Phenolic Characterization and Geographical Classification of Commercial Extra Virgin Olive Oils Produced in Turkey

The aim of this research was to characterize the extra virgin olive oil samples from different locations in the Aegean coastal area of Turkey in terms of their phenolic compositions for two consecutive years to show the classification of oil samples with respect to harvest year and geography. Forty seven commercial olive oil samples were analyzed with HPLC–DAD, and 17 phenolic compounds were quantified. Hydroxytyrosol, tyrosol, vanillic acid, p-coumaric acid, ferulic acid, cinnamic acid, luteolin and apigenin were the characteristic phenols observed in all oil samples for two harvest years. Syringic acid, vanillin and m-coumaric acid were the phenolic compounds appeared in the olive oil depending on the harvest year. Partial least square-discriminant analysis (PLS-DA) of data revealed that oils from the north Aegean and south Aegean areas had different phenolic profiles. The phenolic compounds, which played significant roles in the discrimination of the olive oils, were tyrosol, oleuropein aglycon, cinnamic acid, apigenin and hydroxytyrosol to tyrosol ratio. The Aegean coastal region is the largest olive oil producer and exporter of Turkey. This study shows that the olive oils from different parts of the region have their own defining characteristics that can be used in the authentication studies and geographical labeling of Turkish olive oils.     

Influence of Water Deficit in Bioactive Compounds of Olive Paste and Oil Content

The main objective of this study was to evaluate the effect of different deficit irrigation treatments (control, regulated deficit irrigation [RDI]‐1, RDI‐2, and RDI‐3) on the phenolic profile of the olive paste and oil content. Irrigation treatments with more stress water led to a considerable increase in the phenolic compounds of olive paste, especially in oleuropein (60.24%), hydroxytyrosol (82%), tyrosol (195%), and verbascoside (223%) compared to control. A significant increase in the content of total flavonoids and phenolic acids was also observed for these samples. In virgin olive oils (VOO) elaborated from the most stressed olive trees (RDI‐2 and RDI‐3), a noticeable increase in phenolic substances with antioxidant properties (oleuropein, hydroxytyrosol, tyrosol, secoiridoid derivatives, and o‐vanillin) was observed. Consequently, water stress conditions improved antioxidant activity of VOO.     

Hydroxytyrosol and tyrosol as the main compounds found in the phenolic fraction of steam-exploded olive stones

The lignocellulosic by-products, whole stones, and seed husks obtained from processing pitted table olives and oil olives were pretreated under various conditions of steam explosion, with and without previous acid impregnation. The various water-soluble noncarbohydrate compounds generated during steam explosion, such as sugar degradation compounds (furfural and hydroxymethylfurfural), lignin degradation compounds (vanillic acid, syringic acid, vanillin, and syringaldehyde) and the simple phenolic compounds characteristic of olive fruit (tyrosol and hydroxytyrosol), were identified. The amount of hydroxytyrosol solubilized was higher than that of the other compounds, and increased with increasing steaming temperature and time. This suggests its presence as a structural component of the olive stone.     

LC–ESI–MS Characterization of Phenolic Profiles Turkish Olive Oils as Influenced by Geographic Origin and Harvest Year

The purpose of this investigation was to evaluate and compare the differences in the phenolic fractions and antioxidant properties of virgin olive oils from the Nizip yaglik and Kilis yaglik olive varieties cultivated in native and different olive growing areas of Turkey. The phenolic composition of olive oils was carried out by HPLC-DAD and identifications were made by LC–MS. Fourteen phenolic compounds were identified and among these compounds elenolic acid, tyrosol and hydroxytyrosol were the most dominant. Based on the results, there was no difference in distribution of phenolic compounds, but the total phenolic content in oil from native regions was higher than in oil from Bornova regions. The antioxidant capacity of olive oil extracts was determined by two different methods, including DPPH and ABTS. In both methods, antioxidant capacity values were higher in oil from native regions.     

