LWT - Food Science and Technology 111 (2019) 270–277

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LWT - Food Science and Technology

journal homepage: www.elsevier.com/locate/lwt

Model prediction of color reversion of soybean oil and its quantitative T

relationship with oxidation under accelerated conditions
Xu Li, Gangcheng Wu, Liyou Zheng, Jianhua Huang, Hui Zhang, Qingzhe Jin, Xingguo Wang∗
State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu, 214122, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Color reversion of edible oil has seriously troubled the vegetable oil industry, but not yet been satisfactorily
Color reversion solved. In this study, Chroma (C*) could be an effective indicator and significantly associated with specific
Oxidation absorbance values of oxidized oils at 243–367 nm (P < 0.01). Effect of heating time and temperature on the
Kinetic model color changes of soybean oil was first described by the combination of two-stage logistic and Arrhenius equations
Free radical mechanism
with R2 higher than 0.90. Total three equations for the start time point, end time point and duration time of color
reversion were provided under accelerated conditions, respectively. The theoretically derived but not validated
equations for predicting the color reversion of oils at room temperature was proposed as well. The certain
relationships between the color reversion and oxidation were deduced and proved based on the kinetic analysis
of free radical mechanism. Data will be expected to provide useful models for manufacturers to predict and
control the color reversion of edible oils.

1. Introduction
Refined edible oil appears in light yellow and pale amber after the
process of degumming, dehydration, deacidification, decolorization,
bleaching, deodorization, and dewaxing (Shahidi & Zhong, 2005, pp.
357–358). However, during the transport, storage and use, the color of
some oils may become darker and develop to deep yellow and light red
as time passes. This phenomenon, named the color reversion of oils,
often happens in refined soybean, cottonseed and corn oils (Taghvaei
et al., 2014). According to the statistics from Chinese Cereals and Oils
Association, 14.1, 1.2 and 0.3 million tons of these three oils were
consumed in 2017 in China, which account for 52% of total oil con-
sumption. More specifically, due to the traditional transparent package
of edible oils, their color changes are obvious and highly concerned by
consumers in East and South Asian countries (Zhang, Xu, Jiang, &
Wang, 2013). The problem has seriously troubled the oil industry and
caught much attention, but not yet satisfactorily explained by re-
searchers and manufacturers.
The color reversion of oils has experienced four stages of develop-
ment: the first period from 1922 to 1960 by Sievers and McIntyre
(1922, pp. 31–34) and Nakamura, Tomita, and Komoda (1960), the
second period from 1960 to 1980 by Tomita, Komoda, Enomoto, and
Onuki (1964), Komoda, Onuki, and Harada (1966) and Harada and
Komoda (1970) in Japan, the third period from 1980 to 2000 by Lai
et al. (1989) in Taiwan, the fourth period from 2000 to now by Zamora,
Olmo, Navarro, and Hidalgo (2004), Taghvaei et al. (2014), Roostaee,
Barzegar, Sahari, and Rafiee (2017). Overall, the precursors of colored
substances and oxidation of oils were summarized to be responsible for
the color reversion of oils. The identification and verification of pre-
cursors, including chroman-5, 6-quinone, γ-tocopherol, γ-tocopherol
dimer and their degradation products, have been studied for a long time
(Harada & Komoda, 1970; Lai et al., 1989). For the oxidation, the
contribution of the oxidized unsaturated fatty acid on the color rever-
sion was certain, but the quantitative relationship was not well ex-
plored until now (Kimoda, Onuki, & Harada, 1967). Theoretically, the
mechanism of color reversion can be converted into the triangle re-
lationships among the precursor, oxidation and color. During the ex-
periment of evaluating precursor products, it is certain that precursors
contribute to the dark color of oils. But in fact, precursors also promote
or inhibit the oxidation of oils, which further promotes the dark color of
oils at the same time (Kreps et al., 2016). In this situation, the effect of
oxidation on the color reversion is out of control and the experiment
design for evaluating suspicious precursors of colored substances may
be not completely accurate. So for these three interrelated variables, the
application of control variable method may be necessary (Montgomery,
2009, pp. 38–39). In this research, the initial content of precursors was
the same and the quantitative relationship between color and oxidation
was to be explored.

