Thermochimica Acta 601 (2015) 3944

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Kinetics of blackberry and raspberry seed oils oxidation by DSC

Darko M. Mici
c a, * , Sanja B. Ostoji
c a , Mladen B. Simonovi
c a , Gordana Krsti
c b,
ca
Lato L. Pezo a , Branislav R. Simonovi
a
b

University of Belgrade, Institute of General and Physical Chemistry, Studentski trg 1216, 11158 Belgrade, Serbia
University of Belgrade, Institute of Chemistry, Tehnology and Metallurgy, Center for Chemistry, Studentski trg 1216, 11158 Belgrade, Serbia

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 26 September 2014
Received in revised form 16 December 2014
Accepted 17 December 2014
Available online 19 December 2014

Differential scanning calorimetry (DSC) technique is used to study the oxidative stability of blackberry (R.
 cak Thornless cultivar) and raspberry (Rubus idaeus L., Willamette cultivar) seed oils.
fruticosus L., Ca9
Oxidative stability of the oil samples was studied in an oxygen atmosphere, isothermally at eight
temperatures, Ti (110, 115, 120, 125, 130, 135, 140 and 145
C) and non-isothermally at six heating rates, bi
(2, 5, 7.5, 10, 15, 20
C/min). Fatty acid composition was analyzed by gas chromatography (GCMS). High
content of essential fatty acids (linoleic and linolenic acid) was detected in both oils. Reaction rate
constants (k) and activation energies (Ea) of oil oxidation process were calculated for both isothermal and
non-isothermal conditions. Blackberry seed oil was shown to have greater oxidative stability than
raspberry seed oil because of a smaller quantity of linolenic fatty acid.
2014 Elsevier B.V. All rights reserved.

Keywords:
Raspberry seed oil
Blackberry seed oil
Oxidative stability
Oxidation kinetics
DSC

1. Introduction
Fats and oils are important ingredients of the human diet, both
in terms of nutritional value, and in terms of organoleptic
properties (smell, taste). As the body of evidence that links health
benets to the consumption of vegetable oils continues to grow,
many consumers now prefer to use vegetable oils instead of animal
fats. Several phytochemicals that have been detected in edible seed
oils may include tocopherols, carotenoids, phenolic and polyphenolic compounds, and especially fatty acids such as linolenic acid
(18:3, n-3). Linolenic acid is an essential n-3 fatty acid that cannot
be synthesized by the human body and must be obtained through
the diet. Linolenic acid can be converted to longer-chain n-3 fatty
acids through elongation and desaturation reactions. These
n-3 fatty acids are reported to provide potential health benets
in terms of reducing the risk of heart disease, cancer, hypertension
and autoimmune disorders [13].
Oxidation of polyunsaturated fatty acids is the main reaction
that affects the quality of oil and oil products during storage and
use. Different chemical mechanisms (autoxidation and photosensitized oxidation) are responsible for the oxidation of edible
oils, depending on the types of oxygen. Two types of oxygen can
react with edible oils. One is atmospheric triplet oxygen, 3O2 and
the other is singlet oxygen, 1O2. 3O2 reacts with lipid radicals and

* Corresponding author. Tel.: +381 112182389.

E-mail address: micic83@gmail.com (D.M. Mici
c).
http://dx.doi.org/10.1016/j.tca.2014.12.018
0040-6031/ 2014 Elsevier B.V. All rights reserved.

causes autoxidation, which is a free radical chain reaction [4].

