Food Chemistry 123 (2010) 976982

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Formation of trans fatty acids in edible oils during the frying and heating process
Wakako Tsuzuki *, Akiko Matsuoka, Kaori Ushida
National Food Research Institute, Kannondai 2-1-12, Tsukuba, Ibaraki 305-8642, Japan

a r t i c l e

i n f o

a b s t r a c t
To assess an impact of heated edible oils on intake of trans fat, the formations of trans fatty acids (TFAs) in cooking conditions was estimated by a frying and heating model system. For the frying model, sliced raw potatoes (10% of the frying oil (w/w)) were fried in commercially available canola oil at 160, 180 and 200 C, and the 10 frying cycles were performed. The TFAs contained both in fried potatoes and in frying oils were measured by gas chromatography (GC). Lipids content of raw potatoes was about 0.1% (w/w) and TFAs in the raw potatoes were negligible. On the other hand, fried potatoes contained lipids at the level of 8.8%9.2% and their fatty acid composition was mostly in correspondence with that of the frying oil. The TFAs amount of potatoes fried by the tenth frying operation was at the level of 0.991.05 g/100 g lipids. When 100 g potatoes fried in this process were consumed, the TFAs intake was estimated at less than 0.1 g. After 10 frying operations, TFAs content, acid values and peroxide values of the frying oils were measured and compared with those of corresponding heated canola oils without food. The amounts of trans 18:1 FAs contained both in the frying oil and in heated oil were less than the quantitative limit (0.047 g/100 g oil). The increases of trans 18:2 FAs and trans 18:3 FAs of the used frying oil were 0.02 g/100 and 0.05 g/100 g, respectively, compared with those of the fresh oil. trans 18:2 FAs accumulation in the heated oil was slightly less than that in the frying oil. To elucidate TFAs accumulation in various edible oils during cooking, six kinds of commercially available edible vegetable oils were heated to 180 C in glass test tubes. Small changes in TFAs amounts were observed after four hours heating. These results suggested that an ordinary frying process using unhydrogenated edible oils has little impact on TFAs intake from edible oils. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 16 December 2009 Received in revised form 18 March 2010 Accepted 11 May 2010

Keywords: trans Fatty acid Frying oils Heated oil

1. Introduction Since epidemiological evidence and case-control studies suggested that there was a relationship between the level of trans fatty acids (TFAs) intake and the risk of cardiovascular disease (Ascherio et al., 1996; Mozaffarian et al., 2004; Oh, Hu, Manson, Stampfer, & Willett, 2005; Oomen et al., 2001; Pietinen et al., 1997), there has been considerable debate on TFAs contained in food materials. Because of the adverse effects of excess TFAs intake on health, some countries have offered the labeling of TFAs contents in processed foods for the purposed of increasing awareness of TFAs by the consumers. The exact quantication of TFAs in food is therefore important for the righteous evaluation of TFAs consumption. TFAs are generally dened as unsaturated fatty acids that contain non-conjugated carboncarbon double bounds in the trans conguration. TFAs in foods are derived from the chemical hydrogenation of vegetable and sh oils, the renement process of edible oils from crude ones and microbial biohydrogenation in the digestive tract of ruminant animals. The main sources of TFAs for consumers are partially hydrogenated oils and TFAs consumption from rened
* Corresponding author. Tel.: +81 29 838 8074; fax: +81 29 838 7996. E-mail address: wakako@affrc.go.jp (W. Tsuzuki). 0308-8146/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodchem.2010.05.048