∗
Corresponding author.
E-mail address: wangxg1002@gmail.com (X. Wang).

https://doi.org/10.1016/j.lwt.2019.05.051
Received 14 February 2019; Received in revised form 6 May 2019; Accepted 10 May 2019
Available online 12 May 2019
0023-6438/ © 2019 Published by Elsevier Ltd.
X. Li, et al. LWT - Food Science and Technology 111 (2019) 270–277

To figure out the variation of color of oils along with the oxidation,
the model was established referred to the kinetic modeling of peroxide
value (POV) of oils. Chemical reactions of these two indices were much
similar, which experienced the same process of generation, accumula-
tion and degradation. In addition, they were both considered to be
initiated and promoted by the free radical of LOO· (Lai et al., 1989). In a
recent research, the kinetic of POV was satisfactorily fitted by the two-
stage logistic and Arrhenius equations proposed by Patstowa, Ziaiifar,
Smith, Menzel, & Vitrac (2017). Equations were derived based on the
free radical reaction mechanism and well verified by the oxidation
experiment. So the fitted parameters can be used to represent the free
radical chain reaction rate constants of initiation, propagation and
termination reactions (ki, kp and kt), which would support the further
theoretical discussion. Therefore, the model establishment of color
change of oils was based on the similar kinetics.
In this research, the most consumed soybean oil was selected and
oxidized under accelerated conditions. The heated temperature ranged
from 90 °C to 170 °C, covering the special points of 100 °C and 150 °C as
highlighted by Gertz (2014). The two-stage logistic and Arrhenius
equations were used for the dynamic and thermodynamic analysis,
respectively. Equations for the start time point, end time point and
duration time of color reversion would be provided. The quantitative
relationship between the color reversion and oxidation would be dis-
cussed based on the kinetic analysis of free radical mechanism. Data
will be expected to provide useful kinetic models for the satisfactory
solution of color reversion of edible oils in the future.
2. Materials and methods
2.1. Materials
Refined soybean oil, without exogenous antioxidants, was obtained
from Xiangchi Co., Ltd. (Boxing, China) and stored at 4 °C. Initial acid
value and peroxide value of oil were 0.07 mg/g and 0.76 mmol/kg,
respectively. The main fatty acid composition of soybean oil was
11.02 ± 0.31% C16:0, 4.28 ± 0.16% C18:0, 24.52 ± 0.23% C18:1,
51.87 ± 0.85% C18:2, 6.41 ± 0.53% C18:3. The acetic acid, chloro-
C* = ((a*)2+(b*)2)1/2
In addition to the L*a*b*, the absorbance of oil was also measured
at wavelengths from 300 nm to 1000 nm by the HunterLab colorimeter.
For further analysis, Photometric Color Index (PCI) was calculated
using the following equation based on the AOCS Official Method Cc
13c-50:
PCI = 1.29(Ab460) + 69.7(Ab550) + 41.2(Ab620) - 56.4(Ab670)
Where Ab460, Ab550, Ab620 and Ab670 are the absorbance values of oil at
wavelengths of 460 nm, 550 nm, 620 nm and 670 nm, respectively.
2.4. Conductivity, peroxide value and specific absorbance value
The conductivity of water in the measuring vessel was monitored by
the probe equipped by the Rancimat (Herisau, Switzerland). Peroxide
value (POV) of oil was determined according to the AOCS Official
Method Cd 8b-90. A 1% solution of oil samples in cyclohexane was
prepared and absorbance values of solutions were measured from
200 nm to 1000 nm at an interval of 1 nm with the spectrophotometer
(Shimadzu UV-1800, Japan). Measured absorbance values divided by
the concentration is the specific absorbance values, which were re-
presented like K232 and K270.
2.5. Kinetic data analysis
2.5.1. Heating time as variable
The effect of heating time on physical and chemical indices of oils
was fitted by the two-stage logistic model described by Patsioura,
Ziaiifar, Smith, Menzel, and Vitrac (2017) as follows:
For 0 ≤ t ≤ tsteady,
Ysteady
Y=
exp(−r 1 ∗ t )(
Ysteady
− 1) + 1
Y0
For t > tsteady,
Y∞
Y= Y∞
exp(−r 2 ∗ (t − tsteady ))( − 1) + 1
Ysteady

