Short‐chain fatty acids as marker for the degradation of frying fats and oils

The determination of fatty acid composition by gas chromatography as a routine task is established in most laboratories dealing with oils and fats. The scope of this method can be enlarged for a preliminary quality control of used frying fats and oils, which is commonly characterized by the determination of polar compounds and polymerized triacylglycerols. However, for screening purposes the determination of the short‐chain fatty acids C7:0 and C8:0 can give an early indication about the quality of used frying fats and oils.     

Quantitation and distribution of altered fatty acids in frying fats

The distribution and quantity of polar compounds and altered fatty acids in used frying oils, collected by Food Inspection Services of the Junta de Andalucía in Spain, was measured. Additional samples evaluated were sunflower oil, high-oleic sunflower oil, and palm olein that were subjected to thermoxidation and frying in laboratory experiments. A combination of adsorption and high-performance size-exclusion chromatography was applied to the oil samples both before and after transesterification. Through analysis of fatty acid methyl ester derivatives, differentiation of four groups of altered fatty acids (oxidized monomers, nonpolar dimers, oxidized dimers, and polymers) could be attained. Evaluation of real frying samples with polar compound levels around the limit for fat rejection (21.1–27.6% polar compounds) gave values of total altered fatty acids ranging from 8.1 to 11.3%, and levels higher than 20% were found in the most degradated samples. The results obtained clearly support the need for control and improvement of the quality of used fats in fried-food outlets.     

Utilization of high‐oleic rapeseed oil for deep‐fat frying of French fries compared to other commonly used edible oils

Changes in chemical, physical and sensory parameters of high‐oleic rapeseed oil (HORO) (NATREON?) during 72 h of deep‐fat frying of potatoes were compared with those of commonly used frying oils, palm olein (PO), high‐oleic sunflower oil (HOSO) and partially hydrogenated rapeseed oil (PHRO). In addition to the sensory evaluation of the oils and the potatoes, the content of polar compounds, oligomer triacylglycerols and free fatty acids, the oxidative stability by Rancimat, the smoke point and the anisidine value were determined. French fries obtained with HORO, PO and HOSO were still suitable for human consumption after 66 h of deep‐fat frying, while French fries fried in PHRO were inedible after 30 h. During the frying period, none of the oils exceeded the limit for the amount of polar compounds, oligomer triacylglycerols and free fatty acids recommended by the German Society of Fat Science (DGF) as criteria for rejection of used frying oils. After 72 h, the smoke point of all oils was below 150 °C, and the amount of tocopherols was reduced to 5 mg/100 g for PHRO and 15 mg/100 g for HORO and HOSO. Remarkable was the decrease of the oxidative stability of HOSO measured by Rancimat. During frying, the oxidative stability of this oil was reduced from 32 h for the fresh oil to below 1 h after 72 h of frying. Only HORO showed still an oxidative stability of more than 2 h. From the results, it can be concluded that the use of HORO for deep‐fat frying is comparable to other commonly used oils.     

Formation of Polar Compounds During Deep‐frying—Determination by 1H NMR and ESR

The present study aims to elucidate the factors influencing the generation of polar compounds in oils during deep‐frying. Oils with different fatty acid compositions, including palm oil (PO), refined palm kernel oil (RPKO), and refined coconut oil (RCO), are applied in successive frying processes. ¹H NMR spectra reveal that heated PO has a higher percentage of allyl acyl group and is more prone to formation of non‐polar dimeric triglycerides as compared to other types of oils. In addition, electron spin resonance (ESR) spectra indicate that alkyl radicals are more predominant than alkoxy radicals in heated PO. In contrast, RPKO and RCO are inclined to generation of alkoxy radicals during the thermal treatment. The results reveal that oils with high unsaturated fatty acid content are more prone to generation and oxidation of non‐polar dimeric triglycerides. Practical Applications: The change in free radical profile and concentration is one of the indicators of lipid oxidation and polymerization. Alterations in the levels of alkyl and alkoxyl radicals, revealed by ESR, can be used to illustrate the formation of polar compounds in deep‐fried oils with different fatty acid compositions. The percentage of allyl acyl group, revealed by ¹H NMR, can be used to predict the generation of polar compounds. Therefore, this study provides useful information for the development of different methods to reduce polar compound formation in oils during thermal processing depending on the fatty acid composition of different deep‐fried oils.     