edible oils is not particularly large. However, for the assessment of TFAs intake from edible oils, TFAs induced during cooking should be considered, in addition to the TFAs produced in the manufacturing deodourising process. TFAs accumulation in edible oils by heating has been investigated in association with the thermal oxidative deterioration of unsaturated FAs (Chen, Tai, Chen, & Chen, 2001; Grandgirard, Sobedio, & Fleury, 1984; Liu, Inbaraj, & Chen, 2007; Moreno, Olivares, Lopez, Adelantado, & Reig, 1999). These previous studies concluded that TFAs were formed only under severe conditions. TFAs formation in the oil during frying have also been investigated (Aladedunye & Przybylski, 2009; Bansal, Zhou, Tan, Neo, & Lo, 2009; Liu, Lu, Inbaraj, & Chen, 2008; Romero, Cuesta, & Sanchez-Muniz, 2000; Sebedio, Catte, Boudier, Prevost, & Grandgirard, 1996). Among these studies, degrees of TFAs formation during frying depended on the frying condition and on the frying materials and even on the methods of TFAs measurements. Furthermore, when the frying materials contained TFAs were introduced to frying process, TFAs release from the materials into the frying oil during frying should also be considered (Bansal, Zhou, Tan, Neo, & Lo, 2009). TFAs formation in the frying oil by the frying process itself should be distinguished from TFAs that are present initially in the frying materials. The food which has little TFAs is recommended as a frying test material. Detailed monitoring about

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TFAs accumulation both in the frying materials and in frying oil will be necessary in order to investigate TFAs formation in edible rened oils during domestic or commercial cooking conditions. In the last few years, analysis of TFAs by gas chromatography (GC) has remarkably been progressed through the efforts of scientists and with the technical development of the GC columns. The American Oil Chemists Society proposed the Ofcial Methods for TFAs measurements in edible oils and the hydrogenated oils by GC (AOCS Ofcial Methods Ce 1f-96; Ce 1h-05). Recently, more appropriate analysis methods for simultaneous separation of trans and cis FAMEs than the previous ones were developed (Bansal et al., 2009; Liu et al., 2007). These methods were excellent in terms of retention times and separation numbers of TFAs in hydrogenated and unhydrogenated edible oils. Furthermore, the sensitivity of TFAs were improved and TFAs contents could be determined at a quantitation limit ranging from 2.6 to 3.9 ppm (based on Signal/Noise (S/N) > 10) (Liu et al., 2007). In the present study, TFAs formation during frying process was investigated using fresh raw potatoes and the commercially available canola oil, as the frying materials and the frying oil. The TFAs levels of fried potatoes and frying oils were monitored by GC. The amounts of trans isomers of 18:1 FA, 18:2 FA and 18:3 FA in the frying oils were satisfactory determined by AOCS Ofcial Method Ce 1h-05 with some modication. To estimate TFAs formation in unhydrogenated edible oils during frying, several commercially available edible oils were heated in the simple model system without food and the TFAs formation prole was investigated. The purpose of this study was to obtain fundamental information about TFAs formation in the edible oils during domestic or commercial frying process through model systems. 2. Materials and methods 2.1. Reagents Standard FAMEs (12:0, 14:0, 16:0, 18:0, cis 6, cis 7, cis 9, cis 11 and cis 12, 18:1 FAMEs, trans 9 and trans 11, 18:1) were purchased from Nu-Chek Prep Inc. (Elysian, MN, USA). FAMEs of 18:2 isomer mixture and 18:3 isomer mixture were obtained from Supelco Inc. (Bellefonte, PA, USA). The commercially available edible oils (rened canola oil, cooking oil (mixture of rapeseed oil and soybean oil), soybean oil, rice oil and sesame oil) were purchased from a local retail market and stored at 4 C until use. n-Hexane and other solvents of analytical grade were obtained from Wako Pure Chemical Co. Ltd. (Osaka, Japan) and Kanto Chemical Co. Ltd. (Tokyo, Japan). Chemicals, including potassium hydroxide, anhydrous sodium sulphate, sodium chloride and boron triuoride (BF3) methanol solution were obtained from Wako Pure Chemical Co. Ltd. 2.2. Preparation of potatoes for frying Potatoes harvested in Hokkaido, Japan, were purchased from a local market and stored at room temperature until use. The potatoes were pared and cut into pieces 1.0 1.0 cm in thickness and 8.010.0 cm in length with a French fry cutter (Coupe-Frites, Argenteuil, France). The pieced potatoes were soaked in water for 20 min to remove the harshness. After that, they were drained and weighted exactly to be 1/10 (w/w) of the frying oil. 2.3. Frying procedure Deep fat frying was carried out in commercially available electrical fryers (TF-20; Taiji Co., Ltd., Tokyo, Japan). The temperature of the oil in the fryer was monitored by a thermo reorder (TR-81,

