Temperature dependence of the autoxidation and antioxidants of soybean, sunflower, and olive oil

Effects of temperature on the autoxidation and antioxidants changes of soybean, sunflower, and olive oils were studied. The oils were oxidized in the dark at 25, 40, 60, and 80 °C. The oil oxidation was determined by peroxide (POV) and p-anisidine values (PAV). Polyphenols and tocopherols in the oils were also monitored. The oxidation of oils increased with the oxidation time and temperature. Induction period decreased with the oxidation temperature; 87 and 3.6 days at 25 and 60 °C, respectively, for sunflower oil. The activation energies for the autoxidation of soybean, sunflower, and olive oils were 17.6, 19.0, and 12.5 kcal/mol, respectively. Olive oil contained polyphenols at 180.8 ppm, and tocopherols were present at 687, 290, and 104 ppm in soybean, sunflower, and olive oils, respectively. Antioxidants were degraded during the oil autoxidation and the degradation rates increased with the oxidation temperature of oils; for tocopherols, 2.1 × 10⁻³ and 8.9 × 10⁻²%/day at 25 and 60 °C, respectively, in soybean oil.     

A kinetic study of oxidation development in sunflower oil under microwave heating: Effect of natural antioxidants

The antioxidative effects of carnosic acid and sesamol on sunflower oil under temperature-controlled microwave heating were investigated as a function of time and temperature. The concentration of conjugated diene hydroperoxide and p-anisidine value were determined spectrophotometrically, as measures of oxidation, during microwave heating of sunflower oil with or without added antioxidants at 40 °C, 60 °C and 80 °C. The kinetics of hydroperoxide formation was examined on the basis of previously proposed mechanisms and found to be of the half-order with respect to the concentration of conjugated diene hydroperoxide. The amounts of added antioxidants remaining in sunflower oil after different microwave heating periods at different temperatures were determined by HPLC-DAD. The results were interpreted in terms of antioxidative effects of carnosic acid and sesamol. Carnosic acid was found to be a more effective antioxidant than sesamol for sunflower oil.     

Oxidative stabilization of cold‐pressed sunflower oil using phenolic compounds of the same seeds

It is known that sunflower seeds are rich in phenols, constituting approximately 1–3 g per 100 g of seeds. The principal phenol is chlorogenic acid (CGA), followed by caffeic acid (CA) and lower quantities of several other compounds. On the contrary, it is known that phenols are present only in trace amounts in cold‐pressed sunflower seed oils. In this study, the possibility of improving the oxidative stability of cold‐pressed sunflower oil is evaluated using phenolic substances constitutive of seeds. Phenols, extracted from two different dehulled sunflower seed samples, were identified, measured and added to a cold‐pressed sunflower oil and compared with butylated hydroxyanisole (BHA), pure CGA and pure CA. Raw phenolic extract (RPE) was composed of CGA exclusively, whereas CA was present only in traces in its free form was not present. On the contrary, hydrolysable phenol acids (HPAs) were constituted prevalently from CA, released by CGA alkaline hydrolysis. The stabilization effect on oil oxidation at 110 °C was evaluated as 41% and 118% for RPE and HPAs respectively with respect to the control. At 30 °C, no significant differences were recorded between the two seed extracts. Their antioxidant effect was lower than that at 110 °C and evaluated to be, on average 13%. In comparison with BHA, at 30 °C, both seed extracts were more effective than this synthetic phenol; at 110 °C, the antioxidant effect of RPE and BHA was similar, whereas HPA was significantly more effective than BHA. In conclusion, this study demonstrates that the phenols present in sunflower seeds can be considered natural antioxidants suitable for stabilizing the oxidation of cold‐pressed sunflower oil, at both low and high temperatures. Copyright © 2003 Society of Chemical Industry     

Short-Chain Fatty Acid Formation during Thermoxidation and Frying

Formation and evolution of the short-chain fatty acids originated by oxidation and remaining bound to the parent triglyceride, specifically heptanoate and octanoate, were studied during thermoxidation of palm olein, conventional sunflower oil and high-oleic sunflower oil at 180°C, as well as in real used frying oils of unknown history collected by Food Inspection Services. Fatty acids were quantified by gas–liquid chromatography following transesterification of samples and using methyl nonanoate and methyl heptadecanoate as internal standards. Alteration level was determined through analyses of polar compounds and polar fatty acids. Results showed high correlation coefficients between short-chain fatty acids and polar compounds or polar fatty acids, thus suggesting that quantification of short-chain fatty acids is a good indication of the total alteration level in used frying oils.     