Photosensitized oxidation of edible oils occurs in the presence of
light, sensitizers, and atmospheric oxygen, which produce 1O2.
Temperature has little effect on photosensitized oxidation due to
low activation energy [5], and will thus be discussed only
autoxidation.
Autoxidation of lipids proceeds through a radical mechanism
involving the following steps: initiation (RH ! R, R + O2 ! RO2),
propagation (RO2 + RH ! RO2H + R, R + O2 ! RO2), branching
(RO2H ! RO + OH, RO + RH + O2 ! ROH + RO2,OH + RH + O2 !
H2O + RO2), chain stopping inhibition (InH + RO2 ! In + RO2H),
peroxide decomposition (RO2H ! inert products). Low molecular
weight products, which result from the cleavage of hydroperoxide
chain, form aldehydes, ketones, alcohols and hydrocarbons. These
low molecular weight compounds are responsible for the rancid
scent and off-avor produced by oxidized fats [6].
There are various methods available for measurement of lipid
oxidation. Changes in chemical, physical or organoleptic properties
of fats and oils during oxidation can be monitored to assess the
extent of lipid oxidation. Over the years, thousands of studies have
focused on monitoring and evaluating the oxidation of lipids using
the Rancimat method, peroxide value (PV), anisidine value (AV),
spectrophotometric, GC and NMR analysis of fats and oils from
various sources [7,8].
Since oil oxidation is an exothermic reaction, it releases heat
that can be measured using differential scanning calorimetry
(DSC). Because it is a simple, time saving method that does not
require the use of toxic chemicals, DSC could be used for routine

40

D.M. Micic et al. / Thermochimica Acta 601 (2015) 3944

analysis in the oils and fats industry. Thus, in recent times, DSC has
been one of the most commonly used techniques for examination
of the oxidative stability of different types of oils [914].
High-value vegetable oils (like berry seed oils) are gaining
attention, owing to their health benets, which are linked to their
high content of polyunsaturated fatty acids and antioxidants. All
berry seed oils have in common a high content of polyunsaturated
fatty acids, providing essential fatty acids [1517]. Recently, the
properties of some berry seed oils have been reported in literature.
Parry et al. [18,19] found signicant amounts of a-linolenic acid,
tocopherols, polyphenols and carotenoids in marionberry,
boysenberry, red raspberry and blueberry seed oils.
The objective of the present work was to evaluate and compare
 cak
the oxidative stability of blackberry (R. fruticosus L., Ca9
Thornless cultivar) and raspberry (Rubus idaeus L., Willamette
cultivar) seed oils and to determine the kinetic parameters related
to the oxidation process by DSC in isothermal and non-isothermal
mode.
2. Materials and methods
2.1. Materials
 cak Thornless cultivar) and
Blackberry (R. fruticosus L., Ca9
raspberry (Rubus idaeus L., Willamette cultivar) were obtained
 cak, Serbia. Berry seeds were
from Fruit Research Institute, Ca9
obtained by fruit pulp cold-pressing. Seeds were dried at room
temperature to the constant moisture of 67% and milled by coffee
grinder. Oil was extracted from milled berry seeds, using hexane as
described in literature [20]. The sample (5 g) was stirred for 2 h at
4
C with hexane (50 ml). The solvent was removed by vacuum
ltration and the sample was extracted two additional times. After
the last ltration, the extracts were pooled and the hexane was
removed by rotary vacuum evaporation at 30
C. The oil was stored
at 20
C until analysis. All chemicals and reagents used were of
the highest purity.
2.2. Fatty acid determination by GC/MS
The fatty acid composition of the oils was determined by GC/MS
analysis, after transesterication. The GC analyses were performed
on Agilent 7890A GC system (Agilent Technologies, California, USA)
equipped with a 5975C MSD and FID detector, using a DB-23
column (60 m  250 mm  0.25 mm). Helium was used as the
carrier gas at a ow rate of 0.9 ml/min. The column temperature
was linearly programmed in the range of 175235
C at the rate
4
C/min and held at 235
C for 5 min. The transfer line was heated
at 240
C. The FID detector temperature was 300
C. The EI mass
spectra (70 eV) were acquired in the m/z range 40500. The fatty
acid methyl esters were prepared in the following manner: 30.0 mg
of oil and a drop of concentrated sulfuric acid were added in 6 ml of
methanol and the mixture was reuxed for 2 h with constant
stirring. Acid was neutralized by addition of saturated potassium
hydrogen carbonate upon completion of the transesterication
process (the change in pH value is monitored by a universal pH
indicator (SigmaAldrich, Missouri, USA)). Following neutralization, the mixture was extracted with hexane (3  6 ml). The hexane
solution was dried over anhydrous sodium sulfate, ltered and
evaporated to dryness. The obtained transesterication oil was
used for the preparation of an oil solution, in the concentration of
about 1 mg/ml, which was then analyzed by GC/MS.
2.3. DSC analysis
Oxidative stability of the oil samples was determined by TA
Instruments DSC Q1000, Differential Scanning Calorimeter

