LWT - Food Science and Technology 107 (2019) 1–8

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LWT - Food Science and Technology

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

Evaluation of butter oil adulteration with soybean oil by FT-MIR and FT-NIR T
spectroscopies and multivariate analyses
Cristina Guimarães Pereira, Antonio Iranaldo Nunes Leite, Jonathan Andrade,
Maria José Valenzuela Bell, Virgílio Anjos∗
Grupo de Engenharia e Espectroscopia de Materiais, Departamento de Física, Universidade Federal de Juiz de Fora, Rua José Lourenço Kelmer, s/n - São Pedro, 36036-900,
Juiz de Fora, Minas Gerais, Brazil

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

Keywords: The use of Fourier-transform mid-infrared (FT-MIR) and near-infrared (FT-NIR) spectroscopies associated with
Butter oil multivariate modeling was explored to obtain a rapid method that can detect adulteration of butter oil (BO) with
Fraud soybean oil (SO). A total of 11 treatments comprising original BO, SO and their mixtures (10–90%, w/w) were
Vegetable oil analyzed. The substitution of BO by SO in the samples resulted in clear changes in the spectra intensities and
Infrared spectroscopy
positioning. The second and first derivative of MIR and NIR spectra, respectively, pointed out differentiations
Chemometrics
mainly in regions associated to unsaturated fatty acids. Principal component analyses could explore the simi-
larities and differences among the samples, validating the spectral observations. Partial least squares models
using both MIR and NIR spectral data allowed the prediction of the percentage of BO adulteration with SO with
high accuracy, low relative errors and determination coefficients of the global fit above 0.9 for all calibration and
validation datasets. Therefore, the spectroscopic tools applied in our work, when associated with chemometric
approaches, showed good performance in the detection of BO adulterations. They can be of great importance in
the development of new methodologies applied to quality control and authenticity of foods.

1. Introduction
Butter oil (BO) is a fatty product derived exclusively from milk and
holds a valuable place in human diet (Cuibus et al., 2015). It is an
anhydrous milk fat which can be manufactured from either butter or
cream, and the final product is concentrated in 99.5% or greater in fat
(Van Ruth et al., 2008). Its production and consumption occurs
worldwide, with main examples in South America, Africa, Middle East
and Asia, being the product named differently depending on the
country, like “ghee” in India, “maslee” in the Middle East, “roghan” in
Iran, “Sadeyağ” in Turkey and “butter oil” in Brazil (Fındık & Andiç,
2017).
Milk fat is one of the most expensive commodities in the dairy in-
dustry. Thus, BO is a high valued product and due to this economic
reason, the detection of fat from different sources in it must be eval-
uated rigorously (Fadzillah et al., 2017). Adulteration of BO by adding
vegetable oil is an actual fraudulent practice that thrives on making the
cheap commodity (vegetable oil) resemble the genuine and more ex-
pensive product (BO) (Heussen, Janssen, Samwel, & van Duynhoven,
2007). Even though BO adulteration mostly does not pose as a threat to
public health, it can cause significant economic damage and it is con-
sidered an unethical practice being a severe abuse of consumer thrust
(Heussen et al., 2007). Due to the complex composition of butter fat and
vegetable oils, their proofs of authenticity are an analytical challenge
and, therefore, an interesting issue for the fats and oils industry
(Fadzillah et al., 2017).
Around 25% of fat in milk is monounsaturated, while 2.3% is
polyunsaturated. The BO is mainly composed of saturated fatty acids,
followed by monounsaturated fatty acids and small amounts of poly-
unsaturated fatty acids (Antony, Sharma, Mehta, Ratnam, & Aparnathi,
2017; Cuibus et al., 2015). On the other hand, vegetable oils like soy-
bean oil (SO) are highly composed by unsaturated fatty acids, such as
linoleic acid (C18:2) (Fonseca & Gutierrez, 1974; Kadamne, Jain, Saleh,
& Proctor, 2009). Therefore, the principal variation in composition of
milk fats and vegetable oils are the degree of unsaturation of the
component fatty acids and their chain length (Antony et al., 2017).
Nowadays, several physical and chemical tests have been reported
to address the problem of adulteration of commercial food products,
even in butter (Danezis, Tsagkaris, Camin, Brusic, & Georgiou, 2016;
Jabeur et al., 2014; Jabeur, Zribi, & Bouaziz, 2016) however not much

