Fuel Processing Technology 183 (2019) 1–7

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Fuel Processing Technology

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

Research article

Evaluation of molecular spectroscopy for predicting oxidative degradation T

of biodiesel and vegetable oil: Correlation analysis between acid value and
UV–Vis absorbance and fluorescence
José N. Conceiçãoa, Bruno S. Marangonib, Flávio S. Michelsa,b, Ivan P. Oliveirac,
⁎
Wilson E. Passosa, Magno A.G. Trindadea, Samuel L. Oliveirab, Anderson R.L. Cairesb,
a
Faculdade de Ciências Exatas e Tecnologia, Universidade Federal da Grande Dourados, CP 533, 79804-970 Dourados, MS, Brazil
b
Grupo de Óptica e Fotônica, Instituto de Física, Universidade Federal de Mato Grosso do Sul, CP 549, 79070-900 Campo Grande, MS, Brazil
c
Instituto de Ciências Biomédicas, Universidade de São Paulo, 05508-900 São Paulo, SP, Brazil

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

Keywords: The present study evaluated the applicability of UV–Vis absorption and fluorescence spectroscopy for monitoring
Biodiesel oxidation level of oil extracted from white sesame seeds (Sesamum indicum L.) and its respective biodiesel de-
Vegetable oil graded at 110 °C for various times. Correlations between spectroscopic data and acid value of the samples de-
Oxidative stability monstrated that both optical techniques could be used to monitor the oxidative degradation. Additionally, a
Optical spectroscopy
quantitative model to predict the acid value of oil and biodiesel using the UV–Vis absorption data was proposed.
Acid value
The prediction model was tested using a cross-validation (leave-one-out) analysis and demonstrated, for the first
time, that the acid value of both biodiesel and vegetable oil can be predicted by applying the same protocol for
UV–Vis spectra analysis. An average error of about 3 and 8% was achieved for the predicted acid value of the oil
and biodiesel samples with respect to the measured acid values, respectively. Therefore, UV–Vis absorption
technique could be applied to quantitatively monitor the oxidative degradation of vegetable oil and biodiesel in
a rapid and practical way.

1. Introduction induction time related to a given sample submitted to accelerated

The importance of vegetable oils and their use as biodiesel feedstock
has grown considerably in the global energy scenario. Biodiesel re-
presents an alternative renewable source to the fossil diesel, con-
tributing to minimize the increased pollution caused by fossil fuels, for
example [1–4]. Despite the environmental advantages, biodiesel is very
susceptible to oxidation because of the unsaturation (carbon‑carbon
double bonds) present in the fatty acid carbon chain [5]. Further,
during the handling, transportation and/or storage period, the oxida-
tion process may be accelerated by several factors such as high tem-
perature, ultraviolet light illumination, metal contaminants, and water
presence [5–12]. For instance, the biodiesel stability is strongly de-
pendent on metal content which acts as potent catalysts to accelerate
the oxidation of biodiesel [6,7]. Additionally, the biodiesel degradation
induced by microbial contamination is another issue and it is closely
related to the water content [13,14].
The oxidative stability of biodiesel and vegetable oils is con-
ventionally assessed by Rancimat® analysis that provides the typical
oxidation [15]. Despite the induction period be the most used para-
meter to evaluate oil and biodiesel stability [16–18], physico-chemical
properties, such as acid value [19], peroxide index [20], density, and
viscosity can be applied for the same purpose [20–23]. Additionally,
UV–Vis and fluorescence approaches have been recently reported as
alternative methods for evaluating the oxidative stability of vegetable
oils and biodiesels [24–32]. Magalhães et al. used UV–Vis spectroscopy
to monitor stages of the biodiesel oxidation by measuring the absor-
bance at 232, 270, 300, and 315 nm, revealing the formation of con-
jugated dienes, trienes, and tetraenes as well as other degradation
products [30]. Fan and Krahl demonstrated that the fluorescence sig-
nals of the oxidation products (such as hydroperoxides and oligomers)
could be used to assess the oxidation stability of rapeseed biodiesel
[28]. In turn, Silva et al. demonstrated that fluorescence and absorption
techniques could be employed to evaluate Baru oil oxidation by ana-
lyzing the carotenoid and chlorophyll degradations [24]. UV–Vis ab-
sorption changes during the sample oxidation can be understood by
means of the reactions involving double bond conjugation in