Effects of frying on the trans‐fatty acid formation in soybean oils

To evaluate the effects of repeated deep‐frying on the trans‐fatty acid (TFA) formation in soybean oils, simultaneous frying experiments were carried out. French fries were prepared using three different types of soybean oil (pressed soybean oil, PSBO; first‐grade solvent extracted soybean oil, FG‐SESBO; and third‐grade solvent extracted soybean oil, TG‐SESBO). French fries were fried intermittently at 180–185°C for a total frying time of 32 h and at an interval time of 30 min. It was found that the initial amount of total TFAs was 0.29 g/100 g, 0.31 g/100 g, and 0.90 g/100 g in PSBO, TG‐SESBO, and FG‐SESBO, respectively. Before the frying started, the C18:1,t‐9, trans‐linoleic acid (TLA), trans‐linolenic acid (TLNA), and total TFA content of the PSBO and TG‐SESBO were significantly lower than in the FG‐SESBO (p<0.05). However, in the frying oil samples, the final concentration of total TFA in the PSBO, TG‐SESBO, and FG‐SESBO were 1.79 ± 0.17 g/100 g, 1.12 ± 0.10 g/100 g, and 1.70 ± 0.07 g/100 g, which was 6.17‐, 3.61‐, and 1.89‐fold higher that in fresh oil, respectively. The highest increasing slopes of C18:1,t‐9, TLA, TLNA, and total TFA were observed in the PSBO. Practical applications : A high intake of TFAs has been shown to lead to an increased risk of coronary heart disease. Plant oils, particularly soybean oil, have been widely used in the food industry in China. Frying is one of the most common methods to cook food. The formation of TFAs during frying has been shown to be closely related to the temperature and duration of the frying process. However, the effects of frying on the formation of TFAs in different soybean oils have not been well studied. In the present study, we demonstrated that increasing the number of frying cycles can cause an intensive increase in the concentration of TFAs in different types of soybean oil, but especially in PSBO.     

Formation and distribution of oxidized fatty acids during deep‐ and pan‐frying of potatoes

The formation of cis‐9,10‐epoxystearate, trans‐9,10‐epoxystearate, cis‐9,10‐epoxyoleate, cis‐12,13‐epoxyoleate, trans‐9,10‐epoxyoleate, trans‐12,13‐epoxyoleate and the co‐eluting 9‐ and 10‐ketostearates during eight successive pan‐ and deep‐frying sessions of pre‐fried potatoes in five different types of vegetable oils – namely cottonseed oil, sunflower oil, vegetable shortening, palm oil and virgin olive oil – was followed and quantified both in fried oils and in fried potatoes by GC/MS after derivatization to methyl esters. These oxidized fatty acids were present at relatively low concentrations in the fresh oils and pre‐fried potatoes while they increased linearly with frying time, reaching up to 1140.8 µg/g in virgin olive oil (VOO) and 186.9 µg/g in potatoes pan‐fried in VOO after eight pan‐frying sessions, with trans‐9,10‐epoxystearate predominating in all cases. The formation of polymerized triacylglycerols (PTG) was also quantified in frying oils by size exclusion HPLC. Pan‐frying caused higher oxidized fatty acid and PTG formation compared to deep‐frying. Epoxyoleates and PTG concentrations were increased after frying in polyunsaturated oils, while epoxystearate and 9‐ and 10‐ketostearate concentrations were increased after frying in monounsaturated oils. No specific absorption of the oxidized fatty acids by the fried potatoes seems to occur. The dietary intake of oxidized fatty acids and PTG by the consumption of fried potatoes was discussed.     

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.     

Analysis of used frying oils

The analysis of used frying oils to ensure quality of fried foods has become a subject of great concern for health administrations, food processors and consumers, especially since some compounds formed at high temperatures impair the nutritional value of fats and have adverse health effects. At present, three lines of research on the analysis of frying oils stand out: first, development of techniques for the quantitative analysis of the new compounds formed; second, the evaluation of useful rapid methods to be applied in situ for monitoring oil quality in fried food outlets; and third, the application of the most advanced analytical techniques to delve into the structure of individual oxidized compounds present in fried foods.     

