Thermoxidation of substrate models and their behavior during hydrolysis by porcine pancreatic lipase

The behavior of thermoxidized triacylglycerols during hydrolysis catalyzed by porcine pancreatic lipase was evaluated using nonpolar triacylglycerols isolated from palm olein (NPTPO), triolein, and sn-1,3 diolein substrates. Substrates were thermoxidized at 180°C for 1 to 4 h. Owing to formation of polymers and dimers of triacylglycerols, the molecular weight of the thermoxidized substrates increased. After 1 h heating, the concentration of polymers and dimers was similar for the sn-1-3 diolein and triolein samples but higher in NPTPO samples. Conjugated double bonds were formed in all samples, and α,β-unsaturated carbonyl compounds developed through allylic oxidations. These caused increased ultraviolet absorbance at 232 nm. The hydrolysis of heated and unheated samples by the lipase can be described by a Michaelian equation. The enzyme showed a higher apparent V _max and K _M with heated sn-1,3 diolein and triolein than with their unheated counterparts. This was due to the generation of polar compounds which acted as emulsifiers and which favored the formation of an oil/water microemulsion. This behavior was not observed in NPTPO, where heating decreased the apparent V _max and K _M over the first 2 h. Later, a tendency to increase these values was observed. The results could be explained by a balance between concentration of surfactants and of natural emulsifiers in the thermoxidized samples.     

Heat Treatment Improves Olive Oil Extraction

To determine the effect of hot water pre-treatment on olive oil extraction, six cultivars of olive fruit (Olea europaea L. cvs. “Arbequina”, “Hojiblanca”, “Lechín”, “Manzanilla”, “Picual”, and “Verdial”) were heated at 50, 55, and 60 °C prior to laboratory scale oil extraction. Heat treatment resulted in higher oil extraction than unheated control samples. Quality parameters of the oils were not significantly (P < 0.05) affected by these treatments; however, oil stability and bitterness intensity were reduced and pigment content was increased through pre-heat treatment. This process may be incorporated economically into olive oil processing.     

Frying Quality Characteristics of French Fries Prepared in Refined Olive Oil and Palm Olein

The objective of this study was to compare two oils with different polyunsaturated/saturated (P/S) fatty acid ratios, refined olive oil (P/S 0.75) and palm olein (P/S 0.25), in frying French fries. The chemical qualities of the oil residues extracted from the French fries were assayed for five consecutive batches fried at 1-h intervals. The levels of total polar compounds, free fatty acids, p-anisidine value and phytosterol oxidation products (POPs) were elevated in French fries fried in both oils. The level of total polar compounds increased from 4.6 in fresh refined olive oil to 7.3% in final batches of French fries. The corresponding figures for palm olein were 9.8–13.8%. The level of free fatty acid in fresh refined olive oil increased from 0.06 to 0.11% in final products. These figures for palm olein were 0.04–0.13%. The p-anisidine value increased from 3.7 to 32.8 and 2.5 to 53.4 in fresh oils and in final batches of French fries in refined olive oil and palm olein, respectively. The total amount of POPs in fresh refined olive oil increased from 5.1 to 9.6 μg/g oil in final products. These figures were 1.9 to 5.3 μg/g oil for palm olein.     

Effect of natural antioxidants in virgin olive oil on oxidative stability of refined,bleached, and deodorized olive oil

The factors influencing the oxidative stability of different commercial olive oils were evaluated. Comparisons were made of (i) the oxidative stability of commercial olive oils with that of a refined, bleached, and deodorized (RBD) olive oil, and (ii) the antioxidant activity of a mixture of phenolic compounds extracted from virgin olive oil with that of pure compounds andα-tocopherol added to RBD olive oil. The progress of oxidation at 60°C was followed by measuring both the formation (peroxide value, PV) and the decomposition (hexanal and volatiles) of hydroperoxides. The trends in antioxidant activity were different according to whether PV or hexanal were measured. Although the virgin olive oils contained higher levels of phenolic compounds than did the refined and RBD oils, their oxidative stability was significantly decreased by their high initial PV. Phenolic compounds extracted from virgin olive oils increased the oxidative stability of RBD olive oil. On the basis of PV, the phenol extract had the best antioxidant activity at 50 ppm, as gallic acid equivalents, but on the basis of hexanal formation, better antioxidant activity was observed at 100 and 200 ppm.α-Tocopherol behaved as a prooxidant at high concentrations (>250 ppm) on the basis of PV, but was more effective than the other antioxidants in inhibiting hexanal formation in RBD olive oil.o-Diphenols (caffeic acid) and, to a lesser extent, substitutedo-diphenols (ferulic and vanillic acids), showed better antioxidant activity than monophenols (p- ando-coumaric), based on both PV and hexanal formation. This study emphasizes the need to measure at least two oxidation parameters to better evaluate antioxidants and the oxidative stability of olive oils. The antioxidant effectiveness of phenolic compounds in virgin olive oils can be significantly diminished in oils if their initial PV are too high.     

