Food Research International 40 (2007) 406414

www.elsevier.com/locate/foodres

Rapid evaluation of frying oil degradation using ultrasonic technology

a,*
Jose Benedito , Jose V. Garca-Perez a, M. Carmen Dobarganes b, Antonio Mulet a

a
Universidad Politecnica de Valencia, Food Technology Department, Camino de Vera s/n, 46022 Valencia, Spain
b
Instituto de la Grasa (CSIC), Food Quality and Characterization Department, Avda. Padre Garca Tejero, 4, 41012 Sevilla, Spain

Received 14 June 2006; accepted 26 October 2006

Abstract

The quality of frying oils covering a wide range of oil degradation and degree of unsaturation was analyzed using ultrasonic tech-
niques. Ultrasonic velocity and attenuation decreased with temperature, and the average velocity temperature coecients were 3.59
and 3.51 m s1 C1 for monounsaturated (MUO) and polyunsaturated (PUO) oils, respectively. Velocity was linearly related to vis-
cosity, showing higher values for PUO than for MUO. Velocity was also related to the percentage of polar compounds (R2 = 0.77 and
0.86 for PUO and MUO, respectively) and polymers (R2 = 0.86 for PUO and MUO together). The use of velocity and viscosity in a
single prediction model allowed to classify 97.5% of the samples correctly, according to the 25% polar compounds limit. Therefore, ultra-
sonic techniques can be used to characterize thermal degradation of oils when subjected to dierent frying conditions, which could be
useful for frying operators or inspection services.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Frying oil; Polar compounds; Ultrasonics; Viscosity

1. Introduction (Challis, Povey, Mather, & Holmes, 2005) or melting and

Ultrasound is a non-invasive technique and is thus
potentially suitable for monitoring the progress of indus-
trial processes in real time. In the literature many applica-
tions can be found regarding the use of ultrasound in
dierent types of products, ranging from solid to liquid
materials (Mulet, Benedito, Golas, & Carcel, 2002). The
multipurpose character of ultrasonic assessment can be
seen from the wide range of products that have been previ-
ously examined. In this regard, low intensity ultrasonics
(LIU) has been used for the quality control of vegetables,
fruits, meat and sh and dairy products (McClements,
1997; Mulet et al., 2002). In these applications, ultrasonics
has been used among other things to assess the texture of
fruits and cheese (Benedito, Simal, Clemente, & Mulet,
2006; Mizrach, 2004), temperature (Haeggstrom & Luuk-
kala, 2000), particle distribution of colloidal dispersions
*
Corresponding author. Tel.: +34 963879366; fax: +34 963879839.
E-mail address: jjbenedi@tal.upv.es (J. Benedito).
freezing (McClements & Povey, 1987; Sigfusson, Ziegler,
& Coupland, 2004).
Composition assessment by using ultrasonics has also
been widely reported in the literature. The composition
of meat, sh and meat products can be determined by using
ultrasonics (Benedito, Carcel, Rossello, & Mulet, 2001;
Ghaedian, Coupland, Decker, & McClements, 1998; Mor-
lein, Rosner, Brand, Jenderka, & Wicke, 2005). The solid
fat content has also been ultrasonically assessed because
it has an important implication on the texture, spreadabil-
ity and consistency of many materials such as margarine or
butter (McClements, 1997). Besides these applications,
ultrasonics has been applied to assess the sugar content
of melons (Mizrach, Galili, Rosenhouse, & Teitel, 1991)
or the oil content of olive oil mill wastewater (Benedito,
Mulet, Clemente, & Garca-Perez, 2004).
Ultrasonics can also be applied to solve some problems
found in the oil related industries. In this respect, ultrasonic
velocity has been measured to determine the chemical
structure of dierent oils including the chain length and
degree of unsatturation (Javanaud & Rahalkah, 1988).

