J Therm Anal Calorim

DOI 10.1007/s10973-016-5605-5

Characterization, thermal properties and phase transitions

of amazonian vegetable oils
Juliana J. R. Pardauil1 • Fábio Alberto de Molfetta3 • Miguel Braga2 •
Luiz K. C. de Souza1 • Geraldo N. R. Filho2 • José R. Zamian2 • C. E. F. da Costa2

Received: 8 January 2016 / Accepted: 1 June 2016

 Akadémiai Kiadó, Budapest, Hungary 2016

Abstract Thermal profiles of buriti pulp oil (Mauritia set, examining the presence or absence of natural group-
flexuosa Mart.), tucumã pulp and kernel oils (Astrocarium ings between samples.
vulgare Mart.), rubber seed oil (Hevea brasiliensis),
passion fruit oil (Passiflora edulis) and ucuúba butter Keywords DSC
Melting
Crystallization
PCA
HCA
(Virola surinamensis) were analyzed by thermogravime-
try (TG/DTG) and differential scanning calorimetry
(DSC). Gas chromatography and calculated iodine values
were performed to determine the fatty acid profile and to Introduction
measure the degree of unsaturation in these oils, respec-
tively. The TG curves showed three steps of mass loss, The Amazon region, with its richness of vegetable species,
which can be attributed to the degradation of polyunsat- produces vegetable oils with unique aromas and flavors.
urated, monounsaturated and saturated fatty acids. The The properties of these vegetable oils have been intensely
DSC crystallization and melting curves are reported and researched, mainly by international companies, due to their
depended on the fatty acid composition. Usually, oil various applications in food, pharmaceutical, cosmetic and
samples with a high degree of saturation showed crys- other industries. Because the use of Amazonian veg-
tallization and melting profiles at higher temperatures etable oils has increased in recent years, it is important to
than the oils with a high degree of unsaturation. The data acquire a better knowledge of their properties to optimize
obtained by physicochemical analysis of oil samples were the use of these materials [1, 2].
analyzed by principal component analysis and hierarchi- Among the palm trees across the tropical region, the
cal cluster analysis to increase understanding of the data buriti (Mauritia flexuosa Mart.) can be highlighted. Buriti
oil is an important source of proteins, energy and vitamins.
The concentration of b-carotene corresponds to 90 % of
the carotenoids present in the extracted pulp oil, which
makes this oil effective in xerophthalmia treatment [3].
& Juliana J. R. Pardauil Additionally, this oil is commonly used to treat burns as a
[email protected]
potent vermifuge and can be used as an adjuvant in sun
1
Department of Chemistry, ICE, Federal University of protection [4].
Amazonas (UFAM), Av. Rodrigo Otávio, Campus The tucumã palm tree (Astrocarium vulgare Mart.) is
Universitário Senador Arthur Vigı́lio Filho, Setor Norte, found in Pará and Amapá states. Tucumã ripe fruits are
Coroado., Manaus, AM 69077-000, Brazil
orange, consisting of pulp and kernel which corresponding
2
Laboratory of Catalysis and Oil Chemistry, Department of to approximately 53.2 and 24.5 %, respectively, of the fruit
Chemistry, Federal University of Para (UFPA), Rua Augusto
Corrêa, 01 – Guamá, Belém, Pará 66075-110, Brazil [5]. A micronutrient analysis showed that tucumã presents
3 one of the highest concentrations of b-carotene, with
Laboratory of Molecular Modeling, Department of
Chemistry, Federal University of Para (UFPA), Rua Augusto 52 mg per 100 g of pulp; this concentration is approxi-
Corrêa, 01 – Guamá, Belém, Pará 66075-110, Brazil mately eight times higher than that found in carrots [6, 7].

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 J. J. R. Pardauil et al.

