Industrial Crops and Products 74 (2015) 592599

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Industrial Crops and Products

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Improvement of vegetable oils quality in frying conditions by adding

rosemary extract
Nadia Chammem a, , Salma Saoudi a , Ines Sifaoui b , Samira Si c , Marine de Person d ,
Manef Abderraba b , Fathi Moussa d , Moktar Hamdi a
a

Laboratoire dEcologie et de Technologie Microbiennes, INSAT, University of Carthage, Tunisia

Laboratoire Matriaux Molcules et Applications, IPEST, University of Carthage, Tunisia
c
National Ofce of Oil, Tunis, Tunisia
d
LETIAM, Groupe de Chimie Analytique de Paris Sud EA 4041, IUT dOrsay, Universit Paris Sud 11, Plateau de Moulon, 91400 Orsay, France
b

a r t i c l e

i n f o

Article history:
Received 13 November 2014
Received in revised form 21 May 2015
Accepted 22 May 2015
Available online 12 June 2015
Keywords:
Rosemary extract
Frying oil
Heat treatment
Oxidation
Sensorial analysis
Stability

a b s t r a c t
The effect of rosemary extract (Rosemarinus ofcinalis L.), a natural antioxidant, on stability of frying
oil during heat treatment and on sensorial quality of fried potato was studied. A mixture of soybean
and sunower oils in an equal proportions and containing 0.08% of rosemary extract was evaluated for
thermo-oxidation at 180 C for 30 h. This evaluation was carried out comparatively to an oil mixture
without antioxidant. Results showed a signicant difference (p < 0.05) between oils according to the
measured parameters especially at the end of treatment. The addition of the rosemary extract in the
mixture of soybean and sunower oil reduce the peroxide value by 38% after 30 h of heating. This oil
resists to oxidation and conserves the higher amount of unsaturated fatty acids even after 30 h of heating.
The evolution of saturated fatty acid composition is estimated at 5.5% and 25% in the oil with and without
extract, respectively, at the end of the heating treatment. Sensorial analysis carried out showed that the
fried potato prepared in oil with rosemary extract had the best crispiness and taste until the fteenth
frying. The oil with rosemary extract showed an enhanced stability and therefore a best quality compared
to the oil without rosemary extract.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Deep fat frying is one of the most procedures used for preparing
food (Rababah et al., 2012). It leads to obtain products with appreciated sensorial properties. However, the limit of this technique lies
into the rapid deterioration of the quality and the stability of the oil
during its use in frying. This deterioration takes place following a
series of reactions leading to a qualitative and a nutritional change
(rancidity, discoloration and loss of essential fatty acids). These may
also be responsible for the production of toxic compounds such as
peroxides, aldehydes, and epoxides (Zhang et al., 2012).
Oxidation is one of the most signicant chemical reactions
occurring during the frying process. This reaction is inuenced by
several factors such as high temperatures, presence of oxygen and
presence of unsaturated fatty acids in a high rate, targets of this
reaction (Gupta, 2005). To improve the quality of the oil, increase its
stability and subsequently its duration of use, different approaches

Corresponding author. Tel.: +216 71703829/71703929; fax: +216 71704329.

E-mail address: nadia.chammem@insat.rnu.tn (N. Chammem).
http://dx.doi.org/10.1016/j.indcrop.2015.05.054
0926-6690/ 2015 Elsevier B.V. All rights reserved.

have been implemented by several companies in the world such as

the mixture of different oils, research and use of new plant species
producing better stable oils and the use of synthetic or natural
antioxidants.
Several studies are interested in nding new sources of natural antioxidants could be more efcient than synthetic ones. For
instance, it is known that plant extracts are a mixture of different phenolic compounds known for their antioxidant activity
(Michalowska and Korezak, 2007). Several plants were therefore
tested for this activity and even how do their extract act in oils.
Nowadays, the most studied extracts are sage extract (Salvia
ofcinalis L.) and rosemary extract (Rosemarinus ofcinalis L.), coffee
beans, tea leaves, vegetables especially onions and peppers (Jaswir
et al., 2000a; Lalas and Dourtoglou, 2003) and olive leaves (Chiou
et al., 2009).
Among these natural extracts that are likely to be used industrially, the rosemary ones have a signicant antioxidant effect even at
high temperatures. Their effectiveness was tested in soybean oils
(Lalas and Dourtoglou, 2003; Ramalho and Jorge 2008) and Palm
oil (Jaswir et al., 2000a) used for frying. Several studies in this context have shown that the rosemary extracts added to the frying oil