0963-9969/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2006.10.017
 J. Benedito et al. / Food Research International 40 (2007) 406414
Therefore, velocity measurements can be used to assess oil
composition and adulteration (McClements, 1997; Raghu-
pathi, Siva, & Prabhu, 1980).
Attenuation and velocity have also been correlated to
rheological properties of edible oils (castor, olive, ground-
nut, sunower and rapeseed) (Gladwell, Javanaud, Peers,
& Rahalkar, 1985).
The ultrasonic velocity in fatty materials decreases as
the temperature increases, showing three dierent regions
(McClements, 1997). In the rst region, the triglycerides
are completely solid and therefore, the decrease in velocity
is due to the negative temperature coecient of the ultra-
sonic velocity in the solid fat. In the second region, some
triglycerides start melting, which causes a faster velocity
decrease. Finally, for higher temperatures, only liquid oil
is found (third region) and the decrease is due to the nega-
tive temperature coecient of velocity, as was the case for
solid fat.
Velocity was the ultrasonic parameter used in most of
the aforementioned studies. However, when low attenua-
tive materials (mainly liquids) are examined, attenuation
can also be considered. Both velocity and attenuation can
be related to the physico-chemical properties of the ana-
lyzed materials, like for example, composition or structure,
and can be used for their analysis. The advantages of the
ultrasonic techniques are that they are non-destructive,
low cost and can be easily automated on-line for real time
analysis.
Deep frying is widely used for the preparation of many
types of foods. The high temperatures reached during food
frying lead to a complex series of reactions that result in
hydrolysis, oxidation and polymerization of the oil (Ros-
sell, 2001). The spoilage of the oil directly aects both the
quality and safety of the fried foods. As a consequence,
and to protect consumers from contaminated food prod-
ucts, regulations or guidelines have been established in
many countries. Limits for the polar compounds of around
25% have been established in most of the ocial regula-
tions, limiting frying fat and oil degradation for human
consumption, although polymers and free fatty acids have
also been considered in some countries. Viscosity is another
important physical parameter considered in some countries
(Lacey & Payne, 1994). Eciency in frying oil quality con-
trol depends on the existence of objective analytical meth-
ods compatible with the needs of the fryer operator. In this
regard, ocial methods do not meet these requirements
and can only be used in the laboratory for inspection ser-
vices and in research studies.
Conventional methods for determining the discard point
of fats in fried food are often based on physical changes
subjectively assessed by the fryer operator, which often
results in oil abuse and higher than permitted values of
polar compounds and polymers. Furthermore, inspection
services can only cover a small amount of frying activities
(industries, bars, cafeterias, etc.) since ocial methods
are expensive and time consuming, requiring technical per-
sonnel and laboratory facilities.
407
Consequently, new rapid measurements, i.e., viscosity,
color, ultrasonics, etc., should be developed to dene cuto
levels at which the fats should be replaced. This would be
interesting not only for fryer operators but for the inspec-
tion services that could increase the number and periodicity
of the inspections.
In the last few years, several methods have been studied
in order to achieve a rapid assessment of the quality of fry-
ing oils and these have suggested the need for new systems
to increase the quality of frying fats and fried foods. These
studies include the use of FTIR spectroscopy (Innawong,
Parameswarakumar, Irudayaraj, & Marcy, 2004), elec-
tronic noses (Innawong, Parameswarakumar, & Marcy,
2004), chromametric methods (Xin Qing, 2003) or the mea-
surement of the dielectric capacitance of the fried oils
(Inoue, Hagura, Ishikawa, & Suzuki, 2002). In this respect,
ultrasonic techniques are robust, inexpensive and meet the
characteristics needed for frying oil quality assessment.
In a previous study Lacey and Payne (1994) reported the
relationship between viscosity and ultrasonic velocity for a
corn oil subjected to dierent heating periods. Benedito,
Mulet, Velasco, and Dobarganes (2002) studied the
changes in the ultrasonic properties during thermooxida-
tion of virgin olive oil. Changes in ultrasonic velocity and
attenuation were strongly related to changes in the percent-
age of polar compounds and polymers. In both studies the
oil was heated in laboratory fryers under controlled condi-
tions but not food was fried. The ability of ultrasounds to
characterize dierent types of frying oils from real frying
processes has not yet been evaluated.
The objective of this work was to study the feasibility of
assessing the quality of actual frying oils from restaurants,
cafeterias and catering companies using ultrasonic mea-
surements of velocity and attenuation.
2. Materials and methods
2.1. Frying oils
In this study 39 frying oils were used. The samples were
collected by the Food Inspection Services of the Junta de
Andalucia (Spain), from restaurants, cafeterias and cater-
ing services and they were selected to cover a wide range of
oil degradation and degree of unsaturation.
2.2. Ultrasonic measurements
The experimental set-up used for the experiments con-
sisted of two narrow band ultrasonic transducers
(1 MHz, 0.75 in. crystal diameter, A314S-SU Model, Pan-
ametrics, Waltham, MA), attached to a cubic container
(49 49 49 mm) where the oil samples were placed. The
container was introduced into a temperature-controlled
bath to maintain the sample temperature and the oil was
moderately stirred to avoid formation of bubbles. The
ultrasonic measurements were carried out while the oil
was cooled from 45 to 25 C. The transducers were linked
408 J. Benedito et al. / Food Research International 40 (2007) 406414
to a pulserreceiver (Toneburst Computer Controlled,
Model PR5000-HP, Matec Instruments, Northborough,
MA) which sent the electrical signal to a digital storage
oscilloscope (Tektronix TM TDS 420, Tektronix, Inc. Wil-
sonville, OR). For each ultrasonic measurement, ve signal
acquisitions were taken and averaged. The time of ight
was computed on the averaged signal and the ultrasonic
velocity calculated taking into account the system delay
(which was previously calibrated as described in Benedito
et al. (2004)).
The attenuation coecient (a) was computed by tting
the experimental data to Eq. (1).
ln A ln A0  ad
where d is the distance traveled by the wave, A0 is the initial
amplitude of the signal measured as the peak-to-peak volt-
age and A is the amplitude of the signal at distance d. Four
ultrasonic echoes were considered to compute attenuation.
2.3. Viscosity
The viscosity of the samples was measured using a fall-
ing ball viscometer (Haake falling ball viscometer C, Kar-
lsruhe, Germany) for transparent liquids. The apparatus
had a tempering jacket, which allowed the temperature of
the experiments to be controlled in the range considered
(2545 C). The temperature was measured by directly
inserting a probe into the falling tube. The experiments
were carried out in triplicate and the average was
considered.
2.4. Density
The density of the samples was measured with a specic
gravity hydrometer (Proton, Mod. 72082, Barcelona,
Spain) at 20 C. The oil samples were placed into a glass
container, which was introduced into a temperature con-
trolled bath at 20 C and allowed to reach temperature
equilibrium for 2 h. Next, the hydrometer was inserted in
the cylinder and the density was directly read on the scale.
2.5. Chemical analyses
2.5.1. Polar compounds
Polar compounds were quantied by adsorption chro-
matography following the IUPAC Standard Methods
2.507 (IUPAC, 1992).
2.5.2. Polymers
Triacylglycerol polymers were quantied by high-per-
formance size exclusion chromatography (HPSEC) follow-
ing the IUPAC Standard Method (Wolf, Mordret, &
Dieenbacher, 1992).
2.5.3. Fatty acids
Fatty acids were analyzed by GLC after derivatization
to fatty acid methyl esters (FAME) with KOH 2N in meth-
anol and triheptadecanoin as internal standard according
to the IUPAC Standard Method (IUPAC, 1992). A HP
6890 chromatograph on a HP Innowax capillary column
(polyethylene glycol, 30 m 0.25 mm i.d., lm thickness
0.25 lm) (Hewlett Packard, USA), was used under the fol-
lowing temperature program: 180 C (4 min), 4 C/min to
230 C (15 min). Samples were introduced into the column
via a split injector (split ratio 1:40) at 250 C and the ow
rate of hydrogen, used as carrier gas, was 1 mL/min. Tem-
perature of both split injector and ame ionization detector
was 250 C.
1 3. Results and discussion
3.1. Physico-chemical characteristics
Due to both the highly heterogeneous nature and the
thermal history of frying oils, and in order to group
together those oils, which had similar characteristics, the
39-sample set was divided into monounsaturated (MUO)
and polyunsaturated oils (PUO). Tables 1 and 2 (MUO)
(PUO) show the results of the physico-chemical analysis
carried out on the oil samples. Note that the saturated fatty
acid composition of 16 and 18 carbon atoms is very similar
for MUO and PUO except for some samples (6 and 17,
Table 1). Therefore, the dierences in the composition of
the oils mainly arise from the dierences in the composition
of oleic (C18:1) and linoleic (C18:2) fatty acids. The sam-
ples were considered polyunsaturated oils (PUO) when
the percentage of C18:2 was equal or higher than 50%.
Considering the main oils used in Spain in the discontinu-
ous frying process, i.e., olive, pomace, high-linoleic and
high-oleic sunower oils, the samples corresponded to con-
ventional sunower oils, rich in linoleic acid. As for mono-
unsaturated oils (MUO), with percentages of C18:2 lower
than 50%, the samples were more variable, probably due
to the practice these days of mixing low-price polyunsatu-
rated oils with highly stable monounsaturated oils. The
exceptions were Sample 17 with a composition similar to
that of palm olein and Sample 6 with a higher content of
palmitic acid than that corresponding to oils derived from
olives and sunower seeds. With respect to the level of deg-
radation, three sample groups were selected. Thirteen sam-
ples had polar compound percentages lower than 20%, 13
samples had polar compound percentages between 20%
and 30% (the zone in which the oil should be rejected)
and 13 samples had polar compound percentages higher
than 30%.
The change of viscosity (l) with temperature (T) for oils
and in particular for fried oils can be modeled using an
Arrhenius-type equation (ln l = ln A + B/T) (Benedito
et al., 2002; Reid, Prausnitz, & Sherwood, 1987; Silva &
Singh, 1995). The Arrhenius equation was successfully t-
ted to the experimental data (Fig. 1, R2 > 0.99) which indi-
cates that this model can be used in the 2545 C
temperature range and for oils that have been heated under
very dierent conditions and hence have dierent composi-
 J. Benedito et al. / Food Research International 40 (2007) 406414 409