form and sodium thiosulphate were supplied by Sinopharm Chemical

where Y represents the value of indices including color parameter,
Reagent Co., Ltd. (Shanghai, China). Ultrapure water was produced by
conductivity and POV of oil, t represents the heating time, r1 and r2
the purification system of Millipore Corporation (Boston, USA).
represent the reaction rates at two stages, Y0 represents the initial value
of Y, Ysteady represents the estimated maximum value of Y, Y∞ re-
2.2. Preparation of oxidized oils presents the value of Y when heating time is infinite, tsteady represents
the heating time when Y equals to Ysteady.
Oxidized oils were prepared using the Metrohm Rancimat 743
equipment (Herisau, Switzerland). Total 3.0 g of soybean oil was heated
2.5.2. Heating temperature as variable
at seven temperatures of 90 °C, 100 °C, 120 °C, 140 °C, 150 °C, 160 °C
The effect of heating temperature on reaction rates was fitted by the
and 170 °C with an air flow rate of 20 L/h. Values of Induction Period
Arrhenius model as follows:
(IP) of the oil were 24.45 h, 11.80 h, 5.87 h, 3.07 h, 1.27 h, 1.01 h,
0.60 h, 0.37 h and 0.31 h respectively. At each temperature, eight For 0 ≤ t ≤ tsteady,
samples were selected and the sample selection was followed as fresh −Ea1 1
ln(r1) = R
(T ) + In(A1 )
oil, three points before IP, IP and three points after IP. Oxidized oil
For t > tsteady,
samples were collected and stored at 4 °C. Experiments were repeated at
−Ea2 1
least five times. ln(r2 ) = R
(T ) + In(A2 )

where r1 and r2 represent the reaction rates at two stages, T represents

2.3. Quantification of color parameters
the absolute temperature (in kelvin), Ea1 and Ea2 represent the acti-
vation energy for the reaction, R represents the universal gas constant,
Color of oils expressed as lightness (L*), yellowness (b*) and redness
A1 and A2 represent the pre-exponential factor for each chemical re-
(a*) were measured using a HunterLab colorimeter (Hunter Associate
action.
Laboratory, Inc., Reston, VA). The oil sample was detected in a shallow
plastic dish and recorded in Hunter units of L* (L* = 0 = black,
2.6. Statistical analysis
L* = 100 = white), a*(+a* = red, -a* = green) and b*
(+b* = yellow, -b* = blue) (Su & White, 2004). Measurements were
Regression analysis was performed with the Origin 8.0 software
repeated triplications.
(OriginLab Corporation, Massachusetts, USA). Pearson analysis was
For further analysis, parameter of Chroma (C*) was calculated using
carried out with SPSS 17.0 (IBM, Chicago, USA). Non-linear fitting
the following equation:
procedure based on the least square method was conducted with the