∗
Corresponding author.
E-mail address: virgilio.anjos@ufjf.edu.br (V. Anjos).

https://doi.org/10.1016/j.lwt.2019.02.072
Received 24 August 2018; Received in revised form 15 January 2019; Accepted 23 February 2019
Available online 27 February 2019
0023-6438/ © 2019 Elsevier Ltd. All rights reserved.
C.G. Pereira, et al.
attention has been paid to the general properties and authenticity of BO
(Fındık & Andiç, 2017).
Most of the traditional analytical methods for characterization of
edible fats and oils require the use of chemicals and solvents, which
lead to potential health hazards and environmental pollution. Also, the
techniques are time-consuming, with requirements of extensive sample
preparation and experienced staff that might result in higher cost of
analysis (Antony et al., 2017).
Infrared (IR) spectroscopic analyses as mid-infrared (MIR) and near-
infrared (NIR) became effective alternatives in the determination of
quality and authenticity of edible fats and oils (Antony et al., 2017;
Danezis et al., 2016; Zribi, Jabeur, Matthäus, & Bouaziz, 2016). They
offer simple, efficient and low-cost tools, being fast, non-destructive
and non-invasive techniques to provide multi-constituent results
(Andrade et al., 2019).
The importance of IR spectroscopy in the assessment of the au-
thenticity of fats and oils is due the possibility of identification of
molecular structures through bands and shoulders of the spectrum
which are assigned to certain absorption bands to specific functional
groups (Bendini, Cerretani, Di virgilio, Belloni, & Bonoli-Carbognin,
2007). The MIR spectra results is more associated to fundamental
stretching, bending and rotating vibrations of the molecules, whereas
NIR spectra results from complex overtone and high frequency combi-
nations at the shorter wavelengths (Danezis et al., 2016). The spectra
are usually supported by chemometric analyses based on unsupervised
exploratory approaches; and multivariate calibration (Varmuza &
Filzmoser, 2016).
Considering the fact of BO is a valuable fat for human nutrition
which are gaining popularity in worldwide (Fadzillah et al., 2017) and
due to the lack of information in monitoring adulteration of this pro-
duct, the current study was carried out. We assessed the potential ap-
plication of the use of the MIR and NIR spectroscopy coupled with
multivariate approaches (Principal Component Analysis (PCA) and
Partial Least Squares (PLS) regression) for simultaneous characteriza-
tion and prediction of adulteration of BO by SO.
2. Material and methods
2.1. Sample preparation
A total of 11 treatments were analyzed by FT-NIR and FT-MIR
spectroscopy, totalizing 33 measurements in each technique. Three
pure BO samples were obtained in a Dairy Industry in the state of Rio
Grande do Norte in Brazil and three SO samples were purchased at the
local supermarket in the same state. From the pure samples 9 adul-
terations in the levels from 10 to 90% (w/w) (10% steps) of replace-
ment of BO by SO were prepared. Before carrying out the mixtures, the
pure samples were homogenized and for each treatment, the amounts of
components were weighted, mixed and vigorously homogenized in
vials for 1 min.
2.2. FT-NIR spectroscopy analysis
A Fourier-transform spectrometer (FT) model FT-NIR MPA (Bruker
Optik GmbH, Ettlingen, Germany) equipped with a TeeInGaAs detector
and quartz optics was used. The analyses were performed in triplicate,
in reflectance mode using OPUS 6.5 software, from 12000 to
4000 cm−1 and a total of 64 scans were collected on each sample with a
spectral resolution of 2 cm−1. A volume of 5 ml of sample was placed in
glass vials and placed directly into the equipment compartment for the
acquisition of the spectra.
