling. Both models achieved over 95% correct classification in external validation at the adulteration levels as low as 5% (w/w). The root mean squared errors of prediction (RMSEP) of the regression model were 0.9865 and 1.9080 for UHPLC-ELSD and UHPLC-UV, respectively. Non-targeted chemometrics analyses based on pointwise chromatographic profiles could be valuable for detecting adulterated butter.

Determination of 3-monochloropropanediol esters and glycidyl esters in fatty matrices by ultra-high performance liquid chromatography-tandem mass spectrometry.

The development and validation of a method for the analysis of traces of 3-monochloropropanediol (3-MCPD) esters (19) and glycidyl esters (7) of fatty acids in vegetable oils, margarine, biscuits and croissants was performed. An extraction method based on the use of solvents (tert­butyl methyl ether (20% ethyl acetate, v/v)) was carried out and cleaning of the extract with a mixture of sorbents (Si-SAX, PSA and Z-sep+) was optimized for the elimination of fatty interferents. The analysis of the targeted compounds was carried out by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry, using a triple quadrupole analyzer (UHPLC-MS/MS-QqQ). The validation of the method provided trueness values between 72 and 118% and precision lower than 20%. The limits of quantification ranged from 0.01 to 0.1 mg kg-1, which were below the current legal limits. Twenty samples of vegetable oils as well of 4 samples of margarine, biscuits and croissants were analyzed. Six out of the 24 samples (25%) exceeded the limits set by European legislation, and a maximum contamination of 3-MCPD esters at 2.52 mg kg-1 was obtained in a sample of corn oil (being 1-myristoyl-3-MCPD the compound detected at the highest concentration). A maximum concentration of glycidyl esters at 7.84 mg kg-1 was determined in a soybean oil sample (glycidyl linoleate as the main compound). Only one sample of olive oil exceeded the maximum allowable limit for 3-MCPD esters with a value of 1.72 mg kg-1, expressed as 3-MCPD.

Properties of margarines prepared from soybean oil oleogels with mixtures of candelilla wax and beeswax.

The aim of this study was to examine the physical properties of margarines prepared from oleogels with binary mixtures of candelilla wax (CDW) and beeswax (BW) in soybean oil. Some of the margarines made from oleogels with mixtures of CDW and BW had higher firmness than those made with one wax. For example, a 3% wax margarine made with 25% CDW and 75% BW had significantly higher firmness (0.97 N) than those with 100% CDW (0.59 N) and with 100% BW (0.11 N). Differential scanning calorimetry (DSC) and solid fat content (SFC) analyses revealed eutectic melting properties for binary wax margarines, which may be desirable since wax oleogel-based margarines often have higher melting points than conventional margarines. For example, the major melting point of 3% wax margarine made with 50% CDW and 50% BW was 43.85 °C, while for margarines made with 100% CDW or 100% BW, the melting points were at 46.00% and 47.61 °C, respectively. SFC was lowest for margarines with 50 or 75% BW; for example, 3% wax margarine with 25% CDW and 75% BW had 0.72% SFC at 40 °C while those with 100% CDW and 100% BW had 1.19 and 1.13% SFC, respectively. However, dropping point constantly decreased with increasing BW ratios. This study demonstrated that by mixing two waxes, the firmness of oleogel-based margarines could be increased, and the melting point could be tailored by the ratio of two waxes. PRACTICAL APPLICATION: This study demonstrated that firmness and melting properties of margarines prepared from wax-oleogels can be improved by mixing two waxes, making their practical application more feasible. Firmness of margarines prepared with oleogels of binary mixtures of candelilla wax and beeswax were higher than those with pure waxes. The melting point of wax oleogel-based margarines was decreased by use of binary mixtures of candelilla wax and beeswax.

Preparation and characterization of oleogel emulsions: A comparative study between the use of recovered and commercial sunflower waxes as structuring agent.

