Separation Science and Technology

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A study on the extraction of essential oil of

Persian black cumin using static supercritical CO2
extraction, and comparison with hydro-distillation
extraction method

Saeed Zarrinpashne & Soheila Gorji Kandi

To cite this article: Saeed Zarrinpashne & Soheila Gorji Kandi (2018): A study on the
extraction of essential oil of Persian black cumin using static supercritical CO2 extraction, and
comparison with hydro-distillation extraction method, Separation Science and Technology, DOI:
10.1080/01496395.2018.1541907

To link to this article: https://doi.org/10.1080/01496395.2018.1541907

Published online: 02 Nov 2018.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2018.1541907

A study on the extraction of essential oil of Persian black cumin using static
supercritical CO2 extraction, and comparison with hydro-distillation extraction
method
Saeed Zarrinpashne and Soheila Gorji Kandi
Independent Researcher, Tehran, Iran

ABSTRACT ARTICLE HISTORY

The essential oil of Persian black cumin was extracted using static supercritical CO2 technique at Received 21 February 2018
different temperatures, extraction times, and number of extractions. The composition of extracted Accepted 25 October 2018
oil was measured by GC-MS analysis and 25 components were identified. It was found that the oil KEYWORDS
recovery was reduced by increasing the temperature. Maximum recovery was achieved at two- Supercritical extraction;
step extraction that was about 49%. Both dissolution rate and solubility limited the oil recovery at hydrodistillation; bunium
the tested extraction conditions. The oxygenate components have less dissolution rate than the persicum; CO2; essential oils
terpenes. The application of experimental data for design of an efficient dynamic extraction
system was discussed.

Introduction cosmetics industries.[6,7] It does have many promising

properties that make it a proper solvent for extraction of
Essential oil is a common name given to volatile oils
essential oils. It is nonflammable, nontoxic and will not
extracted from some plant materials. These oils consist
remain in the extracted product(s) as an impurity. CO2
of many hydrocarbons (mainly terpenes) and their
extraction could be done at lower temperatures than that
oxygenated derivatives, such as alcohols, ketones, alde-
of distillation (e.g., in the range of 40–70○C, its critical
hydes, ethers, and esters. Essential oils are being used in
temperature is 31.1°C) and CO2 is chemically inert to
perfumery, food industry, and pharmaceuticals. The
most of the natural components.[8–10]
classical methods of essential oil extraction are hydro-
Its solubility power strongly depends on the extraction
distillation, steam distillation, and solvent extraction.
pressure (more precisely, on CO2 density) and by adjust-
Despite the wide spread use of these methods, they
ing the pressure, one can extract the desired components
have some drawbacks. The heat used in distillation
of a plant material almost selectively.[11–16] Two major
may cause some thermal degradation of sensitive com-
commercialized applications of supercritical CO2 extrac-
ponents of the plant. Besides, water or steam can enter
tion are decaffeination of tea and coffee and extraction of
to chemical reaction with some plant components,
hops flavor for beer industry.[7] However, its wide appli-
especially with of esters, which are usually responsible
cation has been faced with some technical limitations. To
for scent of the essential oil and are regarded as valu-
achieve supercritical state, CO2 must be compressed to
able components for perfumery.[1–4] As an example, the
above 74 bar pressure (its critical pressure is 73.8 bar) and
hydrolysis of linalyl acetate, which is present in laven-
since the concentration of essential oil and/or other valu-
der, to linalool and acetic acid during the hydro dis-
able extraction materials are rather low in plant materials,
tillation of the plant can be mentioned.[5] Liquid
their large-scale production requires large, high pressure
extraction of essential oil has also some drawbacks
vessels which makes investment on the equipment very
such as the presence of trace amounts of the solvent
high.[17–21] Besides, to extract heavier natural components
in the extracted essential oil. Besides, some solvents like
such as caffeine, much higher pressures (even above
hexane are highly flammable and therefore require
500 bar) may be required which impose higher invest-
some expensive measures for the safe operation of the
ments to the extraction plants.[7] In order to make the
extraction process.
supercritical extraction process competitive to conven-
Supercritical CO2 extraction has wide applications
tional ones, one should try to reduce the energy
especially in the areas of the food, pharmaceutical, and