N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

can inhibit the decomposition of polyunsaturated triacylglycerols,

inducing the formation of polar compounds and polymers. It seems
that, these extracts are more effective in the inhibition of oil oxidation than synthetic antioxidants such as Butylated hydroxyanisole
(BHA) and Butylated hydroxytoluen (BHT) (Jaswir et al., 2000b).
On one side, many compounds have been isolated from
rosemary, including avones, diterpenes, and triterpenes. The
antioxidant activity of rosemary extract has been attributed primarily to the presence of carnosic acid and carnosol (Frankel et al.,
1996; Nogala-Kalucka et al., 2005). On the other side, it was conrmed that this activity may also be related to the existence of other
phenolic diterpenes like Rosmanol, isorosmanol, epirosmanol, and
phenolic acids such as rosmarinic acid. These compounds are
present at low proportions in the rosemary extract (Nogala-Kalucka
et al., 2005).
It has been observed that in fresh rosemary, carnosic acid is
the major phenolic diterpene. During the extraction process, this
compound can be converted, in part, into carnosol or into other
diterpenes which can be degraded further to produce other phenolic diterpenes such as rosmanol or isorosmanol (Huang et al.,
1996; Richheimer et al., 1996; Nogala-Kalucka et al., 2005). These
compounds act as antioxidants. However, they are more lipophilic
and their antioxidant activities are relatively lower than that of
carnosic acid (Huang et al., 1996). However, their activity is more
important if they are subjected to high temperatures such as at frying (Nogala-Kalucka et al., 2005). Several degradation products are
likely to be created once the temperature exceeds 100 C. Some of
these products are active as antioxidants.
When applying antioxidants in oils for frying, their activity
depends largely on their composition and type of compounds
involved. Thus, as the polar paradox, and in oil phase, polar
antioxidants are more active than non polar. This is explained by
the fact that hydrophilic antioxidants are oriented towards the
airoil interface where they are more effective in protecting fatty
acids against oxidation than lipophilic antioxidants which remain
in solution in the oil phase (Frankel et al., 1996).
The purpose of this study was to formulate stable frying oil
based on the antioxidant effects provided by an ethanolic rosemary
extract. To improve the stability of frying oil, it was proposed to
study the effectiveness of rosemary extract in retarding oxidation
of the formulated oil.

2. Materials and methods

2.1. Materials
In the present work, two oils are selected for the formulation of the frying oil: sunower oil and soybean oil. These oils
and fresh potatoes for sensorial analysis were purchased from
a local market. The Rosemary leaves (Rosemarinus Ofcinalis L.)
used in this study were collected in October from the region of
Zaghouan in the north-east of Tunisia. Vouchers specimens are
kept in the herbarium of the National Institute of Applied Science
and Technology (Tunis, Tunisia). All chemical reagents used were
of analytical grade. HPLC-grade acetonitrile and methanol were
both from Carlo-Erba (Rodano, Italy), and formic acid was from
Interchim (Montlucon, France). All of them were used without any
further purication.

2.2. Preparation of the rosemary extract

Rosemary leaves were dried in the open air and then blended.
The resulting powder was extracted using a Soxhlet apparatus for
2 h with ethanol as solvent at a 1/10 ratio (powder/solvent).

593

Table 1
Characteristics of individual oil before mixture.
Oilsa

PV (meq O2 /kg)

Acidity (%)

UFA (%)

SFA(%)

Soybean oil
Sunower oil

2.8 0.03
2.1 0.06

0.05 0.01
0.03 0.01

85.73 0.12
87.32 0.18

15.12 0.10
12.74 0.12

PV: peroxide value; UFA: unsaturated fatty acids; SFA: saturated fatty acids.
a
Mean standard deviation (n = 2).

The solvent containing the plant extract is then ltered. It is

recovered by using a rotary evaporator (Heidolph, Germany). The
nal extract was stored at 18 C until use (Erkan et al., 2008).
2.3. Mixture preparation
In the present work, the choice of oils mixture was based on a
preliminary study that was aiming a new frying oil formulation for
a Tunisian industry. During this preliminary study, different mixtures of oils (corn oil, sunower oil, soybean oil, and palm olein oil)
were prepared and studied (data no shown). The mixture that was
characterized by an interesting fatty acid composition, specically
unsaturated fatty acid one, was chosen to be used for formulation.
Other parameters were also taken into account, especially those
related to food security, physico-chemical properties, respective
stability and costs of the oils considered. As a result, the mixture
used in this study was formulated with sunower oil and a soybean one in equal proportions. Characteristics of both oils before
mixture are described in Table 1. An amount of rosemary extract
(RE) was added to this mixture. A control was prepared with the
same amounts of oils and obviously without any extract.
2.4. Characterization of the rosemary extract
2.4.1. Polyphenols content of rosemary extract
The polyphenols content in the RE was determined using
FolinCiocalteu reagent (Erkan et al., 2008). A volume of 1 ml of
RE solution, prepared in ethanol at a concentration of 0.1 mg/ml,
was mixed with 7.5 ml FolinCiocalteu reagent diluted 10 times.
The mixture is left 5 min at room temperature before mixing
with 7.5 ml of 60 mg/ml of aqueous sodium bicarbonate solution
Na2 CO3 . The prepared mixture is placed at room temperature and
darkness for 2 h.
The absorbance of the sample was measured at 725 nm using
spectrophotometer (Varian, Inc., CA, USA). The concentration was
determined using gallic acid as reference and the result is expressed
in gallic acid equivalents per gram extract (GAE/g).
2.4.2. HPLC-DAD and HPLCMS analysis.
HPLCMS experiments were performed on a U-3000 system
(Dionex, Voisins-Le Bretonneux, France) coupled to an Exactive
mass spectrometer equipped with an H-ESI ion source (Thermo
Scientic, Courtaboeuf, France).
The mass spectrometer was operated in positive ion mode. Spray
voltage was set at 4.5 kV. The capillary temperature was set at
250 C. Tube lens and skimmer voltages were set at 50 and 20 V,
respectively. Nitrogen was used as sheath, auxiliary and sweep cone
gas at ow rate of 15, 2 and 1 (arbitrary units), respectively. Heater
temperature was set at 200 C.
Separations were carried out on a 50 2.1 mm Atlantis T3C18
(3 m), column (Waters, St-Quentin-en Yvelines, France) protected
with a 10 2.1 mm pre-column lled with the same stationary
phase. All experiments were carried out at 25 C at a ow-rate of
0.3 mL/min. The mobile phase consisted of 1% formic acid in a mixture of water/acetonitrile (30/70, v/v). 84 mg of the dry residue of
the extract are dissolved in 10 ml of methanol. After dilution in
water (1/1, v/v) and centrifugation (15 min at 2000 g), the super-

