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Food Chemistry 120 (2010) 5965

Contents lists available at ScienceDirect

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

Emissions of volatile aldehydes from heated cooking oils

Harinageswara Rao Katragadda a, Andrs Fullana b, Sukh Sidhu a, ngel A. Carbonell-Barrachina c,*
a

University of Dayton, Environmental Sciences and Engineering Group, 300 College Park, Dayton, OH 45469-0132, USA
Universidad de Alicante, Departamento de Ingeniera Qumica, Apartado de correos 99, 03080 Alicante, Spain
c
Universidad Miguel Hernndez, Departamento Tecnologa Agroalimentaria, Grupo Calidad y Seguridad Alimentaria, Carretera de Beniel, km 3.2, 03312 Orihuela, Alicante, Spain
b

a r t i c l e

i n f o

Article history:
Received 18 May 2009
Received in revised form 27 July 2009
Accepted 21 September 2009

Keywords:
Acrolein
Canola oil
Coconut oil
Deep-frying
Indoor emissions
Olive oil
Safower oil

a b s t r a c t
Emissions of volatile organic compounds, including aldehydes, formed during heating of cooking oils:
coconut, safower, canola, and extra virgin olive oils were studied at different temperatures: 180, 210,
240, and 240 C after 6 h. Fumes were collected in Tedlar bags and later analysed by GCMS. The emissions of volatiles were constant with time and increased with the oil temperature. When the temperature
of the oil was above its smoke point, the emission of volatiles drastically increased, implying that oils
with low smoke point, such as coconut, are not useful for deep-frying operations. Canola was the oil generating the lowest amount of potentially toxic volatile chemicals. Acrolein formation was found even at
low temperatures, indicating that home cooking has to be considered as an indoor pollution problem.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
The operation known as deep-fat frying is widely used both
domestically and commercially. Frying may be considered as a rapid combination of drying and cooking (Moyano & Pedreschi,
2006). During deep-frying, fats and oils are repeatedly used at elevated temperatures (between 160 and 240 C, with an optimal value of 180 C) in the presence of atmospheric oxygen and receive
maximum oxidative and thermal abuse (Andreu-Sevilla et al.,
2008; Frankel, 1998; Moreira, Castell-Perez, & Barrufet, 1999).
Different oils (both of animal and vegetable origin) are used for
deep-frying in different cultures. However, recent studies have
shown that unsaturated oils like olive and canola oils are healthier
to use than hydrogenated oils or animal based fats such as butter
and lard. (Frankel, 1998; Medina-Navarro, Mercado-Pichardo, Hernndez-Prez, & Hicks, 1999; Moreira et al., 1999). For instance,
the benecial properties of olive oil have been attributed to its
fatty acid composition characterised by a high monounsaturatedto-polyunsaturated fatty acid ratio and the presence of minor compounds with powerful antioxidant activity, among which polyphenols stand out (Aparicio & Harwood, 2003; Velasco & Dobarganes,
2002).
Aldehydes, ketones, alcohols, dienes and acids, commonly
formed during edible oil degradation, create unpleasant avour, re* Corresponding author. Fax: +34 966749754.
E-mail address: angel.carbonell@umh.es (.A. Carbonell-Barrachina).
0308-8146/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2009.09.070

duce the shelf-life of edible oils, and may further cause health
problems (Fullana, Carbonell-Barrachina, & Sidhu, 2004a, 2004b).
Recent reports indicate that oil fumes resulting from heating edible
oils, such as rapeseed oil, soybean oil, peanut oil and lard, to high
temperature exhibit mutagenicity and genetic toxicity (Chiang
et al., 1997; Moreira et al., 1999; Qu et al., 1992). Since aldehydes
are major products of this degradation and due to their capacity to
induce toxicological effects (e.g., their reactivity with amino groups
of proteins), aldehydes like acrolein are considered to have high
relevance (Umano & Shibamoto, 1987; Yen & Wu, 2003; Zhu,
Wang, Zhu, & Koga, 2001). Within this chemical family, unsaturated aldehydes, such as alkenals and alkadienals, show more severe toxicity than alkanals (Meacher & Menzel, 1999; Tovar &
Kaneda, 1977).
Nowadays consumers are demanding healthier oils; this demand is based on a proper fatty acid composition (high content
of monounsaturated fatty acids, such as oleic acid), and also on a
reduced emission of potentially toxic compounds, such as aldehydes. The correct choice of an oil for frying is important for several reasons. Firstly, the oil is used as the heat transfer medium
and must be able to withstand high temperatures and have high
enough stability to allow its reuse. Secondly, products being fried
will take up some of the oil, and therefore the oil needs to maintain
a high oxidative stability during the life of the product, and be both
palatable and nutritious (Andreu-Sevilla, Hartmann, Burl, Poquet,
& Carbonell-Barrachina, 2009; Andreu-Sevilla et al., 2008; Talbot &
Zand, 2006). Finally, the oil should be as stable as possible during