Table 1
Physico-chemical characteristics of monounsaturated oils
Sample Polymers Polar compounds Major fatty acids (%) Density (kg/m3), Viscosity (mPa s),
(%) (%) 20 C 35 C
C16:0 C18:0 C18:1 C18:2
1 3.0 8.1 9.6 3.0 37.6 40.8 0.920 37.60
2 3.5 9.6 5.1 3.7 66.2 23.9 0.916 45.02
3 3.4 10.1 10.0 3.4 53.5 28.5 0.917 42.39
4 7.8 12.8 8.7 4.0 47.0 39.1 0.920 44.61
5 4.4 12.8 9.4 3.6 49.4 34.9 0.923 46.20
6 3.5 16.0 23.5 3.8 33.7 35.3 0.918 42.73
7 6.7 18.1 11.1 3.4 59.8 22.1 0.921 47.95
8 3.9 18.3 5.5 3.8 66.5 21.9 0.916 46.34
9 4.0 19.0 5.4 3.7 66.9 22.8 0.917 45.92
10 4.7 20.1 8.1 4.0 63.7 22.7 0.918 45.49
11 8.6 21.0 6.3 3.9 55.2 33.2 0.920 47.36
12 7.7 22.7 9.8 3.6 51.6 32.8 0.923 51.48
13 10.6 23.3 8.5 3.7 55.8 30.2 0.922 52.21
14 15.1 23.3 4.5 3.9 69.5 18.9 0.921 63.82
15 17.0 30.5 13.9 4.4 37.5 43.0 0.925 64.32
16 18.8 33.2 14.8 3.8 57.7 21.7 0.926 68.25
17 12.6 34.8 46.5 4.7 39.6 7.4 0.930 71.73
18 21.0 36.0 7.5 3.8 63.9 21.7 0.925 75.22
19 25.5 39.8 10.1 4.5 34.9 49.6 0.931 77.51
20 24.6 40.2 12.7 3.7 40.3 36.4 0.930 70.98
21 25.1 38.6 9.0 4.4 35.8 49.8 0.930 75.44
22 25.9 38.8 8.7 2.8 54 27.1 0.931 78.85