(Delaware, USA), with TA Universal analysis 2000 software. The

apparatus was calibrated with a high-purity indium standard.
ICTAC Kinetics Committee recommendations for collecting kinetic
data [21] and for performing kinetic computations [22] were
followed when performing kinetic studies. Oil samples of
3.0  0.3 mg were weighed into open aluminum pans and placed
in the equipment's sample chamber. An empty open aluminum
pan was used as reference. Both isothermal and non-isothermal
experiments were performed under an oxygen (99.95% purity)
ow of 50 ml/min. During oil oxidation, the oxygen consumption
can be neglected due to the large excess of oxygen generated by a
constant ow rate. Such conditions allow the formation of
peroxides independent of the oxygen concentration, which also
means that the autoxidation is a rst order reaction [23]. This is an
essential assumption for the calculation of kinetic parameters:
activation energy, Ea (J/mol), pre-exponential factor or frequency
factor, A (min1), and reaction rate constant, k (min1).
2.3.1. Non-isothermal DSC method
In non-isothermal DSC method, the oil samples were heated at
six different heating rates, bi (2, 5, 7.5, 10, 15, 20
C/min), starting
from 40
C to the beginning of the oxidation process. Three
characteristic points can be observed on DSC curve of the oil
oxidation (Fig. 1A): onset temperature (Ton), rst peak (Tp1) and
second peak (Tp2).
The isoconversional method of KissingerAkahiraSunose
(KAS) [24] was employed for the calculation of activation energy
and pre-exponential factor for the onset temperature (Ton),
because onset occurs at about the same extent of conversion,
which is close to zero. The following equation was used:
!


bi
1
(1)
b
a
ln 2
T on;i
T on;i
where bi is heating rate (K/min) and Ton,i is onset temperature (K).
The index i is introduced to denote an individual heating rate. By
plotting lnbi =T 2on;i vs. 1=T on;i , the activation energy and the preexponential factor for onset were determined directly from the
slope and the intercept according to:
a

Ea;on
R

(2)

Fig. 1. (A) Non-isothermal DSC curve during heating of raspberry seed oil sample at
rate 10
C/min in oxygen ow 50 ml/min (T on onset temperature, T p1 the rst
peak and T p2 the second peak); (B) effect of different heating rates on T on
and T p1 .

D.M. Micic et al. / Thermochimica Acta 601 (2015) 3944

 0 
A R
b ln on
Ea;on

(3)

where a and b are the slope and the intercept from Eq. (1),
respectively, R is the universal gas constant (8.314 J/molK), and
A0 on Aon =ga  ga, g(a) is the integral form of reaction model,
and a is extent of conversion, because a = const for onset, g(a) is
also constant). Therefore, the activation energy is calculated from:
Ea;on R

dlnbi =T 2on;i
d1=T on;i

(4)

The Kissinger method [25] was used for the calculation of

activation energy and pre-exponential factor for the peak
temperature (Tp):
!


Ap R 0
Ea;p
b
f ap 
(5)
ln 2i ln 
Ea;p
RTp;i
T p;i
0

where f a df a=da, and f a is the differential form of

0
reaction model. For a rst order reaction f a 1 [22], and
Eq. (5) can be rewritten as:
!


