Emission of Volatile Aldehydes from DAG-Rich and TAG-Rich Oils with Different Degrees of Unsaturation During Deep-Frying

The purpose of the present study was to compare the emission of volatile aldehydes from diacylglycerol-rich oils (DAG-OILs) and triacylglycerol-rich oils (TAG-OILs) with different degrees of unsaturation of fatty acid moieties during the deep-frying of sliced potatoes. To examine the effect of fatty acid composition, four kinds of oils with different fatty acid compositions were selected: rape seed (RS); sunflower oil as a high oleic (HO); safflower oil as high linoleic (HL); and, perilla oil as high linolenic (HLn) oils. The emissions of volatile aldehydes were determined during the deep-frying of sliced potatoes by using the above fresh test oils or deteriorated RS oils. The statistical analysis showed no significant difference in volatile aldehyde emission and profile between the DAG-OIL and TAG-OIL with the fatty acid composition of RS, HL, and HLn. Although a statistically significant difference was noted in the volatile aldehyde emission between the DAG-OIL and TAG-OIL with HO, this difference was extremely small when compared to the variations found in the oils with four types of fatty acid composition. Finally, no difference was found in the volatile aldehyde emissions between the deteriorated DAG-OIL and TAG-OIL, although volatile aldehyde emissions increased with frying time. In addition, the acrylamide contents in potato chips prepared with RS–DAG or RS–TAG were at comparable levels.     

Deterioration of diacylglycerol‐ and triacylglycerol‐rich oils during frying of potatoes

The stabilities of a commercial diacylglycerol‐rich oil (DAG) and a salad oil (TAG) that had been prepared from a mixture of rapeseed and soybean oils were compared while frying potatoes at 180 °C for 3 h. The representative chemical and physical characteristics of the oils were assessed before and after frying, together with the amount of volatile aldehydes in the exhaust of frying. Among the deterioration indications, the carbonyl value, polymer content, and residual polyunsaturated fatty acid content were similar and not significantly different between the TAG and DAG. On the other hand, the characteristics relating to free fatty acids, i.e. the acid value and emission of chemiluminescence at 100 °C, were greater and the smoke and flash points were lower in the DAG than in the TAG. An irritating odor was generated from the DAG after 1 h of frying and got stronger as frying continued. These results suggested that DAG more easily forms free fatty acids under frying conditions than TAG.     

Nutritional characteristics of DAG oil

Excess calorie intake in industrialized countries has prompted development of fat substitutes and other lower-calorie dietary items to enhance health. DAG cooking oils, with a 1,3 configuration, taste and have the texture of commonly used TAG cooking oils. Because they are not hydrolyzed to 2-MAG in the gut, the absorption and metabolism of DAG oil differs from that of TAG. Among the physiological differences are lower postprandial lipemia and an increased proportion of FA being oxidized instead of stored. Preliminary studies suggest that these differences in energy partitioning between DAG and TAG may be usefully exploited to reduce the amount of fat stored from cooking oil and oil components of food items. Over 70 million bottles of DAG oil have been sold in Japan since its introduction in February 1999, and the product is being test-marketed in the United States. It is hoped that wider use of DAG oil may provide one additional means of preventing obesity.     

Palm olein quality parameter changes during industrial production of potato chips

New legislation introduced in South Africa for the quality of used frying oils has resulted in the need to identify quicker, more suitable methods that correlate well with results from two official methods, namely, total polymerized glycerides and total polar components. Oil and product samples were taken at regular intervals during a commercial frying process in palm olein. Oil samples were analyzed for a number of different quality parameters viz. tocopherol content, dielectric constant, total polymerized glycerides, total polar components, tertiary butylhydroquinone (TBHQ) content, anisidine value, Rancimat induction period, and free fatty acid content, and the results statistically compared to results from official methods. Oil was expressed from product stored under accelerated conditions and analyzed for the same quality parameters. Fried product was also subjected to sensory evaluation to measure the degree of oil deterioration and sensory preference. The frying trial was successfully executed with refined, bleached, and deodorized palm olein and the frying oil used to a free fatty acid (FFA) content of 0.41%. Oil and product sampling were done at different FFA value levels. Frying oil quality was verified at the onset of the trial and at regular intervals. The frying oil total polar component value increased to approximately half of the limit set by the official regulation. This point was reached mainly due to the high starting value of the fresh oil. Frying oil total polymerized glycerides increased from below 1% to 2.1%. This increase is negligible when compared to the general trend for polyunsaturated oils. The alternative laboratory methods used for predicting oil quality can be rated as follows: total tocopherol content >dielectric constant >FFA >TBHQ content >anisidine value >Rancimat induction period. The first three methods correlated well with total polar component levels and it is recommended that the dielectric constant and FFA measurements be applied for monitoring oil condition during frying. It is possible that viscosity changes could be used for the monitoring of polyunsaturated frying oils. Evaluation of oil extracted from product revealed a negligible effect of non-oil components on oil quality parameters. The same was observed when product was stored at −10°C and at 37°C.     