Table 2
Physico-chemical characteristics of polyunsaturated oils
Sample Polymers Polar compounds Major fatty acids (%) Density (kg/m3), Viscosity (mPa s),
(%) (%) 20 C 35 C
C16:0 C18:0 C18:1 C18:2
1 4.6 11.2 7.1 4.3 26.4 61.6 0.921 36.73
2 5.4 13.4 7.6 4.1 38.0 50.0 0.921 42.39
3 6.9 14.7 7.9 3.9 26.8 60.7 0.924 44.14
4 11.5 17.7 7.2 4.2 30.2 56.6 0.924 45.28
5 11.7 21.3 8.0 4.1 32.1 55.0 0.924 49.46
6 16.1 23.6 7.5 4.4 29.6 57.5 0.925 52.55
7 16.1 24.8 9.0 4.9 25.2 60.9 0.926 50.31
8 13.9 25.0 8.9 4.4 29.7 56.5 0.926 54.27
9 17.9 27.7 13.7 3.8 31.8 50.0 0.927 57.93
10 19.3 28.3 8.1 4.2 29.5 50.4 0.926 57.83
11 20.5 28.9 8.4 4.3 31.8 53.8 0.926 59.27
12 18.7 29.8 11.7 4.2 33.0 50.0 0.926 58.11
13 17.7 36.4 8.3 3.9 34.6 51.5 0.927 57.20
14 26.5 37.3 7.9 4.3 31.6 54.0 0.930 72.11
15 25.3 37.9 7.8 4.2 31.9 54.3 0.931 72.66
16 25.4 39.2 11.2 5.0 30.1 51.1 0.930 68.62
17 25.8 41.7 9.3 4.1 33.9 51.2 0.932 76.77

