Hot water dipping of olives (Olea europaea) for virgin oil debittering

Olives (Olea europaea L.) of the Manzanilla, Picual, and Verdial varieties harvested at the green mature stage of ripening were dipped in hot water at a range of temperatures between 60 and 72 degrees C for 3 min. Immediately after treatment, oils were physically extracted from the olives. Olive heating promotes a reduction of oil bitterness in direct relationship to the temperature used. Fruit heating at > or =60 degrees C for 3 min did not cause significant changes in acidity, UV absorption, peroxide index, and panel test score of the oils obtained but decreased its oxidative stability. Oils extracted from heated fruit showed higher concentrations of chlorophylls and carotenes and lower total phenol content.     

Effect of added caffeic acid and tyrosol on the fatty acid and volatile profiles of camellia oil following heating

Camellia oil is widely used in some parts of the world partly because of its high oxidative stability. The effect of heating a refined camellia oil for 1 h at 120 degrees C or 2 h at 170 degrees C with exogenous antioxidant, namely, caffeic acid and tyrosol, was studied. Parameters used to assess the effect of heating were peroxide and K values, volatile formation, and fatty acid profile. Of these, volatile formation was the most sensitive index of change as seen in the number of volatiles and the total area count of volatiles in gas chromatograms. Hexanal was generally the dominant volatile in treated and untreated samples with a concentration of 2.13 and 5.34 mg kg(-1) in untreated oils heated at 120 and 170 degrees C, respectively. The hexanal content was significantly reduced in heated oils to which tyrosol and/or caffeic acid had been added. Using volatile formation as an index of oxidation, tyrosol was the more effective antioxidant of these compounds. This is contradictory to generally accepted antioxidant structure-activity relationships. Changes in fatty acid profiles after heating for up to 24 h at 180 degrees C were not significant.     

Identification and quantitation of volatile compounds in two heated model compounds, trilinolein and linoleic acid esterified propoxylated glycerol

Static headspace (HS) and capillary gas chromatography/infrared spectroscopy-mass spectrometry (GC/IR-MS) were used to collect, separate, identify, and quantitate the oxidative and thermal decomposition products in two heated model compounds, linoleic acid esterified propoxylated glycerol (EPG-08 linoleate) and trilinoleylglycerol, both without added antioxidants. Approximately 4 L of EPG-08 linoleate or trilinoleylglycerol was heated in a deep-fat fryer at 192 +/- 8 degrees C for 12 h each day until the oil sample contained > or =20% polymeric material, which occurred after 24 h of heating. The major volatile compounds both in heated EPG-08 linoleate and in heated trilinoleylglycerol were pentane, hexanal, 2-heptenal, 1-octen-3-ol, 2-pentylfuran, 2-octenal, and 2, 4-decadienal. The identified volatile compounds from heated EPG-08 linoleate are those generally expected from the oxidative and thermal decomposition of fats and oils containing linoleic acid, except acetoxyacetone (1-acetoxy-2-propanone). Acetoxyacetone was found at 2.1, 3, and 2.4 ppm in the unheated, 12 h heated, and 24 h heated samples, respectively.     

Reduction of virgin olive oil bitterness by fruit cold storage

Green mature olives (Olea europaea L. cv. 'Manzanilla', 'Picual', and 'Verdial') were stored at 5 degrees C, and the oil extracted from them showed a middle intensity level of sensory-evaluated bitterness. The storage times necessary for this reduction were different for the three varieties tested, requiring 4, 6, and 8 weeks, respectively, for 'Manzanilla', 'Picual', and 'Verdial' olives. The level of commercial quality of the extracted oil did not deteriorate as a consequence of previous fruit storage. Olives matured during refrigeration at 5 degrees C, as the increase of maturation index and the decrease of color index and fruit firmness indicated. Similarly, as the fruit storage period progressed, the total phenolic compound content of the extracted oils decreased. Although the use of green mature olives may require a more prolonged storage time, it allows for a better postharvest handling of the fruits, which are more resistant to physical damage or fungal infections than the riper ones.     

Vegetable oil stability at elevated temperatures in the presence of ferric stearate and ferrous octanoate

The thermoxidative stability of partially hydrogenated soybean oil (PHSBO) was examined after addition of ferric stearate and ferrous octanoate, and then heating the samples at 120, 160, 180, and 200 degrees C. In a second experiment, the effect of iron concentration (ferric stearate) on PHSBO stability was examined at 180 degrees C, and at concentrations of approximately 0.5 and 1.2 mg of added iron/kg PHSBO. Oil samples were heated continuously for 72 h and sampled every 12 h. The acid value, p-anisidine value, color, dielectric constant and the triacylglycerol polymer content of oil samples were compared to oil samples containing no added iron. Generally, the value of each oxidative index increased with (1) an increase in temperature, (2) an increase in heating time, and/or (3) an increase in iron. The results demonstrate that low concentrations of iron will substantially increase the rate of oxidation for vegetable oil samples heated to temperatures of 120 degrees C to 200 degrees C.     

