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Comparison of OXITEST and RANCIMAT methods to evaluate the oxidative


stability in frying oils

Article  in  European Food Research and Technology · October 2017


DOI: 10.1007/s00217-017-2995-y

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Eur Food Res Technol
DOI 10.1007/s00217-017-2995-y

ORIGINAL PAPER

Comparison of OXITEST and RANCIMAT methods to evaluate


the oxidative stability in frying oils
Federica Tinello1 · Anna Lante1 · Michele Bernardi2 · Francesca Cappiello2 ·
Fernanda Galgano3 · Marisa Carmela Caruso3 · Fabio Favati2   

Received: 20 July 2017 / Revised: 22 September 2017 / Accepted: 13 October 2017


© Springer-Verlag GmbH Germany 2017

Abstract  The oxidation of fatty acids in the presence of Keywords  Oxidative stability · Induction period ·
atmospheric oxygen is recognized as one of the main fac- RANCIMAT · OXITEST · Frying oils · Fatty acids
tors affecting the shelf life of oils and fats causing rancidity
by the formation of off-flavors due to aliphatic aldehydes or
other volatile compounds. Therefore, the oxidative stability Introduction
is one of the most important parameters to be evaluated in
the formulation of commercial frying oils. In this regard, the Frying, which is one of the most commonly used cook-
induction period of 15 frying oils has been measured using ing procedures in household, restaurants, fast-food chains,
two different methods of accelerated oxidation, OXITEST and food industry, is a system involving oil, food, fryer and
and RANCIMAT, and correlated to their fatty acid content processing [1]. The deep- and shallow-frying techniques
previously detected by gas chromatographic technique. include, respectively, the dipping or contact of food with
Frying oils containing high contents of saturated fatty acids hot oil at the temperature range of 150–190 °C to increase its
mainly from the palm oil achieved an improved oxidative organoleptic quality and shelf life [2]. The hydrolysis, oxi-
stability by increasing their induction period. Moreover, dation and polymerization reactions occurring in the heated
the linear regression analysis showed a good correlation oil during frying lead to the formation of non-volatile and
between the induction period values of the two instruments. volatile compounds which affect the sensory and nutritional
Hence, the innovative OXITEST method may be an easy, properties not only of the oil but also of the fried food. These
fast, and eco-friendly alternative to the official RANCIMAT chemical reactions depend on several factors such as frying
method for evaluating the oxidative stability in oil- and fat- temperature and time, oxygen concentration, the presence
containing products. of antioxidants, and the type of oil and fryer [3]. The frying
stability of oils is associated mainly to their tocopherol and
fatty acid contents and profiles [4–6]. Mixtures of differ-
ent vegetable oils containing saturated and unsaturated fatty
acids are recommended in the formulation of frying oils. In
All authors contributed equally to this work.
fact, the inclusion of oils rich in saturated fatty acids such as
* Fabio Favati palm oil in mixtures of unsaturated fatty acid-containing oils
fabio.favati@univr.it can reduce the formation of oxidized products because of the
1
faster oxidation of the unsaturated rather than the saturated
Department of Agronomy, Food, Natural Resources,
fatty acids [7, 8].
Animals, and Environment‑DAFNAE, Agripolis, University
of Padova, Viale Università 16, 35020 Legnaro, PD, Italy There are several methods to evaluate the quality and
2 stability of frying oils. Some measurements of the oxi-
Department of Biotechnology, University of Verona, Strada
Le Grazie 15, 37134 Verona, Italy dation degree in frying oils are focused on oil physical
3 properties and volatile and non-volatile decomposition
School of Agricultural, Forestry, Food and Environmental
Sciences, University of Basilicata, Viale dell’Ateneo Lucano products [9]. Other methods which measure the resist-
10, 85100 Potenza, Italy ance to oxidation in forced conditions take into account