2.3. FT-MIR spectroscopy analysis
A FT-MIR spectrophotometer (Bruker, model Vertex 70) was used
with ATR accessory and OPUS 6.5 software. Spectra were recorded
2
LWT - Food Science and Technology 107 (2019) 1–8
through 64 scans in the absorbance mode from 4000 to 400 cm−1 with
a resolution of 4 cm−1. To avoid spills and maintain the sample cov-
ering the entire ATR crystal during the measurement, a small plastic
cylinder (with diameter of 4 mm and 3 mm height) was placed around
it. The measurements were performed in triplicate by adding 50 μl of
sample over the ATR crystal.
2.4. Data processing
Prior to data analysis each spectrum was pre-processed via baseline-
correction through the application of a background subtraction in order
to eliminate background noises from the environment. Pre-processing
continued by selecting areas of interest and normalizing the data (0–1).
After, the data used were the average of the normalized spectral sets of
each treatment.
2.5. Chemometric analysis
2.5.1. Principal Component Analysis (PCA)
PCA was applied to each treatment. The wavenumber range used for
NIR analysis was from 9000 to 4000 cm−1. Regarding the MIR range,
the dataset consisted in wavenumbers from 3050 to 2800 cm−1, 1800
to 1670 cm−1, 1500 to 935 cm−1 and 740 to 650 cm−1. The analyses
were carried out using OriginPro 2015 software.
2.5.2. Partial Least Squares regression (PLS)
PLS was applied to calibrate the NIR and MIR spectral profiles and
predict the percentages of adulteration. According to Christy,
Kasemuran, Du & Ozaki (2004), PLS calibration gives optimum results
compared to many other multivariate calibration methods.
The samples were divided into calibration and validation datasets.
The optimum number of latent variables was obtained using full cross-
validation (leave-one-out) method. Each calibration set contained 7
random treatments while the validation dataset consisted of 4 treat-
ments, which were not part of the calibration set (Kaylegian, Houghton,
Lynch, Fleming, & Barbano, 2006).
The prediction performance of each model was evaluated
throughout the root mean square error (RMSE - which represents the
standard deviation of the residuals), the relative prediction errors (RE
%), and the coefficient of determination (R2) of both calibration and
validation data sets. In general, as low as the RMSE and RE% values can
be, and R2 as close as possible to 1, the better will be the model pre-
dictions. RMSE and RE% parameters were calculated according to
Andrade et al. (2019).
3. Results and discussion
3.1. Spectroscopic analyses
3.1.1. FT-MIR spectra results
The spectra recorded between 4000 and 400 cm−1 presented two
important regions (3050–2750 cm−1 and 1850 to 625 cm−1), where
appeared the main absorbance bands.
Fig. 1 shows the normalized spectra obtained for all the samples. It
can be noted that the vibrational spectra are very similar, even com-
paring the pure samples (BO and SO). However, as soon as SO was
added to the BO, it is clearly observed changes in the spectra intensities.
Overall, BO spectra showed higher maximum absorbance than SO at
the bands from 2 to 12. As SO was added to the mixture there was a
decrease in the absorbance intensities in these bands, as better observed
in Fig. S1. Koca, Kocaoglu-Vurma, Harper, and Rodriguez-Saona (2010)
found similar behavior in study with butter adulteration with mar-
garine fat at levels ranging from 0% to 100% (v/v). Bands at 2922 cm−1
and 2853 cm−1 were more intense for butter than to margarine fat,
which is probably associated to a higher number of CH2 groups (with
asymmetric and symmetric stretching) present in butter than in
C.G. Pereira, et al. LWT - Food Science and Technology 107 (2019) 1–8