tion of polar compounds. The slopes were very similar with
only the intercepts changing according to the dierent
types of oils.
The degradation of oils during frying aects both viscos-
ity and the composition of polar compounds and polymers.
Benedito et al. (2002) found that the viscosity and the per-
centage of polar compounds in olive oil heated at 200 C
for up to 16 h could be related using a quadratic equation.
Fig. 2 shows the relationship between the viscosity at 35 C
calculated using the Arrhenius-type equations and the per-
centage of polar compounds, for the 39 samples considered
in the present study. Although in this case dierent oils
subjected to unknown frying conditions are considered, a
quadratic relationship is also found. Furthermore, the rela-
tionship is very similar for MUO and PUO, although for
the same percentage of polar compounds, and therefore
the same degree of oil degradation, the viscosity is slightly
lower for PUO than for MUO. As both types of oils
behave similarly, this shows that the viscosity seems to be
more aected by thermodegradation and therefore by the
percentage of polar compounds formed through oxidation
and thermal and hydrolytic reactions than by the composi-
tion of the fatty acids and in particular the degree of
unsaturation.
410 J. Benedito et al. / Food Research International 40 (2007) 406414

5 Dobarganes, 1995). In addition, viscosity was linearly

4.8 11.20% PUO related to the density of the samples (viscosity = 2480.6
16% MUO density = 2232.6; R2 = 0.80 and viscosity = 3332.6 den-
4.6
sity = 3030.5; R2 = 0.92 for MUO and PUO, respectively);
ln(Viscosity (mPa s))

38.80% MUO
4.4 39.20% PUO the higher the viscosity, the higher the density of the oil. As
4.2 was found when considering polymers for the same viscos-
4
ity, the density was higher for PUO than for MUO.
3.8
3.2. Ultrasonic measurements
3.6

3.4 The ultrasonic properties (velocity and attenuation) are

temperature dependent (Mulet et al., 2002). Ultrasonic
3.2
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 velocity increases when the temperature increases in water,
1/T (K-1) but decreases when it happens in fats (McClements, 1997).
Attenuation is also aected by temperature, although few
Fig. 1. Relationship between viscosity and temperature for MUO and
PUO with dierent percentages of polar compounds. Solid line Arrhenius
references are found in the literature. Benedito et al.
model. (2002) found that attenuation in heated olive oil decreased
when temperature increased. It is essential to know the tem-
perature in the ultrasonic measurements, either because the
90 inuence of this variable on the ultrasonic parameters pro-
vides information on the composition of the food (Benedito
80 y = 0.0175x2 + 0.345x + 36.101
R2 = 0.925
et al., 2001; McClements, 1997) or simply to make accurate
measurements at particular experimental temperatures.
70
Fig. 3a and b show the inuence of temperature on the
Viscosity (mPa s)

