Food Research International xxx (xxxx) xxx

Contents lists available at ScienceDirect

Food Research International

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

CO2 supercritical fluid extraction of pulp and nut oils from Terminalia
catappa fruits: Thermogravimetric behavior, spectroscopic and fatty
acid profiles
Orquídea Vasconcelos Santos a, Natasha Dantas Lorenzo b, Amanda Larissa Garça Souza a,
Carlos Emmerson Ferreira Costa a, Leyvison Rafael Vieira Conceição a,
Suzana Caetano da Silva Lannes c, Barbara Elisabeth Teixeira-Costa d, *
a
Federal University of Pará, Rua Augusto Corrêa, 1, Guamá, 66075-110, Belém, PA, Brazil
b
Brazilian Company of Agricultural Research – EMBRAPA Eastern Amazon, Rua Dr. Enéas Pinheiro, Curió Utinga, 66095-100 Belém, PA, Brazil
c
University of São Paulo, Avenida Prof. Lineu Prestes, 580, Bloco 16, 05508-900, São Paulo, SP, Brazil
d
Federal University of Amazonas, Avenida General Rodrigo Octavio, 1200, Coroado I, 69067-005 Manaus, AM, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: The aim of this study was to investigate the attributes of the pulp and nut oils from Terminalia catappa fruits
Sea almond obtained by supercritical fluid extraction (SFE) with pressurized CO2. The yield, physico-chemical character­
Tropical almond ization and fatty acid profiles of both oils were assessed based on their acidity and peroxide indices, thermog­
Pressurized carbon dioxide
ravimetric behavior, infrared spectroscopic and gas chromatographic analyses. The extraction yields were 7.4%
Lipids
Unsaturated fatty acids
and 61.5% for the pulp and nut from T. catappa, respectively. The pulp and nut oils exhibited low levels of
Vegetable oil acidity, 3.3 and 1.9 mg KOH g− 1, and peroxides, 3.8 and 1.7 mEq kg− 1, respectively. These values are lower than
Atherogenicity the maximum recommended levels given by the Codex Alimentarius for virgin oils (4.0 mg KOH g− 1 and 15 mEq
Peroxides Kg− 1, respectively). Unsaturated fatty acids were a major constituent of the oils (58%), of which omegas 3 and 6
were predominant. The infrared spectroscopy of the nut oil showed high intensity bands between 2912 and 716
cm− 1, representative of chemical groups commonly present in unsaturated fatty acids. The pulp oil displayed
higher thermal stability than the nut oil, whereby the initial degradation temperatures (Tonset) were 280 ◦ C and
230 ◦ C, respectively. This difference may be related to a greater amount of saturated fatty acids in the pulp oil
compared to the nut oil. Thus, both pulp and nut oils displayed good physicochemical properties, which are
desirable in diverse industrial sectors.

1. Introduction
Terminalia catappa Linn., commonly known as tropical almond or sea
almond, is a member of the Combretaceae family. More than 500 plant
species comprise this group, with almost half the species belonging to
the genera Combretum and Terminalia. T. catappa is commonly cultivated
in tropical countries as an ornamental tree and for its edible fruits and
seeds (Janporn et al., 2015; Kaneria, Rakholiya, Marsonia, Dave, &
Golakiya, 2018). The fruiting of the trees begins at three to five years
old, producing fruit twice to three times a year (Thomson & Evans,
2006).
Each tree can produce 20–30 kg of fruit per year with a global pro­
duction of 700,000 tons recorded in 2004 (Agu, Menkiti, Nwabanne, &
Onukwuli, 2019; Singh & Choudhary, 2012). The seeds from T. catappa
are a good source of lipids, due to an oil yield of 30–60%, a value higher
than that of the main common oil sources, such as soybean, palm and
peanuts (Agu et al., 2019; Chavan et al., 2017; Iha et al., 2014; Jokić,
Svilovic, & Vidovic, 2015; Ladele et al., 2016). This highlights the
economic potential of the utilization of T. catappa seeds as an alternative
vegetable oil matrix. As it is a non-conventional fruit crop, data
regarding its agricultural production are scarce. However, there is a
growing demand for new sources of oils with good nutritional properties
from unexploited resources (Ozcan, Endes, & Er, 2010).
The T. catappa fruits have also been described as having nutritional
importance related to their antioxidant, hypoglycemic and gastro-
protective activities, as well as the nutritional composition of its pulp

* Corresponding author.
E-mail addresses: orquideavs@ufpa.br (O.V. Santos), emmerson@ufpa.br (C.E.F. Costa), scslan@usp.br (S.C.S. Lannes), betcosta@gmail.com (B.E. Teixeira-Costa).

https://doi.org/10.1016/j.foodres.2020.109814
Received 7 January 2020; Received in revised form 4 October 2020; Accepted 11 October 2020
Available online 22 October 2020
0963-9969/© 2020 Elsevier Ltd. All rights reserved.