Oxidative Stability and Changes in Chemical Composition of Extra Virgin Olive Oils After Short‐Term Deep‐Frying of French Fries

We aimed at investigating oxidative stability and changes in fatty acid and tocopherol composition of extra virgin olive oil (EVOO) in comparison with refined seed oils during short‐term deep‐frying of French fries, and changes in the composition of the French fries deep‐fried in EVOO. EVOO samples from Spain, Brazil, and Portugal, and refined seed oils of soybean and sunflower were studied. Oil samples were used for deep‐frying of French fries at 180 °C, for up to 75 min of successive frying. Tocopherol and fatty acid composition were determined in fresh and spent vegetable oils. Tocopherol, fatty acid, and volatile composition (by SPME–GC–MS) were also determined in French fries deep‐fried in EVOO. Oil oxidation was monitored by peroxide, acid, and p‐anisidine values, and by Rancimat after deep‐frying. Differential scanning calorimetry (DSC) analysis was used as a proxy of the quality of the spent oils. EVOOs presented the lowest degree of oleic and linoleic acids losses, low formation of free fatty acids and carbonyl compounds, and were highly stable after deep‐frying. In addition, oleic acid, tocopherols, and flavor compounds were transferred from EVOO into the French fries. In conclusion, EVOOs were more stable than refined seed oils during short‐term deep‐frying of French fries and also contributed to enhance the nutritional value, and possibly improve the flavor, of the fries prepared in EVOO.     

Optimising the baking and frying process using oil‐improving agents

Despite slimness mania and acrylamide scare, the market of fried products is still growing. Frying is an extremely effective way to cook food. A fried product tastes good, has a good flavour and is prepared within a few minutes. Every effort has been made to optimise the frying process. With regard to the quality of the fried food, the quality of the frying oil is very important. In the past, important characteristics of industrial frying oils were oxidative stability, high smoke point and low foaming. Nowadays, new frying fats with various additives, with a healthier fatty acid profile and higher heat stability are emerging. Emulsifiers, anti‐polymerising agents, and natural and synthetic antioxidants improve the performance during frying. Sesamol, rosemary and other natural extracts display strong stabilising effects during the frying operations. Filtration and the use of heat‐stabilising additives help to retard fat degradation and give the producer a larger time‐window for optimum frying. The effectiveness of the treatment with filter aids or mineral adsorbents and the stabilising effects of synthetic and natural agents were compared by using the Rancimat test for testing oxidative stability and the OSET (oxidative stability at elevated temperature) test to determine the stability at the frying temperature.     

Seed roasting improves the oxidative stability of canola (B. napus) and mustard (B. juncea) seed oils

Animal fats and partially hydrogenated vegetable oils (PHVO) have preferentially been used for deep‐frying of food because of their relatively high oxidative stability compared to natural vegetable oils. However, animal fats and PHVO are abundant sources of saturated fatty acids and trans fatty acids, respectively, both of which are detrimental to human health. Canola (Brassica napus) is the primary oilseed crop currently grown in Australia. Canola quality Indian mustard (Brassica juncea) is also being developed for cultivation in hot and low‐rainfall areas of the country where canola does not perform well. A major impediment to using these oils for deep‐frying is their relatively high susceptibility to oxidation, and so any processing interventions that would improve the oxidative stability would increase their prospects of use in commercial deep‐frying. The oxidative stability of both B. napus and B. juncea crude oils can be improved dramatically by roasting the seeds (165 °C, 5 min) prior to oil extraction. Roasting did not alter the fatty acid composition or the tocopherol content of the oils. The enhanced oxidative stability of the oil, solvent‐extracted from roasted seeds, is probably due to 2,6‐dimethoxy‐4‐vinylphenol produced by thermal decarboxylation of the sinapic acid naturally occurring in the canola seed.     

Applications of chromatographic techniques to evaluate enzymatic hydrolysis of oxidized and polymeric triglycerides by pancreatic lipase in vitro

With the aim of studying the susceptibility to enzymatic hydrolysis of oxidized and polymeric triglycerides (TG) that are formed during frying, various chromatographic techniques were applied in combination, i.e., adsorption chromatography, high-performance size-exclusion chromatography (HPSEC), and thin-layer chromatography-flame ionization detection (TLC-FID). Polar fractions, isolated by adsorption chromatography from thermoxidized trilinolein as model system, and real used frying fats and oils, were analyzed by HPSEC before and after incubation with pancreatic lipase in vitro. Also, the influence of degradation level of used frying oils on hydrolysis of intact TG was investigated with the additional aid of TLC-FID. Results showed the high hydrolysis rate of oxidized TG monomers in contrast to the significant discrimination of pancreatic lipase against TG dimers and, particularly, TG polymers. On the other hand, hydrolysis of intact TG can be affected by the presence of dimers and polymers in abused frying oils.     

