Fuel 282 (2020) 118684

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Full Length Article

Application of low-field and medium-resolution 1H NMR spectroscopy T

combined with chemometric methods for automotive gasoline quality
control
Leticia Magalhães de Aguiara, Evandro Bonab, Luiz Alberto Colnagoc,
⁎
Jarbas J. Rodrigues Rohwedderd, Mario Henrique M. Killnera,
a
Departamento de Química, Universidade Estadual de Londrina, 86.057-970 Londrina, PR, Brazil
b
Programa de Pós-Graduação em Tecnologia de Alimentos, Universidade Tecnológica Federal do Paraná, 87.301-899 Campo Mourão, PR, Brazil
c
Embrapa Instrumentação, Rua XV de Novembro, 1452 13.560-970 São Carlos, SP, Brazil
d
Instituto de Química, Universidade Estadual de Campinas, 13.084-971 Campinas, Brazil

G R A P H I C A L A B S T R A C T

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

Keywords: This work describes the application of low-field and medium-resolution 1H NMR (LF-1H NMR) combined with
Low-field NMR PLS and SVM multivariate regression techniques for fast prediction of five fundamental quality parameters of
Chemometrics commercial Brazilian gasoline (specific gravity, distillation temperatures of 50 and 90 percent of recovered and
Gasoline olefinic and aromatic content). All these five parameters are of paramount importance to predict the fuel quality
PLS
and the application of the developed PLS and SVM models showed prediction errors compared to the reference
SVM
Desktop NMR
methodologies applied for these essays. Nevertheless, it is important to highlight that in a different way of the
reference methodologies, such as distillation or chromatographic methods, the application of LF-1H NMR
combined with PLS or SVM models enables the fast determination of those five parameters directly from a single
LF-1H NMR spectrum, which is acquired without any sample pre-treatment nor dilution in deuterated solvents,
and this whole process takes no more than 15 s.

1. Introduction economy of any country. In Brazil, like in US, such economic depen-
dence is even greater, once domestic transportation is majorly based on
Gasoline is one of the major liquid fuels and plays a key role in the automobiles powered by gasoline [1]. Briefly, gasoline fuel is a complex

⁎
Corresponding author.
E-mail address: killner@uel.br (M.H. M. Killner).