The rubber tree (Hevea brasiliensis) originated from the of the vegetable raw material and for determining its fea-
basin of the Amazon River, but it is widely cultivated in sibility for later use in cosmetic products, medicines and
Southeast Asia. Rubber seeds contain 17–20 % saturated other industrial applications.
fatty acids and 77–82 % unsaturated fatty acids, which
gives it the characteristics of a semi-secant oil. Semi-secant
oils provide quick sealing to treated surfaces [8]. Materials and methods
Passion fruit (Passiflora edulis) is a tropical climate
plant with a widespread geographical distribution, pre- Vegetable oils
dominantly in regions with hot and humid climates, and is
commonly cultivated in Brazil. Passion fruit oil has a Oil was extracted from the tucumã pulp (TP), tucumã
yellow color, a pleasant flavor and a smooth odor, which is kernel (TK) and rubber seeds (RS) using a Soxhlet appa-
comparable to cotton oil in terms of nutritional level and ratus and hexane as solvent. The passion fruit (PF), buriti
digestibility, and the tea prepared by the infusion of the pulp (BP) oils and ucuúba butter (UB) were obtained from
leaves has been recognized for its anti-inflammatory a local oil provider, Amazon Oil Industry (Ananindeua,
potential. Additionally, the oil is susceptible to oxidative Pará, Brazil). These samples were unrefined and had no
rancidness due to the presence of a large amount of linoleic added preservatives. All of the chemicals and reagents used
acid [9]. were of the highest purity.
Ucuúba (Virola surinamensis) is a myristicaceous tree
growing in the Amazonian flood plains and produces seeds Fatty acid determination (GC)
during the rainy season. The fat extracted from the seeds
(ucuúba butter) is rich in trimyristin. Phytochemical The fatty acid compositions of the oils were determined by
investigations on these species revealed the presence of gas chromatography (GC) using the AOCS Ce 1-62 method
steroids, flavonoids, polyketides, tetrahydrofuran lignans [15]. The fatty acid methyl esters were prepared by the
and one aryltetralinneolignan. Scientific studies are being AOCS Ce 2-66 method [16]. Chromatographic analysis
conducted on the use of butter in the treatment of malaria was performed with a Varian CP 3800 gas chromatograph
and the trypanocidal activity against the trypomastigote equipped with a hydrogen flame ionization detector and a
forms of Trypanosoma cruzi [10]. capillary column (30 m 9 0.32 mm CP WAX 52 CB;
Recently, thermal analytic methods, such as thermo- 1 lm DF) (California, USA). The column temperature was
gravimetry/derivative thermogravimetry (TG/DTG) and programmed to ramp from 80 to 250 C at 10 C min-1,
differential scanning calorimetry (DSC), have been used to the injector temperature was set to 200 C, and the detector
characterize oils and fats [11]. The DSC data of oils and temperature was set to 250 C. Helium was used as the
fats have not given relevant information on the melting and carrier gas.
crystallization temperatures as well as the heats of fusion
and crystallization [12]. The phase transitions of lipids Physicochemical characterization of oils
have been evaluated by DSC, mainly due to the observa-
tion of polymorphic transformations. Polymorphism in The physicochemical assays were performed in accordance
complex lipids is more complicated; the presence of a with the standards established by the American Oil Che-
number of different triacylglycerols (TAGs) causes the mists’ Society (AOCS): acid value Cd 3d-63 [17]; peroxide
coexistence of different fat crystals, including mixed value Cd 8-53 [18]; saponification value Tl 1a-64 [19]; and
crystals, which could undergo polymorphic transformations calculated iodine value—CIV–Cd 1c-85 [20]. The kine-
as a consequence of temperature changes [13]. Therefore, a matic viscosity was determined using a thermostatic bath at
consequence of the phenomenon of polymorphism is that 40 C 52 SCHOTT coupled to a controller SCHOTT AVS
the DSC melting curves of TAGs are not easily inter- 350 with a Cannon–Fenske routine viscometer that com-
pretable. Additionally, DSC crystallization curves are plies with standards ISO/DIS 3105, ASTM D 2515, BS 188
reproducible and simpler than melting curves because they from SCHOTT Instruments (Mainz, Germany).
are influenced only by the chemical composition of the oil
or fat and not by the initial crystalline state [14]. Thermal analysis
The goal of this study was to evaluate the thermoana-
lytical profile (TG/DTG) and the phase transitions, melting The thermogravimetric curves (TG/DTG) were obtained in
and crystallization, of vegetable oils found in the Amazon a Shimadzu DTG 60H (Kyoto, Japan) simultaneous ther-
region. These characteristics were investigated by DSC, mal analyzer (TG/DTG/DTA) by the dynamic method
and the thermal profiles were correlated with their com- using an alumina crucible containing between 5 and 8 mg
positions and it can be applied for use in the quality control of oil sample and an empty alumina crucible as a reference.