Direct and mediated effects onBactrocera oleae (Gmelin) (Diptera; Tephritidae) of natural polyphenols and some of related synthetic compounds: Structure-activity relationships

Among the main polyphenols occurring in olive oil vegetation waters (VW), catechol showed the most deterrent action on the oviposition ofBactrocera oleae (Gmelin); 4-methylcatechol was less active, whereas hydroxytyrosol and tyrosol were inactive. In contrast, synthetico-quinone was found to be stimulant at 7.5 × 10^–2 M. Two other synthetic derivatives of catechol, diacetylcatechol and guaiacol, were also deterrent, suggesting these compounds undergo a biochemical transformation into catechol by means of the bacterial symbionts ofB. oleae. VW and their phenolic extracts showed deterrence only when highly concentrated, while natural olive juice was strongly deterrent. Experiments carried out to evaluate the effect of olive juice and catechol on the fecundity ofB. oleae showed that they strongly reduce this function. Moreover, the possible utilization of VW and their bioactive polyphenols in protection of olives againstBatrocera oleae is discussed.     

Evolution of phenols and pigments in extra virgin olive oil from irrigated super‐intensive orchard

Phenolic compounds have a high importance in olive oil because of their effect on shelf life and sensory properties. This study reports on the HPLC profiles of the phenolic compounds of virgin olive oils obtained from Arbequina olives from the harvesting in a super‐intensive orchard under a linear irrigation system. In addition, phenolic content, carotenoid and chlorophyllic pigments, and oxidative stability were analyzed. Total phenol content and 3,4‐DHPEA‐EDA increased up to a maximum throughout the ripening process. The simple phenols tyrosol and hydroxytyrosol acetate increased throughout the ripening process, however, there was not found a clear trend in hydroxytyrosol content. Minor constituents such as vanillic acid and p‐coumaric acid increased up to a maximum and then decreased, since vanillin decreased progressively throughout the time of harvest. 3,4‐DHPEA‐EDA and lignans were present in considerable amounts in the studied samples, while oleuropein aglycone was present in a low amount. Total phenol content and oil stability followed the same trend throughout the study, so a very good correlation was established between them. Total secoiridoids and, specifically, 3,4‐DHPEA‐EDA seemed to be responsible for oil stability. The pigment content decreased during ripening, and not a positive correlation was found between pigments and oil stability. Practical applications : The results can be used to determine the best time for harvesting in order to obtain olive oils with different phenols and pigment contents. This is important for sensory characteristics of the olive oils and also for olive oil stability.     

Changes in Quality Indices,Phenolic Content and Antioxidant Activity of Flavored Olive Oils during Storage

The chemical characteristics, phenolic content and antioxidant activity of olive oils flavored with garlic, lemon, oregano, hot pepper, and rosemary were evaluated during 9 months of storage. At the end of the storage period, the unflavored and the garlic-flavored oils maintained their chemical parameters within the limits fixed for extra-virgin olive oils. After 9 months of storage, a noticeable decrease in phenolic content was observed in all the oils. The highest (35.0 ± 3.9 mg/kg oil) and the lowest (6.3 ± 0.4 mg/kg) phenolic contents were detected in the unflavored and garlic-flavored oils, respectively. Compounds such as 3,4-DHPEA-EDA (3,4-dihydroxyphenylethyl 4-formyl-3-formylmethyl-4-hexenoate, the dialdehydic form of decarboxymethyl elenolic acid linked to hydroxytyrosol) and p-HPEA-EDA (dialdehydic form of the decarboxymethyl elenolic acid linked to tyrosol) were the most abundant in both unflavored and lemon-flavored oils up till 6 months of storage. At the end of the storage period, increases in 3,4-DHPEA (hydroxytyrosol) and p-HPEA (tyrosol) were measured in almost all the oils. During storage, the antioxidant activity coefficients of the phenolic extracts, calculated according to the β-carotene bleaching assay, significantly decreased and, after 9 months, were in a decreasing order: rosemary (51.3 ± 4.2), hot pepper, lemon, oregano, unflavored, and garlic (8.5 ± 0.7).     