Stabilization of soybean oil with heated quercetin and 5-caffeoylquinic acid in the presence of ferric ion

The effect of heated quercetin (400 mg/kg of oil) or 5-caffeoylquinic acid (5-CQA) and the presence of ferric ion (2.2 mg/kg of oil) on the stability of soya oil oxidized in an oxidative stability index (OSI) instrument was investigated. After heating the phenolic at 100 degrees C or 150 degrees C, the OSI values of treated oils were not significantly (p < 0.001) different, whereas, at 200 degrees C, the values decreased significantly with addition of quercetin, but not with 5-CQA. However, the antioxidative activity of quercetin remained significantly greater than that of 5-CQA. The antioxidative potency of quercetin was reduced significantly by addition of ferric palmitate (FP), but that of 5-CQA was not. Reaction between the ortho-dihydroxy groups of the quercetin and ferric ion may reduce the number of hydroxyls available to react with free radicals. Chelating action of 5-CQA might be provided by ortho-dihydroxy grouping of the quinic acid moiety.     

Evaluation of the influence of thermal oxidation on the phenolic composition and on the antioxidant activity of extra-virgin olive oils

A comparison between the results obtained by using HPLC-UV, HPLC-MS, and CE-UV for characterizing the deterioration of extra-virgin olive oil during heating (180 degrees C) was investigated, taking into account phenolic compounds. The concentration of several compounds belonging to four families of phenols (simple phenols, lignans, complex phenols, and phenolic acids) was determined in the samples after the thermal treatment by all three techniques. Hydroxytyrosol, elenolic acid, decarboxymethyl oleuropein aglycon, and oleuropein aglycon reduced their concentration with the thermal treatment more quickly than other phenolic compounds present in olive oil. HYTY-Ac and Lig Agl were demonstrated to be quite resistant to this kind of treatment, and the behavior of lignans could be outstanding, as they belong to the family most resistant to thermal treatment. Several "unknown" compounds were determined in the phenolic profiles of the oils after the thermal treatment, and their presence was confirmed in refined olive oils. The oxidative stability index (OSI time) was reduced from 25 to 5 h after 3 h of heating, whereas the peroxide value showed a minimum after 1 h of heating.     

Influence of thermal treatments simulating cooking processes on the polyphenol content in virgin olive oil

Virgin olive oils were subjected to simulated common domestic processing, including frying, microwave heating, and boiling with water in a pressure cooker. The impact of these processes on polyphenol content and physicochemical characteristics of oils was assessed. Thermal oxidation of oils at 180 degrees C caused a significant decrease in hydroxytyrosol- and tyrosol-like substances. In contrast, oils heated for 25 h still retained a high proportion of the lignans 1-acetoxypinoresinol and pinoresinol. Thermal oxidation also resulted in a rapid degradation of alpha-tocopherol and the glyceridic fraction of oils. Microwave heating of oils for 10 min caused only minor losses in polyphenols, and the oil degradation was lower than that in thermoxidation assays. Again, lignans were the least affected polyphenols and did not change during microwave heating. Boiling a mixture of virgin olive oil and water in a pressure cooker for 30 min provoked the hydrolysis of the secoiridoid aglycons and the diffusion of the free phenolics hydroxytyrosol and tyrosol from the oil to the water phase. Losses of polyphenols were detected only at pH lower than 6. Moreover, alpha-tocopherol and the glyceridic fraction of oils were not modified during this process. It is worth noting that all the heating methods assayed resulted in more severe polyphenols losses and oil degradation for Arbequina than for Picual oil, which could be related to the lower content in polyunsaturated fatty acids of the latter olive cultivar. These findings may be relevant to the choice of cooking method and olive oil cultivar to increase the intake of olive polyphenols.     

Chemical composition, antioxidant properties, and thermal stability of a phytochemical enriched oil from Acai (Euterpe oleracea Mart.)