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natant is diluted in the mobile phase (1/1, v/v), before injection of

10 L in the chromatograph.
2.4.3. Radical scavenging activity of rosemary extract
The antioxidant activity of RE was evaluated by determining
its anti-radical activity against the radical 2,2-diphenyl-1picrylehydradzyle (DPPH) (Erkan et al., 2008). Rosemary extract
solutions in ethanol were prepared at different concentrations
0.02%, 0.05%, and 0.08%.
A volume of 1.5 ml of each solution was added to 1.5 ml of a
methanol DPPH solution (0.2 mmol/l). The absorbance (A) was
measured at 515 nm after 30 min at 25 C. The blank control consists of 1.5 ml of methanol DPPH solution mixed with 1.5 ml of
methanol without the extract. The radical-scavenging activity of
each solution is calculated as the inhibition percentage using Eq.
(1):
%Inhibition =

(Ablankcontrol Asample )
Ablankcontrol

100

(1)

where Ablankcontrol is the blank control absorbance at 515 nm and

Asample is the sample absorbance at 515 nm.
2.5. Heating test
To evaluate their behavior during the frying, the formulated oils
were subjected to heating at constant temperature and without
food. These oils were heated separately in an electric fryer (Ufesa,
EEC) at 180 C (2 C) for 6 h/day for 5 consecutive days. At the end
of each essay, 60 ml of oil is taken for physicochemical characterization and evaluation of the fatty acid composition. The samples
were stored at 4 C until analysis.
2.6. Characterization of frying oil
During the heating test, the peroxide value (PV), acidity and fatty
acid composition were determined for different samples.
2.6.1. Peroxide value
PV was determined according to the Norme ISO 3960 (1977).
About 5 g of oil was mixed with 10 ml of chloroform then 15 ml of
acetic acid. 1 ml of saturated potassium iodide (KI) was then added.
The mixture was kept 5 min in darkness with continuously shaking,
and then 75 ml of distilled water were added. Sodium thiosulfate
solution (Na2 S2 O3 ) 0.01 mol/l was used for titration in the presence
of starch solution as indicator until brown coloration disappeared.
PV was calculated according to the following Eq. (2):

 meqO 
2

(V Vb ) T
1000
m

2.6.3. Fatty acid composition

Fatty acid composition was determined according to the
Tunisian Norm NT 118.05 (1995). The oil samples were analyzed on
a HP gas chromatograph Hewlett Packard type 5890 (Agilent technologies, CA, USA) equipped by 100 m 0.25 mm capillary column.
The injected volume was 1 l and the carrier gas owing inside the
column is Helium. The chromatograph was equipped with ame
ionization detectors (FID). The temperature of injector was 250 C.
The temperature of the detector placed at the column outlet is
280 C.
2.7. Sensory evaluation of potato chips: frying test
Sensory properties of fried potato prepared in oil with RE were
evaluated comparatively with those fried in control oil. Fresh potatoes were peeled, washed and sliced into discs with a thick of
1.1 mm. Fifteen frying were conducted for ve consecutive days
with three daily frying. The frying temperature is a xed one
(180 C 2 C). At each frying, 150 g of sliced potatoes are fried for
3 min in 2 l of oil. The oil is then cooled at least 30 min before using
it for a new frying.
Sensory evaluation of fried potatoes was conducted after the 1st,
the 8th, and the 15th frying by a panel of 10 individuals from the
staff and the students of the National Institute of Applied Science
and Technology, Tunis, Tunisia. Although, they were regular consumers of fried potatoes, we have explained to them the procedure
and the conditions of tasting. It is important to point that these
panelists were isolated from each others during the analysis to
ovoid mutual inuence (Jaswir, 2000b). Hedonic sensory attributes
evaluated in this study were odor, color, crispiness, and taste. All
these attributes were evaluated by applying a 7- point rating scale.
Numerical values were then assigned to each attribute in which 1
represents dislike extremely and 7 represents like extremely.
2.8. Statistical analysis
The statistical analysis of the data and correlation was carried out with STATGRAPHICS Centurion XVI software (Statpoint
Technologies, Warrenton, USA). Signicance differences between
mean values were evaluated by variance analysis (ANOVA), standard deviation and Duncans test in calculating probability. P-value
less than 0.05 were considered signicant.
3. Results and discussion
3.1. Characterization of the rosemary extract

(3)