https://doi.org/10.1016/j.fuel.2020.118684
Received 10 October 2019; Received in revised form 26 June 2020; Accepted 7 July 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
L. Magalhães de Aguiar, et al.
liquid mixture majorly composed of aliphatic (paraffin and olefins) and
cyclic (naphthenic and aromatics) hydrocarbons [2–8] containing
carbon atoms from C4 to C12 [9]. Its composition can vary according to
its origin and storage process, parameters which also determine the fuel
quality [10].
In Brazil, the government fixed the addition of 27% of anhydrous
alcohol to regular gasoline and 25% to premium gasoline destined to
final consumers [11]. This established percentage can also vary ac-
cording to ethanol availability and market costs.
The tremendous dependence of the country on fossil fuel sources
justifies the continuous quality control over its distribution chain,
especially at the gas stations, to avoid any kind of illicit activities of fuel
adulteration, aiming at the increase of the profits on its selling to the
final consumer. Unfortunately, these illicit practices are not uncommon
in the Brazilian scenario, resulting in taxing evasion and low-quality
fuel distribution.
In 2017, according to National Petroleum Agency (ANP), from a
total of 41,689 existing gas stations around the country, an amount of
only 2585 samples were collected for police control, where 2.5% of
these samples were not under the standards for commercialization [12].
Such numbers continuously reinforce the need for new, faster, and low-
cost analytical techniques that would enable more efficient control of
fuel quality.
Table 1 shows the main required quality parameters for the analysis
of gasoline established by ANP. Majorly, the analytical techniques ap-
plied to determine such parameters are based on physicochemical or
chromatographic methods.
Although these methods are robust, they are time-consuming and
not easily automated. Consequently, they are not used for the in situ
monitoring of the fuel quality at gas stations.
Thus, spectroscopic techniques have been studied as possible sub-
stitutes for the physical essays, especially NIR and FTIR techniques
combined with chemometric methods, which have shown a great po-
tential for police control [5,6,8,9,13–17]. Fluorescence [18], mass
spectrometry [19], TD-NMR [20–22], and Raman spectroscopy have
also been used for adulteration control and classification of fuels
[23,24].
1
H and 13C NMR spectroscopy are emerging techniques in terms of
fuel quality control, as shown by Turanov et al. [25] who applied 1H
NMR for the determination of ethanol and benzene in fuel. Cunha et al.
[26] and Obeidat et al. [27] successfully applied 1H NMR for the de-
termination of gasoline adulteration with kerosene and Flumignan et al.
[28] applied 13C NMR for the determination of distillation curve,
density, ethanol and benzene content of gasoline.
The above-mentioned works showed the power and versatility of
high-field NMR (HF-NMR) as an analytical tool for application to fuel
quality control. Nevertheless, HF-NMR is based on superconducting
magnets, which demands high costs for the acquisition of the
Table 1
The most important quality parameters for commercial Brazilian gasoline es-
tablished by ANP and their respective reference assays to determine it.
Quality parameter Testing method (ANP
Resolution [29–35])
Specific Gravity at 20 °C ASTM D4052
Distillation Temperature (T10%, T50% e T90%) ASTM D86
Final Boiling Point (PFE) ASTM D86
Residue ASTM D86
Benzene ASTM D6277
Anhydrous ethyl alcohol fuel NBR 13992
Saturated content ASTM D1319
Olefin content. ASTM D1319
Aromatic content ASTM D1319
Motor Octane Number (MON) and Research ASTM D2699/D2700
Octane Number (RON)
Anti-knock index (IAD). ASTM D2699/D2700
2
Fuel 282 (2020) 118684
instrument and its maintenance. Also, nowadays there is no possibility
of using HF-NMR spectroscopy for in situ applications.
Some interesting applications of low-field (LF) NMR devices have
also been reported. Romanel et al. [36] applied time-domain (TD) NMR
to investigate gasoline adulteration by ethanol, a common practice in
Brazil. Voigt et al. [37] applied medium-resolution LF-NMR, Raman
and NIR spectroscopies to determine the research octane number (RON)
quality parameter and Montes et al. [38] proposed the application of
LF-1H NMR for aromatic determination of petroleum products. Cunha
et al. [20] applied TD-NMR to quantify adulteration of diesel fuel with
soybean oil and Kock et al. [22] to quantify adulteration of ethanol fuel
with methanol.
In this way, the present work proposes a new application of a low-
field and medium-resolution 1H NMR (LF-1H NMR) desktop device with
partial least squares (PLS) and support vector machine (SVM) chemo-
metric regression methods for the quality control of gasoline fuel. This
device is based on permanent magnets allowing a significant decrease
in operational costs of NMR with no significant losses regarding sample
information [39,40].
PLS is a well-established chemometric method and more details can
be found in [41–45]. SVM is a more recent method, a machine learning
supervised technique, based on the statistics learning and optimization
theories [46–48]. It is primarily applied to solve classification pro-
blems, as detection and classification of standards with high general-
ization capacity [47,49,50]. It is a powerful chemometric tool used in
many multivariate cases, once it works with high linear and nonlinear
dimensionality of data. Thus, it can solve many multivariate calibration
issues in a robust way [49,51].
2. Experimental part
2.1. Instrumentation
The LF-1H NMR spectra were recorded in a benchtop NMR spec-
trometer (Spinsolve, Magritek) equipped with a permanent magnet,
generating a magnetic field of 1 T (43 MHz for the proton Larmor
frequency), with homogeneity of 0.01 ppm (better described in [39]).
For comparison reasons, a 400 MHz (HF-NMR) spectrometer (Bruker)
was also used.
All LF-1H NMR spectra were collected without any dilution of the
sample in deuterated solvents. For that, 1.0 mL of each gasoline sample
was directly inserted in a 5 mm NMR glass tube. Each spectrum was
acquired after the application of a single 90° RF pulse and a single scan.
The 43 MHz spectrometer operates essentially with factory-settings
parameters [52]. These parameters are 32 k complex pointsfor mea-
suring the free induction decay with a bandwidth of 5 kHz.
As a pre-processing step, baseline, zero-order phase correction was
applied to the obtained spectra after the Fourier transformation auto-
matically performed by the operating software. Moreover, the spectra
were aligned according to their maximum peak intensity at δ = 1.19
and normalized.
For the HF-1H NMR spectra acquisition, 25 mg of sample was di-
luted in 650 μL of CDCl3. The experimental paramenters for each
spectrum used were single pulse, spectral width of 8012 Hz, relaxations
delay of 1 s, an average of 16 scans of a 90° RF pulse each, and an
acquisition time of 4,089 s.
For the HF-1H NMR spectra acquisition, 25 mg of sample was di-
luted in 650 μL of CDCl3. Each spectrum is an average of 16 scans of a
90° RF pulse each.
2.2. Gasoline samples
A set of 345 commercial gasoline samples was used in this work.
These samples were collected at gas stations located all over the country
(Brazil) and an ANP accredited laboratory determined the 14 required
parameters, previously showed in Table 1. This set was composed by
L. Magalhães de Aguiar, et al. Fuel 282 (2020) 118684