Evaluation of medium polarity materials isolated from fried edible oils by RP‐HPLC

Some frying by‐products of medium polarity called medium polarity materials (MPMs) were isolated by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) from three different cooking oils used for frying during the domestic successive deep‐frying of potatoes. The cooking oils investigated were virgin olive oil, sunflower oil and a vegetable shortening oil. The relative RP‐HPLC increments of the MPM fractions showed a significant correlation to the total polar material and to the polymerised triacylglycerol increment. They could be used as a new method for the assessment of fried oil deterioration. The capillary gas chromatography/mass spectrometry analysis revealed two main groups of peaks for the MPM fractions, which are almost identical in the three examined oils. This indicates that the MPM constituents rather result from the triglycerides than from minor constituents of the oils.     

HPLC Analysis of Oxidative and Polymerized Decomposition Products in Commercial Vegetable Oils and Heated Fats

A high performance liquid chromatographic (HPLC) method has been developed to analyze oxidative and polymerized decomposition products in commercial vegetable oils and heated fats. The oil was passed through a SEP-PAK where the minor constituents were concentrated. The SEP-PAK was eluted with hexane-ether 1:1 (v/v), and 2-propanol. The first eluate contained unsaponifiables and neutral lipids, and the second eluate contained the more polar oxidative and polymerized decomposition products. The second eluate was analyzed by normal phase HPLC. Five commercial vegetable oils were analyzed, and similarities and differences were observed. Four soybean oil samples from different manufacturers also showed differences. Soybean oil heated at 185°C was collected periodically and analyzed. As the heating time increased, the oxidation and polymerization products also increased. Used frying fat samples from a commercial fried chicken manufacturer were analyzed. The frying oil quality reached an equilibrium during three days of operation, because the oil lost in frying was replenished daily with fresh shortening.     

Antioxidative properties of phenolic acids and interaction with endogenous minor components during frying

The ability of selected phenolic acids to improve the frying performance of canola oil was evaluated in a frying test. The frying performance of the oil was assessed by analysis of total polar components (TPC), level of 4‐hydroxynonenal (HNE), and the rate of formation of volatile carbonyl compounds (VCC). All the tested phenolic acids; ferulic acid (FA), caffeic acid (CA), dihydrocaffeic acid (HCA), gallic acid (GA), and vanillic acid (VA) significantly increased the frying performance of canola oil triacylglycerols (CTG). At the end of the frying test, the amount of TPC in CTG was 22.9 ± 1.0% compared to a maximum of 18.8 ± 0.8% in CTG fortified with the phenolic acids. Similarly, the level of HNE was reduced by up to 45% when it was supplemented with phenolic acids. The results showed that ethyl ferulate (EF) was a better antioxidant than FA under frying conditions; HCA offered a slightly better protection than CA; and the cinnamic acid derivative, FA was better than VA, its benzoic acid analogue. A significant synergy was observed between phenolic acids and the sterol fraction isolated from canola oil. The observed synergy was attributed to the possible formation of steryl phenolates during the frying test. Practical applications: The poor thermal stability of polyunsaturated oils limits their application for prolonged frying. PUFA offer important health benefits and can improve nutritional value of fried foods. Contrary to the commonly applied synthetic antioxidants, the phenolic acids tested in this study often are part of endogenous oil components present in oilseeds and also in some oils, and are known for their positive health benefits. Thus, the simple phenolic acids, especially the cinnamic acid derivatives may be applied as potent antioxidants to protect oils during thermal processes used for food production.     