The objective of this study was to evaluate the capacity of recovered sunflower waxes (RW) to be used as a structuring agent of oleogel emulsions in comparison with commercial sunflower waxes (CW). RW were recovered from filter cake with a simple hexane extraction procedure. For this purpose, oleogel-based emulsions were prepared using 2%, 3.5%, and 5% w/w wax in oleogel and characterized using several physicochemical techniques in order to evaluate the potential of these materials to develop products with functionality similar to commercial margarines. The total wax esters content of RW was similar to that of the CW and was mainly composed of wax esters with more than 44 carbon atoms (crystallizable waxes). Polarized light and scanning electron microscopy showed that RW produced emulsions with more intricate crystalline networks composed of smaller platelets than CW. The melting enthalpy was greater in CW emulsions than RW emulsions, which was in agreement with the thermal behavior found for CW and RW. The oil binding capacity of CW oleogel emulsions was higher than the RW ones, and this property improved with the increase in wax concentration. Likewise, the elastic behavior, as well as hardness and adhesiveness, increased with the wax content as a result of a greater amount of microstructural elements composing the network of these semisolid materials. The oleogel emulsions stability was monitored for 2 months at room temperature. The increase of CW concentration slowed down the coalescence process, but this behavior was not observed for RW emulsions. Obtained results demonstrated that RW oleogel emulsions have the potential to replace the functionality of soft spreadable products. PRACTICAL APPLICATION: Wax esters are organogelators that have been shown to successfully gel liquid oil at low concentrations. In this work, we are interested in evaluating the potential of sunflower waxes recovered from filter cake, a waste generated during refined oil production, to structure oil and produce oil-in-water emulsions with functionality similar to commercial margarines. With this, it is sought not only the development of healthier fats but also the use of wastes to generate more sustainable products.

Simultaneous Analysis of Epoxidized and Hydroperoxidized Triacylglycerols in Canola Oil and Margarine by LC-MS.

The progress of lipid oxidation in foods is evaluated by measuring the peroxides and their scission products. However, hydrogen abstraction-independent pathways are not considered by commonly applied methods despite the known reactivity of epoxides toward biomolecules. Herein, a novel liquid chromatography tandem-mass spectrometry method was developed to detect hydroperoxidized and epoxidized triacylglycerols (TAGs) without derivatization or hydrolyzation of food samples. Epoxidized TAGs could be detected in refined canola oil at concentrations of 96.8 ± 2.08 µM, while only 5.77 ± 0.04 µM hydroperoxidized TAGs could be determined. In contrast to canola oil, margarine was more resistant to lipid oxidation since generation of epoxidized TAGs could only be marginally enhanced from 21.7 ± 0.48 to 28.8 ± 0.64 µM in margarine after treatment at 180 °C for 60 min, as also reflected by a peroxide value of 0.80 ± 0.00 mequiv O2/kg, which remained unchanged. The new method allows the assessment of food safety by the simultaneous measurement of hydroperoxidized and epoxidized TAGs without hydrolysis and laborious sample preparation.

Development of a partitioned liquid-liquid extraction- dispersive solid phase extraction procedure followed by liquid chromatography-tandem mass spectrometry for analysis of 3-monochloropropane-1,2-diol diesters in edible oils.

A fast and effective method using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach which includes partitioned liquid-liquid extraction (PLLE) and dispersive solid phase extraction (dSPE) clean-up step for the determination of seven 3-monochloropropane-1,2-diol (3-MCPD) fatty acid diesters in vegetable oils is developed and validated according to the Food and Drug Administration (FDA) guidelines. Due to the complexity of the matrices, combination of silica based sorbents (Silica Strong Anion Exchange (Si-SAX), Supel™ QuE Z-Sep+ (Z-Sep+) and Primary Secondary Amine (PSA) were tested for lipid removal. The effect of several experimental factors on the efficiency of the extraction procedure was studied by a screening design 3422//16 and a response surface Doehlert design. The separation and determination was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The method provided suitable linearity (r2 > 0.9960), precision (relative standard deviation (RSD) lower than 10%) and accuracy, in terms of recovery. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 10 to 20 µg kg -1 and from 25 to 50 µg kg-1, respectively. The recoveries at three spiking levels of 100, 250, and 500 µg kg-1 were over the range of 71.4-122.9% with RSD lower than 13%. The method was successfully applied in edible oils and fatty food samples. The results provide valuable information to assess the risk of exposure to these foodborne contaminants.

A low trans margarine fat analog to beef tallow for healthier formulations: Optimization of enzymatic interesterification using soybean oil and fully hydrogenated palm oil.

The health hazard of tallow and partial hydrogenated oils is well known in margarine productions. For this, food manufactures are urged to develop novel alternatives for healthier margarine formulations. The highest interesterification degree acquired with lipase Lipozyme 435 standing out from other catalysts (solid acid, sodium hydroxide and methoxide) was applied to produce low trans margarine fat analogs to beef tallow (BT) with the blend of soybean oil (SO) and fully hydrogenated palm oil (FHPO) in a mass ratio of 4:3. Reaction parameters like enzyme dosage (4.2 wt%), temperature (95 °C) and time (245 min) were optimized using the Box-Behnken design. Regarding fatty acid profiles, triacylglycerol species, solid fat content, polymorphism, melting and crystallization behaviors, the resulting interesterified oil was characterized in comparison with BT, FHPO and the SO-FHPO blend so as to prove its potential in formulating low trans fat margarines because of desirable physicochemical properties and polymorphs.

Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters.

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (TM), programmable TM during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension (1D) phase polarity combined with a lower 2D phase polarity, for instance 1D IL111i with 2D IL59 gave the best result; the greater difference in 1D/2D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

Physical compatibility between wax esters and triglycerides in hybrid shortenings and margarines prepared in rice bran oil.

BACKGROUND: Wax esters contribute to the transformation of liquid oils into solid-like oleogel systems, which can act as alternatives for trans- and/or saturated fats in food products. The use of solely waxes reduces the solid content, consistency and sensory quality in the final products. Therefore, a combination of sunflower wax and palm fat in rice bran oil was created to accomplish the hybrid low-saturated shortenings and margarines with a compatible structure and lower amounts of saturated fats. RESULTS: During cooling of the hybrid shortenings, sunflower wax crystallized first and acted as nucleation sites for the crystallisation of palm fat. At 5 °C, a mixture of different crystal morphologies (α, ß', and ß crystals) existed in the hybrid shortening. In margarine processing, the hybrid samples were subjected to a simultaneous cooling-emulsification, in which sunflower wax crystallised first at the interface and adsorbed onto the water droplets. Based on the hardness measurements, the maximum amount of palm fat replaceable by 1.0%wt sunflower wax was up to 40% in shortenings and 25% in margarines. A higher amount of sunflower wax (2.5%wt) reduced up to 40% of saturated fats in the hybrid emulsions. CONCLUSION: The addition of 1.0%wt sunflower wax enhanced the solid content and network strength of hybrid palm-based shortenings. Sunflower wax helped to stabilise the water droplets inside the wax-based crystalline network without flocculation during shear-cooling. This research provides fundamental insight into the structuring of hybrid systems containing waxes, which could be interesting for the production of low-saturated fat products in the food industry. © 2017 Society of Chemical Industry.

Margarines and Fast-Food French Fries: Low Content of trans Fatty Acids.

The lipid fraction of margarines and fast food French fries, two types of foods traditionally high in trans fatty acids (TFA), is assessed. TFA data reported worldwide during the last 20 years have been gathered and show that some countries still report high TFA amounts in these products. The content of TFA was analysed in margarines (two store and four premium brands) and French-fries from fast-food restaurants (five chains). All samples were collected in Pamplona (Navarra, Spain). The margarines showed mean values of 0.68% and 0.43% (g TFA/100 g fat) for the store and premium brands, respectively. The French fries' values ranged from 0.49% to 0.89%. All samples were lower than the 2% set by some European countries as the maximum legal content of TFA in fats, and contained less than 0.5 g/serving, so they could also be considered "trans free products". This work confirmed that the presence of TFA is not significant in the two analysed products and contributes updated food composition tables, key tools for epidemiological and nutrition studies.

Omega-3 fatty acids, phenolic compounds and antioxidant characteristics of chia oil supplemented margarine.

BACKGROUND: Chia (Salvia hispanica L.) is known as power house of omega fatty acids which has great health benefits. It contains up to 78% linolenic acid (ω-3) and 18% linoleic acid (ω-6), which could be a great source of omega-3 fatty acids for functional foods. Therefore, in this study, margarines were prepared with supplementation of different concentrations of chia oil to enhance omega-3 fatty acids, antioxidant characteristics and oxidative stability of the product. METHODS: Margarines were formulated from non-hydrogenated palm oil, palm kernel and butter. Margarines were supplemented with 5, 10, 15 and 20% chia oil (T1, T2, T3 and T4), respectively. Margarine without any addition of chia oil was kept as control. Margarine samples were stored at 5 °C for a period of 90 days. Physico-chemical (fat, moisture, refractive index, melting point, solid fat index, fatty acids profile, total phenolic contents, DPPH free radical scavenging activity, free fatty acids and peroxide value) and sensory characteristics were studied at the interval of 45 days. RESULTS: The melting point of T1, T2, T3 and T4 developed in current investigation were 34.2, 33.8, 33.1 and 32.5 °C, respectively. The solid fat index of control, T1, T2, T3 and T4 were 47.21, 22.71, 20.33, 18.12 and 16.58%, respectively. The α-linolenic acid contents in T1, T2, T3 and T4 were found 2.92, 5.85, 9.22, 12.29%, respectively. The concentration of eicosanoic acid in T2, T3 and T4 was 1.82, 3.52, 6.43 and 9.81%, respectively. The content of docosahexanoic acid in T2, T3 and T4 was present 1.26, 2.64, 3.49 and 5.19%, respectively. The omega-3 fatty acids were not detected in the control sample. Total phenolic contents of control, T1, T2, T3 and T4 samples were 0.27, 2.22, 4.15, 7.23 and 11.42 mg GAE/mL, respectively. DPPH free radical scavenging activity for control, T1, T2, T3 and T4 was noted 65.8, 5.37, 17.82, 24.95, 45.42 and 62.8%, respectively. Chlorogenic acid, caffeic acid, quercetin, phenolic glycoside k and phenolic glycoside Q in T3 were present 0.78, 0.73, 1.82, 4.12 and 4.49 mg/mL, respectively. After 90 days of storage period, free fatty acids and peroxide value of all the treatments were less than 0.2 (% and MeqO2/kg). Sensory characteristics of treatments were not different from the control. CONCLUSION: Margarines supplemented with chia oil showed enhanced level of omega-3 fatty acids and antioxidant characteristics. These results suggest that chia oil can be used for formulation of margarine with increased level of omega-3 fatty acids and acceptable sensory characteristics.