209 regular gasoline samples (27% v/v of ethanol), 117 additive-con-

taining gasoline samples (27% v/v of ethanol plus detergent polymers)
and 19 premium gasoline samples (25% v/v of ethanol and higher anti-
knock index compared to regular gasoline).

2.3. Multivariate calibration

Gamma 3.0 chemometric package of routines [53], running in a

Matlab 2015 environment was used to perform all chemometric ana-
lysis, including Principal Component Analysis (PCA), Partial Least
Squares Regression (PLS) and Support Vector Machines Regression
(SVM).
The SVM was developed as binary classifiers with decision bound-
aries f(x) = wϕ(x) + b, where ϕ(x) is known as the kernel function. For
a nonlinear regression, the learning algorithm was modified to mini-
mize the ε-insensitive loss function. In this work, an ε-support vector
regression (ε-SVR) model was available in the LIBSVM package [53],
which may be described by the following regression function:

l
f (x) = ∑ (αi∗ − αi ) K (xi, x) + b
i=1 (1)

where l is the number of support vectors (SV), αi∗ and αi are the La-
grange multipliers for the ith support-vector, and b is the bias. K (xi, x)
is the kernel function, in this work a radial base kernel was applied, cf.
Eq. (2), which is the most used kernel function [54]. In Eq. (2), γ
controls the amplitude of the function and, therefore, the generalization
capacity of the SVM [55–58].

K (xi, x) = exp (−γ‖xi − x2‖) (2)

