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2017 Oxitest Rancimatfryingoils EFRT
2017 Oxitest Rancimatfryingoils EFRT
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ORIGINAL PAPER
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
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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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Eur Food Res Technol
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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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)
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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
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Eur Food Res Technol
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