271
X. Li, et al.
Fig. 1. Representative C* value from 12 to 60 and oxidized oil samples prepared at seven temperatures from 90 °C to 170 °C.
Curve Fitting Toolbox of Matlab R2010a (MathWorks, Natick, USA). In
practice, a first guess of the value of r1 and r2 can be estimated from the
slope of Y/Y0 and of (Y0*Y0*Y)/(Ysteady*Ysteady*Y0) versus time re-
spectively before and after the maximum value of Y.
3. Results and discussion
3.1. Effect of heating time and temperature on color and oxidation
Fig. 1 shows the oxidized oils prepared at seven temperatures from
90 °C to 170 °C. The temperature was set to cover the special points of
100 °C and 150 °C as highlighted by Gertz (2014). The accelerated
process under 100 °C was similar to the auto oxidation during the
transport and storage of oil while the condition above 150 °C was si-
milar to some situations with a lower oxygen solubility (Farhoosh,
2007). The temperature setting between 100 °C and 150 °C was applied
for the thermodynamic analysis. Visual results showed a similar trend
that the color of oil become darker first and lighter later along with the
heating time at each temperature. The same behavior was found during
the storage of soybean oil at room temperature monitored by Lai et al.
(1989). Comparing with the situation at 90 °C, the color change at
170 °C was much smaller than that at 90 °C. The lighter color resulted
from the fewer colored substances in the oil, which may be explained by
the lower oxygen solubility at the higher temperature as reported by
Patstowa et al. (2017). For further analysis, the degree of color and
oxidation of oil was quantitatively measured.
Fig. 2 shows the effect of heating time and temperature on the
changes of color and oxidation of oil. Conductivity and POV were se-
lected to monitor the oxidation and these two indices increased posi-
tively with the heating time due to the deterioration of oil (Farhoosh,
2007). Increase of conductivity in water was resulted from the dis-
solution of volatile short chain fatty acids of oxidized oil (Carvalho
et al., 2016; Li et al., 2019). Increase of POV was resulted from the
generation of hydroperoxides. During the propagation reaction, alkyl
radicals (L·) reacted very rapidly with molecular oxygen to form free
peroxyl radicals (LOO·), which then absorbed hydrogen from un-
saturated lipids to form hydroperoxides (see chapter 1 in Frankel,
2005). It described the accumulation stage of hydroperoxides as the
fundamental primary products and explained the increase of POV for all
situations in this research. LOO· also participated in the color reaction
as indicated by Lai et al. (1989). Since these hydroperoxides were un-
stable, they would breakdown into secondary oxidation products,
leading to the decay of POV (see chapter 4 in Frankel, 2005). Fur-
thermore, it should be noted that the maximum POV decreased with the
272
LWT - Food Science and Technology 111 (2019) 270–277
increasing temperature. Similar results were previously reported by
Ghnimi, Budilarto, and Kamal-Eldin (2017) and explained by temper-
ature's affecting chemical reactivity as well as the organization and
stability of colloidal structures. Comparatively, it can be explained by
the theory of no-radical decomposition of hydroperoxides especially at
high temperatures proposed by Schaich, Shahidi Zhong & Eskin (2013).
In addition, the color of oil was represented by the L*a*b*, absorbance
at selected wavelengths and their derived indicators including C* and
PCI as mentioned in the method part. After analyzing all these curves,
the maximum or minimum values of color occurs in the middle field of
the process and the variation of color is continuous.
For the dimensionality reduction, the Pearson correlation was con-
ducted among all these color parameters and the results were shown in
the Supporting Information Table S1. It was demonstrated that all color
indicators except Ab620 and Ab670 were significantly correlated with
each other at P < 0.01. Ab620 and Ab670 may be more sensitive to
various carotenoid and chlorophyllic pigments, rather than these oxi-
dized colored substances of oil (Escolar, Haro, & Ayuso, 2002). After the
comparison among L*, a*, b*, C*, Ab460, Ab550 and PCI, the parameter
of C* could represent the information covering red, green, yellow and
blue and the higher value of C* indicated the visual darker color of oils.
Therefore, Chroma (C*) of oil could be an effective indicator of the
color reversion and its quantitative data would be convenient for the
following model discussion.
3.2. Model prediction of color reversion of oxidized oil
The two-stage logistic model presented in the method part was
proposed based on the main generic assumptions of Denisov and Afanas
(2005) to the context of free radical reaction of oil oxidation. The
mechanistic model was fully comprehensive and suitable for all stages