Digestibility of fatty acid monomers,dimers and polymers in the rat

This study was designed to determine digestibilities of fatty acid monomers, dimers and polymers as components of diets containing thermally oxidized oils. Male Wistar rats were fed semipurified diets supplemented with unheated, heated and a 1:1 mixture of unheated/heated olive oils at 6, 12 and 20% w/w of diet. In a 14-d experimental period, fecal lipids were extracted and analyzed by a combination of adsorption and high-performance size-exclusion chromatographies. Thus, it was possible to separate and quantitate five groups of fatty acids—nonpolar monomers, oxidized monomers, nonpolar dimers, oxidized dimers and polymers. Nonpolar fatty acid monomers showed high digestibilities, although significantly influenced by the alteration level of the dietary oil. The apparent absorption of oxidized fatty acid monomers averaged 76.6%. Among polymeric fatty acids, the lowest digestibilities were found for nonpolar dimers (10.9% on average), whereas oxidized dimers and polymers possessed higher apparent absorbability than expected, ranging from 22.7% to 49.6%. Chemical modifications prior to absorption, leading to less complex products, may have contributed to enhanced digestibility of polymers.     

Oil fractionation as a preliminary step in the characterization of vegetable oils by high-resolution 13C NMR spectroscopy

One hundred nine oil samples were separated chromatographically to obtain oil fractions with a decreased TAG content but with enhanced levels of the minor components that define oil genuineness and quality. The oils, which included virgin olive oils from different cultivars and regions of Europe and north Africa and refined olive, “lampante” olive, refined olive pomace, hazelnut, rapeseed, high-oleic sunflower, corn, grapeseed, soybean, and sunflower oils, were fractionated on a silica gel column with hexane/diethyl ether as the mobile phase eluent. The method was highly reproducible, and the fraction obtained contained about 15% unmodified TAG and 85% polar compounds, which included polymeric TAG, oxidized TAG, DAG, MAG, and FFA, in addition to other minor polar components of the oils. The presence of these compounds, in an enriched fraction, should provide information about the thermal, oxidative, and hydrolytic alterations of the oils, as well as many compounds of interest in determining oil genuineness. The results indicate that these fractions can provide more information than the original oils for NMR or other spectroscopic studies used in the determination of oil quality.     

Protective effect of olive oil and its phenolic compounds against low density lipoprotein oxidation

The protective effect of phenolic compounds from an olive oil extract, and of olive oils with (extra-virgin) and without (refined) phenolic components, on low density lipoprotein (LDL) oxidation was investigated. When added to isolated LDL, phenolics [0.025–0.3 mg/L caffeic acid equivalents (CAE)] increased the lag time of conjugated diene formation after copper-mediated LDL oxidation in a concentration-dependent manner. Concentrations of phenolics greater than 20 mg/L inhibited formation of thiobarbituric-acid reactive substances after AAPH-initiated LDL oxidation. LDL isolated from plasma after preincubation with phenolics (25–160 mg/L CAE) showed a concentration-dependent increase in the lag time of conjugated diene formation after copper-mediated LDL oxidation. Refined olive oil (0 mg/L CAE) and extra-virgin olive oil (0.1 and 0.3 mg/L CAE) added to isolated LDL caused an increase in the lag time of conjugated diene formation after copper-mediated LDL oxidation that was related to olive oil phenolic content. Multiple regression analysis showed that phenolics were significantly associated with the increase in lag time after adjustment for effects of other antioxidants; α-tocopherol also achieved a statistically significant effect. These results indicate that olive oil phenolic compounds protect LDL against peroxyl radical-dependent and metal-induced oxidation in vitro and could associate with LDL after their incubation with plasma. Both types of olive oil protect LDL from oxidation. Olive oil containing phenolics, however, shows more antioxidant effect on LDL oxidation than refined olive oil.     

