Fuel 236 (2019) 1458–1464

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Full Length Article

Prediction of HEFA content in jet fuel using FTIR and chemometric methods T
b,⁎
a
Dan Vrtiška , Petr Vozka , Veronika Váchová , Pavel Šimáček , Gozdem Kilaz
a a b

a
Department of Petroleum Technology and Alternative Fuels, University of Chemistry and Technology, Prague, Technicka 5, Prague 6 16628, Czech Republic
b
School of Engineering Technology, Fuel Laboratory of Renewable Energy (FLORE), Purdue University, 401 N Grant St., West Lafayette 47907, IN, USA

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: Alternative aviation fuel blending components are becoming a common component in gas turbine engines fuels.
Biojet One of the blending components is Hydroprocessed Esters and Fatty Acids (HEFA). Predictive models based on a
HEFA chemometric processing of FTIR spectra were developed as a reliable method for the determination of HEFA in
Jet fuel petroleum jet fuel/HEFA blends. The concentration of HEFA in blends with jet fuel ranged between 0 and 60 wt
FTIR spectroscopy
%. The sample set composed of calibration and validation subsets. Additionally, several pre-processing techni-
Principal component analysis
ques were evaluated, such as mean centering, variance scaling, derivation, and smoothing. The effectiveness of
Partial least square regression
these models was highly dependent on the model parameters (pre-processing techniques and latent variables).
The most robust model was able to predict HEFA content in all samples with a good predictive ability (root mean
square error of prediction of 0.7 wt%).

1. Introduction those of petroleum-derived aviation fuels [1]. Here it should be noted

In spite of the fact that biofuels have become a common component
in diesel and gasoline in many countries, it is still a problem for aviation
fuels. Use of the conventional biofuels, such as ethanol or fatty acid
methyl esters (FAME, biodiesel), as a replacement of petroleum-derived
aviation fuel, is virtually unthinkable. The conventional biofuels usage
limitation is mostly related to their low calorific value, low stability,
undesirable low-temperature properties, which are poor compared to
that there are two main types of the aviation fuels: spark-ignition en-
gine fuel, aviation gasoline (Avgas) that has similar properties to au-
tomotive gasoline and jet engine kerosene, JET fuel. Jet fuels take on
additional tasks compared to those of other liquid transportation fuels
such as being the hydraulic fluid and the cooling medium. Hence,
stringent regulations are imposed on aviation fuels and their safety [2].
The approval process (ASTM D4054) for a candidate jet fuel is very
challenging, taking up to 5 years, and costing up to $10 million [3]. As

⁎
Corresponding author.
E-mail addresses: vrtiskad@vscht.cz (D. Vrtiška), pvozka@purdue.edu (P. Vozka), vachovav@vscht.cz (V. Váchová), simacekp@vscht.cz (P. Šimáček),
gkilaz@purdue.edu (G. Kilaz).