123
Characterization, thermal properties and phase transitions of amazonian vegetable oils

The curves were recorded at a 10 C min-1 heating rate, which ranges from zero to one; a smaller distance means a
ranging from room temperature to 800 C under synthetic larger index and therefore a larger similarity [21]. Statis-
air and nitrogen flow (50 mL min-1). tical analysis (PCA and HCA) was performed using the
DSC analyses were determined by a Shimadzu DSC-60 software Minitab 15.
differential scanning calorimeter (Kyoto, Japan). The
equipment was calibrated with pure indium (melting point
156.6 C, DHf = 28.45 J g-1) and n-dodecane (melting Results and discussion
point -9.65 C, DHf = 216.73 J g-1), and the baseline
was obtained with an empty hermetically sealed aluminum The values obtained by gas chromatography for the
pan. An empty hermetically sealed aluminum pan was used chemical composition of the fatty acids in the veg-
as a reference. Samples of oils (5 ± 0.5 mg) were weighed etable oils are presented in Table 1. The analyzed oils had
into aluminum pans, and the covers were hermetically a high content of unsaturated fatty acids (62 % oleic acid
sealed into place. for TP, 33 % linoleic acid for RS, 68 % linoleic acid for PF
For the TP, TK, BP and UB oil samples, the cooling and and 68.8 % oleic acid for BP), except for TK, which had a
heating programs were: first heating the oil to 80 C using high content of saturated fatty acids that gave it the
a 10 C min-1 heating rate and remaining 80 C for appearance of solid fat (48 % lauric acid and 25 % myristic
10 min to erase the crystal sample history, immediately acid). UB had approximately 71 % myristic acid. These
followed by cooling to -80 C using a 10 C min-1 oils can be classified as lauric fats. Lauric fats are com-
cooling rate and maintaining this temperature for 10 min monly used in the food industry and oleochemical industry;
and then heating at 10 C min-1 to 80 C. For the RS and palm kernel oil (PKO) is the most typical example of this
PF oil samples, the cooling and heating program were: first category and is characterized by high contents of lauric and
heating the oil at 30 C using a 10 C min-1 heating rate myristic acids. PKO and its fractions can be hydrogenated
and holding at 30 C for 10 min, cooling to -100 C using to different degrees to produce a wide range of PKO-based
a 10 C min-1 cooling rate and maintaining this tempera- products, which are widely used in the food industry [22].
ture for 10 min and then heating at 10 C min-1 to 30 C. The high concentration of oleic acid found in TP and BP
Nitrogen was the purge gas and flowed at 50 mL min-1. oils makes it useful for the food industry as a frying or
Liquid nitrogen was used as the cooling agent. The curves salad oil. Additionally, oleic acid is an essential fatty acid
were analyzed with a TA-60WS thermal analysis system (Omega 9) that participates in human metabolism, playing
(Shimadzu, Kyoto, Japan) to obtain the onset temperature a key role in the synthesis of hormones; therefore, its
(To), the offset temperature (Tf) (points where the extrap- inclusion in the diet is essential. RS oil displayed a fatty
olated leading edge of the endotherm/exotherm intersects acid composition similar to linseed oil, whereas PF oil was
with the baseline), and the various peak temperatures (Tp) found to be a good source of linoleic and linolenic acids.
of the maximum/minimum different heat flows. Linoleic and linolenic acids are essential in human

