Electron spin resonance spectroscopy for evaluation of early oxidative events in semisolid palm oil

Electron spin resonance (ESR) spectroscopy was applied to study early oxidative events in semisolid palm oil in bulk. Oil was stored at mildly accelerated conditions of 50°C for 7 days and the free radical formation was followed with the addition of spin trap N‐tert‐butyl‐α‐phenyl‐nitrone. Dissolution of the oil samples in isooctane prior to ESR measurements stabilized the ESR signal allowing the changes in relative free radical concentrations during oil storage to be monitored. Formation of lipid hydroperoxides as primary lipid oxidation products was found to correlate with the tendency for the formation of free radicals in the oil during the storage and accordingly, ESR spectroscopy may be used to detect the early events in lipid oxidation in palm oil. However, the interference of added rosemary extract (RE) in ESR analyses was seen as an increased ESR signal while the efficiency of RE as antioxidant in palm oil was confirmed by isothermal DSC. Practical applications : ESR spectroscopy may be used to evaluate early events of oxidation in semisolid oils such as palm fat, which is widely used in food industry.     

Effect of various packaging materials on storage stability of refined,bleached, deodorized palm oil

Refined, bleached, deodorized palm oil (RBD palm oil) was packaged in lacquered metal cans (LMC), green glass bottles (GGB), amber glass bottles (AGB), clear glass bottles (CGB), clear plastic bottles (CPB) and sealed polyethylene film (POLET), and stored in direct sunlight (40 ± 1°C) or in darkness (27 ± 1°C). Measurements of free fatty acid (FFA), peroxide value and anisidine value, at 14-day intervals for a period of 98 days, were used to assess the stability of the oil towards hydrolytic and oxidative deterioration. Total oxidation values for packaged oils stored in direct sunlight showed that LMC gave the greatest protection against oxidative deterioration, followed by GGB and AGB. POLET offered the least protection to the oil against oxidative deterioration, while CPB and CGB proved superior to POLET but inferior to GGB and AGB. For storage in the dark, LMC, AGB and GGB gave the greatest protection to RBD palm oil against oxidative deterioration, with no significant statistical differences between them, while CPB, CGB and POLET followed in that order, with significant differences between their respective abilities to protect the oil against oxidative deterioration. Oils packaged in CPB gave the highest FFA levels (statistically significant). The investigations clearly indicated that LMC is superior to all other tested packaging materials in offering maximum protection to RBD palm oil against hydrolytic and oxidative deterioration. Amber and green glass bottles could serve as viable alternatives to LMC, while CGB and CPB could be tolerated as suitable packaging systems for RBD palm oil. However, the study also clearly showed that POLET is unsatisfactory for use as packaging material for RBD palm oil.     

Effect of packaging materials on storage stability of crude palm oil

Lacquered metal cans, green glass bottles, amber glass bottles, clear glass bottles and clear plastic bottles filled with freshly produced Nigerian crude palm oil were stored in direct sunlight (40±1°C) and in the dark (27±1°C). Assessment of the stability of the oils towards hydrolytic and oxidative deterioration was made periodically by measuring the free fatty acid, peroxide and anisidine values over a period of 98 days. The study showed that crude palm oil packaged in plastic bottles and clear glass bottles recorded higher total oxidation values than oils packaged in either lacquered metal cans or amber and green glass bottles. Lacquered metal cans gave the greatest protection against oxidation. Oxidation proceeded faster in cases where the packaging materials were stored in direct sunlight.     

