Fuel 283 (2021) 118854

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Discrimination of oils and fuels using a portable NIR spectrometer T

a a a a a,b
Francine D. Santos , Layla P. Santos , Pedro H.P. Cunha , Flávia T. Borghi , Wanderson Romão ,
Eustáquio V.R. de Castroa, Elcio C. de Oliveirac,d, Paulo R. Filgueirasa,
⁎

a
UFES – Federal University of Espírito Santo, Av. Fernando Ferrari, 514, Goiabeiras, Vitória, ES 29075-910, Brazil
b
IFES – Federal Institute of Espírito Santo, Av. Ministro Salgado Filho, Soteco, Vila Velha, ES 29106-010, Brazil
c
TRANSPETRO – Department of Technological Development and Automation on Petrobrás Transporte S.A, Av. Pres. Vargas, 328 - Centro, Rio de Janeiro, RJ 20091-060,
Brazil
d
PUC-RJ – Pontifical Catholic University of Rio de Janeiro, R. Marquês de São Vicente, 225, Gávea, Rio de Janeiro, RJ 22451-900, Brazil

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Improper mixtures of: motor oil with crude oil; and derivatives mixed with other derivatives of lesser com­
Crude oil mercial value were identified in Brazil by companies in the energy sector. This study shows the great response
Fuels that a portable NIR spectrometer had to discriminate crude oils and derivatives and to quantify them in blends
Chemometrics (crude oils with used motor oil; and naphtha, gasoline, diesel, and kerosene). NIR spectra set were acquired in
NIR portable
triplicate using a microNIR™ portable spectrometer, where it was possible to discriminate crude oil from used
motor oil with 100% sensitivity, specificity, and precision. Regression models can quantify the oil content of a
ternary mixture containing two crude oils (light and heavy oil) and a used motor oil with root mean square error
of prediction (RMSEP) of 6.2 and 4.8 wt%, and R2p = 0.9871 and 0.9870 for support vector regression (SVR)
and partial least squares (PLS), respectively. About the NIR spectra of naphtha, gasoline, diesel, and kerosene,
partial least squares discriminant analysis (PLS-DA) allows the identification of any of these products with
sensitivity, specificity, and precision of 100%. For the blends of gasoline and naphtha, the limit of detection
(LOD), limit of quantification (LOQ), and RMSEP were 1.3, 4.4, and 1.4 wt%, respectively. Likewise, for diesel
and kerosene blends, the PLS model allows the identification of the diesel with LOD, LOQ, and RMSEP of 2.8 wt
%, 9.3 wt%, and 11.4 wt%, respectively.

⁎
Corresponding author.
E-mail address: paulo.filgueiras@ufes.br (P.R. Filgueiras).

