On the importance of total polar phenols to monitor the stability of Greek virgin olive oil

A large number of virgin olive oil samples obtained from different areas in Greece were analyzed for various quality parameters. The work focuses on the colorimetric determination of total phenols with the Folin‐Ciocalteu reagent and its importance in predicting shelf life of virgin olive oil. The results indicate a good correlation of total polar phenol content with the stability of the oil. Colorimetric determination of ortho‐diphenol content does not seem to be a better means for predicting virgin olive oil stability. RP‐HPLC quantification of hydroxytyrosol and tyrosol in their free form gives poor results in the case of freshly extracted oils. It is concluded that until an easy‐to‐manage HPLC method will be available, which will quantify accurately both free and bound forms of hydroxytyrosol and other phenolics, the colorimetric method for the determination of total polar phenols remains a good practical means to evaluate the stability of virgin olive oil.     

Effect of filtration on virgin olive oil stability during storage

The effect of filtration and dehydration on the stability and quality of virgin olive oil during storage at room temperature (25 °C) and under accelerated conditions (40 °C) was studied. Different types of monovarietal olive oil, namely unfiltered (UF), filtered (F) and filtered‐dehydrated (FD), were obtained from Arbequina, Colombaia, Cornicabra, Picual and Taggiasca cultivars. Results showed that filtration and dehydration decreased the rate of hydrolysis of the triacylglycerol matrix, especially at the higher temperature and in oils with a higher initial free acidity (e.g. free acidity of 0.82% and 0.63% in UF and FD Colombaia samples, respectively, after 8 months of storage), and delayed the appearance of rancid defects (e.g. UF and FD Arbequina samples lost extra‐virgin grade after 10 and 12 months of storage, respectively). The formation of simple phenols due to the hydrolysis rate of their secoiridoid derivatives was also greater in unfiltered olive oils (e.g. 174 μmol/kg and 137 μmol/kg in UF and FD Picual samples, respectively, after 8 months of storage). Thus, filtration and especially dehydration could help to prolong the shelf life of high‐quality and less stable olive oils like those obtained from the Arbequina and Colombaia varieties.     

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.     

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.     

Effect of growing area on pigment and phenolic fractions of virgin olive oils of the arbequina variety in Spain

The purpose of this investigation was to study differences in the chlorophyll, carotenoid, and phenolic fractions of virgin olive oils from the Arbequina variety cultivated in different olive growing areas of Spain. Virgin olive oil from Lleida was less heavily pigmented, and these oils showed more negative values for the ordinate a^* (of the CIELAB colorimetric system). Pheophytin a was the major chlorophyll pigment, and lutein was the major component of the carotenoid fraction in all oils analyzed. The chlorophyll a concentration in virgin olive oils from Lleida was 700 μg kg⁻¹, but was 175 μg kg⁻¹ in oils from Jaén, and 200 μg kg⁻¹ in oils from Tarragona. Finally, the chlorophyll a/chlorophyll b ratio was 9 in oils from Lleida and around 0.6 in the other two Arbequina olive oils. In relation to the phenolic fraction, the hydroxytyrosol and tyrosol contents were significantly higher in olive oils from Jaén (grown at higher altitude and precipitation rates). The secoiridoid derivatives showed a significantly higher concentration in olive oils from Tarragona, probably due to the low altitude where they grow, and finally the ratio of (dialdehydic form of elenolic acid linked to tyrosol)/lignans had a value of 1.4 in olive oils from Lleida, whereas this value was around 0.7 in the other Arbequina olive oils.     

Antioxidant activity of tocopherols and phenolic compounds of virgin olive oil

The antioxidant effects of hydrophilic phenols and tocopherols on the oxidative stability in virgin olive oils and in purified olive oil have been evaluated. Total hydrophilic phenols and the oleosidic forms of 3,4-dihydroxyphenolethanol (3,4-DHPEA) were correlated (r=0.97) with the oxidative stability of virgin olive oil. On the contrary, tocopherols showed low correlation (r=0.05). Purified olive oil with the dialdehydic form of elenolic acid linked to 3,4-DHPEA, an isomer of oleuropeine aglycon, and 3,4-DHPEA had good oxidative stability. A synergistic effect was observed in the mixture of 3,4-DHPEA and its oleosidic forms with α-tocopherol in purified olive oil by the Rancimat method at 120°C.     