Phenolic compounds present in crude oil extracts from acai fruit ( Euterpe oleracea) were identified for the first time. The stability of acai oil that contained three concentrations of phenolics was evaluated under short- and long-term storage for lipid oxidation and phenolic retention impacting antioxidant capacity. Similar to acai fruit itself, acai oil isolates contained phenolic acids such as vanillic acid (1,616 +/- 94 mg/kg), syringic acid (1,073 +/- 62 mg/kg), p-hydroxybenzoic acid (892 +/- 52 mg/kg), protocatechuic acid (630 +/- 36 mg/kg), and ferulic acid (101 +/- 5.9 mg/kg) at highly enriched concentrations in relation to acai pulp as well as (+)-catechin (66.7 +/- 4.8 mg/kg) and numerous procyanidin oligomers (3,102 +/- 130 mg/kg). Phenolic acids experienced up to 16% loss after 10 weeks of storage at 20 or 30 degrees C and up to 33% loss at 40 degrees C. Procyanidin oligomers degraded more extensively (23% at 20 degrees C, 39% at 30 degrees C, and 74% at 40 degrees C), in both high- and low-phenolic acai oils. The hydrophilic antioxidant capacity of acai oil isolates with the highest phenolic concentration was 21.5 +/- 1.7 micromol Trolox equivalents/g, and the total soluble phenolic content was 1252 +/- 11 mg gallic acid equivalents/kg, and each decreased by up to 30 and 40%, respectively, during long-term storage. The short-term heating stability at 150 and 170 degrees C for up to 20 min exhibited only minor losses (<10%) in phenolics and antioxidant capacity. Because of its high phenolic content, the phytochemical-enriched acai oil from acai fruit offers a promising alternative to traditional tropical oils for food, supplements, and cosmetic applications.     

Oxidative stability of algal oils as affected by their minor components

Algal oils, namely, arachidonic acid single-cell oil (ARASCO), docosahexaenoic acid single-cell oil (DHASCO), and a single-cell oil rich in both docosahexaenoic acid and docosapentaenoic acid (OMEGA-GOLD oil), were evaluated for their oxidative stability, as such and after stripping of their minor components, in the dark at 60 degrees C and under fluorescent light at 27 degrees C. Several analytical methods were used to assess the oxidative stability of these oils. Oil extracts were also investigated for their scavenging of 1,1-diphenyl-2-picrylhydrazyl radical by a spectrophotometric method and by measuring their total phenolic contents. The results indicated that minor oil constituents play a major role in their oxidative stability in the dark as well as under fluorescent light. The stability of the oils was dictated by their fatty acid composition, total tocopherols, and the type of pigment present. DHASCO contained a significant level of natural radical scavengers and phenolic compounds that contributed to its higher stability compared to the ARASCO and OMEGA-GOLD oils. Thus, the importance of minor components in the stability of the oils examined was demonstrated.     

Qualitative and semiquantitative analysis of phenolic compounds in extra virgin olive oils as a function of the ripening degree of olive fruits by different analytical techniques

Capillary electrophoresis (CE) can be effectively used as a fast screening tool to obtain qualitative and semiquantitative information about simple and complex phenolic compounds of extra virgin olive oil. Three simple phenols (tyrosol, hydroxytyrosol, and vanillic acid), a secoiridoid derivative (deacetoxy oleuropein aglycon), and two lignans (pinoresinol and acetoxypinoresinol) were detected as the main compounds in extra virgin olive oils by high-performance liquid chromatography (HPLC) and capillary zone electrophoresis (CZE). Spectrophotometric indices, radical scavenging activity, and oxidative stability of extra virgin olive oil samples obtained from olives hand-picked at different ripening degrees were statistically correlated with the CZE and HPLC quantification. The concentration of phenols in extra virgin olive oil decreased with ripeness of olive fruits. The high correlations found between CZE and the other analytical results indicate that CE can be applied as a rapid and reliable tool to routinely determine phenolic compounds in extra virgin olive oils.     

Identification of alpha-tocopherol oxidation products in triolein at elevated temperatures

The effect of high-temperature treatment on the stability of alpha-tocopherol (1) in triolein was assessed under a reduced-pressure atmosphere (4-40 mbar) simulating the deodorization step of the refining of vegetable oils. A marked degradation of 1 was observed, which increased with increasing temperature (180-260 degrees C) and heating time (20-80 min). The degradation of 1 in triolein at 240 degrees C was inhibited by the addition of the synthetic antioxidant TBHQ or when heating was performed under nitrogen atmosphere, indicating oxidative degradation. The oxidation products were isolated and identified as alpha-tocopherolquinone (2), 4a,5-epoxy-alpha-tocopherolquinone (3), and 7,8-epoxy-alpha-tocopherolquinone (4).     