Statistical analysis
Table 1 Fatty acid compositions of oils
Principal component analysis (PCA) is based on the cor- Fatty acid composition/% Oils
relation among variables, and it is used to identify groups
of analyzed variables, based on the factor loadings, i.e., UB BP TP TK RS PF
correlations between the variables and the principal com- 12:0/Lauric acid 16 0.1 48
ponents (PCs) and groups of individuals based on the 14:0/Myristic acid 71 0.2 25 0.1
principal component scores. The score vectors describe the 16:0/Palmitic acid 4.3 19.4 25 6 8.5 11
relationship between the samples and allow checking 16:1/Palmitoleic acid 0.1 0.2 0.05
whether they are similar or dissimilar, typical or outlier, 18:0/Stearic acid 0.7 3 2 5 3
while the loading vectors describe the importance of each 18:1/Oleic acid 4 68.8 63 13.5 27 17
variable. The PCs are built as linear combination of the 18:2/Linoleic acid 0.9 11.1 2 3.7 33 68
original independent variables and have the important 18:3/Linolenic acid 0.6 4 23 3.5
property of being completely uncorrelated [21]. 20:0/Araquidic acid 0.3 0.2 0.1 0.3
Hierarchical cluster analysis (HCA) examines the dis- 22:0/Behenic acid 0.1
tances between the samples in a data set and represents this
SFA 92.4 19.4 28.5 81.1 13.5 14.1
information as a two-dimensional plot called dendrogram.
MUFA 4.1 68.8 63.2 13.5 27 17.05
In HCA, the distances between samples or variables are
PUFA 0.9 11.7 6 3.7 56 71.5
calculated and compared through the similarity index

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 J. J. R. Pardauil et al.