of the oxidation process of edible oils including the initiation, propa-
gation and termination reactions. Effect of heating time on the POV,
conjugated dines and p-Anisidine of sunflower oil at 140 °C, 160 °C and
180 °C was well described by the model (Patsioura et al., 2017). In this
research, the effect of heating time on the color of oxidized soybean oil
was also well fitted by the two-stage logistic model as shown in Sup-
porting Information Fig. S1. When the heating time was lower than
tsteady, R2 ranged from 0.7402 to 0.9862, and when the heating time
was higher than tsteady, R2 ranged from 0.6409 to 0.9984. For the si-
tuations at 90 °C and 100 °C, a sharp decrease of color after the peak
was found and C* values were even lower than those of fresh oil, which
lead to the lower fitting effect. In fact, the color would be stabilized to a
constant value, Y∞, with the heating time prolonged indefinitely, which
X. Li, et al.
Fig. 2. Changes of color parameters of oil samples as the effect of heating time and temperature. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)
still agreed with the overall trend of the logistic model.
Furthermore, the fitness of two-stage logistic model was verified by
the data of color reversion of oils published by former researches, as
shown in Supporting Information Table S2. Values of R2 of fitted
equation were 0.9835, 0.9048, 0.9672 and 0.8744 for the data of
Komoda et al. (1966) in America, 0.9967, 0.9734, 0.9780, 0.9419,
0.9982, 0.9972, 0.9446 and 0.9585 for the data of Tomita et al. (1964)
in Japan, 0.9982 and 0.9922 for the data of Lai et al. (1989) in Taiwan.
Overall, results indicated that the model can accurately predict the
color reversion of oils heated at the high temperatures or stored at room
temperature.
The Arrhenius equation is a formula for the temperature depen-
dence of reaction rates. It has a vast and important application in
predicting the chemical reaction rate and calculating the energy of
activation (Denisov & Afanas, 2005). In this research, the effect of
heating temperature on the reaction rate of the color of oxidized oil was
satisfactorily fitted with the Arrhenius model as shown in Supporting
Information Fig. S2. When the heating time was lower than tsteady, the
relationship at the first stage was ln(r1)=(-8744)*(1/T)+22.59 with
R2 = 0.9900, SEslope = 359.0, SEintercept = 0.8907. When the heating
time was higher than tsteady, the equation at the second stage was found
to be ln(r2)=(-22290)*(1/T)+54.25 with R2 = 0.9031, SEslope = 2956,
SEintercept = 7.336. Results indicated the good fitting effect of the Ar-
rhenius model. The energy of activation at the second stage was much
higher than that at the first stage, similar to the results calculated by
Patstowa et al. (2017). In addition, further comparisons of parameters
were conducted. The fitted values of Y∞ were from 0.02 to 18.61 and
values of Y0 were from 7.58 to 12.93 at all seven temperatures. Similar
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LWT - Food Science and Technology 111 (2019) 270–277
results of Y∞ and Y0 exhibited that the color of oil would turn back to
the light yellow and pale amber as the heating time approached to
infinity due to the degradation of colored substances (Lai et al., 1989).
However, it should be noted that values of Ysteady may be different at
these seven temperatures. Values of Ysteady from 90 °C to 150 °C were
close to 50 while those at 160 °C and 170 °C ranged from 30 to 40. It
agreed with the visual observation in Fig. 1. The different oxygen so-
lubility of oil and oxidation rate may be responsible for this phenom-
enon (Gertz, Klostermann, & Kochhar, 2015). The accelerated condi-
tions with the heated temperature higher than 150 °C were obviously
different from the situations at room temperature (Farhoosh, 2007).
Therefore, based on the combination of the two-stage logistic and
Arrhenius equation, all variation curves of oil color as the effect of
heating time and temperature can be presented as shown in Fig. 3. The
ratio of heating time and IP was set as the abscissa in order to compare
with curves obtained from different temperatures. For the conductivity
and POV, their variation curves at different temperatures were similar
and almost all their values decreased with the rising temperature as
previously mentioned in Fig. 2. However, it was found that the max-
imum values of C* at 160 °C and 170 °C were much lower than those at
other temperatures, which can also be observed in vision from Fig. 1.
Lighter colors may lead to the weaker anti-interference capability. So in
the practical application, heated temperatures higher than 150 °C may
be not recommended.
According to these variation curves, once a threshold of the color of
oils, Ythreshold, was set, the start time point of color darkening can be
obtained as:
X. Li, et al. LWT - Food Science and Technology 111 (2019) 270–277