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Eur Food Res Technol

the oxidative stability as one of the most important factors of solid [19–21] or liquid [22, 23] samples, without prior
to evaluate the shelf life, palatability, nutritional quality preparation. The instrument monitors the oxygen uptake
and toxicity of oils and fats by determining the induction of the reactive components present in food/feed samples to
period (IP), a parameter representing the time needed to evaluate the oxidative stability under accelerated oxidation
reach the starting point of lipid oxidation. Therefore, a conditions, and the reactor temperature can be regulated
longer IP can be associated with a higher oxidation stabil- from room temperature to 110 °C, while the oxygen pres-
ity. The active oxygen method (AOM) and the analysis of sure can reach up to 0.8 MPa. A few papers have investi-
carbonyl value (CV) have been the mostly used tests to gated its use for evaluating the oxidation stability of oils,
detect the oxidative stability of oils by measuring primary chia seeds, and bakery products [20, 22–25] and recently
or secondary oxidation products, such as hydroperoxides, the AOCS has approved a new analytical procedure (Cd
aldehydes and ketones, respectively [10]. However, these 12c-16) based on the use of this instrument.
chemical techniques, which are non-reproducible, time Aim of this work was to compare the OXITEST and
consuming, expensive and involve the use of toxic rea- the RANCIMAT methods in evaluating the oxidative sta-
gents, have been then replaced with accelerated oxidation bility of commercial frying oils, taking also into account
methods [11]. In this regard, the official oil stability index the relationship between the IP values and the fatty acid
(OSI) method of American Oil Chemists’ Society (AOCS) composition of the oils.
requires the use of different analytical instruments that
can be utilized as an alternative, RANCIMAT (Metrohm,
Herisau, Switzerland) being one of these [12]. The RAN-
CIMAT method allows to evaluate not only the oxidative Materials and methods
stability of edible [13] and non-edible oils [14], fats [11],
nanoemulsions [15], encapsulated extract within nanoe- Samples
mulsion and multiple emulsions [16] but also the antioxi-
dant performance of plant extracts [17, 18] by monitor- A total of 15 frying oils from different commercial brands
ing over time the water conductivity, which increases as a were purchased from a local market and stored at room
consequence of volatile acids formed after heating samples temperature under dark conditions until the analyses. All
under atmospheric pressure and constant values of temper- of the commercial oils were manufactured and packaged
ature and air flow. The OXITEST—Oxidation Test Reactor in Italy with the exception of sample D, coming from Bel-
(VELP, Usmate, MB, Italy)—is an innovative instrument gium (Table 1).
that can be utilized to investigate the oxidation stability

Table 1  Composition and fat Code Composition Fat (g/100 mL)


content declared in the label of
the frying oil samples analysed A Sunflower oil high in linoleic acid, sunflower oil high in oleic acid, cori- 92.0
in the study ander essential oil (0.0002%)
B Sunflower, peanut oils 100a
C Sunflower, palm, peanut oils 92.0
D Sunflower oil, rapeseed oil, sunflower oil high in oleic acid, corn oil, 92.0
dimethylpolysiloxane (anti-foaming agent)
E Sunflower, fractionated vegetable oils NR
F Sunflower, fractionated palm oils 91.6
G Sunflower, fractionated palm oils 91.4
H Sunflower, fractionated palm oils 91.4
I Sunflower, fractionated palm, peanut oils 91.6
J Sunflower, fractionated palm, peanut oils 92.0
K Sunflower, soybean, fractionated palm oils 92.0
L Sunflower, bi-fractionated palm, peanut oils 92.0
M Sunflower, bi-fractionated palm, peanut oils 91.4
N Sunflower, bi-fractionated palm, peanut oils 91.6
O Sunflower (70%), bi-fractionated palm (20%), soybean (5%) oils 92.0