ultrasonic velocity measurements for MUO and PUO,

60
50
40
30
20
0 10
Polar compounds (%)
Fig. 2. Relationship between viscosity (35 C) and the percentage of polar
compounds for MUO and PUO.
A similar relationship was found between viscosity and
the percentage of polymers, but in this case the curve for
the PUO (viscosity = 0.0357polymers2 + 0.429poly-
mers + 37.43; R2 = 0.95) is clearly below that of the
MUO (viscosity = 0.0047polymers2 + 1.6922poly-
mers + 36.93; R2 = 0.96). As an example, for a value of
polymers of 16% (limit in the Netherlands) viscosity is
53.5 mPa s for PUO while for MUO a value of 62.8 mPa s
is found. Polymers form one of the groups of polar com-
pounds and of those originating at the high temperatures
of the frying process, they are the most representative.
The reason why, for the same viscosity, the percentage of
polar compounds is similar for both types of oils but the
percentage of polymers is higher for PUO than for
MUO, is that polyunsaturated fatty acids have a higher
tendency to polymerization than monounsaturated fatty
acids the latter originating a higher proportion of oxidized
monomers, which is the second most important group of
polar compounds (Marquez-Ruz, Tasioula-Margari, &
respectively and for dierent percentages of polar com-
pounds. As expected, ultrasonic velocity decreased linearly
2
y = 0.0079x + 0.7316x + 29.981 with the increase in temperature as occurs in other solid
R2= 0.9217
and liquid fats (McClements, 1997). The average velocity
temperature coecient was 3.59 and 3.51 m s1 C1
MUO
for MUO and PUO, respectively which is very close to
PUO
the value reported for olive oil (3.37 and 3.54 m s1
C1 for 0 and 16 h heating, (Benedito et al., 2002)). Those
20 30 40 50
values are higher than those for solid fats that decrease to
5 m s1 C1 (McClements, 1997). When solid fats are
partially melted the temperature coecient is comprised
within the values for solid and liquid fats.
As shown in Fig. 3a and b the higher the percentage of
polar compounds the higher the velocity for both types of
oils. Since the temperature coecients are not exactly the
same for all the oils analyzed, the dierence in velocity
between samples with a dierent composition of polar
compounds depends on temperature.
As previously reported by Benedito et al. (2002), atten-
uation decreases in line with the increase in temperature
for both types of oils (Fig. 4a and b), although a high var-
iability is also observed. On average, as observed for veloc-
ity, the attenuation is also higher for the samples with
higher concentration of polar compounds, although for
this parameter the higher variability makes the curves over-
lap in many samples.
3.3. Relationships between ultrasonic measurements and the
physico-chemical characteristics of oil
Fig. 5 shows the relationship between viscosity at 25 C
and the ultrasonic velocity at 25 C. The velocity used in
 J. Benedito et al. / Food Research International 40 (2007) 406414 411

1470 10.5
1460 8.10%
10.0
14.30% 18.30%
1450
18.30% 9.5 23.30%
1440

Attenuation (neper/m)
23.30% 39.80%
Velocity (m/s)

1430 9.0
39.80%
1420 8.5
1410
8.0
1400
1390 7.5

1380 7.0
1370
6.5
1360
20 25 30 35 40 45 50 6.0
Temperature (C) 20 25 30 35 40 45 50
Temperature (C)
1470

1460
10.0
13.4% 11.20%
1450 9.5 17.70%
21.3%
1440 31.3% 31.30%
9.0

Attenuation (neper/m)
Velocity (m/s)

1430 37.3% 37.90%

8.5
1420
8.0
1410

1400 7.5

1390 7.0
1380
6.5
1370
20 25 30 35 40 45 50 6.0
Temperature (C) 20 25 30 35 40 45 50
Temperature (C)
Fig. 3. Inuence of temperature on ultrasonic velocity for MUO (a) and
PUO (b) with dierent percentages of polar compounds. Fig. 4. Inuence of temperature on ultrasonic attenuation for MUO (a)
and PUO (b) with dierent percentages of polar compounds.

Fig. 5 was calculated from the linear t to the experimental

1460
data (Fig. 3a and b). The velocity appears to be higher for
PUO than for MUO, increasing in line with viscosity in 1458 MUO
both cases. Due to the high variability found in the atten- 1456 PUO
uation measurements, a poor relationship (R2 = 0.37) was
1454
Velocity (m/s)

found between attenuation and viscosity. Since the scatter-

ing eect is not expected to be signicant in fried oils where 1452
the solid particles have been removed and the air content 1450
was negligible, viscous attenuation should be what deter-
1448
mines the absorption of sound in the samples. Nonetheless,
the variability found in the attenuation measurements 1446
results both in poor relationships with viscosity and also 1444
means that this parameter is useless for characterizing the
1442
frying oils. In fact, most studies into the ultrasonic assess- 40 60 80 100 120 140
ment of food properties use ultrasonic velocity, as it is sim- Viscosity (mPa s)
pler and more reliable than attenuation (McClements, Fig. 5. Relationship between ultrasonic velocity (25 C) and viscosity
1997). (25 C).
As long as the ultrasonic velocity is related to the phys-
ical properties of the medium like viscosity and the percent-
age of polar compounds and polymers greatly aect for MUO than for PUO (Fig. 6). For equal percentages
viscosity (Fig. 2), velocity should also be related to these of polar compounds, the velocity was higher for PUO.
chemical indicators. The relationship between velocity When plotting velocity versus the percentage of polymers
and the percentage of polar compounds was also dierent it was also found that velocity increased linearly while
412 J. Benedito et al. / Food Research International 40 (2007) 406414