Flavor and oxidative stability of hydrogenated and unhydrogenated soybean oils. Efficacy of plastic packaging

Soybean oils were packaged in polyvinylchloride, acrylonitrile, clear glass and amber glass bottles and their flavor stabilities were evaluated by a trained sensory panel. Hydrogenated and unhyrdogenated oils showed similar patterns of flavor deterioration regardless of container or type of aging. In accelerated light-exposure tests with air in the headspace, oils in plastic bottles showed flavor and oxidative stability equivalent to the same oils in clear glass bottles. Packaging in the amber glass bottle provided, as expected, significantly improved oil stability during light-exposure tests. In accelerated storage tests at 60 C with air in the headspace, sensory evaluation and peroxide determination showed no significant differences in oils packaged in clear glass and PVC, but sometimes oils received lower scores in glass compared with those in acrylonitrile bottles. During long-term storage, oils in plastic bottles with nitrogen in the headspace had flavor and oxidative stabilities equal to oils in glass bottles with nitrogen. These investigations indicate that packaging soybean oils in polyvinylchloride or acrylonitrile bottles is a viable alternative to packaging in clear glass bottles.     

Oxidative Rancidity in Refined Sunflower Oil with Respect to Storage Variation

Refined sunflower oil was stored in brown and colorless glass bottles at ambient temperature (18–32°C) and 37°C to assess the effect of light, heat and air on the stability fo the oil and to record the progress of oxidative rancidity especially the secondary stages with respect to storage variation and time. Oil sample stored in brown color bottle was found to be superior (FFA 0.15 to 0.53; PV 0.5 to 80; HV 3 to 12; oxirane oxygen 0.2 to 2.3) over oil stored in colorless bottle (FFA 0.15 to 0.60; PV 0.5 to 91; HV 3 to 8; oxirane oxygen 0.1 to 2.8) at ambient temperature. Samples stored at 37°C deteriorated very fast. Silver nitrate test, oxidised fatty acid formation, urea adduct formation, picric acid-TLC test, Kreis test, DNP-TLC test, DNP-precipitation test have been devised to detect and follow oxidative rancidity. These tests worked well even at the lower levels of oxycompounds. No conjugation was detected in any of the oil.     

The use of electronic and human nose for monitoring rapeseed oil autoxidation

This work was aimed at assessing the effectiveness of the electronic nose to monitor off‐flavor associated with lipid oxidation as a supplementary tool to human sensory panel assessment. Therefore, correlations between electronic nose and sensory analysis were determined. Also GC analyses and chemical analyses of oil samples were run to characterize the analyzed samples with well‐described parameters. Refined rapeseed oil was subjected to an accelerated storage test for 12 days at 60 °C and to an ambient temperature storage test in which it was stored in retail plastic bottles for up to 6 months. PCA of electronic nose data samples stored at an elevated temperature was related to PCA of sensory analysis, and similarities in sample clustering were observed. For samples stored at room temperature, the human panel showed greater sensitivity than the electronic nose. Prediction models based on PLS of electronic nose data were able to predict the sensory quality changes during storage at elevated and room temperature, ranging from 0.721 to 0.989 and from 0.849 to 0.881 (p <0.05), respectively. PV and p‐AV were well predicted on the basis of both electronic nose (0.989, 0.998 for elevated temperature; 0.907, 0.881 for room temperature) and sensory analysis data (0.973, 0.993 for elevated temperature; 0.939, 0.886 for room temperature). Applicability of the electronic nose technology to verify sensory and rancidity changes during storage showed to be promising in quality control of oils.     

Effect of roasting on oxidative and tocopherol stability of walnut oil during storage in the dark

The effect of roasting on the oxidative stability of oil from walnut (Juglans sinensis Dode) was investigated by observing changes in the characteristics of oils from unroasted and roasted kernels during storage in the dark at 60°C. Walnut kernels were roasted at 160°C for 15 min prior to oil extraction with the solvent, hexane. Roasting of kernels increased the peroxide value (POV) and conjugated dienoic acid (CDA) value of the oil. The rate of increase in the POV was significantly lower in roasted than in the unroasted walnut oil during storage at 60°C (1.90 vs. 1.06 and 4.45 vs. 3.55 meq/kg/day during induction period (IP) and post‐IP, respectively). Roasting of kernels significantly increased the IP of walnut oil from 0.89 to 3.39 days during storage. The total tocopherol content in roasted walnut oil was lower as compared to that in unroasted one (277.77 vs. 314.88 µg/g). However, the rate of degradation of total tocopherol during storage was lower in roasted walnut oil compared to unroasted one (1.18 vs. 2.17%/day), which showed that the tocopherol retention was higher in roasted walnut oil. These results indicate that roasting of kernels increased the oxidative and tocopherol stability of oil during storage in the dark.     