NR value not reported in the label


a
  g/100 g

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Eur Food Res Technol

Oxidative stability measurement using the RANCIMAT Assessment of the oil fatty acid content
instrument
The saturated and unsaturated fatty acid content in the fry-
The oxidative stability of the frying oils was evaluated using ing oils was assessed by gas chromatographic analysis of
a RANCIMAT apparatus (Metrohm, model 743, Herisau, the respective methyl esters (FAMEs) [26]. The analyses
Switzerland) and measuring over time the water conductiv- were carried out using an Agilent 7890A GC system (Agi-
ity [18]. A fixed amount of oil (3.0 ± 0.1 g) was added to lent Technologies, Cernusco sul Naviglio, Milano, Italy)
each reaction tube and subjected to accelerated oxidation equipped with an Agilent 7683 autosampler and a Flame
by raising the temperature to 110 °C under a 20 L h−1 air Ionization Detector (FID). FAMEs were prepared by weight-
flow. The volatile oxidation products formed under forced ing 40 mg of each frying oil in a small glass test tube and
conditions were transported by the air stream into the con- adding 2 mL of hexane and 200 µL of 2 M methanolic KOH.
ductometric cell, previously filled with 60 mL of distilled The mixture was then vortexed at room temperature for
water, and detected by continuously measuring the water 2 min and then let to stand after the addition of about 0.5 g
electrical conductivity (µS cm−1) over time (h). The oxi- of anhydrous ­Na2SO4 to eliminate any water formed during
dative stability was expressed as the IP corresponding to the hydrolysis process. After the phase separation occurred,
the time (h) at the intersection point between the horizontal an aliquot of the upper hexane layer (1 μL) was injected
(conductivity, µS min−1) and vertical (time, h) tangents of in split mode (1:50) into a S­ LB®-IL111 capillary column
the fitted exponential oxidation curves. At this break point (100 m × 0.25 mm × 0.20 μm) (Sigma-Aldrich, Milano,
the water conductivity increased over time because of the Italy). Helium (grade 6.0, SOL, Monza, Italy) was used as
fat oxidation. Two samples per frying oil were placed in the carrier gas (1 mL min−1), while nitrogen (grade 5.0, SOL,
equipment and analysed simultaneously in triplicate. Monza, Italy) was used as make-up gas. The injector and
FID temperatures were set at 250 °C and separation of the
Oxidative stability measurement using the OXITEST various FAMEs was achieved using an initial oven tempera-
instrument ture of 100 °C, which after being kept constant for 13 min
was then raised to 240 °C at 4 °C min−1. The various fatty
The oxidative stability of the frying oils was also assessed acids were identified according to their retention time and
using the OXITEST apparatus (­ Velp® Scientifica, Usmate, by spiking the samples, using a commercial mixture of pure
Italy), featuring two thermostated and hermetically sealed standards (Supelco 37 Component FAME Mix CRM47885,
titanium chambers, each one able to contain up to three Sigma-Aldrich, Milano, Italy). The fatty acid content was
round 35-mL titanium sample holders, that can be piled up expressed as percentage based on the sum of the detected
when working with large sample amounts. When the sample peak areas.
size requires the use of less than three holders, the unused
ones are replaced with titanium spacers, so to keep constant Statistical analysis
the void volume in each chamber [22]. An amount equal to
10 g of frying oil, thoroughly mixed immediately before The data concerning the IP values and fatty acid content
being sampled, was loaded in each chamber and due to the were analysed by a one-way analysis of variance (ANOVA),
limited sample amount only one holder was utilized, being after verifying the normal distribution and homogeneity of
then necessary the use of two spacers. The working tempera- variance, using the PROC GLM of Statistical Analysis Sys-
ture was set at 110 °C, while the initial ­O2 pressure (grade tem (SAS) [27]. The model included the type of frying oil as
5.0; SAPIO, Monza, Italy) was set at 0.6 MPa. The instru- fixed effect. Least-square means were chosen for presenting
ment was controlled by a specific software (OXISoft™, all data and compared using the Tukey’s multiple range test.
­Velp® Scientifica, Usmate, Italy) that allowed to measure Differences among means with P ≤ 0.05 were accepted as
over time the absolute pressure change in the two chambers, representing statistically significant differences. The box-
monitoring the oxygen uptake of the active components of plots were computed using the SAS software package [27].
the samples. For each chamber at the end of the test, the Linear regression analysis was carried out using the
program automatically calculated the IP from the resultant PROC REG of SAS [27]. The OXITEST IPs were correlated
oxidation curve, by means of a graphical method (two tan- with those obtained using the RANCIMAT instrument, and
gent methods). Each analysis was repeated three times for a the assessed IPs of both instruments were correlated with
total of six data acquired for each oil. the fatty acid content.

