Patricia Sopelana

Characterisation of the lipidic components of margarines by 1H Nuclear Magnetic Resonance.

In this work, (1)H Nuclear Magnetic Resonance ((1)H NMR) has been used to study the lipidic fraction of margarines of different compositions, determining simultaneously both major components, which is to say triglycerides, and other minor ones, such as 1- and 2-monoglycerides, 1,2-diglycerides, vegetable stanols and sterols, and sorbic acid. The results show a wide variety of acyl group compositions, with polyunsaturated groups ranging from 22% to 50%, monounsaturated from 23% to 50%, and saturated from 21% to 55%. 1,2-Diglycerides and vegetable stanols and/or sterols have been detected in all the studied margarines, in concentrations varying between 2.73 and 26.06 mmol/kg, and between 3.40 and 240.01 mmol/kg, respectively. A good agreement has been found between the results obtained by (1)H NMR and some composition data of these margarines, showing the usefulness of this technique to analyse the lipidic composition of margarine in a quick and easy way.

Load of polycyclic aromatic hydrocarbons in edible vegetable oils: importance of alkylated derivatives.

The presence of polycyclic aromatic hydrocarbons (PAHs) has been studied in different samples of olive oil, extra virgin olive oil, and refined seed oils. A high number of PAHs have been found, with a wide range of molecular weights and in concentrations that are high or even very high compared with the data obtained by other authors, especially in the seed oils. Among the PAHs identified, more than half are alkylated compounds, which account for the major part of the total PAH concentration in some of the samples. The total PAH concentrations in olive oils and extra virgin olive oils are similar, but the former present a higher proportion of heavy PAHs than the latter. The seed oils, in general, have much higher concentrations than the different types of olive oil and their PAH profiles are different. One of the olive oil samples exhibited a PAH distribution similar to that observed in olive pomace oil, suggesting possible adulteration. These data reveal that, in some cases, PAH profile provides useful information in relation to the possible origin of the contamination. We also observed large differences in PAH distribution between oils with the same label but from different batches. PAHs with varying degrees of carcinogenicity have been identified in all the samples, including benzo[a]pyrene, although this PAH was identified neither in the extra virgin olive oils nor in two of the seed oil samples.

Contamination of cheese by polycyclic aromatic hydrocarbons in traditional smoking. Influence of the position in the smokehouse on the contamination level of smoked cheese

This paper sets out to determine the polycyclic aromatic hydrocarbon (PAH) contamination degree of a traditionally smoked cheese: Herreño cheese, which comes from one of the Canary Islands. Its PAH profile is thoroughly studied by means of gas chromatography-mass spectrometry in SIM mode, and compared with that of an unsmoked cheese. Furthermore, a parameter not previously studied is evaluated, namely the influence of the position of the individual cheeses in the smokehouse on their PAH contamination level. Heavy PAH, among which are included most of the carcinogens, are very scarce and their concentrations low. In fact, benz[a]anthracene, together with chrysene+triphenylene, are the only heavy PAH detected in all of the smoked samples studied. The concentration of benzo[a]pyrene, detected only in 1 of the samples, is below the limit established in Spain for the rind of smoked cheese. In contrast, high concentrations of light PAH have been found, especially of naphthalene and its alkyl derivatives, whose effect on human health is not yet well established. The results derived from the analysis of the PAH profile suggest the potential usefulness of certain ratios between some pairs of PAH (phenanthrene/anthracene, naphthalene/acenaphthylene) to provide information on the PAH contamination source. Furthermore, differences have been found, depending on the position of the cheeses in the smokehouse, those placed in the path followed by the smoke being more contaminated. Therefore, the findings of this study could help in improving the design of smokehouses, to decrease the PAH contamination degree of smoked cheese.

Application of multivariate analysis to the effects of additives on chemical and sensory quality of stored coffee brew.

The aim of this work was to obtain a black coffee brew to be consumed hot by extension of its shelf life, by addition of additives. Four pH-regulator agents (sodium and potassium carbonates and bicarbonates), one pH regulator and antioxidant (sodium citrate), three antioxidants [sodium ascorbate, ethylenediaminetetracetic acid (EDTA), and sodium sulfite], and lactoserum were tested by sensory analysis. Sodium carbonate and bicarbonate were selected for a study of the physicochemical (soluble and volatile compounds related to the sensory properties) and sensorial quality of coffee brew stored for 90 days at 4 degrees C. Although both additives extended the shelf life of the coffee brew up to 60 days, sodium carbonate was the chosen additive because it was the most useful in limiting the pH decrease and perception of sourness, which are some of the main factors involved in the rejection of stored coffee brews, and it better maintained the aroma and taste/flavor. Moreover, the application of multivariate analysis facilitated first the description of the global changes of the coffee brews with or without additives throughout the storage using principal component analysis and second the obtainment of a simple equation only with pH and caffeic acid parameters to discriminate the three types of coffee brews and simplify the analytical process, by means of the stepwise discriminant analysis.