https://doi.org/10.1016/j.fuel.2020.118854
Received 27 January 2020; Received in revised form 1 July 2020; Accepted 27 July 2020
Available online 13 August 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
F.D. Santos, et al.
1. Introduction
The energy industry handles a large volume of money and trans­
actions around the world. This makes it a target of criminal groups [1].
Thus, forensic investigations of thefts, tampering, and leakages are
necessary to mitigate the problems and to make the process safe. The
great difficulty lies in the complexity of the matrices. Fossil fuels and
oils are predominantly hydrocarbons. Crude oils are complex mixtures
that can contain hundreds to thousands of compounds, whilst fossil
fuels are by-products obtained by thermal cracking in different tem­
perature ranges [2]. However, since physicochemical differences in­
fluence the final quality of products, it is very common to mixture crude
oils to obtain products with the best qualities. Thus, although crude oils
from different locations have certain distinguishable characteristics[3],
this information can become more difficult to read in blends. Also, in
cases of leakage accidents, the response to action must be rapid so that
the damage caused does not endanger society and the environment.
In Brazil, the National Agency of Oil, Natural Gas and Biofuels –
ANP, regulates the activity of authorized companies, and the limits for
each important property in the products, in order to maintain a quality
and safety standard in the process and products [4]. However, refineries
for the reprocessing of waste oils buy stolen oils and derivatives, in
order to obtain better quality products or sell clandestine fuels with the
aim of having higher profits. This illegal market, in the past four years,
diverted 42 million liters of crude oil and derivatives from the pipeline
network in Brazil [1].
Thus, the classification of crude oil and derivatives is of great in­
terest. Chromatographic methods such as thin layer (TLC), high-per­
formance liquid (HPLC), gas (GC) and gel permeation (GPC) are the
most used in oil/fuel analysis [5]. The answer brings detailed in­
formation about the chemical composition of each class of hydro­
carbons present, the so-called fingerprint [3,5,6]. However, most of the
methods employed are destructive, laborious, and consume a large
volume of solvents. Still, other analytical techniques can be used for the
same purpose, showing reliability and accuracy, such as spectroscopic
techniques: Raman [7], near-infrared (NIR) [8-10] and mid-infrared
(MIR) [11-13].
Among them, NIR spectroscopy has been used in fuel quality control
applications such as water and methanol quantification in ethanol fuel
and gasoline, [8,9,14-16] biodiesel, and total sulfur content in diesel,
[17-21] and determination of physicochemical properties such as
viscosity, sulfur content, density, among others, for the various fuels
[2,22-25]. MIR spectroscopy has also been successfully used [2,11,26-
29]. MIR presents lower interference and higher vibrational resolution
than NIR. However, it is very difficult to build a remote MIR system due
its hygroscopic optical elements and the characteristic of the source.
The interaction in NIR system between light beam and sample is more
effective[30].
Recently, the innovation in NIR spectroscopy is in the portability,
i.e., in situ analysis. Some analytical advantages are fast-time analysis,
ergonomic design, low operation costs, low power consumption, easy
handling with little or no sample preparation [29-31]. In less than 10 s,
the NIR spectra is collected and sent over the internet, a fascinating
advantage in cases of leakage, and accidents, for example. Portable
spectrometers combine portability with a variety of accessories that
allow the analysis of different products [29,30,32].
Chemometric models of classification and quantification are useful
in the study of complex matrices, as they allow the affiliation of an
unknown sample to a known set of samples or, as missing from the
correlation of physicochemical properties [33]. The portable spectro­
scopy technique combined with chemometric tools has been a powerful