Ap R
Ea;p
b
(6)

ln 2i ln
Ea;p
RTp;i
T p;i
The left hand side of Eq. (6) is plotted against 1=T p;i giving rise to a
straight line whose slope and intercept yield the activation energy
and pre-exponential factor, respectively.
Values of Ea and A can be used to calculate the rate constant of
reaction, given by the Arrhenius equation:


Ea
(7)
k A  exp
RT
2.3.2. Isothermal DSC method
In isothermal DSC mode, the oil samples were held at eight
different temperatures, Ti (110, 115, 120, 125, 130, 135, 140 and
145
C) until the start of the oxidation process. Samples were
heated in nitrogen ow (50 ml/min) to an appropriate temperature. The process of oil oxidation can be seen on the DSC curve in
the form of exothermic heat ows appearing during initiation of
the oxidation reaction. Oxidation induction time, OIT (min), was
determined from the resulting curve, as the intersection of
the extrapolated baseline and the tangent line (leading edge) of
the exothermal peak. OIT denes the oxidation process time
needed to reach a same extent of conversion (close to zero) at
different temperatures. The integral isoconversional method for
isothermal conditions [22] was used for the calculation of
activation energy and pre-exponential factor:


ga
Ea;a
(8)

lnta;i ln
Aa
RTi

41

where ta;i (min) is the time to reach a given extent of conversion

(a) at different temperatures Ti (K), ga is integral form of reaction
model (ga const for a const), Ea;a and Aa are activation
energy and pre-exponential factor at a given extent of conversion.
For OIT, Eq. (8) can be rewritten as:
lnkOIT;i lnA0OIT 

Ea;OIT
RTi

(9)

where kOIT 1=OIT, and A0 OIT is proportional to AOIT . Activation

energy and frequency factor were determined from the slopes and
intercepts, respectively, of the curves generated by regressing
lnkOIT;i vs. 1/Ti using least squares linear regression, with
implemented LevenbergMarquardt algorithm. In this case, the
slope and intercept were -Ea,OIT/R and lnA0OIT , respectively.
2.4. Statistical analysis
All DSC experiments and measurements were performed in
triplicate and the values are presented as mean values  SD. T on , Tp
and OIT were used to calculate Arrhenius parameters (Ea, A, k). All
kinetic data were subjected to analysis of variance (ANOVA) for the
comparison of means, and signicant differences are calculated
according to post-hoc Tukeys HSD (honestly signicant
differences) test at p < 0.05 signicant level, 95% condence
limit. The linear regression analyses for tting of kinetics data, was
performed using STATISTICA 10.01 (StatSoft Inc., Tulsa, OK, USA)
software. The accuracy of T on , Tp and OIT was tested based on
coefcients of variation.
3. Results and discussion
Table 1 shows GCMS results for individual fatty acids
percentage contribution in oil samples obtained from raspberry
and blackberry seeds.
It can be seen that these oils are rich in essential fatty acids
(linoleic and linolenic acid). Insufcient dietary intake of these
acids causes dry, rough skin, eczema, rash, weak hair, weak nails. It
is also shown that the ratio of n-6 and n-3 fatty acids (linoleic and
linolenic, respectively) is about 2:1 in raspberry and 4:1 in
blackberry seed oil. This indicates that the raspberry seed oil could
be recommended for use in nutrition, since it was previously
shown that oils with a low ratio of n-6 to n-3 fatty acids reduced
the risk of cancer and heart disease [26,27].
Fig. 1A shows a typical non-isothermal DSC curve during
heating of raspberry seed oil sample at the rate of 10
C/min in
oxygen ow. As already mentioned, three characteristic points can
be observed: onset temperature (T on ), rst peak (T p1 ) and second
peak (T p2 ). DSC curves at other heating rates show the same shape
for both oils. Since two exothermic peaks occur, it is clear that two
main processes take place during oil oxidation. Litwinienko and
Kasprzycka-Guttman [28] have shown that the model of sequential
reactions with autocatalytic onset is the best explanation for the
shape of the DSC signal during oil oxidation. This model
demonstrates that the rst peak is caused by hydroperoxide