Fig. 1. Normalized spectra of pure samples (BO and SO) and the mixtures (SO - 10–90% of replacement of BO by SO). The arrows show the increase of SO content.

margarine. Also the differences in spectra could be associated to their Table 1

differences in composition related to chain length, degree of un- Fatty acid composition of soybean oil (SO) and butter oil (BO) (Fonseca &
saturation and presence of trans fatty acids in partly hydrogenated oils Gutierrez, 1974; Yan et al., 2018).
(Koca et al., 2010). Fatty acid % by weight of total fatty acids
On the other hand, the two bands, around 721.3 cm−1 and
3006.8 cm−1 have shown a behavior of increased intensity as SO was SO BO
added (Fig. S1). The band around 721.3 cm−1 is produced by rocking
4:0 – 2.00
vibrations of groups eHC]CHe (cis), characteristic of long chain un- 6:0 – 1.00
saturated fatty acids (Kadamne et al., 2009). The polyunsaturated fats 8:0 – 1.00
are a mixture of triacylglycerols derived from n-3/n-6 fatty acids. The 10:0 – 1.50
band near 3006.8 cm−1 represents stretches of groups eC]CH (cis) 12:0 – 1.50
13:0 – 0.20
present in double bonds of unsaturated fatty acids, such as linoleic acid 14:0 – 9.00
(C18:2) and α-linolenic acid (C18:3) (Kadamne et al., 2009; Koca et al., 15:0 – 1.90
2010), which are highly present in SO, but in low concentrations in BO 16:0 10.90 24.00
as shown in Table 1 (Cuibus et al., 2015; Fonseca & Gutierrez, 1974; 17:0 – 1.00
18:0 1.80 13.00
Yan et al., 2018). This fact can explain the spectrum behavior observed
19:0 – 0.40
in our work. A study demonstrated that the band at 3004 cm−1 was 20:0 – 0.50
presented in the margarine spectrum, but not in the butter spectrum
(Koca et al., 2010). Total saturated 12.70 57.00
In our work, for the band around 3006.8 cm−1 (Fig. 1), besides the
6:1 – 0.01
differentiation in terms of absorbance intensity, it was observed a shift 8:1 – 0.02
in the maxima. The band in pure BO appeared at 3006.8 cm−1, while all 10:1 – 0.20
the adulterated samples and the pure SO have shown a shift in the 10:3 – 0.09
maximum absorbance to 3008.7 cm−1. The exact position and intensity 12:1 – 0.20
12:2 – 0.20
of this band is affected by the composition of the oil, and therefore, by
12:3 – 0.40
the proportion of unsaturated fatty acids present on it (Koca et al., 14:1 – 0.80
2010). Also, the areas near 1120.5–1112.8 cm−1, showed a shift in the 14:2 – 0.45
band. The wavenumber increased and the band intensity decreased as 14:3 – 0.50
addition of SO was carried out. Once the higher adulteration levels have 16:1 – 2.50
16:2 – 0.5
more content of SO and consequently more unsaturated fatty acids 18:1 22.00 32.00
(Table 1), such behavior may be explained by the fact that according to 18:2 59.90 3.00
Guillén, Ruiz, Cabo, Chirinos, and Pascual (2003) in the area of the 18:3 5.40 1.00
band 10, the IR spectra of vegetable oils demonstrate an increase in
Total unsaturated 87.30 41.87
frequency and a decrease in intensity as the degree of unsaturation
increases. SO – soybean oil and BO – butter oil.
The second derivative transformation of the MIR spectra was ap-
plied to understand slight differentiations and to resolve overlapped regarding unsaturated fatty acids at 3006.8 cm−1,
bands. Fig. 2 shows the second derivative for the ranges of 3050 to 1120.5–1112.8 cm−1, 966.3 cm−1, and 721.3 cm−1.
2800 cm−1 (Fig. 2A) and 1400 to 600 cm−1 (Fig. 2B).
The major differentiations occurred in the wavenumber areas
pointed out by a circle (3035–2970 cm−1, 1195 to 1050 cm−1, 980 to 3.1.2. FT-NIR spectra results
900 cm−1 and 780 to 675 cm−1), confirming the observations made In order to assess the sources of variation in the NIR spectra of the
BO and SO set, the data were subjected to Savitzky-Golay smoothing

3
C.G. Pereira, et al. LWT - Food Science and Technology 107 (2019) 1–8

Fig. 2. Comparison of the second derivative infrared spectra of pure BO and pure SO showing the information of spectral regions of (A) 3050 - 2800 cm−1 and (B)
1400 - 600 cm−1.

