Stability of furanoid fatty acids in soybean oil

Analysis of the positional distribution of the furanoid fatty acids, 10,13-epoxy-11,12-dimethyloctadeca-10, 12-dienoic acid (F20) and 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoic acid (F22), in soybean oil (SBO) indicated that they were preferentially esterified with the primary-OH groups of glycerol molecules. Hydrogenation of SBO reduced the concentrations of F20 and F22 somewhat. During exposure of SBO to daylight, F20 and F22 were completely degraded within two days, whereas linoleic acid and linolenic acid were not affected. β-Carotene inhibited both the degradation of the furanoid fatty acids and their oxidation to the odorant 3-methyl-nonane-2,4-dione (MND), which contributes strongly to the light-induced off-flavor of SBO. A model experiment indicated that two days of light exposure of SBO, followed by filtration through silica gel and further refining, prevented the formation of MND during subsequent storage of the oil. Presented at the 86th Annual Meeting of the American Oil Chemists’ Society, San Antonio, Texas, May 7–11, 1995.     

Detection of Furanoid Fatty Acids in Soya-Bean Oil – Cause for the Light-Induced Off-Flavour

The following furanoid fatty acids were detected in soya-bean oil (SBO), wheat germ oil, rapeseed oil and corn oil: 10,13-epoxy-11-methyloctadeca-10,12-dienoic acid(I),10,13-epoxy-11,12-dimethyloctadeca-10,12-dienoid acid (II), 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoic acid (III). A model experiment indicated that II and III were quickly photooxidized with formation of the intense flavour compound 3-methyl-2-4-nonanedione (MND) as secondary product. MND causes the light-induced off-flavour of SBO. A method for the quantification of the three furanoid fatty acids in vegetable oils was developed. The amounts of II and III were relatively high (0.02-0.04%) in unprocessed and refined SBO and in one sample of wheat germ oil and quite low (0.0015–0.0035%) in corn oil and rapeseed oil. The furanoid fatty acids I, II and III were absent on olive and sunflower oils.     

Effects of hydrogenation and additives on cooking oil performance of soybean oil

Soybean oil was continuously hydrogenated in a slurry system to investigate the effects of linolenate content and additives on cooking oil performance. Room odor evaluations carried out on oils heated to 190 C after frying bread cubes showed that the oils hydrogenated with Cu catalyst to 2.4% linolenate (Cu-2.4) and with Ni catalyst to 4.6 linolenate (Ni-4.6) had a significantly lower odor intensity score than the unhydrogenated soybean oil (SBO). Other hydrogenated oils (Cu-0.5 and Ni-2.7) were not significantly better than SBO. Oil hydrogenated with Ni (Ni-0.4) scored poorly because of its strong “hydrogenated-paraffin” odor. The performance of all partially hydrogenated oils (2.4, 2.7 and 4.6% linolenate) was improved by adding methyl silicone (MS), but the most hydrogenated oils (0.5 and 0.4% linolenate) were not improved. Although with tertiary butyl hydroquinone (TBHQ) no improvement was obtained, with the combination of TBHQ + MS all odor scores were lower, indicating a synergistic effect. Evaluations of bread cubes after intermittent heating and frying showed that the breads fried in most hydrogenated oils (Ni-0.4, Cu-2.4 and Ni-2.7) were rated significantly better in flavor quality than breads fried in SBO. The bread cubes fried in MS-treated oils had significantly higher flavor quality scores than breads fried in SBO or SBO containing TBHQ. Dimer analyses by gel permeation chromatography and color development after heat treatments also did not correlate with sensory analyses.     

The effect of deodorization prior to hydrogenation on the development of hydrogenation odor in fats

Summary The direct precursors of hydrogenation odor are removed by steam deodorization. The primary precursors remain in the oil since the reversion of deodorized oil by autoxidation in the presence of light and heat forms certain compounds which again give rise to hydrogenation odor. Thus, in order to prevent the formation of hydrogenation odor, the deodorized oil must be protected from the effects of heat, light, and autoxidation, and hydrogenated in a unit which is free of residues from previous hydrogenations that were not carried out in a manner to prevent the formation of odor. The best results were obtained with palladium catalyst at temperatures below 90°C. The high flavor stability of hydrogenated soybean oil which was deodorized and protected from autoxidation prior to hydrogenation indicates that certain compounds responsible for hydrogenation flavor may also be involved in flavor reversion. Presented at the 46th annual meeting, American Oil Chemists’ Society, New Orleans, La., April 18–20, 1955.     