Table 1
Fatty acid compositions (% w/w) of blackberry and raspberry seed oils.
Fatty acids (% w/w)

Blackberry seed oil

Raspberry seed oil

(16:0) Palmitic acid

(18:0) Stearic acid
(18:1) Oleic acid
(18:2) Linoleic acid
(18:3) Linolenic acid
Non-identied methyl ester of C18 acid, unknown position of double bond

3.65  0.07
2.27  0.04
12.53  0.14
66.33  0.13
14.62  0.32
0.60  0.01

3.47  0.09
1.06  0.03
11.55  0.10
55.29  0.24
27.80  0.21
0.83  0.01

D.M. Micic et al. / Thermochimica Acta 601 (2015) 3944

42

Table 2
T on and T p1 values obtained at different heating rates (bi ) for blackberry and raspberry seed oils*.
Heating rate, b (
C/min)

Blackberry seed oil

20
15
10
7.5
5
2
CV (%)

Raspberry seed oil

Ton (K)

Tp1 (K)

Ton (K)

Tp1 (K)

470.16  3.15d
466.13  3.30cd
459.52  2.95bc
455.43  1.29ab
446.52  2.65a
435.31  3.12e
1.14

509.72  4.48c
498.59  3.28bc
490.09  3.14ab
485.91  1.79a
484.81  2.57a
461.69  5.04d
1.09

464.05  4.15c
458.50  2.95ac
453.31  1.00a
449.78  2.62ab
441.60  1.67b
429.33  3.33d
1.19

502.22  3.63d
491.43  4.35b
481.66  1.69ab
478.55  3.62a
475.21  4.03a
453.29  3.14c
1.09

*
Values printed in one column, with the same letters (ae) in superscript are not statistically different at the p < 0.05 level, 95% condence limit, according to Tukeys HSD
test; CV coefcient of variation.

Table 3
Linear regression parameters obtained by KAS method for Ton and Kissinger method for Tp1, for blackberry and raspberry seed oils.
Parameters

a
b
R2
Ea*(kJ/mol)
A* (1010 min1)
*

Blackberry seed oil

Raspberry seed oil

Ton

Tp1

Ton

Tp1

12194  499
16.60  1.10
0.99
101  4
19.7

10870  1198
11.95  2.46
0.95
90  10
0.17

12301  410
17.23  0.91
0.99
102  3
37.3

10274  943
11.11  1.97
0.97
85  8
0.69

Ea,on and A0 on for Ton; Ea,p and Ap for Tp1.

formation, while the second peak is the result of decomposition of

hydroperoxides to further products.
Based on this, it is clear that only the onset of oxidation and the
rst peak should be considered in assessing the oil oxidative
stability from non-isothermal DSC method.
T on and T p1 values determined from DSC curves, which are
obtained at different heating rates, are shown in the Table 2, for
both oils. The post-hoc Tukeys HSD tests have been employed for
comparison of samples of blackberry and raspberry seed oil within
T on and T p1 assays, and statistically signicant (p < 0.05) difference
were found between all samples. As can be seen, these values
increase with an increase in the heating rate (Fig. 1B). This is due to
the fact that at lower heating rates, primary oxidation products
(such as hydroperoxides), which are generated during the initial
stage of oxidation, subsequently react with excess oxygen to form
low molecular weight compounds such as aldehydes and acids
(intermediate oxidation products), which remain in solution,
accelerating the degradation process. On the other hand, at higher
heating rates, these intermediate products evaporate before they
can react further with the oil solution, shifting DSC signal toward
higher values [23].
Table 3 shows the kinetic parameters (activation energy and
pre-exponential factor) obtained by KAS method for Ton and
Kissinger method for Tp1, as explained in the Section 2.3.1. Good
tting to experimental results were obtained, for both samples,
using linear regression with a high coefcient of determination of
R2 > 0.95 for both methods.
As can be seen, activation energies calculated using Tp1 are
lower than those obtained using Ton for both oils. This indicates
that two different reactions are taking place at the onset and the
peak of DSC curve. This can be explained by the autoxidation
mechanism which are chain reactions initiated by the formation of
free radicals. At the initial stage of chain reactions, a relatively
higher energy is needed to initiate the chain reactions. While the
accumulation of free radicals occurs as the oxidation process
progresses, a lower energy which is related to the concentration of
free radicals and reactants is reached. According to that, the
oxidative stability of oils is dominantly inuenced by the reaction
at the onset of the DSC curve (reaction of radical formation).

