Quality and consumption of oxidized lipids from deep-frying fats and oils in New Zealand

Samples of beef dripping and plant oil-based deep-frying fat were obtained from fast-food premises in Christchurch, New Zealand, as well as samples of deep-fried battered fish and potato chips. The fat in these samples was analyzed for level of oxidation by measuring acid value, peroxide value, polar compounds, thiobarbituric acid-reactive substances (TBARS), and conjugated dienes. The acid and peroxide value results were contradictory when compared with limits set in the New Zealand Food Regulations 1984, but the levels of polar compounds were generally below 25%, indicating that the fats were well maintained. The TBARS and conjugated diene levels were compared with those for oxidized corn oil used in a feeding trial and indicated a similar oxidation level, although the amount of fat consumed in the feeding trial would be 30–50% higher. These results show that well-maintained deep-frying fat has oxidation levels sufficient to cause elevation of plasma lipid oxidation levels as observed in a human feeding trial.     

Frying oil and fat quality measured by chemical,physical, and test kit analyses

The performance of soybean oil (SBO) and a partially hydrogenated soybean oil (PHSBO) was monitored by chemical, physical, and test kit analyses during 50 h of deep-frying of potatoes in SBO and 50 h of deep-frying of potatoes in PHSBO. The oxidative stability of SBO and PHSBO was measured by the iodine value, color index, FFA content, total polar compounds, and FA analysis of deep-frying SBO and PHSBO. SBO, with higher levels of unsaturated FA, had the faster rate of formation of geometric and positional isomers of unsaturated FA as measured by GC with standards. PHSBO performance under deep-frying conditions was significantly better than SBO with respect to iodine value, color index, and total polar compounds. The results from analyses using test kits had a good correlation with analytical parameters.     

Oxidative Stability of Conjugated Linoleic Acid Rich Soy Oil

This study was conducted to determine the oxidative stability of conjugated linoleic acid rich soy oil (CLARSO) and the effects of conjugated linoleic acid (CLA) levels on volatile oxidation products formed during CLARSO oxidation. CLARSO oxidative stability was determined by gravimetric analysis, peroxide value, headspace oxygen analysis and p-anisidine value. Volatile oxidation compounds were analyzed by solid phase microextraction–gas chromatography with a flame ionization detector and a mass spectrometer. CLA oxidation results were highly dependent on analytical methods used and oxidation parameters measured. The gravimetric study showed a CLA concentration effect on oxidation, which was not seen in the headspace oxygen depletion and peroxide value. Volatile oxidation data indicate that CLARSO had significantly higher (p < 0.05) levels of pentanal and trans-2-heptenal than the other oils, but there was no significant difference between the amounts of any volatiles present in 8 and 15% CLARSO. This suggests that oxidation was greater in CLARSO and that CLA concentration did not affect oxidation.     

Linoleic acid hydroperoxide concentration in relation to mutagenicity of repeatedly used deep-frying fats

A high-performance liquid chromatography procedure was developed to measure linoleic acid hydroperoxides (LAHPO) in 19 used, deep-frying fat samples that were screened for mutagenicity. The detection limit of the method was found to be 10 nmol of LAHPO/g of fat. In eight samples, LAHPO were not detected; levels in the other samples ranged from 17 to 267 nmol/g of fat. LAHPO were not detectable in unusued hydrogenated frying fat samples. Concentrations of LAHPO correlated positively with mutagenicity to Salmonella tester strains TA97 and TA100, in presence of S9 mix only; coefficients of correlation were, respectively, r=0.48 (p<0.05) and r=0.24 (n.s.). Without metabolic activation no significant associations were observed. These results suggest that metabolites or secondary autoxidation products of linoleic acid generated in presence of liver S9 mix may contribute to mutagenicity of some of the used deep-frying fat samples.     

