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To cite this article: A. Rohman & Y.B. Che Man (2013) Application of FTIR Spectroscopy for
Monitoring the Stabilities of Selected Vegetable Oils During Thermal Oxidation, International
Journal of Food Properties, 16:7, 1594-1603, DOI: 10.1080/10942912.2011.603874
Fourier transform infrared spectroscopy has been developed for rapid monitoring of the
oxidative stabilities of selected vegetable oils, namely corn oil, rice bran oil, soybean
oil, and sunflower oil during thermal treatment at 160◦ C for 120 h. There were several
absorbance changes between non-oxidized and oxidized vegetable oils during thermal oxi-
dation. Peak intensities at 3470, 1655, and 967 cm−1 were increased; meanwhile peak
intensities at 3008 and 722 cm−1 were decreased. The R2 values for the correlation between
the absorbance changes at 3008 cm−1 and the specific absorptivities of conjugated dienes
for corn oil, rice bran oil, soybean oil, and sunflower oil were 0.938, 0.845, 0.978, and 0.824,
respectively. The absorbance changes of Fourier transform infrared spectra at 3008 cm−1
were also correlated with the specific absorptivities of conjugated trienes and p-anisidine
values with the acceptable R2 values. Compared with the conventional technique, the use of
Fourier transform infrared spectroscopy for measurement the thermal oxidative stability has
some advantages, i.e., it is a rapid technique and no sample preparation. In addition, Fourier
transform infrared spectroscopy reduces or eliminates solvents and chemical reagents that
are hazardous to human health or to the environment; therefore, Fourier transform infrared
spectroscopy can support the campaign of “green analytical chemistry.”
INTRODUCTION
The oxidation of fats and oils has been known as a major problem affecting the qual-
ity of edible oils[1] because it can change the flavor and nutritional quality of foods and
produce toxic compounds, all of which can make the foods less acceptable to consumers.
The oxidation products typically include low molecular weight compounds that are volatile
as well as undesirable off-flavor compounds, which take place primarily from the break-
down of unsaturated fatty acids during the lipid autoxidation.[2] The oil stabilities during
storage or upon heating are vital parameters for ensuring that oil has good performance at
1594
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1595
Sample Preparation
First, 200 ml of CO, RBO, SO, and SFO were placed in a 500 mL beaker and sub-
jected to heating in a conventional oven (Memmert Laboratory, Memmert, Germany). at
160 ± 1◦ C for a period of 120 h. To follow the degradation process of vegetable oils during
the heating period, at each 12-h interval, 5 mL of the oil samples were immediately taken
from the oven and were collected in glass vials. These oils were kept at room temperature
until being cooled and were further subjected to analytical measurements in the same day.
1.2A2 − A1
p − AV = 25 ,
m
where A1 and A2 are the measured absorbancies, as described above; m is the mass of oil.
Statistical Analyses
All measurements of CDs, CTs, and p-AV were done in at least three replications.
Data were presented as mean ± standard deviation (SD). Data from chemical and fatty acid
analyses were subjected to analysis of variance (ANOVA) using SPSS version 17 (SPSS
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1597
Inc., Chicago, IL, USA) to identify the differences among means. Statistical significance
was declared at P < 0.05.
Table 1 FA composition and IV of studied oils (CO, RBO, SO, and SFO).†,‡
monounsaturated fatty acid; PUFA: polyunsaturated fatty acid; IV: iodine value.
‡ Different letters within each row are significantly different at P < 0.05. CO: corn oil; RBO: rice bran oil; SO:
Figure 1 FTIR spectra of non-oxidized oils (corn oil, rice bran oil, soybean oil, and sunflower oil) measured at
frequency 4000–650 cm−1 . (Color figure available online.)
Figure 2 FTIR spectra changes of CO during heating for 120 h. The increase and decrease of absorbency at
certain frequencies were assigned with arrows (↑ = increased; ↓ = decreased). (Color figure available online.)
were several FTIR spectral changes of CO, RBO, SO, and SFO at mid infrared region
(3600–650 cm−1 ). Figure 2 is an example of FTIR spectra change of corn oil during thermal
oxidation at 160◦ C up to 120 h.
