Journal of Food Engineering 108 (2012) 290296

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Journal of Food Engineering

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

Lycopene extraction from tomato peel by-product containing tomato seed

using supercritical carbon dioxide
Siti Machmudah a,b, Zakaria b, Sugeng Winardi b, Mitsuru Sasaki c, Motonobu Goto a,, Nami Kusumoto d,
Kiro Hayakawa d
a

Bioelectrics Research Center, Kumamoto University, Kumamoto 860-8555, Japan

Chemical Engineering Department, Sepuluh Nopember Institute of Technology, Surabaya 60111, Indonesia
Graduate School of Science and Technology, Kumamoto University, Kumamoto 860-8555, Japan
d
Kagome Co. Ltd., 17 Nishitomiyama, Nishinasuno-Machi, Nasu-gun, Tochigi 329-2762, Japan
b
c

a r t i c l e

i n f o

Article history:
Received 15 December 2010
Received in revised form 12 July 2011
Accepted 13 August 2011
Available online 26 August 2011
Keywords:
Lycopene
Tomato peel by-product
Tomato seed
Supercritical CO2 extraction

a b s t r a c t
This work discusses the extraction of lycopene from tomato peel by-product containing tomato seed
using supercritical carbon dioxide. The presence of tomato seed in the peel by-product improved the
yield of extracted lycopene. Extraction was carried out at temperatures of 7090 C, pressures of
2040 MPa, a particle size of 1.05 0.10 mm and ow rates of 24 mL/min of CO2 for 180 min extraction
time. Oil from tomato seed was extracted under similar operating conditions and analyzed using GCMS
and GCFID, while carotenoids extracted were analyzed by HPLC. The optimum operating condition to
extract lycopene, under which 56% of lycopene was extracted, was found to be 90 C, 40 MPa, and a ratio
of tomato peel to seed of 37/63. The presence of tomato seed oil helped to improve the recovery of lycopene from 18% to 56%. The concentration of lycopene in supercritical carbon dioxide as a function of density at various temperatures was determined.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
The tomato is one of the most widely cultivated vegetable crops
and is used globally for human nutrition. Millions of tons of tomatoes are processed yearly to produce products such as ketchup and
sauce, resulting in large amounts of tomato peel, pulp, and seed as
industrial waste, an amount almost equivalent to 40% of the raw
material. Concentrations of lycopene in tomato vary from 30 to
200 mg/kg in fresh fruit and from 430 to 2950 mg/kg on a dry basis
(Vasapollo et al., 2004). Lycopene represents more than 85% of the
total carotenoids; tomato peel contains about ve times more lycopene than tomato pulp (Lazos and Kalathenos, 1988; Sharma and
Le Maguer, 1996).
Carotenoids are important compounds in the human diet as anticarcinogens, cardiovascular disease preventers, and immune system
regulators. Moreover, they can act as antioxidants and precursors of
vitamin A (Singh and Goyal, 2008). Due to their association with human health, carotenoids have also been used in medicines and cosmetics. One of the most important carotenoids is lycopene (C40H56)
an open chain hydrocarbon with 11 conjugated double bonds. It is a
Corresponding author. Address: Bioelectrics Research Center, Kumamoto University, Kurokami 2-39-1, Kumamoto shi, Kumamoto 860-8555, Japan. Tel.: +81 96
342 3664; fax: +81 96 342 3665.
E-mail addresses: sitimach@yahoo.com (S. Machmudah), mgoto@kumamoto-u.ac.jp
(M. Goto).
0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.08.012