Chemical Changes and Oxidative Stability of Peanuts as Affected by the Dry-Blanching

The oxidative changes of peanuts subjected to the dry‐blanching process were evaluated and compared with those of their in‐shell counterparts. In general, the fatty acid profile was not influenced. The content of α‐tocopherol decreased, but the remaining tocopherol homologs were unaffected. Nonanal, an oxidation product of oleic acid, increased. However, the contents of several volatile compounds with potential antioxidant properties were also increased. The higher oxidative stability of dry‐blanched peanuts was demonstrated by accelerated tests as evaluated by peroxide value, thiobarbituric acid reactive substances (TBARS) and the induction period of cold‐pressed oils and this was confirmed by the higher antioxidant properties of oils from such sample as evaluated by the DPPH radical scavenging activity. These results were further confirmed during long‐term storage of dry‐blanched and in‐shell peanuts. The decrease of tocopherols in peanuts due to dry‐blanching did not negatively influence their oxidative stability. In fact, dry‐blanched peanuts showed higher stability as compared with in‐shell peanuts; therefore, we suggest that loss of tocopherol might be less important than the generation of several volatile antioxidant compounds as well as possibly Maillard reaction products upon the dry‐blanching process. These results may be of practical interest to the peanut and peanut oil industries.     

Soybean and Soybean/Beef-Tallow Biodiesel: A Comparative Study on Oxidative Degradation During Long-Term Storage

Vegetable oils are the primary raw materials used in biodiesel production; however, they usually present oxidative stabilities inferior to the EN 14214 specifications. An alternative to improve the oxidative quality of vegetable oil biodiesel is blending it with animal fat biodiesel. In this paper, we studied the oxidative degradation of soybean/beef-tallow biodiesel (SB) 70/30 and 50/50 (w/w) during long-term storage. Soybean biodiesel (SO) was used as a control sample. The biodiesel samples were stored for 350 days and analyzed periodically via oxidative stability, tocopherol content, peroxide value, polar compounds, and kinematic viscosity. The results showed that SB 70/30 and 50/50 biodiesel samples presented higher oxidative stabilities than SO biodiesel. Additionally, the blends met the limits proposed by EN 14214 for oxidative stability (8 h). During long-term storage, the SB biodiesel showed greater resistance to oxidative degradation, which was indicated by the lower formation of hydroperoxides and polar compounds. Similarly, the decline in the tocopherol content was slower in SB biodiesel. Blends of soybean and beef-tallow biodiesel at levels of 70/30 and 50/50 are, therefore, proper alternatives to improve the oxidative quality of this biofuel.     

γ‐ and δ‐tocopherols are more effective than α‐tocopherol on the autoxidation of a 10% rapeseed oil triacylglycerol‐in‐water emulsion with and without a radical initiator

