Research Article
Marcelle Guth de Freitas Batista
Marcelle Guth de Freitas Batista
Corresponding
Author
Department of
Chemical Engineering, Federal University of Paraná, CEP 81531-990,Curitiba, PR,
Brazil.
E mail: marcelleguth@ufpr.br;
Tel: +55 41 99638-7824
Mônica Beatriz Kolicheski
Mônica Beatriz Kolicheski
Department of Chemical Engineering, Federal University of Paraná, CEP 81531-990, Curitiba, PR, Brazil
E mail: monica.beatriz@ufpr.br
Juliano Marques Fiorani
Juliano Marques Fiorani
Department of Chemical Engineering, Federal University of Paraná, CEP 81531-990, Curitiba, PR, Brazil.
E mail: Juliano.fiorani@gmail.com
Marcos Lúcio Corazza
Marcos Lúcio Corazza
Department of Chemical Engineering, Federal University of Paraná, CEP 81531-990, Curitiba, PR, Brazil
E mail: corazza@ufpr.br
Fernando Augusto Pedersen Voll
Fernando Augusto Pedersen Voll
Department of Chemical Engineering, Federal University of Paraná, CEP 81531-990, Curitiba, PR, Brazil
E mail: fernando_voll@ufpr.br
Abstract
The tangerine juice
corresponds to 47 wt.% of the fruits and it is normally extracted by pressing
generating agro-industrial waste rich in compounds with market value. Thus, the
objective of this study was to obtain the essential oil from Citrus reticulata Blanco peels and
compare it with those obtained from the waste of the ponkan tangerine juice industry, rich in d-limonene. The waste and peels were cut into pieces of approximately
1 cm², dried in an oven with air circulation at 50 °C for 15 h, ground, and
classified by sieving with particle size between 20 to 28 mesh. The
moisture content in dried waste and peels were 8.5 wt.% and 6.0 wt.%, respectively. A particle size was
defined for the extractions. The essential oil extractions were performed by
hydrodistillation, in Clevenger method, with 50 g of sample, 500 mL of
distilled water for 2 h. The essential oil yield was 0.22 wt.% (88.5 % of d-limonene)
for ponkan waste and 1.65 wt.% of for ponkan peel (89.7 % of d-limonene). The
results showed that separation of the Ponkan peel before processing the fruit
enables more efficient extraction of the compounds of interest.
Abstract Keywords
Tangerines, d-limonene,
hydrodistillation, extraction, waste, terpenes
1.
Introduction
Ponkan peels essential oil has the same
characteristics as the essential oils of citrus, which present high antioxidant,
fungicidal, and mainly bactericidal capacity [1–3]. This is characterized, as green oil, yellow oil,
and red oil, according to the degree of maturity of the fruit and the
extraction method used [4]. Furthermore, these oils are applied in several
areas, such as the perfumery, food and beverage, cleaning materials and
pharmaceutical industries [5]. Kwangjai et al. [6] reported that Ponkan peel essential oil
contains anxiolytic compounds that modify brain waves (95.7% d-limonene),
contributing to the sleep phase of increased physical energy recovery occurring
more often and for longer periods. Similar properties to the essential oil of
tangerine or mandarin (Citrus reticulata)
and bergamot (Citrus bergamia), which
have antidepressant, tranquilizing, calming and sedative properties [7]. Ferreira, Silva and Nunes [8] concluded that Citrus reticulata Blanco peel extract has antioxidant properties
due to the high d-limonene content. Dosoky and Setzer [9] reported protective activity against pulmonary
fibrosis (74.2% d-limonene). Oliveira et al. [10] showed the efficacy of Ponkan peel essential
oil against Leishmania amazonensis, and Zhang et al. [11] proved the bactericidal
activity of this same essential oil.