T and D Co. Ltd., Nagano, Japan). The fryer could control the oil temperature within 5 C from the set temperature. The oil (1500 g of canola oil) was heated to 160, 180 and 200 C and the potato strips, whose weight was set 1/10 of that of the oil remaining in the fryer (w/w), were fried to the desirable colour and texture for 7, 6 and 5 min, respectively. After every frying cycle at 160, 180 and 200 C, intervals were set for 3, 4 and 5 min, respectively. It took 10 min for one frying cycle at each temperature. No oil was added during the frying operations and after the last frying, about 1425 5 g oil was left in the fryer. After 10 frying operations, frying oil (10 ml) was collected and all samples were stored at 20 C for further chemical analysis. To keep a constant temperature prole of the frying oil, the ratio of potatoes to frying oil was set at 1/10 (w/w). In the preliminary experiment, the weight of the frying oil left in the fryer was measured after every frying operation. The decrease in canola oil during one frying was about 9.0 1.0 g. The weight of the potatoes used for the following frying was set at 1/10 of that of the canola oil left in the fryer. For the rst frying operation, 150 g of raw potato strips were fried in 1500 g canola oil. The weight of raw potato strips for the tenth frying operation was set at 143 g according to weight of the frying oil. Triple frying experiments were carried out for each temperature. 2.4. Lipid extraction from potatoes The total lipids contained in the fried potatoes were extracted according to the method by Folch, Lees, and Sloane-Stanley (1957). In the case of the fried potatoes, all potatoes fried in one frying operation were simultaneously crushed to be homogenous by a food processer (CQ-36R; Toshiba, Tokyo, Japan). A portion of the crushed potatoes (0.5 g) was used for lipid extraction. 3.6 ml chloroform/methanol (2:1, v/v) and 1.2 ml water were added to the potatoes fraction and then homogenised with a mixer (Physcotron NS-310EII; Microbes. Co. Ltd., Tokyo, Japan) for 10 min. The mixture was separated by centrifugation at 3000g for 20 min. The resultant lower layer of chloroform was withdrawn and transferred to another tube. The upper layer was similarly extracted with 3.6 ml chloroform/methanol (2/1, v/v). The rest was similarly extracted with 2.4 ml chloroform. These two chloroform layers were combined with the initial chloroform extract. The combined chloroform extract was washed with 3 ml 0.88% potassium chloride and dried under a stream of argon gas. The residue was then weighed exactly, after being washed twice with 3.0 ml hexane. In case of the raw potatoes, the total lipids were extracted according to the method described above. 5.0 g of the crushed raw potatoes were used for lipid extraction with a corresponding large scale of solvents, because of their low lipid contents. Triple extractions of lipids were carried out. 2.5. Heating of canola oil in the fryer without foods For the comparison of TFAs formation of the heated canola oil with that of the frying canola oil, 1500 g canola oil was heated in the fryer without foods at 160, 180 and 200 C. Every 10 min during heating, 8.010.0 g canola oil was removed to imitate the decrease in frying process. After 100 min heating, 10 ml of oil was collected and stored at 20 C for further chemical analysis. Triple experiments were carried out for each temperature. 2.6. Heating of other vegetable oils (1.0 g) in the glass tube For the comparison of the thermal TFAs formation prole of various edible oils, six kinds of commercially available vegetable oils (1.0 g) were transferred into a glass tube and heated in a silicon oil bath (OHB-2000S; Tokyo Rika Co. Ltd., Tokyo, Japan) at 180 C

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for 2 and 4 h. The incubation temperature was controlled within 0.2 C. After incubation, each oil was transferred to a small vial and stored at 20 C until further chemical analysis. A fresh vegetable oil was used as a control sample to compare with corresponding heated oil. Triple experiments were carried out for each temperature and heating time.