Quantitation of flavor volatiles in oxidized soybean oil by dynamic headspace analysis

A dynamic headspace procedure was developed for isolating the volatiles from oxidized soybean oil and trapping them on an adsorbent under conditions that gave minimal decomposition of hydroperoxides (50°C for 30 min at a helium flow of 75 mL/min). The volatiles were desorbed from the adsorbent and separated by gas chromatography (GC) on a methyl silicone capillary column. Equations were derived from theoretical considerations that allowed the actual concentration of each flavor component in the oxidized oil to be calculated from the area of the GC peaks. The reliability of the method and calculations was demonstrated by recovery experiments. The concentration of 2-heptanone in a mineral oil emulsion, equivalent in flavor intensity to each component, was calculated and summed to estimate the overall flavor intensity of the samples. The overall estimations were compared with the concentrations of 2-heptanone observed to be equivalent in flavor intensity to the oxidized oil samples when these were tasted in emulsion. The concentrations of individual components calculated from the headspace volatiles data were all present at concentrations below their flavor thresholds, and the simple sum of the intensities of their flavors generally accounted for less than half of the flavor intensities of the oil samples. The differences in the headspace and sensory analyses might be attributed to the flavor of the unoxidized oil, synergistic interactions, and/or the presence of unmeasured flavors components.     

A review of soybean oil reversion flavor

Crude soybean oil has a characteristic “greenbeany” flavor, which during refining, bleaching and deodorization is eliminated to produce a bland tasting, light colored oil. However, flavor returns during storage and has been characteristically called the “reversion flavor” of soybean oil. This deleterious characteristics flavor has influenced the utilization of soybean oil and its fatty acids. Several theories for the cause of reversion flavor include: (a) oxidation of linolenic acid; (b) oxidation of isolinoleic acid of the 9,15-diene structure; (c) phosphatide reactions; (d) unsaponifiables; and (e) oxidative polymers. References are presented that support or contradict these theories. Recent publications concerning the isolation and characterization of the components of reversion flavor indicate slight oxidation of the fatty acids is the major cause. Techniques that are effective in increasing the flavor stability of soybean oil are presented.     

Flavor stability of soybean oil. 1. The role of the non-saponifiable fraction

Summary It has been found that the addition of the nonsaponifiable extract of hydrogenated soybean oil to either refined cottonseed oil or refined peanut oil caused these oils to develop odors and flavors characteristic of reverted soybean oil. The non-saponifiable material from linseed oil did not produce a similar effect. When the non-saponifiable extract of hydrogenated soybean oil was added to mineral oil, a sweet, syrupy odor and flavor developed. By selective absorbents it was possible to produce a much greater improvement in hydrogenated than in unhydrogenated soybean oil. These observations are discussed in terms of their relationship to the various theories on the mechanism of reversion.     

Odor Significance of the Volatiles Formed During Deep-Frying With Palm Olein

Palm olein is currently considered to be one of the best options for deep-frying, but as with any other edible oil, during frying, deteriorative reactions produce off-flavor compounds that reduce the oil sensory quality. This study assessed the odor significance of the volatiles formed during 136 h of deep-frying a chicken product in palm olein, aiming to identify potential markers of the oil sensory quality during frying. The volatiles were isolated by solid phase microextraction, and identified by GC–MS. Trained judges assessed the odor intensity and quality of the volatiles formed during frying, evaluating the GC effluents through a GC–olfactometry technique called OSME. Two hundred and eight volatiles were detected by GC/MS in the palm olein after 136 h frying. Of these, heptanal, t-2-heptenal, decanal and t-2-undecenal were identified as potential markers of the sensory quality of palm olein during frying. Hexanal, pentanal and pentane, usually associated with lipid oxidation, showed no odor impact in the GC effluents, and were thus proven not to be good markers of the sensory quality of palm olein when used for a long frying period.     

Effects of antioxidants,methyl silicone and hydrogenation on room odor of soybean cooking oils

Room odor characteristics produced by heated soybean oil (SBO) and soybean oils hydrogenated with copper (CuHSBO) and nickel (NiHSBO) catalysts were evaluated by a trained panel. Oils were intermittently heated to 190 C for total heating periods of 5, 15 and 30 hr. Oil additives investigated included methyl silicone (MS), tertiary butylhydroquinone (TBHQ) and a polymeric antioxidant in various combinations with citric acid (CA). In room odor tests directly comparing SBO, CuHSBO and NiHSBO, panelists rated the hydrogenated oils as having significantly less odor intensity than the SBO. The combination of CA+MS had the greatest effect in lowering odor intensity of the heated oils, followed by the mixture of CA+MS+TBHQ. The low odor intensity of the MS-treated oils remained fairly constant throughout the tests, while the higher intensity associated with all the other additive-treated oils decreased with increasing heating times, possibly as the result of formation of more volatile decomposition products in the initial heating stages. Methyl silicone had the strongest effect of any additive in decreasing objectionable room odors in the oils. Partially hydrogenated SBO treated with up to 5 ppm of MS produced cooking oils with low room odor intensity and low color development during prolonged heating.     

