How heating affects extra virgin olive oil quality indexes and chemical composition

Two monovarietal extra virgin olive oils from Arbequina and Picual cultivars were subjected to heating at 180 degrees C for 36 h. Oxidation progress was monitored by measuring oil quality changes (peroxide value and conjugated dienes and trienes), fatty acid composition, and minor compound content. Tocopherols and polyphenols were the most affected by the thermal treatment and showed the highest degradation rate although their behavior was different for each cultivar. Alpha-tocopherol loss was more important in Arbequina oil whereas, total phenol content loss was greater in Picual oil. The later showed an important decrease in hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA), while lignans decrease was lesser. For Arbequina oil these compounds remained stable, and a lowering tendency was observed for tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA). In general, flavone content showed a decrease during heating, being higher for Arbequina oil. On the other hand, oleic acid, sterols, squalene, and triterpenic alcohols (erythrodiol and uvaol) and acids (oleanolic and maslinic) were quite constant, exhibiting a high stability against oxidation. From these results, we can conclude that despite the heating conditions, VOO maintained most of its minor compounds and, therefore, most of its nutritional properties.     

Synthesis of volatile compounds of virgin olive oil is limited by the lipoxygenase activity load during the oil extraction process

The aim of this work was to determine whether the lipoxygenase (LOX) activity is a limiting factor for the biosynthesis of virgin olive oil (VOO) volatile compounds during the oil extraction process. For this purpose, LOX activity load was modified during this process using exogenous LOX activity and specific LOX inhibitors on olive cultivars producing oils with different volatile profiles (Arbequina and Picual). Experimental data suggest that LOX activity is a limiting factor for the synthesis of the oil volatile fraction, this limitation being significantly higher in Picual cultivar than in Arbequina, in line with the lowest content of volatile compounds in the oils obtained from the former. Moreover, there is evidence that this limitation of LOX activity takes place mostly during the milling step in the process of olive oil extraction.     

Acid hydrolysis of secoiridoid aglycons during storage of virgin olive oil.

The main change found in the phenolic composition of virgin olive oils of Arbequina, Hojiblanca, and Picual varieties during storage in darkness at 30 degrees C was the hydrolysis of the secoiridoid aglycons. This reaction gave rise to an increase in the free phenolics hydroxytyrosol and tyrosol in the oil. Filtration of oil and acidity influenced the hydrolysis to a large extent. Thus, the addition of commercial oleic acid to Hojiblanca and Picual oils increased the hydrolysis rate of the secoiridoid aglycons. In contrast, the concentration of lignans 1-acetoxypinoresinol and pinoresinol remained constant during storage. It must also be stressed that the total molar concentration of the phenolic compounds analyzed in the oils changed slightly (<20% reduction) after one year of storage, which is important from a nutritional point of view. However, the transformation of the secoiridoid aglycons into free phenolics may have consequences on oil taste and antioxidant capacity.     

Oxygen concentration affects volatile compound biosynthesis during virgin olive oil production

The effect of O 2 concentration on oil volatile compounds synthesized during the process to obtain virgin olive oil (VOO) was established. The study was carried out either on the whole process or within the main steps (milling and malaxation) of this process with two olive cultivars, Picual and Arbequina, at two ripening stages. Data show that O 2 control during milling has a negative impact on VOO volatile synthesis. This effect seems to depend on cultivar and on the ripening stage in cultivar Picual. Because most VOO volatiles are synthesized during olive fruit crushing at the milling step, O 2 control during malaxation seems to affect just slightly the volatile synthesis. The highest effect was observed when control of O 2 concentration was performed over the whole process. In this case, the content of volatile compounds of oils obtained from both cultivars and ripening stages showed quite similar trends.     