The chemical composition of essential oils is
genetically determined, but can be altered due to environmental stimuli,
causing selectivity or the biosynthesis of other compounds. Among these stimuli
are the plant interaction with other living beings, the time of the year and
the harvest time. Furthermore, different abiotic stresses, such as drought,
concentration of salts and heavy metals in the soil, temperature, and UV
radiation can reduce the uptake and diffusion of CO2 and alter the
different biochemical reactions of the plant. Different stimuli affect
photosynthesis and essential oil production and consequently its chemical
composition [12–14].
The essential oil of Citrus reticulata
has 70% to 85% d-limonene, 5% linanool and 2% furanocoumarins [7], and regarding the essential oil from Ponkan
peels, as expected, studies by different authors have shown that d-limonene
is the main component in the essential oil. According to the literature
Kwangjai et al. [6] and Singh et al. [15] it ranges from 89% to 95% in composition. Table 1
presents the chemical composition in terms of major compounds found in
essential oils from Ponkan peel.
Table 1. Chemical composition of the essential oil from citrus reticulata Blanco
Majority components, 5.1 to 96.0% |
Intermediate components, 1.0 to 5.0% |
Minority components, 0.0 to 0.9% |
Country
of study |
References |
d-Limonene,
γ-Terpinene |
myrcene |
α-tujene, α-pinene, sabiene, trans-β cymene,
citronellal, geraniol, geranial, α -terpineol, limonene oxide |
Brazil |
[16] |
d-Limonene |
γ-terpinene |
- |
India |
[15] |
d-Limonene |
β-pinene, -3-carene |
α-pinene, β-fellandrene |
Thailand |
[6] |
d-Limonene |
β-pinene, γ-terpinene |
α-tujene, α-pinene, sabienol, myrcene, p-cymene,
terpinolene, linalool, n-decanal |
Brazil |
[5] |
d-Limoneno,
γ-Terpinene |
α-pineno, β-pineno, β-mirceno |
Sabieno, p-cimeno, n-metil antranilato
de metilo |
Brazil |
[17] |
d-Limoneno,
γ-Terpinene |
β-mirceno |
α-tujeno, α-pineno, sabieno, β-pineno,
α-terpineno, o-cimeno, terpinoleno, terpinen-4-ol, α-terpineol, metil
éter timol |
Brazil |
[18] |
Besides d-limonene and other terpenes can
be identified essential of Ponkan peel, such as γ-terpineno, β-pinene, γ-3-carene, β-myrcene, in amounts ranging from 1% to 5%. Terpenic
alcohols (linalool, terpinen-4-ol, α-terpineol), esters (n-methyl
anthranilate), aldehydes (n-decanal) and methyl ether phenols (methyl
ether thymol) are present in amounts less than 1%.
d-Limonene (C10H16),
the major component of essential oils from Ponkan peel is an aliphatic
hydrocarbon (non-oxygenated monoterpene, cyclic and consisting of two isoprene
units), colorless, non-toxic, and identified as the main component of essential
oils from different citrus species. Being known for its pleasant citrus
fragrance it is commonly used as a flavoring and antioxidant in beverages and
foods [15,19].
Because of this, it has applications in numerous
industries, such as in perfumes, paints, component of bio-pesticides [20]. Besides the organoleptic and antioxidant
properties, d-limonene has
therapeutic characteristics, being an adrenocortical stimulant, expectorant,
anxiolytic, antiviral, digestive, anti-inflammatory and chemo-preventive [7]. As a raw material for the natural production of
terpenoid flavors and fragrances, d-limonene
can be converted into several high value-added compounds, such as α-terpineol, menthol, carvone, limonene-1,2-diol, and
perillyl alcohol [21–23]. d-Limonene can be obtained
from fruit peel and citrus waste
by extraction techniques such as hydrodistillation [15, 24] and this is the focus of this study.
Hydrodistillation is a traditional essential oil
extraction technique that the matrix is immersed in water and the system is
heated to evaporation, where the water vapors carry the essential oil
particles. The simplicity of the equipment and its high selectivity are
positive aspects of this approach. With the use of the Clevenger-type apparatus
it is possible to extract and separate volatile and non-volatile compounds
present in different plant species [25–28]. However, there is a lack of information on the
extraction of Ponkan essential oil from agroindustrial waste in the literature. Thus, the present work aims
to compare the yield of essential oil and the compounds extracted of the peels
and the waste of Ponkan.