The SVM learning algorithm is based on the structural risk mini-

mization principle derived from statistical learning theory. Briefly, to
build the model the algorithm selects samples from the calibration set
that serves as support vectors. The number of selected support vectors
depends on the complexity of the data and the Lagrange multipliers are
determined to provide the maximum possible separation between the
classes [59].
The other parameters used in SVM application (C, ε and γ) were
Fig. 1. 1H NMR spectra of premium, additive-containing, and regular Brazilian
optimized by particle swarm optimization (PSO) with 20 particles [60]. commercial gasoline. (a) HF-1H NMR spectra where the letters A to F are de-
This procedure is also available in the Gamma routines. scribed in the text. (b) LF-1H NMR spectra.
The 345 acquired spectra were divided into calibration and pre-
diction sets, where 231 samples were used in the calibration step and
3. Results and discussion
114 in the prediction step, representing 67% and 33% of the whole
sample set, respectively. Such division was performed by the Kennard
Fig. 1a and 1b show the HF-1H NMR and LF-1H NMR spectra of
Stone algorithm [61], also available in Gamma routines.
regular, additive-containing, and premium gasoline sold in Brazil.
Thus, part of the collected spectra (from δ = 0.0 to δ = 8.0, re-
In Fig. 1, it is possible to identify different classes of compounds
presenting 4518 points for each spectrum) were applied as X matrix of
present in the mixture, e.g., aliphatics, olefins, and aromatics. Pinto
data and the quality parameters, previously determined by the re-
et al. [3] suggested the subdivision of the gasoline spectrum in aromatic
ference laboratory, as the Y matrix of data.
compounds, δ = 6.7–8.0 (A); olefinic compounds, δ = 4.6–6.5 (B);
For PLS, the autoscaling normalization was performed, while, for
compounds with heteroatoms like oxygen and nitrogen, δ = 3.0–4.5
SVM, normalization by maximum was applied instead. These proce-
(C), α and β protons of aromatic compounds, δ = 2.15–2.8 (D); allylic
dures were performed automatically and performed by a script devel-
compounds, δ = 1.85–2.1 (E) and a mixture of naphthenic and paraf-
oped in Matlab.
finic compounds, δ = 0.5–1.85 (F).
To evaluate the LF-1H NMR application to quality parameters of
In Brazilian gasoline, the heteroatoms region is majorly composed
gasoline fuel, 12 PLS calibration models and 12 SVM calibration models
of the ethanol quartet, because Brazilian gasoline contains approxi-
were built for prediction of specific gravity (Mesp), distillation tem-
mately 27% of ethanol. Its 1H NMR signals are observed at δ = 1.2 for
perature for 10 (T10%), 50 (T50%), and 90 (T90%) percent of re-
the methyl group and δ = 3.7 for the ethylenic group. The hydroxyl
covered, final boiling point (FBP), benzene content (Bz), saturated
group arises at δ = 5.3 in the low-field spectra, due to higher extension
compounds content (Sat), olefinic compounds content (Ole), aromatic
of hydrogen bonds formation once the sample is not diluted in deut-
compounds content (Aro), research octane number (RON), motor oc-
erated chloroform as in high-field spectra, where the hydroxyl protons
tane number (MON), and knock resistance (KR).
peak arises at lower chemical shifts.
The best PLS and SVM calibration models were chosen based on the
Despite the lower resolution of LF-1H NMR spectra, compared to
RMSECV values obtained by leave-one-out cross-validation.
high-field ones, it is still possible to have a satisfactory separation

3
L. Magalhães de Aguiar, et al. Fuel 282 (2020) 118684

between the different chemical groups previously mentioned in the Table 3

spectra, which demonstrates the great potential of applicability of this Comparison between the PLS and SVM methods.
technique for quality control of gasoline fuel. Parameter RMSEPπ RMSEP∑ ASTM Reproducibility
In the low-field spectra, it is also visually easy to distinguish be-
tween regular and additive-containing gasoline from premium one T 50% (°C) 0.2208 0.3505 1.88
T 90% (°C) 1.5548 2.0893 3.97
thanks to the higher percentage of branched-chain paraffin, olefins, and
Ole (%) 1.1048 1.2009 3.13
cyclic hydrocarbons in this type of high-octane fuel. Regular and ad- Aro (%) 0.8863 1.1021 3.7
ditive-containing gasoline fuels are known to have more naphthenic
compounds in their composition [62]. π = PLS.
∑= SVM.