Frying quality and oxidative stability of two unconventional oils

The behavior of crude Sclerocarya birrea kernel oil (SCO) and Sorghum bug (Agonoscelis pubescens) oil (SBO) during deep-frying of par-fried potatoes was studied with regard to chemical, physical, and sensory parameters, such as content of FFA, tocopherols, polar compounds, oligomer TG, volatile compounds, oxidative stability, and total oxidation (TOTOX) value. Palm olein was used for comparison. Whereas potatoes fried in SCO that had been used for 24 h of deep-frying at 175°C were still suitable for human consumption, potatoes prepared in SBO that had been used for 6 to 12 h were not, considering the sensory evaluation. In looking at the chemical and physical parameters, SBO exceeded the limits, after no later than 18 h of use, for the amount of polar compounds, oligomer TG, and FFA recommended by the German Society of Fat Sciences (DGF) as criteria for the rejection of used frying oils. In contrast to SBO, SCO oil did not exceed the limits for the content of polar compounds and oligomer TG during the frying experiment. Only the amount of FFA was exceeded; this was because the amount of FFA at the beginning of the experiment was higher than for refined oils. The results showed that both oils were suitable for deep-frying of potatoes, but remarkable differences in the time during which both oils produced palatable products were found.     

Effect of Flaxseed Meals and Extracts on Lipid Stability in a Stored Meat Product

Flaxseeds have been recently in focus due to the antioxidant capacity of some of their compounds. However, there is a lack of easily accessible information concerning their activity against lipid oxidation in food systems. Therefore, the aim of the study was to determine the effect of defatted meals (DFM) and the aqueous extracts (AFE) obtained from brown and golden flaxseeds on lipid oxidation in pork meatballs. Fatty acid composition, peroxide value (PV), thiobarbituric acid reactive substances (TBARS) and cholesterol content were monitored during 6 months of freezer storage. Cholesterol oxidation products were identified and quantified. Both DFM and AFE limited fatty acid and cholesterol oxidation during meatball storage. Their antioxidant effect depended on flax variety (brown or golden) and preparation type (DFM or AFE). Lower level of PV and TBARS, compared with the ones with AFE, were noted in meatballs with DFM. Both DFM and AFE, from the brown seed variety, protect the lipids against oxidation to a higher extent. During the storage, a cholesterol degradation was observed. AFE (particularly from the brown variety) limited changes in cholesterol content. Moreover, they stabilized fatty acid composition of stored meatballs. However, DFM efficiently inhibited cholesterol oxidation.     

Influence of blanching treatment and drying methods on the drying characteristics and quality changes of dried sardine (Sardinella gibbosa) during storage

The aim of this study is to examine the drying characteristics of blanched and unblanched sardine during indoor and open sun drying processes. Changes in temperature and relative humidity of the air during drying were recorded. The color, peroxide value (PV), thiobarbituric acid reactive substances (TBARS), free fatty acid (FFA) content, fatty acid composition, and sensory attributes of dried samples were also evaluated once a month for 5 months of storage. High drying rates were obtained in all samples at the start of drying and then decreased with increasing drying time. The highest drying rate and effective water diffusivity (D_eff) were observed in blanched sardine during open sun drying. Blanching treatment slowed down the FFA progression during product storage but adversely affected the color, PV, and TBARS content as well as sensory properties. Although sardine dried for a longer time under indoor drying conditions, it attained a stable moisture ratio that was lower than in open sun-dried samples. Indoor drying produced a quality stable product with less lipid oxidation and the desired moisture content, higher polyunsaturated fatty acids and sensory properties. Blanching treatment negatively affected the fish quality and is therefore not recommended for commercial sardine drying.     

Impact of Frying on Changes in Clam (Ruditapes philippinarum) Lipids and Frying Oils: Compositional Changes and Oxidative Deterioration

The current study shows the compositional changes and oxidation development of clam (Ruditapes philippinarum, R. philippinarum) lipids and frying oils when subjected to different processing conditions. Parameters measured include acid value, peroxide value (POV), thiobarbituric acid-reactive substances (TBARS), total oxidation (TOTOX), lipid classes, fatty acid composition, phosphatidylcholine (PC), and phosphatidylethanolamine (PE) contents together with major glycerophospholipid (GP) molecular species. Deep-fat frying increased triacylglycerol (TAG) content and decreased the contents of PC, PE, and GP molecular species in clam in a time-dependent manner. Meanwhile, minor amounts of free fatty acids, diacylglycerols, monoacylglycerols, and polar lipids were detected in frying oils, indicating lipid migration between the clam and frying oils. The time-dependent increase of POV, TBARS, and TOTOX in fried clams and frying oils with concurrent reduction of docosahexenoic acid and eicosapentaenoic acid indicates extensive oxidative degradation of clam lipids. Moreover, the moisture-rich clam aggravated the deterioration of frying oils. Consequently, deep-fat frying significantly altered the lipid profile and decreased the nutritional value of clams.     