CONTACT Saeed Zarrinpashne Zarrinpashne@gmail.com Independent Researcher, Tehran, Iran

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2018 Taylor & Francis Group, LLC
2 S. ZARRINPASHNE AND S. GORJI KANDI
consumption in the former as much as possible. These
energies include the mechanical work required for com-
pression of CO2 to supercritical pressure, heating the CO2
to supercritical temperature and/or cooling the subcritical
CO2 to liquid state in some cyclic extraction systems. To
achieve this goal, the solubility behavior of essential oil
constituents in CO2 should be studied. The static method
of essential oil extraction is a simple and cheap tool for
this study. In the present study, the static supercritical
CO2 extraction method is applied for extraction of essen-
tial oil from Persian black cumin (Bunium Persicum)
which is a widely cultivated spice in Iran. The effect of
extraction temperature, extraction time, and number of
extractions are studied on the yield of essential oil extrac-
tion. It is assumed that the essential oil content of the
plant can be measured via the classical extraction method
of hydrodistillation in a Clevenger apparatus. The com-
positions of the extracted essential oil samples were deter-
mined using a proper GC-MS system. By comparing the
composition of the samples, one can grasp some informa-
tion about dissolution rate of particular group of compo-
nents. Also, the extent of thermal degradation or reaction
with water (in hydrodistilled oil) of some constituents can
be observed in comparison with the essential oil obtained
with supercritical extraction.
Materials
Plant material: Fresh Persian black cumin (Bunium
Persicum) cultivated from Kerman province in Iran
was supplied from a herbal store at Tehran. The charge
was kept in a refrigerator at 4°C and all the experiments
were done using this charge.
CO2: Dry Ice pellets (5 mm × 5 mm) produced from
food grade CO2 (purity above 99.9 wt.%)
Water: Deionized water was used for hydrodistillation
process.
Essential oil dehydration agent: Anhydrous sodium
sulfate from Merck was used for dehydration of the
extracted essential oils.
Apparatus
Static supercritical extraction setup
A schematic of the experimental setup is shown in
Figure 1. The extractor vessel is a 2.5-L, high pressure
stainless steel vessel equipped with a quick sealing top
head and an internal 1.1-L perforated metal basket. The
extractor’s top head is equipped with a degassing/purging
ball valve and a pressure gauge. The extractor vessel is
submerged in a constant temperature water bath. The
temperature of the bath can be controlled with ±0.1oC
accuracy using a digital temperature controller
(HANYOUNG NUX, model AX2) which is connected
to a 2.5-KW electrical heater and a precision RTD type,
temperature sensor. To achieve a uniform temperature in
the bath, a circulating pump is installed at the bottom of
the bath which takes the water from the bottom and
discharges it at the top of the bath. The bottom side of
the extractor vessel is connected to a small cyclone
separator via a needle valve, in the shortest possible
distance to minimize the waste of extracted essential
oils in dead volumes and tubing. The cyclone is equipped
with a sight glass in its bottom section to allow for visual
observation of the extracted essential oil. The top side of
the cyclone is connected to a back pressure regulator
valve and a pressure gauge to allow pressure control in
the cyclone. The exit stream of this valve is vented to
atmosphere. To obtain a reasonable amount of essential
oil, the perforated metal basket should be filled comple-
tely with plant material. Since the volumes allocated to
the plant material and to the dry ice pellets were fixed,
then the ratio of CO2 to plant material mass for a parti-
cular plant was almost constant and it was not practical
to study the effect of CO2 to plant mass ratio on extrac-
tion performance by using this setup. Also, the extraction
pressure was depended on extraction temperature and,
contrary to dynamic supercritical extraction systems,
could not be varied independently from extraction
temperature.
Hydrodistillation apparatus
A Clevenger apparatus was utilized for extraction of
Bunium Persicum’s essential oil. The complete setup con-
sists of a 1-L flask for charging the plant material and
water, an electrical heater mantle with adjustable heating
power, a source of 14°C circulating cooling water with
150 L/h flow rate and the Clevenger apparatus itself.
Grinding device
The grinding device was a batch, rotary blade mill by
the name Artisan 5000 (made in Iran). It has a 1.5-L
stainless steel grinding chamber and its blade can rotate
up to 25,000 rpm.
Extraction procedures
Grinding the plant material
It has been reported that grinding the plant material
had a significant effect on essential oil recovery.[22] In
a study on essential oil extraction from Caraway
seeds, it has been found that the essential oil recovery
 SEPARATION SCIENCE AND TECHNOLOGY 3