natural red pigment principally responsible for the characteristic

deep-red color of tomatoes and tomato products. Lycopene is widely
used as a food additive as colorants and antioxidants (Machmudah
et al., 2008a; Vagi et al., 2007; Topal et al., 2006). The large amount
of lycopene and other carotenoids contained by tomato processing
by-products make their recycling desirable both from an environmental and health viewpoint.
Solubility and stability of lycopene are the main problems in
extracting lycopene from tomato by-products. Lycopene is insoluble
in water but soluble in highly toxic organic solvents such as benzene,
chloroform, and dichloromethane; it also decomposes easily during
storage. Development of the supercritical uid extraction (SFE)
method is one way scientists have worked to circumvent these
problems.
Separation for food products and medicine are limited by the
requirement of low temperatures since the product usually has
poor stability at high temperatures. Also, solvents must be nontoxic and not remain as residue in the product. SFE is an extraction
method which operates above the solvents critical pressure and
temperature, enhancing the solvating power of the solvent. Carbon
dioxide is a solvent frequently used in the SFE method due to its
low critical temperature, it being neither toxic nor ammable,
and its availability at low cost and high purity (Brunner, 1994).
Several papers have reported on the use of supercritical carbon
dioxide extraction to obtain lycopene and other carotenoids from tomato by-product at lower temperature and pressure as well as on

S. Machmudah et al. / Journal of Food Engineering 108 (2012) 290296

the use of organic solvents as a modier (Baysal et al., 2000; Rozzi

et al., 2002; Sabio et al., 2003; Vagi et al., 2007; Huang et al.,
2008). Through response surface regression, Huang et al. (2008) predicted a 93% lycopene recovery using supercritical CO2 and 16% ethanol as a co-solvent. Topal et al. (2006) reported on the effects of
temperature, pressure, and CO2 ow rate on extraction of lycopene
from tomato peel by-product without the addition of any modier;
they did, however, use the toxic organic solvent tetrahydrofuran/
THF to rinsing the remaining lycopene in the system. It was shown
that temperature and pressure had an effect on lycopene extraction,
and that the highest yield of lycopene, 85%, was obtained at 40 MPa,
100 C, and 2.5 mL/min of CO2 with the THF rinsing method. Rozzi
et al. (2002) examined the effects of temperature, pressure, ow
rate, and CO2 volume on extraction of lycopene from tomato peel
and seed. A lycopene recovery of 61.0% was obtained at 86 C and
34.47 MPa with 500 mL of CO2 at a ow rate of 2.5 mL/min. Vasapollo et al. (2004) showed the presence of hazelnut oil worked both to
improve the yield up to three times of lycopene extracted over 8 h
and also to prevent degradation of lycopene during storage; however, they did not quantify stability. The maximum amount of
extractable lycopene from dried tomato obtained at 45 MPa and
66 C in the presence of hazelnut oil (10%) at a ow rate of 20 kg
CO2/h for extraction time more than eight hours was 60%. The use
of vegetable oil as a co-matrix with the tomato matrix for supercritical CO2 extraction of lycopene has also been reported with mixed olive oil and ethanol (Shi et al., 2009a) and hazelnuts (Ciurlia et al.,
2009; Lenucci et al., 2010). Lenucci et al. (2010) reported that the
addition of an oleaginous co-matrix consisting of roughly crushed
hazelnuts made it possible to recover approximately 80% of the lycopene in the oleoresin.
This work reports on supercritical CO2 extraction of lycopene
from tomato peel by-product carried out with the use of indigenous
oil from tomato seed obtained along with the tomato peel. The aim of
this work was to determine the effect of temperature, pressure, and
CO2 ow rate on lycopene recovery from tomato peel in the presence
of tomato seed oil as a co-solvent. We considered that the presence
of tomato seed oil can improve the extraction of lycopene and have a
benecial role in the stability of lycopene due to its fatty acid content
(Vasapollo et al., 2004; Lenucci et al., 2010). In addition, the effect of
extraction conditions on the b-carotene extracted and the concentration of lycopene in supercritical CO2 in the presence of tomato
seed oil was also investigated.

2. Materials and methods

2.1. Materials
A dried tomato by-product sample including tomato seed and a
mixture of tomato peel and seed sample (37:63 w/w) was obtained
from Kagome Co. Ltd. Japan. Initially, the sample was ground using
a coffee grinder and sieved to 1.05 0.10 mm. Standard lycopene
and b-carotene, HPLC grade of acetonitrile, methanol, and 2-propanol were obtained from Wako Pure Chemical Industries Ltd., Japan,
and CO2 from Uchimura Co., Japan.