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Results and discussion Furthermore, other studies have shown that when using the
OXITEST the working temperature may affect the oxygen
Correlation between RANCIMAT and OXITEST solubility in lipids, with a reduction of the assessed IP val-
ues of about 25% for each 10 °C increment [22]. Anyhow it
The frying oils consisted of edible mixtures derived from should also be pointed out that when using the RANCIMAT
two or three different vegetable oils achieving a total fat apparatus the oil sample was exposed to a continuous flow of
content around 92 g/100 mL (Table 1). As regards the com- air at atmospheric pressure, having an oxygen concentration
position declared in the label of the frying oils analysed in of about 21%. Conversely, when working with the OXITEST
this study, sunflower oil was present in all samples. Moreo- instrument the oil sample was exposed to pure ­O2 under
ver, both A and D frying oils contained sunflower oil high pressure (0.6 MPa).
in oleic acid, while only the former contained also sunflower The OXITEST and RANCIMAT instruments achieved
oil high in linoleic acid. The enrichment of oleic [4] and the same results in spite of their different measurement
linoleic acids [5] in sunflower oil leads to health benefits, approach. In this regard, the effect of the type of frying
improved shelf life and fast formation of polar compounds oil on the IP value was statistically significant (P ≤ 0.001)
during frying. The D sample from Belgium contained also regardless of the analytical method applied. The boxplots in
rapeseed and corn oil, and dimethylpolysiloxane as anti- Fig. 1 divided the frying oil samples into three main groups
foaming agent to further protect lipids from thermal deg- based on their IP values obtained using both the OXITEST
radation [28], while the A sample contained also coriander and the RANCIMAT methods. In the first group the K and N
essential oil (0.0002%) to improve the flavor. Palm oil was samples, with IP mean values of about 5.42 and 10.47 h for
present in most of the investigated frying oils and the F–K OXITEST and RANCIMAT methods, respectively, showed
and L–O samples contained the fractionated and bi-frac- the highest oxidative stability (Table 2). In the second group,
tionated forms of palm oil to improve the oxidative stability the C–J and L–M samples, with IP mean values of about
and shelf life of the products [29]. Peanut oil was found in 3.73 and 7.00 h for OXITEST and RANCIMAT methods,
the composition of 7 out of the 15 studied oils (B, C, I, J
and L–N samples) but reasonably at different percentages,
being reported in the labels at the second place for the B
sample and at the third place for the others. Only K and O
samples contained soybean oil as second and third ingredi-
ent, respectively, while the E oil composition resulted to be
not well defined, being only reported in the label that the
second of the two ingredients was represented by “fraction-
ated vegetable oils”.
The oxidative stability of the frying oil samples was eval-
uated by measuring their IPs with two different methods.
In particular, with the RANCIMAT instrument, where the
accelerating oxidation factors are temperature and air flow,
the IP values were assessed as the time needed for achieving
an increase in the measured water conductivity due to the
production of oxidation-related moieties. Conversely, with
the OXITEST method, where the accelerating factors are
temperature and high levels of pure ­O2, the IP values rep-
resented the time needed to achieve a significant pressure
decrease of the oxidizing gas in the chamber, thus a sudden
change in the lipid oxidation rate.
To compare the two instruments at similar analytical
conditions, the working temperature was set at 110 °C for
both, taking into account that temperature can play a cru-
cial role in fat oxidation, therefore, affecting the determina-
tion of the IP values. In particular, some authors studying
the relationship between RANCIMAT and active oxygen
method at different temperatures have reported an oxidative
stability decrease of about 27% for sunflower, palm, soybean Fig. 1  Boxplots of the IP values of the frying oils obtained by OXIT-
and rapeseed oil when moving from 110 to 130 °C [11]. EST (a) and RANCIMAT (b) methods