TIC

~
PSV P-1 V-1

2
1

6 7

P-2

V-2

V-3
5 3

V-4

Figure 1. Schematics of the static, supercritical CO2 extraction setup. 1: extraction vessel, 2: constant temperature water bath, 3:
cyclone separator, 4: sight glass, 5: water circulating pump, 6: electrical heater element, 7: temperature sensor, TIC: digital
temperature indicator and controller, V-1: ball valve for degassing and purging, V-2: extractor discharge needle valve, V-3: back
pressure regulator valve, V-4: essential oil drain valve P-1: Bourdon pressure gauge (0–160 bar), P-2: Bourdon pressure gauge (0–
16 bar).

in supercritical extraction method was increased by
the factor of 28 upon grinding of the seeds and also
increased about 23% in steam distillation method.[22]
Therefore, in this study, all the essential oil extrac-
tion operations were performed on ground black
cumin seeds. In the grinding process, care should
be taken not over heat the charge. To achieve this,
the material was kept in a refrigerator at temperature
lower than 4○C and then immediately brought for
grinding; the grinding was allowed to continue for
less than 30 s time intervals at dry condition, then
the contents of the mill were sieved with a mesh
number 35 and the coarser particles were returned
back to the mill. This process was repeated three
times and the collected fines were weighted and
loaded to extraction vessel immediately.
Determination of essential oil content by
hydrodistillation method
A total of 100 g of ground black cumin was poured in a
1-L round flask and 600 ml deionized water was added
and the mixture was thoroughly mixed to achieve a
homogeneous mixture. Then, the Clevenger system
was set up on the flask. The flask was heated through
an electric mantle heater gently and the circulating
cooling water with about 14○C inlet temperature was
4 S. ZARRINPASHNE AND S. GORJI KANDI
connected to the condenser. The heat input to the flask
was adjusted to achieve about 1 ml/min distillation.
The process was continued for 8 h according to the
procedure given elsewhere[23] and the volume of accu-
mulated essential oil was measured at the end of the
test. Due to the high altitude of the test site (ambient
pressure of 660 mmHg), the mixture boiled at 95–96°C.
Supercritical extraction
About 590–595 g of ground black cumin was loaded in a
cotton cloth bag and its top was tightly closed using a
plastic strap. Then, the extraction vessel was loaded with
1100–1250 g of granular dry ice. This amount of dry ice
would fill the allocated space for CO2 in the extraction
vessel. The filled cloth was put in the perforated metal
basket and the basket was put in the extraction vessel. The
vessel’s cap was then closed, purged through its connected
ball valve (V-1) to remove the remaining air in the vessel
and then quickly shut and sealed. Then, the water bath
was filled with water such that the whole extraction vessel
was submerged. The water circulating pump and electri-
cal heater were turned on and the desired bath tempera-
ture was set to the temperature controller. The duration of
temperature rise to its set point was between 30 min and
1 h depending on the set point temperature and initial
water bath temperature. After establishment of the
desired supercritical conditions in the extraction vessel,
the condition was kept for a preset extraction time
(between 2 and 12 h) to ensure that essential oil dissolu-
tion in CO2 was practically achieved.
After the extraction time was lapsed, the needle
valve V-2 was gradually and carefully opened and the
back pressure regulator V-3 was set to 8 bar. The
flow of CO2 was adjusted by the needle valve to
minimize icing on the valve and the tubing to the
cyclone. The icing on the valve and tube was
removed via a warm air stream periodically (a small
hair dryer was used for this purpose). After the
pressure of extraction vessel fell to 8 bar (pressure
equalization with cyclone), the accumulated essential
oil in the bottom part of the cyclone was gradually
drained in a 10-ml graduated glass cylinder and its
volume and weight (with ±0.1 ml and ±0.01 gr accu-
racy, respectively) were measured. The accumulated
volumes of essential oil in each experiment varied
between 3.2 and 4.6 ml. The essential oil extraction
recovery was calculated as:
R ¼ Essential oil recoveryðv=w %Þ ¼
Extracted essential oil volume ðmlÞ
 100 (1)
Initial weight of the plant chargeðgrÞ
Chemical analysis of extracted essential oils
After measurement of extracted essential oil’s volume
and weight, they were dehydrated by addition of some
anhydrous sodium sulfate powder. The dehydrated
essential oil samples were analyzed by a GC/MS
(Thermo Quest-Finnigan, Waltham, MA, USA, Model
TRACE MS). The GC column was of DB-5 capillary
type (30 m × 0.25 mm i.d. × 0.25 μm film thickness).
The carrier gas was Helium with 1.1 ml/min flowrate.
The injected sample volume was 0.1 ml with split ratio
of 1:100. The injector temperature was kept at 250°C.
The temperature program of the column was 60°C for
2 min, and then increased to 250°C with 5°C/min rate.
The mass spectrometer section was of quadruple type
with ionization energy of 70 ev. The electron ionization
scan mode was utilized with scan range of 40–460 amu
and 0.4 s scan time and the ionization chamber was
kept at 200°C.
The components were identified by comparing their
retention indices and also their mass spectra with those
of pure reference components.[24] The weight percent of
a particular component in a sample was approximated
by its corresponding GC peak area divided by total area
of all detected peaks (i.e., area percent method).
Design of experiments
Using the described static extraction device, it is
possible to study some important issues in supercri-
tical extraction of essential oils. Prior to proceed
further, it is useful to give a clear definition of
some terms as follows:
● Essential Oil content: is defined as the volume of
essential oil (expressed in milliliter) that exists in
100 g of a specified plant material. Its value is
followed by the symbol (v/w%). In this study, it
is assumed that the essential oil content can be
measured by the Clevenger apparatus provided
that the plant material be effectively ground and
the extraction be continued for sufficient time.
● Essential Oil recovery: is defined as the volume of
essential oil (expressed in milliliter) that is
extracted from 100 g of a specified plant material.
Its value is also followed by the symbol (v/w%).
Essential oil recovery depends on plant material,
extraction method, and extraction conditions
● Extraction Efficiency: is defined as the percentage
of essential oil content of a particular plant that has
been extracted by a particular extraction method.
This term is the ratio of “essential oil recovery” to
“essential oil content” multiplied by 100.