2.2. Supercritical CO2 extraction

Experiments were carried out in a semi-continuous supercritical CO2 extractor used in previous work (Machmudah et al.,
2008a). The apparatus was equipped with an extractor (10 cm of
length, 2 cm of inside diameter, and 10 ml of capacity) (Thar Tech,
Inc., USA); a back pressure regulator (SCF-BPG, Jasco, Japan); a chiller (Cooling Unit CLU-33, Iwaki Asahi Techno Glass, Japan); a high
pressure pump for CO2 (Intelligent Prep. Pump. PU-2086 Plus,

291

Jasco, Japan); collection vials; and a wet gas meter (Sinagawa Co.,
Japan).
Initially, 4 g of material was placed in the extractor. Glass beads
were placed in the bottom and top of the extractor vessel to avoid
channeling during the extraction. Liquid CO2 from a cylinder tank
with a siphon was passed through a chiller kept at 5 C and compressed to the operating pressure by a high pressure pump.
Compressed CO2 was owed continuously into the extractor placed
in the heating bath and maintained at the operating pressure. The
exit uid from the extractor was expanded to the atmospheric
pressure by the back pressure regulator. The extract was collected
in vials every 5 min for the rst 30 min and then every 30 min for
180 min of extraction, weighed immediately after the collection,
and refrigerated at 20 C prior to analysis. To minimize decomposition and oxidation of extracted compounds, all samples were protected from light and ambient oxygen with aluminum foil.
The extractions were carried out at temperatures ranging from
70 to 90 C, pressures of 2040 MPa, CO2 ow rates of 24 mL/min,
and various ratios of peel, seeds and particle sizes. To investigate
the composition of tomato seed oil, oil from tomato seeds was extracted under identical operating conditions. Each experiment was
conducted in triplicate and cited as mean standard deviation.
2.3. Chemical analysis
Analysis for tomato seed oil was performed using a gas chromatography-ame ionization detector (GC-FID). Tomato oil consists of
polyunsaturated fatty acids (PUFAs) that must be analyzed by high
temperature gas chromatography. Before injection, the extracted
oil was converted to methyl esters according to the method of
Roy et al. (1996). Two ml of hexane was added to 50 mg of extracted oil. Then, 0.2 ml of 2 M KOH solution in methanol was
added to the sample and shaken at 100 C for 10 min. The sample
was centrifuged at 1500 rpm (309.5 G-force) for 15 min. Methyl esters dissolved in the hexane layer were separated by a funnel and
analyzed by GC-FID (Gas Chromatography GC-14A, Shimadzu, Japan) equipped with a DB-5 capillary column (15 m  0.250 mm 
0.25 lm). The oven temperature was increased from 70 to
320 C at 5 C/min intervals. The injector and detector temperatures were controlled at 250 and 300 C, respectively. The injection
volume was 0.6 ll. All samples were injected in duplicate. The peak
area percentage of each PUFA in the extract at each extraction condition is cited as mean standard deviation.
Carotenoids in the extract were analyzed by high performance-liquid chromatography (HPLC) equipped with STR-ODS-II column
(5 lm; 4.6 mm  250 mm) (Nacalai Tesque, Inc., Japan) and UVvisible detector (UV-970, Jasco, Japan) as reported by Machmudah et al.
(2008a). A mixture of 2-propanol:acetonitrile:methanol:water in
52:39:5:4 v/v ratio was used as a mobile phase t a ow rate of
1.2 mL/min. The sample dissolved in the solvent mixture, consisting
of 1:2 chloroform:acetone, was injected in 20 ll units. The column
temperature was controlled at 30 C by a column heater (Sugai U620, Japan) and detection was measured at 450 nm. Detector signals
were recorded using BORWIN Chromatography software. Peaks of
lycopene and b-carotene were identied by comparing the retention
time in the extract with standard compounds. The content of lycopene and b-carotene in the extract were estimated by comparing
the peak areas with their respective standards. Calibration curves
of the standards were prepared by plotting standard concentrations
(0.254 mg/mL) versus their peak areas detected at 5.7 and 8.9 min
for lycopene and b-carotene, respectively. All samples were analyzed in duplicate. The recovery of lycopene and b-carotene in the
extract at each extraction condition is cited as mean standard
deviation.
Recovery of lycopene and b-carotene extracted was calculated
based on the maximum lycopene and b-carotene extracted with