Effect of storage on secoiridoid and tocopherol contents and antioxidant activity of monovarietal extra virgin olive oils

The degradation of secoiridoid, tocopherol, and antioxidant activity in extra virgin olive oils (EVOOs) was studied during 8 months of storage in closed bottles in the dark, at 40 and 25 degrees C. Picual, Arbequina, Taggiasca, and Colombaia monovarietal EVOOs possessing quite different fatty acid and antioxidant contents were used. The secoiridoid aglycones, namely, the oleuropein and ligstroside derivatives, and alpha-tocopherol decreased following pseudo-first-order kinetics. In all EVOOs oleuropein derivatives were less stable than the corresponding ligstroside derivatives and alpha-tocopherol. Accordingly, overall antioxidant activity decreased following pseudo-first-order kinetics, with rate constants ranging from 0.85 x 10(-)(3) to 4.1 x 10(-)(3) days(-)(1) at 40 degrees C and from 0.8 x 10(-)(3) to 1.5 x 10(-)(3) days(-)(1) at 25 degrees C. According to both the antioxidant activity and the hydrolysis and oxidation indices established by EU regulation to assess EVOO quality, Colombaia oil was the least stable, followed by Taggiasca, Arbequina, and Picual oils. Despite antioxidant degradation, EVOOs with high antioxidant contents were still "excellent" after 240 days of storage at 40 degrees C. These data led to the conclusion that the beneficial properties of EVOOs due to antioxidant activity can be maintained throughout their commercial lives.     

Changes induced by UV radiation during virgin olive oil storage

The effects of UV radiation on the chemical and sensory characteristics of virgin olive oils (cv. Arbequina and Picual) were assessed. Even small doses of UV radiation induced oxidation of the virgin olive oil samples. Total phenols and fatty acids contents decreased during the process as well as the intensity of the bitter and fruity sensory attributes, while the intensity of the rancid sensory attribute notably increased. Acetaldehyde, 2-butenal, 2-pentenal, octane, octanal, hexanal, nonanal, and 2-decenal were the volatile compounds most affected, showing an important increase during the irradiation process. Nonanal, hexanal, and pentanal showed high correlation with the rancid sensory attribute (90%, 86%, and 86%, respectively). 2-Decenal and nonanal concentrations allowed us to predict the alteration level of the samples by mean of multiple Ridge regression.     

Cultivar differences on nonesterified polyunsaturated fatty acid as a limiting factor for the biogenesis of virgin olive oil aroma

The relationship between the content of nonesterified polyunsaturated fatty acids and the contents of oil aroma compounds that arise during the process to obtain virgin olive oil (VOO) was studied in two olive cultivars, Picual and Arbequina, producing oils with distinct aroma profiles and fatty acid compositions. Results suggest that the biosynthesis of VOO aroma compounds depends mainly on the availability of nonesterified polyunsaturated fatty acids, especially linolenic acid, during the process and then on the enzymatic activity load of the lipoxygenase/hydroperoxide lyase system. Both availability of substrates and enzymatic activity load seem to be cultivar-dependent.     

Influence of cultivar and fruit ripening on olive (Olea europaea) fruit protein content, composition, and antioxidant activity

Proteins of olive fruit mesocarp are not very well-known at present. However, they have been shown to pass, at least partially, to the olive oil during its elaboration and therefore might be contributing to some of the special characteristics of this vegetable oil. In this study, protein content and composition were determined in olive fruits, cv. Arbequina and Picual, at three stages of ripening: green, spotted, and purple. Mesocarp proteins constituted 1.3-1.8% of the dry weight of the olive fruit, and cultivar and fruit ripening did not produce important changes in mesocarp protein content or composition. In addition, this composition was also similar to the amino acid composition of a 4.6-kDa polypeptide, which is the major protein component of olive oils and of oil bodies of olive fruit mesocarp, suggesting that this polypeptide is likely to be a major component of mesocarp proteins. There was, also, a relationship between the oil content of the olive fruit and the protein content determined, suggesting a stabilizing function of these proteins in the oil bodies of the olive fruit, analogously to the role suggested for oleosins. This stabilizing function does not seem to be extended to olive oils because when the polypeptides isolated were added at 20 ppm to soybean oil, the stability of the oil increased only slightly, suggesting that if these compounds play some role in the stability of the oils, this should be mostly a consequence of the possible interactions among these protein components and other olive oil antioxidant constituents.     