3.1.1. Polyphenols content of rosemary extract

The phenolic content of the RE was evaluated using the
FolinCiocalteu reagent. It was about 112 mgGAE/g extract. This
amount is less than that found by Erkan et al. (2008) on the
methanolic rosemary extract and which is about 162 mg GAE/g
extract. This difference may be the cause of the higher polarity of
methanol used in their study and which allows better extraction of
the polar phenolic compounds.
Therefore, the nature of the solvent used in the extraction may
affect the phenolic content (Liu et al., 2007). The choice of ethanol
in our study was based on its food security character (Nor Aini et al.,
2008). Other factors may also affect the polyphenols composition
of the RE mainly genetics, season of collection and the maturity of
the plant.

where V is the ml of NaOH, C is the concentration of NaOH solution

(mol/l), m is the mass of oil (g) and M is the molecular weight of the
fatty acid used for the expression of the result (Oleic acid is selected
for expression of the acidity (M = 282 g/mol)).

3.1.2. HPLC-DAD and HPLCMS analysis of the rosemary extract

Fig. 1 shows the UV-chromatographic prole of the rosemary
extract. The peaks 1 and 2 eluting at 1.95 and 2.96 min exhibit spectral features (Fig. 1, insert) characteristic of carnosol and carnosic

PV

kg

(2)

where V is the ml of Na2 S2 O3 , Vb is the ml of Na2 S2 O3 for the blank

simple (without oil), T is the normality of Na2 S2 O3 solution and m
is the mass of oil (g).
2.6.2. Acidity
About 10 g of oil was mixed with 50 ml of neutralized alcohol.
The mixture was titrated with NaOH (0.1 mol/l) and phenolphthalein as indicator until pink color appeared and persisted (Norme
ISO 660, 1996). The acidity was calculated by using the following
Eq. (3):
Acidite(%) =

V C M
10 m

N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

595

Fig. 1. LC-DAD chromatographic prole of the rosemary extract (284 nm). Insert: UVvis spectra extracted from the chromatogram of (1) carnosol and (2) carnosic acid (A).

acid, respectively, (Almela et al., 2006; Chang et al., 2008). The MSchromatographic proles unambiguously conrm the presence of
carnosol and carnosic acid (Fig. 2). Indeed, the MS spectrum of the
pic eluting at 1.99 min exhibits a pseudo-molecular ion [M+ H + ]
with an m/z = 331.19, while the theoretical mass for the [M+ H + ] of
carnosol is 331.1909 amu. In the same way, the MS spectrum of the
pic eluting at 3.04 min exhibits a pseudo-molecular ion [M+ H + ]
with an m/z = 333.20, while the theoretical mass for the [M+ H + ] of
carnosic acid is 333.2066 amu. The pic at m/z = 287.20 amu (Fig. 2E)
is attributed to the loss of a formic acid molecule.

improve the antioxidant activity of the extract. However, these

mechanisms are at present low mastered (Romano et al., 2009).
After studying its antioxidant effect, the rosemary extract was
added to the mixture of soybean and sunower oils at a proportion of 800 mg/kg. This percentage was also chosen in reference to
other studies. According to Ramalho and Jorge (2008), an amount of
1.000 mg/kg represents the highest proportion commercially recommended.

3.2. Effect of heating on the quality of the frying oil

3.1.3. Radical scavenging activity of rosemary extract
The antioxidant activity of the RE was performed based on the
reduction of the free radical DPPH by antioxidants present in the
plant extract. This results in a decrease of a DPPH radical absorbance
at 515 nm. Fig. 3 shows the scavenging activity variation provided
by RE at different concentrations (0.02%, 0.05%, and 0.08%) comparatively to a synthetic antioxidant (BHT).
This variation depends on the nature and the concentration
of the antioxidant used. A relatively high antioxidant activity is
noticed for rosemary extract and was estimated at 81% for a concentration of 0.08%. This activity was signicantly better (p < 0.05) than
that provided by BHT used at a concentration of 0.1% and which
inhibits only 52% of free radicals. This shows that the prepared
RE contains compounds which are responsible for a free radicals
capture and therefore could be used to stabilize and retard oil oxidation. This antioxidant activity can be attributed especially to the
presence of carnosic acid and carnosol previously identied in the
RE (Nogala-Kalucka et al., 2005).
Generally, the antioxidant activity of phenolic compounds
depends on their structure but also and especially on the chemical
entities existing in the molecules. In general, scavenging activity of
phenol compounds increase with the number of hydroxyl groups
OH (Chaiyasit et al., 2005). It should be further noticed that the
synergistic effect existing between the phenolic compounds can

3.2.1. Evolution of a peroxide value during heating treatment

The PV is a measurement of total peroxides, primary products
formed in oils during the oxidation process. The effectiveness of
an antioxidant in delaying the oxidation of oils can be assessed by
a stable or a slower increase of a peroxide value compared to a
control, in absence of phenolic extracts.
Fig. 4(a) shows that the RE can signicantly reduce (p < 0.05)
the frying oil oxidation during heating treatment. Before being
subjected to heat, PV for control and rosemary treated oils
were respectively 3 and 2.8 meq oxygen/kg. The peroxide value
does not exceed 3.5 meq oxygen/kg in oil with added antioxidant. This value was reached after 18 h of heating. After 6 h of
heating, the PV increase by about 100% in the control oil. This
can be attributed to the polyinsatureted fatty acids oxidation
and the hydroperoxides formation accelerated at high temperatures.
The RE used in this study, and which was previously characterized by a relatively high scavenging activity, seems to be interesting
in the inhibition of frying oils oxidation. Its addition in the mixture
of soybean and sunower oil reduced the PV by 38% after 30 h of
heating. According to Che Man and Jaswir (2000), the addition of a
RE, at a percentage of 0.4%, affect the stability of palm oil used in
frying potatoes for about 32 h were the PV was reduced by 37%.