Analytical evaluation of six monovarietal virgin olive oils from Northern Tunisia

The characterization of virgin olive oils from six Tunisian cultivars, namely Chétoui, Ain Jarboua, Jarboui, Regregui, Rekhami and Neb Jmel, grown in Nebeur (a region of the Kef) was carried out. These cultivars dominate their natural habitats, but with the exception of the Chétoui cultivar they are only scattered throughout the nation. Several analytical parameters were evaluated; these include quality index, fatty acid composition, chlorophylls, carotenoids, sterols, α‐tocopherol and phenolic compounds. Their relationship with oxidative stability was also tested. The main phenols found were tyrosol, hydroxytyrosol, the dialdehydic form of elenolic acid linked to tyrosol and hydroxytyrosol, oleuropein aglycon and pinoresinol. These phenolic compounds, the colorimetric total phenol content and o‐diphenols showed significant correlations with oxidative stability. Furthermore, most of the analytical parameters of the oils that were determined in this study were greatly influenced by genetic factors (cultivar).     

Evaluation of the bitter taste in virgin olive oil

An analytical method has been developed to evaluate the intensity of the bitter taste in virgin olive oil. Results from the proposed method, based on extraction of the bitter constituents of virgin olive oil with methanol/water and measurement of the absorbance at 225 nm, show a significant correlation with the intensity of bitterness that had been evaluated in a sensorial manner by a panel. The developed method, therefore, offers a real alternative to the panel test for the evaluation of this attribute.     

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.     

Influence of seasonal conditions on the composition and quality parameters of monovarietal virgin olive oils

The aim of this work was to determine the effect of the climatological conditions of the olive crop season on the composition of monovarietal virgin olive oils obtained from the Arbequina cultivar with special emphasis on the phenolic fraction, its percent distribution, and related oil quality parameters such as oxidative stability and bitter index. The main differences were due to freeze injuries caused by low temperatures in December 2001. The levels of chlorophylls and carotenoids in olive oil or pulp from frost-damaged olive trees were lower as a consequence of faster ripening. The olive oil extracted from frost-damaged olive pulp had lower contents of secoiridoid and especially lower levels of 3,4-DHPEA-EDA (the dialdehydic form of elenolic acid linked to hydroxytyrosol). In the following crop seasons, a significant increase in phenolic compounds, especially in secoiridoid derivatives such as 3,4-DHPEA-EDA, was observed. This increase may be due to the fact that olive trees that suffered frost damage in December 2001 were more sensitive to stress caused by the water deficit during summer in the subsequent crop seasons, which is usual in this olive-growing region. Moreover, important correlation coefficients were observed between the main secoiridoid derivative compound (3,4-DHPEA-EDA) and oxidative stability and the bitter index.     

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.     

Characterization of olive paste volatiles to predict the sensory quality of virgin olive oil

One of the main challenges that virgin olive oil producers face today is an accurate prediction of the sensory quality of the final product prior to the milling of the olives. The possibility that olive paste aroma can be used as a predictive measurement of virgin olive oil quality is studied in this paper. The study was centered on distinguishing the aroma of olive pastes that produced virgin olive oils without sensory defects from the aroma of olive pastes the virgin olive oils of which showed sensory defects. Olive pastes were analyzed by solid‐phase microextraction‐gas chromatography and a sensor system based on metal oxide sensors. Forty‐four volatile compounds were identified in olive pastes, all of them being also present in virgin olive oil. Six volatile compounds – acetic acid, octane, methyl benzene, (E)‐2‐hexenal, hexyl acetate and 3‐methyl‐1‐butanol – distinguished both kinds of pastes with only five misclassified samples. Five metal oxide sensors were able to classify the olive pastes with only two erroneous classifications.     