Fig. 3. Values of conductivity (a), POV (b) and C* (c) were affected by the ratio of heating time to induction period (IP). Data were obtained from samples heated at
seven temperatures from 90 °C to 170 °C and calculated with the two-stage logistic and Arrhenius equation.

Ysteady Ysteady Y∞ Y∞
ln( − 1) − ln( Y − 1) ln( Y − 1) − ln( Y − 1)
Y0 threshold steady threshold
tstart = Δt = tend − tstart = + tsteady
r1 A2 ∗ exp(−Ea2/(R ∗ (25 + 273.15)))
Ysteady Ysteady
ln( − 1) − ln( Y − 1)
The end time point of color darkening was as follows: −
Y0 threshold
A1 ∗ exp(−Ea1/(R ∗ (25 + 273.15)))
Y∞ Y∞
ln( Y − 1) − ln( Y − 1)
steady threshold Summarizing these prediction equations, tsteady acted as an in-
tend = + tsteady
r2 dependent variable and seemed to be very important for the calcula-
tion. In fact, tsteady represented the heating time when the value of Y
The duration time of color darkening was as follows: reaches the maximum. For a further understanding, this special point of
color reversion and its quantitative relationship with the oxidation
Y∞ Y∞
ln( Y − 1) − ln( Y − 1) would be discussed in detail in the next part.
steady threshold
Δt = tend − tstart = + tsteady
r2
Ysteady Ysteady 3.3. Quantitative relationship between color reversion and oxidation
ln( Y0
− 1) − ln( Y − 1)
threshold
−
r1 For the color reversion and oxidation of oils, they are different
chemical reactions. They are closely related with each other in the as-
Since values of r1 and r2 were both related to the heating tem- pect of free radical mechanism (Denisov & Afanas, 2005; Lai et al.,
perature by the Arrhenius equation, the prediction equation can also be 1989). In the application process, the quantitative relationship between
expressed as: them was established based on the comparison of these special time
points with the same units. So two special time points, tsteady and
Y∞ Y∞
ln( Y − 1) − ln( Y − 1) tinflection were analyzed. Both tsteady and tinflection can be obtained from
steady threshold
Δt = tend − tstart = + tsteady the process of color reversion while only tinflection can be obtained from
A2 ∗ exp(− Ea2/(R ∗ T ))
Ysteady Ysteady the process of oxidation. tsteady represented the time when color reached
ln( Y0
− 1) − ln( Y − 1) the deepest value and differentiated the two stages of the logistic
threshold
−
A1 ∗ exp(− Ea1/(R ∗ T )) equation. The inflection time, tinflection, was usually used to indicate the
turning point from the initiation reaction to the propagation reaction
To validate the model, the comparison results of tstart, tend and Δt and calculated as the maximum value of the first derivative.
between the true and predicted values were showed in Table 1. Values The color reversion of oil was represented by the C* and the oxi-
of relative standard deviation ranged from −0.13 to 0.05 and proved dation was monitored by the POV of oil and conductivity of water
the predictive capability of these proposed equations. (Carvalho et al., 2016). The value of tinfelction, conductivity equals to the IP
For the further exploration, the theoretically derived but not vali- provided by the Rancimat method. It can be detected in a much shorter
dated prediction equation at room temperature can be provided as: time than tsteady, which may be an important supplement to the model
prediction of Δt. The internal relationship among the values of tinfelction,
conductivity, tinflection,POV, tinflection,C* and tsteady,C* was displayed in

Table 1
Comparison of tstart, tend and Δt between the true and model predicted values under the situation that C* = 30 was set as the Ythreshold.
Temperature (°C) tstart tend tend-tstart

a
True(h) Model(h) Bias(h) RSD True(h) Model(h) Bias(h) RSD True(h) Model(h) Bias(h) RSD

90 11.60 10.29 −1.31 −0.11 24.25 23.54 −0.71 −0.03 12.65 13.25 0.60 0.05
100 5.29 4.72 −0.57 −0.11 11.68 11.03 −0.65 −0.06 6.39 6.31 −0.08 −0.01
120 1.08 1.18 0.10 0.09 2.95 2.81 −0.14 −0.05 1.87 1.63 −0.24 −0.13
140 0.39 0.35 −0.04 −0.10 0.97 0.91 −0.06 −0.06 0.58 0.56 −0.02 −0.03
150 0.28 0.24 −0.04 −0.14 0.58 0.53 −0.05 −0.09 0.30 0.29 −0.01 −0.03
160 0.16 0.16 0.00 0.00 0.33 0.31 −0.02 −0.06 0.17 0.15 −0.02 −0.12
170 NA 0.23 NA NAb NA 0.24 NA NA 0.00 0.01 0.01 NA

a
RSD, Relative Standard Deviation.
b
NA, Not Available.