Determination of vitamin E in margarines and edible oils using square wave anodic stripping voltammetry with a glassy carbon paste electrode.

A new electroanalytical method for determination of vitamin E in the form of the total content of tocopherols present in margarines and edible oils has been developed. The method is based on extraction of these biologically active compounds into silicone oil, acting as lipophilic binder of glassy carbon paste electrode, with subsequent electrochemical detection by square wave anodic stripping voltammetry (SWASV) in 0.1M HNO3. The values of vitamin E contents were expressed as mass equivalent of α-tocopherol known as the most active form of this lipophilic vitamin. The linear ranges for α-tocopherol determination were 5×10-7-4×10-5 and 5×10-8-1×10-5molL-1 with the detection limits of 1×10-7 and 3.3×10-9molL-1 for 5 and 15min accumulation, respectively. The results have shown that SWASV with extraction step is very sensitive method for the determination of vitamin E, being comparable to reversed-phase high performance liquid chromatography chosen as reference method.

Effect of Fatty Acid Chain Length on the Crystallization Behavior of Trans-free Margarine Basestocks during Storage.

In order to obtain margarine free of trans-fatty acids, four interesterified basestocks were prepared by chemical interesterification (CIE) of oil blends. Different ratios of palm stearin, palm olein and soybean oil were mixed without and with 1) fully hydrogenated Acer truncatum oil (FHATO), 2) fully hydrogenated rapeseed oil or 3) palm kernel oil containing a similar amount of saturated, monounsaturated and polyunsaturated fatty acids, but different saturated fatty acid length for CIE. Compared to the physical blends, the CIE samples demonstrated lower slip melting points and decreased solid fat contents, especially at high temperatures, indicating that the CIE samples might have improved mouthfeel. In all CIE samples, the ß crystal form disappeared and only the ß' crystal form was observed, except for sample 2, which contained a mixed ß and ß' forms. Furthermore, in all CIE samples, except sample 1, the ß' crystal forms began transforming to ß form after only two cycles of higher temperature treatments indicating that the CIE sample with FHATO had the most resistance to temperature fluctuation during storage which may be attributed to its longer saturated chains. In conclusion, the CIE basestocks containing longer saturated fatty acids could be more suitable for margarine use.

Thermal stability of plant sterols and formation of their oxidation products in vegetable oils and margarines upon controlled heating.

Fat-based products like vegetable oils and margarines are commonly used for cooking, which may enhance oxidation of plant sterols (PS) present therein, leading to the formation of PS oxidation products (POP). The present study aims to assess the kinetics of POP formation in six different fat-based products. Vegetable oils and margarines without and with added PS (7.5-7.6% w/w) in esterified form were heated in a Petri-dish at temperatures of 150, 180 and 210°C for 8, 12 and 16min. PS and POP were analysed using GC-FID and GC-MS-SIM, respectively. Increasing PS content, temperature and heating time led to higher POP formation in all tested fat-based products. PS (either naturally occurring or added) in margarines were less susceptible to oxidation as compared to PS in vegetable oils. The susceptibility of sitosterol to oxidation was about 20% lower than that of campesterol under all the applied experimental conditions. During heating, the relative abundance of 7-keto-PS (expressed as% of total POP) decreased in all the fat-based products regardless of their PS contents, which was accompanied by an increase in the relative abundance of 7-OH-PS and 5,6-epoxy-PS, while PS-triols were fairly unchanged. In conclusion, heating time, temperature, initial PS content and the matrix of the fat-based products (vegetable oil vs. margarine) showed distinct effects on POP formation and composition of individual POP formed.