2.
Materials and methods
The waste of ponkan (PW) was purchased in the region of Cerro Azul, state of Paraná, Brazil. This raw material consisted of peel, seeds and pulp and was cut into pieces of approximately 1 cm². Citrus reticulata Blanco fruits were purchased in the same region as PW. The peels were manually separated from the fruit and cut into pieces of approximately 1 cm2, thus this raw material (named PP) consisted only of peels. The raw materials were dried in an oven with air circulation at 50 °C for 15 hours until they obtained moisture below 10 wt% [29], ground in a Willey-type knife mill and classified into two fractions (Tyler between 20 to 28 and 28 to 35 mesh). Moisture was determined according to Sluiter et al. [30] in a Shimadzu infrared balance (Model ID200). The analyses were performed in triplicate, using approximately 1.0 g of sample. The essential oil was extracted by hydrodistillation in Clevenger apparatus, for 2 h, using 50 g of dry solid (mss) and 500 mL of distilled water (Vw) [2]. PW extractions were performed for two fractions with different particle diameter to verify the influence of surface area on extraction yield, while PP extractions used only 20 to 28 mesh. The amount of essential oil obtained (mE) was determined in a Radwag AS C/220/2 analytical balance and then dried with NaSO4 and stored in amber flasks at - 4 °C. FIGURE 1 shows the Clevenger used (A) and the oil obtained (B).
Figure
1. Hydrodistillation (a): Clevenger apparatus, (b): Essential oil (detail) and water in
the decanter.
EO yield (ηEO) of the extractions was obtained by the ratio between the mass of EO (mEO), and the mass of dry solid (mDS) on wet basis (WB) and dry basis (DB), in which the moisture (χw) was considered, according to Equations 1 and 2.
(1)
(2)
The essential oil was analyzed by gas chromatography mass
spectroscopy (GC-MS), after dilution in chromatographic grade hexane (Panreac -
UV-IR-HPLC). Chromatographic analyses were performed on a Shimadzu TQ8040
chromatograph with a ZB-5MS column (30 m x 0.25 mm x 0.25 μm)
following a method proposed by Ozturk, Winterburn and Gonzalez-Miquel [31] for identification and quantification of
d-limonene. The NIST (National Institute of Standards and Technology) mass
spectrometry library was adopted for the identification of the other compounds
present. The 30 largest peaks were considered for
quantification, with a minimum area
of 100.000 ua and the mass fraction of each compound was calculated from the
area of each peak using Postrun GC-MS software.
The d-limonene mass (mL), in g, was calculated with the mass fraction of d-limonene (mL) present in the EO (mEO) as shown in Equation (3).
(3)
The d-limonene selectivity was calculated according to Equation 4.
(4)
To verify the possible
profitability of the process, a simplified calculation was performed for the
production of essential oil (PEO), according to Equation 5.
(5)
In which:
mp= annual Ponkan production
(tons)
χj
= juice mass fraction in fruits
χw =
moisture mass fraction of waste
ηEO = essential oil mass fraction yield
3. Results
and discussion
3.1
Characterization of raw
material
The characteristics shown
of PW and PP
are in TABLE 2. It can be observed that the final moisture content of PW was
higher than PP due to the initial
characteristics of this raw material that contains much higher water content
(77.20 ± 0.60%), since it is obtained after the juice extraction process.
Table
2. Characteristics of the
raw materials used to obtain the essential oil
Characteristic |
Agroindustrial waste (PW) |
Fruit Peel (PP) |
Color |
Orange |
Orange |
Aroma |
Citric |
Citric |
moisture raw material (wt%) |
77.20 ± 0.60 |
64.17 ± 0.02 |
Moisture dry material (wt%) |
8.5 ± 0.4 |
6.01
0.06 |
3.2 Essential oil
extraction
The essential oil of Citrus reticulata
Blanco obtained from PW and PP
for the particles sorted between 20 and 28 mesh was extracted by
hydrodistillation. Due to the small volume (0.2 mL) of essential oil obtained from PW, because of the mixed composition of PW, there was difficulty in handling the essential oil.