Factors limiting the synthesis of virgin olive oil volatile esters

The aim of the present work was to establish the limiting factors affecting the biosynthesis of volatile esters present in virgin olive oil (VOO). Oil volatile fractions of the main Spanish olive cultivars, Arbequina and Picual, were analyzed. It was observed that acetate esters were the most abundant class of volatile esters in the oils, in concordance with the high content of acetyl-CoA found in olive fruit, and that the content of C6 alcohols is limited for the synthesis of volatile esters during the production of VOO. Thus, the increase of C6 alcohol availability during VOO production produced a significant increase of the corresponding ester in the oils in both cultivars at two different maturity stages. However, the increase of acetyl-CoA availability had no effect on the VOO volatile fraction. The low synthesis of these C6 alcohols seems not to be due to a shortage of precursors or cofactors for alcohol dehydrogenase (ADH) activity because their increase during VOO production had no effect on the C6 alcohol levels. The experimental findings are compatible with a deactivation of ADH activity during olive oil production in the cultivars under study. In this sense, a strong inhibition of olive ADH activity by compounds present in the different tissues of olive fruit has been observed.     

Study of the cultivar-composition relationship in Sicilian olive oils by GC,NMR, and statistical methods

The aim of this research is to find if there is direct evidence relating the fatty acid composition of olive oils to specific cultivars grown within a well-limited geographical region. To group olive oils according to their own cultivars,(13)C high-field nuclear magnetic resonance (NMR) and gas chromatography (GC) were used to analyze 60 extra virgin olive oils from the same Italian region (southwestern Sicily) obtained from four monovarietal cultivars. The (13)C NMR spectrum provides information about glycerol triesters of olive oils, i.e., about the acyl composition of major components and about the fatty acids' positional distribution on the glycerol moiety. GC gives the complete fatty acid profile of olive oil samples. Selection of NMR and GC peaks on the basis of their sensitivity to the different cultivars was performed by using multivariate analysis of variance (MANOVA). Principal component analysis, tree clustering analysis, multidimensional scaling (MDS), and linear discriminant analysis (LDA) were then performed on the MANOVA-selected peaks. Results obtained from (13)C NMR and GC techniques combined with the multivariate statistical procedure are in good agreement and prove the usefulness of fatty acids analysis to group the monovarietal olive oils belonging to the same cultivars. Grouping of olive oils according to their cultivars occurs for particular (13)C resonances all belonging to fatty chains in the sn 1,3 position of the glycerol moiety.     

Solid-phase microextraction in the analysis of virgin olive oil volatile fraction: characterization of virgin olive oils from two distinct geographical areas of northern Italy

SPME was employed to characterize the volatile profile of virgin olive oils produced in two geographical areas of northern Italy: the region of the Gulf of Trieste and the area near Lake Garda. There are as yet no data on the headspace composition of virgin olive oils from these regions, characterized by particular conditions of growth for Olea europaea. Using the SPME technique coupled to GC-MS and GC-FID, the volatile components of 42 industrially produced virgin olive oil samples were identified and the principal compounds quantitatively analyzed. Significant differences in the proportion of volatile constituents from oils of different varieties and geographical origins were detected. The results suggest that besides the genetic factor, environmental conditions influence the volatile formation.     

Monovarietal extra virgin olive oils: correlation between thermal properties and chemical composition

Thermal properties of monovarietal extra virgin olive oils were evaluated by means of differential scanning calorimetry (upon cooling) and related to their chemical composition (triacylglycerols, diacylglycerols, total and free fatty acids, oxidation status). The overall crystallization enthalpy did not significantly differ among samples and did not account for the differences observed in chemical compositions. On the contrary, a higher degree of unsaturation in the lipid profile induced a shift of the crystallization onset towards lower temperatures and narrowing of the crystallization temperature range. The presence of triacylglycerol lysis and lipid oxidation products shifted the crystallization towards higher temperatures and the phase transition developed over a larger temperature range. Differential scanning calorimetry thermograms were deconvoluted into three constituent exothermic peaks for all samples. The area of the two lower-temperature exotherms was found to be statistically correlated with the amount of triunsaturated and monosaturated triacylglycerols present in the oil. Thermal properties of extra virgin olive oil were found to be affected by oil chemical composition.     