(20 points, 2 orders) and normalization before multivariate analysis.
In the NIR spectroscopy, the main absorbance bands occurred in the
regions between 8750 and 8000 cm−1, 7370 to 6600 cm−1, 6100 to
5125 cm−1 and 4800 to 4000 cm−1 which point to variation in levels of
free fatty acids, degree of unsaturation, trans fatty acids and lipid oxi-
dation (Heussen et al., 2007). However, according to Mehrotra (2000),
in vegetable oils like SO, most differences in NIR spectra patterns are
evident from 6250 to 5555 (bands 6 and 7 – Fig. 3) and 4760 to
4545 cm−1 (bands 10 to 12 – Fig. 3). These areas were taken into ac-
count in our discussion.
Fig. 3 shows the normalized spectra of NIR spectroscopy with the
assignment of the main absorbance bands (Christy, Kasemsuran, Du, &
Ozaki, 2004).
The bands in FT-NIR (Fig. 3) were broader than those of FT-MIR

Fig. 3. Normalized spectra and main chemical group assignment for the bands obtained by NIR spectroscopy analysis for pure samples (BO and SO) and the mixtures
(SO - 10–90% of replacement of BO by SO).

4
C.G. Pereira, et al.
spectra (Fig. 1). In general, NIR spectrum contains more overlapped
bands while the MIR spectrum presents more isolated bands. Yang,
Irudayaraj, and Paradkar (2005) found similar behavior by studying
edible oils and fats by FT-MIR, FT-NIR and FT-Raman spectroscopy.
Also, the bands in MIR spectra are more associated to fundamental
stretching, bending and rotating vibrations of the molecules, whereas
NIR spectra result from complex overtone and high frequency combi-
nations at shorter wavelengths (Danezis et al., 2016).
Oils have NIR absorption areas around 9090 cm−1 to 6250 cm−1
(bands 1 to 4 – Fig. 3) and around 4350 cm−1 to 4150 cm−1 (bands 13 –
Fig. 3), with few distinctive features. The region between 5350 and
6000 cm−1 (bands 6 and 7) is characterized by the first overtone of the
CeH stretching from eCH2 groups in edible oils and fats, including SO
and BO (Christy et al., 2004; Yang et al., 2005). When an oil sample is
adulterated, the whole spectrum is affected (Christy et al., 2004). That
behavior was observed in our data. In the bands 6 and 7, as soon as SO
was added into the BO sample, their intensities were reduced (better
visualized in Fig. S2) and the shape was modified (Fig. 3). The band 7
totally disappeared in the pure SO, while it is noticeably pronounced in
the pure BO sample. Band 6 showed a shift in the wavenumber, as soon
as the BO was adulterated with SO.
Visually, the region around the bands 8 and 9 showed very subtle
differences. The shape and intensity of the bands are very similar to all
samples, except for pure SO. These small differences were better
exploited by multivariate data analysis.
The region between 4500 and 4800 cm−1 is related to CeH
stretching of double bonds. As the addition of SO was carried out, the
intensity of the bands in this region increased with the total degree of
unsaturation. Therefore the higher presence of double bonds of un-
saturated fatty acids, such as linoleic acid (C18:2) and α-linolenic acid
in SO (Hourant, Baeten, Morales, Meurens, & Aparicio, 2000; Kadamne
et al., 2009) justifies this behavior found in the bands 10 to 12.
The first derivative transformation of the NIR spectra was applied to
point out slight differentiations between the samples as shown in Fig. 4.
The major spectral variations in the first derivative of the NIR
spectra are located in two spectral regions as assigned by a circle in
Fig. 4. The regions 6250 - 5580 cm−1 (referring to bands 5 to 7 - Figs. 3)
and 4800 - 4400 cm−1 (referring to bands 10 to 12 – Fig. 3). Both
observations point towards variations of fatty acid levels in the samples.
Heussen et al. (2007) found similar results by studying butter fat con-
tent of spreads. Variations were observed in the 5200–5360 cm−1 re-