60

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

its heating and originated a low emission of potentially toxic volatile organic compounds.
The emission of indoor air pollutants is related to the smoke
point of the oils being heated. The smoke point is the temperature
at which oil begins to smoke continuously. In the present experiment, different oils covering a wide range of smoke points were
used (Table 1): coconut (175 C), extra virgin olive oil (195 C), saf-

ower (212 C), and canola (238 C). To our knowledge, no studies
have been conducted that compare the impact of heating oils with
different smoke points on the emission of volatile organic compounds. In this paper, gas chromatographymass spectrometry
(GCMS) was used to isolate, identify, and quantify the volatile
compounds from four types of cooking oils: coconut, extra virgin
olive, safower, and canola oils at four different temperatures:
180, 210, 240 and 270 C, for 6 h. In previous studies (Fullana
et al., 2004a, 2004b), this research group studied the emissions of
aldehydes from two different types of olive oils, (a) extra virgin olive (edible oil prepared without any chemical treatment) and (b)
olive (oil physically rened, eliminating off-avours but also natural antioxidant compounds); canola oil was used as a control
material.

Table 1
Fatty acid composition and smoke points of coconut, safower, canola, and extra
virgin olive oils.
Oil

MUFAa (%)

PUFA (%)

SFA (%)

Smoke point (C)

Coconut
Safower
Canola
Extra virgin olive

61
15 1
58 3
72 4

31
75 4
32 2
14 1

91 5
81
10 1
14 1

175 4
212 4
238 5
195 4

2. Materials and methods

a
MUFA = monounsaturated fatty acids; PUFA = polyunsaturated fatty acids;
SFA = saturated fatty acids.

Thermo couple

2.1. Materials
Canola (liquid at room temperature; 58% and 38% of monounsaturated and polyunsaturated fatty acids, respectively), extra virgin olive (liquid at room temperature; 72% of monounsaturated
fatty acids), safower (liquid at room temperature; 75% of polyunsaturated fatty acids), and coconut (solid at room temperature;
91% of saturated fatty acids) oils were purchased from a local
supermarket in Dayton (OH, USA).

Tedlar bag

Air

2.2. Experimental system and sampling

T controller
The experimental system used to conduct this study is shown in
Fig. 1. This system consists of a hermetic Pyrex reactor heated by a
hemispherical heating mantle and the heating is controlled by a
thermocouple that was placed inside the oil. For this study, cooking
oils were heated to 180 C (regular deep-frying temperature), 210,
240, and 270 C (temperature above the maximum smoke point of
the cooking oils studied) for 6 h and samples were taken every

Cooking oil

ON

180C

Food
OFF

Heating system

Air

Fig. 1. Schematic representation of experimental system used in frying simulation.

Table 2
Emission rate (mg h

loil ) of volatile aldehydes from safower oils heated at 210 C during different times (16 h).

Chemical compound

ANOVA test

Time of heating (h)