https://doi.org/10.1016/j.fuel.2018.09.102
Received 27 June 2018; Received in revised form 7 September 2018; Accepted 22 September 2018
Available online 29 September 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
D. Vrtiška et al.
of this writing, five alternative aviation blending components have been
approved in varying ratios: Fischer-Tropsch Hydroprocessed Synthe-
sized Paraffinic Kerosine (FT-SPK), Synthesized Paraffinic Kerosine
from Hydroprocessed Esters and Fatty Acids (HEFA), Synthesized Iso-
Paraffins from Hydroprocessed Fermented Sugars (SIP), Synthesized
Kerosine with Aromatics Derived by Alkylation of Light Aromatics from
Non-Petroleum Sources (SPK/A), and Alcohol-to-Jet Synthetic Paraf-
finic Kerosene (ATJ) [4]. None of these components, except SPK/A in
Europe, can be utilized as neat (100%) drop-in replacement for jet fuel
in current gas turbine engines due to their property limitations. These
alternative blending components have no aromatic content (except
SPK/A), which results in a lower density and propensity to swell o-ring
seals compared to petroleum-based aviation fuel. This issue was miti-
gated by adding a minimum limit value of 8 vol.% for aromatics into
ASTM D7566. Minimum aromatics level was established based on
current experience with the approved alternative fuel blending com-
ponents [4]. The research on the actual need for aromatic compounds
in the fuel is currently ongoing. Consequently, further blending with
petroleum-derived jet fuels is required for deploying biofuels and other
alternative fuels in air transportation. Here it should be noted that the
term “alternative fuels” implies all fuels produced from feedstocks other
than the petroleum (e.g. coal or natural gas), while “biofuels” refers to
fuels produced from only biomass (e.g. vegetable oils). The alternative
jet fuels mentioned above thus need not be simultaneously renewable
fuels. Hence, biofuels are a renewable subset of alternative fuels.
One of the alternative fuel blending components is Hydroprocessed
Esters and Fatty Acids (HEFA). HEFA in kerosene distillate range is
known as Hydroprocessed Renewable Jet (HRJ) and in diesel distillate
range it is referred to as Hydrotreated Vegetable Oils (HVO) or Green
diesel, in spite of the fact that they can be also made from animal fats.
HEFA is produced by hydroprocessing the vegetable oils and/or animal
fats. Biofuel production; including that of HEFA is still relatively ex-
pensive compared to the process for petroleum-derived fuels. However,
currently, it is one of the few options to effectively reduce the green-
house gas emissions from air transportation. Therefore, HEFA is widely
utilized [5]. There is a current need for a practical and affordable
method for the HEFA content determination in HEFA/jet fuel blends for
various reasons. One reason is to check compliance with the specifi-
cation requirement (blends with petroleum-derived fuels up to 50 vol.%
via ASTM D7566). Another reason is to be able to enable a reliable
supplier-end user relationship while establishing a technique for control
by the state authorities.
HEFA is mainly composed of n- and iso-paraffins in the range of
C8–C16. Although HEFA does not contain aromatics, its chemical com-
position is very similar to that of Jet A/A-1; therefore, it is very chal-
lenging to determine the exact amount of HEFA in blends with Jet A/A-
1. One such method is the ASTM D6866 standard test method. This
method, either using liquid scintillation counting (LSC) or accelerated
mass spectrometry, is based on quantifying the amount of radiocarbon
C14, which is only found in biofuels [6]. However, this method is highly
time-consuming, cost-intensive, and biofuel type agnostic. Although
some researchers simplified the radiocarbon analysis, like direct LSC
development [7,8], this method is rarely utilized. Simultaneously,
quantification of paraffinic renewable fuels in mixtures with petroleum-
based diesel were studied [9–13]. Both studies were utilizing near-in-
frared (NIR) spectroscopy combined with chemometric methods. These
techniques were reported to produce very accurate results. The utili-
zation of NIR spectroscopy for the determination of HEFA content in jet
fuels was first introduced in 2017 by Terra et al. [14]. Results from this
study were within a similar accuracy to those from ASTM D6866.
The first study published on the prediction of HVO content in HVO/
diesel blends using mid-infrared (MIR) spectroscopy can be found in
recent work [15]. The scope of this study was a development of pre-
dictive models based on multivariate calibration of spectral data. The
procedure using FTIR spectra and partial least square (PLS) regression
was shown to enable a very accurate quantification of HVO in HVO/
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Fuel 236 (2019) 1458–1464
Table 1
Fuel samples together with their origin and manufacturer.
Sample Fuel Origin Manufacturer/Supplier
J1 Jet A-1 petroleum-based Unipetrol, a.s., Czech Republic
J2 Jet A-1 petroleum-based Twin Trans, s.r.o, Czech Republic
J3 Jet A petroleum-based Shell, USA
J4 Jet A petroleum-based Exxon Mobil, USA
H1 HEFA camelina UOP, USA
H2 HEFA tallow UOP, USA
H3 HEFA mixed fats Dynamic Fuels, USA
diesel blends. Nevertheless, the predictive models were very sensitive to
the preprocessing techniques applied to the spectral data. This issue
was mainly attributed to the variability of the chemical composition of
the samples used for the model calibration and validation. The biggest
hurdle to overcome in the future is developing the predictive models
that are independent or less dependent on spectra preprocessing.
The aim of this work was the development of HEFA quantification
method for HEFA/jet fuel blends. MIR spectra, PLS regression, and si-
multaneous spectra preprocessing were employed for this purpose.
2. Materials and methods
2.1. Samples
Jet fuel and HEFA samples utilized in this study are listed in Table 1.
Samples J3, J4, H1, H2, and H3 were provided by the Wright-Patterson
Air Force Base, Dayton, Ohio, while samples J1 and J2 were provided
directly by manufacturer/supplier mentioned in Table 1.
Selected parameters and properties of all samples utilized are dis-
played in Table 2. Several HEFA sample properties such as flash point,
freezing point, and distillation profile were similar to those of petro-
leum-derived jet fuel samples. On the other hand, HEFA samples had
lower density and higher hydrogen content, kinematic viscosity, and
net heat of combustion. This can be contributed to their chemical
composition. HEFA samples were composed of iso-paraffins and n-
paraffins, cycloparaffins content was very low and the content of aro-
matics was negligible.
The entire sample set utilized in this study was composed of 85
samples. Four samples of petroleum-derived jet fuel (J1-J4) and three
samples of HEFA (H1-H3) were used in the preparation of 78 blends.
Additionally, neat samples of petroleum-derived jet fuel and HEFA were
tested. HEFA content in the blends varied within the range of 1–60 wt
%. The ratios of the blends were provided in weight percentage values
as this parameter does not fluctuate with temperature as opposed to the
volume percentage. Six subsets, designated as C, H, R, X, Y, and Z were
prepared. Subsets C, H, and R were composed of 6 samples each, while
subsets X, Y, and Z were composed of 20 samples. An overview of the
subset compositions and HEFA content distribution in the subsets is
shown in Fig. 1.
2.2. Instrumentation, software and methods
FTIR spectrometer IRAffinity-1S (Shimadzu Corporation, Japan)
with LabSolution IR software (Shimadzu Corporation, Japan) was uti-
lized for recording FTIR spectra of all samples. The spectra were mea-
sured in the wavenumber range of 4000–650 cm−1 and with a spectral
resolution of 2 cm−1. FTIR transmission technique utilizing liquid
transmission cell (International Crystal Laboratories, USA) was em-
ployed. The cell windows were composed of ZnSe. The cell optical
pathlength was 0.1053 mm. The models for prediction of HEFA content
in jet fuel were developed in TQ Analyst 8 (Thermo Fisher Scientific
Inc., USA).
Two chemometric methods were utilized for processing the spectral
data: principal component analysis (PCA) was carried out in order to
D. Vrtiška et al. Fuel 236 (2019) 1458–1464