Phenolic Compounds and Antioxidant Capacity of Monovarietal Olive Oils Produced in Argentina

Virgin olive oil has high levels of phenolic compounds that are highly bioavailable; these compounds are receiving considerable attention for their antioxidant activity, closely related to the prevention of non‐communicable chronic diseases. The aim of this work was to characterize the phenolic profile and antioxidant capacity of monovarietal olive oils cvs. Arauco, Arbequina, Farga and Empeltre produced in Argentina. This study focused on the relationship between the single molecules or classes of molecules quantified by SPE‐CZE, the corresponding Folin‐Ciocalteu results, and antioxidant capacity using three different tests. Fifteen compounds were simultaneously determined: tyrosol, vinylphenol, oleuropein, hydroxytyrosol, rutin, catechin, naringenin, cinnamic acid, chlorogenic acid, syringic acid, luteolin, apigenin, vanillin acid, quercetin, and caffeic acid. The phenolic contents of the monovarietal olive oils show significant differences between different varieties (p < 0.05), with positive and significant Pearson's correlation found between Folin–Ciocalteu and CZE. Besides, the correlation between the content of total polyphenols and antioxidant capacity was high for all the antioxidant assays performed. When analyzing the correlation coefficients of the different families of phenolic compounds studied, simple phenols and cinnamic acid derivatives show a higher correlation with antioxidant capacity. Thus, findings obtained in this study demonstrated that Arauco olive oil, autochthonous for Argentina, possesses the highest antioxidant/free‐radical scavenging properties, which are very likely due to the presence of high contents of phenolic compounds.     

High‐temperature pre‐conditioning of rapeseed: A polyphenol‐enriched oil and the effect of refining

In this work, a pretreatment process for rapeseeds, which involves the use of high‐temperature steam, is presented. This method, besides accomplishing the beneficial effects of the conventional industrial thermal treatment, leads to an enrichment of some important minor compounds (polyphenols and phosphatides) in the resulting oil. Rapeseeds were pretreated at different operative conditions. Then, the seeds were pressed and the press‐cake was solvent extracted. The obtained oils were then refined by both chemical and physical refining techniques, and the influence of each refining step on the content of minor compounds was evaluated. The results show that the amounts of polyphenols and phospholipids present in the oil coming from pretreated seeds increase and that their concentrations depend on the conditioning time. The polyphenols present in the oil correspond mostly to 2,6‐dimethoxy‐4‐vinylphenol (vinylsyringol). The content of polyphenols was only slightly reduced during degumming. Neutralization resulted in a complete removal of these minor compounds. For the physical refining process, the type and amount of bleaching clay used had a significant influence on the content of polyphenols. After deodorization, oil samples with a considerable amount of polyphenols were obtained. These samples show a higher oxidative stability than chemically refined oils.     

Acidification of Alperujo Paste Prevents Off-Odors During Their Storage in Open Air

Alperujo is the main paste produced by the olive oil industry that must be stored in big open air ponds for months before pomace olive oil is extracted. During this period, malodorous 4-ethylphenol is formed, and it represents a big environmental problem for the oil extracting factories. The aim of this investigation was to prevent the formation of this substance by acidification of the fresh paste. Several batches of fresh Alperujo were stored in 100-L plastic containers for 6 months without pH control and acidified up to pH 2 or 3. Acidification inhibited the formation of 4-ethylphenol as well as the growth of yeasts. By contrast, acidification of the paste did not affect oil acidity, triterpenic acid concentration, waxes or fatty acid composition. An increase in hydroxytyrosol of the aqueous phase of Alperujo was also observed because of hydroxytyrosol glucoside hydrolysis. The results indicated that acidification of Alperujo during storage under open air conditions reduced the formation of 4-ethylphenol, thereby diminishing the environmental impact of the pomace olive oil production.     