Effect of a modified deep-fat fryer on chemical and physical characteristics of frying oil

We designed a modified deep-fat fryer (MDF) to have a smaller oil area (A) relative to depth or height (H) such that H/√A=0.93. The modification was intended to retard the thermal degradation of the frying oil and the production of waste oil. Frozen croquettes were fried in vegetable oil using the MDF (H/√A=0.93) and three conventional deep-fat fryers (CDF1, H/√A=0.25; CDF2, H/√A=0.20; CDF3, H/√A=0.30) at 180°C for 72 h at 8 h/d. Frying oils were periodically collected, and their chemical and physical characteristics were examined. The acid value (AV) of frying oils used for 72 h in the MDF was lower than that for oils used in the CDF, although the AV was similar in all fryers until 32 h. The oil deep-fried with MDF had a higher degree of color than that with CDF until 48 h. Polymerized materials and the carbonyl value of frying oil after heating 72h with MDF were lower than those with CDF. The residual tocopherol content of frying oil with MDF was 83% of the content in fresh oil, whereas with CDF the tocopherol contents were less than 63%. The oil consumption by MDF was less than that by CDF, although the turnover rate was higher in MDF than in CDF. These results suggest that during deep-fat frying the MDF may retard the thermal deterioration of vegetable oils and generate less waste oil.     

Comparison of the frying stability of regular and high-oleic acid sunflower oils

The frying stability of a regular sunflower oil (RSFO) was compared with that of a high-oleic acid sunflower oil (HOSFO). The rate of FFA formation was greater for HOSFO than RSFO during 72 h of frying. The content of tocopherols was much higher in RSFO and their degradation was markedly slower than that observed for HOSFO. The formation of total polar compounds, however, was similar for both oils despite the dramatic differences in FA composition. This study further confirms the limitations in predicting frying stability based solely on the FA composition and is consistent with earlier studies conducted in our laboratory.     

Effects of trace acrylamide intake in Wistar rats

Frying oil in use of cooking may contain acrylamide formed from frying foodstuffs. We have reported that administration of a diet containing 7% practically used frying oil for 12 weeks damaged liver and kidneys severely in Wistar rats. Then, male Wistar rats were fed ad libitum for 12 weeks a powdered diet (AIN93G; no fat) containing 7 wt% of fresh oil (control group) or frying oil heated with Asn + glucose for 20 h at 180 degrees C under a nitrogen flow in order to form acrylamide under the least thermal deterioration (experimental group). The rats were subjected to anthropometric measurements, hematological analyses, and observations of the liver and kidneys. All of the rats grew well, and no gross symptoms attributable to the experimental oil were observed. But the experimental rats had significantly low insulin and triacylglycerol levels. The liver and kidneys from the experimental rats had damages, but the degree of the histological changes looked lighter than that of the rats fed practically used frying oil described above. The serum levels of aspartate aminotransferase (AST) and alanine aminotransferase (ALT) were also not much increased. Thus, it was suggested that continuous intake of trace acrylamide induced characteristically low serum insulin level and that the effects of the used frying oil on the liver and kidneys were hardly attributable to acrylamide possibly contained therein.     

Verhalten und Beurteilung von Fritierfetten in der Praxis

Behaviour and Assay of Frying Fats in the Practice Studies on coconut oil palm oil, peanut oil, soybean oil and hardened peanut and fish oils revealed that the oils rich in polyenoic acids as well as animal fats are unsuitable for prolonged use in frying. The content of oxidized fatty acids, saponification colour number, flavour, acid value, smoke point and appearance served as criteria for assay. The limiting values determining whether the frying fat is edible, and the significance of each of these characteristic properties used for such evaluations are discussed. Finally, a new rapid method is introduced for the direct determination of the degree of oxidative deterioration in frying plants. This methods can be practiced without a prior knowledge of chemistry.     