A multivariate study of the relationship between fatty acids and volatile flavor components in olive and walnut oils

The relationships between FA and the volatile profiles of olive and walnut oils from Argentina were studied using GC and solid-phase microextraction coupled with GC-MS. The major volatiles were aldehydes and hydrocarbons, produced mainly through the oxidative pathways. n-Pentane, nonanal, and 2,4-decadienal were predominant in walnut oils, whereas nonanal, 2-decenal, and 2-undecenal were the most abundant components in olive oils. A multivariate analysis applied to the chemical data emphasized the differences between the oils and allowed us to see a pattern of covariation among the FA and the volatile compounds. The main differences between walnut and olive oils were the presence of larger amounts of short-chain (C₅–C₆) saturated hydrocarbons and aldehydes in the former and the greater quantities of medium-chain (C₇–C₁₁) compounds in olive oil. This can be explained by their different origins, mainly from the linoleic acid in walnut oil or almost exclusively from the oleic acid in olive oil.     

Sterol fractions in hazelnut and virgin olive oils and 4,4′-dimethylsterols as possible markers for detection of adulteration of virgin olive oil

Reports on the methylsterol fractions of hazelnut oils are scarce. The objectives of this study were to characterize methylsterols in hazelnut and virgin olive oils and to study the possibility of detection of adulteration of virgin olive oils. In hazelnut oils, 4-desmethylsterols were present in higher proportions (86 to 91%) than in virgin olive oils where this fraction was ca. 50% of the total sterol. In the 4-monomethylsterol fraction, citrostadienol was the major component in both kinds of oils followed by cycloeucalenol and obtusifoliol in virgin olive oils, and obtusifoliol in hazelnut oils. 24-Methylenecycloartanol was predominant in both kinds of oils in the 4,4′-dimethylsterols. For the first time, δ-amyrin was tentatively identified by comparing published mass spectral data in the analyzed samples of both kinds of oils. An unknown compound X (containing a lupane skeleton) and lupeol were detected only in the 4,4′-dimethylsterols fraction of hazelnut oils at a level of 2–8 and 6–10%, respectively. GC-MS analysis showed that adulteration of virgin olive oil by hazelnut oil could be detected at a level less than 4% by using these two compounds as possible potential markers.     

Changes in Total Polar Compounds,Peroxide Value,Total Phenols and Antioxidant Activity of Various Oils Used in Deep Fat Frying

In this study, the effect of deep fat frying on oil degradation, total phenols (TP) and total antioxidant activity (TAA) of hazelnut, corn, soybean and olive oils were investigated. Oil degradation and oxidation were monitored by measuring the total polar compounds (TPC) and the peroxide value (PV). The amount of TPC in corn, soybean and olive oils increased significantly with the time increment (p < 0.05). The PV of the oils did not exceed the maximum acceptable limit of 10 mequiv O₂/kg after 125 min frying except for hazelnut oil (10.64 mequiv O₂/kg). Deep-fat frying did not cause any significant change in the TP of corn oil, soybean oil and olive oil (p < 0.05). A significant decrease in the antioxidant activity was observed after 50 min frying using hazelnut oil and corn oil (p < 0.05). However, the antioxidant activity of soybean oil and olive oil significantly decreased after 75 and 25 min frying, respectively.     