2.9. Statistical analysis The data are given as means SD. The results were analysed by multiple tests to identify signicant differences among groups. P values <0.05 were considered signicant. All analyses were performed using StatView software (Abacus Concepts, Berkeley, CA, USA).

2.7. Fatty acid determination 3. Results and discussion After the frying and heating process, 20 mg of each oil, whose weight was exactly measured, was transferred to a small vial with 2.00 mg of margaric acid (Nu-Chek Prep) as an internal standard. Methylation was accomplished with a BF3-Methanol solution following the AOCS Ofcial Method Ce 2-66. The FAMEs were analysed by the AOCS Ofcial Method Ce 1h-05, using a Shimadzu GC-2010 tted with a split injector (250 C) and a ame ionisation detector (250 C) coupled with a GC solution integrating system (Shimadzu). A SP-2560, 100 m 0.25 mm I.D., 0.2 lm lm thickness (Supelco) column was utilised and operated at 180 C. For this column, helium was used as a carrier at a velocity of 23.6 cm/s. Each FAME peak was identied with its standard FAME. The absolute amounts of cis and trans FAs in the oil were calculated based on the peak intensity of the internal standard. 3.1. Trans fatty acid measurements Under the GC analysis conditions, all fatty acids contained in the examined oils were adequately resolved with the exception of trans isomer of 18:1 FAME. However, each trans isomer of 18:1 FAME was completely separated from cis ones. The partial overlap of trans isomers of 18:1 FAME did not affect the quantitation of the total amount of trans 18:1FAs. For polyunsaturated FA, trans 9, cis 12, cis 15,18:3 FAME partially overlapped with cis 11,20:1 FAME, which was reported in the previous studies (AOCS Ofcial Method Ce 1h-05; Liu et al., 2007). On the other hand, the TFAs contained in the edible oils examined in the present study were primarily trans 911,18:1 FAs, trans 9, cis 12,18:2 FA, cis 9, trans 12,18:2 FA, trans 9, cis 12, trans 15,18:3 FA, cis 9, trans 12, trans 15,18:3 FA, cis 9, cis 12, trans 15,18:3 FA and cis 9, trans 12, cis 15, 18:3 FA, whose FAME peaks did not overlap with those of any cis isomers of unsaturated FAs contained in the edible oils under this GC condition. The gas chromatograms of 18:1, 18:2 and 18:3 FAMEs from fresh, frying and heated canola oil were shown in Fig. 1. Although partial overlaps among trans isomers of 18:1 FAMEs were detected in the chromatogram, these trans 18:1 FAMEs did separate from any cis 18:1 FAMEs. Furthermore, the peak intensity of each trans 18:1 FAME in the canola oil was under the QL based on S/N > 10 in

2.8. Measurements of peroxide value (POV) and acid value (AV) The peroxide value (POV) was determined by a standard iodo metric titration procedure following the Japan Oil Chemists Society (JOCS) Ofcial Method (2.5.2 Peroxide Value). The acid value (AV) by alcoholic KOH titration was determined by the JOCS Ofcial Method (4.2.1-1996 Acid Value). Chemicals and solvents required for all of the analysis were purchased from Wako Pure Chemicals Co. Ltd.

Fig. 1. Gas chromatogram of fatty acid methyl esters derived from a commercially available fresh canola oil (A), a canola oil heated at 180 C for 100 min (B) and a canola oil used for 10 frying operations at 180 C (C).