Table 2
Properties of neat jet fuel samples.
Parameter Method Neat jet fuel samples

J1 J2 J3 J4 H1 H2 H3

a
n-Paraffins (wt%) GC × GC-FID 23.4 22.8 21.5 21.0 8.5 8.9 10.1
iso-Paraffins (wt%) GC × GC-FIDa 27.5 32.1 33.1 30.6 89.7 90.5 88.5
Cycloparaffins (wt %) GC × GC-FIDa 28.4 27.5 27.6 24.4 1.7 0.6 1.4
Aromatics (wt%) GC × GC-FIDa 20.7 17.6 17.8 24.0 0.03 0.01 0.02
Hydrogen content (wt%) ASTM D7171 14.0 14.2 14.1 13.8 15.4 15.4 15.1
Density at 15 °C (kg·m−3) ASTM D4052 802.5 792.9 804.0 805.7 759.8 757.3 761.2
Kin. viscosity at −20 °C (mm2·s−1) ASTM D7042 3.8 3.2 4.7 3.8 5.2 5.0 5.6
Freezing point (°C) ASTM D2386 −54 −63 −50 −51 −55 −59 −49
Flash point (°C) ASTM D56 50 42 48 43.0 42.5 52.5 41.5
Net heat of combustion (MJ·kg−1) ASTM D4809 43.3 43.3 43.3 43.1 44.0 44.2 44.2
Distillation temperature: ASTM D86
10 vol.% recovery (°C) 179 170 176 170 161 173 179
50 vol.% recovery (°C) 196 186 204 197 214 210 222
90 vol.% recovery (°C) 219 216 245 248 269 242 257
Final boiling point (°C) 233 243 269 266 281 254 273

a
GC × GC-FID parameters can be found in [16].

