Determination of Peroxide Value in Edible Oils Based On Digital Image Colorimetry
Determination of Peroxide Value in Edible Oils Based On Digital Image Colorimetry
A R T I C L E I N F O A B S T R A C T
Keywords: Edible oils are naturally oxidized under heat or light, generating compounds responsible for undesirable flavors
Lipids and tastes, which lead to the depreciation of products that contain them. The first compounds formed in oil
Oxidation oxidation are hydroperoxides, which can be estimated by determining the peroxide value (PV, meq O2/Kg) based
Smartphone
on iodometric titration, requiring large amount of hazardous reagents and presenting difficulties detecting the
Hydroperoxides
endpoint. Thus, this work aimed to develop an economical and non-subjective method to predict the PV in edible
Peroxide index
oils based on Digital Image Colorimetry. First, six standards were prepared with hydrogen peroxide solutions.
After reaction with potassium iodide, the mixtures were imaged using a smartphone camera. The color pa
rameters from the RGB, HSV, CMYK, L*a*b*, or XYZ systems were calibrated against the meq O2 of standards. A
test set of 50 edible oil samples was used for validation based on the standard method. RMSE and R2 values of
3.21 meq O2/kg and 0.97 were obtained using M from CMYK color system as analytical signal. The amount of
reagents consumed in the proposed method was 98.7% reduced compared to that of the standard method.
* Corresponding author.
E-mail addresses: [email protected] (A.C.S.A. Anconi), [email protected] (N.C.S. Brito), [email protected] (C.A. Nunes).
https://doi.org/10.1016/j.jfca.2022.104724
Received 23 February 2022; Received in revised form 18 May 2022; Accepted 30 June 2022
Available online 2 July 2022
0889-1575/© 2022 Elsevier Inc. All rights reserved.
A.C.S.A. Anconi et al. Journal of Food Composition and Analysis 113 (2022) 104724
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Fig. 3. Color scale obtained according to the amount of meq O2 for standards.
The models obtained from the L*, X, and Y parameters had the worst
Table 1
performances, with mean relative errors for the prediction above 44%,
Linearity between RGB, HSV, CMYK, Lab, and XYZ
worse fit to the linear model, compared to the others (R2 of 0.78, 0.68,
color parameters and the meq O2 of the standards.
and 0.75, respectively) and non-existence of congruence between pre
Color Component R2 dicted and measured values, mainly for X and Y (R2m of 0.29 and 0.30
R 0.85 respectively). Thus, the L* parameter and the XYZ system were
G 0.99 considered unsuitable for predicting the amount of meq O2 in vegetable
B 0.47
oil samples. Despite the RGB color system being the most used in the
H 0.98
S 0.47 specialized literature, the model with the G parameter did not have the
V 0.81 best performance in predicting the meq O2 in the samples. This model
C 0.00 had an R2 of 0.86 and a high RMSE (0.0021 meq O2), representing a
M 0.98 mean relative error for prediction of 31.16%. Even so, this parameter
Y 0.47
K 0.81
was kept in the next step to confirm its low predictive quality compared
L 0.99 to the other chosen models.
a 0.96 The meq O2 values predicted by the models in the above step were
b 0.63 converted to PV (dividing by the mass of oil in kg) and compared to PV
X 0.98
determined by titration to validate the proposed method. The PV of
Y 0.94
Z 0.74 samples ranged from 4.3 to 63.6 meq O2/kg. The results are shown in
Table 3.
Remarkably, there was a relative poor correlation between the
The standards (after reaction with potassium iodide) presented measured PVs and PVs estimated by the model based on the G param
colors varying from brownish-yellow (for low meq O2) to reddish-brown eter, noticed by the lowest R2 (0.87), higher RMSE (9.93 meq O2/kg),
(for high meq O2) (Fig. 3). The range spanned from 1.816 × 10-4 to and mean relative error of 31.16%. The parameter a* also performed
1.227 × 10-2 meq O2. poorly, with R2 of 0.92 and RMSE of 7.25 meq O2/kg, producing a mean
In color systems, each parameter contains a fraction of information relative error of 22.76%. On the other hand, excellent results were
that could describe the predicted response. Thus, it is crucial to select an produced by the models using H and M parameters. The models per
appropriate color parameter to obtain a better performance of the pre formed similarly, with R2 of 0.96 and 0.97 and R2m of 0.98 for both.
diction models. The analysis of the relationship between the meq O2 in However, the results indicated a better relationship between the
the standards and the color parameters revealed the remarkable line measured and predicted PVs to the model obtained for the M parameter,
arity of the data (Table 1). with lower values of RMSE (3.21 meq O2/kg) and RE (10.23%), in
The color parameters with a linear correlation higher than 90% (R2 ≥ addition to the excellent congruence between these data (R2m = 0.98).
0.90) were used to build calibration models. Thus, calibration models Thus, the model built from the M parameter of the CMYK color system
were built using G data from RGB, H data from HSV, M data from CMYK, was considered the best for predicting PV in vegetable oil samples
L* and a* data from L*a*b*, X and Y data from XYZ color systems as among those presented in this study, with LOD and LOQ of 0.00017 meq
descriptors to predict the meq O2 values of edible oil samples. According O2 and 0.00050 meq O2, respectively. The graphical representations of
to Table 2, the analytical curves showed an excellent fit to the linear the analytical curve, meq O2 prediction, and PV prediction for this
model, with R2c value varying from 0.94 to 0.99 and RMSEc from model are shown in Fig. 4.