0

Alkanals
Acetaldehyde
Propanal
Butanal
Pentanal
Heptanal
Octanal
Nonanal

*A

N.S.
N.S.
*

N.S.
N.S.
*

11.2 0.56a
5.75 1.03
17.9 1.9
190 10a
78.9 3.9
19.7 1.0
51.2 2.6a

9.09 0.45b
5.17 0.85
18.9 1.7
186 9a
82.3 4.1
18.1 0.9
49.8 2.5a

129 7a
84.4 10.2
643 32a
68.4 3.4a
22.1 3.1

106 5.3b
70.2 3.5
234 12d
61.1 3.1a
22.3 2.5

89.6 4.5c
59.2 7.5
255 13d
62.7 3.1a
22.8 3.1

87.1 4.4c
69.3 3.5
209 10d
58.5 2.9b
23.1 2.3

74.1 3.7d
65.1 3.3
432 22b
40.8 2.0c
23.4 3.2

95.5 4.8c
69.7 3.5
368 18c
56.2 2.8b
21.3 2.5

23.3 2.2
24.8 1.2

19.1 1.0
24.6 1.2

20.3 1.9
25.1 1.3

20.1 1.6
24.9 1.2

19.0 1.3
24.3 1.2

19.2 1.1
23.2 1.2

408 20a
947 47a
48.1 2.4a
1403 70a

349 18b
494 25c
43.7 2.2a
886 44d

365 18b
489 25c
45.4 2.3a
900 45c

400 20ab
447 22c
45.0 2.3a
892 45c

375 19b
635 32b
43.3 2.2a
1053 53b

369 19b
611 31b
42.4 2.1a
1022 51b

13.4 5.7
15.3 6.8

317 16c
653 33b
28.7 4.4b
999 50bc

* **

**
*
*

10.4 0.52ab
5.69 1.28
22.4 1.1
204 10a
86.9 4.3
19.0 0.95
52.1 2.61a

N.S.
N.S.

Total
Alkanals
Alkenals
Alkadienals
ALDEHYDES

9.76 0.49b
5.51 0.88
19.3 1.0
182 9a
80.2 4.0
18.2 0.9
50.2 2.5a

Alkadienals
2,4-Heptadienal
2,4-Decadienal

9.17 0.46b
5.39 0.99
10.8 7.5b
195 10a
59.8 3.0
17.5 0.9
51.2 2.6a

N.S.

**

8.81 0.44b
5.66 1.08
22.8 3.1
190 10a
109 16
17.4 0.9
54.1 2.7a

87.2 4.4c
69.6 3.5
436 22b
46.0 2.3c
14.0 4.7

5.17 0.26BcC
2.99 1.15
20.3 2.0
152 8b
79.9 4.0
16.7 0.9
40.1 2.0b

Alkenals
Acrolein
2-Hexenal
2-Heptenal
2-Octenal
2-Decenal

N.S.

, , and ***, signicant at p < 0.05, 0.01, and 0.001, respectively.

A
N.S. = not signicant F ratio (p < 0.05).
B
Treatment means of the ANOVA test (mean of three replications) standard error.
C
Values followed by the same letter, within the same raw, are not signicant different (p < 0.05), Tukeys multiple-range test.

61

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

hour. Air at ow rate of 1 l min 1 was supplied to the reactor. This

air ow ensured total removal of fumes generated from heating the
oil. The inlet air line was designed such that it was far enough from

14000

-1

-1

Total Volatiles (mg h L )

12000

Coconut
Safflower
Canola
Extra Virgin Olive

10000

8000

6000

4000

2000

0
170

180

190

200

210

220

230

240

250

260

270

280

Temperature (C)
1

oil surface to minimise changes in the diffusion layer but at the

same time the air ow was sufcient enough to prevent stagnant
ow zones and was able to transport all the compounds evolved
during heating of cooking oils. The reactor exhaust gases were collected in 500 ml clear layered Tedlar bags (Supelco, Bellefonte, PA,
USA; Supelco catalogue number 24655). The collected gas samples
were then analysed by GCMS. The product stability was analysed
according to the specications in US. EPA sampling method 40 during the time between sampling and analysis. Experiments were run
in six replicates.
Authors checked that no artefacts were introduced by the Pyrex
reactor or the Tedlar bags. Different set ups for trapping the volatile compounds were previously used in different studies using olive oils: (a) Tedlar bags (Fullana et al., 2004a) and (b) tenax traps
(Fullana et al., 2004b); results were quite similar with the only
exception that tenax traps were unable to trap small and reactive
compounds such as acrolein or acetaldehyde. These previous results advise that Tedlar bags were the best way of collecting fumes
from frying simulations.

2.3. Analytical procedure

Fig. 2. Emission rates of total volatiles (mg h loil ) being released from coconut,
safower, canola, and extra virgin olive oils heated at four different temperatures
(180270 C).