nutrition because they represent a group of essential fatty 8.5 %, and the values for the kinematic viscosity were 38,
acids, omega six and three, respectively. A deficient intake 34 and 21.4 mm2 s-1, respectively.
of these essential fatty acids causes dry, rough skin, a Table 2 shows that data related to the physicochemical
tendency for eczema and rash, weak hair, eventual alopecia parameters were used for the principal component analysis
and weak nails [23]. (PCA) and hierarchical cluster analysis (HCA). Initially,
In Table 2, the physicochemical properties of the sam- was used the complete data set, i.e., the set containing all
ples are shown. The acidic value and peroxide value are variables. Before applying the PCA method, all variables
described as reference parameters to determine the quality were autoscaled (focused on medium and scaled by the unit
of the conservation of oils. The Ministry of Health of variance), so they can be compared with each other on the
Brazil (Ministério da Saúde-MS), through the National same scale.
Health Surveillance Agency (Agência Nacional de Vigi- The three variables responsible for the separation of oils
lância Sanitária-ANVISA), legalized the production of were peroxide value, saponification value and calculated
edible oils from an adopted technical regulation (resolution iodine value. The score graphs which are the new coordi-
no. 270 of September 22, 2005) [24]. According to this nates of each type of oil in the new coordinate system (PC)
resolution, the maximum acidic value and peroxide value are shown in Fig. 1a. PCA results showed that first two PCs
for cold-pressed unrefined oils and fats is 4 mgKOH g-1 described 97.6 % of total information (variance) of the data
and 15 mEq kg-1, respectively. The acidic and peroxide set. PC1 is responsible for 66.6 % of the information, and
values for the analyzed samples are in agreement with the PC2 has 31 % of information.
specifications of the Brazilian legislation, except for the From the graph of the PCA scores can be observed the
acidic value found for UB. This high value can be attrib- formation of three distinct classes of oils in relation to their
uted to the presence of resin in the uccúba butter, which physicochemical characteristics. Figure 5b shows the
contains large amounts of lignans and neolignans [25]. loading graphic for each one of the used variables in PCA
The saponification value and calculated iodine value are analysis. When analyzing the score and loading graphics, it
related only to the specific characteristics of each veg- can be observed that the UB and TK samples were in the
etable oil, such as the length of the chains and the number same quadrant, and the variable responsible for this sepa-
of unsaturation. If the oil or fat has fatty acids with a low ration was the saponification index.
molecular weight, the saponification value will be higher Through score graphic, the samples UB and TK showed
and more of the oil or fat can be used for food. The oils TP, PC1 \ 0 values, because these samples have high con-
RS, PF and BP showed high amounts of MUFA and PUFA centrations of saturated fatty acids. Also, RS, PF and BP
and had high CIVs (C63.86). The lowest CIVs (B18.07) samples showed positive values of PC1 and PC2 as shown
were for the fats TK and UB due to the high amounts of in Fig. 1a, b and the responsible variable for the separation
SFA. These fats also had the highest saponification values was CIV. High CIV values for these samples are related to
(236.4 and 235.5, respectively), whereas for the more their large content of unsaturated fatty acids. However, the
unsaturated oils, the saponification value was C171.5. TP sample had positive values in PC1, but negative in PC2;
The viscosity increases when the chain length of the even noting that TP has a composition very similar in fatty
fatty acid in the triglycerides is larger and decreases when acids in relation to the BP sample (Table 1). The physic-
unsaturation in the fatty acid chain is high. It is a function ochemical characteristic that describes this sample TP by
of the dimensions of the molecule and its orientation, i.e., it the loading graph was the high peroxide value, as it is
increases with hydrogenation. In the case of the studied associated with the storage conditions of the fruits and the
oils, UB showed the highest kinematic viscosity oil extraction process.
(92.8 mm2 s-1) due to the high amounts of myristic acid. HCA dendrogram (Fig. 2) correlates with the results
The palmitic acid content for BP, PF and RS is 19.4, 11 and obtained by PCA plot, PC1 versus PC2. Figure 2 shows the

Table 2 Physicochemical analyses of oils

Physicochemical analyses Oils
TP TK RS PF BP UB
-1
Acidic value/mgKOH g 3.80 0.45 2.40 3.30 2.67 33.69
-1
Peroxide value/mEq kg 10.52 1.9 3.92 1.50 4.03 1.80
Saponification value/mgKOH g-1 180.40 236.40 171.55 193.86 175.50 235.50
Kinematic viscosity/mm2 s-1 19.40 15.40 21.40 33.60 38.04 92.80
CIV 67.77 18.07 140.26 133.85 79.96 5.05

123
Characterization, thermal properties and phase transitions of amazonian vegetable oils

(a) 4
1.0 100
PF
3
Second component

0.5

DTG/mg s–1
RS
5 80 A
0.0 6 2
TK BP
–0.5 UB

60

Mass/%
–1.0
–1.5 1
B
TP 40
–2.0 UB 0 200 400 600
Temperature/°C
–2.0 –1.5 –1.0 –0.5 –0.0 0.5 1.0 1.5 TK
First component 20 TP
BP
(b) CIV 0
PF
0.50 RS

0.25 0 100 200 300 400 500 600 700 800

Second component

Temperature/°C
Saponif
0.00
Fig. 3 TG (a) and DTG (b) curves for the oils in a synthetic air
–0.25 atmosphere
–0.50

–0.75 Peroxide 100

–1.00

DTG/mg s–1
–0.75 –0.50 –0.25 –0.00 0.25 0.50 80 A
First component
60 B
Fig. 1 Plot of the first two score vectors (a) and (b) loading vectors
Mass/%