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.     

Changes in the phenolic composition of virgin olive oil from young trees (Olea europaea L. cv. Arbequina) grown under linear irrigation strategies.

This study reports the HPLC profiles of phenolic compounds of virgin olive oils obtained from young olive trees (Olea europaea L. cv. Arbequina) and how the application of a linear irrigation strategy affected these. Hydroxytyrosol, tyrosol, vanillic acid, vanillin, 4-(acetoxyethyl)-1,2-dihydroxybenzene, p-coumaric acid, the dialdehydic form of elenolic acid linked to hydroxytyrosol and to tyrosol, lignans, and the oleuropein aglycon were found in all the oils. Hydroxytyrosol, tyrosol, vanillic acid, and p-coumaric acid contents in the oils were unaffected by linear irrigation. The concentration of lignans was lower in the oils from the least irrigated treatment and the concentration of vanillin increased as the amount of irrigation water applied to olive trees increased. However, 4-(acetoxyethyl)-1,2-dihydroxybenzene, the dialdehydic form of elenolic acid linked to hydroxytyrosol and to tyrosol, and the oleuropein aglycon, all of them hydroxyphenyl derivatives, decreased as the level of irrigation water increased. The latter three compounds represented the most considerable part of the phenolic fraction of the oils and they were shown to be correlated to the oxidative stability, the bitter index (K(225)), and the bitter, pungent, and sweet sensory attributes. Linear irrigation strategy changed the profile of the oil phenolic compounds and, therefore, changed both the organoleptic properties and the antioxidant capacity of the product.     

Fatty acid, triacylglycerol, and phytosterol composition in six Tunisian olive varieties

The physicochemical and stability properties as well as the fatty acid, triacylglycerol, sterol, and triterpenic dialcohol compositions of Tunisian olive oil varieties were analyzed. On the basis of our results, we classified all of the monovarietal oils into the extra virgin category. Oleic and linoleic acids were the most useful fatty acids to discriminate three cultivars, Neb Jmel, Chétoui, and Ain Jarboua, from the others. Of the six monovarietal virgin olive oils analyzed, the main triacylglycerols were OOO, POO, PLO plus SLL, and OLO, which was expected given the high oleic acid and low linoleic and linolenic acids content observed in total fatty acids. In total, these accounted for more than 80% of the total HPLC chromatogram peak area. The main sterols found were beta-sitosterol, Delta5-avenasterol, and campesterol. The statistical analysis showed significant differences between oil samples, and the obtained results showed a great variability in the oil composition between cultivars, which is influenced exclusively by genetic factors.     

Correlations of the phenolic compounds and the phenolic content in some Spanish and French olive oils

The total content of phenolic compounds (TAP) in 29 different monocultivar olive oil samples from France (Aglandau and Tanche) and Spain (Cornicabra, Picual, and Verdial) was assessed by the colorimetric Folin-Ciocalteu method. Also, individual phenolic compounds were determined and quantified by liquid chromatography coupled to mass spectrometry (LC-MS). The French olive oil samples had a lower TAP compared to Spanish samples. The quantity of individual phenolics was similar except for pinoresinol, which was lower in the French olive oil samples. TAP moderately correlated to the sum of quantified compounds (r = 0.64 and p < 0.01) Partial least-squares (PLS) regression analysis emphasized the importance of hydroxytyrosol and the total amount of quantified phenolic compounds by LC-MS in the prediction of the total amount of phenolic compounds as determined by the Folin-Ciocalteu method. The amount of alpha-tocopherol was generally different among the cultivars (Tanche > Picual > Verdial > Aglandau > Cornicabra). Of all quantified phenolic compounds in French olive oil samples, only luteolin correlated well to the altitude of the olive orchards (r = 0.76, p < 0.01).     

