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.     

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.     

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.     

Nutritional and biological properties of extra virgin olive oil

The nutritional benefits generally recognized for the consumption of extra virgin olive oil (EVOO) are based on a large number of dietary trials of several international populations and intervention studies. Unfortunately, many authors in this field used questionable analytical methods and commercial kits that were not validated scientifically to evaluate the complex bioactive constituents of EVOO and lipid oxidation and decomposition products. Many questionable antiradical methods were commonly used to evaluate natural polyphenolic antioxidants, including an indirect method to determine low-density lipoprotein (LDL) cholesterol. Extensive differences were observed in experimental design, diet control, populations of different ages and problems of compliance intervention, and questionable biomarkers of oxidative stress. Analyses in many nutritional studies were limited by the use of one-dimensional methods to evaluate multifunctional complex bioactive compounds and plasma lipid profiles by the common applications of commercial kits. Although EVOO contains polyphenolic compounds that exhibit significant in vitro antioxidant activity, much more research is needed to understand the absorption and in vivo activity. Many claims of in vivo human beneficial effects by the consumption of EVOO may be overstated. No distinctions were apparently made between in vivo studies based on general health effects in large populations of human subjects and smaller scale well-controlled feeding trials using either pure or mixtures of known phenolic constituents of EVOO. More reliable protocols and testing methods are needed to better validate the complex nutritional properties of EVOO.     

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 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.     

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.     

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.     

Qualitative and semiquantitative analysis of phenolic compounds in extra virgin olive oils as a function of the ripening degree of olive fruits by different analytical techniques

Capillary electrophoresis (CE) can be effectively used as a fast screening tool to obtain qualitative and semiquantitative information about simple and complex phenolic compounds of extra virgin olive oil. Three simple phenols (tyrosol, hydroxytyrosol, and vanillic acid), a secoiridoid derivative (deacetoxy oleuropein aglycon), and two lignans (pinoresinol and acetoxypinoresinol) were detected as the main compounds in extra virgin olive oils by high-performance liquid chromatography (HPLC) and capillary zone electrophoresis (CZE). Spectrophotometric indices, radical scavenging activity, and oxidative stability of extra virgin olive oil samples obtained from olives hand-picked at different ripening degrees were statistically correlated with the CZE and HPLC quantification. The concentration of phenols in extra virgin olive oil decreased with ripeness of olive fruits. The high correlations found between CZE and the other analytical results indicate that CE can be applied as a rapid and reliable tool to routinely determine phenolic compounds in extra virgin olive oils.     

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.     

Determination of furan fatty acids in extra virgin olive oil

The presence of 4 different furan fatty acids (F-acids) was detected in 18 samples of transmethylated monovarietal extra virgin olive oil: methyl 10,13-epoxy-11,12-dimethyloctadeca-10,12-dienoate [diMeF(9,5)], methyl 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoate [diMeF(11,5)] and both olefinic derivatives of diMeF(11,5) with one unsaturation on the side chains conjugated with the furan ring. Transmethylated oils were analyzed by normal phase high-performance liquid chromatography coupled on-line with capillary gas chromatography. After the gas chromatographic separation step, a more selective detection of F-acids was achieved by using a photoionization detector mounted in series with a flame ionization detector. The concentration of F-acids ranged between 50 ppb (detection limit of the method) and 2.1 ppm in the oil. The olefinic derivatives of diMeF(11,5) acids detected were not artifacts created during the sample preparation or during the chromatographic analysis.     

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 in phenolic composition and antioxidant activity of virgin olive oil during frying

The concentration of hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA) in virgin olive oil decreased rapidly when the oil was repeatedly used for preparing french fries in deep-fat frying operations. At the end of the first frying process (10 min at 180 degrees C), the concentration of the dihydroxyphenol components was reduced to 50-60% of the original value, and after six frying operations only about 10% of the initial components remained. However, tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA) in the oil were much more stable during 12 frying operations. The reduction in their original concentration was much smaller than that for hydroxytyrosol and its derivatives and showed a roughly linear relationship with the number of frying operations. The antioxidant activity of the phenolic extract measured using the DPPH test rapidly diminished during the first six frying processes, from a total antioxidant activity higher than 740 micromol of Trolox/kg down to less than 250 micromol/kg. On the other hand, the concentration of polar compounds, oxidized triacylglycerol monomers (oxTGs), dimeric TGs, and polymerized TGs rapidly increased from the sixth frying operation onward, when the antioxidant activity of the phenolic extract was very low, and as a consequence the oil was much more susceptible to oxidation. The loss of antioxidant activity in the phenolic fraction due to deep-fat frying was confirmed by the storage oil and oil-in-water emulsions containing added extracts from olive oil used for 12 frying operations.     

Comparison of natural polyphenol antioxidants from extra virgin olive oil with synthetic antioxidants in tuna lipids during thermal oxidation

Polyphenols extracted from extra virgin olive oil (EVOO) were tested for their ability to inhibit lipid oxidation of canned tuna. Hydroperoxide formation during oxidation was monitored by measurement of peroxide value and decomposition of hydroperoxides by static headspace gas chromatographic analysis of volatiles. In tuna oxidized at 40 and 100 degrees C, 400 ppm of the EVOO polyphenols was an effective antioxidant as compared with 100 ppm of a 1:1 mixture of the synthetic antioxidants butylated hydroxytoluene and butylated hydroxyanisole. However, at concentrations <100 ppm, the EVOO phenolic compounds promoted hydroperoxide formation and decomposition. The EVOO polyphenols were effective antioxidants when added to heated tuna muscle in the presence of either brine or refined olive oil. The oxidation rate in tuna muscle packed in brine was higher than that of tuna packed in refined olive oil. The EVOO polyphenols had higher antioxidant activity in the brine samples than in the refined olive oil. The higher antioxidant activity of EVOO polyphenols in tuna packed in brine may be explained by their greater affinity toward the more polar interface between water and the fish oil system.     