Study of several aspects of a general method for the determination of polycyclic aromatic hydrocarbons in liquid smoke flavourings by gas chromatography-mass spectrometry

The effectiveness of the steps of a general method, which includes alkaline treatment of the samples, extraction, clean-up and analysis, for the determination of polycyclic aromatic hydrocarbons in liquid smoke flavourings and smoked foods have been studied, by using mixtures of pure polycyclic aromatic hydrocarbons and of smoke flavouring compounds. All these products were applied to samples of liquid smoke flavourings in order to test the effectiveness of each step of the method, as well as to investigate its effect on real samples, and thus obtain a suitable procedure for the study of polycyclic aromatic hydrocarbons in liquid smoke flavourings. The alkaline treatment has been proved to be necessary because of its capability for removing some smoke components. Both cyclohexane and dichloromethane are able to extract polycyclic aromatic hydrocarbons with high recovery percentages; however, cyclohexane is more adequate due to its lower ability to extract other smoke flavourings components. It is important to note that the elution sequence of polycyclic aromatic hydrocarbons during the clean-up step is quite different depending on the solvent used to dissolve the extract, which determines the ability of this process to isolate polycyclic aromatic hydrocarbons for their accurate identification and quantification by gas chromatography-mass spectrometry in selected ion monitoring mode. Finally, the PAHs present in a liquid smoke flavouring and their concentrations were determined; it was observed that, despite the different extraction solvents and clean-up procedures used, the results were very similar.

1H Nuclear Magnetic Resonance monitoring of the degradation of margarines of varied compositions when heated to high temperature

In this study, (1)H Nuclear Magnetic Resonance was used to monitor the evolution of three margarines of varied compositions when submitted to heating at 180°C in an oven with aeration. Heating causes degradation of polyunsaturated acyl groups and this depends not only on their unsaturation degree, but also on the concentration of the different acyl groups. The evolution of monounsaturated groups varies depending on the disappearance rate of the groups with higher unsaturation degree. Heat treatment also causes hydrolysis reactions that lead to a reduction in 1-monoglycerides and an increase in 1,2-diglycerides, especially in the margarines with higher water content, as well as degradation of some vegetable sterols. Different types of aldehydes and epoxides were identified and quantified, above all in the margarine with the highest proportion of polyunsaturated groups, especially linoleic; some of these are toxic, such as 4-hydroxy- and 4,5-epoxy-2-alkenals.

Occurrence of Polycyclic Aromatic Hydrocarbons in Smoke Flavourings

Abstract The presence of Polycyclic Aromatic Hydrocarbons (PAHs) in four liquid smoke flavourings of different origins has been studied, in order to test whether a relation between their PAH content and their composition could be established, and to evaluate whether the use of these flavourings could involve a risk to human health. The samples were subjected to an alkaline treatment, extracted with cyclohexane, cleaned up, and the PAHs determined by gas chromatography-mass spectrometry. The results reveal a wide range of PAHs, especially in the commercial flavourings studied, which present higher concentrations of both total and carcinogenic PAHs than those obtained in the laboratory. Benzo(a)pyrene has been detected in three of the samples studied, but its levels do not exceed, in any of the cases, the 10 μg/kg value fixed by the FAO/WHO.

A new methodology capable of characterizing most volatile and less volatile minor edible oils components in a single chromatographic run without solvents or reagents. Detection of new components

The possibilities offered by a new methodology to determine minor components in edible oils are described. This is based on immersion of a solid-phase microextraction fiber of PDMS/DVB into the oil matrix, followed by Gas Chromatography/Mass Spectrometry. It enables characterization and differentiation of edible oils in a simple way, without either solvents or sample modification. This methodology allows simultaneous identification and quantification of sterols, tocols, hydrocarbons of different natures, fatty acids, esters, monoglycerides, fatty amides, aldehydes, ketones, alcohols, epoxides, furans, pyrans and terpenic oxygenated derivatives. The broad information provided by this methodology is useful for different areas of interest such as nutritional value, oxidative stability, technological performance, quality, processing, safety and even the prevention of fraudulent practices. Furthermore, for the first time, certain fatty amides, gamma- and delta-lactones of high molecular weight, and other aromatic compounds such as some esters derived from cinnamic acid have been detected in edible oils.

Prooxidant effect of α-tocopherol on soybean oil. Global monitoring of its oxidation process under accelerated storage conditions by 1H nuclear magnetic resonance

The effect of adding α-tocopherol in proportions ranging from 0.002 to 5% in weight on the oxidative stability of soybean oil was studied. For the first time, the oxidation process under accelerated storage conditions including evolution of the molar percentages of the several types of oil acyl groups, and formation and evolution of various kinds of oxidation products comprising hydroperoxides, hydroxy-dienes and other alcohols, epoxides, aldehydes and keto-dienes, was followed by 1H nuclear magnetic resonance. It is proved that, except in the lowest proportion, α-tocopherol not only exerts a prooxidant effect on soybean oil but also modifies its oxidation pathway, affecting the oxidation products generation rate, their nature, relative proportions and concentrations. It is noticeable that the highest α-tocopherol concentrations induce the generation of some toxic compounds at earlier stages of the thermoxidation process and sometimes in higher concentration, such as certain oxygenated α,β-unsaturated aldehydes and monoepoxides derived from linoleic groups.

Influence of fat and phytosterols concentration in margarines on their degradation at high temperature. A study by 1H Nuclear Magnetic Resonance

The objective of this work was to study the influence of several factors, especially fat and phytosterols concentration, on the behavior of margarine under thermo-oxidative conditions. For this purpose, margarines with similar compositions in acyl groups, but differing in the concentration of both fat and phytosterols, were heated at 180°C. The changes in the main components of margarine lipids and the formation of new compounds throughout the thermal treatment were monitored by (1)H Nuclear Magnetic Resonance. The results show that the presence of high concentrations of phytosterols seems to have an antioxidant effect, since it slows down the thermo-oxidation rate of margarine and, consequently, the generation rate and concentrations of secondary oxidation products such as some aldehydes, epoxides and alcohols. The oil-water ratio also seems to have an important effect on margarine behavior, in such a way that the lower the fat concentration is, the higher its thermo-oxidation rate.