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the most cases. Thus, this GC condition was adequate in terms of retention time and separation for TFAs measurement in edible oils. 3.2. Lipids contained in raw and fried potatoes The lipid content in the raw potatoes was 0.11% (w/w), and there were undetectable trans isomers of unsaturated FAs in the lipid, as shown in Fig. 2A. On the other hand, the lipid contents of potatoes fried at 160, 180 and 200 C were 8.8 0.1% (w/w), 8.8 0.1% and 9.2 0.1%, respectively. No difference was found in lipid contents depending on the number of the frying operation.

As shown in Fig. 2B, the FA composition of the fried potatoes was coincident with that of the frying oil rather than with that of the original raw potatoes, suggesting that the most lipids composed of the fried potatoes would be transferred from the frying oil. The TFAs amount of the potatoes fried at 160, 180 and 200 C was monitored after each or every second frying process (Fig. 3). Although small FAME peaks were detected at the retention time of trans 18:1 FAMEs, the amounts were less than QL. So, the amounts of trans 18:1 FAs of the fried potatoes could not be evaluated. On the other hand, the amounts of trans 18:2 FAs and trans 18:3 FAs in potatoes fried at 180 C in the second frying operation

Fig. 2. Gas chromatogram of fatty acid methyl esters derived from raw potatoes (A) and the potatoes fried at 180 C in the canola oil (B).

(A) 160C
1.0 1.0 0.9 0.8 0.7
C18:1t C18:2t C18:3t

(B) 180C
1.0 0.9 0.8 0.7
C18:1t C18:2t C18:3t

(C) 200C

trans Fatty acid (g/100g)

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 2 4 6 8 10 12

0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 2 4 6 8

0.6 0.5 0.4 0.3 0.2 0.1 0.0

C18:1t C18:2t C18:3t

10

12

10

12

Frying operation

Frying operation

Frying operation

Fig. 3. Accumulated trans 18:1 FAs, trans 18:2 FAs and trans 18:3 FAs in potatoes fried at 160 C (A), 180 C (B) and 200 C (C). The amounts of TFAs under the quantitative limit (QL) are indicated by a broken line. The values represent the means SD of three experiments.

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were 0.13 g/100 g lipids and 0.88 g/100 g lipids, and these values in potatoes fried in the tenth operation were 0.14 g/100 g lipids and 0.92 g/100 g lipids, respectively (Fig. 3). Even in the frying operation conducted at 200 C, the total TFAs amount (the sum of trans 18:2 and trans 18:3) of the potatoes fried in the second process and that of potatoes fried in the tenth process was 1.01 g/100 g lipids and 1.07 g/100 g lipids, respectively. These results suggested that the number of frying operation did not have a large effect on the TFAs level in the fried potatoes. Based on the TFAs amount and the lipid contents in the fried potatoes, the intakes of TFAs were calculated. When 100 g potatoes fried at 160, 180 and 200 C in this study were served, the range of TFAs intake was estimated to be 0.091 0.004, 0.094 0.005 and 0.099 0.004 g, respectively. Thus results suggested that the repetition of the frying process using canola oil and raw potatoes and the frying temperature in the range from 160 to 200 C would not give a large effect of TFA intakes. As described above, the lipids contained in fried potatoes prepared with raw potatoes were dominantly transferred from the frying oil (Fig. 2). The absolute amount of the frying oil contained in fried potatoes and the TFAs concentration of the frying oil itself would contribute to TFA intakes from such fried potatoes. 3.3. Trans fatty acids in frying canola oil and in control heated canola oil After ten frying operations at three different temperatures, TFAs in frying oils were analysed and compared with those in the heated