gion, which has been assigned to the second overtone of saturated
acyclic esters (Re(CO)eO-R’) and between 5655 and 5880 cm−1,
which can be assigned to the first overtone of saturated alkyl chains
(CH3-(CH2)n-).
Fig. 4. Overlay of the first derivatives of the NIR spectra recorded for the pure SO and pure BO set (6250 - 4000 cm−1).
5
LWT - Food Science and Technology 107 (2019) 1–8
3.2. PCA
PCA was performed to explore the similarities and differences
among the samples. Fig. 5A presents the score plot of PCA applied to
MIR data, where the first two principal components accounted for ap-
proximately 80% of the total variability of the data. There is a clear
separation between the pure BO and pure SO regarding PC1, which
explained 64.38% of the variance of the data. On the other hand, PC2
explained only 15.04% without a proper relation with the attributes
studied as it has shown intense positive loadings mostly in wave-
numbers where no bands were present.
In Fig. 5A the samples with higher amount of BO are located in the
positive side of the PC1 (pure BO and SO – 10–50%). On the other hand,
those higher in SO (SO – 60–90% and pure SO) are situated in the
negative side. This result suggests that the negative variation found by
PCA analysis, regarding PC1, is related to the increase in concentration
of SO present in the mixture.
The loading plot of the MIR data is presented in Fig. 5B. The range
between 3020 and 2987 cm−1 (band 1 – Fig. 1) and between 800 and
625 cm−1 (band 13 – Fig. 1) weighted significantly on the negative
scale of PC1, which agrees with the previous observations of the deri-
vative (Fig. 2) and with the fact of the higher presence of unsaturated
fatty acids in SO comparing to BO (Table 1). Fig. 5B also reveals that
PC1 is positive in the most intense bands of the whole spectra (bands 2
to 12 - Fig. 1), which reflects the quantitative reduction of characteristic
compounds of BO. The positive scale of PC1 was influenced mostly by a
wide range between 1800 and 1670 cm−1 and from 1380 to
1150 cm−1. These were areas where not much differentiation was ob-
tained when analyzing the derivatives spectra (Fig. 2). However, other
regions seemed to be particularly important, such as the surroundings
of the symmetric stretching of CH2 (2852.5 cm−1, band 3 – Fig. 1), and
the two regions related to trans double-bonds: the band between 1112.9
and 1120.5 cm−1 (band 10 – Fig. 1) and the one at 966.2 cm−1 (band
12 – Fig. 1).
In case of the near infrared data, the first two principal components
explained above 95% of the variability of the data (Fig. 5C). Once
again, in the score plot presented in Fig. 5C, there is separation of the
pure BO and pure SO in relation to PC1. It accounted for 75.89% of the
variance of the data and divided the samples in two clusters, one
comprising the samples that contain BO and another with the pure SO
alone. Our results show that pure SO was the one with most different
spectra (especially in region between 6250 and 4000 cm−1, Fig. 3).
Heussen et al. (2007), found out a cluster in butter samples containing
high levels of butyric acid (used as authenticity marker in butter fat),
separating them from the vegetable oils.
With respect to PC2, which explained 19.75% of the variability, the
pure SO sample was also kept isolated from the others. However,
among the other samples, it was observed a trend (as indicated by the
C.G. Pereira, et al. LWT - Food Science and Technology 107 (2019) 1–8

Fig. 5. Principal Component Analyses of the MIR and NIR spectra of pure BO, pure SO and adulterated samples (SO - 10–90%). PCA using MIR spectra: (A) Score plot;
(B) Loading plot. PCA using NIR spectra: (C) Score plot; (D) Loading plot.

Table 2
Evaluation of the PLS models predicting the percentage of adulteration of BO by SO.
X matrix Calibration n = 7 Validation n = 4

