Effects of tocopherols and their mixtures on the oxidative stability of olive oil and linseed oil under heating

The tested tocopherols (γ,δ,α) showed antioxidative activity at all levels of addition to the monounsaturated olive oil, the effects increased as a function of concentrations (maximum: +287% with 800 mg γ‐tocopherol/100 g oil compared to the control oil). In the highly unsaturated linseed oil, which contains 58 mg/100 g initial concentration of γ‐tocopherol, γ‐tocopherol showed antioxidative behavior up to the addition of 100 mg/ 100 g oil. Additions of more than the 100 mg/100 g affected the oil, resulting in a faster oxidation. Mixtures of γ/δ‐tocopherols in olive oil were found to protect more efficiently than both vitamins when added separately α‐tocopherol reduced effects of other tocopherols in both plant oils. The stabilizing effect of added tocopherols and their mixtures (100 mg/100 g oil each) in olive oil are γ/δ‐T>γ‐T>δ‐T>γ/α‐T>δ/α‐T>α‐T and in linseed oil γ‐T>γ/δ‐T>δ‐T>γ/α‐T>α‐T>α/δ‐T.     

Changes in the main components and quality indices of virgin olive oil during oxidation

This work reports on changes in the major and minor components of virgin olive oil during oxidation, details modifications found in the standardized quality indices, and analyzes the most significant relationships between the components of the oil and its oxidative stability. During the induction period or slow phase of oxidation, polyphenols, tocopherols, and pigments undergo the most important alterations. Other compounds, such as FA or volatiles, suffer significant modifications only during the rapid or exponential phase of oxidation when the natural antioxidant systems fall to minimal values. Among the quality indices, PV and the specific extinction coefficients K ₂₃₂ and K ₂₇₀ increase markedly from the earliest stages of oxidation, whereas titratable acidity does not change appreciably during the induction period. The evolution of the different compounds and parameters analyzed suggests that the tocopherol and orthodiphenol contents are the best indices to determine the average life of the oils.     

Effect of extraction systems on the quality of virgin olive oil

Research has been carried out to ascertai the effects of different processing systems on olive oil quality. Tests were performed in industrial oil mills that were equipped with both pressure and centrifugation systems. Results show that oils extracted from good-quality olives do not differ in free fatty acids, peroxide value, ultraviolet absorption and organoleptic properties. Polyphenols ando-diphenols contents and induction times are higher in oils obtained from good-quality olives by the pressure system because it does not require addition of water to the olive paste. The centrifugation system requires the addition of warm water to the olive paste and helps to obtain oils with a lower content of natural antioxidants. Oils obtained from poorquality or from ripe olives in continuous centrifugal plants are lower in free fatty acids than those obtained by the pressure system. Dr. Mario Solinas is deceased—May 23, 1993.     

Effects of the cold percolation system on the quality of virgin olive oil

The effects of the cold percolation system on the quality of virgin olive oil from two different Italian cultivars (Coratina and Oliarola) were determined. The quality was also compared with that of oil extracted with the current centrifugation system using a two‐phases decanter. Tests were performed in an industrial oil mill equipped with the two extraction systems. The oils extracted with cold percolation system showed, in all cases, lower free acidity, peroxide value, and ultraviolet (UV) absorption (K₂₃₂ and K₂₇₀) and higher polyphenol contents in comparison to oils obtained by two‐phases centrifugation. These results were confirmed by the autoxidation stability of the oils examined.     

Use of nitrogen to improve stability of virgin olive oil during storage

Experiments were carried out to study the possibility of improving the stability of extra virgin olive oil by using nitrogen as a conditioner gas during storage. With this aim, virgin olive oil samples, obtained from Leccino and Coratina cultivars, were stored in the dark, in closed bottles conditioned with air or nitrogen at 12–20 and 40°C. Results indicated that the FFA percentage increased over 1% only when oils were stored at 40°C. The PV and the K ₂₃₂ value (light absorbance at 232 nm) of oils increased over the limit value allowed by European Union law when the bottles were only partly filled and air was the conditioner gas. The use of nitrogen as conditioner gas helped to avoid this risk during 24 mon of storage at 12–20°C. The total phenolic content of both cultivars oils decreased during storage because their oxidation protected the oils from autoxidation. The content of total volatile compounds in oils decreased continuously during storage at 12–20°C, whereas it increased over 10 (Coratina cv.) and 15 (Leccino cv.) mon and then diminished when the storage temperature was 40°C. The same behavior, i.e., increase then decrease, was ascertained for trans-2-hexenal. The hexanal content of oils increased continuously during storage because this compound is formed by the decomposition of the 13-hydroperoxide of linoleic acid.     