Please cite this article as: Orquídea Vasconcelos Santos, Food Research International, https://doi.org/10.1016/j.foodres.2020.109814
O.V. Santos et al.
with a good amount of carbohydrates (~76%) and low proportion of
lipids (~3%) (Ladele et al., 2016; Marques et al., 2012; Nunes et al.,
2014). Specifically, antioxidant substances and polyphenols, such as
gallic acid, citric acid and punicalagin, have been identified (Kaneria
et al., 2018; Marques et al., 2012; Santos, Lorenzo, & Lannes, 2016).
Nonetheless, the maintenance of both the nutritional and functional
properties of the raw materials depends not only on the matter itself but
also on the type of technique applied in its processability. For seed
processing, the oil extraction step is one of the most critical stages.
Conventional methods that use thermal processing may be detrimental
to some natural substances by changing the organoleptical and nutri­
tional properties, as many of these substances are thermo-susceptible (Al
Juhaimi, Uslu, & Özcan, 2018; Nde & Foncha, 2020). In this context, the
supercritical fluid extraction (SFE) has gained interest because it can
overcome the utilization of organic solvents and some other limitations
of conventional methods (Aydi et al., 2020). Rapid penetration of the
supercritical fluids into the matrix, which increases the extraction effi­
ciency, is one of many advantages of using the SFE (Jokić et al., 2013).
Furthermore, this technique allows the efficient extraction of thermo­
sensitive substances since it uses relatively mild conditions, yielding
extracts with good bioactive and nutritional quality, thereby increasing
the aggregated value of natural resources (Aydi et al., 2020; de Melo,
Silvestre, & Silva, 2014; Melgosa, Sanz, Benito-Román, Illera, & Beltrán,
2019). Researchers have already used the SFE technique to evaluate the
volatile constituents of roasted tropical almond nuts while others have
investigated the T. catappa suitability as a transformer fluid (Agu et al.,
2019; Lasekan & Abbas, 2010; Menkiti, Agu, & Udeigwe, 2015).
Therefore, the aim of this study was to compare the properties of the
pulp and nut oils from T. catappa fruits obtained by supercritical fluid
extraction (SFE) with pressurized CO2. The yield, physico-chemical
characterization and fatty acid profiles of both oils were investigated
based on acidity and peroxide indices, thermogravimetric behavior,
infrared spectroscopic and gas chromatographic analyses.
2. Material and methods
2.1. Material
Tropical almonds (~10 kg) from Terminalia catappa (Linn.) were
collected in an experimental area at the Brazilian Company of Agricul­
tural Research (EMBRAPA Eastern Amazon) in the city of Belém, Pará,
Brazil (latitude, 01 0 28′ S and longitude 048 0 27′ W). The fruits were
harvested in the second semester of 2019 at their maximum maturity,
which was determined by the purple color of the peel. To ensure the
proper taxonomic identification of the plant, some parts of it, such as the
leaves and fertile material, were collected and deposited in the herbar­
ium “João Murça Pires” in the Museum Emílio Goeldi (Belém, PA,
Brazil) under the code MG n◦ . 70506. The samples were transported in
low-density polyethylene bags and stored under refrigeration for further
analyses in the Laboratory of Food Analysis at the Federal University of
Pará (UFPA). All the chemicals used in this study were of analytical
grade purchased from Sigma-Aldrich Brazil Ltd. (São Paulo, SP, Brazil).
Carbon dioxide (CO2) with 99.9% purity was supplied from Linde Gases
(Belém, PA, Brazil).
2.2. Sample preparation
The samples used in the extraction procedure were dried in an air
recirculation oven (510.150 model, Thoth Equipment, SP, Brazil) at
60 ◦ C for 24 h until water content was less than 5% and subsequently
crushed in a Willey mill (TE-650 model, Tecnal, SP, Brazil). Before using
the dried samples for the supercritical CO2 fluid extraction, the particles
were standardized by passing them through a sieve series (Mesh n◦ 14,
16, 20, 24) coupled to a magnetic sieve shaker (model 1713, Bertel
Metallurgic Industry, SP, Brazil). The samples retained in each sieve
were weighed on an analytical balance and the mean diameter of the
2
Food Research International xxx (xxxx) xxx
particles (mm) was calculated according to Eq. (1):
[∑
n
]
d= i=1 = (wi logdi
∑n (1)
i=n w
where di = (di di+1 )0.5 , di is the nominal opening of the ith sieve (mm),
di+1 is the nominal sieve opening larger than the ith sieve (mm), and wi is
the weight of the retained mass in the ith sieve.
2.3. Supercritical CO2 fluid extraction of lipids from T. catappa
The lipid content in the pulp (TCP) and nuts (TCN) of T. catappa was
isolated using a Speed TM SFE apparatus (7071 model, Allentown, PA,
USA) equipped with a compressor (CSA 7.8 model) and internal volume
of 19.7 L from Schulz S/A (Joinville, SC, Brazil), a Polyscience recir­
culator (F08400796 model, Nilles, IL, USA) and CO2 output meter from
Alicat Scientific (5SLPM model, Tucson, AZ, USA). Pressurized CO2 was
used as a solvent in the SFE. The extraction conditions were performed
according to the methodology adapted from Ko, Weng, Lin, and Chiou
(2003). Initial extraction tests were carried out at different tempera­
tures, 40, 50 and 60 ◦ C, and pressures, 100, 200 and 300 bar. Exhaustive
extraction was executed at 60 ◦ C and 300 bar, which were the param­
eters that presented the highest oil yield according to previous work
(Santos, Corrêa, Carvalho, Costa, & Lannes, 2013). The general extrac­
tion yield was based on the maximum amount of soluble material
extracted from a solid matrix under specific temperature, pressure, and
time conditions. The extraction yield (%) was calculated according to
Eq. (2).
( )
Yield =
Woil
x100 (2)
Wsample
where Woil is the weight of extracted oil and Wsample is the total weight of
the solid material from T. catappa.
2.4. Acidity and peroxide indices of the T. Catappa oils
The acidity and peroxide values of the oils extracted from TCP and
TCN, as a source of edible lipids, were evaluated according to American
Oil Chemists Society official methods Cd 3d-63 (AOCS, 2004) and Cd 8-
53 (AOCS, 2004), respectively.
2.5. Fatty acid compositions
The fatty acid (FA) compositions were determined by gas chroma­
tography (GC) using the following methodologies. Methyl esterification
of FAs was prepared according to the boron trifluoride (BF3) method in
ISO 5509:2000(E) from the International Standardization Organization
(2000) for determination of the FA profile. The glycerides were sapon­
ified with methanolic sodium hydroxide and converted into methyl es­
ters by reaction with a boron trifluoride/methanol complex. The methyl
esters were phase-separated after addition of isooctane to the solution,
the supernatant was collected and submitted to GC analysis according to
Milinsk, Matsushita, Visentainer, Oliveira, and Souza (2008). For this, a
gas chromatographer coupled to a microcomputer with Galaxie Chro­
matography software was used. The chromatography parameters
applied were as follows: a fused silica capillary column SP-2560
(Supelco, USA), 100 m long and 0.25 mm internal diameter coated
with 0.2 μm polyethylene glycol. The operation conditions were: split
injection at 50:1 ratio, column temperature at 140 ◦ C for 5 min with an
increasing rate of 4 ◦ C min− 1 up to 240 ◦ C, helium as carrier gas at 29
mL min− 1, isobaric pressure of 37 psi, 20 cm s− 1 of linear velocity,
temperature injector and detector at 250 ◦ C and Varian CP 8410 model
autosampler. The qualitative composition was determined by comparing
the time of peak retention with their respective standards for FAs. The
quantitative composition was determined by area normalization,
O.V. Santos et al. Food Research International xxx (xxxx) xxx