⁎
Corresponding author.
E-mail address: anderson.caires@ufms.br (A.R.L. Caires).

https://doi.org/10.1016/j.fuproc.2018.10.022
Received 23 August 2018; Received in revised form 24 October 2018; Accepted 25 October 2018
Available online 04 November 2018
0378-3820/ © 2018 Elsevier B.V. All rights reserved.
J.N. Conceição et al.
unsaturated fatty acids as discussed [33], highlighting that the oxygen
triplet reactions in the allylic sites of the carbon chains lead to the
formation of radical peroxides and carbonyl compounds [33,34].
Otherwise, the oxidation process can also be assessed by analyzing the
fluorescence response of natural antioxidants (vitamin E, carotenoids,
chlorophylls, etc.) and oxidation products (conjugated tetraenes, oli-
gomers, etc.) [28–30].
In addition, optical analysis of diesel and biodiesel can be performed
using different experimental setups with the aid of bench or portable
instruments capable to examine either diluted samples or samples
without any preparation (non-diluted) [29,32,35–37]. The need for the
sample pre-preparation depends on the chromophore and/or fluor-
ophore to be analyzed as well as on the optical experimental setup. In
most cases, a proper optical analysis of petrodiesel and biodiesel re-
quires a sample dilution to avoid saturation of UV–Vis absorption and
inner-filter effects during fluorescence measurements [29,35]. How-
ever, direct sample examination may be performed in standard quartz
cells by measuring the steady-state fluorescence or time-resolved
fluorescence using the front-face geometry setups when excitation and
emission signal is provided either in an optical arm of spectro-
photometer [36] or with the help of a Y-type fiber [32] as well as when
the head of measurement set-up is modified and fuel sample is ex-
amined in capillary [37]. In a recent study, it was demonstrated that
thermal degradation of fatty acid methyl esters (biodiesel) can be po-
tentially monitored by optical measurements, associating the UV–Vis
absorption and fluorescence with the acid value of the degraded bio-
diesel samples [38]. Nonetheless, there is still a lack of a prediction
model for quantifying the acid value of both biodiesel and vegetable oil
by means of the optical measurements.
In this work, oxidative stability of white sesame (Sesamum indicum
L.) oil and biodiesel was investigated by acid value, Rancimat, UV–Vis
absorption, and fluorescence measurements. Correlations between acid
value and absorbance and fluorescence data of the samples submitted to
heating at 110 °C for different times were investigated. Finally, a pre-
diction model for determining the acid value using UV–Vis absorption
data was proposed and tested by cross validation.
2. Materials and methods
2.1. Oil extraction and biodiesel production
White sesame (Sesamum indicum L.) seeds were obtained from a
local supplier. The seeds were dried at 110 °C for 48 h using an oven
with air circulation at atmospheric pressure (Sterilifer®, SX CR 42,
Brazil). Then, the white sesame oil (WSO) was obtained by cold
pressing method using a mini press (Ecirtec®, MPE-50F AC, Brazil) and
filtered on a Buchner funnel containing filter paper (Unifil®, Brazil)
with pore size of 26–44 μm, thickness of 500 μm, and base weight of
80 g/m2. The filtration was performed under 200-mm Hg pressure
provided by a vacuum pump (Marconi®, MA 059, Brazil). WSO was
used to produce white sesame biodiesel (WSB) via transesterification.
For biodiesel production, 250 g of WSO, 83 g of methanol (CH3OH), and
5.0 g of catalyst potassium hydroxide (KOH) were added in a beaker on
a stirring plate. The solution was stirred for 2 h at 50 °C and then
transferred to a separating funnel, staying for about 24 h. In the end,
two phases were observed, the glycerin at the bottom of the funnel and
WSB at the top. To eliminate polar compound traces (KOH, glycerol,
etc.), WSB was washed three times with distilled water (6.6% v/v).
Subsequently, it was washed twice with a saturated solution of sodium
chloride (NaCl) (6.6% v/v). The washes were done at room tempera-