食用油高温煎炸质变过程的研究

通过对菜籽油、花生油、豆油高温煎炸前后的色泽、吸光度、酸价、过氧化值、碘值的比较,分析说明油脂高温煎炸前后这些理化指标的变化规律。并从碘值的降低程度得出花生油、菜籽油适合煎炸使用。此研究对人们直观认识经高温煎炸后的食用油腐化程度具有指导意义。     

Oxidative Stability of Liposomes Composed of Docosahexaenoic Acid-Containing Phospholipids

Oxidative stability of liposomes made of (Docosahexaenoic acid) DHA-containing phosphatidylcholine (PC) was examined during preparation and storage. After preparation of the liposomes, the concentration of primary (conjugated dienes) and secondary oxidation products (Thiobarbituric acid-reactive substances, TBARS) were significantly higher compared to the initial value. During cold storage, formation of conjugated dienes and TBARS remained more or less constant in large unilamellar vesicles (LUV), whereas in mulitilamellar vesicles (MLV) they were seen to increase over a period of 21 days. Evaporation of solvent traces from a lipid film should preferably be done under nitrogen as vacuum evaporation was found to increase oxidation of the phospholipid.     

Veränderungen der Fette unter Fritierbedingungen und deren analytische Erfassung Chemische Veränderungen der Fette beim Fritieren

Alterations of Fats Under Conditions of Deep-Frying and Their Analytical Detection: Artefacts Formation in Frying Fats During Deep-Frying During deep-frying the fats decompose with the formation of volatile, monomeric and polymeric compounds. Their amount and chemical structure depends on the fat blend, the temperature, the frying time, the frying good, and in a high degree on the accessibility of oxygen. As we have shown a quantitative determination of polymeric material in frying fats is possible using gel permeation chromatography. However, gel permeation chromatography determines the size of the molecules only and does not destinguish between various degrees of oxidation. For his purpose we apply liquid chromatography on silica gel which separates various fractions according to their polarity. In combination with a “moving wire” and flame ionisation detector a semi-quantitative evaluation of the amount of polar material in heated fats in possible. Liquid chromatography is applicable for preparative purposes and enables the non-destructive isolation of sufficient material for feeding experiments.     

Chemical and physical analyses and sensory evaluation of six deep-frying oils

The performance of three high-oleic canola oils with different levels of linolenic acid [low-linolenic canola (LLC), medium-linolenic canola (MLC), and high-linolenic canola (HLC)], a medium-high-oleic sunflower oil, a commercial palm olein and a commercial, partially hydrogenated canola oil, was monitored by chemical and physical analyses and sensory evaluation during two 80-h deep-frying trials with potato chips. Linolenic acid content was a critical factor in the deep-frying performance of the high-oleic canola oils and was inversely related to both the sensory ranking of the food fried in the oils and the oxidative stability of the oils (as measured by color index, free fatty acid content, and total polar compounds). LLC and sunflower oil were ranked the best of the six oils in sensory evaluation, although LLC performed significantly better than sunflower oil in color index, free fatty acid content, and total polar compounds. MLC was as good as palm olein in sensory evaluation, but was better than palm olein in oxidative stability. Partially hydrogenated canola oil received the lowest scores in sensory evaluation. High-oleic canola oil (Monola) with 2.5% linolenic acid was found to be very well suited for deep frying.     

Antioxidant Activity of Soybean Oil Containing 4-Vinylsyringol Obtained from Decarboxylated Sinapic Acid

4-Vinylsyringol was produced by decarboxylation from sinapic acid. To evaluate the antioxidant activity of 4-vinylsyringol, 500 ppm of 4-vinylsyringol, sinapic acid, or α-tocopherol was added to soybean oil and the oxidation processes were monitored by the peroxide value (PV), the thiobarbituric acid reactive substances value (TBARS) assay, and ¹H-NMR spectroscopy. The results obtained by PV and TBARS indicated that soybean oil containing 4-vinylsyringol (SBO-VS) showed the highest oxidative stability. ¹H-NMR analysis also showed concurring results. After 19 days of oxidation, the degradation rates of linoleic acid (4.2 %) and linolenic acid (4.4 %) in SBO-VS were significantly lower than those in other oils. Secondary oxidation products (i.e. aldehydes) were undetectable in SBO-VS by ¹H NMR, whereas concentrations of such compounds in soybean oils containing α-tocopherol or sinapic acid were 38.0 ± 0.4 and 2.75 ± 0.2 mM oil, respectively. In addition, synergistic antioxidant effect between any two antioxidants was not observed.     