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N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

Fig. 2. LCMS Chromatographic proles and extracted mass spectra of the rosemary extract: (A) total ion current, (B and C) Extracted ion chromatograms at 331 amu
(carnosol) and 333 amu (carnosic acid), respectively, and (D and E) corresponding mass spectra.

However, peroxides products formed are still unstable, decomposes under frying conditions, giving rise to secondary products
such as carbonyl and aldehydic compounds (Abdulkarim et al.,
2007). The oil deterioration continues, but the peroxides formed
are no longer assayed. This therefore results in a decrease of PV.
This explanation conrms the phenomenon observed in control oil
in the last three days of heat treatment.
It should be noticed that the nature of foods frying seems to have
an inuence on the PV. In fact, Manral et al. (2008) reported that, in
the case of frying sh in sunower oil, the PV can rise from 0.1 meq
oxygen/kg to 28.98 meq oxygen/kg after 12 h of frying.

3.2.2. Evolution of acidity during heating treatment

The measure of acidity is a test commonly used to evaluate the
oil quality especially during frying. The acidity evolutions of the formulated oils during heating experiments are shown in Fig. 4(b). This
parameter was still stable in both oils until 6 h of heating. The oil
formulated with a RE kept stability in its content of free fatty acids
until 12 h. The acidity increase signicantly (p < 0.05) and reach 0.1%
and 0.075% in control and rosemary treated oils respectively after
18 h of heating. This difference between the values of acidity is
indicative of polyphenols ability to retard oils oxidation causing
the fatty acids releasing. Che Man and Jaswir (2000) reported the

N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

597

3.2.3. Evolution of fatty acids composition during heating

treatment
Evaluation of fatty acid composition is an effective way to evaluate oxidative changes occurring in oils during heating. The man
results of percentage composition in fatty acids for control oil and
oil with RE can be observed in Table 2.

Fig. 3. Scavenging activity of BHT (0.1%), and rosemary extract (RE) at different
concentrations (0.02%, 0.05% and, 0.08%) against the DPPH radical expressed as
percentage of inhibition.

effectiveness of RE add to palm oil and use to fry potatoes for about
32 h where the acidity for this oil and the control is about 0.42% and
0.59% respectively.
The oil hydrolysis caused by the water effect introduced by the
fried food is a phenomenon that does not occur during our study
because the heating was conducted in the absence of food. The
increase in free fatty acids value is attributed in this study mainly
to the degradation of secondary oxidation products formed during heating and the presence of oxygen. The moisture that may be
provided by air could have an inuence on increasing acidity.
The decrease in acidity after 24 h and 30 h may be explained by
the evaporation of the volatile free fatty acids under the heating
effect. The polymerization of fatty acids during the heating process may also block the acids functions that are no longer assayed
(Ndjouenkeu and Ngassoum, 2002).

3.2.3.1. Changes in unsaturated fatty acids during heating treatment.

When evaluating changes in fatty acids prole during heating of
the frying oils, there was a difference in the unsaturated fatty
acid composition depending on the oil nature. This composition
decreased when time of frying increased. A signicant difference
was observed between oils after 24 h of heating (p < 0.05). Oil
treated with RE conserves the higher amount of unsaturated fatty
acids even after 30 h of heating which suggests that this oil resist
to oxidation.
Therefore, this can prove the action of the phenolic extract to
inhibit the unsaturated fatty acids oxidation. It has been already
demonstrated that the involvement of phenolic compounds in the
oxidation chain can be done in two ways: some of them inhibit
the propagation of radical reactions (Masuda et al., 2001), others
prevent the free radicals formation which are the initiators of the
oxidation reaction. It was also proved that the phenolic compounds
of the rosemary are active against oxygen free radicals involved in
the initiation of radical reactions (Lalas and Dourtoglou, 2003). In
addition, some phenolic compounds may react with metals known
as initiators of lipid oxidation, they are active as metal chelators
and can prevent the oxidation process (Basaga et al., 1997).
3.2.3.2. Changes in saturated fatty acids during heating treatment.
For the saturated fatty acids composition, a signicant difference
(p < 0.05) was observed between oils after 24 h of heating. The evolution of this composition is estimated at 25% and 5.5% in control
and rosemary treated oils respectively at the end of the heating
treatment. As mentioned above, the unsaturated fatty chains are
highly sensitive to oxidation reactions, their oxidation induced a
decrease in the rate of unsaturated fatty acids which will be converted into saturated fatty acids or even into trans fatty acids. In
their studies, Jaswir et al. (2000a) found that the addition of rosemary, sage extract and citric acid to the palm olein before frying
retard effectively the thermal oxidation of the unsaturated fatty
acids thus reducing the increase of saturated fatty acid especially
the palmitic acid.
3.3. Sensory analysis of potato crisps

Fig. 4. Changes in peroxide value (a) and acidity (b) during heating of control oil (n)
and oil with RE ().