Use crude olive leaf juice as a natural antioxidant for the stability of sunflower oil during heating

Olive leaves (Kronakii cultivar) were obtained from the annual pruning of olive trees and pressed to obtain a crude juice. Aliquots from the concentrated crude olive leaf juice, representing 400, 800, 1600 and 2400 ppm as polyphenols, were added to sunflower oil. Samples of sunflower oil mixed with olive leaf juice were heated intermittently at 180 ± 5 °C for 5 h day^?1 and the heating process was repeated for five consecutive days. A control experiment was performed where butylated hydroxyl toluene (BHT) at 200 ppm was added to sunflower oil prior to intermittent heating in order to compare the antioxidant efficiency between the natural polyphenolics of olive leaf juice and synthetic antioxidant BHT. Some physical and chemical constants for the unheated and heated sunflower oil were determined. The data indicate that the addition of olive leaf juice to sunflower oil heated at 180 °C induced remarkable antioxidant activity and at 800 ppm level was superior to that of BHT in increasing sunflower oil stability.     

Characterization of Hazelnut Oil Oleogels Prepared with Sunflower and Carnauba Waxes

In this study, hazelnut oil oleogels prepared with sunflower wax and carnauba wax were analyzed and compared with a commercial shortening. Oil binding capacities of sunflower wax oleogels were higher than 99%, while carnauba wax had a maximum value of 97.6% for 10% addition level. At 3% addition level of carnauba wax, no gel developed. The crystal formation time of sunflower wax was shorter. Although the highest (8.5%) solid fat content was observed in the 10% carnauba wax containing oleogel (HC10) sample, it was 30.4% in the commercial shortening sample at 20°C. The peak melting temperature of commercial shortening was 52.3°C, and among all organogels, sunflower wax oleogel at 3% addition level had the closest value (58.4°C). The melting enthalpies of the oleogels ranged from 4.3 to 20.3 J/g, while it was 10.9 J/g for the commercial shortening sample. The firmness and stickiness values in the oleogel samples were lower than that of commercial shortening sample. On the other hand, there was no significant change of firmness and stickiness during storage, indicating good stability (p ≤ 0.001). Especially the sunflower wax oleogels were very homogenous and smooth in structure. The polarized light microscopy pictures revealed needle-like crystals for sunflower wax and aggregate-like crystals for carnauba wax oleogels. The x-ray diffraction measurements of the crystals showed the β´ types of the polymorphic structures. Furthermore, the oleogels were very stable against oxidation during the storage period. Hazelnut oil organogels prepared with sunflower wax can be good source material for shortening or margarine-like products.     

Antioxidant activity of 1,4-dihydropyridine derivatives in β-carotene-methyl linoleate,sunflower oil and emulsions

The antioxidant activity of six synthetic 1,4-dihydropyridine (DHP) derivatives was tested in an azobis-amidinopropane dihydrochloride initiated β-carotene-methyl linoleate peroxidation model system. Radical scavenging activity of the derivatives was estimated by measuring their reactivity with stable N,N-diphenyl-N′-picrylhydrazyl radicals. The antioxidant activity of these different derivatives was also evaluated in traditional sunflower oil and its 20% oil-in-water emulsion in the dark at 60°C, as well as during storage of sunflower oil in the dark and with light exposure at ambient temperatures. The primary (conjugated diene hydroperoxides) and secondary (hexanal, pentanal) oxidation products were monitored during different periods of storage. Butylated hydroxytoluene was used as a standard antioxidant and different plant extracts were used for comparison of antioxidant activities throughout this study. All synthetic compounds showed antioxidant activity, while plant extracts acted as pro-oxidants upon light exposure. Three derivatives of DHP, without substitution at position 4, showed highest antioxidative activity in model system and sunflower oil and its emulsion in the dark at 60°C as well as during storage of sunflower oil in the dark and with light exposure at ambient temperature. The hydrophilic derivative of DHP with a phenyl group at position 4 showed high radical scavenging activity, and high antioxidant activity in sunflower oil-in-water emulsion, but was less active in model system and sunflower oil. The hydrophobic derivatives of DHP with a phenyl group at position 4 showed high antioxidant activity in model system but were the lowest active derivatives in sunflower oil and its emulsion. ©     

Oxidative Stability of ω3-rich Camelina Oil and Camelina Oil-based Spread Compared with Plant and Fish Oils and Sunflower Spread

ABSTRACT: The oxidative stability of ω3‐rich oil from Camelina sativa and the storage stability of a camelina oil‐based spread were evaluated. Camelina oil was more stable than fish oil and linseed oil, but less stable than sunflower, corn, sesame, and olive oils, indicated by measuring peroxide values (PV), ρ‐anisidine values (AV), total oxidation values (Totox), thiobarbituric acid reactive substances (TBARS), conjugated diene levels (CD), and conjugated triene levels (CT) during storage at 65 °C for 16 d. The camelina oil‐based spread had higher PV, AV, Totox, TBARS, CD, and CT than the sunflower spread but maintained adequate sensory quality for 16 wk of storage at 4 °C or 8 °C.     