expressed in mass percentage, as according to the established method Ce Table 1

2-66 (AOCS, 2004). Fatty acid profile and nutritional indices of T. catappa oils.
Fatty acids (%) Pulp oil Nut oil
2.6. Hypocholesterolemic/hypercholesterolemic ratio, atherogenicity and Saturated fatty acids (SFAs)
thrombogenicity indices C14:0 2.2 ± 0.5 –
C16:0 41.9 ± 1.4 35.9 ± 0.3
The FAs were classified into fractions according to the presence and C18:0 3.9 ± 0.8 4.6 ± 0.3
C22:0 2.1 ± 0.7 0.08 ± 0.03
number of double or triple bonds: saturated fatty acids (SFA), unsatu­ C24:0 – 0.03 ± 0.01
rated fatty acids (UFA), monounsaturated fatty acids (MUFA) and Monounsaturated fatty acids (MUFAs)
polyunsaturated fatty acids (PUFA). These fractions were used to C16:1 – 0.42 ± 0.01
determine the indices of atherogenicity (AI) and thrombogenicity (TI) C18:1 10.3 ± 0.8 33.2 ± 1.7
Polyunsaturated fatty acids (PUFAs)
according to Ulbricht and Southgate (1991), and the hypocholester­
C18:2n-6 26.0 ± 0.6 24.5 ± 1.4
olemic/hypercholesterolemic ratio (H/H) as defined by Santos-Silva, C18:3n-3 9.06 ± 0.01 0.06 ± 0.01
Bessa, and Santos-Silva (2002). The following equations were used to C20:4n-6 2.4 ± 0.5 0.34 ± 0.02
calculate the indices: Σ SFAs 50.11 40.61
Σ UFAs 47.76 58.52
[(C12:0 + (4 × C14:0 ) + C16:0 )] Σ MUFAs 10.26 33.62
AI = (3) Σ PUFAs 37.50 24.90
(PUFA + MUFA)
Σ n-6 28.44 24.84
Σ n-3 9.06 0.06
(C12:0 + C16:0 + C18:0 )
TI = (4) Total 97.87 99.13
[(0.5XMUFA) + (0.5Xn6PUFA) + (3Xn3PUFA) + (n3PUFA
n6PUFA
)] Nutritional indices
P/S 0.75 0.61
C18:1 + PUFA AI 1.06 0.62
H/H = (5) TI 1.03 1.38
(C14:0 + C16:0 )
H/H 1.08 1.62

2.7. Infrared spectroscopy
The absorption spectra were obtained by Fourier-transform infrared
spectroscopy (FTIR) in a Shimadzu spectrometer (IR Prestige 21 Cat. n◦
206-73600-36, Kyoto, Japan) with spectral absorption ranging from
4000 to 400 cm− 1. The samples were incorporated using potassium
bromide (KBr) pellets, analyzed at 4 cm− 1 of resolution and 100 scans.
The spectral curve bands were analyzed with the Origin 8.0 software.
2.8. Differential and thermogravimetric analyses
The thermogravimetric and differential (DTG) analyses were per­
formed using a thermogravimetric analyzer (Shimadzu-DTG-60 H,
Tokyo, Japan) with 60 mL min− 1 of air flow, 10 ◦ C min− 1 of heating
ramp, temperature ranging from 20 ◦ C to 800 ◦ C, aluminum crucible and
sample mass of 5 ± 0.5 mg.
3. Results and discussion
3.1. Extraction yield, acidity and peroxide indices of the T. catappa oils
The characteristics of raw materials, such as humidity and particle
size, are important factors that may influence the extraction yield
(Durante, Lenucci, D’Amico, Piro, & Mita, 2014; Rai, Mohanty, &
Bhargava, 2016). The TCP and TCN were dried until less than 5% of
water content remained and ground into a fine powder with a particle
size of ~0.70 mm (24 mesh). The oil extraction yields obtained by SFE
were 7.4% and 61.5% from the TCP and TCN, respectively. The amount
of TCP oil obtained in the present study was 2 times higher than the
value of 2.8% found by Marques et al. (2012) for T. catappa pulp from
Brazil. Using organic solvents for lipid extraction, Ladele et al. (2016)
and Menkiti et al. (2015) obtained oil yield values from T. catappa nuts
ranging from 60.5% to 64.7%. The oil extraction yield from the
T. catappa seeds using Soxhlet apparatus with hexane achieved a value
of 57.5% (Janporn et al., 2015). According to Ladele et al. (2016),
T. catappa nuts produce greater quantities of oil than most conventional
oilseeds like palm kernel (36%) and groundnut (42%). The TCN oil yield
was also similar to the values determined for hazelnut (up to 63.6%) and
higher than that for peanut (51.5%) as reported by Al Juhaimi et al.
(2018). The oil extracted from soybean by CO2 SFE in the work of Jokić
et al. (2015) presented a yield of 19.3%, much lower than that of the
Results are expressed as mean ± standard deviation (n = 3). - Not detected or not
informed. P/S: spolyunsaturated/saturated fatty acids. AI: atherogenicity index,
TI: thrombogenicity index and H/H: Σ hypocholesterolemic/Σ hypercholester­
olemic ratio.
TCN using the same method. This could, however, be related to the
intrinsic characteristics of the oilseed matrix. The comparison of the
extraction yield from other oilseed commodities with that of the TCN
highlight this underutilized fruit as a great source of lipids.
Standard parameters of lipid oxidation or hydrolysis can be based on
the determination of peroxide and acidity values. Both indices should be
low as possible in edible oils for human consumption (Ratusz, Symo­
niuk, Wroniak, & Rudzińska, 2018). A high acidity value is an indication
of the degree of hydrolytic degradation associated with the content of
free fatty acids and oil changes (Ghafoor, Özcan, Al-Juhaimi, Babiker, &
Fadimu, 2019; Ratusz et al., 2018). The acidity values of the TCP and
TCN oils, 3.3 ± 0.5 and 1.9 ± 0.3 mg KOH g− 1, respectively, were lower
than the maximum recommended value, 4.0 mg KOH g− 1, for virgin fats
and oils (Codex Alimentarius, 2001). Several reasons have been pro­
posed for the high levels of acidity in vegetable oils, including fruit yield
per tree, ripening stage, nitrogen supplementation and fungal infesta­
tion (Bustan et al., 2014). The acidity in the T. catappa oils may likely be
related to the ripening stage of the fruits, as they were harvested at the
point of maturity. Bustan et al. (2014) suggested that although the high
acidity in extra virgin olive oil can be associated to several factors, the
advanced ripening of its olives (Olea europaea L.) presented a substantial
risk for degrading its quality. The n-hexane solvent extraction of
T. catappa nut oil from Thailand (Janporn et al., 2015) and Nigeria
(Menkiti et al., 2015) revealed acidity values of 2.3 and 4.7 mg KOH g− 1,
respectively, which are higher than the values reported in the present
study. These differences could be attributed to the extraction method, as
the SFE does not promote deleterious effects that are typically caused by
the high temperatures or organic solvents employed in conventional
techniques such as Soxhlet (de Melo et al., 2014).
The peroxide values observed in the TCP and TCN oils from tropical
almond were 3.75 ± 0.25 and 1.73 ± 0.55 mEq kg− 1, respectively. These
results were higher than that reported (0.65 mEq kg− 1) by Janporn et al.
(2015) for the tropical almond nut from Thailand. According to the
Codex Alimentarius (2001), virgin oils should have a maximum
peroxide value of 15 mEq active oxygen kg− 1. Variables such as climate,
region, storage, type of processing and higher composition of