Table 3 shows the sensory characteristics evolution of fried

potato (odor, color, crispness, and taste) as a function of two factors: nature of oil and number of frying. Except for color and odor,
the RE improves signicantly (p < 0.05) the sensory scores of fried
potato after the 15th frying. When evaluating the color of potato
chips, similar variation were noticed depending on the nature of oil
and the number of frying. The fried products were characterized by
a yellow color even after the 15th frying. The odor scores of potato
fried using oil with RE, diminish slowly and reach only 4.8. But no
signicant difference was observed between samples even after the
15th frying. It should be noted that during frying, a pleasant avor
was detected in oil treated with RE. This can positively improve the
organoleptic characteristics and especially the avor of the product
fried in this type of oil. Unlike synthetic antioxidants, the phenolic
compounds of rosemary extract are responsible for the generation
of a desirable avor in the fried product (Zheng and Wang, 2001).
The intensity of this avor has a tendency to decrease with the number of frying. The crispness and taste evolution of potatoes fried in
oil with natural antioxidant were stable independently of the number of frying. After the 15th frying, a signicant decrease (p < 0.05)

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N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

Table 2
Fatty acids composition of control oil and oil with RE during thermoxidation at
180 C.
Fatty acids (%)a
C16:0

Control oil
09.43 0.04
09.81 0.02
09.50 0.02
09.67 0.04
12.54 0.03
13.00 0.04

Oil with RE
08.61 0.02
09.26 0.05
08.72 0.03
09.36 0.04
09.91 0.01
09.26 0.03

0
6
12
18
24
30

0.12 0.03
0.13 0.02
0.11 0.02
0.12 0.03
0.15 0.02
0.14 0.03

0.10 0.02
0.10 0.01
0.12 0.03
0.12 0.03
0.18 0.02
0.11 0.02

C18:0

0
6
12
18
24
30

4.40 0.02
4.32 0.03
4.36 0.02
4.33 0.04
4.17 0.01
4.12 0.03

4.33 0.02
4.37 0.03
4.47 0.01
4.48 0.04
4.63 0.04
4.44 0.01

C18:1

0
6
12
18
24
30

23.25 0.03
23.64 0.04
24.00 0.02
24.02 0.04
23.54 0.03
23.72 0.02

24.17 0.05
23.88 0.03
23.92 0.03
24.07 0.04
24.03 0.02
24.05 0.03

0
6
12
18
24
30

57.09 0.02
56.74 0.04
56.56 0.03
56.60 0.05
55.00 0.02
54.70 n0.03

57.65 0.02
57.05 0.04
57.15 0.05
56.59 0.03
55.64 0.04
56.75 n0.03

C18:3

0
6
12
18
24
30

2.70 0.02
2.89 0.03
2.98 0.04
2.86 0.02
2.60 0.02
2.53 0.04

2.92 0.03
2.88 0.01
2.97 0.04
2.85 0.03
2.79 0.02
2.65 0.02

C20:0

0
6
12
18
24
30

0.44 0.02
0.37 0.01
0.43 0.03
0.42 0.02
0.34 0.04
0.72 0.03

0.43 0.01
0.42 0.02
0.45 0.02
0.40 0.03
0.45 0.02
0.41 0.02

C20:1

0
6
12
18
24
30

0.17 0.01
0.11 0.02
0.17 0.03
0.17 0.02
0.10 0.03
0.10 0.01

0.17 0.04
0.13 0.03
0.19 0.05
0.13 0.01
0.15 0.02
0.14 0.03

UFA

0
6
12
18
24
30

83.33 0.11bA
83.51 0.10aA
83.82 0.14aA
83.77 0.16aA
81.39 0.12bB
81.19 0.13bB

85.01 0.16aA
84.04 0.12aBC
84.35 0.20aB
83.76 0.14aC
82.79 0.12aD
83.70 0.13aC

SFA

0
6
12
18
24
30

14.27 0.08aC
14.50 0.06aC
14.29 0.07aC
14.42 0.10aC
17.05 0.08aB
17.84 0.10aA

13.37 0.05bC
14.05 0.10aB
13.64 0.06bC
14.24 0.11aB
14.99 0.07bA
14.11 0.06bB

C16:1

C18:2

Heating time (h)

0
6
12
18
24
30

ab: means within a row with different letters are signicantly different (p < 0.05).
AB: means within a column with different letters are signicantly different
(p < 0.05). (C16:0, palmitic acid; C16:1, palmitoleic acid; C18:0, estearic acid; C18:1,
oleic acid; C18:2, linoleic acid; C18:3, -linolenic acid; C20:0, arachidic acid; C20:1,
eicosenoic acid; UFA, unsaturated fatty acids; SFA, saturated fatty acids; RE : rosemary extract).
a
Mean standard deviation (n = 2).

