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2, 2014
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Research article
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1. Introduction
Essential oil from citrus is a large type of natural flavours and frangrances, which is popularly used in food
industries, daily chemical product and health care field (Sheng-min, et al., 2012). The citrus species are a
potential source of variable oil which might be utilized for edible and other industrial application (Maria C.
et al, 2012). Essential oils are broadly used as pharmaceutical components, in nutritious supplements and
for cosmetic industry and aromatherapy (Maria, et al., 2012). Guenther E., 1955, also stated that the oil is
also employed in perfumes, toilet waters, eaux de cologne, and in cosmetics to which it impacts a
refreshing top note.
Essential oils are a product obtained from vegetable raw materials (Berger, 2007) , and are complex mixtures
whose composition may include volatile terpenic compounds, which have the formula (C5H8)n , where the
compounds are monoterpenes if n=2, sesquiterpenes when n=3, diterpenes when n=4 etc. (Smith, et al.,
2001). These are secondary metabolites in plants (Mazen, 2002) and responsible for the characteristic aroma
on the fruit.
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Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
Lemon essential oil are complex mixtures of chemical compounds like limonene, Y-terpinene, citral,
linalool and -caryophyllene among others, which can be represented by three main classes, namely
terpenes, oxygenates, and sesquiterpenes (Benvenuti, et al., 2001 and Van Straten et al., 1983). The most
significant flavour compound is citral, while linalool possesses highly distinctive organoleptic
characteristics. In addition, limonene, myrcene, octanol, and Y-terpene among others contribute with high
aroma flavour of lemon oil (Benvenuti, et al., 1983).
The composition of orange oil varies for several reasons. Region and seasonal changes as well as the
method used for extraction lead to these variation. Gamarra, et al., (2002) also stated that the quality of
essential oil depends on different factors; among them are the chemotype and biotype of the plant, the
climatic conditions as well as the extractive process. Several compounds have been identified in orange oil
with gas chromatograph-mass spectrometry. Most of the substances are part of the terpene group
(limonene, -pinene, sabinene, -pinene, myrcene and -3-carene) with limonene being the dominant one.
Long chain aliphatic hydrocarbon alcohols and aldehydes like octanol, decanal, and octanal are second
important group of substances (Verzera, et al., 2004).
Citrus fruits have a rough, robust and bright (green to yellow) coloured skin. They are usually 4 to 30cm
long and 4 to 20cm in diameter, with a leathery surrounding rind or skin known as epicarp (or flavedo) that
cover the fruits and protect it from damages. Citrus fruits are notable for their fragrance, partly due to
flavanoids and limonoids contained in the rind (Manthey, 2004). The endocarp is rich in soluble sugar and
contains significant amounts of vitamin C, pectin, fibres, different organic acids and potassium salt which
give the fruits its characteristic citrus flavour (Ezejiofor, et al., 2011). Citrus juice also contains a high
quality of organic acids (citric, malic, acetic and formic acids).
In Nigeria and other parts of the world, citrus sinensis (sweet orange) are cheaply available, thus serves as
a major source of vitamins in diets. Orange fruit and its juice have several beneficial, nutritive and health
properties (Okwu and Emenike, 2006). They are rich in vitamins especially ascorbic and folic acids. Over
the last decades, many other virtues and medicinal benefits of orange fruits have been discovered besides
their anti-scurvy property (Rapisararda, 1999). There is convincing epidemiological evidence that the
consumption of orange fruit is beneficial to health and contributes to the prevention of degenerative
process, particularly lowering incidence of degenerative process, particularly cardio and cerebro- vascular
diseases (Rapisararda, 1999). The protection that orange fruit provides against these diseases has been
attributed to the various antioxidant phytonutrients contained in citrus species (Okwu and Emenike, 2006;
Rapisararda, 1999).
Ezejiofor, et al., 2011 reports that of the 36.0 million metric tonnes world production, Nigeria produces 0.3
million metric tonnes and has the potential to produce more orange wastes ( orange peels) in high
production.
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
The orange peels were then pureed using MARLEX ELECTROLINE (Excella) blender.
The pureed orange peel was then carefully transferred into a 1000ml flat bottom flask. 650ml of de-ionized
water was measured using a 1000ml measuring cylinder and then added to the 1000ml flat bottom flask
(distilling flask). Boiling chips was then added to the distilling flask to ensure that boiling occurs calmly
without bumping. The experiment was then set-up as shown in Figure 1 below;
3. Experiments
3.1 Determination of the solubility of citrus peel essential oil in water
Approximately 6 drops of water was added to the test tube containing 3 drops of orange peel essential
oil. The test tube was stirred thoroughly with a glass stirring rod. Two separate phases was observed. The pH
of the water was measured to determine if the essential oil is partially soluble in water and whether it has
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Njoku V.I., Evbuomwan B.O.
Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
changed the pH of the water. It was observed that the pH paper did not change colour. Thus, the orange peel
essential oil is a water insoluble compound. The above experiment was carried out on lemon and lime
essential oil, and same result was obtained.
3.5. Determination of peroxide value of orange, lime and lemon essential oil
30ml of acetic acid chloroform solution was measured into a flask containing 2g of the oil sample. A
0.5ml saturated solution of potassium iodide was then added, followed closely by the addition of 30ml of
distilled water. The flask content was then titrated against 0.1M sodium thiosulphate (Na2S2O3) until the
yellow colour almost disappeared. 0.5ml starch indicator was added and the titration continued until the
end-point (where the blue-black colour just disappeared). A blank titration was also performed.
Where S and B represent sample and blank titrations respectively.
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Njoku V.I., Evbuomwan B.O.
Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
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Njoku V.I., Evbuomwan B.O.
Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
Plant
material
Weight
(gm.)
Volume of
distilled
water(ml)
Time of
heating(min)
Temp.( c)
Volume of
essential
oil (ml)
ORANGE
PEEL
370
650
60
100
14
370
650
100
100
16
370
650
140
100
18
370
650
180
100
20
Plant
material
Weight
(gm.)
Volume of
distilled
water(ml)
Time of
heating(min)
Temp.(0c)
Volume of
essential
oil (ml)
LIME
PEEL
370
650
60
100
370
650
100
100
370
650
140
100
4.5
370
650
180
100
Plant
material
Weight
(gm.)
Volume of
distilled
water(ml)
Time of
heating(min)
Temp.(0c)
Volume of
essential
oil (ml)
LEMON
PEEL
370
650
60
100
370
650
100
100
4.5
370
650
140
100
370
650
180
100
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Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
Figure 2: Graph of Time of heating (min) Vs Volume of Essential oil for orange peel.
Figure 3: Graph of Time of heating (min) Vs Volume of Essential oil for lemon peel.
Figure 4: Graph of Time of heating (min) Vs Volume of Essential oil for lime peel.
Figure 5: Multiple bar chart showing Volume of Essential oil Extracted from citrus
peel at different times.
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Njoku V.I., Evbuomwan B.O.
Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
The GC-MS analysis of the citrus peel essential oil was done using (5975 Series MSD with an Agilent
7890A) shown in Figure 4.5. 0.5ml of each of the oil sample was diluted to 5ml using 4.5ml of methylene
chloride (diluents). Helium was used as the carries gas because of it inert nature. The result of the GC-MS
analysis of the orange, lemon and lime peels essential oil are shown in Table 4, Table 5 and Table 6
respectively.
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
COMPONENT
PERCENT
COMPOSITION
1R--Pinene
4.452
Cyclohexene
1.912
D-Limonene
54.151
(Z)-3-Carene
3.707
1,3,8-p-Menthatriene
2.808
Pulegone
11.652
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Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
1-Methylcyclohexa-1,3-diene
4.348
1,3-Cycloheptadiene
3.982
2-Cyclohexen-1-ol
5.231
10
1,4-Cyclohexadiene
2.299
11
2-Cyclohexen-1-one
(L-Carvone)
5.457
COMPONENT
PERCENTAGE
COMPOSITION
1R--Pinene
3.197
-Phellandrene
3.523
-Pinene
3.822
D-Limonene
64.000
1,4-Cyclohexadiene
1.957
Cis-p-Mentha-2,8-dien-1-ol
3.150
1,3,8-p-Menthatriene
2.909
1,4-Cyclohexadiene
2.968
3-Cyclohexen-1-ol
2.461
10
2-Cyclohexen-1-ol
6.210
11
1,4-Cyclohexadiene
2.539
12
2-Cyclohexen-1-one (L-Carvone)
3.265
COMPONENT
PERCENTAGE
COMPOSITION
-Phellandrene
1.331
1R--Pinene
10.399
Ocimene
0.733
-Pinene
23.124
D-Limonene
17.070
1,4-Cyclohexadiene
5.516
Bicyclo[4.1.0]hept-2-ene
1.108
3-Carene
2.030
Bicyclo[3.1.0]heptan-3-ol
1.320
10
3-Cyclohexen-1-ol
4.955
11
3-Cyclohexene-1-methanol
3.611
12
E,Z-4-Ethylidenecyclohexene
1.149
13
2-Cyclohexen-1-ol
1.116
14
1,3,8-p-Menthatriene
0.834
15
2-Cyclohexen-1-one
0.810
16
2,6-Octadienal
1.320
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Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
17
1,3-Cyclohexadiene
1.006
18
1S--Pinene
0.793
19
1H-Cycloprop[e]azulene
1.237
20
Caryophyllene
4.800
21
Trans--Bergamotene
4.670
22
Bicyclo[3.1.1]hept-2-ene
2.475
23
Cyclohexene
6.924
24
Caryophyllene oxide
1.668
From Table 4, the 3 highest occurring components in orange peel essential oil are D-Limonene (54.151%),
Pulegone (11.652%) and L-Carvone (2-cyclohexen-1-one) (5.457%). Table 5 showed that the 3 highest
occurring components in lemon peel essential oil are D-limonene (64%), 2-cyclohexen-1-ol (6.21%) and
-Pinene (3.822%), while Table 6 showed that the 3 highest occurring components in lime peel essential
oil are -Pinene (23.124%), D-limonene (17.07%) and -Pinene (10.399%). The result of lemon peel
essential oil for D-limonene and -Pinene is in agreement with Soumaya, et al.(2012) findings that
D-Limonene (37.63-69.71%) , -Pinene (0.63-31.49%), -Terpene(0.04-9.96%), and p-Cymene
(0.23-9.84%) were the highest ones in lemon. However percentage composition of sweet orange (Citrus
sinensis) did not agree with that of Soumaya, et al., (2012), which had a percentage of (81.52-86.43%).