X (J1-H1) Y (J2-H1) Z (J3-H1)
C (J4-H1) H (J4-H2) R (J4-H3)
0 10 20 30 40 50
HEFA content (wt. %)
Fig. 1. Overview of the subset compositions.
investigate the relationship between neat jet fuel samples and the
blends and partial least square regression (PLS) was employed to de-
velop models for the quantification of HEFA in blends.
PCA is an exploratory data analysis with the main goal of variable
number reduction or data compression. For each data matrix composed
of m rows (samples) and n columns (variables), each row vector (e.g.
FTIR spectrum) can be plotted in the n-coordinate system as a single
point. PCA replaces the original coordinate system by one composed of
principal components (PC). The direction of the first new variable (PC1)
is adjusted so that it captures the largest part of the data variability.
Since PCA aims to capture the highest data variability with the lowest
number of the variables possible, every other PC captures the largest
part of the remaining variability. All PCs are obtained as linear com-
binations of the original variables and are mutually orthogonal (linearly
uncorrelated). Every sample can then be plotted in the new coordinate
system formed by PCs. The position of the samples in the new co-
ordinate system is given by their score value [17–20].
PLS is a widely used method of multivariate calibration. Although
this method is also composed of data compression to the new variables,
these variables, called factors or latent variables, are calculated dif-
ferently than in the PCA. Unlike PCA, PLS is working with two data
matrices (e.g. spectral data and concentrations). The latent variables
are obtained by maximizing the covariance between both matrices,
which means that these variables are more closely related to the matrix
with concentrations than in the regression method based on PCs, which
is called principal components regression [18–21].
In addition to the two above-mentioned chemometric methods,
several techniques of spectra preprocessing (mean centering, variance
scaling, derivation, and smoothing) were also employed and an optimal
combination was sought.
Mean centering is a preprocessing tool that subtracts the average
from each variable (e.g. absorbance). This operation modified relative
differences in the value of each affected variable so a better distinction
of the spectra can be observed [18,19]. When variance scaling is uti-
lized, each variable is divided by the value of its standard deviation.
Since the scale of the variables is unified, even the variables with the
low signal intensity achieve similar significance such as the variables
with the high intensity of their signal [18,19]. Derivation of the spectra
and using of their first or second derivative is commonly utilized pre-
processing tool for spectral scatter reduction which uncovers or high-
60 light feebly detectable and overlapped peaks. However, since spectral
derivation usually decreases the overall signal intensity and S/N ratio,
due to the nature of derivatives calculation, it is highly encouraged to
include data smoothing method [18,20,21]. Savitzky-Golay (S-G)
smoothing technique is an effective method used for infrared spectra
preprocessing [22]. During the S-G smoothing, the data within the
smoothed frame are interlaced by a suitable polynomial function at the
bases of the least squares method. A number of S-G smoothing para-
meters combinations (i.e., second, third, fourth, fifth, polynomial order
and width of the smoothed frame) allows obtaining numerous models.
A separate data smoothing technique, a method developed by Karl H.
Norris, is called Gap-Segment (G-S) derivative [23]. In the course of G-S
derivative, averages of variables within two segments (width is given by
a number of variables) are acquired. When the difference between these
two averages is utilized for spectra derivation, a less noisy curve is
obtained. Utilization of this smoothing technique offers many para-
meters combinations such as the width of the smoothed segment and
the size of the space of segments of the smoothed points.
Except for the spectral data preprocessing techniques briefly de-
scribed above, the number of latent variables used for the PLS model
development is another important parameter of PLS models [24]. The
most widespread procedure used to generate the optimal number of
latent variables is called cross-validation (CV); however, utilization of

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the external validation procedure provides more meaningful results, for 1.5
example as demonstrated in [15,19]. The validation procedure based H-J blend
on the CV uses just the calibration standards, an independent validation JET J1

PC2 score (5.8 % of variance)

set is utilized throughout the external validation [19]. The external HEFA
validation procedure was applied in this work to find the optimal J3
number of the latent variables. The choice of the number of the latent
variables is based on low values of root mean square error of prediction
1.3
(RMSEP). Nonetheless, leave-one-out (LOO) cross-validation was uti-
lized for comparison. One standard was omitted during each run of CV
while others were utilized for the calibration [19]. The values of RMSEP
cross-validation (RMSECV) were calculated for the standards left out.
RMSEP and RMSECV were used for evaluating the quality of the pre- 1.1 J4
dictive models. Computation of RMSE parameters was based on Eq. (1):

N
∑i = 1 (yp, i −ym, i )2
RMSE =
N (1)
J2
where N is the number of observations (number of samples), yp,i is 0.9
predicted the value of i-th observation and ym,i is a measured value of i- -9.5 -8.6 -7.7 -6.8 -5.9
th observation. The average difference between the actual and pre-
dicted values of the property of interest is given by the two RMSE PC1 score (89.5 % of variance)
parameters whose units are the same with the property being studied. Fig. 3. PCA score plot (PC1 vs. PC2) of spectral data.