A Hewlett-Packard (HP) model 5890 gas chromatograph combined with an HP-5970 series mass selective detector equipped
with a 30.0 m  0.25 mm i.d. DB 625 was used to perform the anal-

1600
Aldehydes
Alkanals
Alkenals
Alkadienals

1400

-1

-1 -1

2-Heptenal (mg h L )

4000

-1

Concentration (mg h L )

5000

3000

2000

1000

1200

Coconut
Safflower
Canola
Extra Virgin Olive

1000
800
600
400
200

0
160

180

200

220

240

260

280

180

210

Temperature (C)

-1 -1

2-Hexanone (mg h L )

-1

6000

4000

2000

0
160

270

2000
Hydrocarbons
Alcohols
Ketones

-1

Concentration (mg h L )

10000

8000

240

Temperature (C)

180

200

220

240

260

280

Temperature (C)
Fig. 3. Emission rates of aldehydes, hydrocarbons, alcohols, and ketones
1
1
(mg h loil ) being released from coconut oil heated at four different temperatures
(180270 C).

1500

Coconut
Safflower
Canola
Extra Virgin Olive

1000

500

0
180

210

240

270

Temperature (C)
1

Fig. 4. Emission rates of 2-heptenal and 2-hexanone (mg h loil ) being released
from coconut, safower, canola, and extra virgin olive oils heated at four different
temperatures (180270 C).

62

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

yses of collected gas samples. For this analysis, 1.0 ml of gas was
directly injected in the gas chromatograph. The limit of detection
observed (1 mg m 3) was enough for the purposes of this study,
and therefore no concentration or derivatisation methods were
used. The oven temperature was held at 35 C for 5 min and then
programmed to 230 C at 5 C min 1 and held for another
12 min. Products were identied by comparing product mass spectra with mass spectral database (NIST).
Standards of acrolein, pentanal, hexanal, heptanal, 2-octenal,
and 2,4-heptadienal in the available purest form were bought from
Aldrich Chemicals (Milwaukee, WI). These chemicals were diluted
in methanol and injected into GCMS to obtain response factors
from the standard calibration curves. The average value of all the
response factors from these standards was calculated and used to
quantify experimental results.

2.4. Statistical analyses

Data from volatile aldehydes emissions were examined by analysis of variance (ANOVA) using STATGRAPHICS Plus 5.0 software
(Manugistics Inc., Rockville, MD). Wherever F values were signicant, Tukeys multiple-range test was used to separate the mean
effects (different temperatures for each oil type). Signicance
was dened at p 6 0.05. Graphics were done using Sigma Plot 9.0
(SPSS Science, Chicago, IL, USA).

2-Decenal (mg h-1L-1)

Coconut
Safflower
Canola
Extra Virgin Olive

400

200

0
180

3.1. General
A total of 30 compounds were tentatively identied, based on
matches with library mass spectral data, including aldehydes, ketones (2-hexanone, 2-heptanone, and ethylcyclopentanone),
hydrocarbons (pentane, 1-heptene, heptane, cyclopropane, octane, nonane, decane, butylbenzene, undecane, and 6-dodecene),
and alcohols (pentanol, hexanol, and 1-octen-3-ol). From these
compounds, the most interesting are aldehydes due to their potential toxicity for those working in restaurants or home kitchens.
It has been reported that large amounts of aldehydes are present
in the headspace of cooking oil containers, and they are considered as possible contributors to carcinogenicity (Yen & Wu,
2003; Zhu et al., 2001). Sixteen aldehydes were tentatively identied in this study and can be grouped as follows: (a) alkanals:
acetaldehyde, propanal, butanal, pentanal, heptanal, octanal, and
nonanal; (b) alkenals: acrolein, 2-hexenal, 2-heptenal, 2-octenal,
and 2-decenal, and (c) alkadienals: 2,4-heptadienal and 2,4decadienal.