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Table 2  IP values of the frying oils obtained by OXITEST and


RANCIMAT methods
Sample IP OXITEST (h) IP RANCIMAT (h)
Mean ± SD CV% Mean ± SD CV%

A 2.69i ± 0.08 2.97 4.78h ± 0.26 5.36


B 2.79i ± 0.05 1.79 4.80h ± 0.15 3.08
C 3.61fg ± 0.15 4.16 6.72fg ± 0.08 1.21
D 3.85cde ± 0.15 3.90 7.74c ± 0.20 2.52
E 4.07bc ± 0.08 1.97 7.43cd ± 0.38 5.11
F 3.93bcd ± 0.02 0.51 7.35cd ± 0.16 2.19
G 3.79def ± 0.08 2.11 6.84ef ± 0.13 1.90
H 3.64efg ± 0.15 4.12 6.66fg ± 0.19 2.81 Fig. 2  Correlation between the IP values of the frying oils obtained
I 3.51g ± 0.12 3.42 7.03def ± 0.13 1.85 by OXITEST and RANCIMAT methods
J 3.89bcd ± 0.05 1.28 7.15de ± 0.11 1.57
K 5.38a ± 0.11 2.04 10.67a ± 0.21 1.98
L 3.72defg ± 0.11 2.96 6.74ef ± 0.09 1.32 E, the CV% values resulted to be higher than 5%, specifically
M 3.27h ± 0.10 3.06 6.31g ± 0.22 3.53 5.11 and 5.36% (Table 2).
N 5.46a ± 0.09 1.65 10.27a ± 0.27 2.65
O 4.11b ± 0.16 3.89 9.03b ± 0.12 1.29 Correlation between oxidative stability and fatty acid
content
SD standard deviation, CV% coefficient of variation
a–h
   Values are the mean (±  standard deviation) of three replicates.
Means within each column and with different superscripts are statisti- The oxidative stability is affected by several factors includ-
cally different (P ≤ 0.05) ing the content of saturated and unsaturated fatty acids [4],
tocopherols [5] and other antioxidants compounds [15] in
the oil samples and the storage conditions [30]. The fatty
respectively, showed an intermediate oxidative stability. In acid profile of oils is generally recognized as the most deci-
the third group, the oils A and B, with IP mean values of sive parameter influencing the oxidation stability of oils [8].
about 2.74 and 4.79 h for OXITEST and RANCIMAT meth- Moreover, some authors highlighted that the frying stability
ods, respectively, showed the lowest oxidative stability. of high oleic sunflower oil is influenced by the fatty acid
Only for sample O, the IPs assessed with the two methods content rather than the tocopherol isomeric composition
resulted in a different ranking of the oil as regards its oxida- [5]. Therefore, the oxidative stability of frying oils has been
tion stability. In particular, when tested with the OXITEST discussed on the basis of their fatty acid content which was
method its IP was not significantly different from those of determined by GC analysis. As reported in Table 3 all frying
samples E, F and I, oils with an intermediate relative oxi- oil samples were rich in unsaturated and poor in saturated
dative stability. Conversely, when using the RANCIMAT fatty acids with a total mean of 83.7 and 16.3%, respec-
instrument its IP resulted more similar to those of oils K and tively. Moreover, the fatty acid content differed significantly
N, characterized by the highest stability (Table 2). (P ≤ 0.001) based on the formulation of frying oils. In detail,
Statistical analysis of the oils IP data assessed with the the boxplot in Fig. 3 divided the frying oil samples into three
OXITEST and the RANCIMAT methods revealed a signifi- groups based on their saturated fatty acid content: (1) K
cant positive correlation (r = 0.97; r2 = 0.93; P ≤ 0.001) and N samples high in saturated fatty acids whose content
between the IP values of these different methods (Fig. 2). was on average of 27.3%; (2) C, E–J, and O samples with
In detail, the IPs obtained when using the OXITEST were an averaged content of saturated fatty acids around 17.3%;
approximately two times lower than those obtained when (3) A, B, D, L, and M samples low in saturated fatty acids
using the RANCIMAT instrument. As a consequence, the whose content was on average 10.3% (Table 3). The boxplot
OXITEST method was comparable to the RANCIMAT one in Fig. 4 divided the frying oil samples into three groups
for evaluating the relative oxidative stability of the frying based on their unsaturated fatty acid content: (1) A, B, D, L,
oils but it accelerated more the fat oxidation, thus detecting and M samples high in unsaturated fatty acids whose content
the IP value in a shorter time. In addition, both methods was on average of 89.7%; (2) C, E–J, and O samples with an
showed good CV% values, mainly below 5%. In particular, averaged content of unsaturated fatty acids around 82.7%;
for OXITEST the assessed CV% values ranged from 0.51 to (3) K and N samples low in unsaturated fatty acids whose
4.16, while for RANCIMAT the values ranged from 1.21 to content was on average of 72.7% (Table 3). The boxplot in
3.53. However, with the latter instrument for two oils, A and Fig. 5 divided the frying oil samples into three groups based