Oxidation of sunflower oil during storage

Effects of temperature and oxygen concentration on oxidative deterioration during storage of crude sunflower oils, obtained by pressing and solvent extraction, were studied. Oxidation was monitored through several analytical and chromatographic methods that determine chemical and physical changes or analyze specific oxidation compounds at different stages of the process: peroxide value, p-anisidine value, free fatty acids, weight gain, total content and distribution of polar compounds, and composition of fatty acids. Extracted oil showed a higher oxidative stability than pressed oil. Oxidative deterioration was strongly dependent on temperature, oxygen availability, and the ratio of exposed surface to sample volume. A kinetic model of two series reactions was developed to represent oxidation rate in terms of peroxide value, the reaction rate constants and their temperature dependence being evaluated by nonlinear regression. Finally, good correlations between the percentage of polar compounds or oxidized triglyceride monomers and the peroxide value were found.     

Effect of oil replenishment during deep-fat frying of frozen foods in sunflower oil and high-oleic acid sunflower oil

Frying stability of sunflower oil (SO) with 23% oleic acid and 61% linoleic acid, and of high-oleic acid sunflower oil (HOSO) with 74% oleic acid and 13% linoleic acid was studied during 20 discontinuous deep-fat fryings of various frozen foods, with or without frequent replenishment of the used oil with fresh oil. Alterations of both oils were measured by column, gas-liquid and high-performance size-exclusion chromatography. Total polar content and compounds, related to thermoxidative changes, and diacylglycerides, related to hydrolytic changes, increased in all oils during frying but reached higher levels in SO than in HOSO. Nevertheless, the increased levels of diacylglycerides observed may result from the frozen potatoes prefried in palm oil. Oleic acid in HOSO and linoleic acid in SO significantly decreased, but the fatty acid modifications that occurred during the repeated fryings were not only related to thermoxidative alteration but also to interactions between the bath oil and the fat in the fried products. Data from this study also indicated that HOSO performed more satisfactorily than SO in repeated fryings of frozen foods. Moreover, frequent addition of fresh oil throughout the deep-frying process minimized thermoxidative and hydrolytic changes in the frying oils and extended the frying life of the oils.     

Capillary gas chromatographic analyses of headspace volatiles from vegetable oils

Eight different vegetable oils obtained commercially were analyzed for volatiles by capillary gas chromatography (GC). Volatiles generated in a GC static headspace sampler at 180 C were injected automatically onto a chemically bonded capillary column. Only a small number of GC peaks of low intensity were observed in the fresh samples, which varied in peroxide values from 0.2 to 3. Several major peaks were evident in the oils aged eight and 16 days at 60 C with peroxide values ranging from 16 to 65. Thirty-four GC peaks were identified on the basis of relative retention time of reference compounds and on the basis of gas chromatography-mass spectrometry (GC-MS). Volatile compounds identified were those expected from the autoxidation of principal unsaturated fatty acid components of each vegetable oil tested. The relative concentrations of volatile components increased with the level of oxidation as determined by peroxide value. Presented at the AOCS Meeting in Chicago, May 1983.     

Effect of Different Frying Methods on the Total <Emphasis Type="Italic">trans</Emphasis> Fatty Acid Content and Oxidative Stability of Oils

The main objective of this study was to determine the effect of different frying oils and frying methods on the formation of trans fatty acids and the oxidative stability of oils. Sunflower, canola and commercial frying oils, the most commonly used oils for frying potatoes in the fast food industry, were used as the frying medium. The value for total polar compounds was highest when commercial frying oil was used in the microwave oven (22.5 ± 1.1). The peroxide value, as an indicator of oil oxidation, was lowest for microwave oven frying (2.53 ± 0.03). The K₂₃₂ and K₂₇₀ values were 0.41 ± 0.04 and 0.18 ± 0.02, respectively, for commercial frying oil in the microwave oven. The lowest free fatty acid content was recorded for the commercial frying oil used in the deep‐fat fryer at 190 °C. The highest iodine value was measured for sunflower oil used in the deep‐fat fryer (148.14 ± 0.07), indicating a greater degree of unsaturation. The lowest trans fatty acid value was recorded for sunflower oil in the microwave oven (0.17 ± 0.05), with a higher overall amount of total trans fatty acids observed for oils after frying in the electrical deep‐fat fryer compared to the microwave. Sunflower oil was favourable for both frying methods in terms of the trans fatty acid content.     