3.2. Effect of time

In this experiment oils were heated at 210 C up to 6 h and samples were taken every hour. The generation rate of aldehydes was
almost constant with respect to time for all four oils under study.
As an example, data for the generation of aldehyde during heating
of safower oil are compiled in Table 2. The concentrations of total
aldehydes were 999, 1403, 887, 900, 892, 1053, and
1
1
1002 mg h loil for 0, 1, 2, 3, 4, 5, and 6 h of heating at 210 C
1
1
(mean of 1019 75 mg h loil ). Similar patterns were found for
(a) coconut oil: 894, 1215, 1893, 1143, 1064, 1200, 1139
1
1
mg h loil , for 0, 1, 2, 3, 4, 5, and 6 h, respectively (mean of
1
1
1221 119 mg h loil ); (b) canola oil: 1302, 993, 1167, 1033,
1
1
1053, 1056, and 1076 mg h loil , respectively (mean of
1
1
1097 43 mg h loil ); and (c) extra virgin olive oil: 1908, 1049,
1
1
2338, 2185, 2440, 1731, and 2001 mg h loil , respectively (mean
1
1
of 1950 193 mg h loil ).
Consequently, the effect of time was omitted in the next experiments (averages of all concentrations at different time intervals
will be used).

800

600

3. Results and discussion

210

240

270

Temperature (C)
800

300

Acrolein (mg h-1L-1)

Nonanal (mg h-1L-1)

600

400
Coconut
Safflower
Canola
Extra Virgin Olive

400

200

Coconut
Safflower
Canola
Extra Virgin Olive

200

100

0
180

210

240

270

Temperature (C)

0
180

210

240

270

Temperature (C)
1

Fig. 5. Emission rates of 2-decenal and nonanal (mg h loil ) being released from
coconut, safower, canola, and extra virgin olive oils heated at four different
temperatures (180270 C).

Fig. 6. Emission rates of acrolein (mg h loil ) being released from coconut,
safower, canola, and extra virgin olive oils heated at four different temperatures
(180270 C).

63

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

3.3. Effect of temperature

The total amounts of volatile compounds present in the fumes
of cooking oils were positively correlated with the frying temperature. Fig. 2 represents the total volatile generation rate for coconut,
safower, canola and extra virgin olive oils as affected by the heating temperature. Total concentrations of aldehydes, hydrocarbons,
alcohols and ketones (Fig. 3) increased with increasing frying temperatures. The dependence of volatile emissions with temperature
was more evident for alkanals and hydrocarbons. Therefore, the
rst recommendation is to use the lowest possible temperature
for reaching the desired cooking and technological effects during
deep-frying operations.
3.4. Effect of the smoke point
The smoke point is the temperature at which oil begins to
smoke continuously and can be seen as bluish smoke. This smoke
is an indication of chemical breakdown of the fat to glycerol and
free-fatty acids (FFA). The glycerol is then further broken down
to acrolein (2-propenal), which is one of the main components of
the bluish smoke. This point is greatly dependent on the content
of free-fatty acids and to a lesser degree on partial glycerides.
The inuence of degree of unsaturation is minimal but chain length
Table 3
Emission rate (mg h

loil ) of volatile aldehydes from coconut and safower oils heated 6 h at different temperatures (180, 210, 240 and 270 C).

Chemical compound

Coconut oil
Alkanals
Acetaldehyde
Propanal
Butanal
Pentanal
Heptanal
Octanal
Nonanal
Alkenals
Acrolein
2-Hexenal
2-Heptenal
2-Octenal
2-Decenal
Alkadienals
2,4-Heptadienal
2,4-Decadienal
Safower oil
Alkanals
Acetaldehyde
Propanal
Butanal
Pentanal
Heptanal
Octanal
Nonanal
Alkenals
Acrolein
2-Hexenal
2-Heptenal
2-Octenal
2-Decenal
Alkadienals
2,4- Heptadienal
2,4- Decadienal
* **

has an important effect; oils containing short chain fatty acids (e.g.,
lauric acid) have lower smoke appoint than oils with predominantly longer chain fatty acids. A general rule is that the higher
the smoke point, the better suited a fat is for frying; fats with
smoke point below 200 C are not suitable for deep-fat frying.
Volatile aldehyde emission from all four oils increased gradually
with temperature until they reached their smoke point (Tables 3
and 4); from this point, emission increased more sharply (Fig. 2).
For instance, in safower oil (smoke point = 212 C) the emission
1
1
rate of total volatile compounds increased 879 mg h loil when
the temperature was raised from 180 to 210 C, while the incre1
1
ment was signicantly higher, 1971 mg h loil , when the temperature was raised from 210 to 240 C (above the smoke point of this
oil). The same behaviour was found for the other oils.
This experimental nding is very important and leads us to the
following conclusion: the temperature of any oil used for deep-frying operations should be established below its smoke point, because
otherwise the emission of potentially toxic compounds will increase
signicantly. This rst conclusion leads us to a second one: coconut
oil should not be used as a deep-frying matrix because its smoke
point (175 C) is below the optimal temperature for frying operations (180 C). However, even emissions below the smoke point of
oils might be harmful, especially those of acrolein and acetaldehyde
in closed rooms/kitchens with limited ventilation.