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.     

Correlation between physicochemical analysis and radical‐scavenging activity of vegetable oil blends as affected by frying of French fries

The main goal of the present work was to compare and correlate the results of physicochemical parameters and antiradical performance of some oil blends during deep‐frying, which will be an initial indicator for applying antiradical tests for monitoring deep‐frying oils. Two oil blends were prepared. The first blend was a mixture (1 : 1, wt/wt) of sunflower seed oil and palm olein (SO/PO) and the second was a mixture (1 : 1, wt/wt) of cottonseed oil and palm olein (CO/PO). The oil blends were evaluated during intermittent frying of French fries on two consecutive days for 16 h, with oil replenishing after 8 h. Changes in the fatty acid profile and some physicochemical parameters (peroxide value, color index, viscosity, total polar compounds and UV absorbance at 232 and 270 nm) were used to evaluate the alterations during frying. A quick spectrophotometric method was developed to assess deep‐frying oil quality. With the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) method, the neutralization of the stable radical DPPH by antioxidants present in the oil during frying was measured. Radical‐scavenging activity (RSA) of both oil blends was recorded during frying, wherein the results showed that the SO/PO blend had the highest RSA. It was evident from the results that a proportional correlation and positive relationship existed between the levels of fatty acids and the physicochemical characteristics of the vegetable oil blends and their RSA. The initial results obtained allow us to suggest that antiradical measurements could be used to quantify the oxidative and hydrolytic deterioration of vegetable oils upon frying.     

Stability of fat‐soluble vitamins and PUFA in simulated shallow‐frying

Fat‐soluble vitamins and essential polyunsaturated fatty acids (PUFA) are nutrients that are sensitive to heat treatment and oxidation and therefore can be partly lost during cooking. It is well‐documented that a long‐term deep‐frying process leads to a substantial degradation of PUFA and vitamins in a frying medium. In this study, the stability of vitamins and fatty acids was investigated in a series of liquid margarines (82% fat) varying in fat blend and the content of minor components. The tested samples were subjected to the standardised treatment that has been developed to mimic shallow‐frying of food at 180°C and the recovery of individual nutrients is reported. The results show that fat‐soluble vitamins possessed reasonable stability under the condition of the shallow‐frying test. Essential PUFA of the frying medium were hardly affected by the treatment. Overall evaluation of the results suggests that oil‐based cooking media rich in vitamins and PUFA have a positive impact on nutritional value of food prepared by appropriate means of cooking.     

Carbon dioxide blanketing impedes the formation of 4‐hydroxynonenal and acrylamide during frying. A novel procedure for HNE quantification

Acrylamide and 4‐hydroxynonenal (HNE) are among the most detrimental compounds formed during high temperature processing of food. The effect of carbon dioxide blanketing (CDB) on the formation and accumulation in food of these compounds during deep‐fat frying was investigated. French fries were fried for 7 h daily and for 7 days in canola oil at 185 ± 5°C without and with CO₂ protection. The amount of acrylamide and HNE accumulated in the French fries were analyzed. Compared to standard frying conditions (SFC), frying under CDB reduced the amount of HNE by 62%. On the 3rd day of frying, the amount of acrylamide in fries fried under SFC was 3.3 times higher compared to frying with CO₂ protection. Frying with carbon dioxide protection is an effective and practical way to impede formation of toxic components during deep‐fat frying. To assess formation of HNE a simple, sensitive and reliable procedure for HNE analysis in frying oils and fried products was developed and evaluated. Practical applications : The toxicity of HNE and acrylamide, coupled with the increasing consumption of fried foods necessitates that measures be taken to reduce their formation and subsequent accumulation in fried foods. The frying method proposed in this study is very effective and requires only a simple modification to the fryer. Developed rapid and simple procedure for HNE analysis allows more accurate quantification.     