R2 RMSE RE% R2 RMSE BIAS SEP RPD RE%

MIR spectra 0.99982 0.461 0.007 0.99858 1.548 0.426 1.488 12.265 0.003
NIR spectra 0.99926 0.8937 0.014 0.99877 1.257 0.501 1.153 21.679 0.024

arrow in Fig. 5C). Also, it can be observed two groups. The first one,
containing the set of samples up to SO - 40% was positioned in the
negative side of PC1, while from SO – 50–90% (group 2) in the positive
one. All these samples (pure BO and SO – 10–90%) were found to be
somehow similar, since their spectra have similar shapes.
When observing the loading plot (Fig. 5D), most of the range used in
PCA weights positively in PC1. Two main regions, from 5850 to
5760 cm−1 and from 4450 to 4000 cm−1, weighted negatively in PC1.
These are regions where the highest intensities were found (and nor-
malized to 1) and where a decreasing trend on the spectra was observed
as the amount of SO increased in the sample, respectively. These results
agree with what was observed in the spectra analysis, since PC1
weighted positively in regions where there was more influence of the
presence of the SO.
Although the minority of the data was explained by PC2, this
component revealed positive loadings between 6000 and 4850 cm−1,
where the main differences between the spectra (BO and adulterations)
are. At the end of the spectra, from 4440 to 4000 cm−1, negative
loadings were found in PC2, in agreement with the decreasing trend
observed in the spectra as more SO was present in the mixture.

6
C.G. Pereira, et al.
Fig. 6. Calibration and validation predictions of the percentage of BO adulteration by the PLS models based on the (A) MIR and (B) NIR spectra.
3.3. PLS models
Since adulteration ratios can vary significantly (Koca et al., 2010),
calibration models were developed covering adulteration range from 0
to 100%. The percentage of adulteration of BO with SO was used as Y
matrix of the prediction models based on the X matrix containing the
spectrometric data. For the first method, the X matrix consisted of the
normalized MIR spectra of the samples in the selected range previously
used (3050–2800 cm−1, 1800 to 1670 cm−1, 1500 to 935 cm−1 and
740 to 650 cm−1), with a total of 539 variables. The second method,
with the normalized NIR spectra from 9000 to 4000 cm−1, a total of
1297 variables was used. In both cases, full cross validation was used
during the calibration. Table 2 shows the PLS performance and accu-
racy parameters. For each model, RMSE, RE% and R2 were calculated
for both calibration and validation datasets, while BIAS, SEP and RPD
to the validation dataset. The calibration and validation regressions can
be seen in Fig. 6A and B, together with the actual and predicted values
obtained by the models using MIR and NIR spectral data, respectively.
Regarding the MIR spectra (Table 2 and Fig. 6A), the model with 4
factors represented the one with best prediction results. The first two
factors explained more than 76% and 99% of the cumulative variance
of the MIR spectra and the percentage of BO adulteration, respectively.
In the NIR spectra (Table 2 and Fig. 6B), the best prediction model
covered 99.9% of the total variance of the data, with 6 factors. In both
models, the coefficient of determination of calibration and validation
data was above 0.99 with very low relative errors. Although the RMSE
of validation was higher than the calibration, which can be explained
by the number of spectra used in the validation, it was obtained a well
dispersed and random distribution of the residuals (data not shown).
Regarding the precision of the predictive models, they resulted in low
positive BIAS, reflecting in a low contribution to the SEP value. These
results, together with obtained RPD (above 8), indicated very good
overall accuracy of the models (Williams, 2001). Therefore, both MIR
and NIR spectra resulted in prediction models that fitted well the ex-
perimental measurements and can be of great importance in the de-
velopment of new methodologies applied to quality control and au-
thenticity of foods.
4. Conclusions
The potential of MIR and NIR spectroscopy coupled to PCA and PLS
for qualitative and quantitative characterization of the adulteration of
BO by SO was carried out. The MIR and NIR spectra and their deriva-
tives allowed the identification of the main chemical groups driving the
changes in the spectra which were evaluated by PCA. PLS regressions
based on the MIR and NIR profiles resulted in low relative errors and
precise predictions of the percentage of BO adulteration. Moreover, in
each PLS model, it was found coefficients of determination of the global
fit of 0.99 for the calibration and validation datasets with superposed
7
LWT - Food Science and Technology 107 (2019) 1–8
curves. In conclusion, this work reinforces MIR and NIR spectroscopy
associated with chemometrics as a good tool for quality control and
authenticity of oils and fats.
Acknowledgements
This work was funded by CAPES, FAPEMIG and Conselho Nacional
de Desenvolvimento Científico e Tecnológico.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.lwt.2019.02.072.
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