analytical tool for the industry and in the quality control of food and
chemicals [34].
Different qualitative multivariate methods have been developed for
the classification of samples or quality control. Among them, highlight
the supervised models such as partial least squares discriminant
2
Fuel 283 (2021) 118854
analysis (PLS-DA) and linear discriminant analysis (LDA)[18,35-39],
and unsupervised, such as principal component analysis (PCA) and
hierarchical cluster analysis (HCA) [38,40,41]. While in quantitative
studies, partial least squares (PLS) is the commonly chosen method
[2,42], but support vector regression (SVR), a nonlinear method, can
provide an answer for complex matrices[37,43-46].
PLS models constructed with data obtained in portable spectro­
meters showed similar or better results when compared with benchtop
equipment [19,47,48]. There are publications using portable spectro­
meters to analyze different types of fuels and parameters [19,21,23,49-
54]. Thus, a portable NIR spectrometer was used in this study to solve
problems of classification and quantification in crude oils and fuels. For
the classification, the PLS-DA model was used and the performance
parameters evaluated were sensitivity, specificity, and precision. Crude
oils samples were discriminate from used motor oil, Motor Oil (visually
similar to crude oil, and a potential adulterant). Fuels were classified
according to their type (naphtha, gasoline, diesel, and kerosene). In the
quantification section, PLS and SVR models were constructed and
compared to quantify ternary mixtures (varying from 0 to 80 wt%) of
light oil (API gravity of 56.0), heavy oil (API gravity of 19.9) and motor
oil (API gravity of 29.1). The parameters used for this evaluation were
the root mean squared error calibration (RMSEC), root mean square
error of prediction (RMSEP), coefficient of determination of the cali­
bration sets (R2c) and coefficient of determination of the test sets (R2p).
On the other hand, PLS models were constructed to quantify binary fuel
blends (naphtha and gasoline, diesel and kerosene) ranging from 0 to
100 wt%.
2. Methodology
All the samples of crude oils and fuels were obtained with Brazil
companies in the energy sector. Therefore, refer to samples from the
production fields of the Brazilian territory. The used motor oil is a re­
sidue taken from the oil change in cars and stored in metal barrels for
correct environmental disposal. The samples of used motor oil were
donated by local gas stations.
2.1. MicroNIR analysis
NIR spectra were performed on a spectrometer model MicroNIR ™
Pro 1700 with software 3.0 of Viavi Solutions Inc. [55]. The spectral
parameters set were: range from 908 to 1676 nm, 200 scans, integration
time of 8 ms, and acquisition of 125 points per scan. Accessories em­
ployed were Vial Holder for fuels and Droplet for oils. Both are attached
to the light source, so light strikes off the sample for data collection.
Reference spectra of 100% of reflectance were collect using Teflon
pieces – Spectralon® – and the data of 0% of reflectance were collected
with the equipment empty and the lights off. These reference spectra
were collected every ten minutes of analysis.
2.2. Qualitative model
Two samples set were studied: the first containing 275 crude oil
samples. And the other set of used motor oil (named Motor Oil, n = 70,
that is visually similar to a crude oil sample). The samples were pre­
pared in triplicate and the NIR spectra were acquired in random order,
sampling a droplet in the sapphire window of the accessory. We used
the mean of the triplicate. Therefore, a data set of 345x125. The second
dataset was formed with samples of naphtha, gasoline, diesel, and
kerosene transferred to clear glass vials with a volume capacity of 4 mL.
Each fuel set containing 40 vials filled up. The NIR spectra data set of
160x125.
All spectra were preprocessed using the first derivative by the
Savitzky–Golay algorithm [56] with a second-order polynomial and 7-
point window. For both sample sets, NIR spectra were split into cali­
bration and test sets to construct the model and evaluate the
F.D. Santos, et al.
discriminatory ability. The calibration set contained 70% of all samples,