Evolution of thermograph parameters during the oxidation of extra virgin olive oil

The modulated differential scanning calorimetry (M‐DSC) was used as a rapid and effective method to characterize the olive oil at different levels of oxidation. Thermograph parameters have been related to oxidative degradation of the triglycerides. In this study, their relation to the characteristic off‐flavor compounds, correlated to the oxidative degradation of the oil, was also investigated. Extra virgin olive oil samples were subjected to the following oxidation treatments: a) purged with air using glass washing bottles at two flow rate values, b) heated in a conventional oven at two area/oil mass ratios, and c) heated in a microwave oven also at two area/oil mass ratios. Samples were withdrawn and analyzed at predetermined intervals. Flavor and off‐flavor compounds were isolated using a dynamic thermal stripping apparatus and transferred into a gas chromatograph by using a thermal desorption unit. All oil samples were analyzed by M‐DSC during cooling from 25 °C to ?60 °C at 7 °C/min, and heating back to 40 °C at 10 °C/min. High correlation values were obtained between various M‐DSC thermograph parameters and certain volatile compounds. Results showed that M‐DSC could be used as a simple method to indicate compositional changes in olive oil during oxidation.     

Air exposure time of olive pastes during the extraction process and phenolic and volatile composition of virgin olive oil

The time of exposure of olive pastes to air contact (TEOPAC) during malaxation was studied as a processing parameter that could be used to control endogenous oxidoreductases, such as polyphenoloxidase, peroxidase, and lipoxygenase, which affect virgin olive oil quality. Phenolic and volatile compounds were analyzed in the oils obtained using progressive TEOPAC at three ripening stages of olives. Multivariate statistical analysis was applied to the raw data. The phenolic concentration of virgin olive oil progressively decreased with increasing IEOPAC. On the contrary, a positive relationship was found with the concentration of several volatile compounds responsible for virgin olive oil aroma. The effect of TEOPAC, however, was strictly related to fruit ripening.     

Hydrophilic antioxidants of virgin olive oil. Part 1: Hydrophilic phenols: A key factor for virgin olive oil quality

Virgin olive oil (VOO) consumption is increasing all over the world due to its excellent organoleptic and nutraceutical properties. These beneficial traits stand from a prominent and well‐balanced chemical composition, which is a blend of major (98% of total oil weight) and minor compounds including antioxidants. The main antioxidants are phenolic compounds, which can be divided into lipophilic and hydrophilic phenols. While lipophilic phenols such as tocopherols can be found in other vegetable oils, most hydrophilic phenols in olive oil are exclusive of the Olea europaea species endowing it with a chemotaxonomic interest. This review is focused on VOO antioxidant profile and, particularly, on hydrophilic phenols that are divided into different sub‐families such as phenolic acids and alcohols, hydroxy‐isochromans, flavonoids, secoiridoids, lignans and pigments. Analytical methods for qualitative and/or quantitative determination of these compounds are assessed. The implementation of efficient sample preparation protocols, separation techniques such as liquid chromatography, GC and capillary electrophoresis, as well as detection techniques such as ultraviolet absorption, fluorescence or MS are critical to succeed in the quality of the results. The effects of hydrophilic phenols on increasing VOO stability, its nutraceutical interest and organoleptic properties are also considered.     

Automated ultrasound‐assisted method for the determination of the oxidative stability of virgin olive oil

A fast and automated method is proposed for determining the oxidative stability of virgin olive oil by using ultrasound. The ultrasound microprobe (3 mm in diameter) was directly immersed into the olive oil sample contained in a test tube. The most influential variables in the oxidation process, namely pulse amplitude, duty cycle, irradiation time, and sample amount, were optimized. The oil absorbance at 270 nm was continuously monitored by oil recirculation through a 0.1‐mm path length flow cell connected to a fiber optic microspectrometer. This short path length allowed the direct monitoring of absorbance without needing any sample dilution. The ultrasound energy was applied during 35 min, and the resulting increase in absorbance was continuously monitored. The difference between the final and the initial absorbance at 270 nm of a set of virgin olive oil samples was closely correlated with their oxidative stability calculated by the Rancimat method (R² = 0.9915). The resulting equation enabled the prediction of the oxidative stability of virgin olive oil in a short period of time (35 min), by using a simple, inexpensive, automatic and easy‐to‐use system.     