The peak intensities at 722 cm−1 were decreased, caused by the loss of cis double
bonds; meanwhile, the increase of trans double bonds during thermal oxidation can be
observed by increasing peak intensities at 967 cm−1 . The increase of another peak can
be seen in regions of 1744 and 1655 cm−1 , which is due to the formation of carbonylic
compounds and cis allylic during thermal oxidation. Two peaks at 2853 and 2923 cm−1
remained nearly unaffected. The peak at 3008 cm−1 was decreased because of the decrease
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1599
of cis allylic (C=CH) bonds. Finally, a low absorbance increase was observed around
3470 cm−1 , corresponding to the formation of hydroxyl group (-OH) formed during thermal
oxidation.[9]
Table 2 The specific absorptivity values of CDs of CO, RBO, SO, and SFO during thermal oxidation
for 120 h.†,‡
Figure 3 The relationship between absorbance changes at 3008 cm−1 and CDs values of corn oil. (Color figure
available online.)
such correlation of studied oils were in the range of 0.824–0.978, indicating that a linear
relationship exists for both parameters. These results suggested that the absorbance changes
at 3008 cm−1 can be proposed as a stability index for lipid-containing foods.
Table 3 compiled the specific absorptivity values of CTs of CO, RBO, SO, and SFO
during thermal treatment at 160◦ C for 120 h. As CDs values, the similar modes were
observed for CTs. An increase of CTs values was observed for the studied vegetable oils
during thermal oxidation. It can be stated that the conjugated trienoic systems were devel-
oped during thermal oxidation. Among the studied oils, SO exhibited the highest increase
of CTs values during oxidation for 120 h, followed by SFO, CO, and RBO. The CTs values
were not significantly different at 48 and 60 h, 24 and 36 h, as well as 36 and 48 h at a
significance level of 0.05, for CO, RBO, and SO. In SFO, there is no significant difference
(P = 0.05) during thermal oxidation between 36 and 48 h, 60 and 72 h, as well as between
84 and 96 h.
In order to propose that absorbance changes at 3008 cm−1 can be used as an alterna-
tive method for the measurement of CTs values rather than conventional technique using
Table 3 The specific absorptivity values of CTs of CO, RBO, SO, and SFO during thermal oxidation.†,‡
spectroscopic UV, the relationship between absorbance changes at 3008 cm−1 (x-axis) and
CTs values (y-axis) was built. The equations obtained were as follows: y = −54.91x +
21.64, R2 = 0.993 (CO); y = −104.8x + 30.57, R2 = 0.829 (RBO); y = −60.06x + 21.77,
R2 = 0.964 (SO); and y = −22.56x + 13.62, R2 = 0.887 (SFO). From these equations and
taking into account the R2 values, FTIR absorbance changes at 3008 cm−1 can be an alter-
native method for the determination of CTs due to its capability to provide good linearity
between absorbance changes and CTs values.
Table 4 p-AVs of CO, RBO, SO, and SFO heated at a high temperature of 160◦ C for 120 h.
frequency were subsequently used to be correlated with p-AV. The equations obtained from
the relationship between absorbance changes at 3008 cm−1 (x-axis) and p-AVs (y-axis) of
evaluated vegetable oils are as follows: y = −1113.0x + 382.7, R2 = 0.952 (CO); y =
−1836.0x + 483.0, R2 = 0.844 (RBO); y = −796.8x + 248.4, R2 = 0.922 (SO); and y =
−173.2x + 237.7, R2 = 0.948 (SFO).
Based on the R2 values obtained, the absorbance changes at 3008 cm−1 were chosen
to be correlated with p-AV because of the higher R2 values obtained compared with those
at a frequency of 1654 cm−1 . These results suggested that measurements of absorbance
changes at 3008 cm−1 can be used as an alternative technique for the determination
of p-AV.
CONCLUSION
The application of FTIR spectroscopy as an alternative technique for measuring the
oxidative stabilities of edible oils can overcome some drawbacks when using chemical anal-
ysis, such as time consuming, destructive to the evaluated oils, involvement of the number
of samples, glass apparatus, toxic solvents, and hazardous reagents, which are harmful to
human health and to the environment. During thermal oxidation, absorbance changes at a
frequency region of 3008 cm−1 can be used to measure the conjugated dienes (CDs) and
trienes (CTs) as well as p-anisidine value.
ACKNOWLEDGMENTS
The first author wishes to thank The Directorate for Higher Education (Dikti), The Ministry
of National Education, Republic of Indonesia, for the scholarship during his Ph.D. program in
Halal Products Research Institute, UPM, Malaysia. The authors also wish to thank the Ministry of
Science, Technology, and Innovations (MOSTI), Malaysia for providing the funding support awarded
to Professor Dr. Yaakob B. Che Man.
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