oils without foods. The amounts of trans 18:1 FAs in the fresh canola oils were less than the QL (0.047 g/100 g oil). Even after the tenth frying operation at 160, 180 and 200 C, they were still smaller than QL as described above. In case of 100 min-heating at 160, 180 and 200 C without foods, the amounts of trans 18:1 FAs were less than QL level and trans 18:1 FAs could not be considered the TFAs evaluation. Fig. 4 showed the amounts of trans 18:2 and trans18:3 FAs in the 10 frying operated canola oil and in the heated canola oil at 160, 180 and 200 C for 100 min. Depending on the temperature of frying and heating, these TFAs accumulations increased slightly. Furthermore, the accumulation of trans 18:2 FAs in frying oil was distinguished statistically, from that in heated oil (Fig. 4). To investigate the relation between TFAs formation and lipid oxidative deterioration, the oils examined for their TFAs contents were also evaluated for their thermal deterioration by acid value (AV) and peroxide value (POV). As shown in Fig. 5, these two values of frying and heated oils increased gradually and statistical differences were shown depending on the frying temperature. It was shown that POV and AV of the frying oil were larger than those of the heated oil at every examined temperature. The previous study suggested that the hydrolysis reaction happened by water from frying materials would relate to a rapid deterioration of the frying oil (Hara, Ogawa, & Totani, 2006). With respect to TFAs accumulation in the frying oil, hydrolysis might somewhat participate in the isomerisation of the double bonds in unsaturated FAs. These ndings suggested that the low temperature frying (for example at 160 C) might be preferable not only for less

(A) trans-18:2

(B) trans-18:3

0.16

1.00 Fried Heated

trans Fatty acids (g/100g)

0.15 0.14 0.13

c b b a a
0.95

Fried Heated

a
0.90 0.85

aa a

ba

bb

0.12 0.11 0.10 nonheated 160 180 200 0.80 0.75 nonheated 160 180 200

Fig. 4. Amounts of trans 18:2 FAs (A) and trans 18:3 FAs (B) in canola oils after heating at 180 C for 100 min, and after 10 frying operations. The values represent the means SD of three experiments. The values at the temperature points not sharing a common letter are signicantly different (P < 0.05).

0.40 Fried Heated 0.30

(A)AV

10

(B)POV
Fried Heated

c c bb

d c
POV
8 6

f d b c e

AV

0.20

a
0.10

a
2 0 nonheated 160 180 200 nonheated 160 180 200

0.00

Fig. 5. Changes of acid value (A) and peroxide compounds value (B) of canola oils after heating at 180 C for 100 min and after 10 frying operations. The values represent the means SD of three experiments. The values at the temperature points not sharing a common letter are signicantly different (P < 0.05).

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TFAs intakes but also for the consumption of less deterioration edible oils. 3.4. TFAs formation in various edible oils by heating Rened edible oils originated from various plants are commercially available and are occasionally used in the frying process. As described above, TFAs formation in the frying oil was slightly larger than that in the heated oil in the case of canola oil. To presume TFAs formation in the frying process, six commercially available vegetable oils were heated in the model system and TFAs formations were monitored. The edible oil (1.0 g) was heated at 180 C for 2 and 4 h in a small glass tube as a model heating system. The amount of total TFAs (sum of trans FAs more than QL) in these fresh oils were in the range of 1.422.08 g/100 g. Before heating, cooking oil, canola oil and corn oil mainly contained trans 18:2 FAs and trans 18:3 FAs, whilst trans 18:1 FAs and trans 18:2 FAs were dominantly detected in the fresh safower oils and the fresh sesame oil (Fig. 6). These trans isomers in the fresh oils are supposed to be produced in the deodourisation process of crude oils. During 4 h-heating at 180 C in the model system, the changes in the TFAs amounts of the examined edible oils were as follows. Small increases in trans 18:1 FAs in safower oil and rice bran oil (from 0.05 g/100 g to 0.14 g/100 g, from 0.09 g/100 g to 0.11 g/ 100 g, respectively), and in trans 18:1 FAs and trans 18:2 FAs in sesame oil (from 0.14 g/100 g to 0.25 g/100 g, from 0.31 g/100 g to 0.59 g/100 g, respectively) were observed. trans 18:3 FAs in cooking oil, corn oil and rice oil decreased slightly depended on the period of heating, as shown in Fig. 6.