S. Machmudah et al. / Journal of Food Engineering 108 (2012) 290296

chloroform as solvent in soxhlet apparatus for 15 h. During the

extraction, the soxhlet extractor was covered with aluminum foil
to prevent oxidation and degradation of the valuable carotenoids.
Tomato seed oil was also extracted using soxhlet apparatus with
hexane as solvent for 15 h to obtain the maximum amount of oil
in tomato seed. The soxhlet extraction was carried out in triplicate
for both tomato peel and seed.
2.4. Statistical analysis
To determine the interaction of extraction variables and their effect on the lycopene and b-carotene recovery, an analysis of variance
(ANOVA) was carried out according to the Excel Statistics 2004 program. The signicance level was stated at 95%, with p-value 0.05.

100

Component Recovery (%)

292

Lycopene (with tomato seed)

Lycopene (without tomato seed)
-carotene (with tomato seed)
-carotene (without tomato seed)

80

60

40

20

0
0

30

90

120

150

180

Time (min)

3. Results and discussion

Lycopene and b-carotene contents in the tomato by-product
(37:63 w/w of peel/seed) provided by Kagome Co. Ltd. Japan, extracted by chloroform sohxlet extraction for 15 h, were 0.82 0.02
and 1.51 0.06 mg/g dry tomato peel, respectively. The content of
oil in the tomato seed determined by soxhlet extraction was
0.34 0.01 g/g dry tomato seed. The seed oil mainly contained linoleic acid (C18:3; 62 5%), followed by oleic acid (C18:1; 20 4%),
linolenic acid (C18:2; 15 4%), palmitic acid (C18:0; 2 0.5%), stearic acid (C16:0; 0.5 0.1%) and unidentied fatty acid (0.5 0.2%).
This work studied the effects of temperature, pressure, and CO2
ow rate on the recovery of lycopene and b-carotene extracted
from tomato peel by-products containing tomato seed oil as cosolvent as well as the composition of oil from tomato seed. The extracted tomato seed oil was golden yellow in color and, as in most
vegetable oils, the major lipid components were essentially triglycerides (Machmudah et al., 2007, 2008b). On the basis of GC analysis, the fatty acid composition of tomato seed oil comprised linoleic
acid (C18:3) as the main component, followed by oleic acid
(C18:1), linolenic acid (C18:2), palmitic acid (C18:0), and stearic
acid (C16:0). Composition of linoleic, oleic, linolenic, palmitic and
stearic acid in the extract were around 44.1172.55%, 14.14
27.65%, 0.6226.49%, 011.31% and 0.0312.06%, respectively.
Organic solvents may be used as a co-solvent in order to increase the solvating power of supercritical CO2, but traces of organic solvent may cause consumer concerns related to health and
environment (Wu et al., 2010). In this work, tomato seed oil was
used rather than an organic solvent to increase the solvent power
of supercritical CO2.
First, the effects of the presence of tomato seed oil in the extraction process were investigated. Tomato seeds were mixed with tomato peel at the ratio of 63/37 (seeds/peel). Seed oil was extracted
by supercritical CO2 in this way, with the oil acting as co-solvent
to enhance the supercritical CO2 solvating power for lycopene and
b-carotene extraction. Fig. 1 shows the effect of the presence of tomato seed oil on the recovery of lycopene and b-carotene. Recovery
of lycopene and b-carotene was calculated based on that extracted
from tomato peel using soxhlet extraction. The recovery of lycopene
and b-carotene without tomato seed oil as co-solvent was practically constant at 17.5% and 37%, respectively, from 60 to 180 min
of extraction time. In the presence of tomato seed oil, recovery of
lycopene and b-carotene signicantly increased and, after 120 min
of extraction, was practically constant at 46% and 68%, respectively.
This increase in efciency of lycopene recovery may be attributed to
better solubilization of lycopene and b-carotene in supercritical
CO2/tomato seed oil solvent compared with supercritical CO2 alone.
The presence of tomato seed oil promotes a better transport and
higher solubility of the lycopene and b-carotene from the solid matrix into supercritical CO2. The solubility of lycopene in vegetable oil