1460 polymers, similar bell-shaped curves were obtained for

1458
MUO and PUO (Maximum R2 = 0.92 and 0.82 for
MUO MUO and PUO, respectively), and the best temperature
1456 PUO for the experiments was 23 C for both types of oils. Con-
1454 sequently a better prediction of the chemical characteristics
Velocity (m/s)

1452
1450
1448
1446
1444
1442
0 10 20 30 40 50
% PC
Fig. 6. Relationship between ultrasonic velocity (25 C) and the percent-
age of polar compounds.
polymers increased although, in this case, no dierence was
found between MUO and PUO (velocity = 0.4977%poly-
mers + 1444.4, R2 = 0.86; MUO and PUO together). In
this case, the single measurement of velocity allows an esti-
mation of the percentage of polymers regardless of the
group in which the sample is categorized (MUO or
PUO). Poorer relationships were found between attenua-
tion and the chemical characteristics (R2 < 0.38). As previ-
ously mentioned, the dierences in velocity for oils with
dierent amounts of polar compounds depended on tem-
perature (Fig. 3a and b), and therefore it is expected that
the relationships between velocity and the percentage of
polar compounds will also be temperature dependent.
Fig. 7 shows the percentage of explained variance for the
relationships between velocity and the percentage of polar
compounds for temperatures from 0 to 45 C. Velocity at
the dierent temperatures was calculated from the linear
t to the experimental velocity data (from 0 to 25 C veloc-
ity was extrapolated). The temperature that allows for a
better description of the percentage of polar compounds
for MUO was 21 and 23 C for PUO. In the case of
1 atoms and double bonds is not signicant when explaining
0.9
MUO
0.8
PUO
0.7
0.6
R2
was found for MUO than for PUO.
These results show that in order to assess the chemical
degradation of frying oils using ultrasonics, temperature
control is necessary, not only because it will determine
the accuracy of the velocity measurements, but also
because the selection of a temperature range far from the
optimum values can lead to poor relationships between
the ultrasonic and the chemical analysis.
As previously seen, the ultrasonic velocity is related to
the physico-chemical properties of the media. In the case
of fried oils velocity was related to the percentage of polar
compounds and polymers. For the percentage of polar
compounds and viscosity, two dierent types of behavior
were observed for MUO and PUO, which reveals that, in
addition to the degradation of the triglycerides that results
in the formation of polar compounds and an increase in
viscosity, the composition of the oil, and in particular the
degree of unsaturation also aects the ultrasonic velocity.
In order to gain a better understanding of the inuence
of composition on the ultrasonic velocity, a linear equation
(Eq. (2)) which relates the ultrasonic velocity (V) to the
number of carbon atoms (NCA) and double bonds
(NDB) similar to the one used by Javanaud and Rahalkah
(1988) to assess velocity in triglycerides, was used.
V a bNCA cNDB 2
Where a, b and c are constants. The NCA and NDB was
calculated as the weighted average considering the compo-
sition shown in Tables 1 and 2. The equation was tted to
the experimental data by calculating the constants a, b and
c that minimized the square dierences between the exper-
imental and calculated (Eq. (2)) velocity, using the tool Sol-
ver from Excel. The equation was tted to each set of oils
(MUO and PUO) separately.
In both cases a very poor relationship (R2 < 0.06) was
obtained, which demonstrates that the number of carbon
the dierences in the ultrasonic velocity within each set of
oils.
On the contrary, the formation of polar compounds,
which increases viscosity, clearly aected the ultrasonic
velocity and hence this ultrasonic parameter can be used