Antioxidant activity of ginger extract in sunflower oil

The antioxidant activity of dichloromethane extract from ginger was evaluated during 6 months of storage of refined sunflower oil at 25 and 45 °C. Free fatty acid (FFA) content, peroxide value (POV) and iodine value (IV) were used as criteria to assess ginger extract as an antioxidant. After 6 months of storage at 45 °C, sunflower oil containing 1600 and 2400 ppm ginger extract showed lower FFA contents (0.083 and 0.080%) and POVs (24.5 and 24.0 meq kg^?1) than the control sample (FFA contents 0.380%, POV 198.0 meq kg^?1). Sunflower oil containing 200 ppm butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) showed FFA contents of 0.089 and 0.072% and POVs of 26.5 and 24.7 meq kg^?1 respectively after 6 months of storage at 45 °C. Similarly, after 6 months of storage at 45 °C, IVs of sunflower oil containing 1600 and 2400 ppm ginger extract were 80 and 92 respectively, higher than that of the control sample (53). However, IVs of sunflower oil treated with 200 ppm BHA and BHT were 94 and 96 respectively after 6 months of storage at 45 °C. These results illustrate that ginger extract at various concentrations exhibited very strong antioxidant activity, almost equal to that of synthetic antioxidants (BHA and BHT). Ginger extract also showed good thermal stability and exhibited 85.2% inhibition of peroxidation of linoleic acid when heated at 185 °C for 120 min. Therefore the use of ginger extract in foods is recommended as a natural antioxidant to suppress lipid oxidation. © 2003 Society of Chemical Industry     

Effect of an Ethanol Extract from Summer Savory (Saturejae hortensisL) on the Stability of Sunflower Oil at Frying Temperature

The effect of the ethanol extract from Saturejae hortensis L on the oxidative and thermal processes occurring in sunflower oil during its high-temperature treatment (180°C) was investigated. The changes during simulated deep fat frying were monitored by determination of the oxidation stability at 100°C, as well as by determination of unchanged triacylglycerols. It was established that the addition of 1 and 5 g kg^-1 ethanol extract from S hortensis L leads to a decrease in the oxidative and thermal changes in the oil. The ethanol extract from S hortensis L improved the oxidative stability of sunflower oil even after 50 h at 180°C and it inhibited the oxidative processes more than the thermal processes under these conditions. © 1997 SCI.     

Measurement of Thermal Conductivity of Edible Oils Using Transient Hot Wire Method

Thermal conductivities of three different edible oils, namely sunflower oil, corn oil and olive oil, were measured at temperatures 25, 40, 60, and 80°C. The measurements were carried out using a hot wire probe method. The calibration of the probe was performed using 0.3% agar gel with water and glycerin. In general, thermal conductivities of oils used in this study are found to be decreasing with temperature. The values of thermal conductivity measured are quite near to each other, the highest and the lowest being respectively 0.168 W/m K for sunflower oil at 25°C and 0.152 W/m K for corn oil at 80°C.     

Stabilization of Sunflower Oil During Accelerated Storage: Use of Basil Extract as a Potential Alternative to Synthetic Antioxidants

The antioxidant efficacy of basil extracts was estimated in stabilization of sunflower oil. The basil essential oil was analyzed by gas chromatography–mass spectrometry. Twenty-two compounds were identified representing 93.74% of the total essential oil. Basil methanolic extract was thermally evaluated by heating at 185°C. At the 100 min heating time, the extract exhibited antioxidant activity higher than that of butylated hydroxytoluene. Different concentrations of methanolic extract were added to sunflower oil. Selected parameters (i.e., weight gain, induction period to primary oil oxidation, peroxide value, conjugated dienes, and conjugated trienes) were considered for evaluating the effectiveness of basil in stabilization of sunflower oil. Basil methanolic extract showed good antioxidant activity according to synthetic antioxidants. Basil may be used as a natural antioxidants to prevent vegetable oils oxidation.     