Impact of pecan nut shell aqueous extract on the oxidative properties of margarines during storage.

BACKGROUND: The oxidative properties of margarines supplemented with pecan nut shell extract, rosemary extract and butylated hydroxytoluene (BHT) were investigated. RESULTS: The extracts of pecan nut shell and rosemary showed a high content of total phenolics and condensed tannins (93 and 102.9 mg GAE g-1 and 46 and 38.9 mg CE g-1 respectively) as well as a high antioxidant activity (1257 and 2306 µmol TEAC g-1 and 293 and 856 mg TEAC g-1 by ABTS and DPPH methods respectively). Gallic acid, chlorogenic acid, p-hydroxybenzoic acid, epicatechin and epicatechin gallate were identified in the pecan nut shell extract. Peroxide and p-anisidine values of 3.75-4.43 meq kg-1 and 1.22-2.73 respectively, Totox values of 9.88-10.8 and specific extinction values of 4.38-4.59 and 0.92-0.94 at 232 and 268 nm respectively were observed after 8 months of storage in the studied samples. CONCLUSION: Margarines supplemented with pecan nut shell extract, rosemary extract or BHT during prolonged storage were found to be of equal quality within the degree of confidence limits. The extract of pecan nut shell may be considered as a natural product replacement for the synthetic antioxidant BHT. © 2016 Society of Chemical Industry.

Rapid fingerprinting of sterols and related compounds in vegetable and animal oils and phytosterol enriched- margarines by transmission mode direct analysis in real time mass spectrometry.

Plant-derived sterols, often referred to as phytosterols, are important constituents of plant membranes where they assist in maintaining phospholipid bilayer stability. Consumption of phytosterols has been suggested to positively affect human health by reducing cholesterol levels in blood via inhibition of its absorption in the small intestine, thus protecting against heart attack and stroke. Sterols are challenging analytes for mass spectrometry, since their low polarity makes them difficult to ionize by both electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI), typically requiring derivatization steps to overcome their low ionization efficiencies. We present a fast and reliable method to characterize the composition of phytosterols in vegetable oils and enriched margarines. The method requires no derivatization steps or sample extraction procedures thanks to the use of transmission mode direct analysis in real time mass spectrometry (TM-DART-MS).

Fat composition of vegetable oil spreads and margarines in the USA in 2013: a national marketplace analysis.

Worldwide, the fat composition of spreads and margarines ("spreads") has significantly changed over the past decades. Data on fat composition of US spreads are limited and outdated. This paper compares the fat composition of spreads sold in 2013 to that sold in 2002 in the USA. The fat composition of 37 spreads representing >80% of the US market sales volume was determined by standard analytical methods. Sales volume weighted averages were calculated. In 2013, a 14 g serving of spread contained on average 7.1 g fat and 0.2 g trans-fatty acids and provided 22% and 15% of the daily amounts recommended for male adults in North America of omega-3 α-linolenic acid and omega-6 linoleic acid, respectively. Our analysis of the ingredient list on the food label showed that 86% of spreads did not contain partially hydrogenated vegetable oils (PHVO) in 2013. From 2002 to 2013, based on a 14 g serving, total fat and trans-fatty acid content of spreads decreased on average by 2.2 g and 1.5 g, respectively. In the same period, the overall fat composition improved as reflected by a decrease of solid fat (from 39% to 30% of total-fatty acids), and an increase of unsaturated fat (from 61% to 70% of total-fatty acids). The majority of US spreads no longer contains PHVO and can contribute to meeting dietary recommendations by providing unsaturated fat.

Heating Two Types of Enriched Margarine: Complementary Analysis of Phytosteryl/Phytostanyl Fatty Acid Esters and Phytosterol/Phytostanol Oxidation Products.

Two phytosteryl and/or phytostanyl fatty acid ester-enriched margarines were subjected to common heating procedures. UHPLC-APCI-MS analysis resulted for the first time in comprehensive quantitative data on the decreases of individual phytosteryl/-stanyl fatty acid esters upon heating of enriched foods. These data were complemented by determining the concurrently formed phytosterol/-stanol oxidation products (POPs) via online LC-GC. Microwave-heating led to the least decreases of esters of approximately 5% in both margarines. Oven-heating of the margarine in a casserole caused the greatest decreases, with 68 and 86% esters remaining, respectively; the impact on individual esters was more pronounced with increasing degree of unsaturation of the esterified fatty acids. In the phytosteryl/-stanyl ester-enriched margarine, approximately 20% of the ester losses could be explained by the formation of POPs; in the phytostanyl ester-enriched margarine, the POPs accounted for <1% of the observed ester decreases.