Effects of fly attack (Bactrocera oleae) on the phenolic profile and selected chemical parameters of olive oil

The phenolic fraction of virgin olive oil influences both its quality and oxidative stability. One of the principal threats of the quality of olive fruit is the olive fly ( Bactrocera oleae) as it alters the chemical composition. The attack of this olive pest has been studied in order to evaluate its influence on the quality of virgin olive oil (free acidity, peroxide value, fatty acid composition, water content, oxidative stability, phenols, and antioxidant power of phenolic fraction). The study was performed using several virgin olive oils obtained from olives with different degrees of fly infestation. They were acquired in different Italian industrial mills from the Abruzzo region. Qualitative and quantitative analyses of phenolic profiles were performed by capillary electrophoresis-diode array detection, and electrochemical evaluation of the antioxidant power of the phenolic fraction was also carried out. These analyses demonstrated that the degree of fly attack was positively correlated with free acidity ( r = 0.77, p < 0.05) and oxidized products ( r = 0.58, p < 0.05), and negatively related to the oxidative stability index ( r = -0.54, p < 0.05) and phenolic content ( r = -0.50, p < 0.05), mainly with secoiridoid compounds. However, it has been confirmed that the phenolic fraction of olive oil depends on several parameters and that a clear correlation does not exist between the percentages of fly attack and phenolic content.     

Antioxidant protection of bulk fish oils by dispersed sugars and polyhydric alcohols

Selected sugars (fructose, sucrose, or raffinose) and polyhydric alcohols (sorbitol or mannitol) were equilibrated directly with bulk fish oil (10% by weight, excess) and exposed to fluorescent lighting (2550 Lx) for 24 h at 5 degrees C. Data for room temperature-equilibrated samples revealed that polyols functioned as antioxidants in fish oil. Increased times and temperatures of equilibration (to 90-110 degrees C, 1-2 mmHg, to 2 h) greatly enhanced the antioxidant activity of polyols in fish oil exposed to light. Under accelerated oxidation conditions (60 degrees C) in the dark, dispersed sorbitol in bulk fish oil greatly suppressed the peroxide value, primarily by chelating transition metals, while fructose showed a limited antioxidant activity. Sugars with a lower molecular weight and smaller numbers of equatorial OH groups exhibited a higher rate of permeation of sugars into fish oil triacylglycerols and hence rendered greater antioxidant activities. The treatment of bulk fish oils with polyols and then using the oils in the preparation of emulsions greatly reduced their antioxidant activities as compared to those observed for treated bulk oils. The introduction of polyols dissolved in propylene glycol into bulk fish oils at 90 degrees C (0.025% polyol, 0.25 h of equilibration) provided a similar antioxidant activity to that imparted by the introduction of polyols into the oil by equilibrating excess polyols (10% by weight) with them at 90-110 degrees C for 2 h. However, regardless of the method of the introduction of polyols to bulk fish oil, an elevated temperature (90 degrees C) exposure during fish oil treatment was required to induce a notable antioxidant activity.     

Effect of harvesting system and fruit cold storage on virgin olive oil chemical composition and quality of superintensive cultivated 'Arbequina' olives

Storage at 3 and 18 °C of 'Arbequina' olives (Olea europaea L.) cultivated in hedgerows and harvested manually or mechanically (wine grape harvester) was tested. Fruit characteristics and oil quality were monitored. Mechanical harvesting caused internal fruit damage that induced its rapid softening and decay, but also facilitated obtaining higher amounts of oil, which suffered a rapid deterioration during fruit storage. This oil presented lower tocopherol and phenol contents and lower oxidative stability than the oil extracted from manually harvested olives, but showed similar fatty acid composition. Cold storage (3 °C) delayed all of these deterioration processes. It allowed maintaining the best commercial level of quality ("extra") in the oil from mechanically harvested olives for 10 days. This cold storage could be considered as an alternative to the increase in machinery for processing the growing olive production, due to both hedgerow cultivation and mechanized harvesting.     

Formation of polycyclic aromatic hydrocarbons in the smoke from heated model lipids and food lipids.

The contents of polycyclic aromatic hydrocarbons (PAHs) in the smoke from model lipids and food lipids during heating were determined and the mechanism of PAH formation was studied. A Rancimat oil stability analyzer was used as a model system for heating model lipids and food lipids at 220 degrees C for 2 h and for adsorption of smoke. The various lipid degradation products and PAHs in the smoke were identified and quantified by a GC/MS technique. Results showed that model lipids were more susceptible to smoke formation than food lipids during heating, but the PAH levels were lower for the former than latter. Methyl linolenate produced the highest amount of PAHs, followed by methyl linoleate, methyl oleate, and methyl stearate. Also, soybean oil generated a larger amount of PAHs than canola oil or sunflower oil. Benzene-like compounds were found to be possible precursors for PAHs formation. Several PAH derivatives were also present in heated model lipids and food lipids.     