The previous study reported that there was a linear relationship between the amounts of trans 18:1 FAs in several vegetable oils and the heated periods (Bansal et al., 2009). This feature could be found in trans 18:1 FAs in heated several oils investigated in this study. As shown in Fig. 6, statistically signicant differences were observed for the amounts of trans 18:1 FAs in rice bran oil, safower oil and sesame oil, although their changes were too small to affect the TFAs intakes. The fatty acid composition of each vegetable oil depends on its plant. Furthermore, the antioxidants coexisting in these vegetable oils were diverse in terms of their kinds and of their concentration. Several factors, such as FA composition of each oil and coexisted antioxidants, would contribute to the variation in the thermal TFAs accumulation proles. Previously, a substantial increase was observed in trans 18:2 FAs and in trans 18:3 FAs in safower oil, when the oils were heated at 250350 C (Grandgirard et al., 1984; Moreno et al., 1999). Those studies also suggested that no remarkable productions of trans isomers of these polyunsaturated fatty acids were detected when corresponding oils were heated at less than 200 C. In this study, trans 18:2 FAs and trans 18:3 FAs in commercially available edible oils were not formed by heating at 180 C, as shown in Fig. 6. Thus results would support the results of the previous studies. In addition to canola oil, total amounts of TFAs in other commercially available edible oils heated in the model system did not change signicantly. Now we are currently studying the TFAs formation during frying using these edible oils. In recent studies with extremely precise GC analysis conditions, a higher amount of elaidic acid in frying oil than in the heated oil

1.4

(A) Cooking Oil

C18:1t C18:2t C18:3t

1.4 1.2 1.0

(B) Canola Oil

C18:1t C18:2t C18:3t

1.4 1.2 1.0 0.8 0.6 0.4

(C) Corn Oil

trans Fatty acids (g/100g)

1.2 1.0 0.8 0.6 0.4 0.2

a2

a2

a2

a3

b3

b3
0.8 0.6

a3

b3

b3

C18:1t C18:2t C18:3t

a2 a1

a2 b1
2

a2

0.4 0.2 0.0

a3

a3

b3

c1
4 6

a2 a1
0

a2 b1
2

b2 c1
4 6

0.2 0.0 0

a1

b1
2

c1
4 6

0.0 0

Heated period (hr)

1.4

Heated period (hr)

1.4 C18:1t C18:2t C18:3t 1.2 1.0

Heated period (hr)

1.4

(D) Rice bran Oil

(E) Safflower Oil

C18:1t C18:2t C18:3t

(F) Sesame Oil

C18:1t C18:2t C18:3t

trans Fatty acids (g/100g)

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 2 4

1.2 1.0 0.8 0.6 0.4

a2

a2

a2

0.8 0.6

c2 b2 a2 b1 c1 b3
4 6

a3 a1

b3 b1

b3 c1
6

0.4 0.2 0.0 0

a2 a1 a3

a2 b1 a3
2

a2 c1 a3
4 6

0.2 0.0 0

a1 a3

b3
2

Heated period (hr)

Heated period (hr)

Heated period (hr)

Fig. 6. Accumulated trans 18:1 FAs, trans 18:2 FAs and trans 18:3 FAs in 1.0 g of cooking oil (A), canola oil (B), corn oil (C), rice oil (D) safower oil (E) and sesame oil (F) heated in a glass tube at 180 C for 2 and 4 h. The amounts of TFAs under the QL are indicated by the broken lines. The values represent the means SD of three experiments. The values at the time points not sharing a common letter are signicantly different (P < 0.05).