Antioxidant activity of grapefruit seed extract on vegetable oils

The antioxidant activities of a grapefruit seed extract (GFSE) which contains tocopherols, citric acid and ascorbic acid, were investigated in vegetable oils. Different amounts of GFSE in powder were dissolved in a mixture of soybean oil–sunflower oil. The oxidation was carried out in an AOM equipment at temperatures of 98·7°C, 75°C and 66·5°C. The results indicated prooxidant effects of GFSE at 97·8°C and 75°C possibly due to a blockade effect of a hydroxyl compound by tocopherol. The inhibitor reaction orders at these temperatures were 0·902 and 0·465, respectively, while at 66·5°C the oxidation rate was inverse to GFSE concentration with reaction order of −0·420. These results seem to indicate different reaction mechanisms depending on temperature conditions. The blockade effects were explained on the basis of a proposed complex between tocopherol and citric acid molecules. © 1998 SCI.     

Improvement in the quality of used sunflower oil by organic and inorganic adsorbents

The objective of the present work was to improve the quality of used sunflower oil. Inorganic (normal and modified silica gel) and organic (normal and modified cellulose powder) adsorbents were used as regeneration agents. Sunflower oil was heated at 180 ± 5 °C, 4 h every day for five consecutive days. The adsorbent materials were individually added to use sunflower oil at 2% level (w/v). Some physico-chemical characteristics were measured to assess the quality of treated-used sunflower oil. The results indicated that all adsorbents under study were effective in improving the overall quality of used sunflower oil. Normal silica gel with small particle size permitted high adsorbing capacity and close to that induced with Magnesol XL which is used commercially in a large scale to improve oil quality. The polarity of the adsorbent substance had a remarkable effect on removing the secondary oxidation products of used sunflower oil. The mode of adsorbents action is discussed.     

Chromatic parameters and oxidation indices for edible vegetable oils submitted to thermal oxidation

Peroxide values, TBA numbers and chromatic parameters of edible vegetable oils (olive, sunflower, corn oils) thermally oxidised (75°C, 100°C, 180°C) during 5 days were determined. For calculating chromatic parameters the recommended standard CIE methods and several simplified methods were employed. With olive oil a remarkable change in spectral characteristics occurred as the temperature and time of heating were increased. Thermal autoxidation, as assessed by peroxide value and TBA number, was only observed at 75°C (Schaal oven test). In none of the three types of vegetable oil was the dominant wavelength modified during the course of the heating process. Luminosity and hue angle showed slight increases in olive and sunflower oils. Colour saturation underwent a remarkable decrease in olive oil. From a comparison and a correlation study it is concluded that the simplified methods could be applied only for certain chromatic parameters and types of vegetable oil. For a comprehensive study of the diverse chromatic parameters the standard CIE methods should be applied.     

The influence of phenolic extracts obtained from the olive plant (cvs. Picual and Kronakii), on the stability of sunflower oil

Summary The phenolic compounds of olive cultivars (Picual and Kronakii) were extracted. The total phenolic content of the extracts was estimated and their ability to reduce the oxidation of sunflower oil was tested at 100 °C by using a Rancimat^®. The fruits, leaves and pomaces were extracted separately with ethanol. Portions of the fruits were crushed to produce an oil/aqueous mixture, which was separated and the two fractions further processed. The oil fraction was extracted with 60% aqueous methanol and was separated further, by the method of Dabrowski & Sosulski (1984 ), into three major fractions. These contained mainly free phenols, soluble phenolic esters or bound phenolic acids, respectively. The phenolic concentrations were measured in all the fractions and were in accordance with expected amounts. When tested at 100, 200 or 400 ppm for their ability to stabilize sunflower oil the results showed that the vast majority of the anti‐oxidant activity found in the ‘total phenols’ fraction was because of a ‘free phenolic’ group. The free phenolics, at a 400‐ppm level, exhibited remarkable anti‐oxidant activity and were superior to that of butylated hydroxy toluene (BHT) in retarding sunflower oil oxidative rancidity. The mode of action is discussed.     

Composition, stability and acceptability of different vegetable oils used for frying peanuts

The purpose of this work was to determine the chemical stability of vegetable oils in the frying process and the consumer acceptance of fried-salted peanuts prepared in different vegetable oils. Fatty acids composition was determined in sunflower, corn, soybean, peanut and olive oils. A chemical study (free fatty acid and p-anisidine values) of these oils at frying temperature (170 °C) was developed during 96 h. Consumer test of fresh products was performed on fried-salted peanuts prepared in the different oils. Peanut oil and virgin olive oil presented oleic acid as predominant fatty acid (44.8% and 64.2%, respectively), making it more resistant to lipid oxidation at frying temperature than the other refined vegetable oils (sunflower, corn and soybean oils). Virgin olive and peanut oils showed less increment of free fatty acids and p-anisidine value than the other oils along the heating essay. In addition, fried-salted peanuts prepared with refined peanut oil showed higher consumer acceptance than those prepared with other vegetable oils such as sunflower, corn, soybean and olive oils. Peanut oil could be used to fry peanuts obtaining products with higher consumer acceptance and shelf-life, thus preventing loss of their sensory and nutritional quality.     