Performance evaluation of hexane-extracted oils from genetically modified soybeans

Soybeans produced by induced mutation breeding and hybridization were cracked, flaked and hexane-extracted, and the recovered crude oils were processed to finished edible oils by laboratory simulations of commercial oil-processing procedures. Three lines yielded oils containing 1.7, 1.9 and 2.5% linolenic acid. These low-linolenic acid oils were evaluated along with oil extracted from the cultivar Hardin, grown at the same time and location, and they were processed at the same time. The oil from Hardin contained 6.5% linolenic acid. Low-linolenic acid oils showed improved flavor stability in accelerated storage tests after 8 d in the dark at 60°C and after 8h at 7500 lux at 30°C, conditions generally considered in stress testing. Room odor testing indicated that the low-linolenic oils showed significantly lower fishy odor after 1 h at 190°C and lower acrid/pungent odor after 5 h. Potatoes were fried in the oils at 190°C after 5, 10 and 15 h of use. Overall flavor quality of the potatoes fried in the low-linolenic oils was good and significantly better after all time periods than that of potatoes fried in the standard oil. No fishy flavors were perceived with potatoes fried in the low-linolenic oils. Total volatile and polar compound content of all heated oils increased with frying hours, with no significant differences observed. After 15 h of frying, the free fatty acid content in all oils remained below 0.3%. Lowering the linolenic acid content of soybean oil by breeding was particularly beneficial for improved oil quality during cooking and frying. Flavor quality of fried foods was enhanced with these low-linolenic acid oils.     

Comparison of the Frying Performance of High Oleic Oils Subjected to Discontinuous and Prolonged Thermal Treatment

Frying is a popular practice because of its unique sensory characteristics and low cost. The high temperature reached with this cooking method alters molecules present in the oil. The deterioration of the oil depends primarily on its chemical composition. The aim of this study was to evaluate the thermal stability of high oleic sunflower oil (HOSO), sunflower oil (SO) and mixed oil (MIX) during deep frying of French fries. Octanoic acid and unsaturated fatty acid (UFA)/saturated fatty acid (SFA) ratio showed a good correlation with total polar compounds (TPC) for all frying samples analyzed. HOSO and MIX were characterized by reduced levels of thermal degradation, while SO resulted in the highest values of oxidation products (highest TPC values). SO was also the oil more retained by the food matrix, whereas MIX was the least absorbed. HOSO and MIX, having a high oleic acid content (77.58 and 59.92 %, respectively) and a low linoleic acid content (13.42 and 25.70 %, respectively), showed the best characteristics for the frying process.     

Odor considerations in the use of frying oils

Odors generated into cooking and serving areas during use of oils in pan frying and deep-fat frying are of concern to home and institutional consumers and, in some respects, to industrial users. Odor considerations are factors in the selection of types of oils to be used in both domestic and foreign markets. Comparative techniques have been developed to evaluate room odor characteristics of frying oils. Evaluation research has been done on various oils and cooking fats for room odors developed during frying. Improved odor characteristics contributed by additives to oils have been studied, as well as relationship between the linolenate content of soybean oil and its characteristic room odor. The nature of the volatile constituents which contribute to room odors during frying is the subject of continuing research efforts. Presented at AOCS meeting, St. Louis, Missouri, May 1978.     

Monitoring of 2,4‐decadienal in oils and fats used for frying in restaurants in Athens,Greece

Some frying by‐products of medium polarity, so‐called medium‐polarity materials (MPM), produced during domestic deep‐frying of French‐fried potatoes in edible vegetable oils, have recently been isolated and linearly correlated to % total polar materials and % polymerized triglycerides. The in vitro oxidation of low‐density lipoproteins in a dose‐dependent manner by MPM has also been reported. In the present study, the MPM constituents were identified after extraction of MPM from the oils, subsequent purification by RP‐HPLC, and GC‐MS analysis. The main constituent of MPM was trans,trans‐2,4‐decadienal, a compound that has previously been reported to be formed during peroxidation of linoleic and arachidonic acid. 2,4‐Decadienal was also quantified in oils and fats used for frying in restaurants in Athens, Greece, by direct injection of oil sample solutions in HPLC. For the most commonly used frying oils, 2,4‐decadienal concentration ranges were 0.3–119.7 mg/kg for sunflower oil, 13.3–92.7 mg/kg for cottonseed oil, 4.1–44.9 mg/kg for palm oil, and 2.0–11.3 mg/kg for vegetable cooking fats. Considering the common catering practices of frying, 2,4‐decadienal was more likely to be found in sunflower oil after deep‐frying of potatoes. Comparing the amounts of this aldehyde found in oils from restaurants to the amounts previously found for domestic frying (up to 30 mg/kg after the 8^th successive frying session in sunflower oil), the probability of consuming a level of 2,4‐decadienal in restaurant‐prepared food that is higher than the level in home‐fried food was determined to be approximately one third.     