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W. Tsuzuki et al. / Food Chemistry 123 (2010) 976982 Bansal, G., Zhou, W. B., Tan, T. W., Neo, F. L., & Lo, H. L. (2009). Analysis of trans fatty acids in deep frying oils by three different approaches. Food Chemistry, 116, 535541. Chen, J. F., Tai, C. Y., Chen, Y. C., & Chen, B. H. (2001). Effects of conjugated linoleic acid on the oxidation stability of model lipids during heating and illumination. Food Chemistry, 72, 199206. Folch, J., Lees, M., & Sloane-Stanley, G. H. (1957). A simple method for the isolation and purication of total lipids form animal tissues. Journal of Biological Chemistry, 226, 497509. Grandgirard, A., Sobedio, J. L., & Fleury, J. (1984). Geometrical isomerization of linolenic acid during heat treatment of vegetable oils. Journal of American Oil Chemists Society, 61, 15631568. Hara, E., Ogawa, Y., & Totani, Y. (2006). Evaluation of heat-deteriorated oils (Part I): TLC-FID method for determining polar compounds content. Journal of Oleo Science, 55, 167172. Liu, W. H., Inbaraj, B. S., & Chen, B. H. (2007). Analysis and formation of trans fatty acids in hydrogenated soybean oil during heating. Food Chemistry, 104, 17401749. Liu, W. H., Lu, Y. F., Inbaraj, B. S., & Chen, B. H. (2008). Formation of trans fatty acids in chicken legs during frying. International Journal of Food Sciences and Nutrition, 59, 368382. Moreno, M., Olivares, D. M., Lopez, F. J. A., Adelantado, J. V. G., & Reig, F. B. (1999). Determination of unsaturation grade and trans isomers generated during thermal oxidation of edible oils and fats by FTIR. Journal of Molecular Structure, 482483, 551556. Mozaffarian, D., Pischon, T., Hankinson, S. E., Rifai, N., Joshipura, K., Willett, W. C., et al. (2004). Dietary intake of trans fatty acids and systemic inammation in women. American Journal of Clinical Nutrition, 79, 606612. Oh, K., Hu, F. B., Manson, J. E., Stampfer, M. J., & Willett, W. C. (2005). Dietary fat intake and risk of coronary heart disease in women: 20 years of followup of the Nurses Health Study. American Journal of Epidemiology, 161, 672679. Oomen, C. M., Ocke, M. C., Feskens, E. J. M., van Erp-Baart, M.-A. J., Kok, F. J., & Kromhout, D. (2001). Association between trans fatty acid intake and 10-year risk of coronary heart disease in the Zutphen Elderly Study: A prospective population-based study. Journal of Lancet, 357, 746751. Pietinen, P., Ascherio, A., Korhonen, P., Hartman, A. M., Willett, W. C., Albanes, D., et al. (1997). Intake of fatty acids and risk of coronary heart disease in cohort of Finnish Men. American Journal of Epidemiology, 145, 876878. Romero, A., Cuesta, C., & Sanchez-Muniz, F. J. (2000). Trans fatty acid production in deep fat frying of frozen food with different oils and frying modalities. Nutrition Research, 20, 599608. Sebedio, J. L., Catte, M., Boudier, M. A., Prevost, J., & Grandgirard, A. (1996). Formation of fatty acid geometrical isomers and of cyclic fatty acid monomers during the nish frying of frozen prefried potatoes. Food Research International, 29, 109116.

was observed and the TFAs release from the pre-fried frozen foods into the oil during frying was suggested (Aladedunye & Przybylski, 2009; Bansal et al., 2009). In this study, the raw potatoes containing undetectable TFAs were introduced as frying materials, and it was revealed that any trans 18:1 isomers including elaidic acid did not accumulate in the canola oil during frying. The result suggested that the frying process itself would scarcely contribute to elaidic acids accumulation in the frying oils. It is at least possible to conclude from this study that the frying process using unhydrogenated edible oils has little impact on TFAs intake. Acknowledgements This research was commissioned by the Research Projects for Utilising Advanced Technologies in Agriculture, Forestry and Fisheries, Ministry of Agriculture, Forestry and Fisheries, Japan. The authors are deeply grateful to Mr. Tetsuo URUSHIYAMA and Mr. Kiyoshi OSHIMA (Ministry of Agriculture, Forestry and Fisheries) for the research planning and for their valuable correspondences. The authors also would like to extend their special thanks to Dr. Akihiko NAGAO and Dr. Akemi YASUI (National Food Research Institute) for their scientic advises. References
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