Formation of genotoxic dicarbonyl compounds in dietary oils upon oxidation

Dietary oils—tuna, salmon, cod liver, soybean, olive, and corn oils—were treated with accelerated storage conditions (60°C for 3 and 7 d) and a cooking condition (200°C for 1 h). Genotoxic malonaldehyde (MA), glyoxal, and methylglyoxal formed in the oils were analyzed by GC. Salmon oil produced the greatest amount of MA (1070±77.0 ppm of oil) when it was heated at 60°C for 7 d. The highest formation of glyoxal was obtained from salmon oil heated at 60°C for 3 d. More glyoxal was found from salmon and cod liver oils when they were heated for 3 d (12.8±1.10 and 7.07±0.19 ppm, respectively) than for 7d (6.70±0.08 and 5.94±0.38 ppm, respectively), suggesting that glyoxal underwent secondary reactions during a prolonged time. The amount of methyglyoxal formed ranged from 2.03±0.13 (cod liver oil) to 2.89±0.11 ppm (tuna oil) in the fish oils heated at 60°C for 7 d. Among vegetable oils, only olive oil yielded methylglyoxal (0.61±0.03 ppm) under accelerated storage conditions. When oils were treated under cooking conditions, the aldehydes formed were comparable to those formed under accelerated storage conditions. Fish oils produced more MA, glyoxal, and methylglyoxal than did vegetable oils because the fish oils contained higher levels of long-chain PUFA, such as EPA and DHA, than did the vegetable oils. A statistically significant correlation (P<0.05) between the α-tocopherol content and the oxidation parameters was obtained from only MA and fish oils heated at 60°C for 3 d.     

Chlorophyll and β-carotene pigments in moroccan virgin olive oils measured by high-performance liquid chromatography

Chlorophyll and β-carotene concentrations were determined by high-performance liquid chromatography (HPLC) in virgin olive oils, which were press-extracted from green and semi-black olives. Pheophytin A was found to be the major chlorophyll isomer in all oil samples. The occurrence of this pigment at higher concentrations in oil extracted from green olives is a possible indication of its time-related destruction during olive ripening. Some evidence for thein vivo existence of pheophytin A is also presented. Beta-carotene concentration in oils was found to decrease during olive ripening.     

Oxidative Evolution of Virgin and Flavored Olive Oils Under Thermo-oxidation Processes

Changes in the oxidative status of Chétoui olive oil were monitored to attest the efficiency of some bioactive compounds from aromatic plants to improve the stability of olive oils after a maceration process at different concentrations. Aromatized olive oils were prepared by addition of lemon and thyme extracts at four different concentrations (20–80 g kg⁻¹ of oils) to virgin olive oils. The following parameters were monitored: free fatty acids, peroxide value, ultra violet absorption characteristics at 232 and 270 nm, fatty acid composition and aromatic profiles. After thermo-oxidation processes, the oleic/linoleic acid ratio remained stable (4.5). Oxidative stability slightly decreased during thermo-oxidation processes. The heating of the oils changed their volatile profile and led to the formation of new volatile compounds, such as the two isomers of 2,4-heptadienal after heating at 100 °C or (E,Z)-2,4-decadienal and (E,E)-2,4-decadienal after thermo-oxidation at 200 °C. The use of lemon and thyme extracts modified the aromatic and the nutritional value of the olive oil by the transfer of some bioactive compounds, such as limonene and carvacrol. In contrast, the oxidative stability of the product did not change. Furthermore, the aromatized oils may be employed in seasoning and cooking of some foods.     

Fractionation of oligomeric triacylglycerides and the relation to rejection limits for used frying oils

Precipitates enriched in oligomeric triacylglycerides were separated from thermally oxidized olive residue oil, conventional and high-oleic sunflower oils, and soybean oil by solvent fractionation in methanol/acetone at 4–5°C for 16 h. Different fractionation conditions were evaluated in an effort to isolate the oligomeric triacylglycerides (OTG). OTG, formed in frying oils upon heating at low concentations, were not detectable with conventional methods to determine polymeric compounds. The best conditions found from the different assays were the following: (i) weight of oil sample-to-solvent volume ratio of 1∶20; and (ii) solvent system methanol/acetone 10∶90 (vol/vol) for monounsaturated oils and 15∶85 (vol/vol) for polyunsaturated oils. Precipitates, enriched in oligomers, were formed when heated oils and used frying oils contained more than 27% polar compounds, a value which is widely accepted as the upper limit for use of frying oils.     

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.     