ANOVAtest

***A
***
***
***
***
***
*

***
**
**
*
**

**
*

**
**
***
***
**
**
*

***
**
**
**
*

**
**

Heating temperature (C)

180

210

240

13.1 2.0BdC
10.8 2.0d
36.5 7.6d
104 18d
94.2 4.2c
51.4 2.2b
60.1 2.6c

44.7 3.9c
44.7 4.9c
155 18c
423 65c
151 11b
66.9 4.3b
66.0 5.3c

99.2 5.8b
86.3 3.4b
297 13b
786 27b
290 22a
135 14a
160 20a

327 11a
217 6a
683 23a
1685 45a
302 27a
131 13a
84.6 4.3b

10.4 2.2d
11.7 0.9d
119 10b
27.7 1.8b
29.9 2.4b

18.6 2.3c
41.9 2.7a
138 14b
26.8 2.8b
30.1 2.6b

44.4 1.7b
30.0 2.3b
268 20a
54.9 5.0a
95.7 3.9a

232 10a
20.7 0.5c
124 8b
26.7 1.5b
27.3 2.8b

10.9 1.7b
4.71 0.34b

8.73 1.81c
5.15 1.26b

20.9 1.6a
13.7 2.8a

12.5 1.3b
5.88 0.94b

9.41 0.84c
6.68 0.58c
16.2 1.4c
133 14d
115 16c
35.4 3.9b
72.4 9.0b

9.09 0.80c
5.17 0.41c
18.9 1.7c
186 7c
82.3 6.0d
18.1 0.4d
49.8 1.9c

1072 34b
12.8 0.3b
47.8 1.2b
281 11b
168 7b
29.0 1.1c
47.9 2.2c

62.7 1.3a
43.3 1.2a
127 4a
600 14a
350 25a
65.4 4.0a
123 11a

57.3 6.7d
63.6 6.2c
586 74b
68.0 10.0b
24.1 3.3a

95.5 7.3c
69.7 3.1c
368 63c
56.2 4.0c
21.3 1.4b

122 5b
82.1 1.1b
691 12b
64.0 2.4b
10.1 0.8c

343 27a
161 16a
1297 135a
113 9a
28.4 2.6a

30.0 5.5b
17.5 2.8c

19.2 1.2c
23.2 1.5b

13.0 4.5d
12.2 0.3d

51.0 4.8a
29.7 4.3a

, , and ***, signicant at p < 0.05, 0.01, and 0.001, respectively.

A
N.S. = not signicant F ratio (p < 0.05).
B
Treatment means of the ANOVA test (mean of six replications) standard error.
C
Values followed by the same letter, within the same raw, are not signicant different (p < 0.05), Tukeys multiple-range test.

270

64

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

3.5. Effect of fatty acid concentration

Different studies have shown that the following compounds derived from linoleic acid (C18:2): acetaldehyde, pentanal, hexanal,
2-heptenal, 2-octenal, 2-nonenal, 2,4-decadienal, pentane, and 1pentanol (Feron et al., 1991; Qu et al., 1992; Ruiz-Mndez, 2003;
Subramanian & Nakajima, 1997; Wan, Pakarinen, & Miscella,
1996). In this way, the emission rates of, for instance, 2-heptenal
should be higher in those oils having higher contents of linoleic
acid: safower > canola > extra virgin olive > coconut. Fig. 4 shows
the emission rates of 2-heptenal and 2-hexanone as examples of
the experimental situation found and, in general, it was clear that
the emissions of compounds such as 2-heptenal and 2-hexanone
were signicantly higher in safower oil compared to the other
three types of oil under study (Tables 3 and 4). The differences
among canola, extra virgin olive and coconut were only visible at
the highest temperature (270 C).
In most cases, coconut oil emissions are out of their supposed
position in this pattern due to the fact that all the assayed temperatures were above its smoke point.
From the literature, heptane, heptanol, octane, octanal, nonanal,
decanal, 2-decenal, 1-undecene, and 2-undecenal are emitted after
degradation of oleic acid (C18:1), and more precisely from the haemolytic ssion of the RO bond of this fatty acid (Feron et al.,
1991; Qu et al., 1992; Ruiz-Mndez, 2003; Subramanian & Nakajima,
Table 4
Emission rate (mg h