0.00044 to 0.001 meq O2. Comparable results were obtained by Singkhonrat and coauthors
The analytical curves were employed to predict meq O2 in the oil (2019) in their research on monitoring lipid peroxidation by the Fenton
samples. The results (Table 2) showed a good predictive ability for the
models built from H, M, and a* parameters, with R2p ranging from 0.92 Table 3
to 0.97, RMSEp ranging from 0.00067 to 0.0015 meq O2, and R2m from Performance of predictive models for PV determination in edible oils.
0.87 to 0.92. The models with H and M parameters were similar, with
G H M a
RMSEp of 0.00073 and 0.00067 meq O2 and R2p of 0.96 and 0.97,
respectively. Among these two models, a better performance was ob RMSE 9.93 3.40 3.21 7.25
R2 0.87 0.96 0.97 0.92
tained for the M parameter of the CMYK system, with a higher R2p and a
R2 m 0.91 0.98 0.98 0.95
lower RMSEp, which represented a mean relative error of 10%. MRE % 31.16 10.64 10.23 22.76
Furthermore, the high R2m (0.91) in this model attested to the
Note: RMSE is expressed in meq O2/kg
congruence between the measured and predicted values.
Table 2
Performance of predictive models for meq O2 determination using color parameters with a R2 of calibration ≥ 0.90.
G H M L a X Y
Note: RMSE is expressed in meq O2; N: number of samples used to test the models.
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proposed method was less expensive, and less chemical waste was
produced.
To physically understand the linearity between the color parameters
and the peroxide content (in terms of meq O2), one must understand the
meaning of each color parameter and how it varies in the calibration
standards. In this context, it should be considered that when the white
light falls on the sample, part is absorbed, and part is reflected, the latter
being captured by the smartphone camera.
The RGB system consists of an additive color model, in which the
linear combination of the three primary colors, red (R), green (G), and
blue (B), form the other colors (Firdaus et al., 2014). As seen in Fig. 3,
the color of the solution formed after KI addition ranged from
brownish-yellow to reddish-brown. According to Table S3, such color
ations were formed by R and G reflection, and their intensities had a
negative variation, decreasing when the peroxide concentration
increased. Although red was the color that most contributed to the color
formation of standards due to higher values of the R parameter, the
variation of G was more relevant, which can justify its higher correlation
with peroxide concentration. On the other hand, the B parameter
remained practically null. Thus, blue was the absorbed color that did not
contribute to the resultant coloring and, therefore, was negligibly
detected by the smartphone camera.
The CMYK system is based on a subtractive linear combination to
form the secondary colors of RGB (Fernandes et al., 2020). For example,
the parameter M (magenta) is formed by red and blue primary colors,
and its complementary color is green. This fact supports the negative
variation of the G parameter and simultaneous positive variation of the
M parameter with increased peroxide content in the standards
(Table S3). Furthermore, as there was practically no variation in B,
corresponding to the blue color, the increase in the M can also be related
to the red reflection. Together, these considerations support the good
description of the reaction medium color by the M parameter.
As well as M, the H parameter (hue angle) also shows an excellent
linear correlation with the reaction medium color. This parameter de
scribes the dominant spectral color component (such as red, green, or
blue), whose value ranges from 0◦ to 360◦ . Each angle corresponds to
one color: 0◦ is red, 120◦ is green, and 240◦ is blue (Fan et al., 2021). As
shown in Table S3, the H parameter values ranged from 59◦ (yellowish)
to 22◦ (reddish) along with standards, which corroborates the color
variation from brownish-yellow to reddish-brown with the increase of
the peroxide content.
The luminosity (L*) varies from 0 to 100 in the L*a*b* system, with
0 corresponding to black and 100 to white. The L* parameter had its
value decreased, which is justified by the solutions’ darkening (in a
grayscale image) with increasing peroxide concentration. Despite its
excellent linearity with the peroxide content, this parameter varies on
grayscale and alone is not efficient in describing color, which may
explain the low predictive performance of the model based on L*.
Already, the parameter a* varies from negative (green) to positive (red)
values (Leão et al., 2007). Then, the increase of a* indicates an increase
in the red proportion in color, which is consistent with the color change
Fig. 4. A – Example of analytical curve based on M from CMYK. B – Graphical in the reaction medium.
comparison of estimated meq O2 determined in a set of edible oils vs. meq O2 The parameters of the XYZ color system can be obtained from a
predicted by model. C – Graphical comparisons of PV measured in the set of mathematical transformation of RGB, where Y is related to the bright
edible oils vs. PV estimated by model.
ness of a color (Fernandes et al., 2020). Therefore, it justifies this
parameter decreases along with peroxide content in standards, which
reaction using DIC. Over the PV range of 3–14 meq O2/kg, the authors less lightness (in a grayscale image) can be related to the increase of
found a good correlation between the proposed method and the UV–Vis color intensity. On the other hand, X is a mix of three RGB curves chosen
method (R2 = 0.98). However, this study did not include the reduction to be nonnegative and, in combination with Y, can describe color vari
of reagents used and waste generated in the analysis. Peamaroon and ations from yellowish to reddish (Ibraheem et al., 2012). However, Y or
coauthors (2021) developed a DIC method based on a smartphone X alone could not produce models with good predictive capacity,
camera to determine iodine value in vegetable oils, using the Wijs probably due to interdependence in describing the color variation of the
iodometric titration method as reference. The authors also replaced the reaction medium. Finally, the same reasoning can be extended to un
titration step with DIC, reducing the amount of chemicals. An analytical derstand the prediction performance of each model built from the color
curve was set up to predict iodine value in vegetable oils, and the results parameters of the studied colorimetric systems.
showed an RSD value between 3.2% and 8.6% and an R2 of 0.99. The The standard method for PV determination (Nielsen, 2017) employs
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