The purpose of this study is to measure the effect of
extraction temperature, extraction time, and number of
extractions on the extraction efficiency and the compo-
sition of the extracted oil in comparison with the oil
extracted by hydrodistillation method.
In a supercritical CO2 extraction system, the mini-
mum extraction temperature should be the critical
temperature of CO2, i.e., 31.1○C. On the other hand,
temperatures higher than 70○C may lead to thermal
decomposition of thermolabile components of the
plant material and may not demonstrate the advantage
of this method over traditional hydrodistillation
method.
In the first set of experiments (run no.’s 1, 2, and 3),
the fresh samples of black cumin were subjected to
supercritical extraction, at almost constant CO2 to
plant material (mass) ratio, and constant extraction
time of 2 h, but at three different extraction tempera-
tures (i.e., 40, 50, and 60°C). In the run no. 4, a test at
the temperature corresponds to maximum essential oil
recovery was repeated, but the extraction time was
increased to 12 h which was much longer than those
of run no.’s 1, 2, and 3. Finally, in the run no. 5, all of
the plant material remained from run no. 4 was sub-
jected to another extraction at the same temperature of
run no. 4 with extraction time of 4 h.
All of the essential oils extracted in experiments 1–5
and the essential oil extracted in the Clevenger appara-
tus were analyzed by GC-MS to study the effects of
extraction method and extraction conditions on the
composition of the resulting essential oils.
Results and discussion
Essential oil content of the Persian black cumin as
measured by Clevenger apparatus was 2.8 v/w%.
In Table 2, the results of the static supercritical extrac-
tion experiments on Persian black cumin are shown. The
quoted extraction pressure was measured at the end of
extraction phase. The pressure values varied between 83
and 115 bar and was strongly dependent on extraction
temperature. The slight variation of pressure in the
Table 1. Characteristics of the designed experiments for evaluation of the performance of static supercritical CO2 extraction of
Persian black cumin.
Run no. 1 2
Manipulated variables (independent variables)
Plant charge status Fresh Fresh
T (°C) 40 50
t extract (h) 2 2
Experiments’ response (dependent variables)
P (bar) P1 P2
Essential oil recovery R1 R2
Essential oil composition
*To be done at temperature corresponds to maximum essential oil recovery in run numbers 1, 2, and 3.
SEPARATION SCIENCE AND TECHNOLOGY 5
experiments 1, 4, and 5 may be attributed to slight varia-
tion in CO2 charge and different levels of dissolved
essential oil in the supercritical phase.
It can be observed that the essential oil recovery
declined almost linearly by increasing the extraction
temperature from 40°C to 60°C (about 1% relative
decrease in recovery with each 1°C rise in extraction
temperature).
Increasing the extraction time from 2 to 12 h leads
to about 13% increase in extraction recovery. This
shows clearly that the allocated time for extraction in
run no. 1 was not enough for saturation of CO2 with
the essential oil available in the plant. Moreover, com-
parison between the extraction recovery in run no. 4
and the essential oil content of the plant material
revealed that the present static system could only
extract about 27.5% of the essential oil content of the
plant. By repeating the extraction on the plant material
left from run no. 4, it was possible to recover more
essential oil in run no. 5 which is about 77% of the
essential oil recovered in run no. 4. This fact demon-
strates the effect of essential oil solubility limitation on
the observed extraction recovery. Note that the total
essential oil recovery from run no. 4 and run no. 5
reaches to 1.36 v/w%. The extraction efficiency of this
combined two-step extraction reached to 48.6%.
The results of GC-MS analysis of essential oil sam-
ples from static supercritical extraction experiments
(run no.’s. 1–5) and the essential oil obtained from
hydrodistillation method in the Clevenger apparatus
are shown in Table 3. There were 25 components
identified in the extracted essential oils. Almost all of
these components are present in all of the extracted oils
but with different concentrations. The major constitu-
ent of black cumin’s essential oil was γ-terpinene; its
concentration in supercritical extracted (SCE) oils was
in the range of 30–38.3 wt.%, while its concentration in
hydrodistillation extracted (HD) oil was 28.8%.
The identified components in the essential oil sam-
ples can be divided into three groups as monoterpenes,
oxygenated terpenes, and sesquiterpenes. For HD oil,
the total amount of monoterpenes, oxygenates, and
3 4 5
Fresh Fresh From run no. 4
60 * Same as run no. 4
2 12 4
P3 P4 P5
R3 R4 R5
To be determined by GC-MS analysis
6 S. ZARRINPASHNE AND S. GORJI KANDI