Modulation of Olive Oil Quality Using NaCl as Extraction Coadjuvant

The use of four concentrations of common salt (NaCl) used as coadjuvant for the extraction of virgin olive oil has been tested on a laboratory scale and the quality attributes of the oils obtained were compared to those obtained with talc as coadjuvant. The oils extracted from Picual fruits after NaCl addition were not significantly affected in terms of the physicochemical requirements established for extra virgin olive oil, the best level of quality of this produce. Addition of NaCl during the extraction process was positively correlated with the presence of o-diphenol compounds and the stability of the oils obtained. Moreover the use of NaCl resulted in a significant increase in contents of pigments (β-carotene, lutein and chlorophylls a and b) and volatile compounds in the oils.     

Effect of Greek sage and summer savory extracts on vegetable oil thermal stability

The effect of ethanol and acetone extracts obtained from Greek sage (Salvia fruticosa) and summer savory (Satureja hortensis L.) on the thermal stability of vegetable oils heated at frying temperature (180 °C) was studied. Virgin olive oil (VOO), refined olive oil (ROO), sunflower oil (SO), and a commercial oil blend suitable for frying (BL), enriched with each extract obtained from the two plant materials at a concentration of 3 g/kg oil, were heated at 180 °C for 10 h. Changes during heating were assessed by quantification of total polar materials and determination of p‐anisidine values. The acetone extract obtained from Greek sage showed a better inhibitory effect against thermal oxidation of heated refined oils (BL, ROO, SO) than the respective ethanol extract, although the latter was found to have a relatively higher total phenol content. Both summer savory extracts effectively retarded the thermal oxidation reactions during oil heating, showing a more pronounced effect than the Greek sage acetone extract. The activity of the acetone extract obtained from summer savory was stronger (SO, BL) or similar (ROO, VOO) to that of the summer savory ethanol extract, although the latter was found to have a higher total phenol content.     

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.     

Evaluation of Authenticity of Iranian Olive Oil by Fatty Acid and Triacylglycerol Profiles

For evaluation of the authenticity of Iranian olive oil, samples from many Iranian olive oil producers especially north of Iran in the production year 2007 were collected. The fatty acid and triacylglycerol compositions were measured. The most recent calculation methods including ∆ECN the difference between the actual and theoretical ECN42 (equivalent carbon number), triglyceride content and R of olive oils according to IOOC methods were applied. On the basis of our results, we were able to classify the olive oils into the extra virgin, virgin olive and olive oil categories. The important fatty acids are oleic, palmitic and linoleic acids and their main triacylglycerols are OOO, POO, OOL, PLO, SOS plus POP, and OLL, respectively. On the basis of the triacylglycerol results, experimental ECN48, ECN46, ECN50, ECN44 and ECN42 were obtained. By using the fatty acids results and a computer program, the theoretical ECN42 and ECN44 were calculated. Then R values, being the ratio of r ECN42/r ECN44 for authenticity of all olive oils and ∆ECN for determining categories of olive oils, were defined. The results of olive oil samples were in the accepted limits of Codex and IOOC. Finally we suggest that the R and ∆ECN can be used in identification of adulteration of olive oils and also they are useful from the point of view of authenticity and classification.     

Chemical Composition of Turkish Olive Oil––Ayvalik

Although large amounts of olive oil are produced in Turkey, not much information on its chemical composition is available in the literature to date. The aim of this study was to evaluate the chemical composition of commercial olive oils produced from the Ayvalik olive cultivar in Canakkale, Turkey. Five different samples corresponding to the olive oil categories of extra virgin (conventional, extra virgin olive oil (EVOO), and organic extra virgin olive oil (OGOO) production), virgin olive oil (OO-1), ordinary virgin olive oil (OO-2) and refined olive oil (RFOO) were evaluated. Olive oils were collected from two consecutive production years. According to the free fatty acids, the absorbance values (K₂₃₂ and K₂₇₀), and peroxide values of all the samples conformed to the European standards for olive oil. The level of oleic acid was in the range of 68–73%; while the linoleic acid content was significantly lower in the refined olive oils. The tocopherol and polyphenol content was in the lower range of some European olive oils. However, pinoresinol was a major phenolic compound (5–77 mg/kg depending on the oil category). Its content was markedly higher than in many other oils, which would be a useful finding for olive oil authentication purposes.