and the spectra remained, i.e., 30%, formed the validation data set. PLS-
DA model was evaluated according to sensitivity, specificity, and pre­
cision, Eqs. (1)–(3), respectively [57,58].
TP
Sensitivity (%) = 100
(1)
TP + FN
TN
Specificity (%) = 100
TN + FP (2)
TP + TN
Precision (%) = 100
TP + TN + FP + FN (3)
FP and FN are the number of false-positive and false-negative
samples, respectively; TP and TN are the number of true positive and
true negative samples, respectively.
2.3. Quantitative model
To evaluate the ability of microNIR technique to quantify used
motor oil added in crude oil samples, it was constructed a multivariate
calibration model containing a mixture of three components: the used
motor oil (API gravity of 29.1) and two virgin crude oil samples, one
having API gravity of 56.0, named Light oil, and another with API
gravity of 19.9, named Heavy oil. The analytical curve prepared had the
proportions, in weighed, varied in the blends from 0 to 100 wt%,
generating 53 samples (Table 1S). The measurements were performed
in triplicate, totalizing 159 acquired NIR spectra.
For fuel quantification, two multivariate calibration models were
constructed from binary mixtures varying the content from 0 to 100 wt
% in an interval of 5–5 wt%. The first model was composed of naphtha
and gasoline, and the second with diesel and kerosene.
NIR spectra were preprocessed with the first derivative algorithm
with a second-order polynomial and a 7-point window [56] and
adaptive iteratively reweighted penalized least squares (airPLS) [59]
for alignment. For noise treatment were tested centralization, normal­
ization, standard normal variance (SNV), and multiplicative signal
correction (MSC). Subsequently, multivariate calibration models were
constructed using PLS and SVR. All calculations were performed in
Mathworks Matlab software R2013a (Eigenvector Research, Inc.).
The samples were separated by the k-fold method in calibration and
prediction groups to cover all percent ranges of the mixtures. In the
construction of the PLS models, the number of latent variables was
Fig. 1. (a) Untreated and (b) treated (first derivate) NIR spectra of crude oil and motor oil.
3
Fuel 283 (2021) 118854
optimized. And in the SVR models, the parameters cost (C), margin (ε),
and gamma (γ) of the kernel function were optimized. The optimization
of the models was performed by the 5-fold cross-validation procedure.
The regression models were evaluated for the performance para­
meters: square root of mean prediction errors (RMSEP, Eq. (4)) and
coefficient of determination (R2, Eq. (5)) [60]:
npred
1 2
RMSEP = (yi Å·i )
npred i=1 (4)
(yi yi )2
R2 = 1 i
2
i
(yi yi ) (5)
Where npred is the number of samples in the prediction group, yi, yi
and yi are, respectively, the reference, predicted and average of the
observation values by the model.
3. Results and discussion
3.1. Oil data set
3.1.1. Qualitative model
The average spectrum of crude oil and used motor oil is shown in
Fig. 1. It is possible to observe a large variation of the spectral baseline
in the untreated data (Fig. 1a) which occurs due to the scattering effect
in the NIR spectral range[42]. It was corrected using the first derivative
(Fig. 1b).
The data sets of crude oils present a higher variability of the spectral
profile when compared to Motor Oil, Fig. 1b. In Fig. 1b, it is possible to
see the bands around 900 nm (OH second overtone) 1200 nm (Second
overtone of CH2) and 1400 nm (CH2 combinations and first overtones)
correspond to hydrocarbons compounds species [61]. The region with
the greatest distinction between petroleum and used motor oils is the
range between 900 and 1000 nm. This region in crude oil is influenced
by asphaltenes [24,62]. However, when the spectra of many crude oils
and used motor oils are acquired it is not possible to distinguish the two
classes.
The PLS-DA identifies the latent variables (LV) that allow the
highest discrimination between two separate groups of samples based
on their spectra (matrix X) and according to their maximum covariance
with a target class established in the matrix Y [57]. To minimize re­
gression errors were selected the number of LV, according to the
F.D. Santos, et al. Fuel 283 (2021) 118854