Therefore, in further discussion, the kinetic parameters calculated

from Ton will be considered in comparison to those obtained from
the isothermal method.
Isothermal DSC oxidation curves of raspberry seed oil at four
different temperatures (110, 120, 130, 140
C) and the way of
determining oxidation induction time (OIT) are presented in Fig. 2.
The effect of different temperatures on oil oxidation is evident. The
obtained DSC curves have the same shape for both oils. Oxidation
induction times were determined from these curves; the results
are presented in Table 4. It can be seen from these results that the
increasing the isothermal temperature by 10
C, OIT values
decrease approximately by half, which is in accordance with the
Q10 law linking reaction rates with temperature [9]. Reaction rate
constants were calculated for each Ti as the reciprocal OIT value;
they are also presented in Table 4. Tukeys HSD tests was calculated
for OIT assay and statistically signicant (p < 0.05) difference was
found between all samples. The obtained results show that
reaction rate constants increase with increasing temperature;
therefore, the oil oxidation is faster at higher temperatures.
Activation energy and pre-exponential factor are obtained by
linear regression model lnkOIT,i vs.1/Ti, from the slope and intercept

Fig. 2. Isothermal DSC oxidation curves of raspberry seed oil at four different
temperatures (110, 120, 130, 140
C) in oxygen ow 50 ml/min, OIT oxidation
induction time.

D.M. Micic et al. / Thermochimica Acta 601 (2015) 3944

43

Table 4
OIT values and reaction rate constants (kOIT = 1/OIT) at eight different temperatures (Ti) obtained for blackberry and raspberry seed oils.
Ti (
C)

Blackberry seed oil

Raspberry seed oil

3

OIT (min)

kOIT (10
f

110
115
120
125
130
135
140
145

284.93  10.70
192.35  9.13e
138.27  2.21d
90.45  2.64c
62.37  3.85bc
51.17  4.37ab
31.44  2.03ab
21.65  1.76a

CV (%)

4.75

min

1

kOIT (103 min1)

OIT (min)
h

142.68  2.92
108.28  2.95g
72.25  2.79f
55.54  3.70e
42.98  1.16d
23.91  1.86c
19.16  1.25b
12.73  1.08a

3.5
5.2
7.2
11.1
16.0
19.5
31.8
46.2

7.0
9.2
13.8
18.0
23.3
41.8
52.2
78.5

7.79

ah

Values printed in one column, with the same letters in superscript are not statistically different at the p < 0.05 level, 95% condence limit, according to Tukeys HSD test; CV
coefcient of variation.

Table 5
Estimated Arrhenius parameters for blackberry and raspberry seed oils oxidation on
isothermal conditions (lnkOIT,i vs. 1=T i ).
Parameters

Blackberry seed oil

Raspberry seed oil

a
b
R2
Ea;OIT (kJ/mol)
A0OIT (1010 min1)