This discrepancy could possibly be as a result of Gamarra, et al. (2002) report that the quality of essential
oil depends on different factors; among them are the chemotype and biotype of the plant, the climatic
conditions as well as the extractive process. Figueiredo, et al. (2008) and Schmidt (2010) also stated that it
needs to be kept in mind that the chemical composition may already vary in the starting material, being
influenced by plant health, growth stage, habitat including climatic, edaphic factors, as well as harvest
time.
Also, Widmark and Blohm (1957) stated that oxygen consumption upon storage of different monoterpenes
has been recorded. El. Nikeety and others (1998); Turek and others (2012) went further to state that
changes in composition as well as physicochemical properties of essential oils were generally more
pronounced in half-filled containers than when only little or no headspace were present.
Asnaashari, et al. (2010), stated that the GC-MS analysis of the essential oils of lime ( C. aurantifolia) was
also performed and approximately 22 main components, with Limonene (28.27%) being the principal one,
were identified and quantified, as against 24 components identified in this work with -pinene ( 23.124%)
being the principal one, and Limonene (17.07%) being the next.
However, from Table 4, 5 and 6, it can be deduced that lemon peel essential oil has the highest percentage
of D-Limonene (64%) when comparing same quantity of the three (3) oil samples. But, from Table 1, 2 and
3, it can also be seen that orange peel produced the highest volume of essential oil when comparing same
mass of the 3 citrus peels and same time of heating.
Therefore, taking the highest time of heating (180 minutes) in Table 1, 2 and 3, and the percentage
composition of D-Limonene in the citrus peels in Table 4, 5 and 6, orange peel produced 20ml of essential
oil, while lemon produced 7ml and lime 5ml. Working out the quantity of D-Limonene in the volume of
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Njoku V.I., Evbuomwan B.O.
Int. Journal of Applied Sciences and Engineering Research, Vol. 3, No. 2, 2014
Quantitative and Qualitative analysis, and comparative study of essential oil extracted from Nigerian orange, lemon and lime
peels
essential oil obtained from the citrus peels at 180 minutes, using the percentage of D-Limonene in the
citrus peels as shown in tables 4, 5 and 6, lime peel essential oil contains 0.85ml D-Limonene, lemon
4.48ml D-Limonene, while orange peel essential oil contains 10.83 ml D-Limonene.
5. Conclusion/ Recommendation
The results obtained showed that lemon peel contains more amount of D-limonene per unit volume of
essential oil, while orange peel contains more amount of essential oil than lime and lemon per unit mass of
peel. However, by obtaining percentage of D-limonene in volume of essential oil obtainable from unit
mass of peel, it was concluded that orange peel is a more viable and economical source of essential oil
which is very rich in D-limonene needed for the production of insecticide. In handling the insecticide
prepared in this work, it is recommended that caution should be applied as no laboratory analysis has been
conducted to ascertain its side effect on man.
The shelf life of citrus peel essential oil have been established from literature to be greatly affected by its
storage conditions such as wrong storage containers, storage temperature and head space in storage
containers. Thus, citrus essential oil should be stored in amber bottles, and below room temperature, with
the avoidance of headspace in storage containers.
Further research to evaluate the effect of fertilizer application on;
a) The physicochemical properties of orange peel essential oil.
b)The chemical constituents in orange peel essential oil.
c) Volume of essential oil in orange peel.
d)Pectin content in orange peel.
6. References
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peels
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