Ultrasonics Sonochemistry 11 (2004) 13–15

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Deterioration of edible oils during food processing by ultrasound q

F. Chemat *, I. Grondin, A. Shum Cheong Sing, J. Smadja
Laboratoire de Chimie des Substances Naturelles et des Sciences des Aliments, Facult

e des Sciences et Technologies, Universit

e de la R

eunion,
15 avenue Ren
e Cassin, B.P. 7151, F-97715 Saint Denis messag cedex 9, La R
eunion, France
Accepted 3 April 2003

Abstract

During food emulsification and processing of sunflower oil (most used edible oil), a metallic and rancid odour has been detected
only for insonated oil and foods. Some off-flavour compounds (hexanal and hept-2-enal) resulting from the sono-degradation of
sunflower oil have been identified. A wide variety of analytical techniques (GC determination of fatty acids, UV spectroscopy, free
fatty acids and GC/MS) were used to follow the quality of insonated sunflower oil and emulsion. Different edible oils (olive,
sunflower, soybean, . . .) show significant changes in their composition (chemical and flavour) due to ultrasound treatment.
Ó 2003 Elsevier B.V. All rights reserved.

Keywords: Ultrasound; Emulsification; Sunflower oil; Off-flavours

1. Introduction nm, acid value, solid phase micro-extraction associated

An important development on the food market is the
demand for fresh like foods. Much research is done on
minimal processing techniques to meet these demands.
Ultrasound (US) technology can be very useful for
minimal processing, because transfer of acoustic energy
to the food product is instantaneous and throughout the
whole product volume. This means a reduction of the
total processing time, higher throughput and lower en-
ergy consumption. Laboratory and pilot scale ultra-
sound equipment are available and have been used for
different processes like emulsification and deactivation of
enzymes. In many cases, combinations of conventional
techniques with ultrasound gave the best results [1–4].
This paper presents the effect of ultrasound treatment
on edible oils especially sunflower oil. The effect of
ultrasound on oil and emulsion quality (sensory and
physicochemical properties of sunflower oil) has been
conducted. A wide variety of analytical techniques, GC
determination of fatty acids, UV values at 232 and 238
q
This paper was originally presented at Applications of Power
Ultrasound in Physical and Chemical Processing (Usound3), Paris,
December 2001.
*
Corresponding author. Tel.: +33-262-938150; fax: +33-262-
938183.
E-mail address: chemat@univ-reunion.fr (F. Chemat).
with GC/MS were used to follow the quality of insona-
ted emulsions and edible oils.
2. Materials and methods
2.1. Materials
The sunflower oil used for experiments was obtained
from the local grocery and represents the oil after refining.
2.2. Ultrasonic treatment
Sonication is achieved at low frequencies 20 kHz
(Branson W 450) or 47 kHz (Branson 5210. An ultra-
sonic generator Branson W-450 fitted with an immer-
sible horn emits the sound vibration into the solution via
a titanium alloy rod (13 mm diameter) dipped in the
liquid at the top of the tank. The reactor is a cylindrical
jacket glass vessel (volume 250 ml). In all experiments
the volume of the liquid is 100 ml.
2.3. Analytical procedures
Determinations of oilÕs physicochemical parameters
were carried out following the analytical methods