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X. Li, et al. LWT - Food Science and Technology 111 (2019) 270–277

Table 2
The internal relationship among the values of tinfelction, conductivity, tinflection,POV, tinflection,C* and tsteady,C*.
Temperature (°C) Oxidation of oil Color of oil Ratio

tinflection, conductivity (h) tinflection,POV (h) tinflection,C* (h) tsteady,C* (h) tinflection,POV/ tinflection,C*/ tsteady,C*/
tinflection, conductivity tinflection, conductivity tinflection, conductivity

90 24.45 25.73 9.19 17.31 1.05 0.38 0.71

100 11.8 12.22 4.08 8.18 1.04 0.35 0.69
120 3.07 3.23 1.21 2.19 1.05 0.39 0.71
140 1.01 1.06 0.35 0.73 1.05 0.35 0.72
150 0.6 0.66 0.2 0.44 1.10 0.33 0.73
160 0.37 0.31 0.12 0.25 0.84 0.32 0.68
170 0.31 0.21 0.07 0.22 0.68 0.23 0.71

Mean ± Standard Deviation 0.97 ± 0.15 0.34 ± 0.05 0.71 ± 0.02

1 d2 [conductivity]
tinflection, conductivity, equals to the IP of Rancimat, which indicates the inflection time point when = 0.
d [time]2
2 d2 [POV]
tinflection,POV, which indicates the inflection time point when = 0.
d [time]2
3 2
d [C∗]
tinflection,C*, which indicates the inflection time point when = 0.
d [time]2
4
tsteady,C*, which indicates the time point when C* of oil reached the maximum value.

Table 2. Experiments at seven temperatures demonstrated the similar whether secondary oxidation products were related to the color rever-
results that tinflection,POV/tinfelction, conductivity = 0.97 ± 0.15, sion. Inspired by indices like K232 and K270, we added the experiment
tinflection,C*/tinfelction, conductivity = 0.34 ± 0.05 and tsteady,C*/tinfelction, of measuring the specific absorbance values of oxidized samples from
conductivity = 0.71 ± 0.02. So values of tinfelction, conductivity, tinflection,POV, 200 nm to 1000 nm at an interval of 1 nm.
tinflection,C* and tsteady,C* may be summarized as IP, 0.97*IP, 0.34*IP and So as shown in Table 3, C* and POV were correlated with these
0.71*IP respectively. specific absorbance values using a statistical significance test. Results
According to the equation derived by Patstowa et al. (2017), the supported the significant correlation between C* and POV (r = −0.54,
inflection time, tinflection, can also be expressed as: P < 0.01) as mentioned above. In addition, values of C* were sig-
Ysteady
nificantly affected by specific absorbance values at 243–367 nm (named
ln( Y0
− 1) as K243∼367, P < 0.01) while values of POV were significantly as-
tinflection = sociated with those at 217–407 nm (named as K217∼407, P < 0.01).
ki
kp
2kt It demonstrated that colored compounds were associated with only
small parts of primary or secondary oxidation products and may con-
where ki, kp and kt are the reaction rate constants of initiation, propa-
tain conjugated alkenes, carbonyl groups or benzene rings according to
gation and termination reactions based on the theory of free radical
the wavelength range. For instance, K232 was normally used to re-
chain reaction as shown in Fig. 4.
present the formation of conjugated dienes, as parts of primary oxida-
Summarizing these two parts, the quantitative relationship between
tion products (Bodoira, Maria, Ribotta, & Marcela, 2017). And it was
color and oxidation of oil can be obtained:
not included in K243∼367 but covered by K217∼407; K270 was in-
[C∗]steady [POV]steady fluenced not only by conjugated trienes (primary products), but also by
ln( [C∗]0
− 1) ln( [POV]0
− 1) 0.34
= ∗ secondary oxidation products (De Marco et al., 2007). And it was
kp′ ki′
kp ki 0.97 covered by both K243∼367 and K217∼407; K250 was stressed due to
2kt′ 2kt
its highest value of r with both C* and POV (P < 0.01) but its chemical
The certain relationship between the color reversion and oxidation structures remained unknown; K292 was related to the colored toco-
of oil was directly proved by this theoretical and empirical equation. pheryl quinones as reported by Kreps et al. (2016) and these com-
The measurement of IP under accelerated conditions may be applied to pounds suspected by Lai et al. (1989) were also covered by K243∼367.
predict the color reversion as well. The internal correlation between the For the following researchers, specific absorbance values at
color reversion and oxidation would be under control of these equa- 243–367 nm can be a good starting point for the project of color re-
tions. For a further exploration, a question would be proposed that version.