Influence of ecological cultivation on virgin olive oil quality

The quality of oil extracted from ecologically cultivated olives of the Picual variety was compared with oil extracted from Picual olives cultivated using conventional methods. Olive trees were grown in a two-section plot. Fruits from each plot were harvested at various stages of ripeness, and acidity value, peroxide index, ultraviolet absorption at 232 and 270 nm, stability to oxidation, sensory analysis, fatty composition, and contents of tocopherols, phenolic compounds, and sterols were determined on oil extracted from each treatment. The results showed that the organic virgin olive oil was of a superior quality to the conventional virgin olive oil in all the quality parameters analyzed.     

“Veiled” extra-virgin olive oils: Dispersion response related to oil quality

A cloudy (“veiled”) extra-virgin olive oil was stored 10 mon at room temperature and monitored at 15-d intervals. The oil was very stable under oxidizing conditions; a slight increase in free acidity (from 0.2 to 0.3%, expressed as oleic acid), a notable rise in the amount of diacylglycerols and a minor increase in peroxide content were observed. Turbidity disappeared after a few months due to chemical bonding between a nitrogen-containing component and the free acids that were released over time. The material in suspension, therefore, contained some chemical groups capable of acting as antioxidants.     

Effect of olive paste kneading process time on the overall quality of virgin olive oil

The influence of the olive paste malaxation time on the composition and the industrial output of oil was investigated. To this purpose, three Italian olive varieties (Leccino, Dritta, Caroleo) were processed with a centrifugal system for six malaxation periods (0, 15, 30, 45, 60 and 75 min). The concentrations of the majority of the oil constituents changed during the malaxation. However, these changes were not significant for all of them: the contents of β‐carotene, the major xanthophylls, chlorophylls a and b, pheophytins a and b in the oils increased progressively with increasing malaxing times, whereas the contents of simple and hydrolysable phenols (secoiridoid derivatives), o‐diphenols and total phenols decreased. A significant increase in total volatiles and green volatiles of the lipoxygenase cascade (C₆ aldehydes, C₆ alcohols, C₅ alcohols and C₅ carbonyls) was detected. An opposite trend was observed for the green C₆ esters. As a result, the global analytical quality, flavour, aroma and shelf‐life of the oils were negatively affected. The oil yield increased substantially up to 45 min of paste malaxation times. Beyond 60 min, the yields tended to decrease.     

Effect of fruit stoning on olive oil quality

Stoning olives has been proposed as an alternative to crushing the whole fruit during the oil extraction process. Seven pairs of oils obtained from stoned and nonstoned olives from five different cultivars were evaluated to determine the effect of the proposed technology on oil quality. The main organoleptic and physicochemical parameters as well as resistance to oxidation showed no obvious influence of stoning on oil quality. Chemometric analysis of the data showed the oils grouped more according to genetics (cultivar) than to technology. Lipoxygenase activity in the paste from whole and stoned olives showed no effect that could be attributed to the technology. Furthermore, the stone did not contribute significantly to increasing the lipoxygenase activity in the olive paste.     

Use of the activation energy concept to estimate the quality reduction of packaged olive oil

In the present study, the probability of packaged olive oil not reaching the end of its shelf life, P _safe, was used as a quality factor to evaluate the time taken for olive oils stored at various conditions to reach the end of their shelf lives. P _safe was used to comment on the activation energy required during the degradation process per actual or simulated case, and hexanal was used as the main quality-related indicator. Based on the month after bottling at which P _safe reached 70%, the activation energy of an “equivalent” chemical reaction, representative of overall quality degradation, was calculated for several storage conditions. Using the differences between activation energies estimated using the above method, we found the most important factors influencing the shelf life of the packaged olive oil to be the initial storage period in the dark, the role of elevated temperatures, and the presence of light, either continuous or in alternating patterns, in association with the packaging materials used in this study. These results were in qualitative agreement with previously reported experimental observations and simulations, indicating the validity of using P _safe, and of activation energies calculated from it, to predict the shelf life of packaged olive oil.     

Oxidation-derived flavor compounds as quality indicators for packaged olive oil

Aroma compounds in packaged extra virgin olive oil can be present naturally or be derived through oxidative degradation under favorable conditions of temperature, light, and oxygen availability. In this study, the identity and quantity of flavor compounds were determined for extra virgin olive oil packaged in 0.5-L glass, poly(ethylene terephthalate), and poly(vinyl chloride) bottles and stored at 15,30, and 40°C under fluorescent light or in the dark for 1 yr. A set of mathematical equations concerning the rates of the most fundamental oxidation reactions in the oil was prepared and numerically solved, and the reaction constants were estimated for specific temperature values. Mainly, the presence of fluorescent light, followed by elevated temperature, stimulated oxidative alterations in the olive oil. Separated and identified flavor compounds were recorded for all the olive oil samples. Based on their abundance and evolution in the oil samples, those most clearly describing oxidation were hexanal, nonanal, (E)-2-decenal, (E)-2-heptenal, and 2-pentyl furan. These compounds could be used as markers of the oxidation process to monitor and describe the quality of packaged olive oil quantitatively.     