Low‐density lipoprotein is oxidized by phospholipase A2 and lipoxygenase in xanthoma lesions

Oxidized LDL has been obtained by incubation with copper ions (Cu‐LDL) or various kinds of cells. LDL incubated with xanthoma tissues (x‐LDL) is considered a model of in vivo oxidized LDL that has extravasated into xanthoma lesions. To investigate the mechanism of x‐LDL formation, we studied the effects of various enzyme inhibitors or antioxidants on the oxidation process of LDL. Thiobarbituric acid‐reactive substance (TBARS) levels, electrophoretic mobility and spectrophotometric pattern of the oxidized LDL were examined. Antioxidants suppressed TBARS formation in both x‐LDL and Cu‐LDL. Enzyme inhibitors inhibited TBARS levels in x‐LDL, but not in Cu‐LDL. All the enzyme inhibitors and antioxidants, except for the cyclooxygenase inhibitor, inhibited the anodic electrophoretic mobility of x‐LDL. The anodic electrophoretic mobility of Cu‐LDL was suppressed only with antioxidants. Spectrophotometry indicated that an increase in the absorbance at 240 nm was observed in Cu‐LDL, but not in x‐LDL. x‐LDL oxidation is primarily catalyzed by phospholipase A₂, and subsequently generated polyunsaturated free fatty acids propagate the peroxidation. Fatty acid hydroperoxides conjugated with dienes are not synthesized in x‐LDL. On the other hand, non‐enzymatic oxidants, such as superoxide anion and hydroxyl radicals generate Cu‐LDL with diene‐conjugated fatty acid hydroperoxides.     

Chemical analysis of ozonized theobroma fat

Ozonized theobroma fat is used as raw material in the manufacture of pessaries and cosmetic creams. Ozonization of theobroma fat with water was carried out at different applied ozone dosages, and the resultant PV, acid value, iodine value, total hydroperoxide content, and FA content were determined. PV and total hydroperoxide content showed a notable increase with applied ozone dosage up to 35.7 mg/g. Acid value varied slightly from 4.1 to 9.9 mg KOH/g, and the iodine value fell to zero. PV and total hydroperoxide content increased slightly with a higher applied ozone dosage. The comparison of total hydroperoxide measurement using ferrous oxidation in xylenol orange assay and traditional iodometric assay for PV determination showed a significant linear correlation. Small amounts of oleic acid were found in ozonized theobroma fat samples with iodine value equaling zero, which demonstrated that iodine value determination is an inexact assay. During ozonization of theobroma fat, an increase in acid value of 18.9-fold with respect to the initial value was observed owing to decomposition of peroxide.     

Stability Profile of Fatty Acids in Yak (<Emphasis Type="Italic">Bos grunniens</Emphasis>) Kidney Fat During the Initial Stages of Autoxidation

Previously, we have shown that the fatty acid composition of yak kidney is of reasonable value and is suitable for further development of possible commercial products. Changes in the fatty acids of yak kidney fat during the initial stages of storage have been investigated. The full period of autoxidation was determined by peroxide value (PV) and thiobarbituric acid-reactive substances (TBARS) at 15 ± 1 °C for up to 70 days. The stability profile of the fatty acids identified by gas chromatography demonstrated that saturated fatty acids increased from 49.68 to 55.96% and that polyunsaturated fatty acids and monounsaturated fatty acids decreased from 10.73 to 6.95% and from 37.85 to 28.22%, respectively. Amounts of all the functional fatty acids except conjugated linoleic acid and linoleic acid, started to decrease after 10 days of storage. These results indicated that the initial stage of autoxidation occurred during the first 25 days of storage. It is suggested that development of potential commercial products should be accomplished within ten days, because the functional fatty acids started to decrease after this period of storage. In addition, the good correlation between PV/TBARS values and changes of individual fatty acids could be used as an indicator to monitor the changes of the functional fatty acid during the development process of yak kidney fat-related commercial products.