(PC1 and PC2) of the variables responsible for the separation of the
oils 40 UB 0 200 400 600
Temperature/°C
TK
TP
20
BP
49.62
PF
0 RS

66.41 0 100 200 300 400 500 600 700 800

Similarity

Temperature/°C

83.21 Fig. 4 TG (a) and DTG (b) curves for the oils in an N2 atmosphere

RS PF showed that in an air atmosphere, the thermogravimetric

100.00
1 5 3 4 2 6 profile presented three decomposition steps, whereas in an
TP BP TK UB
Observations N2 atmosphere, there were only one or two steps, sug-
gesting that in an oxidizing atmosphere, the decomposition
Fig. 2 Dendrogram obtained with HCA for the sample oils
process occurs by combustion, and in an inert atmosphere,
thermodecomposition occurs by pyrolysis.
highest similarity among TP and BP, PF and RS and In the TG curves, the initial temperature (Ti) of the first
between TK and UB samples probably due to the fatty stage of mass loss for the UB, TK, TP, BP, PF and RS,
acids similarities as TP and BP have 63.2 and 68.8 % of respectively, was:
MUFA, PF and RS have 56 and 71.5 % of PUFA, and TK
• Air atmosphere: 204; 260; 257; 268; and 296 C.
and UB have 81 and 92 % of SFA, respectively.
• N2 atmosphere: 225; 295; 322; 350; and 370 C.
The thermal behaviors for the oils are displayed in
Figs. 3a, b and 4a, b. According to the TG/DTG curves, a For UB, TK TP and BP, the Ti values were smaller in
ramp of thermal stability of the oil was observed to both atmospheres than for PF and RS. This may be related
approximately 200–290 C. Until this temperature, the to the volatilization of lauric, myristic and palmitic acids
mass loss corresponds to the removal of water, moisture present in significant amounts in these oils. In this case, Ti
and volatilization of substances, such as fatty acids with may not necessarily be associated with the thermal
12–16 carbons in the chain [26]. The TG/DTG curves decomposition. [27] ascribed these steps to the following

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 J. J. R. Pardauil et al.

processes: (1) decomposition of polyunsaturated fatty (a)

acids, such as linoleic acid, with the formation of com-
pounds, such as dimers, trimers and polymers; (2)
decomposition of monounsaturated fatty acids, such as