Canola oil
Alkanals
Acetaldehyde
Propanal
Butanal
Pentanal
Heptanal
Octanal
Nonanal
Alkenals
Acrolein
2-Hexenal
2-Heptenal
2-Octenal
2-Decenal
Alkadienals
2,4-Heptadienal
2,4-Decadienal
Extra virgin olive oil
Alkanals
Acetaldehyde
Propanal
Butanal
Pentanal
Heptanal
Octanal
Nonanal

Alkadienals
2,4-Heptadienal
2,4-Decadienal
* **

3.6. Activation energy

Temperature is the most important factor to be considered in
evaluating the oxidative stability of fats, especially unsaturated,
because the mechanism of oxidation changes with temperature
and different hydroperoxides of linoleate, acting as precursors of
volatile avours, decompose at different temperatures. Because
the rate of oxidation is exponentially related to temperature, the
shelf-life of a food lipid decreases logarithmically with increasing
temperature (Frankel, 1998).
The activation energy (additional energy needed by reactants to
form products) of lipid oxidation is much higher in the presence of
antioxidants than in their absence because antioxidants lower the
rates of oxidation by increasing the overall energy of activation

loil ) of volatile aldehydes from coconut and safower oils heated 6 h at different temperatures (180, 210, 240 and 270 C).

Chemical compound

Alkenals
Acrolein
2-Hexenal
2-Heptenal
2-Octenal
2-Decenal

1997; Wan et al., 1996). In this way, the emission rates of, for instance, 2-decenal should be higher in those oils having higher contents of oleic acid: extra virgin olive P canola > safower P
coconut. Fig. 5 shows the emission rates of 2-decenal and nonanal
as examples of emission of volatile compounds originating in oleic
acid (Tables 3 and 4). Again the effect of the fatty acid concentrations
on the emission rates was clearer at the highest temperature assayed, 270 C: the emission of compounds such as 2-decenal and
nonanal were signicantly higher in extra virgin olive oil, followed
by canola, and then safower and coconut.

ANOVA test

**A
**
***
***
***
**

***
**
***
***
***

***
***

**
**
*
**
**
***

***
***
***
***
***

**
***

Heating temperature (C)

180

210

240

270

n.d.
21.4 1.8BcC
9.77 0.56c
33.2 1.4d
64.0 4.0c
54.7 5.1b
120 8b

n.d.
36.4 2.9b
23.7 1.9b
50.7 4.1c
85.4 4.1b
51.2 3.3b
88.0 6.8c

n.d.
10.9 0.6d
5.57 0.38d
216 7b
46.8 1.9d
8.80 0.34c
51.0 2.5d

n.d.
93.5 19.0a
86.6 3.7a
564 39a
415 58a
167 15a
365 31a

53.5 3.9d
18.7 0.9b
108 5d
60.1 5.7c
63.7 2.4c

116 8c
18.8 1.9b
156 4c
242 6b
74.8 3.8b

234 14a
62.0 2.7a
463 15b
13.6 0.9d
33.5 1.4d

135 7b
76.1 12.0a
841 73a
359 35a
138 21a

95.8 11.3d
14.9 3.8c

141 3c
17.2 4.7c

163 17b
32.3 2.0b

260 15a
159 12a

n.d.
21.1 6.0b
18.7 4.9c
115 30a
121 15c
71.3 6.6c
134 17d

n.d.
18.4 2.6b
30.1 3.4b
80.1 3.3b
215 13b
150 11b
362 30c

n.d.
40.6 3.7a
82.2 9.5a
139 14a
300 20a
182 28ab
545 15b

n.d.
44.5 0.9a
90.6 6.0a
151 8a
319 11a
193 29a
594 13a

12.1 2.5d
12.2 1.8c
161 39c
92.6 16.2b
32.9 7.5d

39.7 3.7c
36.4 6.0b
213 17b
344 37a
306 73c

106 14b
63.5 14.0a
413 44a
369 29a
611 31b

120 4a
69.7 14.3a
460 7a
352 27a
698 37a

17.6 3.0b
9.7 0.7c

60.5 8.2a
102 21b

50.2 4.3a
587 90a

52.0 4.4a
684 6a

, , and ***, signicant at p < 0.05, 0.01, and 0.001, respectively.