24.63  0.74
11605  298
0.99
96  3
5.00

23.94  1.13
11099  453
0.99
92  4
2.49

(R2 > 0.96), respectively, as explained in the Section 2.3.2. The

obtained values are shown in Table 5.
Based on the differences of activation energy values of these
two oils, it is impossible to accurately conclude which oil is more
prone to oxidation, because they are almost equal within
experimental error. However, Thurgood et al. [29] pointed out
earlier that the activation energy should not be the only parameter
considered in comparing oxidative stability of different lipid
systems and the oxidation rate constant is much more suitable
parameter. From activation energies and pre-exponential factors
the oxidation rate constants at 25
C (k25) and 120
C (k120) are
calculated by Arrhenius equation, for both non-isothermal and
isothermal conditions; these results are presented in Table 6.
By comparing the oxidation rate constants, it can clearly be seen
that the k of raspberry seed oil is about 1.52 times higher than that
of blackberry seed oil, which indicates that blackberry seed oil is
more stable in terms of oxidation. The reason for this lies in a
higher content of linolenic acid in the raspberry seed oil at the
expense of linoleic acid, compared to the content of these fatty
acids in the blackberry seed oil (Table 1), as Fatemi and Hammond
[30] showed earlier that the relative ratio of autoxidation rate of
linoleic and linolenic ester was about 1:2, respectively.
Also, by comparing the oxidation rate constants obtained for
blackberry and raspberry seed oils with those of commercial oils
(olive oil, k120 0:015  0:090 min1 [31], and sunower oil
k120 0:014 min1 [12]) in literature, it can be seen that they
are approximately of the same value or lower, which is contrary to
expectations, being that these oils are highly unsaturated oils

Table 6
Oxidation rate constants at 25
C (k25) and 120
C (k120) by Arrhenius equation for
blackberry and raspberry seed oils.
Oxidation rate
constants

k25* (107 min1)

k120* (103 min1)
*

Blackberry seed oil

(Table 1). This is probably because berry seed oils are very rich in
tocopherols (>1000 mg/kg for both oils) [15] which are among the
most effective natural antioxidants. Tan et al. [32] obtained similar
results for sesame oil, which is also a highly unsaturated oil, but
with very good oxidative stability due to the high antioxidant
content (sesamol and sesaminol, together with tocopherols).
By comparing the kinetic parameters (Ea, k25 and k120) obtained
by non-isothermal method with the ones obtained by the
isothermal method for each of the oil samples, it is estimated
that Ea and k120 have approximately equal values obtained by both
methods, while the values of k25 are different for both oils
(k25 obtained from isothermal method are higher). This is probably
because oxidative stability of the oil, estimated in this way, i.e., by
using parameters obtained at high temperatures to assess the
stability at low temperatures, and should be considered with great
care, because the conditions of oxidation are quite different. The
oxidation reaction can proceed in different ways at low and high
temperatures, depending on the reactivity of metal ions and
antioxidants present in the oil; in addition, the solubility of oxygen
in oil changes with the temperature [32]. Based on these facts, it
can be concluded that both methods, non-isothermal and
isothermal, can be used for quantitative determination of oil
oxidative stability at high temperatures (e.g., during frying), while
for prediction of oxidative stability at low temperatures
(e.g., during storage), they are more reliable as a qualitative
assessment when comparing different oil types.

8. Conclusion
Examined berry seed oils are rich in essential fatty acids.
Raspberry seed oil has a very low ratio of n-6:n-3 fatty acids, which
makes it very convenient for functional food usage. It was shown
that oxidation rate constant is much more suitable parameter than
activation energy, in oxidative stability evaluation of raspberry and
blackberry seed oils. By comparing the oxidation rate constants,
blackberry seed oil was shown to be more oxidatively stable than
raspberry seed oil. Reason for this is a lower quantity of linolenic
fatty acid in blackberry seed oil, as linolenic fatty acid is less stable
in terms of oxidation. Although both oils are highly unsaturated
oils, they show similar oxidative stability as some commercial oils,
probably due to high tocopherols content of berry seed oils.

Raspberry seed oil

Nonisothermal

Isothermal Nonisothermal

Isothermal

Acknowledgement

3.41
6.68

6.09
7.47

16.64
13.53

This study was supported by the Ministry of Education, Science

and Technological Development of the Republic of Serbia, under
the Projects No. TR-31093 and TR-31055.

4.50
9.62

kon for non-isothermal conditions; kOIT for isothermal conditions.

44

D.M. Micic et al. / Thermochimica Acta 601 (2015) 3944

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