Changes occurring in phenolic compounds and alpha-tocopherol of virgin olive oil during storage

Changes occurring in the concentrations of alpha-tocopherol, total phenols, and complex phenols linked to 3,4-dihydroxyphenylethanol (fractions FII and FIV) and p-hydroxyphenylethanol (FIII) during storage of virgin olive oil under environmental conditions were studied. Under diffused light, alpha-tocopherol was decomposed by 79% in 4 months, whereas <45% of the phenols were lost during the same period. Among the phenols, FII showed the least stability, and decreased by 72% in 6 months. Total phenols, FIII, and FIV recorded reductions in the range of 57-63% in 6 months. When the oil was stored in the dark, alpha-tocopherol, total phenols, FIII, and FIV exhibited similar profiles of degradation, reducing by 39-45% in the first 6 months and 50-62% in 12 months. FII was the least stable compound in the dark and recorded a loss of 64% in 6 months and 79% in 12 months. The levels of the above antioxidants were further related to peroxide formation. Remaining levels of these compounds at PV = 20 meq/kg ranged between 50 and 73% under diffused light and between 40 and 62% in the dark.     

The activity of healthy olive microbiota during virgin olive oil extraction influences oil chemical composition

The activity of olive microbiota during the oil extraction process could be a critical point for virgin olive oil quality. With the aim to evaluate the role of microbiological activity during the virgin olive oil extraction process, just before oil extraction freshly collected healthy olive fruits were immersed in contaminated water from an olive mill washing tank. The oils extracted were then compared with control samples from the same batch of hand-picked olives. The presence of lactic and enteric bacteria, fungi and Pseudomonas on the surface of olives was proved to be much higher in washed than in control olives, with increments in cfu/g between 2 and 3 orders of magnitude. The biogenesis of volatile compounds and the extraction of olive polyphenols and pigments were significantly influenced by the microbiological profile of olives even without any previous storage. In most cases the effect of olive microbiota on oil characteristics was greater than the effect exerted by malaxation time and temperature. Oils from microbiologically contaminated olives showed lower amounts of C5 volatiles and higher levels of C6 volatiles from the lipoxygenase pathway and some fermentation products. On the other hand, a decrease of chlorophylls, pheophytins, xanthophylls and the ratio chlorophyll/pheophytin was observed in these oils. Likewise, the microbiological activity during oil extraction led to significantly lower amounts of polyphenols, in particular of oleuropein derivatives. These differences in olive oil chemical composition were reflected in oil sensory characteristics by the decrease of the green and bitter attributes and by the modification of the oil color chromatic ordinates.     

Effect of olive stoning on the volatile and phenolic composition of virgin olive oil

Olive stoning during the virgin olive oil (VOO) mechanical extraction process was studied to show the effect on the phenolic and volatile composition of the oil. To study the impact of the constitutive parts of the fruit in the composition of olive pastes during processing, the phenolic compounds and several enzymatic activities such as polyphenoloxidase (PPO), peroxidase (POD), and lipoxygenase (LPO) of the olive pulp, stone, and seed were also studied. The olive pulp showed large amounts of oleuropein, demethyloleuropein, and lignans, while the contribution of the stone and the seed in the overall phenolic composition of the fruit was very low. The occurrence of crushed stone in the pastes, during malaxation, increased the peroxidase activity in the pastes, reducing the phenolic concentration in VOO and, at the same time, modifying the composition of volatile compounds produced by the lipoxygenase pathway. The oil obtained from stoned olive pastes contained higher amounts of secoiridoid derivatives such as the dialdehydic forms of elenolic acid linked to (3,4-dihydroxyphenyl)ethanol and (p-hydroxyphenyl)ethanol (3,4-DHPEA-EDA and p-HPEA-EDA, respectively) and the isomer of the oleuropein aglycon (3,4-DHPEA-EA) and, at the same time, did not show significant variations of lignans. The stoning process modified the volatile profile of VOO by increasing the C6 unsaturated aldehydes that are strictly related to the cut-grass sensory notes of the oil.     