Heat flow/a.u. Exo up

oleic acid; and (3) decomposition of saturated fatty acids,
such as palmitic acid. Other authors considered that all
three types of fatty acids decompose in the first step. UB
However, others authors attributed the last stage of
decomposition to the oxidation of carbon residues [28, 29]. TK
Garcia et al. [30] reported the first and second mass loss
TP
steps as the oxidation of unsaturated and saturated fatty
acids, respectively, whereas the third step was related to the
BP
decomposition of polymers formed during the oxidation
process. However, according to Vecchio et al. [31], the –80 –70 –60 –50 –40 –30 –20 –10 0 10 20 30 40 50 60 70
results of these studies are often contradictory because Temperature/°C
vegetable oils have a complex chemical composition,
including lipid oxidation products, free fatty acids, phe- (b)
nolic compounds, glycerides and non-glycerides, which are
present in the oil at different percentages; therefore, a clear
RS
assignment of each event as a decomposition of a certain
chemical species is difficult if only analyzing the profile of Heat flow/a.u. Exo up
the TG/DTG curves because the mass losses of various
chemical components due to the decomposition of lipids
most likely occur at the same time during each step.
Crystallization curves often exhibit multiple exothermic
regions corresponding to different triacylglycerol compo-
sitions. Melting causes a volume expansion and an PF
endothermic effect. Additionally, a complex feature of
triglycerides makes the melting process difficult to inter-
–100 –90 –80 –70 –60 –50 –40 –30 –20 –10 0 10 20 30
pret in relation to the crystallization process due to the
Temperature/°C
presence of overlapping peaks [32]. This is a consequence
of the polymorphism phenomena of natural oils and fats, Fig. 5 DSC cooling curves for the studied oils a UB, TK, TP, BP and
and this cannot be established unequivocally by DSC b RS, PF
measurements. Only X-ray diffraction analysis can deter-
mine the exact polymorphic form [32, 33]. DSC cooling peak around at 11 C, which can be related to the amount
curves for the studied oils are shown in Fig. 5a, b. The of SFA (28.5 %) in this oil. The second was a broader peak
main transition parameters as well as the enthalpy for the centered at -6.6 C and followed by a smooth shoulder at
crystallization curves are shown in Table 3. In UB, the -33 C. The last peak at -50.5 may correspond to groups
crystallization curve showed two exothermic overlapping of TAGs with saturated–saturated–unsaturated, saturated–
peaks: the larger one centered at 16.5 C and the smaller unsaturated–unsaturated and unsaturated–unsaturated–un-
one centered at 11.4 C. These peaks in the high-temper- saturated chains of fatty acids [14]. In BP, the crystalliza-
ature regions occur due to the high concentration of SFA, tion pattern was similar to TP oil, except for the absence of
mainly myristic and lauric acids, which are the main con- the exothermic peak in the high-temperature region. The
stituents in this butter. The crystallization curve for TK first broad peak had a Tp at -12.9, followed by a shoulder
exhibits two distinct exothermic peaks: the taller peak had at -37 C, and the last peak was taller and had a Tp at
a Tp at approximately 6 C, and the short one had a Tp at -54 C. These peaks may be associated with the presence
-9 C. These peaks occur due to the presence of TAGs of the same groups of TAGs contained in TP oil, mainly
with three chains of SFA, such as lauric, myristic and because of the high content of oleic acid. Likewise, the RS
palmitic acids. Following these peaks can be observed a crystallization curve had three exothermic regions at
small peak around -29 C, most likely due to the crys- -19.2, -45.4 and -73.4 C, respectively, consistently
tallization of TAGs containing chains of MUFA and lower than the other crystallization curves, most likely due
PUFA. The TP crystallization curve exhibited three to the high amount of linolenic acid. The PF curve showed
exothermic transitions. The first was a sharp and narrow three exothermic peaks at -16.3, -39 and -93 C, but

123
Characterization, thermal properties and phase transitions of amazonian vegetable oils

Table 3 DSC parameters of the main peaks and enthalpy from the cooling curves of the oil samples
Oils 1 peak T/C 2 peak T/C 3 peak T/C DHT/J g-1
To Tp Tf To Tp Tf To Tp Tf

UB 18.5 16.5 7.6 -107.82

TK 8.1 5.9 1.8 -5.1 -9.0 -15.5 -108.22
TP 11.2 9.5 6.1 -1.7 -6.6 -19.4 -44.5 -50.5 -57.2 -61.95
BP -5.1 -12.9 -28.8 -50.5 -54.0 -59.9 -66.61
RS -13.1 -19.2 -32.8 -38.5 -45.4 -56.4 -64.0 -73.4 -85.1 -5.82
PF -16.3 -20.3 -32.1 -39.0 -46.2 -58.6 -78.7 -93.1 -97.7 -19.25
DHT: total cooling enthalpy