60

Fig. 1. Effect of tomato seed oil as co-solvent on the recovery of lycopene and bcarotene at 90 C, 40 MPa, and 3 ml/min.

is about 0.2 g/L at room temperature (Bauernfeind et al., 1958; Borel

et al., 1996), but it clearly rises with increasing oil temperature (Ax
et al., 2003). Thus, the addition of oil as co-solvent may enhance
the recovery efciency by increasing both the solubility of the analyte in the supercritical uid as well as the uid ow rate of the lycopene through the tomato matrix and pipeline. In addition, Lenucci
et al. (2010) reported that the presence of vegetable oil (hazelnut
oil) resulted in no degradative loss of lycopene during the extraction.
3.1. Effects of pressure
Effects of pressure were studied at a constant temperature of
90 C, 3 mL/min of CO2 and the presence of 63% tomato seeds in
the raw material. Fig. 2(a) and (b) show the effects of pressure
on lycopene and b-carotene recovery and tomato seed oil recovery,
respectively. The recovery of lycopene, b-carotene and tomato seed
oil increased with increasing pressure. An increase in pressure is
known to increase the solvent density and solubility of lycopene
in supercritical CO2 (Topal et al., 2006; Shi et al., 2009b; Lenucci
et al., 2010). At lower densities, the polarity of supercritical CO2
is more like that of hexane, while at higher densities, it is more like
that of chloroform (Brunner, 1994). Carotenoids display much
higher solubility in chloroform compared to hexane (Rozzi et al.,
2002). Consequently, increasing density of supercritical carbon
dioxide leads to higher recovery of lycopene and b-carotene during
the extraction process. Moreover, increasing pressure led to a virtuous cycle: it increased the amount of seed oil extracted, which
in turn increased the solvent power of supercritical CO2 to extract
lycopene and b-carotene.
3.2. Effects of temperature
The effects of temperature (70, 80, and 90 C) on the recovery of
the carotenoids are shown in Fig. 3. As can be seen, b-carotene
recovery slightly decreased with increasing temperature. This is
explicable as decreasing the temperature increased the density of
CO2 and solubility of b-carotene in supercritical CO2. Consequently,
the extraction rate of b-carotene increased with decreasing temperature. In addition, under this condition, the change of CO2 density was more effective than that of solute vapor pressure, and the
lower temperature might contribute to lower degradation of bcarotene.
On the other hand, lycopene recovery slightly increased with
increasing temperature. The increasing temperature caused an
increasing in vapor pressure of the lycopene, resulting in

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S. Machmudah et al. / Journal of Food Engineering 108 (2012) 290296

100

80

Component Recovery (%)

Component Recovery (%)

100

P = 20 MPa (-carotene)
P = 30 MPa (-carotene)
P = 40 MPa (-carotene)

P = 20 MPa (Lycopene)
P = 30 MPa (Lycopene)
P = 40 MPa (Lycopene)

60

40

20

80

60

40

20

T = 70 C (Lycopene)
o
T = 80 C (Lycopene)
o
T = 90 C (Lycopene)

30

60

90

120

150

180

30

60

Time (min)

100

P = 20 MPa
P = 30 MPa
P = 40 MPa

Component Recovery (%)

60

40

20

0
0

30

60

90

120

150

180

120

150

180

(a)

100

80

90

Time (min)

(a)

Component Recovery (%)

T = 70 C (-carotene)
o
T = 80 C (-carotene)
o
T = 90 C (-carotene)

120

150

180

T = 70 C
o
T = 80 C
o
T = 90 C

80

60

40

20

0
0

30

60

Time (min)

(b)
Fig. 2. Effect of pressure on the recovery of lycopene and b-carotene (a) and tomato
seed oil (b) at 90 C, particle size of 1.05 0.10 mm and 3 ml/min.

increasing solubility of lycopene and higher lycopene recovery.