ture. The interval between the washes was 30 min. Finally, WSB was
filtered through filter paper in the presence of magnesium sulfate
(MgSO4), and then rotary evaporated at 60 °C during 1 h to remove any
solvent trace. All chemicals used were analytical grade.
2
Fuel Processing Technology 183 (2019) 1–7
2.2. Fatty acids composition
Fatty acid methyl ester (FAME) composition of the WSO was de-
termined by gas chromatography (GC) according to the AOCS Official
Method Ce 2–66, in a GC-2012 Plus (Shimadzu®) with a fused silica SP-
2560 column of 100 m and 0.25 mm, using He as carrier gas. The
temperature was set up at 140 °C for 5 min followed by heating rate of
4 °C min−1 up to 240 °C, resting at this level for 30 min. The vaporizer
and detector temperatures were 250 and 260 °C, respectively. The
analyses were done in triplicate, and results were expressed in percent
based on the internal normalization of the peak areas.
2.3. Accelerated sample degradation
Oxidative stability of WSO and WSB was evaluated by determining
the induction period via Rancimat® method (model 893, Metrohm®).
The analyses were performed by heating 3.0 g of the target samples at
110 °C under an air flow rate of 10 L·h−1, according to European
standard (EN 14112) [18]. WSO and WSB were also thermally degraded
in a laboratory oven with air circulation (Sterilifer® SXCR42) for a
period of 0 to 48 h at the same temperature employed in Rancimat®
method (110 °C). Fifteen aliquots of 5 mL of the samples were initially
introduced in the oven so that one aliquot was taken out of the oven
every hour during the first 12 h, and then the last two aliquots were
collected after 24 and 48 h of heating. The samples were degraded in
triplicate and stored in amber bottles for subsequent analyses.
2.4. Acid value, UV–Vis absorption and fluorescence analyzes
Acid value of the degraded WSO and WSB samples was determined
by classical titration (AOAC method 940.28) using ether:ethanol solu-
tion (2:1), secondary standard aqueous solution of KOH with a con-
centration of 0.1 mol L−1, previously titrated with primary standard
aqueous potassium biphthalate, and alcoholic phenolphthalein solution
1.0% (w/v) as indicator. Triplicate titration was performed with 2.0 g
of an aliquot for each sampling point. All chemicals used were analy-
tical grade. UV–Vis absorption spectra were collected in the
200–800 nm range in a bench spectrometer (Cary 50 Varian®) using a
quartz cuvette with 10 mm optical path length. WSO and WSB samples
were diluted in n-hexane HPLC (0.06%, w/w). In addition, fluorescence
spectra from 400 to 800 nm with excitation at 405 nm were recorded
using a portable fluorometer (MM Optics). A Y-type fiber was employed
for both excitation light delivery and emission collection.
Absorption and fluorescence spectra were analyzed using MATLAB
2012 routines. Initially, the linear correlation between each wave-
length-intensity and the acid value for a given sample was calculated to
establish the most significant linear correlation. A similar procedure is
reported in a previous work [39]. During the analysis, a specific wa-
velength was selected from the spectra and the linear Pearson's corre-
lation (R) between the spectrum intensity and acid value was reached.
This step was repeated for all wavelengths, determining in which wa-
velength was achieved the best R.
3. Results and discussion
3.1. Fatty acids composition and induction period
Table 1 shows the fatty acid composition of the Sesamum indicum L.
oil. Most of the fatty acid composition consists of unsaturated fatty
acids (about 86%), mainly monounsaturated oleic acid (38.54%) and
polyunsaturated linoleic acid (46.54%). On the other hand, only
14.05% of fatty acids are saturated, predominantly palmitic (8.35%)
and stearic (5.01%) acids. The high degree of unsaturations is an im-
portant drawback, since they take part in the oxidation mechanisms
that reduce the storage time of oil and its derivatives [20,40].
The induction period measured for WSO and WSB were
J.N. Conceição et al. Fuel Processing Technology 183 (2019) 1–7