Table 2. The results of the designed experiments. Repeat of oil extraction on the plant material left
Run no. 1 2 3 4 5 from run no. 4 leads to an oil more rich in oxygenates.
T (°C) 40 50 60 40 40 The total concentration of oxygenates has become even
m CO2/m plant (actual) 1.82 1.75 1.92 2 2.1
textract (h) 2 2 2 12 4 more than that of HD oil. One can conclude that the
P (bar) 85 96 115 83 86 solubility of oxygenates in CO2 is lower than that for
Essential oil recovery (v/w%) 0.68 0.61 0.54 0.77 0.59
Extraction efficiency (%) 24.3 21.8 19.3 27.5 21.1 monoterpenes. By repeating the extraction on the same
48.6* plant material, it was allowed for more oxygenates to
*Overall extraction efficiency for the two-step extraction during run no.’s 4 and 5. dissolve in CO2, while most of the monoterpenes has
been already extracted in the first extraction.
A major difference in composition of essential oils
sesquiterpenes were 48%, 50.8%, and 1%, respectively. obtained by SCE and that obtained by HD can be seen
For SCE essential oils of run numbers 1–5, the contents for components number 18 and 19 in the Table 3. The
of each group varied by the experimental conditions. concentration of component no.18 is significantly lower
Comparing the composition of the extracted essential in SCE oils in comparison with that of HD oil and a
oils in run no.’s 1–3 reveals that the oxygenated ter- reverse situation holds for component no. 19. This obser-
penes and sesquiterpenes’ content of the extracted vation has already been reported by Eikani et al. [25] in
essential oils increased significantly by increasing the their study on cumin seeds (Cuminum Cyminum L.).
extraction temperature from 40°C to 50°C. Further They attributed this to conversion of γ-terpinence-7-al
increase in temperature from 50°C to 60°C, however, to α-terpinene-7-al at high temperature of hydrodistilla-
leads to a slight decrease in these components. tion and suggest that this conversion is responsible for
By increasing the extraction time from 2 to 12 h, the lower quality of HD oil in comparison to that of SCE oil
concentration of oxygenates increased significantly. This (the latter’s scent is much more resemble to the scent of
may be attributed to slower rate of oxygenates’ dissolution the original plant than that of HD oil). The figures in
in SC-CO2 in comparison with those of monoterpenes and Table 3 support the Eikani’s theory that the mentioned
sesquiterpenes. Allowing more time for extraction leads to conversion is increased by increasing the extraction tem-
more oxygenated components to dissolve in CO2, while the perature. By comparing the ratio of α-terpinene-7-al to γ-
supercritical phase has been already saturated with mono- terpinene-7-al concentrations in run no.’s 1, 2, and 3, one
terpene components. can find that this ratio increased by increasing the