Effects of free fatty acids on oxidative stability of vegetable oil

The effect of free fatty acid (FFA) content on the susceptibility to thermooxidative degeneration of vegetable oils was determined by Rancimat analysis. A prooxidant effect of FFA was observed in all filtered oils, independently of lipidic substrate and of its state of hydrolytic and oxidative alteration. The intensity of this effect was related to FFA concentration, but regression analysis of the experimental data did not show a general correlation law between FFA concentration and induction time (I _t). Different results were obtained for freshly processed virgin olive oils, characterized by postpressing natural suspension-dispersion: opposite behavior was observed of FFA content as regards oxidative stability, depending on the presence of suspended-dispersed material. This fact is of interest because the dispersed particles play a double stabilizing effect on both oxidative and hydrolytic degradation. These results showed that avoidance of oil filtration is highly desirable to extend olive oil’s shelf life.     

Influence of olive crushing methods on the yields and oil characteristics

In the last years, metallic crushers substituted granite stone mill with some variations in the organoleptic oil characteristics. To control the influence of the crushing method on the yield and oil quality, the olive pastes were obtained using three different ways: (i) new metallic crusher at mobile knives; (ii) granite stone mill; (iii) double olive crushing by the metallic crusher and the granite stone mill. With the aim to ascertain the useful use of a new metallic crusher (at mobile knives), experimental tests were carried out in an industrial oil mill. This oil mill is equipped by a centrifugal decanter generating two oil flows: first and second extraction (recovery) oils. The results showed that the yields obtained by different methods were satisfactory. No statistically significant differences have been observed in terms of oil yield and quality when different crushing devices were used. All first extracted oils are extra virgin with similar organoleptic characteristics, especially for the fruity intensity and for the bitter and pungent taste, as confirmed by the composition of volatile substances and the content of phenolic oil compounds. The recovery oils (second extraction oils) showed, in contrast to first extraction oils, a more intense green colour and a higher content of total phenols. Practical applications: Processing of sound olives with the right ripening grade and good quality allows to easily obtain an extra virgin olive oil, with commercial qualitative parameters according to the European Union requirements. However, different olive crushing systems affect the concentrations of some compounds responsible of aroma and taste (phenolic compounds). The use of the more violent metallic crushers facilitates obtaining oils with total phenol content higher than when using a stone mill. Here we used a particular metallic crusher (at knives) that, however, is suitable to replace the granite stone mill when a less pungent and bitter oil is required.     

Effects of herbs on hydrolytic and oxidative degradation of olive oil in canned tomatoes

The effects of adding mixtures of herbs such as garlic, laurel, and marjoram on selected chemical indices of olive oil from canned dried tomatoes were studied for various storage periods of up to 1 yr. Conventional analytical indices measured included acidity, PV, and p-anisidine value. Flavored samples showed kinetic constant values that were significantly (P=0.001) higher than unflavored ones, whereas oligopolymer and oxidized TG and DG contents were similar to or slightly higher than in the unflavored samples compared with those with herbs. The addition of the mixture of herbs slowed polymerization reactions but did not inhibit TG oxidation. Discrepancies between the results obtained by conventional analyses and high-performance size-exclusion chromatography indicated that the former approaches were insufficient to determine oxidative degradation of oil as a result of interferences from compounds in the food matrix.     

DSC determination of thermally oxidized olive oil

The feasibility of using DSC as an analytical method to evaluate the autoxidation of olive oil at 50°C and thermal oxidation at 93 and 180°C in 10-mL airtight vials was studied. DSC peak enthalpy and peak crystallization temperatures were compared with headspace oxygen depletion and headspace volatiles in oxidized oil samples. A single crystallization peak was found in olive oil. The crystallization peak shifted to lower temperatures, and the enthalpy associated with this phase transition decreased as the exposure time increased at 93 and 180°C. DSC peak enthalpy in olive oil at 50, 93, and 180°C showed correlations of 0.84, 0.91, and 0.95, respectively, with headspace oxygen depletion in sample bottles. Correlation of DSC initial peak temperature with headspace oxygen depletion was 0.53, 0.87, and 0.95 at 50, 93, and 180°C, respectively. Correlations of DSC peak enthalpy and initial peak temperature with headspace volatiles at 180°C were 0.95 and 0.97, respectively. These results indicate that DSC is a good analytical method to determine the oxidative stability of olive oil at frying temperature.     