these peaks were sharper and taller than those present in the myristic and palmitic chains. The TK and TP melting pro-
RS crystallization, possibly due to the greater amount of files were similar to those found by Tan and Che Man [32]
unsaturated fatty acid contained in PF. Also, Tengku- for palm kernel oil and palm oil at the same heating rate. The
Rozaina and Birch [34] analyzing fractionated refined hoki TK heating curve presented one main endothermic transi-
oil observed that DSC curves of crystallization peaks for tion at 28 C with two slight shoulders at 14.5 and 39 C.
the fraction containing higher percentage of unsaturated This major endothermic peak was the fusion of TAGs with
fatty acids tend to be shifted to the lower-temperature saturated fatty acids with high melting points present in
regions. lauric fats [22]. The heating curve of TP showed two major
Due to the complexity of the melting curves, the thermal endotherm regions. This can be matched to the endothermic
events were read at the minimum of the endothermic peaks transitions of MUFA, such as oleic acid (lower-temperature
(Table 4). The DSC melting curves are shown in Fig. 6a, b. peak) and SFA, e.g., palmitic acid (higher temperature
All of the curves showed multiple endothermic events region). The endothermic region at higher temperature
related to the different TAG compositions of the oils. The consisted of a plateau with a pair of shoulders, whereas the
UB melting curve had three main endothermic peaks. The endotherm region at lower temperature contained three
first peak was at 21.5 C, most likely indicating the fusion of overlapped peaks. In contrast, BP oil exhibited a main
TAGs with short chain fatty acids, such as lauric acid, fol- endothermic domain at -4.7 C preceded by two shoulders
lowed by a taller exothermic peak that indicates a poly- at -54 and -36.9 C and an exothermic polymorphic
morphic event, i.e., a rearrangement of polymorphic crystals transition at approximately -30 C. RS and PF were the
into more stable forms [32]. According to Tolstorebrov et al. most unsaturated oils and presented four and seven
[35], the typical DSC melting curves include the endother- endothermic domains at low temperatures, respectively. RS
mic and exothermic peaks, which show the transition of one had a main endothermic peak with two shoulders that can be
form of fat crystals into another. In this way, this event can associated with the highly cooperative melting of TAGs
be related to the melting of a-crystals followed by b-crystal containing chains of oleic, linoleic and linolenic fatty acids.
formation (exothermic peak in the UB melting curve). The The fourth endothermic peak, consistently lower than the
second endotherm located at the high-temperature region others, at 7.5 C can be related to the fusion of SFA, which
was formed by two overlapped peaks at 30.8 and 37.2 C makes up 13.5 % of this oil. For PF, the principal melting
and may be associated with the melting of TAGs containing process happens below -20 C, and the broadening of the

Table 4 DSC transition temperatures and enthalpy from the melting curves of the oil samples
Oils Transition temperatures/C DHT/J g-1
1 2 3 4 5 6 7

UB 21.5 30.8 37.2 119.66

TK 14.5 28.0 39.0 117.35
TP -36.4 -4.7 2.4 15.3 31.8 88.69
BP -54.0 -36.9 -4.7 91.44
RS -33.2 -22.1 -11.2 7.5 18.47
PF -92.6 -79.4 -62.8 -40.2 -31.5 -18.8 -9.8 37.30
DHT: total meting enthalpy

123
 J. J. R. Pardauil et al.

(a) Conclusions
UB

It was confirmed that the melting and crystallization char-

Heat flow/a.u. Endo down

TK acteristics of oils and fats were strongly dependent on the FA

and TAG compositions. The DSC technique does not pro-
TP vide direct information about the chemical composition of
oils and fats. However, it provides useful information about
BP
the nature of the thermodynamic changes associated with
phase transitions that are related to the composition of oils
and fats. The methods of multivariate analysis PCA and
HCA allowed a comparison between physicochemical
characteristics of the samples that are related to chemical
fatty acid composition of the oils studied.
–80 –70 –60 –50 –40 –30 –20 –10 0 10 20 30 40 50 60 70 80
Temperature/°C Acknowledgements The authors would like to thank CAPES
Foundation, Ministry of Education of Brazil, for a Doctoral scholar-
ship to Pardauil, J. J. R, and FINEP/SIPI, FAPESPA/VALE and
(b) RS
CNPq for financial support. Also, the authors would like to thanks to
Amazon Oil Industry for providing the oils used in this study.
PF
Heat flow/a.u. Endo down

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