Evaluation of the antioxidant capacity of individual phenolic compounds in virgin olive oil

Virgin olive oil has a high resistance to oxidative deterioration due to its tryacylglycerol composition low in polyunsaturated fatty acids and due to the presence of a group of phenolic antioxidants composed mainly of polyphenols and tocopherols. We isolated several phenolic compounds of extra virgin olive oil (phenyl-ethyl alcohols, lignans, and secoiridoids) by semipreparative high-performance liquid chromatography (HPLC) and identified them using ultraviolet, atmospheric pressure chemical ionization, and electrospray ionization MS detection. The purity of these extracts was confirmed by analytical HPLC using two different gradients. Finally, the antioxidant capacity of the isolated compounds was evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2-picrylhydrazyl radical, by accelerated oxidation in a lipid model system (OSI, oxidative stability instrument), and by an electrochemical method.     

Changes in volatile and phenolic compounds with malaxation time and temperature during virgin olive oil production

Virgin olive oils produced at wide ranges of malaxation temperatures (15, 30, 45, and 60 degrees C) and times (30, 60, 90, and 120 min) in a complete factorial experimental design were discriminated with stepwise linear discriminant analysis (SLDA) revealing differences with processing conditions. Virgin olive oils produced at 15 and 60 degrees C for 30 min showed the most significant (p < 0.01) differences. Discrimination was based upon volatile and phenolic compounds detected in olive oils, peroxide value (PV), free fatty acids (FFA), ultraviolet (UV) absorbances, and oil yield. There were different discriminating variables for processing conditions illustrating the dependence of virgin olive oil quality on malaxation time and temperature. Volatile compounds were the dominant discriminating variables. Common oxidation indicators of olive oil (PV, K232, and K270) were not among the variables that significantly (p < 0.01) changed with malaxation time and temperature. Variables that discriminated both malaxation time and temperature were hexanal, 3,4-dihydroxyphenyl ethyl alcohol-decarboxymethyl elenolic acid dialdehyde (3,4-DHPEA-DEDA) and FFA, whereas 1-penten-3-ol, E-2-hexenal, octane, tyrosol, and vanillic acid significantly (p < 0.01) changed with temperature only and Z-2-penten-1-ol, (+)-acetoxypinoresinol, and oil yield changed with time only. Virgin olive oil quality was significantly influenced by malaxation temperature, whereas oil yield discriminated malaxation time. This study demonstrates the two modes of hexanal formation: enzymatic and nonenzymatic during virgin olive oil extraction.     

Changes in virgin olive oil quality during low-temperature fruit storage

'Frantoio' olive fruits were stored at low temperature (4 +/- 2 degrees C) for 3 weeks to investigate the effect of postharvest fruit storage on virgin olive oil quality. Volatile compounds and phenolic compounds explained the changes in sensory quality that could not be explained with quality indices (FFA, PV, K232, and K270). Increases in concentrations of ( E)-2-hexenal and hexanal corresponded to positive sensory quality, whereas increases in ( E)-2-hexenol and (+)-acetoxypinoresinol were associated with negative sensory quality. Volatile and phenolic compounds were also indicative of the period of low-temperature fruit storage. Oleuropein and ligstroside derivatives in olive oil decreased with respect to storage time, and their significant ( p < 0.05) change corresponded to changes in bitterness and pungency. ( Z)-2-Penten-1-ol increased during low-temperature fruit storage, whereas 2-pentylfuran decreased. Changes in volatile compounds, phenolic compounds, quality indices, and sensory notes indicated that virgin olive oil quality was lost within the first week of low-temperature fruit storage and regained at 2 weeks. This research suggests that low-temperature olive fruit storage may be beneficial, with a possibility of increasing oil yield and moderating the sensory quality of virgin olive oils. This study demonstrates that deeper insights into virgin olive oil quality changes during low-temperature fruit storage may be gained by studying volatile and phenolic compounds in addition to quality indices and physical appearance of the fruit.     