0.5
0.4
to characterize the degradation of dierent types of fried
0.3
oils.
0.2
Nevertheless, when comparing the results for both types
0.1
of oils, velocity dierences are found (Figs. 5 and 6). The
0
average number of carbon atoms for all the samples is
0 10 20 30 40 50 17.76 (s.d. = 0.189) and 17.82 (s.d. = 0.03) for MUO and
Temperature (C) PUO, respectively, which denotes that the average number
Fig. 7. Dependence of the percentage of explained variance for the of carbon atoms is very similar and probably does not
relationships between velocity and the percentage of polar compounds on aect the dierences in ultrasonic velocity. On the other
temperature. hand, the number of double bonds is 1.14 (s.d. = 0.16)
 J. Benedito et al. / Food Research International 40 (2007) 406414
for MUO and 1.42 (s.d. = 0.04) for PUO, this dierence
would explain the changes in velocity for the same degree
of oil degradation. The average ultrasonic velocity at
20 C for MUO was 1467.4 m s1 and 1470.6 m s 1for
PUO. Using Eq. (2), Javanaud and Rahalkah (1988) found
that at 20 C a double bond increased velocity by 8 m s1.
Taking into account that the dierence in the average num-
ber of double bonds between MUO and PUO was 0.28, the
ultrasonic velocity should be 2.2 m s1 higher for poly than
for monounsaturated oils which is close to the value found
in the present study (3.2 m s1).
On the other hand, the low variability in the number of
carbon atoms and double bonds within each set of oils
(MUO and PUO) could explain why ultrasonic velocity
could not be related to these parameters using Eq. (2).
3.4. Assessment of the chemical characteristics of frying
oils using ultrasonics and viscosity
In order to characterize the chemical degradation of the
frying oils regardless of the degree of saturation, velocity
and viscosity were included in a quadratic model. The
obtained equation (Eq. (3)) only achieved a slightly higher
percentage of explained variance than when only consider-
ing viscosity in the model (R2 = 0.89).
%PC 991:295 0:65844V 1:60224l
 0:008807l2 R2 0:92
When using this equation to elucidate whether the samples
exceeded the polar compounds 25% limit, only Sample 14
(MUO, Table 1) was misclassied, being categorized as
exceeding the limit (29.3%) when really it was slightly be-
low (23.3%).
Eq. (4) was obtained to predict the percentage of poly-
mers. The percentage of explained variance increased from
0.88 to 0.94 when including ultrasonic velocity in the pre-
diction of polymers.
%Polymers 1493:64 1:01947V 0:67837l
 0:00303l2 R2 0:94
When assessing which samples exceeded the polymers limit
of 16% using Eq. (4), three samples with values slightly
above the limit (measured: Sample 6 PUO-16.1%; Sample
7 PUO-16.1% and Sample 9 PUO-17.9%) were considered
as correct samples (predicted: 14.6, 12.8 and 15.6 for sam-
ples 6, 7 and 9, respectively) while Sample 8 (measured:
PUO-13.9% polymers) was categorized as exceeding the
limit (16.5%, predicted). The remaining samples were cor-
rectly classied.
Although the percentage of explained variance for poly-
mers (R2 = 0.94) is higher than the one corresponding to
the polar compounds (R2 = 0.92), a higher number of mis-
classications is obtained since more samples have
observed percentages of polymers closer to the limit of
16%. Therefore, velocity could be used separately or
combined with viscosity in a single equation to assess the
413
quality of frying oils measured by the percentage of polar
compounds and polymers.
4. Conclusion
The percentage of polar compounds and polymers, con-
ventionally used to measure frying oil degradation, were
related to viscosity in dierent frying oils taken by the
Spanish inspection services from real frying processes.
The ultrasonic velocity was also related to the chemical
characteristics of the oils (percentages of polar compounds
and polymers), these relationships were dependent on the
type of oil that was classied as mono and polyunsatu-
rated. Temperature of the ultrasonic measurements aected
not only accuracy but to the goodness of the relationships
between ultrasonic velocity and the percentage of polar
compounds and polymers. Ultrasonic velocity and viscos-
ity could be used to characterize the thermal degradation
of frying oils subjected to very dierent frying conditions.
An ultrasonic system could be used in industrial fryers to
alert the operator when the discard time is close, or by
inspection services to carry out a screening and determine
if the oil samples must be taken to the laboratory for fur-
ther analysis. For that purpose, the particles contained in
the oil should be previously removed to avoid any eect
of the fried product on the ultrasonic measurements.
3 Acknowledgements
The authors acknowledge the nancial support from the
Ministerio de Ciencia y Tecnologa (Spain) and the INIA
(CAL01-077-C3-1).
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