Fig. 2. Calculated response for the probability of samples belonging to a given class ((a) crude oil, (b) motor oil) using the PLS-DA model with 9 LVs.

classification error rate, predicted by the cross-validation process, in 1.41% and R2 of 0.957. Riley et al. [3] obtained MIR spectra of as­
this case, it was nine LV. phaltenes of 11 samples (eight from crude oils of different locations and
The PLS-DA model was applied to the test set and the probability of two from heavy fuel oils). It was possible to differentiate all samples
each NIR spectrum of a given sample belong to each class is shown in with peak height ratio comparisons with 20% relative standard devia­
Fig. 2a,b. The horizontal dotted line refers to the decision limit for the tion as the decision limit to evaluate the sample resemblance. Galtier
sample to belong to a given class. Samples of the calibration and test et al. [39] classified the origin of 36 crude oil samples from four dif­
sets are represented by symbols (o) and (Δ), respectively. ferent regions using MIR spectra combined to SIMCA, PLS-DA, and PLS-
The numbers (Fig. 2a,b) refer to the samples misclassified, 53 and DA-SIMCA models. All models obtained 100% of correct classification.
115. These samples were classified outside the class “crude oil” (Fig. 2a) Thus, compared to the results of the mentioned publications and
and inside class “motor oil” (Fig. 2b). They cannot be considered out­ emphasizing that our study was carried out with a portable spectro­
liers, as they do not have high residue values. These samples have API meter, the sensitivity of crude oil PLS-DA model had similar dis­
gravity above 30 and therefore low asphaltene content. However, the criminatory capacity. Because of the two crude oil samples wrongly
set of crude oils present many other samples with similar character­ classified in the calibration set, the sensitivity for crude oil are below
istics. Thus, there must be other compositional characteristics of these 100% in calibration and cross-validation. This leads to loss in specificity
samples that resemble their response to used motor oils. and precision for motor oil. However, it fulfills the purpose of dis­
In contrast, none of the samples of used motor Oil were mis­ criminating used motor oils from crude oils, with the model presenting
classified, Fig. 2a,b. This aspect proves that the microNIR technique is sensitivity of 100%,
capable to discriminate crude oil samples from used motor oil with no
errors from the calculated response. 3.1.2. Quantitative model
The performance parameters of the PLS-DA model are shown in The microNIR spectra for the 53 samples, composed of a ternary
Table 1. There are no references using a portable spectrometer on the mixture of light oil (API gravity of 56.0), heavy oil (API gravity of 19.9)
NIR region to discriminate the origin of crude oils samples or to dif­ and used motor oil varying the content from 0 to 100 wt%, are shown in
ferentiate products that can be used to mistaken the chemical compo­ Fig. 3a. For the PLS model, six latent variables were used and centering
sition of crude oil (as in the case of motor oil used in the study). But on the mean proved to be the best methodology for spectra correction
using a benchtop instrument and analyzing the fingerprint of MIR-FTIR (Fig. 3b), whereas for the SVR model, the best was the first derivative
region, Garmarudi et al. [63] classified 251 samples from seven Iranian followed by auto-scaling (Fig. 3c). It is not possible to classify petro­
fields and three types of crude oil blends with soft independent mod­ leum samples by origin, just by observing the spectral profile of the
eling of class analogy (SIMCA) with a precision of 96.7%, RMSEP of samples, much less to estimate their properties. As can be seen from
Fig. 3a,b, all samples have the same profile. However, after correction
with the first derivative, the samples with the highest concentration of
Table 1 light oil (represented by orange lines), Fig. 3c, were distinguished from
Performance parameters of the PLS-DA model. the group.
Performance parameters Crude oil Motor oil A total of 17 different pretreatment methods were tested and the
results of the models with the best average precision values are shown
Calibration Specificity 100% 99%
in Table 2. For Light and Heavy Oil, the best results were obtained with
Sensitivity 99% 100%
Precision 100% 96% the SVR model. In the case of Light Oil, values of RMSEC, RMSEP, R2c,
Cross Validation Specificity 100% 98% and R2p were 5.1 wt%, 4.0 wt%, 0.9720 and 0.9923, respectively. On
Sensitivity 98% 100% other hand, better values were obtained for the Heavy Oil
Precision 100% 94% (RMSEC = 2.7 wt%; RMSEP = 0.9 wt%, R2c = 0.9941 and
Test Specificity 100% 100%
R2p = 0.9985). Finally, for Motor Oil, it can be said that PLS is the best
Sensitivity 100% 100%
Precision 100% 100% model because the forecast error was slightly smaller, but all values are
very similar. Generally, PLS model is a much easier tool to handle and