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Table 3  Fatty acid content of the frying oils


Sample Saturated fatty acids (%) Unsaturated Saturated/unsatu-
fatty acids (%) rated fatty acids

A 10.13h ± 0.03 89.87bc ± 0.03 0.11g ± 0.00


B 11.38g ± 0.01 88.63  ± 0.01 0.13fg ± 0.00
c

C 15.65e ± 0.18 84.36e ± 0.18 0.19e ± 0.01


D 7.45i ± 0.66 a
92.56  ± 0.66 0.08a ± 0.01
E 19.88b ± 0.05 80.12h ± 0.05 0.25b ± 0.00
F 18.32c ± 0.10 81.69  ± 0.10 0.23bc ± 0.01
g

G 17.63c ± 0.14 82.38g ± 0.14 0.22cd ± 0.01


H 16.03de ± 0.36 83.97ef ± 0.36 0.20de ± 0.01
I 17.09cd ± 0.02 82.92fg ± 0.02 0.21cde ± 0.00
J 16.18de ± 0.59 83.82ef ± 0.59 0.20de ± 0.01
K 27.44a ± 0.04 72.57i ± 0.04 0.38a ± 0.00
L 9.65h ± 0.08 b
90.35  ± 0.08 0.11g ± 0.00 Fig. 4  Boxplot of the unsaturated fatty acid content of the frying oils
M 12.98f ± 0.31 87.02d ± 0.31 0.15f ± 0.00
N 27.23a ± 0.03 i
72.77  ± 0.03 0.37a ± 0.00
O 17.55c ± 1.09 82.45  ± 1.09 0.22cd ± 0.02
g

a–h
   Values are the mean (±  standard deviation) of three replicates.
Means within each column and with different lowercase letters are
statistically different (P ≤ 0.05)

Fig. 5  Boxplot of the ratio between saturated and unsaturated fatty


acid content of the frying oils

and unsaturated fatty acid content (Figs. 6, 7, respectively).