3. Results and discussion
3.1. FTIR spectra
The recorded FTIR spectra of neat jet fuel samples (4 petroleum-
derived jet fuels and 3 HEFA jet fuels) are shown in Fig. 2. It is shown
that the spectra of the HEFA jet fuels (−) are different from those of the
petroleum-derived jet fuels (−). Although the FTIR spectra of the
samples were measured in the range of 4000–650 cm−1, only two
narrower regions (a: 1633–1579 cm−1 and b: 1348–678 cm−1) were
used for further development of the models. The rest of the spectral
data was considered as irrelevant and was removed, especially due to
the too strong absorbance caused by CeH stretching vibrations in the
region of 3000–2800 cm−1 and CeH deformation vibrations in the re-
gion of 1480–1370 cm−1. Petroleum-derived jet fuels spectra contained
more bands than the spectra of HEFA jet fuel. These bands can be
attributed mainly to stretching of eC]Ce (Fig. 2a) and both in-plane
and out-of-plane deformation vibrations of C]CeH groups (Fig. 2b),
which occur in the ring structure of aromatic hydrocarbons [25]. Ske-
letal vibrations of CeC groups and deformation vibrations of CeH
groups can be observed in Fig. 2b for petroleum-derived fuels as well as
for HEFA samples.
3.2. Principal component analysis (PCA)
The spectra of all samples utilized in this work served as input data
for the PCA. As mentioned above, only two narrower spectral regions
were used for the further processing. No preprocessing techniques were
applied to the spectral data before PCA. Score plot of the first two
principal components is shown in Fig. 3. These two principal compo-
nents captured 95.3% of spectra variance. All three samples of HEFA

1.0
a b

0.8
Absorbance (a.u.)

0.6

0.4

0.2
1633 1620 1606 1593 1579 1348 1214 1080 946 812 678
Wavenumber (cm-1) Wavenumber (cm-1)
Fig. 2. Two selected spectral regions used for the chemometric processing; spectra of HEFA jet fuels (−) and petroleum-derived jet fuels (−).

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were located very close to each other on the left side of the plot. This Table 4
was simply an indication of their similarity. On the other hand, the Models parameters and results of the PLS models development.
samples of the petroleum-derived jet fuels were scattered on the right Model PLS-1 PLS-2 PLS-3 PLS-4 PLS-5
side of the plot. It means that the first principal component captured
sufficient spectral information to create separate clusters of HEFA fuel Number of latent variables 10 13 10 11 10
Preprocessing technique MCa – – – –
and petroleum-derived jet fuel which is in compliance with the results
Spectrum formatb S 2D 2D 2D 2D
obtained in the previous study where PCA of HVO fuel and diesel fuel Method of smoothingc,d S-G S-G S-G G-S G-S
spectra was presented [15]. It should be noted here that the distances Parameters of smoothingc,d 17–4 17–4 21–4 5–0 1–5
between petroleum-derived jet fuel sample points were higher than RMSECV (wt%) 0.08 0.21 0.17 0.15 0.16
those of HEFA. This indicated that petroleum-derived jet fuel chemical RMSEP (wt%) 0.03 0.18 0.54 0.12 0.70