Moreover, increasing temperatures enabled better transport of solute in the matrix and/or from the matrix to the solvent, presumably due to damage to the particles (Vasapollo et al., 2004) and
the partial destruction of the vegetable structures that contain
lycopene. Difculties remain in investigating temperature effects
on the extraction process. In fact, solvent density decreased with
increasing temperature at a constant pressure, resulting in reducing solubility of lycopene, but the magnitude of density change is
smaller than that of solute vapor pressure at higher pressures. In
the case of tomato seed oil extraction, the increasing temperature
had no signicant effect on seed oil recovery. Under these conditions, both density and oil vapor pressure change controlled the
extraction process.

90

Time (min)

(b)
Fig. 3. Effect of temperature on the recovery of lycopene and b-carotene (a) and
tomato seed oil (b) at 40 MPa, particle size of 1.05 0.10 mm and 3 ml/min.

external mass transfer resistance. On the other hand, an increasing

CO2 ow rate decreases residence time and as a result, interaction
between CO2 and the solute becomes shorter. The higher ow rate
may also cause a channeling effect, where the solvent is forced
through the sample at such a high rate that it passes only around
the solid matrix and is not able to diffuse through the pores within
the sample. The increased CO2 ow also could cause the sample to
compact and restrict CO2 movement into and out of the sample,
reducing the amount of CO2 that comes in contact with the sample
(Tonthubthimthong et al., 2001). Based on the contrary reasons
above, it is clear that the extraction process was limited by the solubility of solute in the supercritical CO2.

3.4. Effects of rinsing method

3.3. Effects of CO2 ow rate
This work showed that ow rate of CO2 did not have a signicant effect on the lycopene, b-carotene, or seed oil recovery (data
not shown). CO2 ow rate has been shown to be insignicant in
many extractions using supercritical CO2 (Machmudah et al.,
2006a, 2007, 2008a). An increasing CO2 ow rate is known to increase the number of CO2 molecules contacting with the solute,
thus increasing intermolecular interaction between CO2 and the
solute, then increasing the solute dissolution (Machmudah et al.,
2006a). In addition, an increasing CO2 ow rate may decrease the

In order to determine maximum efciency of the extraction

process, organic solvent was used as a rinsing solvent to dissolve
remaining extracted carotenoids on the tubing wall. The rinsing
method was applied after the extraction using tetrahydro furan
(THF), which was pumped into the tubing line for 5 min at 1 mL/
min of ow rate.
Fig. 4 shows the effect of THF rinsing method with comparison
to previous work carried out by Topal et al. (2006). As shown in
Fig. 4, the THF rinsing method gave higher recovery both for the
lycopene and b-carotene. Use of the rinsing method is known to

S. Machmudah et al. / Journal of Food Engineering 108 (2012) 290296

remove the extracts left in the tubing line and back pressure regulator; unfortunately, may also contaminate the product. Rinsing
product of carotenoids can, though, be used for analytical purposes
(Britton, 1985 and Meyers and Bligh, 1981). Food grade ethanol
solvent may be substituted for THF as the rinsing solvent because
of its non-toxic effect, which is ideal for food products (Kassama
et al., 2008). Moreover, ethanol as modier in supercritical CO2
extraction could improve the solubility of carotenoids that resulted
in 93% recovery of lycopene (Huang et al., 2008). In comparison
with previous work, extraction with tomato seed without rinsing
had a higher efciency than that of Topal et al. (2006), indicating
that even without the use of THF as a rinsing method, yield of
carotenoid can be improved by the addition of tomato seed oil in
the supercritical CO2 extraction. In addition, seed oil may also be
used to replace the toxic organic solvent used to remove carotenoids remaining in the extraction system.
3.5. Effects of tomato peel to seed ratio

100
Peel/Seed=25/75 (Lycopene)
Peel/Seed=37/63 (Lycopene)
Peel/Seed=50/50 (Lycopene)

Peel/Seed=25/75 (-carotene)
Peel/Seed=37/63 (-carotene)
Peel/Seed=50/50 (-carotene)

80

Component Recovery (%)

294

60

40

20

0
0

30

60

90

120

150

180

Time (min)
Fig. 5. Effect of tomato peel and seed ratio on the recovery of lycopene and bcarotene at 90 C, 40 MPa, particle size of 1.05 0.10 mm and 3 ml/min..