Characterization of the Volatile, Phenolic and Antioxidant Properties of Monovarietal Olive Oil Obtained from cv. Halhali

Volatile and phenolic compositions of olive oil obtained from the cv. Halhali were investigated in the present study. Fruits were harvested at the optimum maturity stage of ripeness and immediately processed with cold press. Simultaneous distillation/extraction (SDE) with dichloromethane was applied to the analysis of volatile compounds of olive oil. Sensory analysis showed that the aromatic extract obtained by SDE was representative of olive oil odour. In the olive oil, 40 and 44 volatile components were identified and quantified in 2010 and 2012 year, respectively. The total amount of volatile compounds was 18,007 and 19,178 μg kg^?1 for 2010 and 2012, respectively. Of these, 11 compounds in the 2010 and 12 in the 2012 harvest presented odour activity values (OAVs) greater than 1, with 1‐octen‐3‐ol, ethyl‐3‐methyl butanoate, (E)‐2‐heptenal and (E,Z)‐2,4‐decadienal being those with the highest OAVs in olive oil. The high‐performance liquid chromatographic method coupled with diode‐array detection was used to identify and quantify phenolic compounds of the olive oil. A total of 14 phenolic compounds in both years were identified and quantified in olive oil. The major phenolic compounds that were identified in both years were hydroxytyrosol, tyrosol, elenolic acid, luteolin, and apigenin. Antioxidant activity of olive oil was measured using the DPPH and ABTS methods.     

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.     

Phenolic Composition and Antioxidant Activity of Monovarietal and Commercial Portuguese Olive Oils

Olive oil composition has been investigated using chemical approaches, since the composition has a direct impact on its quality and safety and it may be used for certification purposes. In this paper, eleven monovarietal and twelve commercial Portuguese olive oils were analyzed to determine spectrophotometrically their total polyphenol content, ortho-diphenols and antioxidant activity. The phenolic profiles of these olive oils were also studied by high performance liquid chromatography. The lowest phenolic content and antioxidant activity were observed for monovarietal olive oils, however, among these group, ‘Cobrançosa’ and ‘Redondil’ cultivars showed the highest values of these two chemical parameters. In commercial olive oils, the concentration of polyphenols, determined according to the Folin–Ciocalteu method, and the antioxidant activity (ABTS method) ranged from 97.37 ± 1.10 to 219.7 ± 1.50 mg GAE/kg of oil and from 387.2 ± 20.00 to 997.5 ± 30.90 µmol Trolox/kg, respectively. The study of the phenolic profile demonstrated that the highest concentrations of the most abundant compounds in olive oil (tyrosol, hydroxytyrosol and oleuropein) are present in commercial olive oils. The correlation coefficient between total phenolics and antioxidant activity was statistically significant (r = 0.95, p < 0.0001). The same was observed for ortho-diphenol content and antioxidant capacity (r = 0.94, p < 0.0001).     

Comparative study of olive oil quality from Chemlali Sfax versus Arbequina cultivated in Tunisia

The effects of the geographical region on the behavior of the Arbequina olive cultivar (cv) cultivated in the south of Tunisia (in the arid zone of Sfax) was compared to an autochthonous cultivar (Chemlali Sfax). Various olive parameters were analyzed, such as ripening index, pulp/stone ratio, oil contents, and sensory profiles. Most of the quality indices and fatty acid composition showed significant variations among olive cultivars. Arbequina cv is characterized by high oil yield with a less total phenols and pigments content than Chemlali Sfax cv. Cielab spectrophotometer coordinate L*, b*, and a* values show a great difference in olive oil colors. In spite of their low oleic acid contents, autochthonous cultivar presented a higher induction time (6.82 and 2.68 h for Chemlali and Arbequina, respectively) and high contents of phenolic compounds (158.28 and 110.27 mg/kg for Chemlali Sfax and Arbequina, respectively). The most important compounds identified were oleuropein aglycon (45.50 mg/kg), hydroxytyrosol (3.68 mg/kg), 1‐acetoxypinoresinol (6.23 mg/kg) in Chemlali Sfax oil and hydroxytyrosol glucoside (25.15 mg/kg), tyrosol (12.51 mg/kg), and oleuropein aglycon (30.60 mg/kg) in Arbequina oil. Chemlali Sfax also possessed a very bitter taste, whereas the Arbequina had a sweet taste amongst its attributes. The principal component analysis of the results indicated that the geographical region has significantly affected the olive oil quality.     