Effect of plant extracts on the oxidative stability of sunflower oil and emulsion

The antioxidative activities of six plant extracts (catnip, hyssop, lemon balm, oregano, sage and thyme) were evaluated in sunflower oil and its 20% oil-in-water emulsion in the dark at 60°C. The oxidation process was followed by measuring the formation of primary (conjugated diene hydroperoxides) and secondary (volatile compounds) oxidation products. Sage extracts (600 and 1200 ppm) effectively inhibited the formation of conjugated dienes and volatile compounds (hexanal and pentanal) in oil and emulsion and showed the highest antioxidative activity compared with 300 ppm BHT. Thyme and lemon balm extracts inhibited hexanal generation more than formation of conjugated dienes in both oil and emulsion. Oregano extract was more active in oil than in emulsion. Catnip and hyssop extracts (600 ppm) showed prooxidative action to sunflower oil at 60°C. These two extracts increased the formation of conjugated dienes compared with the control oil. In emulsions, catnip extract (600 ppm) was active and significantly inhibited the formation of conjugated dienes more than BHT (300 ppm) during additional incubation.     

Improving the quality of fried oils by using different filter aids

The present study aimed to improve the quality of fried soybean, sunflower, palm and cottonseed oils. Synthetic (Magnesol XL) and natural (diatomaceous earth and kaolin) filter aids were used at various levels (1, 2 and 4%) to adsorb the secondary oxidation products of the oil. The metal patterns (the cations Si, Mg, Ca, Fe, Na, K, Al, Cu, Mn, Zn and the anions CO₃^2?, HCO₃^?, Cl^?, NO₃^?, NO₂^?, SO₄^2?) of Magnesol XL, diatomaceous earth and kaolin were determined. Some physical and chemical properties (refractive index, viscosity, colour, foam height, acid value, peroxide value, thiobarbituric acid value, iodine value, and conjugated diene and polymer contents) of non‐fried, fried and fried–treated soybean, sunflower, palm and cottonseed oils were determined. The frying process was performed at 180 °C ± 5 °C for 12 h continuous heating. The fried oils were treated with the synthetic and natural filter aids at 105 °C for 15 min. The results indicate that Magnesol XL, diatomaceous earth and kaolin contained Si + Mg, Si + Ca and Si + Al, respectively, as the basic metals. Frying soybean, sunflower, palm and cottonseed oils led to significant increases in refractive index, colour, foam height, viscosity, acid value, peroxide value, TBA value, conjugated diene and polymer contents and decrease in iodine value. Treatment of fried oils with Magnesol XL, diatomaceous earth and kaolin at the 1, 2 and 4% levels greatly improved the quality of fried oils. These findings indicate the high efficiency of the filter aids used in the present study in adsorbing the products of oil degradation. Copyright © 2006 Society of Chemical Industry     

Physical Properties and Oxidation Rates of Unrefined Menhaden Oil (Brevoortia patronus)

ABSTRACT: Unrefined menhaden oil was evaluated for thermal and rheological properties and its temperature-dependent viscosity and lipid oxidation rate were determined. Peroxide value, free fatty acids, density, specific gravity, water activity, moisture content, and enthalpy of the unrefined menhaden oil were 5.70 meq/kg, 3.80%, 0.93 g/mL, 0.93%, 0.52%, 0.15%, and 20.2 kJ/kg, respectively. The melting point range of unrefined menhaden oil was found to be −69.5 to 27.21 °C. The menhaden oil exhibited non-Newtonian fluid behavior at lower temperatures (5 to 25 °C), while it behaved like a Newtonian fluid at 30 °C. The oil apparent viscosity at 5 °C (0.22 Pa.s) was significantly higher (P < 0.05) than that at 30 °C (0.033 Pa.s). The average magnitude of activation energy for viscosity of the unrefined menhaden oil was 50.37 kJ/mol. The predicted apparent viscosity agreed (R²= 0.9837) satisfactorily with the experimental apparent viscosity. The minimal lipid oxidation rate of the oil was found at 25 and 35 °C for 6 h, higher lipid oxidation rates were observed when the oil was heated for 6 h at 45 to 85 °C. The rate of lipid oxidation for unrefined menhaden oil was temperature dependent (R²= 0.9425). This study showed that the magnitude of the apparent viscosity and oxidation rate of the unrefined menhaden oil was greatly influenced by temperature.