3
O.V. Santos et al. Food Research International xxx (xxxx) xxx

unsaturated fatty acids, could account for the differences in peroxides

reported for T. catappa nut oils in the literature, as well as for the TCP oil
(Li, Liu, Sun, & Liu, 2018). Based on the low levels of these parameters
determined in the present study, it can be inferred that the quality of the
extracted oil fractions obtained by CO2 SFE are well-preserved and that
the oil could be acceptable for human consumption and for use in other
food applications.

3.2. Fatty acid compositions, hypocholesterolemic/hypercholesterolemic

ratio, atherogenicity and thrombogenicity indices

The FA profile of the TCP and TCN oils are shown in Table 1. The
UFAs were dominant in the TCN oil with levels greater than 58%. The
most prevalent UFAs were oleic (C18:1) and linoleic (C18:2) acids, which
can be classified as n-9 and n-6, respectively. On the other hand, the
SFAs constituted the majority, ~50%, of FAs in the TCP oil, where
palmitic acid (C16:0) was the most abundant FA at ~42%. When
compared to the UFA content of other oilseeds investigated by Al
Juhaimi et al. (2018), such as peanuts (56.7–57.1%) and hazelnuts
(74.3–75.2%), the TCP oil displayed similar values to the former and
smaller values than the latter. Menkiti et al. (2015) found that palmitic
acid was the major FA (36%) in the oil extracted from the T. catappa
kernel. In the present study, the amount of oleic acid in the TCN oil was
three times higher than that from the TCP. The high content of oleic acid
in the TCN oil could be an indication of a greater potential in terms of
health functionality than the TCP oil, since diets that substitute SFAs for
UFAs have been associated with a reduction of total cholesterol and the
prevention of cardiovascular diseases (Briggs, Petersen, & Kris-Etherton,
2017). Both the TCP and TCN oils presented around 25% of omega-6
fatty acids, expressed as linoleic acid (C18:2) and arachidonic acid
(C20:4). However, the TCP oil exhibited greater amount of omega-3 fatty
acids (C18:3), around 9% compared to ~0.1% in the TCN oil. A study of
tropical almond (T. catappa) nut oil from an African region by Ladele
et al. (2016) showed a predominance of UFAs (~54%), such as oleic
(26%) and linoleic (27%) acids. Menkiti et al. (2015) also described a
lower value of UFAs (56%) as well as a higher value of SFAs (44%) for Fig. 1. FTIR spectrum of the (a) TCP and (b) TCN oils.
the T. catappa kernel oil compared with the values found in the TCN oil
in the present study, 58.6% and 40.8%, respectively. The SFE is more As well as the P/S ratio, other indices, such as the AI, TI and H/H, are
selective for PUFAs than other methodologies, which could explain the linked to the nutritional quality of FAs in edible oils. The AI and TI
higher proportion of UFAs in this study compared to others (de Melo values should be as low as possible (close to zero) in the human diet
et al., 2014). while the H/H value should be high (Pinto et al., 2018). The AI and TI of
Both TCP and TCN oils presented greater amounts of UFAs (up to the palm oil, 2.7 and 3.5, are more than double the values for the TCP
47%) than palm oil (17%) (Mancini et al., 2015). However, the largest and TCN oils (Mancini et al., 2015). Meanwhile the H/H for the TCP and
difference was related to the proportions of PUFAs in the oils from TCN oils is higher than that of the palm oil, which is an indication of the
T. catappa, up to 25%, and from the palm tree, Elais guineensis, 2.4% high proportion of PUFAs to SFAs in the oils from T. catappa. Therefore,
(Mancini et al., 2015). Despite the low proportion of UFAs and high the T. catappa oils have greater amounts of hypocholesterolemic fatty
SFAs, oil from the palm tree has become the most important source of acids than the palm oil. Taken together, it can be inferred that the oils
edible oil in the world (United States Department of Agriculture, 2019; from TCP and TCN possess good nutritional composition and could be
Mancini et al., 2015). The use of palm oil has grown exponentially, used in food products.
mainly due to its improvement of sensory properties in food products The FA composition of the lipid fractions is highly relevant for the
such as cookies, crackers, baked goods and frying fats (Mancini et al., growth, development and maintenance of several functions in human
2015). However, sources of oils that have more beneficial properties, in metabolism and good health. FA activities are particularly related to the
terms of health nutrition, are required for the market, and based on this formation and maintenance of cell membranes, pro- and anti-
comparison, the TCP and TCN oils could potentially be a great option. inflammatory responses of the immune system, as well as functioning
The hypocholesterolemic/hypercholesterolemic ratio, and athero­ as antioxidants, and in the protection against the development of pa­
genicity and thrombogenicity indices of the lipid fractions in the TCP thologies (Pinto et al., 2018; Saini & Keum, 2018). The application of
and TCN oils are listed in Table 1. For comparison purposes, the H/H these parameters in the selection of dietary lipids with improved
ratio, AI and TI indices of palm oil, Elais guineensis, were calculated in nutritional quality may be helpful in the reduction of cardiovascular and
the present work based on the FA profile reported by Mancini et al. other non-transmissible chronic diseases (Janporn et al., 2015).
(2015). The PUFA/SFA (P/S) ratio provides important information
regarding the nutritional properties of edible oils, as a greater propor­
tion of PUFAs in oils can prevent body weight increase in high-fat diets 3.3. Infrared spectroscopy
(Liao, Liou, Shieh, & Chien, 2010). The results of the P/S ratio in the TCP
and TCN oils were 0.7 and 0.6, respectively. These ratios are similar to The Fourier-transform infrared spectroscopy (FTIR) is an analytical
that of extra virgin olive oil (0.6) (Rohman & Man, 2010) and higher tool that enables the identification of some groups of substances by their
than the value (0.02) for palm oil (Mancini et al., 2015). chemical spectral bands (Lerma-García, Ramis-Ramos, Herrero-