A
N.S. = not signicant F ratio (p < 0.05).
B
Treatment means of the ANOVA test (mean of six replications) standard error.
C
Values followed by the same letter, within the same raw, are not signicant different (p < 0.05), Tukeys multiple-range test.

H.R. Katragadda et al. / Food Chemistry 120 (2010) 5965

(Frankel, 1998). Arrhenius plots of the logarithmic of emission

rates of the total volatile compounds versus the reciprocal of the
temperatures (K) were prepared. The adjustments of the experimental data to the Arrhenius equation were good and high coefcients of determinations (R2) were obtained: 0.9885, 0.8070,
0.9571, and 0.9423 for coconut, safower, canola, and extra virgin
olive oils, respectively. The calculated values of the ratio activation
energy (E/R) were: 5919, 4675, 2875, 2140 for coconut, extra virgin
olive, canola, and safower oils, respectively. The experimentally
calculated activation energies are quite logical and fully agree with
the nature and fatty acid composition of the oils under study. The
highest activation energy was found for coconut oil because contains the highest concentration of saturated fatty acids, which require more energy to decompose than unsaturated fatty acids.
The next activation energy was that of extra virgin olive oil due
to its high content of monounsaturated fatty acids and likely high
concentration of natural antioxidants. Safower oil was had the
lowest activation energy due to its high content of polyunsaturated
fatty acids.
3.7. Acrolein
Acrolein (2-propenal) is a compound of special interest among
the emitted volatile compounds because of its carcinogenicity.
Unfortunately, there is no consensus on its origin. For instance,
acrolein can form via thermolysis of glycerol at temperatures higher than 230 C (Fujisaki, Endo, & Fujimoto, 2002; Zhu et al., 2001);
however, in the present study acrolein was formed even at the
lowest studied temperature, 180 C. This means that even at low
temperatures, pathways for its formation also exists. Umano and
Shibamoto (1987) based on their observation of acrolein formation
under a nitrogen stream, proposed that its formation was likely
due to a free-radical mechanism involving homolytic ssion of
RO bond (Schauer, Kleeman, Cass, & Simoneit, 2002). Probably
all three formation pathways previously described in the literature
contributed to the acrolein emissions observed in this study; however, based on the data collected in this study, it is difcult to identify the dominant formation pathway.
Acrolein emission from safower oil was high compared to the
other three oils, especially extra virgin olive oil; this might be due
to the high content of polyunsaturated fatty acids present in safower (Fig. 6). Emission rates were also high for canola oil at temperatures of 240 C and lower. The high increase observed in
coconut oil at 270 C might be due, among other factors, to the fact
that this temperature is quite close to the ash point of this oil
275280 C; the ash point is the temperature at which the volatile products are evolved at such a rate that they are capable of
being ignited but not capable of supporting combustion.
4. Conclusions
From an industrial point of view, one of the most important
conclusions to be drawn from this study is that a proper control
of oil temperature will increase the shelf-life of oils being used
for deep-frying purposes and at the same time it will reduce the indoor emissions of aldehydes. Formation of aldehydes and volatile
compounds during deep-frying operations depends mainly on oil
temperature and formation rate is constant with time. The tendency of formation of volatiles also depends on the fatty acid composition of heated oils and it increases when it reaches its smoke
point and will enhance drastically when oil approaches its re
point. Total volatiles and aldehydes emitted from all four oils increased almost linearly with temperature. Even at temperatures
as low as 180 C (deep-frying optimum), acrolein formation was

65

found in all four cooking oils. Therefore, formation of acrolein in

home cooking has to be considered as an indoor pollution problem.
However, it is important to mention that during cooking operations, acrolein would be distributed into an open ambient area,
so the actual concentration to which persons in kitchen and food
industry workers would be exposed will be lower. Proper ventilation in kitchen will help in reducing the impact of these potentially
toxic compounds. Reheating of the oil is not recommended as
used-oil will contain a higher free-fatty acid content and consequently drastically decrease its original smoke point, which will result in higher emissions of volatiles at lower temperatures.
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