The influence of variety and harvest time on the bitterness and phenolic compounds of olive oil

The influence of harvest time on the intensity of bitterness and the level of phenol compounds in olive oil from the region of western Istria, obtained from 2 local (Bianchera and Busa) and one introduced, Italian variety (Leccino) was studied. Olive fruits were harvested at 3 different harvesting periods, during 4 successive crops seasons. Immediately after harvesting, the fruits were processed under the same conditions in a pilot plant. Basic quality parameters, the content of total polyphenols, o‐diphenols and the intensity of bitterness were determined in oil samples. Samples of oil obtained from the Bianchera and Busa varieties were additionally tested for stability at elevated temperature (98 °C) and under the influence of UV‐light. The results elaborated statistically showed the level of phenol compounds and the intensity of bitterness to be significantly influenced by both the harvest time and olive variety, with the influence of harvest time being more pronounced. The applied tests for accelerated deterioration of oil indicated a more rapid increase in the peroxide value in oil samples of both varieties exposed to UV‐light than in those exposed to elevated temperature. Both tests showed better stability of the oil obtained from the Bianchera variety.     

Polyphenol oxidase from eggplant reduces the content of phenols and oxidative stability of olive oil

Activity of the polyphenol oxidase (PPO) from eggplant fruit (Solanum melongena L.) on phenolic compounds of an extra virgin olive oil (EVOO) was studied. In standardized reaction solutions, the eggplant PPO, isolated in the laboratory, depleted completely chlorogenic and caffeic acids, oleuropein, and verbascoside, while the levels of hydroxytyrosol reduced by half. Conversely, no activity of the PPO was observed on the gallic and protocatechuic acids nor on mono‐phenols, such as tyrosol and the p‐coumaric, o‐coumaric, and ferulic acids. PPO activity on phenols extracted from eggplant fruit and EVOO confirmed the enzyme substrate specificity and caused a significant decrease in the measure of total phenols and o‐diphenols. Similarly, PPO crude extract caused a significant decrease of polyphenols directly in the EVOO. Moreover, maximum degradation of EVOO polyphenols was observed when olive oil was homogenized with eggplant fruit pulp to form a cream‐like purée. In fact, immediately after the preparation, total phenols and o‐diphenols of the olive oil recovered from the eggplant‐oil purée were decreased by ～80% and 100% compared to those of the initial EVOO. As a consequence, the oxidative stability of the recovered oil was ～60% lower than that of the initial EVOO. In conclusion, in the preparation of vegetable preserves, a residual activity of phenol oxidase may adversely affect the quality and shelf life of the extra virgin olive oil used as covering.     

Cyclic FA monomers in high-oleic acid sunflower oil and extra virgin olive oil used in repeated frying of fresh potatoes

The measurement of FA profile, polar material, oligomers, oxidized triacylglycerols (OTG), total polyphenols, and cyclic FA monomers (CFAM) was used to evaluate the alteration of a high-oleic sunflower oil (HOSO) and an extra virgin olive oil (EVOO) used in 75 domestic fryings of fresh potatoes with frequent replenishment (FR) of unused oil. CFAM were absent in the unused EVOO but appeared in small amounts in the unused HOSO. Although polar material, oligomers, OTG, and CTAM contents increased and linoleic acid and polyphenols content decreased in both oils during repeated frying, the changes produced should be considered small and related to the use of very stable oils and FR. Throughout the 75 fryings, the total CFAM concentration was higher in HOSO than in EVOO. OTG increased more quickly in EVOO, whereas oligomers increased more quickly in HOSO. Polar material and oligomer content appear significantly correlated (r=0.9678 and r=0.9739, respectively; for both, P<0.001) with the CFAM content. A 25% polar material and 12% oligomer content would correspond to about 1 mg·kg⁻¹ oil of CFAM. Data suggest that both oils, particularly EVOO, perform very well in frying, with a low production of oligomers, polar materials, and CFAM.     

Effect of olive fruit freezing on oxidative stability of virgin olive oil

Several studies have suggested that the phenolic fraction plays an important role during storage and therefore in the shelf life of virgin olive oil. This investigation examines the effect of freezing olives (–18 °C) before processing into oil on the transfer of the phenolic compounds into the subsequent oil, and the consequential changes in oxidative stability. Oil samples obtained from frozen olives (24 h at –18 °C), crushed with and without preliminary thawing, were compared to a control sample; both oils were obtained using a two‐phase low‐scale mill. The oxidative stability in different samples was assessed in terms of primary and secondary oxidation products as measured by peroxide values and oxidative stability index times, respectively. The quality of the oil samples was also checked through the percentage of free acidity and the phenolic content. Phenols were determined by both spectrophotometric assays (total phenols and o‐diphenols) and HPLC‐DAD/MSD. The antiradical capacity of the phenolic fraction was determined by DPPH and ABTS spectrophotometric tests. These analyses showed that thawing of olives before oil extraction led to a significant loss of oxidative stability and phenols; in contrast, samples obtained from frozen olives that were not thawed before crushing showed qualitative characteristics similar to control samples.