Peroxyl and hydroxyl radical scavenging activity of some natural phenolic antioxidants

The autoxidation of linoleic acid dispersed in an aqueous media and the antioxidant effect of hydroxytyrosol, oleuropein, caffeic acid and tyrosol were studied. Linoleic acid autoxidation rate was estimated by the increase of conjugated diene level and by the decrease of linoleic acid content in the samples. The phenolic compounds exhibited an antioxidant activity which increased in the order: tyrosol < caffeic acid < oleuropein < hydroxytyrosol. The analysis of the hydroperoxide isomers pointed out that hydroxytyrosol, oleuropein and caffeic acid at a concentration of 10⁻⁴M inhibited the formation oftrans- trans isomers in the increasing order: caffeic acid < oleuropein < hydroxytyrosol. This inhibition could be related to the ability of phenolic compounds to scavenge peroxyl radical. Tyrosol did not inhibit the formation oftranstrans isomers. Phenolic compounds were degraded as a consequence of their antioxidant activity and their degradation rate was positively correlated to their antioxidant efficacy. These phenolic compounds, at a concentration of 6 × 10⁻³M, also scavenged hydroxyl radical, with an efficiency which increased in the order: tyrosol < hydroxytyrosol < oleuropein < caffeic acid. Polar substituents at the para position, such as in caffeic acid and oleuropein, were correlated with higher hydroxyl radical quenching ability.     

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.     

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).     

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.     

Effect of storage of olive mill wastewaters on hydroxytyrosol concentration

This investigation was designed to determine the effect of olive mill wastewaters (OMW) storage on the continuous extraction of potentially high‐added‐value phenolic compounds from these effluents. Particular emphasis was made on the extraction of hydroxytyrosol, one of the major compounds occurring in OMW. The hydroxytyrosol concentration was constant in OMW supplemented with 10% ethanol during storage. However, with 5 and 0% ethanol, a noticeable increase was observed in the hydroxytyrosol concentration. At time zero, the main polyphenols detected in two samples of fresh OMW without ethanol addition were hydroxytyrosol, hydroxytyrosol‐4‐β‐glucoside, 3,4‐dihydroxyphenylacetic acid, p‐coumaric acid, ferulic acid, oleuropein, and some other unidentified compounds. After 5 months of storage, significant accumulation of hydroxytyrosol was observed. The corresponding concentration increased from 0.98 to 3.5 g/L for the OMW sample collected in November 2004 and from 0.77 to 3.1 g/L for the sample collected in January 2006. However, the concentrations of the other phenolic compounds were markedly decreased. Furthermore, it was deduced that the OMW storage facilitates the continuous extraction procedure and improves the extraction yield of hydroxytyrosol. This last parameter increased from 85.5 to 96.8%.     

Stability of refined olive oil and olive‐pomace oil added by phenolic compounds from olive leaves

Refined olive oil and olive‐pomace oil were enriched with olive leaf phenolic compounds in order to enhance its quality and bring it closer to virgin olive oil. The changes that occurred in the concentrations of pure oleuropein, oleuropein aglycone, hydroxytyrosol acetyl and α‐tocopherol at 400 µg/kg of oil during the storage of refined olive oil and olive‐pomace oil under accelerated conditions (50 °C) were investigated. In a period of 4 months, α‐tocopherol decomposed by 75% whereas less than 40% of the phenols were lost. During storage, enzymatic olive leaf extract hydrolysate that contains two major compounds, hydroxytyrosol and oleuropein aglycone showed the highest antioxidant activity and the lowest detected stability, followed by oleuropein. The oleuropein in olive leaf extracts exhibited similar degradation profiles, reducing by 60–50% and 80% for the olive oil and olive‐pomace oil in 6 months, respectively. The acetylated extract, however, displayed a loss of 10 and 5% in olive oil and olive‐pomace oil, respectively. In the fatty acid composition, an increase in oleic acid and a decrease in linoleic acid were observed. The antiradical activities of the olive oil and olive‐pomace oil enriched with olive leaf phenolic compounds at 400 ppm showed that enzymatic hydrolysate extract had the highest protective effect against oil oxidation. Based on the Rancimat method, the oils with added leaf enzymatic hydrolysate extract had the lowest peroxide value and the highest stability. After 6 months of storage and at 120 °C, the oxidative resistance of refined olive oil and olive‐pomace oil reached 0.71 and 0.89 h, respectively, whereas that of the non‐enriched samples fell to zero.