The antioxidative effects of γ‐ and mainly δ‐tocopherol in a multiphase system were hardly considered up to now. The aim of this study was i) to assess the effects and ii) to follow the degradation of α‐, γ‐ and δ‐tocopherol in concentrations of 0.01%, 0.05%, 0.1% and 0.25% during the oxidation of a 10% purified rapeseed oil triacylglycerol‐in‐water emulsion at 40 °C in the dark for 15 wk in a system containing a low oxygen concentration. Oxidation experiments were performed weekly by assessing the formation of hydroperoxides and hexanal, and the stability of the tocopherols was determined using high‐performance liquid chromatography. Storage tests were conducted with and without the addition of 0.01% α, α′‐azoisobutyronitrile (AIBN), which is a known radical initiator. α‐Tocopherol increased the formation of hydroperoxides in both tests as well as the generation of hexanal when the radical initiator was added; furthermore it was the least stable. γ‐Tocopherol delayed the formation of hexanal and prolonged the stability of the emulsion in a dose‐dependant manner. δ‐Tocopherol was the most stable and also the most effective in delaying lipid oxidation in the emulsions. Each concentration that was tested reduced the rate of hydroperoxide and especially hexanal formation. Hexanal was only formed to a slight extent after 15 wk of oxidation in the test with AIBN and the lowest dose of 0.01% δ‐tocopherol. For all tocopherols, strong correlations were found between tocopherol stability and the extent of oxidation. Results suggest that i) mainly δ‐tocopherol, but also γ‐tocopherol even less pronounced, are very good antioxidants in order to stabilize and prolong the shelf life of oil‐in‐water emulsions, ii) the antioxidative effects were intensified with increasing amounts.     

Evolution of thermograph parameters during the oxidation of extra virgin olive oil

The modulated differential scanning calorimetry (M‐DSC) was used as a rapid and effective method to characterize the olive oil at different levels of oxidation. Thermograph parameters have been related to oxidative degradation of the triglycerides. In this study, their relation to the characteristic off‐flavor compounds, correlated to the oxidative degradation of the oil, was also investigated. Extra virgin olive oil samples were subjected to the following oxidation treatments: a) purged with air using glass washing bottles at two flow rate values, b) heated in a conventional oven at two area/oil mass ratios, and c) heated in a microwave oven also at two area/oil mass ratios. Samples were withdrawn and analyzed at predetermined intervals. Flavor and off‐flavor compounds were isolated using a dynamic thermal stripping apparatus and transferred into a gas chromatograph by using a thermal desorption unit. All oil samples were analyzed by M‐DSC during cooling from 25 °C to ?60 °C at 7 °C/min, and heating back to 40 °C at 10 °C/min. High correlation values were obtained between various M‐DSC thermograph parameters and certain volatile compounds. Results showed that M‐DSC could be used as a simple method to indicate compositional changes in olive oil during oxidation.     

Application of the Fluorescent Light Test and Some Other Methods for Determination of the Stability of Different Edible Oils

For the stability determination of different kinds of edible oils (sunflower, corn and soybean) various methods have been applied: Fluorescent light test, AOM-method, Oventest and Stability at room temperature. The fatty acid composition, the tocopherol content and the quality characteristics (peroxide value, anisidine value, content of dienes and trienes) were determined before testing of the stability. Special attention has been given to the determination of stability by the Fluorescent light test. This test seems to be very interesting in the determination of oil stability because the action of light is the main factor for the deterioration of the oil, while it is in the supermarkets in clear glass or plastic bottles (oil is not packed in brown glass in Yugoslavia). Oil in 1 liter original glass or plastic bottles or in 50 cm³ jars was exposed to the influence of the light of four 40 W fluorescent cool-white tubes of 1 m. Oxidation rate of the samples was followed by measuring the peroxide value. For the organoleptic evaluation, a three-member panel judged the flavor on a 10 point scale. The obtained results show that, under the conditions of this test, corn oil has the best stability. Sunflower oil has two and half time better stability than soybean oil. Some correlation has been established between the stability obtained by all applied methods.     

Effect of classic sterilization on lipid oxidation in model liquid milk‐based infant and follow‐on formulas