Stability of Essential Fatty Acids and Formation of Nutritionally Undesirable Compounds in Baking and Shallow Frying

During cooking oils and fats are exposed to high temperatures that may affect the nutritional quality of foods that are prepared in this way. Concerns have been raised about the degradation of polyunsaturated fatty acids and the formation of potentially harmful compounds during deep frying, but relatively little is known about these changes in other cooking processes. In the present study sponge cakes and fried potatoes were prepared via standardised baking and shallow frying procedures by using different oils and fats (sunflower oil, rapeseed oil, various margarines or butter). The effect of cooking on the retention of two essential fatty acids (linoleic acid and α-linolenic acid) and the formation of trans fatty acids (TFA) and polymerised triacylglycerols (PTG) was evaluated by analyzing fat extracted from the cooked food. It was found that over 95 % of essential fatty acids were retained upon completion of both cooking techniques. The formation of TFA was not significant. Polymerisation was noticeable only in shallow frying, although the final levels of PTG were negligible (<1.3 %). Overall, in contrast to deep frying, oil-based media high in polyunsaturated fatty acids seem to be a good alternative for domestic cooking techniques as they increase the nutritional value of the prepared food.     

Effectiveness of dimethylpolysiloxane during deep frying

In the last decades, silicones and particularly dimethylpolysiloxane (DMPS) added to oils and fats at very low concentrations (1–5 mg/kg) have been widely applied as inhibitors of thermoxidative reactions in deep frying. In this review, information available on the mechanisms of DMPS action during the frying process is summarised. Studies on samples submitted to high temperature in the absence of foods, as well as those on continuous and discontinuous frying, are commented upon. It is concluded that the different effects reported can be attributed to the high number of variables interacting during frying. The maximum effectiveness of DMPS was obtained in discontinuous frying operations when the oil surface becomes unprotected against oxidation due to the absence of the food. On the contrary, in industrial continuous frying, the addition of DMPS was found to be ineffective due to the protection of the surface by steam originating from the food.     

Comparitive study of monocarbonyl compounds formed during deep frying in different fats

Fresh commercial corn oil, fresh commercial lard, and hydrogenated vegetable shortening were analyzed for carbonyl compounds before and after deep frying. The frying was carried out in an apparatus with a capacity for 2000 g of oil designed to quantitatively trap the volatile materials evolved during frying and which would ordinarily escape into the atmosphere. The trapped distillate was also subjected to carbonyl analysis. Analysis of the fats and distillates showed a carbonyl pattern in essential agreement with the classical autoxidation mechanism for the different fats, i.e., the typical alkanals, alk-2-enals, and alk-2,4-dienals. The pattern correlated generally with the fatty acid composition of the fats. Comparison of the concentrations of the monocarbonyl compounds in the fats before and after frying, and in their distillates, indicated that the deodorization process which accompanies frying is effective in preventing the accumulation of the more volatile compounds formed. The less volatile products, mainly deca-2,4-dienal, were not efficiently removed. Accordingly, it was observed that the oils containing higher proportions of linoleic acid contained more residual monocarbonyl compounds after frying. Scientific Article No. A-1124, Contribution No. 3570 of the Maryland Agricultural Experiment Station.     

Cyclic fatty acids in sunflower oils during frying of frozen foods with oil replenishment

Frying of frozen foods has become popular because it considerably reduces cooking time. Polymers and cyclic fatty acid monomers (CFAM) formed during frying are potentially toxic and therefore their production should be minimized. Twenty discontinuous fryings of different frozen foods were carried out over ten consecutive days, in sunflower oil (SO) and in high‐oleic acid sunflower oil (HOSO), by adding fresh oil after each frying to bring the volume of the fryer oil back to 3 L. CFAM methyl ester derivates were hydrogenated, isolated, concentrated and quantified by HPLC using a reverse‐phase column, followed by gas chromatography. After 20 fryings, significantly higher contents of polar material, polymers and CFAM (all p <0.001) were found in SO than in HOSO. Bicyclic compound formation was four times higher in SO (p <0.001). The fat from the fried potatoes presented a polymer content very similar to that of their corresponding oils. The 100‐g rations of the SO‐fried potatoes from the 20^th frying supply 49 or 15%, respectively, more polymers and CFAM and 1 mg more bicyclic fatty acids than the 100‐g rations of HOSO‐fried potatoes. Because digestion and absorption of polar material, polymers and CFAM occur, the data clearly show the advantageousness and advisability of frying with HOSO rather than SO.