The effects of tomato peel to seed ratio on the lycopene and bcarotene recovery are shown in Fig. 5, which show recovery of
lycopene and b-carotene increased with increasing seed ratio from
50 to 63. Increasing the amount of tomato seed led to an increase
both in oil produced in the extractor as well as, in solvent power
(Brunner, 1994; Sovova et al., 2001; Vasapollo et al., 2004). As a result, recovery signicantly increased with an increased amount of
tomato seed. On the other hand, increasing the seed to peel ratio
from 63 to 75 signicantly decreased the recovery. This could be
due to higher extraction of seed oil which may have hindered
supercritical CO2 transport to penetrate into the solid matrix.
Moreover, the effect of vegetable oil as an entrainer is limited
due to its low solubility in CO2 (Sovova et al., 2001). Furthermore,
the recovery was signicantly decreased.
3.6. Effects of particle size
Raw material pretreatment is important in order to signicantly
increase the yield of lycopene extraction (Baysal et al., 2000;
Vasapollo et al., 2004; Ciurlia et al., 2009). For example, drying and
grinding processes inuence the physical properties and quality of
raw material. The effect of particle size (ungrounded,
1.59 0.12 mm and 1.05 0.01 mm) on the recovery of lycopene
and b-carotene is shown in Fig. 6. As seen, the recovery of both lycopene and b-carotene signicantly increased with decreasing particle
size. Decreasing the particle size decreases mass transfer resistance

and consequently increases the recovery of lycopene and

b-carotene. Research into the effects of particle size on the seed oil
recovery was not performed in this work since it has been reported
by some researchers for other plant seeds oil (Machmudah et al.,
2006b, 2007; Han et al., 2009).
3.7. Concentration of lycopene in supercritical CO2
Also studied was concentration of lycopene in SCCO2 as a function of temperature and SCCO2 density carrying out extractions at
ow rate of 2 ml/min and 10 g of tomato peel and seed. A low ow
rate and high amount of sample gave a saturated solution. The results show a correlation between concentration C of the solute in
the supercritical phase and density q of the uid, according to
the equation proposed by Chrastil (1982). The Chrastil model, in
fact, assumes that the solvation of the solute can be described as
equilibrium between a number of the uid molecules and the solute through formation of a solvate complex; the following equation has been proposed:

ln C k ln q 

a
T

where C is the concentration of the solute in the supercritical phase

(g/L), q is the density of CO2 (g/L) at the absolute temperature (T)
estimated by NIST Chemistry WebBook, k corresponds to the uid

With Tomato Seed (Lycopene)

With Tomato Seed and Rinsing (Lycopene)
Without Tomato Seed (Lycopene)
Topal et al. (Lycopene)
With Tomato Seed (-carotene)
With Tomato Seed & Rinsing (-carotene)
Without Tomato Seed (-carotene)
Topal et al. (-carotene)

80

100

Component Recovery (%)

Component Recovery (%)

100

60

40

20

Unground (-carotene)
1.59 mm (-carotene)
1.05 mm (-carotene)

Unground (Lycopene)
1.59 mm (Lycopene)
1.05 mm (Lycopene)

80

60

40

20

0
0

30

60

90

120

150

CO2 consumption (g CO2/g sample)

0
0

30

60

90

120

150

180

Time (min)
Fig. 4. Effect of rinsing method on the recovery of lycopene and b-carotene at 90 C,
40 MPa, particle size of 1.05 0.10 mm and 3 ml/min..

Fig. 6. Effect of particle size on the recovery of lycopene and b-carotene.