Crystal polymorph structure determined for extra virgin olive oil

No literature data were available on the crystal polymorph structure associated with the crystallization/melting of TAG fractions of extra virgin olive oil until the publication of the article by Barba, Arrighetti and Calligaris in this issue of the European Journal of Lipid Science and Technology [p. 322–329]. The authors determined crystal structure of extra virgin olive oil TAGs using DSC coupled with XRD technique. These findings are of great importance as an increasing number of formulated foods (e.g. salad dressings, sauces, chilled and frozen ready‐to‐eat products) and new products are nowadays produced with this high quality vegetable oil as lipid phase. The significance of these results is underlined in this commentary. See accompanying article by Barba et al. [p. 322–329], http://dx.doi.org/10.1002/ejlt.201200259     

Low molecular weight polypeptides in virgin and refined olive oils

Twenty-eight virgin olive oils—from different regions of Spain and prepared from olive drupes of different varieties—and six refined olive oils were analyzed to determine the presence of proteins in these oils. All oils studied showed the presence of proteins in the range of 7–51 μ/100 g of oil. There were no significant differences in protein content in oils from different varieties or between virgin or refined oils. In addition, all oils exhibited analogous amino acid patterns, suggesting a similarity among protein fractions obtained from different oils. A polypeptide with an apparent M.W. of 4600 Da was common to the isolated protein fractions. These results suggest that this polypeptide is a previously unknown minor component in olive oils. No clear influence of this component on oil stability was observed when oil stabilities were estimated as a function of phenol, tocopherol, phosphorus, and protein contents of the oils.     

The hydrocarbon fraction of virgin olive oil and changes resulting from refining

In numerous Spanish virgin olive oils, 6,10-dimethyl-1-undecene, various sesquiterpenes, the series ofn-alkanes from C14 to C35, n-8-heptadecene and squalene are the only less volatile components detected by gas chromatography in the hydrocarbon fraction. In oils from olives of the Arbequine variety, a series ofn-9-alkenes has also been found. In refined oils, notable features are the absence of the most volatile compounds and the appearance of other hydrocarbons produced during the refining process. Among these,n-alkanes, alkadienes (mainlyn-hexacosadiene), stigmasta-3,5-diene, isomerization products of squalene, isoprenoidal polyolefins coming from hydroxy derivatives of squalene and steroidal hydrocarbons derived from 24-methylene cycloartanol were identified. Physical refining produces larger amounts of degradation products and greater losses ofn-alkanes than chemical processing. Squalene is the major hydrocarbon component in all oils, both virgin and refined. The ranges of concentration for the different hydrocarbons found in Spanish virgin olive oils are presented.     

High-performance liquid chromatography evaluation of phenols in virgin olive oil during extraction at laboratory and industrial scale

Phenolic compounds are of fundamental importance to the quality and nutritional properties of virgin olive oils. In this paper, the high-performance liquid chromatographic analysis of simple and complex olive oil phenols in the streams generated in the two-phase extraction system was carried out using Arbequina and Picual olives. The malaxation stage reduced the concentration of orthodiphenols in oil ca 50–70%, while the concentration of the nonorthodiphenols remained constant, particularly the recently identified lignans 1-acetoxypinoresinol and pinoresinol. Oxidation of orthodiphenols at laboratory scale was avoided by malaxing the paste under a nitrogen atmosphere. Phenolic compounds in the wash water used in the vertical centrifuge were also identified. Hydroxytyrosol, tyrosol, the dialdehydic form of elenolic acid linked to hydroxytyrosol were the most representative phenols in these waters. Hence, phenolic compounds in the wash waters came from both the aqueous and the lipid phases of the decanter oily must.