4
O.V. Santos et al.
Fig. 2. Differential (DTA and DTG) and thermogravimetric (TGA) curves of the (a) TCP and (b) TCN oils.
Martínez, & Simó-Alfonso, 2010). FTIR is also important for the evalu­
ation and prediction of oxidation states and to follow peroxides changes,
as well as to detect adulteration in vegetable oils (Araújo, Do Monte, &
Batista, 2018; Lerma-García et al., 2010; Rohman & Man, 2010). The
FTIR spectra of the TCP and TCN oils are shown in Fig. 1, which pre­
sented typical absorption bands of triglycerides and FAs. The band
designation was registered according to the literature. The TCP and TCN
oil spectra were revealed to be similar, as can be visualized in Fig. 1a–b,
however, slight variations in the band frequencies and intensities can be
observed, due to their different composition and nature.
Both the TCP and TCN oils had bands that ranged between 2912 and
2846 cm− 1 related to the stretching vibration of methylene (–CH2),
with different intensities between these oils (Hernández-Martínez, Gal­
lardo-Velázquez, & Osorio-Revilla, 2010; Lerma-García et al., 2010).
This divergence may be due to the discrepant proportions of linolenic
acyl groups to oleic acyl groups in the oils, since C18:2 exhibits high
frequency for this band region (Rohman, Kuwat, Retno, Sismindari, &
E., & Tridjoko, W. , 2012). The TCN and TCP oils also presented bands
ranging between 1745–1738 cm− 1 and 1462–1449 cm− 1 related to the
stretching vibration of triacylglycerol ester linkages (–C–– O) and to the
bending vibrations of aliphatic CH2 and CH3 groups (–C–H) or to the
5
Food Research International xxx (xxxx) xxx
stretching vibration of amino groups (N– – C), respectively (Hernández-
Martínez et al., 2010; Lerma-García et al., 2010; Rohman & Man, 2010).
The bands in this region had high intensity in the TCN oil (Fig. 1b) when
compared to the TCP oil (Fig. 1a), which may be due to differences in
long-branched FAs, triglycerides and other organic compounds (Lerma-
García et al., 2010; Rohman & Man, 2010).
Other prominent bands between 1257 and 1013 cm− 1 can be linked
to –C–O stretching and are commonly named as a fingerprint region of
the sample (Lerma-García et al., 2010; Rohman & Man, 2010). The band
absorption in this region is again different in both the TCP and TCN oils.
In the TCN oil spectrum, a high intensity band at 1154 cm− 1 can be
observed, which may be linked to its high amount of oleic acyl groups as
has been previously reported in the literature (Rohman et al., 2012).
The bands around 796–716 cm− 1 are associated to the bending vi­
brations of C–H (out of plane vibration of cis-disubstituted olefin) and
saturated carbon-carbon bonds (Rohman et al., 2012; Lerma-García
et al., 2010). The high amounts of SFAs in the TCP oil may be responsible
for the intensity band at 796 cm− 1, due to vibrations of aliphatic chains
of FAs (Santos et al., 2013) or to the addition of CC trans double bonds
(Gardette & Baba, 2013).
It is worth mentioning that spectral bands around 3600–3000 cm− 1
O.V. Santos et al.
and 900 cm− 1 were not observed. The first region can be related to the
formation of hydroperoxides or replacement of their secondary oxida­
tion products, and the second region may be associated to variations in
CC trans and CC cis double bonds, thus the absence of these bands may
suggest good preservation of the T. catappa oils (Gardette & Baba, 2013).
The FTIR results also corroborate the chromatographic FA profile
determined in the present work.
3.4. Differential and thermogravimetric analyses
The differential (DTA and DTG) and thermogravimetric (TGA)
curves were used to study the thermal stability of the TCP and TCN oils
from the tropical almond.
The thermal stability curves of the TCP oil are shown in Fig. 2a. A
first mass loss around 280 ◦ C can be observed in the TGA curve, which is
related to the initial decomposition temperature (Tonset or IDT), during
which the main organic matter begins degradation. This temperature
was higher than the Tonset of the TCN oil (Fig. 2b), which can be
attributed to the larger amounts of SFAs found in the TCP oil. The second
mass loss step (peak temperature) for the TCP oil occurred near 350 ◦ C
(DTA curve in Fig. 2a), followed by a final degradation step until 700 ◦ C,
with 38% carbonized final residues (FR) remaining. The DTA curve
showed three successive exothermal events between 300 and 400 ◦ C as a
result of the intense degradation processes of the organic matter caused
by the increased temperature. This temperature range can be related to
the D1/2 (or D-half), in which 50 wt% of the sample has decomposed,
mainly occurring around 350 ◦ C. These changes result in liberation of
energy that account for the exothermal behavior of samples.
As can be seen from the TGA curve and more precisely from the DTG
curve of the TCN oil (Fig. 2b) a small first mass decay occurred around
100 ◦ C, which was related to the water content and volatile compounds
(Chacón-Fernández, Hernández-Medel, Bernal-González, Durán-Domí­
nguez-de-Bazúa, & Solís-Fuentes, 2019). The second mass loss step
occurred around 230 ◦ C related to Tonset. This may be explained by the
major amounts of linoleic and oleic FAs in the TCN oil, since the Tonset of