Influence of the decrease in oxygen during malaxation of olive paste on the composition of volatiles and phenolic compounds in virgin olive oil

The sensory and health properties of virgin olive oil (VOO) are highly related to its volatile and phenolic composition. Oxygen control in the pastes during malaxation may be a new technological parameter to regulate enzymatic activities, such as polyphenoloxidase, peroxidase, and lipoxygenase, which affect the phenolic and volatile composition of VOO. In this work, we monitored CO2 and O2 concentrations during industrial-scale olive paste malaxation with various initial O2 concentrations within the malaxer headspace. Results show that the O2 concentration in the malaxer headspace did not affect CO2 production during processing, whereas a strong influence was observed on the changes of the phenolic composition of olive pastes and VOOs, with high correlation coefficient for the total phenols (R = 0.94), especially for oleuropein and demethyloleuropein derivatives (R = 0.81). In contrast, aroma production during malaxation was minimally affected by the O2 concentration in the malaxer headspace.     

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.     

Bovine serum albumin produces a synergistic increase in the antioxidant activity of virgin olive oil phenolic compounds in oil-in-water emulsions

Virgin olive oil is valued for its flavor, but unacceptable off-flavors may develop on storage in food products containing this oil due to oxidation. The oxidative stability of oil-in-water emulsions containing bovine serum albumin (BSA) and virgin olive oil phenolic compounds was studied. Four oil-in-water emulsions with and without BSA and phenols isolated from virgin olive oil were prepared. These model systems were stored at 60 degrees C to speed up lipid oxidation. Primary and secondary oxidation products were monitored every three days. Peroxide values and conjugated diene contents were determined as measures of the primary oxidation products. p-Anisidine values and volatile compounds were determined as measures of the secondary oxidation products. This latter determination was carried out by headspace solid-phase microextraction coupled with gas chromatography. Although olive oil phenolic compounds and BSA contributed some antioxidant activity when present as individual additives, the combination of BSA with phenols in an emulsion showed 58-127% synergy, depending on which analytical method was used in the calculation. The emulsion containing phenolic compounds and BSA showed a low level of deterioration after 45 days of storage at 60 degrees C.     

Relationship between virgin olive oil phenolic compounds and acrylamide formation in fried crisps

In this paper the relationship between virgin olive oil (VOO) phenol compounds and the formation of acrylamide in potato crisps was investigated. The phenol compositions of 20 VOO samples were screened by LC-MS, and 4 oils, characterized by different phenol compound patterns, were selected for frying experiments. Slices of potatoes were fried at 180 degrees C for 5, 10, and 15 min, and acrylamide content was determined by LC-MS. Results demonstrated that VOO phenolic compounds are not degraded during frying, and crisp color was not significantly different among the four VOOs. Acrylamide concentration in crisps increased during frying time, but the formation was faster in the oil having the lowest concentration of phenolic compounds. Moreover, the VOO having the highest concentration of ortho-diphenolic compounds is able to efficiently inhibit acrylamide formation in crisps from mild to moderate frying conditions. It was concluded that the use of ortho-diphenolic-rich VOOs can be proposed as a reliable mitigation strategy to reduce acrylamide formation in domestic deep-frying.     

Evolution of minor polar compounds and antioxidant capacity during storage of bottled extra virgin olive oil

We characterized "Olivastra Seggianese" extra virgin olive oil (EVOO) and evaluated its chemical and sensory characteristics and antioxidant and antiradical activities during storage under novel conditions. Two oils (A and B) were analyzed for the commodity characteristics at blending (t0) and after 9, 12, and 18 months; panel tests were performed and minor polar compounds (MPC) content was assessed at blending (t0) and after 6, 9, 12, and 18 months. Antioxidant and antiradical activities in vitro were evaluated at t0 and after 12 months, by human low density lipoprotein (LDL) and 1,1-diphenyl-2-picrylhydrazil radical (DPPH*) tests. Oil A, which had an initially higher MPC content, possessed "harder" organoleptic characteristics than oil B, which had a lower MPC content and was endowed with a "smoother" taste profile. Statistical analyses showed that secoiridoids, particularly deacetoxy-oleuropein aglycone, should be quantified to evaluate EVOO stability during storage. The antioxidant activity toward human LDL was linked to MPC content and to storage time. The tests on the stable free radical DPPH* confirmed the results on human LDL. We propose this as an additional parameter to evaluate olive oil quality and stability over time.     