Phenolic compounds profile of cornicabra virgin olive oil

This study presents the phenolic compounds profile of commercial Cornicabra virgin olive oils from five successive crop seasons (1995/1996 to 1999/2000; n = 97), determined by solid phase extraction reversed phase high-performance liquid chromatography (SPE RP-HPLC), and its relationship with oxidative stability, processing conditions, and a preliminary study on variety classification. The median of total phenols content was 38 ppm (as syringic acid), although a wide range was observed, from 11 to 76 ppm. The main phenols found were the dialdehydic form of elenolic acid linked to tyrosol (p-HPEA-EDA; 9 +/- 7 ppm, as median and interquartile range), oleuropein aglycon (8 +/- 6 ppm), and the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA; 5 +/- 8 ppm). In many cases the correlation with oxidative stability was higher when the sum of the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA) and oleuropein aglycon (r (2) = 0.91-0.96) or the sum of these two and hydroxytyrosol (r (2) = 0.90-0.97) was considered than was observed with HPLC total phenols (r (2)= 0.91-0.95) and especially with colorimetric determination of total polyphenols and o-diphenols (r (2) = 0.77-0.95 and 0.78-0.92, respectively). 3,4-DHPEA-EDA, p-HPEA-EDA, the aglycons of oleuropein and ligstroside, and HPLC total phenols content presented highly significant differences (p = 0.001-0.010) with respect to the dual- and triple-phase extraction systems used, whereas colorimetric total polyphenols content did not (p = 0.348) and o-diphenols showed a much lower significant difference (p = 0.031). The five variables that most satisfactorily classified the principal commercial Spanish virgin olive oil varieties were 1-acetoxypinoresinol, 4-(acetoxyethyl)-1,2-dihydroxybenzene (3,4-DHPEA-AC), ligstroside aglycon, p-HPEA-EDA, and RT 43.3 contents.     

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.     

Mathematical model to predict the formation of pyropheophytin a in virgin olive oil during storage

A mathematical model has been developed that describes the changes of pyropheophytin a (pyphya) in virgin olive oil (VOO). The model has been created using multivariate statistical procedures and is used in the prediction of the stability and loss of freshness of VOO. An earlier thermokinetic study (Aparicio-Ruiz, R.; M??nguez-Mosquera, M. I.; Gandul-Rojas, B. Thermal degradation kinetics of chlorophyll pigments in virgin olive oils. 1. Compounds of series a. J. Agric. Food Chem.2010, 58, 6200-6208) that looked at the characterization of the degradation of pheophytin a (phya), the main chlorophyll compound in VOO and a precursor of pyphya, allowed the authors to obtain the kinetic parameters necessary for mathematically expressing the percentage of pyphya, according to the time and temperature of storage using the Arrhenius model. Data regarding the percentage of pyphya obtained during the actual degradation of VOO in darkness, at room temperature and with a limited supply of oxygen, has allowed the mathematical prediction model to be validated. Using average monthly temperatures in the calculation of kinetic constants, theoretical data are obtained that are generally found to be within 95% confidence levels of experimental data.     

Influence of crystallization on the oxidative stability of extra virgin olive oil

The aim of this study was to evaluate the influence of the extra virgin olive oil (EVOO) physical state on the kinetics of oxidative reactions. To this purpose, EVOO was stored at increasing temperatures from 3 to 60 degrees C and the oxidation was followed by measuring both primary and secondary oxidation products. Results highlighted that crystallization plays an important role in determining EVOO stability. Below the melting point, the oxidation rate was found to be higher than that expected on the basis of the Arrhenius equation. The observed deviation from the Arrhenius equation was attributed to the physicochemical changes occurring as a consequence of phase transitions. In particular, the increase in unsaturated triacylglycerol concentration and the decrease of polyphenol content in the liquid phase surrounding fat crystals were indicated as the main factors causing the deviation. By taking into account these changes it was possible to describe the temperature dependence of the oxidation rate in the entire range of temperatures considered. This model appears to be promising in the challenge to find mathematical models able to predict the stability and, hence, the shelf life of lipid-containing foods.     

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.     

Relation between the endogenous antioxidant system and the quality of extra virgin olive oil under accelerated storage conditions

Three monovarietal extra virgin olive oils (EVOOs) were subjected to accelerated storage conditions (60 degrees C, dark) representative of the autoxidation process during shelf life. Oxidation markers, i.e., the peroxide value, conjugated dienes, the oil stability index, and minor components, were monitored. The changes in minor components, related to the stage of ongoing oxidation and expressed as a percentage of the induction period (IP), followed a similar pattern in all oils: o-diphenols diminished by the highest rate (halved within 15% of the IP), followed by alpha-tocopherol (halved within 35% of the IP). Carotenoids and chlorophylls were also affected by autoxidation, whereas squalene showed high stability (<20% loss within 100% of the IP). Polar phenols (especially o-diphenols) and alpha-tocopherol were deduced to be the most potent antioxidants of EVOO. They efficiently inhibited oxidative lipid deterioration and subsequent development of sensory defects (rancidity, discoloration), which occurred only after substantial depletion of these antioxidants. Therefore, they could also be used as markers for the oxidative status of EVOO particularly in the early stage of oxidation.