Table 3. The composition of essential oils obtained through supercritical CO2 and hydrodistillation extraction experiments (composi-
tions expressed as wt%).
Run no.
No. RI Component 1 2 3 4 5 HD
1 927.4 α-Thujene 0.52 0.30 0.31 0.34 0.20 0.35 Mono terpenes
2 934.8 α-Pinene 1.65 0.95 1.02 1.12 0.70 1.20
3 974.4 Sabinene 1.23 0.81 0.86 0.88 0.60 0.74
4 979.2 β-Pinene 2.15 1.47 1.55 1.64 1.16 1.59
5 991.4 β-Myrcene 1.05 0.78 0.80 0.77 0.53 0.62
6 1013.3 Carene< δ-3-> 0.09 0.00 0.00 0.00 0.00 0.00
7 1018.3 α-Terpinene 0.37 0.29 0.29 0.29 0.21 0.24
8 1025.9 p-Cymene 10.71 9.17 9.51 9.42 7.86 9.54
9 1030.0 Limonene 6.43 5.21 5.34 5.31 4.31 4.56
10 1047.7 Ocimene<(E)-β-> 0.63 0.50 0.51 0.47 0.36 0.33
11 1060.1 γ-Terpinene 38.28 33.58 35.46 34.50 30.06 28.79
12 1090.8 α-Terpinolene 0.35 0.31 0.32 0.28 0.27 0.23
13 1102.7 Linalool 0.21 0.19 0.18 0.00 0.16 0.00 Oxygenates
14 1204.1 Terpinen-4-ol 0.27 0.32 0.33 0.28 0.35 0.52
15 1216.7 Caranone< cis-4-> 0.40 0.45 0.56 0.44 0.86 0.78
16 1254.7 Cumin aldehyde 12.85 16.09 15.14 16.11 18.93 24.24
17 1276.7 p-Menth-2-en-7-ol, trans 0.00 0.00 0.12 0.00 0.14 0.31
18 1289.9 α-Terpinen-7-al 1.25 1.69 2.14 1.58 3.63 10.44
19 1295.3 γ-Terpinen-7-al 20.84 26.93 24.36 25.86 28.30 13.82
20 1334.1 1,4-p-Menthadien-7-ol 0.00 0.00 0.24 0.00 0.00 0.49
21 1425.0 Cymen-7-ol acetate< para-> 0.00 0.00 0.00 0.00 0.16 0.20
22 1485.7 Germacrene D 0.21 0.26 0.28 0.24 0.36 0.31 Sesqui terpenes
23 1498.2 Zingiberene 0.23 0.31 0.30 0.28 0.35 0.29
24 1512.0 Bisabolene< β -> 0.12 0.17 0.17 0.00 0.22 0.18
25 1527.5 Sesquiphellandrene< β -> 0.16 0.21 0.19 0.18 0.25 0.20
Mono Terpenes 63.45 53.38 55.98 55.03 46.28 48.22
Oxygenated Monoterpenes 35.82 45.67 43.07 44.27 52.54 50.80
Sesquiterpenes 0.72 0.95 0.94 0.70 1.18 0.98