Partition behavior of virgin olive oil phenolic compounds in oil-brine mixtures during thermal processing for fish canning

The chemical modifications and partitioning toward the brine phase (5% salt) of major phenol compounds of extra virgin olive oil (EVOO) were studied in a model system formed by sealed cans filled with oil-brine mixtures (5:1, v/v) simulating canned-in-oil food systems. Filled cans were processed in an industrial plant using two sterilization conditions commonly used during fish canning. The partitioning of phenolic compounds toward brine induced by thermal processing was studied by reversed-phase high-performance liquid chromatographic analysis of the phenol fraction extracted from oils and brine. Hydroxytyrosol (1), tyrosol (2), and the complex phenolic compounds containing 1 and 2 (i.e., the dialdehydic form of decarboxymethyl oleuropein aglycon 3, the dialdehydic form of decarboxymethyl ligstroside aglycon 4, and the oleuropein aglycon 6) decreased in the oily phase after sterilization with a marked partitioning toward the brine phase. The increase of the total amount of 1 and 2 after processing, as well as the presence of elenolic acid 7 released in brine, revealed the hydrolysis of the ester bond of hydrolyzable phenolic compounds 3, 4, and 6 during thermal processing. Both phenomena (partitioning toward the water phase and hydrolysis) contribute to explain the loss of phenolic compounds exhibited by EVOO used as filling medium in canned foods, as well as the protection of n-3 polyunsaturated fatty acids in canned-in-EVOO fish products.     

Contribution of the phenolic fraction to the antioxidant activity and oxidative stability of olive oil

Antioxidant activity of the phenolic fraction of extra virgin olive oil (EVOO) was measured by means of a chemical and an electrochemical method. Both methods were tested in predicting the oxidative spoilage and stability to oxidation of 22 EVOO samples and resulted correlated with peroxide values and oxidative stability measured by Rancimat. The main phenolic compounds of EVOOs were detected by HRGC. To study the contribution of single polyphenols (PPs) to antioxidant activity of phenolic fraction and oxidative stability of EVOOs, multivariate statistical analyses were applied on HRGC data. An isomer of oleuropein aglycon was shown to affect significantly antioxidant activity of phenolic fraction but not oil stability to oxidation. No individual compounds was identified as the main cause of the overall antioxidant activity, and the total polyphenol determination by the Folin reagent was better correlated to antioxidant activity and oxidative stability than each tested PP or PPs groups such as o-diphenols.     

Volatile compounds and phenolic composition of virgin olive oil: optimization of temperature and time of exposure of olive pastes to air contact during the mechanical extraction process

The operative conditions of malaxation such as temperature and time of exposure of olive pastes to air contact (TEOPAC) affect volatile and phenolic composition of virgin olive oil (VOO) and, as a consequence, its sensory and healthy qualities. In this paper, optimal temperature and TEOPAC during malaxation were studied, in lab scale, in two Italian cultivars using phenolic compounds, volatile composition, and sensory analysis of VOO as markers. The optimal temperature and TEOPAC, selected by response surface modeling,were cultivar-dependent being 30 min of TEOPAC at the lowest temperature investigated (22 degrees C) and 0 min of TEOPAC at 26 degrees C for Frantoio and Moraiolo cultivars, respectively.     

Wastes generated during the storage of extra virgin olive oil as a natural source of phenolic compounds

Phenolic compounds in extra virgin olive oil (EVOO) have been associated with beneficial effects for health. Indeed, these compounds exert strong antiproliferative effects on many pathological processes, which has stimulated chemical characterization of the large quantities of wastes generated during olive oil production. In this investigation, the potential of byproducts generated during storage of EVOO as a natural source of antioxidant compounds has been evaluated using solid-liquid and liquid-liquid extraction processes followed by rapid resolution liquid chromatography (RRLC) coupled to electrospray time-of-flight and ion trap mass spectrometry (TOF/IT-MS). These wastes contain polyphenols belonging to different classes such as phenolic acids and alcohols, secoiridoids, lignans, and flavones. The relationship between phenolic and derived compounds has been tentatively established on the basis of proposed degradation pathways. Finally, qualitative and quantitative characterizations of solid and aqueous wastes suggest that these byproducts can be considered an important natural source of phenolic compounds, mainly hydroxytyrosol, tyrosol, decarboxymethyl oleuropein aglycone, and luteolin, which, after suitable purification, could be used as food antioxidants or as ingredients in nutraceutical products due to their interesting technological and pharmaceutical properties.     