Relationships between oxidative stability, triacylglycerol composition, and antioxidant content in olive oil matrices

In olive oils, relationships between oxidative stability, glyceridic composition, and antioxidant content were investigated. Lipid matrices, obtained by purification of olive and high-oleic sunflower oils, were spiked with hydroxytyrosol, alpha-tocopherol, and mixtures of them and then subjected to oxidation in a Rancimat apparatus at 100 degrees C. At the same concentration of antioxidants, induction time (IT) decreased as the unsaturation rate of the matrix increased, but only fair correlations were found with fatty acid composition. Oxidative susceptibility (OS(TAG)) was calculated as a function of the relative oxidation rate of the triacylglycerols, and a linear relationship-IT (h) = (a + b)OS(TAG)-between induction time and this parameter showed a good correlation coefficient (r > 0.990, p < 0.001). In the case of matrices with a single antioxidant, origin ordinate (a) and slope (b) can be calculated as a function of the antioxidant concentration. In matrices spiked with mixtures of hydroxytyrosol and alpha-tocopherol, a simple relationship between the coefficients a and b and the concentration of antioxidants cannot be established because additive and subtractive effects occur depending on the relative concentrations of both antioxidants. However, approximate values for these coefficients can be obtained, allowing the estimation of the oil stability. In various olive oils, an acceptable agreement was found between the IT experimentally determined and that calculated from the oil composition. These results confirmed that the Rancimat stability of olive oils mainly depends on triacylglycerol composition and concentrations of o-diphenols and alpha-tocopherol.     

Influence of deep frying on the unsaponifiable fraction of vegetable edible oils enriched with natural antioxidants

The influence of deep frying, mimicked by 20 heating cycles at 180 °C (each cycle from ambient temperature to 180 °C maintained for 5 min), on the unsaponifiable fraction of vegetable edible oils represented by three characteristic families of compounds (namely, phytosterols, aliphatic alcohols, and triterpenic compounds) has been studied. The target oils were extra virgin olive oil (with intrinsic content of phenolic antioxidants), refined sunflower oil enriched with antioxidant phenolic compounds isolated from olive pomace, refined sunflower oil enriched with an autoxidation inhibitor (dimethylpolysiloxane), and refined sunflower oil without enrichment. Monitoring of the target analytes as a function of both heating cycle and the presence of natural antioxidants was also evaluated by comparison of the profiles after each heating cycle. Identification and quantitation of the target compounds were performed by gas cromatography-mass spectrometry in single ion monitoring mode. Analysis of the heated oils revealed that the addition of natural antioxidants could be an excellent strategy to decrease degradation of lipidic components of the unsaponifiable fraction with the consequent improvement of stability.     

Usefulness of the frequency data of the fourier transform infrared spectra to evaluate the degree of oxidation of edible oils

The oxidation process of 13 edible oil samples with different proportions of oleic, linoleic, and linolenic acyl groups has been studied using Fourier transform infrared spectroscopy. The oxidation experiments were carried out by heating the samples in a convection oven at 70 degrees C. Duplicate spectra were recorded from a film of pure oil between two disks of KBr for each sample every day during the course of the oxidation, and frequency data of each band of the spectrum were collected automatically. Changes in the values of the frequency of most of the bands of the spectra were observed. The shiftings of the frequency value of specific bands allowed one to distinguish between the different stages of the oxidation process and to establish the oxidation degree of each oil sample. This methodology could be useful to evaluate the oxidative stability of edible oils in a simple, fast, and accurate way.     

Effects of olive fruit quality and oil storage practices on the diacylglycerol content of virgin olive oils

The evolution of 1,3- and 1,2-isomers of diacylglycerols (DGs) in olive oils obtained from healthy olives and the influence of the olive quality was studied. Healthy olive fruits yielded oils containing almost exclusively 1,2-isomers whereas altered olives produced oils with significant amounts of 1,3-isomers. Virgin olive oils obtained from various olive cultivars and stored at different temperatures showed triacylglycerol hydrolysis and diacylglycerol isomerization depending on the acidity and temperature. The results indicated that the relationship between acidity and total diacylglycerol content has scarce utility for detecting mild refined oil in virgin olive oil. On the other hand, the 1,3-/1,2-DG isomers ratio is useful for assessing the genuineness of virgin olive oils with low acidities during the early stages of storage.