these UFAs is around 200–230 ◦ C (Li et al., 2018). A third mass loss step
(peak temperature) can be visualized between 350 ◦ C and 400 ◦ C
through the exothermal DTA peak, which comprises the D1/2, followed
by a final mass loss step until 700 ◦ C, after which 34% of the carbonized
FR matter remained.
It is well recognized that the degree of unsaturation, length and
branching of the FA chain highly influences the characteristics of ther­
mal stability of oils and can affect its industrial processability (Janporn
et al., 2015). Therefore, the high proportion of UFAs in the TCN oil likely
contributed to its susceptibility to oxidative factors and high tempera­
tures. While the TCP oil, due to the predominance of SFAs, presented
greater stability to the temperature increase.
4. Conclusions
The present study showed that the oil extraction yield from the
T. catappa nuts was 10 times higher than from its pulp, and that the nut
oil had lower levels of acidity and peroxides than the pulp oil. The high
content of free fatty acids and peroxides in the pulp oil may be related to
the ripening stage of the T. catappa fruits. The oils displayed different
fatty acid compositions, with a predominance of saturated fatty acids in
the pulp and unsaturated fatty acids in the nut, with emphasis on omega
3, 6 and 9 fractions. The thrombogenicity, atherogenicity and hypo­
cholesterolemic/hypercholesterolemic ratio of the T. catappa oils
exhibited varied results related to their different proportions of fatty
acids. This data indicates that the inclusion of these oils in the diet may
provide health benefits through the possible reduction of total choles­
terol and LDL fractions. The infrared spectroscopic profile of both oils
confirms the presence of long-chain functional groups, such as tri­
glycerides, with the absence of frequency bands related to their oxida­
tion. The oils had good thermal stability when considering the common
6
Food Research International xxx (xxxx) xxx
temperatures used in industrial products processing. Further studies are
required to determine the effect of the application of blend extractions/
solvents on the nutritional composition and bioactive compounds of the
T. catappa oils. Overall, the present study shows that the T. catappa oils
extracted by supercritical fluid extraction, an advantageous green
extraction technique, have positive features that highlight it as an un­
conventional lipid matrix for potential use in several industries, from
food to the chemical-pharmaceutical fields. These results motivate
further lines of investigation, including additional studies to determine
the thermal-oxidative stability of these oils obtained by applying
different extraction methods, the development of binary and ternary
mixtures with commercial oils, as well as the chemical identification of
their bioactive organic compounds for future incorporation into food
products.
Conflict of interest
The authors declare no conflict of interest.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Acknowledgements
The authors are grateful to the Laboratory of Supercritical Extraction
and Professor Raul Nunes de Carvalho from the Federal University of
Pará (UFPA) for allowing the use of the supercritical fluid extraction
equipment.
References
Agu, C. M., Menkiti, M. C., Nwabanne, J. T., & Onukwuli, O. D. (2019). Comparative
assessment of chemically modified Terminalia catappa L. kernel oil samples – a
promising ecofriendly transformer fluid. Industrial Crops and Products, 140, 111727.
https://doi.org/10.1016/j.indcrop.2019.111727.
Al Juhaimi, F., Uslu, N., & Özcan, M. M. (2018). The effect of preultrasonic process on oil
content and fatty acid composition of hazelnut, peanut and black cumin seeds.
Journal of Food Processing and Preservation, 42, e13335. https://doi.org/10.1111/
jfpp.13335.
AOCS - American Oil Chemists Society. (2004). Official methods and recommended
practices of the AOCS (5th ed.). Champaign, Illinois: AOCS.
Araújo, A. P. C., Do Monte, A. F. G., & Batista, F. R. X. (2018). Evaluation of the
temperature effect on vegetable oils by chemical analysis and ultraviolet–visible
spectroscopy. Bioscience Journal, 34, 28–36. https://doi.org/10.14393/BJ-v34n6a2
018-39934.
Aydi, A., Zibetti, A. W., Al-Khazaal, A. Z., Eladeb, A., Adberraba, M., & Barth, D. (2020).
Supercritical CO2 extraction of extracted oil from Pistacia lentiscus l.: Mathematical
modeling, economic evaluation and scale-up. Molecules, 25, 199. https://doi.org/
10.3390/molecules25010199.
Briggs, M., Petersen, K., & Kris-Etherton, P. (2017). Saturated fatty acids and
cardiovascular disease: Replacements for saturated fat to reduce cardiovascular risk.
Healthcare, 5, 29.
Bustan, A., Kerem, Z., Yermiyahu, U., Ben-Gal, A., Lichter, A., Droby, S., … Dag, A.
(2014). Preharvest circumstances leading to elevated oil acidity in ‘Barnea’ olives.
Scientia Horticulturae, 176, 11–21. https://doi.org/10.1016/j.scienta.2014.06.028.
Chacón-Fernández, M. G., Hernández-Medel, M. R., Bernal-González, M., Durán-
Domínguez-de-Bazúa, M. C., & Solís-Fuentes, J. A. (2019). Composition, properties,
stability and thermal behavior of tamarind (Tamarindus indica) seed oil. Grasas y
Aceites, 70, 333.