Fig. 4. The quantitative relationship between color reversion and oxidation of oils.

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X. Li, et al. LWT - Food Science and Technology 111 (2019) 270–277

Table 3
Results of Pearson correlation analysis among C*, POV and specific absorbance values of oxidized oils (n = 50).
C* POV

r P value Significance r Significance P value

C* −0.54 < 0.01 **

POV −0.54 < 0.01 **

K200∼216 −0.06 ∼ −0.29 > 0.05 ns 0.00–0.25 > 0.05 ns

K217∼242 −0.10 ∼ −0.26 > 0.05 ns 0.36–0.51 < 0.01 **
K243∼367 −0.36 ∼ −0.60 < 0.01 ** 0.36–0.71 < 0.01 **
K368∼387 −0.28 ∼ −0.36 < 0.05 * 0.40–0.52 < 0.01 **
K388∼407 −0.24 ∼ −0.28 > 0.05 ns 0.36–0.40 < 0.01 **
K408∼515 −0.21 ∼ −0.24 > 0.05 ns 0.28–0.36 < 0.05 *
K516∼1000 −0.16 ∼ −0.24 > 0.05 ns 0.06–0.28 > 0.05 ns

K232 −0.12 > 0.05 ns 0.41 < 0.01 **

K250 −0.60 < 0.01 ** 0.71 < 0.01 **
K270 −0.52 < 0.01 ** 0.47 < 0.01 **
K292 −0.52 < 0.01 ** 0.63 < 0.01 **

K, specific absorbance values at the selected wavelength; r, Pearson correlation coefficient; *P < 0.05; **P < 0.01, ns, not significant.

Finally, it may be necessary to discuss how to apply these equations
in the practice. For the triangle relationship among the precursor,
oxidation and color, they can be quantitatively measured by the con-
centration, tinflection, POV and tinflection, C*, respectively. Other chemical
and environmental factors like matrix (fatty acid or triglyceride com-
position), antioxidant, oxygen (sufficient or not) and temperature can
be taken into consideration. In this situation, multi-factor stepwise re-
gression analysis can be used to find the key factors and test the sig-
nificance. In addition, more extensive studies can focus on the reaction
rate constants provided by equations in this paper and research on the
dynamics and thermodynamics of colored compounds.
4. Conclusions
A mechanistic model of color kinetic in oil was proposed and ver-
ified based on the context of free radical chain reaction. Two-stage
logistic and Arrhenius equations were well used for the dynamic and
thermodynamic analysis of color and oxidation of oil. All presented
equations will be useful to predict the color changes of oils at any
heating time and temperature under accelerated conditions. The certain
relationship between color and oxidation of oil was proved. The pre-
diction equation for the duration of color reversion at room tempera-
ture was theoretically derived, but not validated. The triangle re-
lationship among the precursor, oxidation and color of edible oils still
remains to be enriched based on our work.
Acknowledgements
This work was supported by “333 Research Program from Jiangsu
Province” (BRA2016347), “Policy Guidance Program (Enterprise,
University and Research) from Jiangsu Province” (BY2016022-33) and
the National First-Class Discipline Program of Food Science and
Technology (JUFSTR20180202).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.lwt.2019.05.051.
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