Effect of various compounds on virgin olive oil stability measured by Rancimat.

Phenolic and orthodiphenolic compounds together with carotenoids, tocopherols, pigments, and fatty acids were tested for their antioxidant effect in 79 samples of virgin olive oils cv. Picual and Hojiblanca. A linear regression based on the oleic/linoleic ratio and the contents of phenols and tocopherols showed a good correlation (adjusted-R(2) = 0.91) with the stability measured by Rancimat, later verified with an external text set (adjusted-R(2) = 0.95). A tentative study on the percentage contribution of each chemical variable to stability is discussed. The contribution of phenolic and orthodiphenolic compounds was around 51%, the composition of fatty acids 24%, and in less percentage alpha-tocopherol, carotenoids, and chlorophylls. No effect, or very little, was shown by beta- and gamma-tocopherols.     

Effect of the maturation process of the olive fruit on the phenolic fraction of drupes and oils from Arbequina, Farga, and Morrut cultivars

The purpose of the work was to investigate the effect of the maturation process of the olive fruit on the phenolic fraction of drupes and oils from Arbequina, Farga, and Morrut cultivars. The level in the phenolic content of olive drupes declines rapidly during the black maturation phase. A general decreasing trend was observed too in the phenolic content of olive oils during the ripening process in the three varieties studied. Important differences in the high-performance liquid chromatography profile between varieties were observed. These included the presence of very low amounts of lignans in olive oils proceeding from the Morrut cultivar, and the presence of three peaks after elution of 3,4-DHPEA-EDA in the Farga and Morrut cultivars, which could be used as differentiating parameters. Sensory profile differences were observed between olive cultivars and due to the ripening process.     

Modulation of the biosynthesis of some phenolic compounds in Olea europaea L. fruits: their influence on olive oil quality

The phenolic composition of olive fruits (Olea europaea L.) (cv. Picual, Villalonga, Alfafarenca, and Cornicabra) grown in different areas of Spain was studied by high performance liquid chromatography-mass spectrometry. Different levels of tyrosol, catechin, p-coumaric acid, rutin, luteolin, and oleuropein were observed in the different varieties analyzed. Treating the fruit with 0.3% Brotomax 50 days after anthesis had a beneficial effect on fruit size, oil content, levels of polyphenolic compounds, and Trolox-equivalent antioxidant activity (TEAC) in all the varieties analyzed.     

Changes in chloroplast pigments of olive varieties during fruit ripening

Changes in chlorophyll and carotenoid pigments of five olive (Olea europaea L.) varieties destined for milling were investigated at six consecutive ripening stages. There was a manifest dependence between olive variety, moment of picking, and chloroplast pigment composition of the fruits. Although the content of chlorophylls and carotenoids differed with fruit variety, ripening always involved their gradual loss, which becames more pronounced with increased presence of anthocyanin compounds. The relative rates of disappearance of chlorophylls and carotenoids were markedly different between varieties, implying that the catabolism of these pigments takes place at a relative rate inherent to each variety. The varieties less rich in pigments showed the most extreme behavior. The highest relative rate of disappearance was observed in fruits of the Blanqueta variety, and the lowest was observed in those of Arbequina. The chlorophyll a/chlorophyll b ratio remained practically constant during ripening, with a value very similar for Hojiblanca, Picual, Cornicabra, and Blanqueta, but much higher for Arbequina, implying that the structure of the photosynthetic apparatus is different in the latter variety. In the five varieties studied, lutein was the slowest carotenoid to be degraded, so that its percentage in the fruits increased with ripening, whereas beta-carotene was the fastest to disappear. In ripe fruits covered with anthocyanins, chloroplast pigments were retained in both skin and pulp, with the rate of disappearance being much higher in the latter.