Measurement of foaming of frying oil and effect of the composition of TG on foaming

We describe a method developed to quantify the amount of foam in frying oils. In this method the foam was quantified by digitizing photographic images that were taken continuously at 1-s intervals; spots showing more than a certain luminance were considered as foam. The ratio of total foaming area to the whole oil surface was integrated to obtain the intergration of foam (IF) index as a parameter of the extent of foaming. There was a good correlation between this method and the visual evaluation done by a group of panelists. Furthermore, the foaming tendency correlated with the distribution of TG by M.W. when the IF was plotted against the foam index of TG (FIT), which reflects the M.W. distribution. A correlation was found between the FIT value of oil and foaming on frying, indicating that when the FIT value is small, the oil foams less. Based on the results of this investigation, we have designed a method to obtain edible oils consisting of medium-chain FA that not only are nutritious but also have good cooking properties.     

Untersuchungen zur Charakterisierung von Fritierfetten aus der Praxis

Investigations for Characterising Frying Fats According to A. Mankel the simultaneous consideration of the acid value, the content of petroleum ether insoluble oxidised fatty acids and the smoke point is suitable to evaluate the quality of used frying fats and oils. At present this combination is generally considered as the best method of evaluation. Quick tests, which can be carried out adjacent to the fryer and whereby only the content of free fatty acids is measured, have only a limited significance. A novel quick test, the ?Fritest®”? of Messrs. Merck, is supposed to assess the oxidation products – as the saponification colour number does. But the ?Fritest®”? does not take the colour of the fat in account which would partially eliminate the influence of the inherent colour of the fat as also the influence of the frying goods. We carried out this test with soyabean, sunflower and hardened groundnut oil used for frying. In the case of sunflower oil samples from three fryers with different frying goods the ?Fritest®”? indicated the necessity of oil renewal and deterioration of the oil resp. although there was no deterioration recognizable according to the criteria of Mankel. Producers and publications recommend the use of hardened groundnut oil for frying. One such oil which had been used under conditions similar to commercial practice was found by ?Fritest®”? to be not satisfying the specifications of food regulations. In the case of soyabean oil used for fish frying the ?Fritest®”? as well as Mankel's criteria indicated deterioration. K. Lang and coworkers could, however, not observe any detrimental physiological properties on rats as a result of feeding trials with these oils over many years.     

The Effect of Type of Oil and Degree of Degradation on Glycidyl Esters Content During the Frying of French Fries

The aim of the study was to determine the effect of oil degradation on the content of glycidyl esters (GEs) in oils used for the frying of French fries. As frying media, refined oils such as rapeseed, palm, palm olein and blend were used. French fries were fried for 40 h in oils heated to 180 °C in 30‐min cycles. After every 8 h of frying, fresh oil and samples were analyzed for acid and anisidine values, color, refractive index, fatty acid composition, and content and composition of the polar fraction. GEs were determined by LC–MS. Hydrolysis and polymerization occurred most intensively in palm olein, while oxidation was reported for rapeseed oil. The degradation of oil caused increased changes in the RI of frying oils. Losses of mono‐ and polyunsaturated fatty acids were observed in all samples, with the largest share in blend. The highest content of GE found in fresh oil was in palm olein (25 mg kg^?1) and the lowest content of GE was found in rapeseed oil (0.8 mg kg^?1). The palm oil, palm olein and blend were dominated by GEs of palmitic and oleic acids, while rapeseed oil was dominated by GE of oleic acid. With increasing frying time, the content of GEs decreased with losses from 47 % in rapeseed oil to 78 % in palm oil after finishing frying.     

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.     

Hazard analysis and critical control point of frying – safety assurance of fried foods

Deep frying can pose hazards due to oil deterioration (oxidation, polymerization, hydrolysis) and harmful components formation such as trans fatty acids, highly oxidized or polymerized constituents of fatty acids and acrylamide. An analysis of safety hazards of the production of the potato chips and french fries, was carried out from potato harvesting until final products packaging according to hazard analysis and critical control point approach focusing mainly on the first three principles. Since frying is considered a critical control point, the critical limits for the frying temperature and for the potential hazards must be controlled in order to ensure fried products safety.