Effect of Resin Types and Antioxidants on Release of Off-Flavor From HDPE Bottles

The effects of three types of high-density polyethylene (HDPE) resins (A, B, and C) and three antioxidants (vitamin E, Irganox 1010, and BHT) on the release of off-flavor (including off-odor and off-taste) from blow-molded HDPE bottles were investigated using sensory analysis and gas chromatography/mass spectrometry (GC/MS) analysis. Overall the sensory study showed that off- flavor intensity was affected by both resin type and antioxidant. Resin A bottles yielded less off-flavor compared to resin B or C bottles. Vitamin E containing bottles yielded less off-flavor compared to Irganox 1010 or BHT containing bottles for resins A and B; however, the antioxidants have almost the same effect on resin C. The GC/MS study identified more than 60 volatile compounds released from the bottles, ranging from C₅ to C₂₀, which belonged to the groups of n-alkane, 1-alkene, aldehyde, ketone, phenolic, olefin, and paraffin—among them aldehydes and ketones were the most important due to their very low odor thresholds. Resin A bottles yielded less aldehyde and ketone compared to resin B or C bottles. Vitamin E containing bottles yielded less aldehydes and ketones compared to bottles containing Irganox 1010 or BHT. There was a general consistency between the sensory and GC/MS data. The aldehyde and ketone concentration was linearly correlated reasonably well to odor (R ² = 0.78) and taste scores (R ² = 0.67). Another study was also conducted, which shows vitamin E has smaller reduction in melt flow index due to blow molding compared to Irganox 1010 or BHT.     

Natural refining of extruded-expelled soybean oils having various fatty acid compositions

Simple, low-capital-investment oil refining techniques, which may also meet the needs of natural or organic food industries, were explored to process extruded-expelled (E-E) soybean oils with various fatty acid compositions. Most settled E-E oils are naturally low in phosphatides (<100 ppm phosphorus) and were easily water degummed to low phosphorus levels (<55 ppm). Free fatty acids were reduced to 0.04% by adsorption with 3% Magnesol^®. Magnesol reduced residual phosphorus contents to negligible levels. This material also adsorbed primary and secondary oil oxidation products. Our adsorption refining procedure was much milder than conventional refining, as indicated by little formation of primary and secondary lipid oxidation products and less loss of tocopherol. The remaining challenge to effective natural refining is the removal of off-flavor components. Our adsorption treatment reduced the natural flavor of soybean oil but flavor was still present, probably too strong for many consumers. Polyunsaturated oils oxidized more easily than did the other types of oils; therefore, precautions should be taken when refining such oils. High-oleic soybean oil, on the other hand, had excellent oxidative stability and better flavor characteristics after degumming and adsorption with Magnesol compared with other oils.     

Electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. Sensory and compositional characteristics of low Trans soybean oils

Soybean oils were hydrogenated either electrochemically with Pd at 50 or 60°C to iodine values (IV) of 104 and 90 or commercially with Ni to iodine values of 94 and 68. To determine the composition and sensory characteristics, oils were evaluated for triacylglycerol (TAG) structure, stereospecific analysis, fatty acids, solid fat index, and odor attributes in room odor tests. Trans fatty acid contents were 17 and 43.5% for the commercially hydrogenated oils and 9.8% for both electrochemically hydrogenated products. Compositional analysis of the oils showed higher levels of stearic and linoleic acids in the electrochemically hydrogenated oils and higher oleic acid levels in the chemically hydrogenated products. TAG analysis confirmed these findings. Monoenes were the predominant species in the commercial oils, whereas dienes and saturates were predominant components of the electrochemically processed samples. Free fatty acid values and peroxide values were low in electrochemically hydrogenated oils, indicating no problems from hydrolysis or oxidation during hydrogenation. The solid fat index profile of a 15∶85 blend of electrochemically hydrogenated soybean oil (IV=90) with a liquid soybean oil was equivalent to that of a commercial stick margarine. In room odor evaluations of oils heated at frying temperature (190°C), chemically hydrogenated soybean oils showed strong intensities of an undesirable characteristic hydrogenation aroma (waxy, sweet, flowery, fruity, and/or crayon-like odors). However, the electrochemically hydrogenated samples showed only weak intensities of this odor, indicating that the hydrogenation aroma/flavor would be much less detectable in foods fried in the electrochemically hydrogenated soybean oils than in chemically hydrogenated soybean oils. Electrochemical hydrogenation produced deodorized oils with lower levels of trans fatty acids, compositions suitable for margarines, and lower intensity levels of off-odors, including hydrogenation aroma, when heated to 190°C than did commercially hydrogenated oil.     