Table 3
The Sensory characteristic scores attributed for potato crisps.
Sensory characteristica

Number of frying

Control oil

Oil with RE

Odor

1
8
15

5.4 0.16aA
4.6 0.26aA
3.7 0.42aB

5.5 0.22aA
5.0 0.21aA
4.8 0.38aA

Colour

1
8
15

6.0 0.30aA
5.6 0.22aAB
5.1 0.27aB

6.0 0.21aA
5.6 0.22aAB
5.1 0.17aB

Crispiness

1
8
15

5.7 0.26aA
5.3 0.30aA
3.9 0.34bB

5.9 0.23aA
6.0 0.25aA
5.7 0.30aA

Taste

1
8
15

5.4 0.16aA
4.9 0.34aA
3.2 0.38bB

5.5 0.22aA
5.4 0.22aA
5.3 0.26aA

ab: means within a row with different letters are signicantly different (p < 0.05).
AB: means within a column with different letters are signicantly different
(p < 0.05). RE : rosemary extract.
a
Means standard deviation for 10 subjects participating in the tasting test using
a 7 point hedonic scale.
Table 4
Regression between sensory attributes.

Odor
Color
Crispiness
Taste

Odor

Color

Crispiness

Taste

1
0.149
0.408
0.450

1
0.220
0.173

1
0.518

of crispness and taste scores is observed for the potatoes prepared

in control oil compared to those prepared in oil with RE. These are
the crispest and retained their fruity avor even after the 15th frying. An oily feel and a rancid taste were rather detected in potato
prepared in control oil by the end of the test. Correlation between
sensory attributes was also determined (Table 4). An important and
positive correlation between taste and odor (r = 0.450) was noticed.
However, this correlation was more signicant when crispiness
and taste of the potato crisps were considered (r = 0.518). Regression between acceptability and sensory attributes was discussed in
Tortoe et al. (2014) study; these authors have also conrmed an
important positive correlation between the taste and the overall
acceptation of deep-fried yam (Dioscorea rotundata) crisps.
The control oil is the mostly affected by the frying conditions
which negatively inuence the sensorial qualities of fried foods.
Indeed, according to its use, oil is the seat of a multitude of chemical and physical reactions leading to the formation of degradation
products and polymers. Those chemical product, once accumulate in the frying oil, contribute to the reduction of heat transfer
between the oil and the food. This can result in a greater absorption
of oil by the fried product (Paul and Mitta, 1996).
Potatoes fried in oil treated with natural antioxidant have the
best organoleptic properties. This may be explained by the presence
of RE which could improve the oxidative stability of the oil during
frying. This nding is in accordance with the results reported by
Che Man and Jaswir (2000) where the RE improve the taste and the
odor of potato crisps prepare in palm olein until the 60thfrying.
4. Conclusion
In this study, rosemary extract was used to enhance the oxidative stability of vegetable oil during frying. This extract is capable to
retard oil oxidation throughout its use in frying. This may be due to
the presence of phenolic compounds such as Carnosol and Carnosic
acid in the ethanolic extract. The degradation products formed at
a lower level does not affect the oil quality. Oil formulated with
rosemary extract keeps the lower peroxide value, acidity and satu-

N. Chammem et al. / Industrial Crops and Products 74 (2015) 592599

rated fatty acid composition. This extract was able to maintain the
sensory characteristics of fried product until the 15th frying. Further, studies are required to understand mechanisms with which
phenolics compounds inhibit or retard oxidative process.
References
Abdulkarim, S.M., Long, K., Lai, O.M., Muhammad, S.K.S., Ghazali, H.M., 2007. Frying
quality and stability of high-oleic oleifera seed oil in comparison with other
vegetable oils. Food Chem. 105, 13821389.
Almela, L., Sanchez-Munoz, B., Fernandez-Lopez, J.A., Roca, M.J., Rabe, V., 2006.
Liquid chromatograpicmass spectrometric analysis of phenolics and free
radical scavenging activity of rosemary extract from different raw material. J.
Chromatogr. A 1120, 221229.
Basaga, H., Tekkaya, C., Acikel, F., 1997. Antioxidative and free radical scavenging
properties of rosemary extract. Lebensm. Wiss. Technol. 30, 105108.
Chaiyasit, W., Mcclements, D.J., Decker, E.A., 2005. The relationship between the
physicochemical properties of antioxidants and their ability to inhibit lipid
oxidation in bulk oil and oil-in-water emulsions. J. Agric. Food Chem. 53,
49824988.
Chang, C.H., Chyau, C.C., Hsieh, C.L., Wu, Y.Y., Ker, Y.B., Tsen, H.Y., Peng, R.Y., 2008.
Relevance of phenolic diterpene constituents to antioxidant activity of
supercritical CO2 extract from the leaves of rosemary. Nat. Product Res. 22 (1),
7690, Formerly Natural Product Letters.
Che Man, Y.B., Jaswir, I., 2000. Effect of rosemary and sage extracts on frying
performance of rened, bleached and deodorized (RBD) palm olein during
deep-fat frying. Food Chem. 69, 301307.
Chiou, A., Kalogeropoulos, N., Salta, F.N., Efstathiou, P., Andrikopoulos, N.K., 2009.
Pan-frying of French fries in three different edible oils enriched with olive leaf
extract: oxidative stability and fate of microconstituents. Food Sci. Technol. 42,
10901097.
Erkan, N., Ayranci, G., Ayranci, E., 2008. Antioxidant activities of rosemary
(Rosmarinus Ofcinalis L.) extract, blackseed (Nigella sativa L.) essential oil,
carnosic acid, rosmarinic acid and sesamol. Food Chem. 110, 7682.
Frankel, E.N., Huang, S.W., Aeschbach, R., Prior, E., 1996. Antioxidant activity of a
rosemary extract and its constituents, carnosic acid, carnosol, and rosmarinic
acid, in bulk oil and oil-in-water emulsion. J. Agric. Food Chem. 44, 131135.
Gupta, M.K., 2005. Frying Oils. Baileys Industrial Oil and Fat Products. John Wiley &
Sons, Inc.
Huang, S.W., Frankel, E.N., Schwarz, K., Aeschbach, R., German, J.B., 1996.
Antioxidant activity of carnosic acid and methyl carnosate in bulk oils and
oil-in-water emulsions. J. Agric. Food Chem. 44, 951956.
Jaswir, I., Che Man, Y.B., Kitts, D.D., 2000a. Synergistic effects of rosemary, sage,
and citric acid on fatty acid retention of palm olein during deep-fat frying. J.
Am. Oil Chem. Soc. 77, 527533.
Jaswir, I., Che Man, Y.B., Kitts, D.D., 2000b. Use of natural antioxidants in rened
palm olein during repeated deep-fat frying. Food Res. Int. 33, 501508.
Lalas, S., Dourtoglou, V., 2003. Use of rosemary extract in preventing oxidation
during deep-fat frying of potato chips. J. Am. Oil Chem. Soc. 80, 579583.