extraction temperature, an indication that the mentioned
conversion enhanced by the temperature. The maximum
ratio is observed for HD oil which is obtained at much
higher temperature than those of SCE oils (i.e., 95–96°C at
Tehran altitude). Note, however, that the mentioned con-
version was not complete and may be regarded as an
equilibrium reaction.
The main constituent of cumin essential oil which has
pharmaceutical value is cumin aldehyde. [26] Its concen-
tration in SCE oil increased from 12.85% at 40°C to
16.09% at 50°C and then slightly decreased to 15.14%
at 60oC. Allowing more extraction time at 40°C leads to a
significant increase in cumin aldehyde from 12.85% to
16.11% and by repeating the extraction on the plant
charge left from run no. 4, the concentration of cumin
aldehyde reached to 18.93%. However, in all of the SCE
oils the concentration of the cumin aldehyde was less
than that in HD oil (which is 24.24%).
Regarding heavier components (sesquiterpenes), their
total concentration was slightly less than that of HD oil
except for that obtained by two-step extraction of run no.
5. This may be attributed to low solubility of these rela-
tively heavier components in supercritical CO2 at the
current test conditions. It is expected that by increasing
the CO2 density (via increasing its pressure), higher solu-
bility of these component can be achieved.
It can be observed that a small amount of Linalool is
present in SCE oils, but it is totally absent in HD oil.
This may be attributed to its thermal degradation dur-
ing the hydrodistillation. Linalool is also absent in the
SCE oil of run no.4. This observation could not be
explained unless to attribute it to analysis error. The
concentration of Linalool, contrary to other oxygenates,
decreased monotonically with increasing the
temperature.
The component p-mentha-2-en-7-ol trans observed in
SCE oil extracted at 60°C (run no.3) or twice extracted at
40°C (run no.5), but it is more concentrated in HD oil.
The same can be seen for 1,4-p-menthadiene 7-ol. These
components may be very little soluble in CO2 at low
temperatures and they can dissolve in CO2 only at high
temperature (i.e., 60°C) or when they are allowed to have
very long contact time with CO2
The component cymene-7-ol-acetate is only
observed in SCE oil of run no. 5 and in HD oil. Its
concentration in HD oil was slightly higher. This obser-
vation may also be attributed to very low solubility of
this component in CO2 at lower temperatures.
Concluding remarks
The static SCE apparatus and method described here
could not extract all of the essential oil of Bunium
SEPARATION SCIENCE AND TECHNOLOGY 7
Persicum at the conditions depicted in Table 1. Even
by repeating the extraction on a plant material, only
about 49% of essential oil of the plant could be
recovered.
The results of experiments clearly demonstrate the
effects of dissolution rate and solubility limitation on
the attainable extraction efficiencies in static supercri-
tical extraction.
The rate of dissolution of oxygenated terpenes in SC-
CO2 was less than that for terpene hydrocarbons, but the
effect of this limitation could be somewhat overcome by
increasing extraction temperature from 40°C to 50oC
and also by increasing the extraction time.
Degradation and/or conversion of some constituents
in CO2 SCE were less in comparison with HD method
due to lower extraction temperature of the former. This
fact can be clearly seen by comparing the concentration
of γ-terpinene-7-al and Linalool in SCE and HD oils.
As a consequence, the scent of essential oil form SCE
has much more resemblance to original plant than that
obtained from HD method.
It seems that by utilization of a dynamic or contin-
uous SCE, one can significantly increase the extraction
efficiency. As an evidence, Moyler[27] reported that the
essential oil recovery from cumin using a dynamic
supercritical CO2 extraction system can be even three
times more than that achieved by steam distillation
method.
The data obtained from static extraction tests here
may be useful for optimization of CO2 circulation
rate in a dynamic extraction system considering the
extraction time and energy consumption of the pro-
cess. The optimum CO2 flowrate to the extraction
vessel in a dynamic supercritical extraction vessel
may be that corresponding to the exhaust fluid
stream from the vessel that is almost saturated with
the plant extractable materials. The data gathered in
this work can be used to estimate the optimum CO2
residence time (and consequently the CO2 flowrate)
in the extraction vessel for extraction of Persian black
cumin powder.
Acknowledgments
The GC/MS analysis of the extracted essential oils was done
in the Department of Phytochemistry of Medicinal Plants
and Drugs, Research Institute of Shahid Beheshti University
in Tehran, which is acknowledged.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
8 S. ZARRINPASHNE AND S. GORJI KANDI
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