Chavan, S. B., Yadav, M., Singh, R., Singh, V., Kumbhar, R. R., & Sharma, Y. C. (2017).
Production of biodiesel from three indigenous feedstock: Optimization of process
parameters and assessment of various fuel properties. Environmental Progress &
Sustainable Energy, 36, 788–795. https://doi.org/10.1002/ep.12606.
Codex Alimentarius (2001). Codex standards for fats and oils. Codex Stand 210 - 1999.
FAO/WHO Food Standards. Second edition (revised 2001). World Health
Organization, Rome, Italy. http://www.fao.org/3/y2774e/y2774e03.htm#bm3/
(accessed 14 March 2019).
Durante, M., Lenucci, M. S., D’Amico, L., Piro, G., & Mita, G. (2014). Effect of drying and
co-matrix addition on the yield and quality of supercritical CO2 extracted pumpkin
(Cucurbita moschata Duch.) oil. Food Chemistry, 148, 314–320. https://doi.org/
10.1016/j.foodchem.2013.10.051.
Gardette, J.-L., & Baba, M. (2013). FTIR and DSC studies of the thermal and
photochemical stability of Balanites aegyptiaca oil (Toogga oil). Chemistry and Physics
of Lipids, 170–171, 1–7. https://doi.org/10.1016/j.chemphyslip.2013.02.008.
Ghafoor, K., Özcan, M. M., Al-Juhaimi, F., Babiker, E. E., & Fadimu, G. J. (2019).
Changes in quality, bioactive compounds, fatty acids, tocopherols, and phenolic
composition in oven- and microwave-roasted poppy seeds and oil. Lwt – Food Science
and Technology, 99, 490–496. https://doi.org/10.1016/j.lwt.2018.10.017.
O.V. Santos et al.
Hernández-Martínez, M., Gallardo-Velázquez, T., & Osorio-Revilla, G. (2010). Rapid
characterization and identification of fatty acids in margarines using horizontal
attenuate total reflectance Fourier transform infrared spectroscopy (HATR-FTIR).
European Food Research and Technology, 231, 321–329.
Iha, O. K., Alves, F. C. S. C., Suarez, P. A. Z., Silva, C. R. P., Meneghetti, M. R., &
Meneghetti, S. M. P. (2014). Potential application of Terminalia catappa L. and
Carapa guianensis oils for biofuel production: Physical-chemical properties of neat
vegetable oils, their methyl-esters and bio-oils (hydrocarbons). Industrial Crops and
Products, 52, 95–98. https://doi.org/10.1016/j.indcrop.2013.10.001.
International Organization for Standardization, 2000. ISO 5509:2000(E). Animal and
vegetable fats and oils – preparation of methyl esters of fatty acids (2nd ed.). https://
www.sis.se/api/document/preview/616451/ (accessed 16 August 2019).
Janporn, S., Ho, C.-T., Chavasit, V., Pan, M.-H., Chittrakorn, S., Ruttarattanamongkol, K.,
& Weerawatanakorn, M. (2015). Physicochemical properties of Terminalia catappa
seed oil as a novel dietary lipid source. Journal of Food and Drug Analysis, 23,
201–209. https://doi.org/10.1016/j.jfda.2014.06.007.
Jokić, S., Sudar, R., Svilović, S., Vidović, S., Bilić, M., Velić, D., & Jurković, V. (2013).
Fatty acid composition of oil obtained from soybeans by extraction with supercritical
carbon dioxide. Czech Journal of Food Sciences, 31, 116–125. https://doi.org/10.1
7221/8/2012-CJFS.
Jokić, S., Svilovic, S., & Vidovic, S. (2015). Modelling the supercritical CO2 extraction
kinetics of soybean oil. Croatian Journal of Food Science and Technology, 7, 52–57. htt
ps://doi.org/10.17508/CJFST.2015.7.2.05.
Kaneria, M. J., Rakholiya, K. D., Marsonia, L. R., Dave, R. A., & Golakiya, B. A. (2018).
Nontargeted metabolomics approach to determine metabolites profile and
antioxidant study of Tropical Almond (Terminalia catappa L.) fruit peels using GC-
QTOF-MS and LC-QTOF-MS. Journal of Pharmaceutical and Biomedical Analysis, 160,
415–427. https://doi.org/10.1016/j.jpba.2018.08.026.
Ko, T.-F., Weng, Y.-M., Lin, S.-B., & Chiou, R. Y. Y. (2003). Antimutagenicity of
supercritical CO2 extracts of Terminalia catappa leaves and cytotoxicity of the
extracts to human hepatoma cells. Journal of Agricultural and Food Chemistry, 51,
3564–3567. https://doi.org/10.1021/jf034102v.
Ladele, B., Kpoviessi, S., Ahissou, H., Gbenou, J., Kpadonou-Kpoviessi, B., Mignolet, E.,
… Moudachirou, M. (2016). Chemical composition and nutritional properties of
Terminalia catappa L. oil and kernels from Benin. Comptes Rendus Chimie, 19,
876–883. https://doi.org/10.1016/j.crci.2016.02.017.
Lasekan, O., & Abbas, K. (2010). Analysis of volatile flavour compounds and acrylamide
in roasted Malaysian tropical almond (Terminalia catappa) nuts using supercritical
fluid extraction. Food and Chemical Toxicology, 48, 2212–2216. https://doi.org/
10.1016/j.fct.2010.05.050.
Lerma-García, M. J., Ramis-Ramos, G., Herrero-Martínez, J. M., & Simó-Alfonso, E. F.
(2010). Authentication of extra virgin olive oils by Fourier-transform infrared
spectroscopy. Food Chemistry, 118, 78–83.
Li, J., Liu, J., Sun, X., & Liu, Y. (2018). The mathematical prediction model for the
oxidative stability of vegetable oils by the main fatty acids composition and
thermogravimetric analysis. LWT – Food Science and Technology, 96, 51–57.
Liao, F. H., Liou, T. H., Shieh, M. J., & Chien, Y. W. (2010). Effects of different ratios of
monounsaturated and polyunsaturated fatty acids to saturated fatty acids on
regulating body fat deposition in hamsters. Nutrition, 26, 811–817.
Mancini, A., Imperlini, E., Nigro, E., Montagnese, C., Daniele, A., Orrù, S., & Buono, P.
(2015). Biological and nutritional properties of palm oil and palmitic acid: Effects on