Addition of ferulic acid,ethyl ferulate,and feruloylated monoacyl- and diacylglycerols to salad oils and frying oils

To determine antioxidative effects of ferulic acid and esterified ferulic acids, these compounds were added to soybean oils (SBO), which were evaluated for oxidative stability and frying stability. Additives included feruloylated MAG and DAG (FMG/FDG), ferulic acid, ethyl ferulate, and TBHQ. After frying tests with potato chips, oils were analyzed for retention of additives and polar compounds. Chips were evaluated for hexanal and rancid odor. After 15 h frying, 71% of FMG/FDG was retained, whereas 55% of ethyl ferulate was retained. TBHQ and ferulic acid levels were 6% and <1%, respectively. Frying oils with ethyl ferulate or TBHQ produced significantly less polar compounds than SBO with no additives. Chips fried in SBO with TBHQ or ferulic acid had significantly lower amounts of hexanal and significantly less rancid odor after 8 d at 60°C than other samples. Oils were also aged at 60°C, and stability was analyzed by PV, hexanal, and rancid odor. Oils with TBHQ or FMG/FDG had significantly less peroxides and hexanal, and a lower rancid odor intensity than the control. FMG/FDG inhibited deterioration at 60°C, whereas ethyl ferulate inhibited the formation of polar compounds in frying oil. Ferulic acid acted as an antioxidant in aged fried food. TBHQ inhibited oil degradation at both temperatures. Presented at the 94th AOCS Meeting & Expo, Kansas City, MO, May 4–7, 2003.     

Furanoid Fatty Acids and Lipids

The furanoid fatty acids and furanoid lipids are reviewed, present in nature in testes and liver of many fishes, or produced through autoxidation or photo-oxidation of linoleic and linolenic acids. Some recent working hypotheses are examined and analyzed about the bio-synthesis of furanoid fatty acids in fishes.     

Mid-Oleic/Ultra Low Linolenic Acid Soybean Oil: A Healthful New Alternative to Hydrogenated Oil for Frying

To determine the frying stability of mid-oleic/ultra low linolenic acid soybean oil (MO/ULLSBO) and the storage stability of food fried in it, tortilla chips were fried in MO/ULLSBO, soybean oil (SBO), hydrogenated SBO (HSBO) and ultra low linolenic SBO (ULLSBO). Intermittent batch frying tests were conducted up to 55 h of frying, and then tortilla chips were aged up to 4 months at 25 °C. Frying oils were analyzed for total polar compounds to determine the frying stability of the oil. Tortilla chips were analyzed for hexanal as an indicator of oxidative deterioration and by sensory analysis using a trained, experienced analytical panel. Results showed no significant differences between the total polar compound levels for MO/ULLSBO and HSBO after 55 h of frying, indicating a similar fry life. However, total polar compound levels for ULLSBO and SBO were significantly higher than for either MO/ULLSBO or HSBO, indicating a lower oil fry life. Hexanal levels in aged tortilla chips fried in SBO were significantly higher than in chips fried in any of the other oils. Tortilla chips fried in MO/ULLSBO and HSBO had significantly lower hexanal levels than in chips fried in ULLSBO. A sensory analysis of rancid flavor intensity showed similar trends to those for hexanal formation. The chips fried in SBO had the highest rancid flavor intensity, with significantly lower hexanal levels in chips fried in HSBO and MO/ULLSBO. Based on these results, MO/ULLSBO not only had a good fry life but also produced oxidatively stable fried food, and therefore would be a healthful alternative to HSBO. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

An emulsion method for the sensory evaluation of edible oils

The flavor intensity of soybean oils was evaluated in emulsions stabilized with gum acacia. A 10-point scale was used with a blank to establish the bland end of the scale and a standard diacetyl solution to establish a point near midscale. Tasting oils in emulsion gave significantly different scores than tasting oil directly. Evaluation in emulsion decreased panel error for poor quality oils but not for very bland oils. At least six samples could be tasted in emulsion without casusing panel fatigue or reducing accuracy. The concentration of oil in the emulsion could be adjusted to increase sensitivity to weak flavors or improve the evaluation of intensely flavored oils. Soybean oils containing various amounts of linolenic acid were evaluated by the emulsion method, and those with lesser amounts of linolenic acid were shown to be more stable. A gas Chromatographic total volatile method was shown to correlate fairly well with sensory evaluation of oils tasted in emulsions under conditions where both flavors scores and total volatiles changed significantly with time. Journal Paper no. J-10442 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project no. 2143.     

Minor components responsible for flavor reversion of soybean oil

Edible refined, bleached and deodorized (RBD) soybean oil was fractionated by silicic acid column chromatography to identify minor components responsible for flavor reversion. Minor components from oil eluted with diethyl ether/n-hexane (1:1) were compared with those from corn and canola oils. All vegetable oils contain free fatty acids, diglycerides and sterols as major ingredients in this fraction. However, unusual triglycerides consisting of 10-oxo-8-octadecenoic acid and 10-and 9-hydroxy octadecanoic acids were detected in RBD and crude soybean oils.