According to Farrer-Halls [19] the essential oil of Citrus reticulata
Rutaceae, commonly known as tangerine, has an orange-yellow color with sweet
and citrusy top notes - delicate but intense. The essential oil obtained from Citrus reticulata Blanco (Ponkan), for
both PW and PP, had yellow-orange color and citrus aroma and are
like that obtained from mandarin. After 2 hours of hydrodistillation, an
average of 1.5 mL of essential oil was obtained from the peels (related to
50.24 g of peel) and 0.2 mL from the agroindustrial waste (related to 50.08 g of solids). NaSO4
was used to remove the water entrained during the process. The removal of
moisture was necessary so as not to interfere with the composition of the
essential oil obtained. The yields obtained for the two raw materials used in
this study are presented in Table 3.
Table 3. Results of the extractions of Ponkan (PW) waste
and peel (PP) by hydrodistillation (20
to 28 mesh).
Sample |
mS (g) |
mEO (g) |
VEO (mL) |
dEO (g/mL) |
ηEO (%WB) |
dEO (%DB) |
PW |
50.08 ± 0.07 |
0.11 ± 0.01 |
0.20 ± 0.01 |
0.55 ± 0.02 |
0.399 ± 0.002 |
0.436 ± 0.002 |
PP |
50.24 ± 0.34 |
0.83 ± 0.01 |
1.50 ± 0.01 |
0.56 ± 0.01 |
2.970 ± 0.200 |
3.186 ± 0.013 |
mS: solid mass, mEO: essential oil mass, VEO: essential oil volume, ηEO: essential oil yield, dEO: density.
|
Although several studies have been developed for
the valorization of Citrus industrial waste, there are few studies on
obtaining essential Citrus reticulata Blanco oil from peels and waste by hydrodistillation [32–34]. Essential oil yield of 3.186% (WB) was obtained
for PP, a value 7.3 times higher
than that obtained for the waste-approximately
0.44% (DB). Higher yield for PP
was expected, because PW
is composed of peel (50 wt%), pulp (45 wt%), and seed (5 wt%), thus the yield
of essential oil in PP will be higher for the
same mass of dry solid extract.
According to Sharma and Vashist [32], the essential oil yield of Citrus reticulata
Blanco peels was 1.5%wt (WB), and according to Hou et al. [2] the essential oil yield is 3.1%wt
(DB). Those authors performed the extractions for 2 hours, however, the first study
used powdered peels and the second used particles between 20 and 30 mesh.
In this study for 20 to 28 mesh it was obtained approximately 3.0%wt
(DB), a similar value to that obtained by Hou et al. [2].
According to Fetzer et al. [35] and Xiong and Chen [36] particle diameter interferes with the mass transfer rates and diffusion of
the extraction. Thus, it is inferred that smaller particle size could enhance
the mass transfer and improve the extraction yield of the essential oil
obtained from PW. To evaluate this
possibility, hydrodistillation of PW
was performed for particles with diameters of 28 to 32 mesh. The results
compared to those obtained for 20 to 28 mesh are presented in Table 4.
Table 4. Extraction results of
Ponkan (PW) waste by hydrodistillation for 28 mesh and 32 mesh.
Sample |
mS (g) |
mEO (g) |
VEO (mL) |
ηEO (BU) (%) |
20 to 28 mesh |
50.08 ± 0.07 |
0.1100 ± 0.0001 |
0.20 ± 0.01 |
0.3990 ± 0.0005 |
28 to 32 mesh |
50.14 ± 0.20 |
0.1100 ± 0.0001 |
0.20 ± 0.01 |
0.3990 ± 0.0020 |
mS: solid mass, mEO: essential oil mass, VEO: essential oil volume, ηEO: essential oil yield.