The correlation has also been investigated between the IP
values and the ratio between saturated/unsaturated fatty
Fig. 3  Boxplot of the saturated fatty acid content of the frying oils
acids (Fig. 8) to assess the relationship between the fatty
acid composition and the measured oxidative stability.
on their ratio between saturated and unsaturated fatty acid The positive correlation of the IP values obtained using
content (Table 3): (1) K and N samples with an averaged OXITEST (r = 0.83; r2 = 0.69; Fig. 6a) and RANCIMAT
ratio of 0.38; (2) C, E–J, and O samples with an averaged (r = 0.78; r2 = 0.61; Fig. 6b) methods with the saturated
ratio of 0.22; (3) A, B, D, L, and M samples with an aver- fatty acid content was statistically significant (P ≤ 0.001).
aged ratio of 0.12. The IP values increased at increasing saturated fatty acid
A comparison between the results of the IP and fatty acid content. In detail, each 10% increment of the saturated fatty
content suggested that the frying oils with greater IP values acid content in the frying oils extended approximately 1
had a higher saturated fatty acid content. Several authors and 2 h the IPs obtained with OXITEST and RANCIMAT
have reported that fat oxidation decreases at increasing methods, respectively. The negative correlation of the IP
levels of saturated fatty acids and at decreasing levels of values obtained using OXITEST (r = − 0.837; r2 = 0.69;
unsaturated fatty acids [4, 8, 21]. In this regard, the IP val- Fig. 7a) and RANCIMAT (r = − 0.78; r2 = 0.61; Fig. 7b)
ues of the frying oil samples obtained using OXITEST and methods with the unsaturated fatty acid content was statisti-
RANCIMAT methods have been correlated to their saturated cally significant (P ≤ 0.001). The IPs decreased at increasing

13
Eur Food Res Technol

Fig. 6  Correlation of the IP values of the OXITEST (a) and RANCI- Fig. 8  Correlation of the IP values of the OXITEST (a) and RANCI-
MAT (b) methods with the saturated fatty acid content of the frying MAT (b) methods with the ratio between saturated and unsaturated
oils fatty acid content of the frying oils

with the OXITEST and the RANCIMAT instruments,


respectively. Hence, an increased oxidative stability of the
frying oils was related to an increase in the saturated fatty
acid content based on the formulation of the ingredients
declared in the label (Table 1). In details, the frying oils K
and N, which showed to be the most stable according to their
assessed IPs (5.4 and 5.5 h with OXITEST; 10.7 and 10.3 h
with RANCIMAT) (Table 2), were the richest in saturated
fatty acids, (27.4 and 27.2%, respectively) (Table 3) whose
levels may be associated to the use of fractionated palm oil
in the industrial formulations (Table 1). In fact palmitic acid
was found to be present in oils K and N at the highest levels,
22.4 and 22.5%, respectively. Moreover, the fractionation
process applied on the palm oil utilized in these samples
(Table 1) led to a greater oxidative stability in comparison
to the oil C, containing unfractionated palm oil and char-
acterized by a lower palmitic acid level (10.9%) and lower
Fig. 7  Correlation of the IP values of the OXITEST (a) and RANCI- IP values, as assessed with the OXITEST and RANCIMAT
MAT (b) methods with the unsaturated fatty acid content of the fry- methods (3.61 and 6.72 h, respectively) (Table 2). On the
ing oils
contrary, samples A and B, that resulted to be more prone
to oxidation (Fig. 1) according to their lowest IP values
saturated fatty acid content. In detail, each 10% increment of assessed using the OXITEST (2.69 and 2.79 h) or the RAN-
the unsaturated fatty acid content in the frying oils decreased CIMAT (4.78 and 4.80 h) method, did not contain any palm
of approximately 1 and 2 h the IP obtained with OXITEST oil and showed to be poor in saturated fatty acids (10.1 and
and RANCIMAT methods, respectively. The positive cor- 11.4%, respectively) and rich in unsaturated fatty acids (89.9
relation of the IP values obtained using OXITEST (r = 0.86; and 88.6%), due to their composition based on sunflower and
r2 = 0.73; Fig. 8a) and RANCIMAT (r = 0.80; r2 = 0.64; peanut oils (Tables 1, 2, 3). Several authors have reported
Fig. 8b) methods with the ratio saturated/unsaturated fatty that palm oil, rich in palmitic acid, has shown to be less sen-
acid content was statistically significant (P ≤ 0.001). The sitive to oxidation than other vegetable oils rich in unsatu-
IPs resulted to increase at increasing saturated/unsaturated rated fatty acids and olive oil [7, 29, 31]. Furthermore, some
ratios, with a 10% increment of the latter causing roughly an authors evaluating the oxidative stability of several vegetable
increase of approximately 0.8 and 1.5 h of the IPs assessed oils with the RANCIMAT method at different temperatures,