S. Machmudah et al. / Journal of Food Engineering 108 (2012) 290296

molecules associating with one molecule of solute to form the solvate complex, a and b are constants taking into account the total
heat of the reaction and the molecular weight of the species. Using
different temperature values, it is possible to obtain the corresponding density values and plotting ln (C) versus ln (q) at different
temperatures a straight line is obtained whose slope is equal to k.
Fig. 7 shows the concentration of lycopene in the supercritical
phase as a function of the solvent density at various temperatures.
Once the value of k is known, it is possible to calculate the constants
a and b and the following Chrastil equation can be obtained:

C q10:21 e

To estimate the correlation of data between experimental and

calculated values, the percentage of the average absolute deviation
(AAD %) was calculated by consideration of all the concentration
values (Eq. 3). The results showed that the Chrastil equation fairly
represented the concentration behavior of lycopene in SCCO2 with
AAD % less than 10.



calc 
n  exp
1X
C  C 
AAD %
  100


n i1  C exp

On the other hand, some discrepancies were observed when

these results were compared with previous studies on lycopene
solubility (Gomez-Prieto et al., 2003; Vasapollo et al., 2004; Topal
et al., 2006). Vasapollo et al. (2004) have calculated the constants
k, a, and b at 34 MPa for different temperature values to be 4.643,
5157, and 21.17, respectively. Topal et al. (2006) have determined the constants k, a, and b at pressure and temperature range
studied in this work. The constants k, a, and b obtained were 8.59,
5565 and 45.65, respectively. Gomez-Prieto et al. (2003) also
reported the calculated parameters of solubility of trans-lycopene
in SCCO2, obtaining the Chrastil equation points by combining CO2
densities between 400 and 800 g/L with extraction vessel temperatures of 50, 60, and 70 C. For all-trans-lycopene, constant k, a, and b
values were calculated as 8.06, 4336.06, and 47.63, respectively.
The differences of the constants k, a, and b obtained may be caused
by the differences of the extraction system used. In this work, the
tomato seed oil was used to enhance the extraction rate, and as
the result higher concentration or solubility of lycopene in SCCO2
was obtained. In addition, the measurement of lycopene solubility
is possibly affected by factors such as the experimental method,
sampling method, method of quantication, method of measurement of solubility, degradation of lycopene, and the degree of purity
of the starting material (Shi et al., 2009b). In comparison with

0.10
o

T = 70 C
o
T = 80 C
o
T = 90 C

T = 70 C (Chrastil)
o
T = 80 C (Chrastil)
o
T = 90 C (Chrastil)

C (g/L)

0.06

0.04

0.02

0.00
500

550

reported work, the solubility obtained in this work was higher. It

can be seen that a higher constant k value resulted in higher solubility. Saldana et al. (2010) reported that the apparent solubility of
lycopene obtained using oil as a co-solvent was higher than that obtained with ethanol as a co-solvent or pure supercritical CO2. The differences in solubility are mainly due to the polarity of the co-solvent
and the impact of the tomato matrix in the multicomponent complex system.

4. Conclusions

500057:34
T

0.08

295

600

650

700

750

800

850

900

(g/L)

CO2

Fig. 7. Concentration of lycopene (g/L) in SCCO2 as a function of the solvent density

at various temperatures.

Supercritical CO2 extraction of lycopene from tomato peels by

product was conducted with the use of indigenous oil from tomato
seed obtained along with tomato peels. This work emphasizes that
the by-products used for raw material are more meaningfully than
that reported by other researchers who used different vegetable
oil. The optimum operating conditions for lycopene extraction
was a temperature of 90 C, pressure of 40 MPa, a particle size of
1.05 0.10 mm, and ratio of tomato peel to seed of 37/63. Under
these conditions, 56% of lycopene could be extracted, whereas
44% of the lycopene remained both in the pipeline and the solid
matrix. The presence of fatty acid content in the tomato seed oil
improved recovery of lycopene extracted from 18% to 56%.
Acknowledgements
This work was supported by Kumamoto University Global COE
Program Global Initiative Center for Pulsed Power Engineering
and Japan Society for the Promotion of Science (JSPS).
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