composition was more complex than that of HEFA. As expected, H-J a

blend sample points were situated between the neat jet fuel sample
points. The position of the blend sample points varied according to the
HEFA content in the blends. The samples with the lowest HEFA content
were situated close to the neat petroleum-derived jet fuel sample points.
Increasing HEFA content in the blended samples is reflected by moving
the points position closer to the neat HEFA sample points. Although it
can be expected that similar results will be obtained for every PCA of
such samples, the real points separation and distribution in the plots
will always depend on input data (samples composition, measurement
method, and parameters, etc.).
3.3. Predictive models development
The predictive models for HEFA content determination in HEFA/jet
fuel blends were developed using PLS regression. Two data matrices
were used as input data. One composed of FTIR spectra of neat petro-
leum-based jet fuel samples and HEFA/jet fuel blends, reduced by ir-
relevant spectral regions (see Section 3.1). The second one composed of
HEFA contents in the samples. Four models were further developed:
PLS-1, PLS-2, PLS-3, and PLS-4 to evaluate the effectiveness of the
model to predict HEFA content in the HEFA/jet fuel blends. The PLS-1
model was developed in order to evaluate its ability to predict HEFA
content in the blends when validation samples were composed of the
same components as the calibration samples used for the model de-
velopment. The PLS-2 model evaluated the predictive ability when the
validation samples were blended from jet fuel different from the jet fuel
used for the calibration samples preparation. In PLS-2, both calibration
and validation sets were blended using the same HEFA fuel. The PLS-3
and PLS-4 models were developed in order to evaluate the effectiveness
when validation set was composed of both jet fuel and HEFA fuel dif-
ferent from the samples used for the calibration set preparation. An
additional model was developed, designated as PLS-5, which utilized
the validation subsets C, H, and R simultaneously in order to develop a
much more robust model (i.e. less dependent on model parameters). An
overview of the samples subsets distributions in the validation and sets
used for the model development is shown in Table 3.
The main goal of the model development was to choose a suitable
combination of the preprocessing techniques and the number of latent
variables. Hundreds of models were developed for this purpose, each
utilizing a unique combination of the model parameters (preprocessing
techniques and number of latent variables). Mean centering, variance
scaling, derivation, and Savitzky-Golay smoothing or Gap-Segment
derivative were utilized to spectra preprocessing during the models
Table 3
Sample subset distribution in the calibration and validation sets.
Model Samples
Calibration Number Validation Number
PLS-1 Selection of X, Y, Z 42 Selection of X, Y, Z 21
PLS-2 X, Y, Z 63 C 6
PLS-3 X, Y, Z 63 H 6
PLS-4 X, Y, Z 63 R 6
PLS-5 X, Y, Z 63 C, H, R 18
MC – mean centering.
b
S – spectrum, 2D – second derivative.
c
S-G – Savitzky-Golay smoothing (parameters of smoothing correspond to
the data points and polynomial order, respectively).
d
G-S – Gap-Segment derivative (parameters of smoothing correspond to the
segment length and gap between the segments, respectively).
development. Since the models should be able to predict HEFA content
in both calibration and validations samples, the effectiveness of the
models was evaluated using both RMSECV and RMSEP. RMSECV values
were very low for all models and only slightly dependent on the models
parameters. Since RMSEP values showed more variability; thus higher
dependence on the models parameters, the RMSEP values were used as
the indicative parameter for the model efficiency comparison.
As mentioned above, the first model (PLS-1) was developed using
merely subsets X, Y, and Z divided to the calibration and validation sets.
As expected, the model showed very good predictive ability even
without using any spectra preprocessing. Nevertheless, the application
of the preprocessing techniques slightly reduced RMSEP values. The
lowest RMSEP value was obtained using mean centered spectra
smoothed by Savitzky-Golay smoothing and 10 latent variables. The
model parameters and results of the model development are summar-
ized in Table 4. It can be noticed, that both the RMSECV and RMSEP
values were lower than 0.1 wt% which indicated a good accuracy of
HEFA content prediction. It is worth mentioning here that this good
predictive ability of the model was achieved by the arrangement of the
calibration and validation sets. Since the validation set was composed
of samples blended from the same neat jet fuel samples as the samples
in the calibration set, the model was trained for the spectral features of
the validation samples. Distribution of differences (prediction errors)
between the calculated and actual HEFA content in both calibration and
validation sets is shown in Fig. 4a. It can be observed that no significant
trend or outlying values occurred.
Models PLS-2, PLS-3, and PLS-4 were validated by the samples
blended from at least one neat jet fuel unknown for the model, which
led to higher RMSEP values. The calibration set was the same for all
three models (see Table 3). The models parameters and results of their
development are also displayed in Table 4. Although a lot of models
parameters combinations were tested, the data presented in the table
belongs only to the models with the lowest RMSEP values. The lowest
RMSEP values for all models were obtained using a combination of
different preprocessing techniques. Although the best results of all three
models were obtained using uncentered and unscaled second derivative
spectra, smoothing method and its parameters utilized were different.
The number of latent variables used for the models development dif-
fered as well. The differences between the used preprocessing techni-
ques and the number of latent variables indicated that their proper
combination was dependent on variability among the validation sets.
That is, each validation set required a different combination of pre-
processing techniques and the number of latent variables. This was in a
good agreement with the conclusion of the previous study [15]. Dis-
tributions of prediction errors among both calibration and validation
sets for PLS-2, PLS-3, and PLS-4 models are displayed in Fig. 4b–d,
respectively. While the distribution of validation samples prediction
errors for PLS-2 and PLS-4 models (Fig. 4b and d) is similar to the

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0.14 1.2
Calibration Validation Calibration Validation