The objective of this study was to evaluate the effect of classic sterilization on lipid oxidation of liquid infant and follow‐on formulas by analyzing formation of oxidized and dimeric TAGs. Model systems containing similar components and proportions to those normally found in manufactured samples and a mixture of high‐oleic sunflower oil, rapeseed oil, and fish oil were used to obtain a fatty acid composition profile in accordance with the EU regulations. For comparative purposes, some samples were prepared with high‐oleic sunflower or fish oil and others without the protein components and added Tween‐20. Quantification of total oxidized TAGs provided complete information of the oxidation state and showed clear advantages versus the other methods used, i.e., loss of PUFA and peroxide value. The results showed that the heat treatment used for sterilization did not lead to significant lipid oxidation, but the tocopherol concentration decreased significantly. The marked tocoherol losses found in protein‐free formulas together with the significantly lower tocopherol concentrations in infant formulas (80% whey in protein fraction) compared to follow‐on formulas (80% caseinate in protein ratio) showed the protective effect of the protein fraction, specially sodium caseinate. Practical applications: This study provides useful information on the utility of different methods used to evaluate oxidation in infant and follow‐on formulas. Quantification of total oxidized TAGs standed out because it is a direct and sensitive method and provides complete information at any stage of the oxidative process. Also, this study shows that important decreases of tocopherols may occur during formula processing and special cautions should therefore be taken during storage and commercialization to avoid additional antioxidant losses.     

Factors affecting the content of tocopherol in soybean oil

The state of soybeans prior to extraction affected the tocopherol content of crude soybean oils. Soybean flakes with a thickness of 0.16–0.33 mm had higher extracted oil yield but a slightly lower tocopherol content of the oils than did cracked beans and thicker bean flakes. Highmoisture content and long storage of soybeans resulted in lower tocopherol content in the crude oils, with moisture content being more important than storage time at decreasing the tocopherol content of oils. Soybean oil from stored beans with 15±1% moisture content led to a more significant decrease in the tocopherol content than did oil from stored beans with low (12%) or high (18%) moisture contents. Soybean flakes contaminated with oxidized oil had a significant effect on the decrease of the tocopherol content in crude oils. The high amount of phospholipids in crude soybean oil might result in a smaller decrease in the tocopherol content of oil during heating.     

Long term storage of soybean and cottonseed salad oils

Commercially prepared and packaged soybean and cottonseed salad oils from several different processors were evaluated periodically during storage for 12 months. Partially hydrogenated and winterized soybean oils, as well as unhydrogenated soybean salad oils, were stored in bottles and cans at 78 and 100 F. Control samples of all oils were held at 0 F during the entire test. Some lots in bottles and cans were packaged under nitrogen to improve storage stability. Agreement was good between organoleptic and oxidative evaluation of aged oils. After 26 weeks of storage at 100 F, the flavor of partially hydrogenated-winterized oils packaged under nitrogen showed a minimum loss. These same oils did not exhibit much, if any, reduction in their oxidative stability as indicated by storage peroxide values (active oxygen method). Soybean oil not protected with nitrogen demonstrated progressive flavor deterioration at 100 F. After 10 weeks of storage, the deterioration became marked and the flavor score was below 5. From limited observations, bottled oils appear to have a better stability than oils packaged in screw-cap tin cans. Hydrogenated oils packaged under nitrogen in cans had good oxidative stability, but some lowering of the flavor score was observed. Nonhydrogenated soybean oils packaged in tin cans not under nitrogen exhibited the most rapid flavor deterioration of all lots of oil investigated. Presented in part at the AOCS meeting, New York, October 1968 ARS, USDA     

Electron spin resonance spectroscopy for determination of the oxidative stability of food lipids

Evaluation of the oxidative stability of food lipids based on the tendency of formation of radicals is shown to be possible using electron spin resonance (ESR) spectroscopy and the spin-trapping technique. Induction time can be determined for mildly accelerated conditions (50°C for lipid fraction from mayonnaise enriched with fish oil), and the length of the induction time decreases during storage and γ-tocopherol depletion. The protection by ethylenediaminetetraacetic acid against initiation of lipid oxidation is also detected in the new assay. For more oxidatively stable lipids (butter, rapeseed oil, dairy spread) the mildly accelerated conditions can be used in the assay, provided that difference in signal height for fixed times replaces determination of induction time. ESR spin trapping provides a sensitive method for evaluating the oxidative stability of food lipids. Detection of radicals in the lipid as an early event in oxidation allows mild conditions to be used, and future experiments should also include sensory evaluation in relation to determination of practical shelf life.     