Table 1 which should be related to the early degradation stages of methyl esters
Fatty acid composition of the white sesame (Sesamum indicum L.) oil. that change number and position of carbon‑carbon double bonds in the
Fatty acids (%) molecules [33]. In turn, fluorescence bands centered at around 520 and
673 nm have been attributed to conjugated tetraenes and chlorophyll,
Palmitic C 16:0 8.35 ± 0.05 respectively [24,30]. A fluorescence suppression at 673 nm was ob-
Palmitoleic C 16:1 0.08 ± 0.07
served because of the degradation of the chlorophyll molecules caused
Stearic C 18:0 5.01 ± 0.03
Oleic C 18:1 (n−9) 38.54 ± 0.19
by heating [24,45]. Chlorophylls may intervene in oxidation process of
Vaccenic C 18:1 (n−7) 0.20 ± 0.01 the samples preserving fatty acid carbon chains, but degrading them-
Linoleic C 18:2 (n−6) 46.54 ± 0.33 selves [24]. Otherwise, fluorescence intensity at about 520 nm in-
Arachidic C 20:0 0.56 ± 0.03 creased with respect to heating time. This fluorescence band is partially
Eicosenoic C 20:1 0.19 ± 0.01
ascribed to the oxidation products generated during the degradation
Linolenic C 18:3 (n−3) 0.41 ± 0.01
Docosanoic C 22:0 0.13 ± 0.02 process such as conjugated tetraenes, which strongly emit in the 350 to
Erucic C 22:1 nd 600 nm range [30]. Magalhães et al. demonstrated that conjugated
Lignoceric C 24:0 nd tetraenes could be produced during biodiesel degradation being formed
Nervonic C 24:1 nd
from the oxidation of methyl linoleate and methyl linolenate. Accord-
ΣSaturated 14.05 ± 0.13
ΣMonounsaturated 39.01 ± 0.28
ingly, the present results suggest that the oxidation of linoleic fatty
ΣPolyunsaturated 46.95 ± 0.34 acids is the main source of conjugated tetraenes formation during
sample degradation due to the high content of this fatty acid in the
nd (not detected). investigated samples (46.54%).
The correlation between the absorbance at 233 nm and acid value
(7.32 ± 0.02) and (4.19 ± 0.06) h, respectively. The WSO induction for the same sample are displayed in Fig. 3. The linear correlation in-
period is a typical value observed for vegetable oils [41,42], while the dicates the absorbance of the formed conjugated dienes as a parameter
value for WSB is lower than required by the regulatory agencies which to assess the degradation stage of oil and biodiesel. In addition, the data
stipulated an induction period of at least 8 h for the biodiesel [43]. This suggest that absorbance of a given either oil or biodiesel may be used to
low resistance to oxidation, i.e. low thermal stability, may be associated find out its acid value.
with the large amounts of unsaturated fatty acids in its composition Fig. 4 displays fluorescence-acid value correlation in which the
[38]. fluorescence intensities at 460 and 670 nm were chosen based on the
correlation analysis described in Section 2.4. Differently from the
3.2. Acid value UV–Vis absorption results, a linear dependence between fluorescence
intensity and acid value was not verified as a result of sample de-
Thermal degradation of WSO and WSB were studied measuring acid gradation. Despite fluorescence may be used as a qualitative indicator
values by classical titration. Acid value as a function of the heating time of acid value alteration in oils and biodiesels, a quantitative prediction
is exhibited in Fig. 1. The values for the untreated WSO and WSB model cannot be built by using a linear correlation.
samples were 0.48 and 0.07 mg KOH g−1, respectively. Because of the
production of acid compounds related to the oxidation, the acid value 3.4. Prediction of acid value using UV–Vis absorbance
increased at different rates in both WSO and WSB samples. While in
WSO it increased from 0.48 to 0.80 mg KOH g−1 (factor of 1.7), in WSB From the data presented in Fig. 3, an acid value prediction model
it changed from 0.07 to 0.18 mg KOH g−1 (factor of 2.6). was built taking into account the absorption values. As the number of
samples was not high enough, the leave-one-out cross validation
3.3. UV–Vis absorbance and fluorescence method was applied [46]. The method is based on withdrawing one
sample from the total of “n” samples. With the “n − 1” samples re-
The absorption and fluorescence spectra of WSO and WSB submitted maining in the data set, a linear fitting was performed using Eq. (1):
to different heating times at 110 °C are showed in Fig. 2. Absorption Iabs = a·AV + b (1)
bands at around 233 and 287 nm were detected, which has been as-
signed to conjugated dienes and trienes, respectively [44]. A growth in where Iabs is the absorbance at 233 nm, AV represents the acid value,
the absorbance of both WSO and WSB due to heating time was verified, and a and b are the angular and linear correlation coefficient of the