As can be seen in
TABLE 4, there was no change in the essential oil yield with the
variation of the particle size range. Ranges below 20 to 28 mesh were
not evaluated, because during milling there is agglomeration of fines making
separation difficult and with a probable loss of essential oil by friction with the
equipment. This could justify the low yield obtained by Sharma and Vashist [32] that used peel powder for extractions.
3.2 Chemical profile
The Ponkan essential oils obtained for PW and PP (20 to 28 mesh) were
analyzed by GC-MS. The semiquantitative method was adopted to quantify the
chemical composition of the essential oil, so it was possible to compare the
fraction of d-limonene in the
essential oil in the different raw materials used. Table 5 shows the main
components identified.
Table 5. Chemical composition of
the essential oil obtained.
Compound |
Essential oil composition
(%) of
Ponkan (PW)
|
Essential oil composition
(%) of peel (PP) |
γ-Terpineol |
0.20 |
- |
β-Pinene |
- |
0.42 |
β-Myrcene |
- |
1.91 |
Carene |
- |
0.24 |
Decanal |
0.57 |
0.21 |
d-Limonene |
88.50 |
89.72 |
γ -Terpinene |
8.98 |
7.01 |
Hexanal |
0.08 |
- |
Linalool |
1.67 |
0.34 |
o-Cymene |
- |
0.15 |
d-Limonene Selectivity |
7.70 |
8.73 |
It can be observed that the
Ponkan peel essential
oil obtained from PP contains
in its chemical composition more terpene compounds and a higher amount of d-limonene
(approx. 90%). This result was expected since the essential oil glands are in
the fruit peel. However, the amount of d-limonene
present in PW was high (88.5%) and shows
a good quality of the essential oils
obtained. It is worth noting that the amount of linanool was higher in PW,
probably due to the high content of water in the original waste (77.20 ± 0.60%) favored the formation of this
alcohol, and probably its decomposition into γ-terpineol,
according to Filly et al. [37] in the presence of water
occurs the formation of linanlool and terpi-4-ol. The juice processing may also
have favored the transformation of β-myrcene and β-pinene into other terpenes
such as γ-terpinene. However, these hypotheses need to be
confirmed in future studies.
The Ponkan essential oil
also showed the presence of decanal, less than 1%, i.e., 0.57% and 0.21% in PW
and PP, respectively. Value in agreement with that obtained by Simas et al. [5] who obtained 0.28%.
According to Baudoux [7] esters and aldehydes are responsible for the
sedative and calming properties of essential oils, thus the presence of decanal
in the chemical composition of the obtained Ponkan essential oil is an
indication that it has these therapeutic properties that may be beneficial for
aromatherapy purposes.
The essential oil from Citrus peel is recognized as safe by the FDA – Food and Drug
Administration [38], but the ISO 3528:2012 is broader and also includes
pulp from the
fresh fruit of Citrus reticulata Blanco [39]. Thus, the essential oil
obtained from the waste can be used in the food industry or the industries of
perfumery, personal care products, and cleaning materials. It was also observed
that the composition of the waste (peels, pulp and
seeds) practically did not influence the composition of the Ponkan essential oil, especially for d-limonene,
with similar fractions for PW and PP, 88% and 90%,
respectively, and the selectivity in the same order of magnitude, that show the
potential of the essential oil obtained from agro-industrial waste.
Another alternative would be to use the essential oil from Ponkan waste to perform different chemical syntheses that use d-limonene
as a chemical route. As reported by Becerra, Ganzález and Villa [23], Bicas et al. [22] and Rottava et al. [21], it is possible to produce α-terpineol,
menthol, carvone, limonene-1,2-diol and perillyl alcohol from d-limonene.
For this purpose, other extraction methods and more selective solvents can be
used to improve the d-limonene yield in Ponkan essential oil as suggested by Batista [34]. If the separation of d-limonene from the
other terpenoids present in the Ponkan essential oil is necessary, it can be done by deterpenation [40–42].