4
F.D. Santos, et al. Fuel 283 (2021) 118854

Fig. 4a-f shows the reference and predicted values of (4a,c,e) PLS
and (4b,d,f) SVR models for (4a-b) light, (4c-d) heavy and (4e-f) used
motor oils. Briefly, no difference can be observed between the PLS (left)
and SVR (right) model results and how much the data fit the model. For
that, the three built models predict the concentration of the crude oils,
performance parameters (RMSE and R2) were higher for SVR model
when compared to the PLS model. Alves and Poppi [20] evaluated
diesel samples, where SVR models had RMSEP values ranged from 21 to
54% lower than the values obtained in the PLS models. Similar to our
study, the SVR model was superior to PLS. However, when the analy­
tical parameters obtained among the PLS and SVR are similar, it is
better to use the first model, since it is faster to build and test, having
greater availability of publications to compare the performance para­
meters.

3.2. Fuels data set

3.2.1. Qualitative mode

NIR spectra for naphtha, gasoline, diesel, and kerosene samples
show high similarity (Fig. 5a-d). As the difference between these pro­
ducts is in the boiling temperature on the distillation process, there is
compositional similarity in spectral profile observed [23,65]. After
pretreated with the first derivative (seven-point window with second-
degree smoothing polynomial), some spectral regions show subtle dif­
ferences: bands around 1250 and 1510 nm. These bands are related to
the CH second overtones, and combinations of overtones, respectively
[23].
PLS-DA model for these 4 fuel types was constructed with five LVs.
Differently of Fig. 3, none of the NIR spectra were wrongly classified, so
Fig. 3. NIR spectra of the 53 crude oils blends from (a) Untreated and pre­
specificity, sensitivity, and precision for the classification of all the four
treated (b) with mean center data, or (c) the first derivative and autoscaling.
groups were equal 100% (Table 3). In benchtop spectrometer, Balabin
et al. [40] used NIR spectra to classify three sets of gasoline with several
chemometric tools. Within each set, different parameters were used for
Table 2
classification. The first parameter was the different refineries (Refinery
SVR and PLS results for predicting of oils content in ternary mixtures.
1, 2, and 3); the second was the type of processing (straight-run, re­
Property Pretreat Model RMSEC (wt RMSEP (wt R2c R2 p formate, catalysate, isomerizate, hydrocracking gasoline, mixture), and
%) %)
the third, types of gasoline (normal, regular, premium). The PLS-DA
Light oil Deriv/Auto SVR 5.1 4.0 0.9720 0.9923 model presented 9%, 20%, and 10% of classification error for the first,
Light oil Center PLS (6)* 6.1 6.2 0.9626 0.9809 second, and third sets, respectively. Silva et al. [37] used NIR spectra
Heavy oil Deriv/Auto SVR 2.7 0.9 0.9941 0.9985 and different models (LDA, PLS-DA, and support vector machine) to
Heavy oil Center PLS (6) 4.6 2.9 0.9843 0.9844
classify 125 samples of gasoline in two groups: without and with ad­
Motor oil Dariv/Auto SVR 5.3 6.2 0.9678 0.9871
Motor oil Center PLS (6) 5.9 4.8 0.9678 0.9871 ditives. For the PLS-DA models, only 2 of 12 samples of gasoline with
additives were wrongly classified.
* Value in parentheses represents the number of latent variables used. For lubricating oils, Balabin et al. [35] used benchtop equipment
and NIR spectra and different models to classify three different sets. The
that, for all models, errors were below (where the concentration varied classes of each set were: type (set A), viscosity at low temperature (set
by 10 wt% between samples on the analytical curve) with correlation B), viscosity at high temperature (set C). PLS-DA model presented 36%,
coefficient ever higher than 0.96, therefore, it is recommended to uti­ 59%, and 52% of classification error for the set A, B, and C, respec­
lize this model to solve this type of application. tively. Pontes et al. [18] also used a benchtop equipment and con­
Cipullo et al. [64] evaluated 21 regions of five contaminated soils, a structed LDA-SPA and PLS-DA models with NIR data in order to obtain
total of 105 samples, to predict the total and bioavailable amount (mg/ a fast quality control method to classify diesel samples as conforming or
kg) of petroleum hydrocarbons compounds (PHC). The visible-near non-conforming for samples containing biodiesel or vegetable oil above
infrared (VIS-NIR) spectra were obtained in the range of 350–2500 nm, 5% v/v. A total of 140 samples were used. The correct prediction rate
and the model applied was random forest (RF), where the results of R2 was above 97%. Finally, Maldonado et al. [26] used a portable MIR
found were between 0.40 and 0.75. Douglas et al [54] also used VIS-NIR infrared spectrometer. The results demonstrated that the model applied
equipment to predict the total amount of mixtures of oil hydrocarbons (MANOVA) was able to discriminate gasoline, diesel oils, and different
(mg/kg) in 85 soil samples. It was constructed RF and PLS models alcohols (methanol, ethanol, n-propanol, n-butanol, and n-hexanol)
where R2 results found were 0.68, and 0.54, respectively. According to without classification errors. So, based on the comparison with these
the study of Cipullo et al., an RMSEP value below 15% indicated that previous studies, the results of the present work (100% of specificity,
their model was accurate [64]. In this way, the results for the PLS and sensitivity, and precision) show the consistency of the technique to
SVR models constructed in this work can be considered acceptable. discriminate fuels.