1350-4177/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S1350-4177(03)00127-5
14 F. Chemat et al. / Ultrasonics Sonochemistry 11 (2004) 13–15
described by AOCS [5]: FFA or free fatty acids (AOCS
official method Ca 5a-40), conjugated dienes level by UV
spectrophotometric method (AOCS Cd 7-58) and fatty
acid composition by gas chromatography (AOCS Ce
1-62 and Ce 2-66). A Carlo Erba gas chromatograph
(HRGC 5300 Mega Series) equipped with flame ionisa-
tion detector has been used to analyse fatty acid com-
position. Methyl esters of fatty acids were analysed on a
BPX70 capillary column (50 m, 0.32 mm internal dia-
meter, 0.25 lm film thickness). The oven temperature
was programmed from 120 to 200 °C, at 3 °C/min, and
then held at 200 °C for 10 min. The fatty acid compo-
sition (%) was calculated by normalization method using
a C-R6A Shimadzu integrator. Analyses were performed
at least three times, and the mean values are reported.
Volatiles compounds were analysed with by GC/MS
after a solid phase micro-extraction procedure (SPME).
100 g of emulsion and 39 g of NaCl are stirred in a 150 ml
reactor placed in a water bath at 45 °C for 2 h. Volatiles
are simultaneously trapped on a SPME fibre (75 lm
carboxan/polydimethylsiloxane coating). After trapping,
desorption of volatiles takes place in a CG/MS injector at
250 °C. Separation of compounds begin immediately. A
Hewlett Packard HP 5890 GC/MS system is used for
chromatographic separation. The injector mode is split-
less and the ionisation mode is an electron impact at
70 eV. Separation of compounds is achieved on a polar
column (Supelcowax 10 TM, 60 m length, 0.2 mm i.d., 0.2
lm film thickness fused silica). The oven temperature was
held at 40 °C for 5 min and ballistically increased to 60 °C
and programmed to 220 °C at 4 °C/min. The program
was then held at isotherm for 30 min. The flow of helium
(carrier gas) is 1 ml/min. For the identification of eluted
compounds, retention indices of the compounds are cal-
culated from the injection of an n-alcane (C10 –C26 ) and
compared to the indices reported in the literature. The
identification is also confirmed by comparing their mass
spectra to those in the data bank (Wiley/NBS library).
3. Results and discussion
3.1. Ultrasonic treatment and off-flavours generation
During the experimental procedures, a metallic and
rancid odour was detected only for emulsions and oil
Table 1
Ultrasound effects on sunflower oil oxidation
Fatty acid composition (%)
Palmitic Stearic
Sunflower oil without treatment 5.2  0.2 3.2  0.1
Sunflower oil treated with 5.6  0.3 3.4  0.2
US at 20 °C for 1 h
Sunflower oil treated with 5.5  0.3 3.6  0.1
US at 60 °C for 1 h
treated by ultrasound. Some off-flavour compounds
have been extracted by solid phase micro-extraction
method and analysed by GC-MS. Hexanal, hept-2-enal,
decadi-2,4-enal and limonene have been identified.
These volatiles contribute to grassy, fishy, pungent, oxi-
dized notes and result from the degradation of linoleic
acid and sterols [6].
3.2. Ultrasound effects on lipid deterioration
The second part of the study concerns the innocu-
ousness of ultrasound against food products. During the
experimental procedures, we noticed that the flavour of
only insonated emulsions has been changed. A metallic
and rancid odour was detected after sonication. It is well
known that the major cause in the degradation of lipids
present in food products is oxidation. For this reason,
the deterioration of insonated emulsions has been
studied by determination of physicochemical values
and olfactory properties.
These off-flavours appear only after few minutes of
emulsification using US horn. First, the metallic oxida-
tion of sunflower oil catalysed by the metallic part of the
US horn was suspected. But doing the same experiment
in US bath without any contact between the oil and the
metal part give the same off-flavours. After that, the
surfactant was suspected to be sono-degraded, but ex-
periments without surfactant have the same off-flavours.
Insonated pure sunflower oil gives the worst off-fla-
vours. That means that the oil is the only compound
affected by ultrasonic degradation.
To avoid the combination of US and metallic oxi-
dation with the US horn, oil and water have been
emulsified into an Erlenmeyer insonated in an US bath.
To evaluate the consequences of US on food emulsions
and oils, three analysis parameters have been deter-
mined (gas liquid chromatographic determination of
fatty acids, ultraviolet absorbance values at 232 nm, free
fatty acids) and results are presented in Table 1. A de-
crease in the amount of linoleic acid has been observed.
A slight increase of conjugated dienes values has also
been detected, confirming that oxidation has occurred.
Increasing the temperature of US emulsification to
60 °C induced higher ultrasonic degradation of sun-
flower oil.
UV, conjugated FFA, % oleic
Oleic Linoleic dienes (%) acid
26.4  0.4 65.2  0.5 0.012  0.001 0.086  0.003
26.1  0.5 64.8  0.4 0.013  0.002 0.089  0.013
27.1  0.3 63.5  0.7 0.015  0.002 0.111  0.007
 F. Chemat et al. / Ultrasonics Sonochemistry 11 (2004) 13–15
4. Conclusion
Ultrasound assisted food processing is a potential
alternative to conventional processes. However, flavour
and composition have been deteriorated only by ultra-
sound. A recent survey and market study [7] have re-
vealed that food professionals are reluctant to apply new
technologies because of the poor understanding of these
new techniques and the reason of the weight of tradi-
tion. To evaluate the consequences of ultrasound treat-
ment on lipids, some other specific measurements of
lipid oxidation such as peroxide value, thiobarbituric
acid test, carbonyl value, . . . will need to be made. The
by-products after ultrasonic treatment of food products
will need also to be determined to certify (or not) the
innocuousness of ultrasound against food products.
15
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