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confirmed the greatest resistance of palm oil to fat oxida- 6. Gliszczyńska-Swigło A, Sikorska E, Khmelinskii I, Sikorski M
tion, being characterized by higher IP values (19.95, 10.89, (2007) Tocopherol content in edible plant oils. Pol J Food Nutr
Sci 57:157–161
and 5.70 h) than rapeseed (7.38, 4.10, and 1.85 h), soybean 7. De Marco E, Savarese M, Parisini C, Battimo I, Falco S, Sac-
(5.24, 2.61, and 1.51 h) and sunflower oils (3.70, 1.89, and chi R (2007) Frying performance of a sunflower/palm oil blend
0.88 h) at 110, 120, and 130 °C, respectively [11]. in comparison with pure palm oil. Eur J Lipid Sci Technol
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8. De Leonardis A, Macciola V (2012) Heat-oxidation stabil-
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stability measurements for frying oils and fried food flavor. J Am
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The detection of IP value represents an important parameter 10. AOCS (1989) Official methods and recommended practices of the
for evaluating the oxidative stability of frying oils. Acceler- AOCS, 4th edn. AOCS, Champaign, Ill
ated tests such as OXITEST and RANCIMAT are able to 11. Anwar F, Bhanger MI, Kazi TG (2003) Relationship between ran-
speed up the fat oxidation and monitor the oxidative stability cimat and active oxygen method values at varying temperatures. J
Am Oil Chem Soc 80:151–155
in a relatively short period of time without using expen- 12. AOCS (2012) Official methods and recommended practices of the
sive and environmental hazardous reagents. The regression AOCS, 6th edn. AOCS, Champaign, Ill
analysis carried out on the IP values showed a linear correla- 13. Mateos R, Uceda M, Aguilera MP, Escuderos ME, Maza
tion between RANCIMAT and OXITEST instruments which GB (2006) Relationship of Rancimat method values at vary-
ing temperatures for virgin olive oils. Eur J Lipid Sci Technol
achieved the same comparative results following different 223:246–252
procedures. Hence, the OXITEST method may represent 14. Peer MS, Kasimani R, Rajamohan S, Ramakrishnan P (2017)
a valid alternative to the RANCIMAT method and could Experimental evaluation on oxidation stability of biodiesel/die-
be a useful tool for the edible oil industry in formulating sel blends with alcohol addition by rancimat instrument and FTIR
spectroscopy. J Mech Sci Technol 31:455–463
oil mixtures to be utilized for food frying. Furthermore, the 15. Lante A, Friso D (2013) Oxidative stability and rheological prop-
method does not necessitate any specific sample preparation erties of nanoemulsions with ultrasonic extracted green tea infu-
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studies, therefore, allowing higher throughputs. 16. Mohammadi A, Jafari SM, Esfanjani AF, Akhavan S (2016)
Application of nano-encapsulated olive leaf extract in controlling
the oxidative stability of soybean oil. Food Chem 190:513–519
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fica (Usmate, MB, Italy) for lending the OXITEST instrument and Dr. ation of red chicory extract as a natural antioxidant by pure lipid
Paola Ornaghi for technical assistance. oxidation and yeast oxidative stress response as model systems. J
Agric Food Chem 59:5318–5324
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any studies with human or animal subjects. Tolve R, Favati F (2017) Evaluation of the oxidative stability of
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