599

Liu, X., Dong, M., Chen, X., Jiang, M., Lv, X., Yan, G., 2007. Antioxidant activity and
phenolics of an endophytic Xylaria sp. from Ginkgo biloba. Food Chem. 105,
548554.
Masuda, T., Inaba, Y., Takeda, Y., 2001. Antioxidant mechanism of carnosic acid:
structural identication of two oxidation products. J. Agric. Food Chem. 49,
55605565.
Manral, M., Pandey, M.C., Jayathilakan, K., Radhakrishna, K., Bawa, A.S., 2008. Effect
of sh (Catla catla) frying on the quality characteristics of sunower oil. Food
Chem. 106, 634639.
Michalowska, A., Korezak, J., 2007. Polyphenols- potential food improvement
factor. Am. J. Food Technol. 2, 662670.
Ndjouenkeu, R., Ngassoum, M., 2002. Etude comparative de la valeur en friture de
quelques huiles vgtales. J. Food Eng. 52, 121125.
Nogala-Kalucka, M., Korczak, J., Dratwia, M., Lampart-Szczapa, E., Siger, A.,
Buchowski, M., 2005. Changes in antioxidant activity and free radical
scavenging potential of rosemary extract and tocopherols in isolated rapeseed
oil triacylglycerols during accelerated tests. Food Chem. 93, 227235.
Nor Aini, I., Fatihanium, M.N., Razali, I., Suhaila, M., Chek Zaini, H., 2008.
Antioxidative activity of malaysian herb extracts in rened, bleached and
deodorized Palm Olein. J. Oil Palm Res. 20, 517526.
Norme ISO 3960, 1977. Corps gras dorigines animale et vgtale Dtermination
de lindice de peroxyde.
Norme ISO 660, 1996. Corps gras dorigines animale et vgtale Dtermination
de lindice dacide et de lacidit.
NT 118.05, 1995. Corps gras dorigine animale et vgtale Prparation des esters
mthyliques par chromatographie en phase gazeuse des acides gras.
Paul, S., Mitta, G.S., 1996. Dynamics of fat/oil degradation during frying based on
optical properties. J. Food Eng. 30, 389403.
Rababah, T.M., Feng, H., Yang, W., Yucel, S., 2012. Fortication of potato chips with
natural plant extracts to enhance their sensory properties and storage stability.
J. Am. Oil Chem. Soc. 89, 14191425.
Ramalho, V.C., Jorge, N., 2008. Antioxidant action of rosemary extract in soybean
oil submitted to thermoxidation. Grasas Aceites 59, 3841.
Richheimer, S.L., Bernart, M.W., King, G.A., Kent, M.C., Bailey, D.T., 1996.
Antioxidant activity of lipid-soluble phenolic diterpenes from rosemary. J. Am.
Oil Chem. Soc. 73, 507514.
Romano, C.S., Abadi, K., Repetto, V., Vojnov, A.A., Moreno, S., 2009. Synergistic
antioxidant and antibacterial activity of rosemary plus butylated derivatives.
Food Chem. 115, 456461.
Tortoe, C., Akonor, P.T., Nketia, S., Owusu, M., Glover-Amengor, M., Hagan, L., Otoo,
E., 2014. Evaluation of the sensory characteristics and consumer acceptability
of deep-fried yam (Dioscorea rotundata) crisps in the accra metropolitan area. J.
Food Nutr. Sci. 2 (1), 1923.
Zhang, Q., Saleh, A.S.M., Chen, J., Shen, Q., 2012. Chemical alterations taken place
during deep-fat frying based on certain reaction products: a review. Chem.
Phys. Lipids 165, 662681.
Zheng, W., Wang, S.Y., 2001. Antioxidant activity and phenolic compounds in
selected herbs. J. Agric. Food Chem. 49, 51655170.