Calculation error (wt. %)

Calculation error (wt. %)
0.07 0.6

0 0

-0.07 -0.6

a c
-0.14 -1.2
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Actual HEFA content (wt. %) Actual HEFA content (wt. %)
0.5 0.4
Calibration Validation b d Calibration Validation
Calculation error (wt. %)

Calculation error (wt. %)

0.25 0.2

0 0

-0.25 -0.2

-0.5 -0.4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Actual HEFA content (wt. %) Actual HEFA content (wt. %)
Fig. 4. Prediction errors between the calculated and actual HEFA content for models PLS-1 (a), PLS-2 (b), PLS-3 (c) and PLS-4 (d).

distribution of the calibration samples, PLS-3 model validation samples
prediction errors showed a different trend. The prediction errors in-
creased with increasing HEFA content in the samples, except for two
validation samples with the lowest HEFA content. The highest error was
observed for the validation sample with the highest HEFA content,
which led to the high RMSEP value of this model.
The PLS-5 model was developed via simultaneously utilizing all
three subsets used for the validation of PLS-2, PLS-3, and PLS-4 models.
The lowest RMSEP value of PLS-5 was obtained using second derivative
spectra smoothed by a Gap-Segment method. The model parameters
and results are shown in Table 4. Although the RMSEP value was higher
than those of PLS-2, PLS-3, and PLS-4 models, the robustness of this
model was higher as, unlike the previous models, this model was able to
predict HEFA content in all three validation subsets at once and with
good predictive ability. Distribution of prediction errors within the
entire range of calibration and validation samples is shown in Fig. 5. As
expected, prediction errors of the validation samples were higher than
those of the calibration samples. Although the model is able to predict
HEFA content in HEFA/jet fuel blends accurately, the variability of the
validation sample chemical composition (mainly caused by variability
of petroleum-derived jet fuel samples) is responsible for the lower ef-
fectiveness of the model to predict HEFA content in validation samples
compare to calibration samples.
4. Conclusion
In this study, chemometric methods were utilized to develop a
method for prediction of Hydroprocessed Esters and Fatty Acids (HEFA)
content in HEFA/petroleum-based jet fuel blends. The principal com-
ponent analysis was used for investigating the variability in sample
chemical compositions of HEFA and petroleum-derived jet fuels.
Although the HEFA samples utilized in this study were produced from a
different feedstock, their chemical composition was less complex than
those of the petroleum-derived jet fuel samples. Partial least squares
regression was utilized in order to develop predictive models for HEFA
content quantification in HEFA/jet fuel blends. The model that was
calibrated and validated using samples blended from the same neat jet
fuel samples showed very good predictive ability and negligible de-
pendence on the preprocessing technique. RMSEP of this model was
0.03 wt%. Predictive ability of the models validated by samples in-
dependent on the calibration samples was satisfactory as well.
Nevertheless, the effectiveness of these models was highly dependent
on the model parameters. When the models were validated by different
sample subsets, each of those required unique combination of model
parameters. Last model (PLS-5) was developed in order to create a ro-
bust model, whose predictive ability will be less dependent on model
parameters. Although RMSEP of this model was higher (0.7 wt%) than
the preceding ones, the model PLS-5 has a good predictive ability of the
HEFA content in all samples. This indicated the high robustness of this
model.
Although the multivariate calibration of spectral data, either NIR or
MIR, can be utilized for the quantification of HEFA content in blends
with petroleum-based jet fuel, it is necessary to take into consideration
the inconsistency of chemical composition of both fuels. The incon-
sistency is responsible for the variability of the models prediction effi-
ciency. Future steps in mitigating the challenges of HEFA content pre-
diction in jet fuels via FTIR and chemometrics will focus on the
extension of the calibration set by other independent samples. This is
predicted to reduce the dependence on model parameters, which would
enable increase practical applications of this method.
Acknowledgements
This work was supported by the National Program of Sustainability
(NPU I LO1613, MSMT-43760/2015) and specific university research
(MSMT No 21-SVV/2018). Our special thanks extended to Dr. James

1463
D. Vrtiška et al.
1.6
Calibration
0.8
Calculation error (wt. %)
-0.8
-1.6
0 10 20
Actual HEFA content (wt. %)
Fig. 5. Prediction errors between the calculated and actual HEFA content within the entire range of calibration and validation samples (model PLS-5).
Edwards for providing the fuel samples.
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