Fig. 1. Acid value versus heating time at 110 °C for S. indicum L. oil (WSO) and biodiesel (WSB).

3
J.N. Conceição et al. Fuel Processing Technology 183 (2019) 1–7

Fig. 2. Absorbance (top) and fluorescence (bottom) spectra of WSO and WSB for different heating times at 110 °C.

fitting curve, respectively. Then the withdrawing sample was used to
test the correlation model so that the absorbance of this sample was
replaced in Eq. (1) to predict the acid value by using Eq. (2):
Iabs − b
(AV )pred =
a (2)
where (AV)pred is the acid value predicted from the absorbance of the
“leave-out” sample. Finally, the predicted acid value was compared to
the acid value obtained experimentally and a percentage error was
calculated using Eq. 3:
(AV )pred − AV
Pe = 100.
AV
where Pe is the percentage error between the predicted and measured
acid values.
The leave-one-out cross validation was performed for all degraded
samples and a Pe for each sample was obtained. Finally, an average Pe
value was determined, representing the quantification error of the
prediction model.
The predicted acid values as a function of the measured acid value
for WSO and WSB samples are presented in Fig. 5. Average errors of the
predictions were 3 and 8% for oil and biodiesel, respectively.
Therefore, it is possible to determine the acid value of either oil or
biodiesel, with an average error attributed, using an appropriate cali-
bration model and UV–Vis absorption. As oxidation state of oil and
(3)

Fig. 3. Absorbance at 233 nm versus acid value for S. indicum L oil (WSO) and biodiesel (WSB) according to the respective heating time at 110 °C. The lines are result
of linear fitting.

4
J.N. Conceição et al. Fuel Processing Technology 183 (2019) 1–7

Fig. 4. Fluorescence intensity at 460 and 670 nm of WSO and WSB as a function of the acid value for oil and biodiesel from S. indicum L according to the respective
heating time at 110 °C. The lines are guides to the eye.

biodiesel is related to their acid values, data here reported may be
useful in developing an optical approach to assess, in a fast and robust
way, the oil and biodiesel quality. Furthermore, as the proposed pre-
diction model is based on a univariate analysis, this approach can be
used to develop a simple and robust absorption equipment that can be
built exclusively for oil and biodiesel analysis. Although different
techniques have been pointed out as alternative approaches to evaluate
biodiesel and vegetable oil degradation, such as chromatographic and
thermal analysis [47–50], these methods are costly, time-consuming,
not portable, and require complex sample preparation and expensive
equipment. Differently, the present findings demonstrated that UV–Vis
absorption can be used as an innovative and simple analytical tool for
monitoring biodiesel and vegetable oil degradation, allowing in-situ
and on-line measurements using a portable device.
4. Conclusions
FAME composition of white sesame (Sesamum indicum L.) oil was
determined, revealing a high percentage of unsaturated fatty acids
(about 86%). An induction period of (7.32 ± 0.02) and (4.19 ± 0.06)
h was obtained for the oil and biodiesel, respectively. These low in-
duction periods are due to the significant percentage of unsaturated
fatty acids, thus white sesame oil and biodiesel are very susceptible to
the oxidation. Oxidative stability of the oil and biodiesel was also

Fig. 5. Predicted and measured acid value for S. indicum L. oil and biodiesel according to the heating time at 110 °C. A Pearson's linear correlation of 0.96 was
obtained for both fitting curves (dashed lines).

5
J.N. Conceição et al.
investigated by analyzing the acid value, UV–Vis absorption, and
fluorescence measurements. Correlations between acid value and ab-
sorbance and fluorescence data were investigated. Results show that
absorbance values may be used to predict the acid values with an
average error of 3% and 8% for S. indicum L. oil and biodiesel, re-
spectively. Accordingly, UV–Vis absorption and the proposed prediction
model could be used in the development of an analytical method for
assessing the quality of vegetable oil and biodiesel taking into account
that oxidative degradation is related to the acid values.
Acknowledgments
The authors are grateful to CNPq, CAPES and FUNDECT, Brazilian
funding agencies, for their financial support. The authors also ac-
knowledge the support provided by the National Institute of Science
and Technology in Basic Optics and Applied to Life Sciences.
Declarations of interest
The authors declare no competing interests.
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