Oxidative stability of black cumin (Nigella sativa L.), coriander (Coriandrum sativum L.) and niger (Guizotia abyssinica Cass.) crude seed oils upon stripping

Information on stability of edible oils is important for predicting the quality deterioration of the oil during storage and marketing. Stripping of crude oils removes most of non‐triacylglycerol components, including polar lipids and phenolics. Oxidative stability of black cumin (Nigella sativa L.), coriander (Coriandrum sativum L.) and niger (Guizotia abyssinica Cass.) crude and stripped seed oils was investigated and compared. The factors influencing the oxidative stability of different seed oils were also discussed. Oil samples were stored under accelerated oxidation conditions for 21 d. The progress of oxidation at 60 °C was followed by recording the ultraviolet absorptivity and measuring the formation of oxidative products (peroxide and p‐anisidine values). Inverse relationships were noted between peroxide values and oxidative stabilities and also between secondary oxidation products, measured by p‐anisidine value and stabilities at termination of the storage. Absorptivity at 232 nm and 270 nm increased gradually with the increase in time, due to the formation of conjugated dienes and polyenes. In general, oxidative stabilities of crude oils were stronger than their stripped counterparts and the order of oxidative stability was as follows: coriander > black cumin > niger seed. Levels of polar lipids in crude oils correlated with oxidative stability. Thus, the major factor that may contribute to the better oxidative stability of crude oils was the carry‐over of their polar lipids.     

Roasted Sunflower Kernel Paste (Tahini) Stability: Storage Conditions and Particle Size Influence

Sunflower tahini faces quality problems due to the tendency of oil to exudate, causing accelerated rancidity and low marketability. In this study, the colloidal and oxidative stability of different trimodal particle size distributions of sunflower tahini (cumulative volume percentages of small, middle and large class populations of 9.61–16.67, 43.03–55.03 and 47.36–28.3) was evaluated during storage at three different temperatures. Decreasing sample particle size decreased the sunflower tahini colloidal stability. The coarsest prototype, being the most stable tahini in terms of oil separation, was included in the oxidative stability storage test together with a commercial tahini. The peroxide values of the studied sunflower tahini samples increased significantly (p < 0.05) with storage time, irrespective of storage temperature, while the p‐anisidine values showed an irregular pattern. Considering 30‐meq O₂/kg as a PV limit, the commercial tahini showed good oxidative stability as it was under this when stored 3 months at 4 °C, 2 months at room temperature and 1 month at 40 °C. The coarsest tahini sample was under the limit when stored 2 months at 4 °C, 1 month at room temperature and 2 weeks at 40 °C. Particle size was shown to be an essential parameter for controlling sunflower tahini's overall stability.     

Oxidative Stability of Microencapsulated Kenaf Seed Oil Using Co-extrusion Technology

This study investigates the effect of microencapsulation (via co‐extrusion technology using high methoxyl pectin‐enhanced alginate as a shell formulation) on the storage stability and antioxidant properties of kenaf seed oil. Microencapsulated kenaf seed oil (MKSO) and unencapsulated oil were stored at 25 °C for 28 days and at 65 °C for 24 days. The oils were then subjected to stability and quality evaluation based on peroxide, p‐anisidine, and total oxidation values, conjugated diene and triene levels, thiobarbituric acid reactive substances, free fatty acids, total phenolic content, and the radical scavenging activity assays of 2,2‐diphenyl‐1‐picrylhydrazyl and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulphonic acid). The results showed that there was a significant increase (p < 0.05) in oxidation and a significant decrease (p < 0.05) of antioxidant activity in the unencapsulated oil while oxidation changes generally occurred more slowly in MKSO. It was demonstrated that the current microencapsulation method is a feasible approach to enhance oxidative stability of kenaf seed oil.