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.     

Bioaccessibility and antioxidant activity stability of phenolic compounds from extra-virgin olive oils during in vitro digestion

The impact of an in vitro procedure that mimics the physiochemical changes occurring in gastric and small intestinal digestion on the bioaccessibility and antioxidant activity of phenols from 10 extra-virgin olive oil samples was assessed. Extra-virgin olive oil phenols were totally extracted in the aqueous phase, which reproduces gastric fluids during the digestion procedure. A linear bioaccessibility model, based on tyrosol behavior in model oil samples, was used to estimate the bioaccessibility index (BI%) of extra-virgin olive oil phenols. The BI% varied amongst samples from a maximum of 90% to a minimum of 37%, thus indicating that only a fraction of phenols can be considered bioaccessible. The specific antioxidant activity of olive oil phenols proved to be negatively affected by the digestion procedure. By computing a principal component analysis, it was possible to show that differences in the potential bioactive effect of extra-virgin olive oil samples were related to different phenolic profiles.     

Antioxidant effect of phenolic compounds, alpha-tocopherol, and other minor components in virgin olive oil

The effect of acidity, squalene, hydroxytyrosol, aldehydic form of oleuropein aglycon, hydroxytyrosyl acetate, tyrosol, homovanillic acid, luteolin, apigenin, alpha-tocopherol, and the mixtures hydroxytyrosol/hydroxytyrosyl acetate, hydroxytyrosol/tyrosol, and hydroxytyrosol/alpha-tocopherol on the oxidative stability of an olive oil matrix was evaluated. A purified olive oil was spiked with several concentrations of these compounds and, then, subjected to an accelerated oxidation in a Rancimat apparatus at 100 degrees C. Acidity, squalene, homovanillic acid, and apigenin showed negligible effect. At the same millimolar concentrations, the different o-diphenolic compounds yielded similar and significant increases of the induction time, alpha-tocopherol a lesser increase, and tyrosol a scarce one. At low concentrations of o-diphenols and alpha-tocopherol, a linear relationship between induction time and concentration was found, but at high concentrations the induction time tended toward constant values. To explain this behavior, a kinetic model was applied. The effect of the mixtures hydroxytyrosol/hydroxytyrosyl acetate was similar to that of a single o-diphenol at millimolar concentration equal to the sum of millimolar concentrations of both compounds. Concentrations of tyrosol >0.3 mmol/kg increase the induction time by 3 h. The mixtures hydroxytyrosol/alpha-tocopherol showed opposite effects depending on the relative concentrations of both antioxidants; so, at hydroxytyrosol concentrations <0.2 mmol/kg, the addition of alpha-tocopherol increased the induction time, whereas at higher hydroxytyrosol concentrations, the alpha-tocopherol diminished the stability.     

Antioxidant activity of olive pulp and olive oil phenolic compounds of the arbequina cultivar

The aim of this study was to characterize antioxidant activities of phenolic compounds that appear in olive pulp and olive oils using both radical scavenging and antioxidant activity tests. Antiradical and antioxidant activities of olive pulp and olive oil phenolic compounds were due mainly to the presence of a 3,4-dihydroxy moiety linked to an aromatic ring, and the effect depended on the polarity of the phenolic compound. Glucosides and more complex phenolics exhibited higher antioxidant activities toward oxidation of liposomes, whereas in bulk lipids aglycons were more potent antioxidants with the exception of oleuropein. Lignans acted as antioxidants only in liposomes, which could partly be due to their chelating activity, because liposome oxidation was initiated by cupric acetate. The antioxidant activity of virgin olive oil is principally due to the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA), a secoiridoid derivative (peak RT 36, structure unidentified), and luteolin.