The profitability of the extraction of essential
oil from Ponkan waste (PW)
was verified. For the calculation was considered the production of 20222
- 81,000 tons of Ponkan per year-the fraction of juice (47%), the waste (PW) moisture (77%) and
the essential oils yield (0.22%). For these
conditions, the annual production of essential oils from Ponkan waste would be approximately 21.7 tons/year, which has a
market value of approximately US$ 900,00/kg [43,44]. This process could add
value to agroindustrial waste before destined for
composting, animal feed, or landfill [45].
The best option according
to the perspective from a circular economy of ponkan waste is to extract products with high-value
compounds leading to more profitable valorization [45]. Therefore, the previous separation of the peels,
before obtaining the juice, makes it possible to obtain 163.0 tons/year of
Ponkan essential oil1. This increases by more than 7 times the
production of essential oils and reduces the energy expenditure for the
hydrodistillation process. But to guarantee the sustainability of the process,
an economic analysis is necessary.
4.
Conclusions
The ponkan essential oil
obtained from peels and the juice industry waste presented similar mass fraction of d-limonene and both were approximately
90%. Thus, the Ponkan essential oil obtained
from agro-industrial waste can be used in
different types of industries, such as food or personal care and cleaning
products, allowing the use of a natural additive for various products of
interest to society. The essential oil from waste Ponkan
had a low yield from hydrodistillation compared to that obtained from the
extraction of peels. Thus, this study also showed that the composition of the waste is a determining factor in obtaining essential oil
from Ponkan fruits and that the separation of the peels, before processing the
fruits to obtain juice, can be an economically advantageous step.
Footnotes
1Production
of Ponkans in the Vale da Ribeira – Brazil.
2For the same mass fed to the extractor
Authors’ contributions
Conceptualization, M.B.K. and M.L.C.; Methodology, M.G.F.B. and J.M.F.; Investigation, M.G.F.B.; Resources, M.L. C.; Data Curation, M.G.F.B.; Writing– original draft preparation, M.G.F.B; Writing–review & editing, M.B.K., F.A.P.V. and M. L.C.; Supervision, F. A. P. V. and M.B.K.; Funding acquisition, M.L.C.
Acknowledgements
The authors thank to the Federal
University of Paraná and the cooperative of agricultural producers
CopaVale and director Débora Nascimento.
Funding
Federal University of Paraná and authors
own resources.
Conflicts of interest
The
authors declare no conflict of interest.
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This work is licensed under the
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License (CC BY-NC 4.0).
Abstract
The tangerine juice
corresponds to 47 wt.% of the fruits and it is normally extracted by pressing
generating agro-industrial waste rich in compounds with market value. Thus, the
objective of this study was to obtain the essential oil from Citrus reticulata Blanco peels and
compare it with those obtained from the waste of the ponkan tangerine juice industry, rich in d-limonene. The waste and peels were cut into pieces of approximately
1 cm², dried in an oven with air circulation at 50 °C for 15 h, ground, and
classified by sieving with particle size between 20 to 28 mesh. The
moisture content in dried waste and peels were 8.5 wt.% and 6.0 wt.%, respectively. A particle size was
defined for the extractions. The essential oil extractions were performed by
hydrodistillation, in Clevenger method, with 50 g of sample, 500 mL of
distilled water for 2 h. The essential oil yield was 0.22 wt.% (88.5 % of d-limonene)
for ponkan waste and 1.65 wt.% of for ponkan peel (89.7 % of d-limonene). The
results showed that separation of the Ponkan peel before processing the fruit
enables more efficient extraction of the compounds of interest.
Abstract Keywords
Tangerines, d-limonene,
hydrodistillation, extraction, waste, terpenes
This work is licensed under the
Creative Commons Attribution
4.0
License (CC BY-NC 4.0).
Editor-in-Chief
Prof. Dr. Radosław Kowalski
This work is licensed under the
Creative Commons Attribution 4.0
License.(CC BY-NC 4.0).