5
F.D. Santos, et al.
Fig. 4. Reference and predicted values of (a,c,e) PLS and (b,d,f) SVR models for (a-b) Light, (c-d) Heavy and (e-f) Motor oils.
Fig. 6 shows the probability of each sample belongs to each fuel.
Large discrimination is observed for naphtha (Fig. 6a) and gasoline
(Fig. 6b) samples. For diesel (Fig. 6c) and kerosene (Fig. 6d), all sam­
ples were correctly identified, however, looking to the ordinate axis,
smaller distances between the groups were observed. The discrimina­
tion is possible because of the strong influence of the first LV (Fig. 7a).
It is possible to observe a dispersion of the samples on the residuals plot,
6
Fuel 283 (2021) 118854
which could indicate outliers, but these samples don’t compromise the
quality of the model (Fig. 7b).
3.2.2. Quantitative model
Blends of naphtha and gasoline, and diesel and kerosene were
prepared. 20 blends for each set, varying content by 5 wt%, reaching a
range from 0 to 100 wt%. NIR spectra were acquired and, then, used to
F.D. Santos, et al. Fuel 283 (2021) 118854

Fig. 5. (a,b) Untreated and (c,d) treated (first derivative) portable NIR spectra for (a,c) naphtha and gasoline; and (b,d) diesel and kerosene samples.

estimation of the samples (Fig. 8a-b). The samples with 0% of naphtha

Table 3 and diesel were predicted containing wt% lower than the measured
Performance parameters of the PLS-DA model for naphtha, gasoline, diesel, and values. This error may be related to the chemical similarity of these
kerosene (Q-AV) samples. fuels, intrinsic to the distillation process since the distinction between
Parameters Naphtha Gasoline Diesel QAV the spectra of both fuels is minimal.
These results show that it is possible to detect naphtha in gasoline
Calibration Specificity 100% 100% 100% 100%
above 1.3 wt% and quantify above 4.4 wt% with RMSEP of 1.4 wt%.
Sensitivity 100% 100% 100% 100%
Precision 100% 100% 100% 100% For the blends of diesel with kerosene, it is possible to detect and
Cross Validation Specificity 100% 100% 100% 100% quantify above 2.8 and 9.3 wt%, respectively, with RMSEP of 11.4 wt%.
Sensitivity 100% 100% 100% 100% Although no studies quantify the same fuel mixtures, it is valuable
Precision 100% 100% 100% 100% to observe the studies that used portable NIR spectrometers to quantify
Test Specificity 100% 100% 100% 100%
fuel content. For diesel samples, Paiva et al. [17] obtained LOD of
Sensitivity 100% 100% 100% 100%
Precision 100% 100% 100% 100% 0.31% v/v for biodiesel content and RMSEP 0.22% v/v, and LOD of
0.40% v/v for content of vegetable oils in diesel with RMSEP of 0.34%
v/v. However, they evaluated a narrow range of concentration (0–15%
construct the PLS models. RMSEC and RMSEP values were similar for v/v). On the other hand, Correia et al. [21] evaluate 133 of biodiesel/
both models, with RMSEP values less than three times higher the diesel samples on the range of 0–100 wt% and obtained values to
RMSEC. These results indicate that there is no over-adjustment of PLS predict biodiesel concentration of LOD = 0.5 wt%, LOQ = 1.8 wt%,
models (Table 4). The models presented linearity above 90% in the and RMSEP = 1.8 wt%. For gasoline samples, Lutz et al. [51] obtained

Fig. 6. Calculated response for the probability of samples belonging to a given class: (a) naphtha, (b) gasoline, (c) diesel and (d) kerosene using the PLS-DA model
with 5 LVs.