3.1. Multivariate calibration
During the development of PLS and SVM calibration models, the
outlier detection was performed based on data with extreme leverage
and unmodeled residuals in the dependent variable as described in
[44]. A first model was built on an initial calibration set, the outliers
were detected. Later, a second model was built without the identified
outliers, if the new model presented a considerable increase in perfor-
mance, demonstrated by RMSECV, R2cal, and RMSEP values, these
samples were considered outliers. There is not a consensus in the lit-
erature for outlier detection, but the methodology applied in this work
is well recognized by some important works [44,63–65]. In this way, a
total of 12 samples were withdrawn from the original sample set.
Table 2 presents the results found for the PLS and SVM regression
models.
For all PLS and SVM models developed to predict T50%, T90%, Ole,
and Aro, the RMSEP values are lower than the reproducibility values
accepted for the ASTM and NBR reference methods, as shown in
Table 3. Even though the PLS and SVM models, developed to predict the
Mesp parameter, showed RMSEP values higher than the ASTM re-
producibility values (0.0022), they could be used as a good choice for a
fast estimation of this parameter, once these models showed higher
values for the correlation coefficients regarding calibration and pre-
diction.
It is also important to emphasize the high values of R2cal and R2pred
found for these five parameters and the low RMSEP values indicate a
great potential for the application of the LF-1H NMR as a powerful
analytical tool for quality control of commercial gasoline fuel.
Moreover, the calibration models (PLS and SVM) for all these five
parameters showed good accuracy, demonstrated by the elliptical joint
confidence regions test [44], which states that the reference methods
and the PLS and SVM results do not present a significant difference with
95% of confidence.
For the investigated parameters T10%, PFE, Bz, Sat, MON, RON e
IAD, the developed PLS and SVM models have not demonstrated good
performance either in prediction and calibration steps. Such results
were expected due to the poor correlation observed between the LF-1H
NMR spectra and these parameters.
The poor results found for T10%, contradictorily to T50% and
T90%, could be related to the elapsed time between sample collection
and NMR spectrum acquisition, which took more than 30 days. The
evaporation of some high volatile gasoline compounds, which are
strongly related to this parameter, can corroborate the time-dependent
results. For the distillation reference method, the elapsed time between
sample collection and essay does not take more than one day.
Differently, the poor performances of PLS and SVM models applied
to predict PFE, MON, RON e IAD could be related to the low variability
of the sample set, e.g. for the PFE, because the range goes from 178.7 to
229 °C, 82% of the sample set is composed of samples whose values
range from 195 to 205 °C.
Fig. 2 shows the plots of model prediction vs reference values for all
113 prediction gasoline samples evaluated by PLS models developed for
the parameters Mesp, T50%, T90%, Ole, and Aro. It is important to
highlight the higher correlation for prediction and reference values
presented in all plots. In the Supplementary material, one can find the

Table 2
Parameters and figures of merit of all PLS and SVM models.
Parameter LV C γ ε nSV RMSECV RMSEC RMSEP r2cal r2pred Range

π
MEsp (gL ) -1
7 – – – – 1.52 1.23 0.85 0.977 0.981 714.1–753.4
Mesp∑ – 623.8 9.996 0.021 175 1.67 0.97 1.43 0.974 0.984
T10%π(°C) 6 – – – – 0.83 0.74 0.76 0.602 0.489 50.4–57.5
T10%∑ – 696.5 8.432 0.022 216 0.76 0.48 0.76 0.844 0.575
T50%π(°C) 8 – – – – 0.53 0.41 0.22 0.804 0.885 66.1–73.8
T50%∑ – 161.7 135.149 0.011 197 0.44 0.08 0.35 0.993 0.788
T90%π(°C) 7 – – – – 2.90 2.45 1.55 0.944 0.966 110.4–167.2
T90%∑ – 170.6 27.814 0.010 206 2.54 1.44 2.09 0.966 0.972
PFEπ(°C) 9 – – – – 3.28 2.64 2.44 0.769 0.586 178.7–229
PFE∑ – 1335.0 8.881 0.025 178 3.22 1.32 2.90 0.936 0.668
Bzπ(%) 5 – – – – 0.10 0.09 0.13 0.802 0.554 0–1
Bz∑ – 799.3 4.850 0.039 188 0.11 0.08 0.11 0.776 0.861
Satπ(%) 5 – – – – 2.83 2.62 2.26 0.779 0.761 39–72
Sat∑ – 2269.9 2.079 0.096 121 2.79 1.85 2.73 0.821 0.866
Oleπ(%) 7 – – – – 1.37 2.80 1.10 0.871 0.809 0–16
Ole∑ – 988.2 7.424 0.061 167 1.35 0.72 1.20 0.927 0.904
Aroπ(%) 7 – – – – 0.98 0.88 0.89 0.885 0.844 4–19
Aro∑ – 982.3 8.905 0.094 112 1.08 0.67 1.10 0.883 0.889
MONπ(%) 7 – – – – 0.45 0.34 0.35 0.554 0.412 81.2–84.2
MON∑ – 76,397 1.060 0.112 95 0.42 0.21 0.43 0.854 0.127
RONπ(%) 3 – – – – 1.36 1.21 0.60 0.471 0.549 82.7–100
RON∑ – 905.9 2.052 0.053 80 1.22 1.04 0.88 0.591 0.655
IADπ(%) 5 – – – – 0.60 0.52 0.41 0.564 0.398 87–92.1
IAD∑ – 609.2 9.239 0.099 97 0.55 0.30 0.67 0.823 0.485