health. Molecules, 20, 17339–17361. https://doi.org/10.3390/molecules200917339.
Marques, M. R., Paz, D. D., Batista, L. P. R., Barbosa, C.de. O., Araújo, M. A. M., &
Moreira-Araújo, R. S.dos. R. (2012). An in vitro analysis of the total phenolic
content, antioxidant power, physical, physicochemical, and chemical composition of
Terminalia Catappa Linn fruits. Food Science and Technology, 32, 209–213. https://
doi.org/10.1590/S0101-20612012005000023.
Melgosa, R., Sanz, M. T., Benito-Román, Ó., Illera, A. E., & Beltrán, S. (2019).
Supercritical CO2 assisted synthesis and concentration of monoacylglycerides rich in
omega-3 polyunsaturated fatty acids. Journal of CO2 Utilization, 31, 65–74. https://
doi.org/10.1016/j.jcou.2019.02.015.
Food Research International xxx (xxxx) xxx
de Melo, M. M. R., Silvestre, A. J. D., & Silva, C. M. (2014). Supercritical fluid extraction
of vegetable matrices: Applications, trends and future perspectives of a convincing
green technology. Journal of Supercritical Fluids, 92, 115–176. https://doi.org/
10.1016/j.supflu.2014.04.007.
Menkiti, M. C., Agu, C. M., & Udeigwe, T. K. (2015). Extraction of oil from Terminalia
catappa L.: Process parameter impacts, kinetics, and thermodynamics. Industrial
Crops and Products, 77, 713–723. https://doi.org/10.1016/j.indcrop.2015.08.019.
Milinsk, M. C., Matsushita, M., Visentainer, J. V., Oliveira, C. C., & Souza, N. E. (2008).
Comparative analysis of esterification methods in the quantitative determination of
vegetable oil fatty acid methyl esters (FAME). Journal Brazil Chemistry Society, 19,
1475–1483.
Nde, D., & Foncha, A. (2020). Optimization methods for the extraction of vegetable oils:
A review. Processes, 8, 209. https://doi.org/10.3390/pr8020209.
Nunes, P. H. M., Martins, M.do. C. C., Oliveira, R.de. C. M., Chaves, M. H., Sousa, E. A.,
Leite, J. R. S. A., … Almeida, F. R. C. (2014). Gastric antiulcerogenic and hypokinetic
activities of Terminalia fagifolia Mart. & Zucc. (Combretaceae). BioMed Research
International, 2014, 1–14. https://doi.org/10.1155/2014/261745.
Ozcan, M. M., Endes, Z., & Er, F. (2010). Physical and chemical properties of some seed
and kernel oils. Asian Journal of Chemistry, 22, 6531–6536.
Pinto, R. H. H., Sena, C., Santos, O. V., Costa, W. A., Rodrigues, A. M. C., & Carvalho
Junior, R. N. (2018). Extraction of bacaba (Oenocarpus bacaba) oil with supercritical
CO2: Global yield isotherms, fatty acid composition, functional quality, oxidative
stability, spectroscopic profile and antioxidant activity. Grasas y Aceites, 69, 246.
Rai, A., Mohanty, B., & Bhargava, R. (2016). Supercritical extraction of sunflower oil: A
central composite design for extraction variables. Food Chemistry, 192, 647–659.
https://doi.org/10.1016/j.foodchem.2015.07.070.
Ratusz, K., Symoniuk, E., Wroniak, M., & Rudzińska, M. (2018). Bioactive compounds,
nutritional quality and oxidative stability of cold-pressed camelina (Camelina sativa
L.) oils. Applied Sciences, 8, 2606. https://doi.org/10.3390/app8122606.
Rohman, A., & Man, Y. B. C. (2010). Fourier transform infrared (FTIR) spectroscopy for
analysis of extra virgin olive oil adulterated with palm oil. Food Research
International, 43, 886–892.
Rohman, A., Kuwat, T., Retno, S., Sismindari, Yuny, E., & Tridjoko, W. (2012). Fourier
transform infrared spectroscopy applied for rapid analysis of lard in palm oil.
International Food Research Journal, 19, 1161–1165.
Saini, R. K., & Keum, Y. S. (2018). Omega-3 and omega-6 polyunsaturated fatty acids:
Dietary sources, metabolism, and significance – A review. Life Sciences, 203,
255–267.
Santos, O. V., Corrêa, N. C. F., Carvalho, R. N., Costa, C. E. F., & Lannes, S. C. S. (2013).
Yield, nutritional quality, and thermal-oxidative stability of Brazil nut oil (Bertolletia
excelsa H.B.K) obtained by supercritical extraction. Journal of Food Engineering, 117,
499–504. https://doi.org/10.1016/j.jfoodeng.2013.01.013.
Santos, O. V., Lorenzo, N. D., & Lannes, S. C. S. (2016). Chemical, morphological, and
thermogravimetric of Terminalia catappa Linn. Food Science and Technology, 36,
151–158. https://doi.org/10.1590/1678-457x.0090.
Santos-Silva, J., Bessa, R. J. B., & Santos-Silva, F. (2002). Effect of genotype, feeding
system and slaughter weight on the quality of light lambs. Livestock Production
Science, 77, 187–194.
Singh, S. P., & Choudhary, M. R. (2012). Indian Almond in Production technology of fruit
crops in Wasteland (pp. 181–185). Jodhpur, India: Scientific Publishers.
Thomson, L. A. J., & Evans, B. (2006). Terminalia catappa (tropical almond)
Combretaceae (combretum family) In: Elevitch, C.R. (Ed.). Species Profiles for
Pacific Island Agroforestry (pp. 1–20). Hawai’i: Permanent Agriculture Resources
(PAR). http://agroforestry.net/tti/T.catappa-tropical-almond.pdf. (accessed
02.06.2019).
Ulbricht, T. L., & Southgate, D. A. (1991). Coronary heart disease: Seven dietary factors.
The Lancet, 338, 985–992.
United States Department of Agriculture (2019). Oilseeds: world markets and trade In
Foreign Agricultural Service/USDA. World Production, Markets, and Trade Reports
(October, 2019) URL https://apps.fas.usda.gov/psdonline/circulars/oilseeds.pdf.
(acessed 21.10.2019).