7
F.D. Santos, et al. Fuel 283 (2021) 118854

Fig. 7. (a) Scores of the first and second LVs with 90,13% of the explained variance; and (b) square values of residue versus Q residuals.

4. Conclusion
Table 4
Performance parameters for PLS models to estimate the content of naphtha and The portable NIR spectrometer is efficient to classify and quantify
gasoline, and diesel and kerosene in the blends. crude oil samples and their derivatives. PLS-DA model could dis­
Parameters Naphtha + Gasoline Diesel + Kerosene criminate crude oils from used motor oils with sensitivity, specificity
and precision over 94%. PLS model is sufficient to quantify the oil
RMSEC (wt%) 2.9 31.7 content of a ternary mixture with crude oil and used motor oil (Light,
RMSEP (wt%) 1.4 11.4
Heavy and Motor Oil) with an average precision of 4.8 wt%. About the
R2c 0.9939 0.9178
R2p 0.9963 0.9443 NIR spectra of naphtha, gasoline, diesel, and kerosene, PLS-DA allows
LOD (wt%) 1.3 2.8 the identification of these products with sensitivity, specificity, and
LOQ (wt%) 4.4 9.3 precision of 100%. For the blends of gasoline and naphtha, LOD is
1.3 wt% and LOQ 4.4 wt% with RMSEP 1.4 wt%. Likewise, for diesel
and kerosene blends, the PLS model allows the identification of the
LOD and LOQ for ethanol concentration in gasoline of 0.68 and 2.04 wt diesel with LOD 2.8 wt%, LOQ 9.3 wt% with RMSEP of 11.4 wt%.
%, respectively, with RMSEP of 0.21 wt% in mixtures containing
0–10 wt%. While, Correia et al. [21] results for gasoline, ethanol and CRediT authorship contribution statement
methanol concentrations in gasoline samples (with concentration range
of 0.0–75.0 wt% gasoline, 25.0–75.0 wt% ethanol, and 0.0–50.0 wt% Francine D. Santos: Methodology, Validation, Investigation, Data
methanol) respectively were LOD of 0.55 wt%, 0.75 wt%, 0.85 wt%; curation, Writing - original draft, Visualization. Layla P. Santos:
LOQ of 1.84 wt%, 2.5 wt%, 2.84 wt%; and RMSEP of 0.81 wt%, 3.81 wt Methodology, Validation, Investigation, Data curation, Writing - ori­
%, and 1.80 wt%. The results for the model constructed to predict ginal draft, Visualization. Pedro H.P. Cunha: Methodology, Validation,
naphtha content are close to other publications. The model to predict Investigation, Data curation, Writing - original draft, Visualization.
diesel got higher results, but the mixtures studied here present greater Flávia T. Borghi: Methodology, Validation, Investigation, Data cura­
chemical composition. They are still interesting values. If these models tion, Writing - original draft, Visualization. Wanderson Romão:
are used in cases of adulteration of fuel, they are applicable. Because Conceptualization, Methodology, Writing - review & editing,
tampering happens with addition of high volumes of adulterant. Supervision. Eustáquio V.R. de Castro: Conceptualization,
Methodology, Writing - review & editing, Supervision. Elcio C. de

Fig. 8. Reference and predicted values for (a) naphtha and (b) diesel contents by PLS model constructed with 4 LVs with a confidence interval of 95%.

8
F.D. Santos, et al.
Oliveira: Conceptualization, Methodology, Writing - review & editing,
Supervision. Paulo R. Filgueiras: Conceptualization, Methodology,
Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgments
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001. The authors would like also to thank: LABPETRO-
UFES; FAPES (33530.503.20537.12092017); CAPES (23038.007083/
2014-40), and CNPq (process number 422515/2016-7; and 305359/
2017-7) for their financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118854.
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