π = PLS; ∑ = SVM; LV = Number of latent variables; nSV = Number of support vectors; RMSECV = Root mean square error of cross validation; RMSEP = Root
mean square error of prediction; r2cal = Correlation coefficient for calibration; r2pred = Correlation coefficient for prediction.

4
L. Magalhães de Aguiar, et al. Fuel 282 (2020) 118684

Fig. 2. Values predicted by the PLS proposed method vs the reference values determined by the reference methods for the following parameters and all 119
validation samples: Mesp, T50%, T90%, Ole, and Aro.

5
L. Magalhães de Aguiar, et al.
loadings and regression coefficients for all the PLS models.
A comparison between the PLS and SVM methodologies were per-
formed by the dependent t-test for paired samples. For our data, the null
hypothesis was not rejected (p greater than 0.05), that is, there is no
statistically significant difference between the values predicted by the
PLS or SVM models. In this way, both techniques could be used to
predict the Mesp, T50%, T90%, Ole, and Aro in Brazilian gasoline
samples directly from the LF-1H NMR spectra.
4. Conclusion
The LF-NMR spectrometer demonstrated a great potential of appli-
cation to quality control of gasoline due to its satisfactory capability of
fast determination of 5 important (Mesp, T50%, T90%, Ole, and Aro)
parameters of gasoline fuel. From these five parameters, only the Mesp
calibration model presented RMSEP values greater than the suggested
by ASTM reference method applied for the determination of the specific
gravity of gasoline. Nevertheless, the determined RMSEP value for its
parameter is good enough for application as a screening parameter.
PLS, and SVM calibration models showed similar results when ap-
plied to build the calibration models for all studied parameters.
Nowadays in Brazil, fuel adulteration is endemic due to the inability
of the state to promote a routine and efficient police control program in
such a huge country, in terms of area. This government disability is an
opportunity for fuel distributors and final sellers to maximize their
profits by fuel adulteration with lower cost solvents.
Given this, the desktop NMR device with PLS or SVM methods is an
important tool to enlarge the police control activities in gasoline sell.
Once this new method is fast (it takes no more than 10 s to acquire a
LF-1H NMR spectrum), and does not need any pre-treatment of the
sample, it can be easily automated and presents a considerable decrease
of analysis costs, taking into account the physicochemical analysis ap-
plied as reference methods for quality control in gasoline.
CRediT authorship contribution statement
Leticia Magalhães de Aguiar: Conceptualization, Methodology,
Formal analysis. Evandro Bona: Conceptualization, Formal analysis.
Luiz Alberto Colnago: Project administration. Jarbas J. Rodrigues
Rohwedder: Project administration. Mario Henrique M. Killner:
Conceptualization, Visualization, Writing - review & editing.
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
We thank São Paulo Research Foundation (FAPESP) grant number
2014/22126-9 and the Instituto Nacional de Ciências e tecnologias
Analíticas Avançadas (INCTAA) for financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118684.
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