Trends in Food Science & Technology 97 (2020) 156–169

Contents lists available at ScienceDirect

Trends in Food Science & Technology

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

Recent advances in subcritical water and supercritical carbon dioxide T

extraction of bioactive compounds from plant materials
Sinemobong O. Essien, Brent Young, Saeid Baroutian∗
Department of Chemical and Materials Engineering, The University of Auckland, Auckland, 1023, New Zealand

A R T I C LE I N FO A B S T R A C T

Keywords: Background: Subcritical water (SWE) and supercritical carbon dioxide extraction (SCCO2) are novel extraction
Subcritical water extraction techniques for recovering compounds with food-enhancement and health promoting properties, from various
Supercritical carbon dioxide extraction plants and biomaterials. These extraction techniques are efficient, economical and promising routes for resource
Bioactive compounds recovery without compromising the quality of the extracted products.
Antioxidants
Scope and approach: Here, the theoretical background, practical application and recent trends associated with
Techno-economic assessment
the use of SWE and SCCO2 in the recovery of bioactive compounds from plant sources are presented. The paper is
organised to allow a refreshed understanding of the main features, benefits, challenges, and possible solutions
involving SCCO2 and SWE based on the enormous number of scientific publications and the very few industrial
applications in the public domain. The utilisation of these methods are advantageous in selective extraction of
better-quality compounds at lowest potential environmental impact. Furthermore, two research publication
databases were queried using specific criteria to show the progress and growth in interest on SWE and SCCO2.
Key findings and conclusions: Subcritical water and supercritical carbon dioxide are viable extraction techniques
for recovery of bioactive compounds. These techniques, standalone or combined sequentially or with other
extraction methods, enhance yield and quality of thermally liable compounds. Mathematical models having a
strong correlation with experimental data can also be used to predict and monitor the process kinetics. Our
findings should be beneficial for professionals concerned with the application of technology in the development
of new and existing food products, their storage and marketability.

1. Introduction
Bioactive compounds can interact with one or more components of
living tissue resulting in a wide range of effects. They are sourced
naturally from plants, algae, foods and by-products or synthetically
produced. Specifically, bioactive compounds sourced from plants have
been shown to impact human health and wellbeing positively (Azmir
et al., 2013). These compounds, including phenolic compounds (gly-
cones or glycosides, monomers or highly polymerised), have excellent
antibiotic, antioxidant and anticancer potential. Phenolic compounds
form a major group of plant bioactive compounds. Their intricate and
variable nature in terms of stability complicates the process of their
extraction and isolation for further use. The recovery of bioactive
compounds from plants is still a topic of interest owing to their po-
tential in the development and manufacture of functional ingredients
and nutraceuticals. These functional ingredients and nutraceuticals will
then be used as antioxidant, antifungal, anticancer, immunological
agents in various food and health applications including prevention of
degenerative diseases. For instance, the skincare product made from
kānuka honey, which is used in the treatment of several skin diseases
(Semprini, Singer, Shortt, Braithwaite, & Beasley, 2017). Extraction
from food by-products, like food waste, and algae have also recorded a
significant increase in the past decade (Gallego, Bueno, & Herrero,
2019; Zakaria & Kamal, 2015). Minimization or elimination of waste
and value addition for a better and sustainable economy are at the
centre of this growing interest.
Extraction is the first and foremost step in the isolation and char-
acterisation of bioactive compounds from plant materials. This unit
operation plays a crucial role in the overall success of qualitative and
quantitative studies of the commonly extracted bioactive compounds.
The process yield depends, not only on the operating parameters, but
also on the pre-treatment methods, chemical composition, and physical
characteristics of the plant and compound of interest. A typical example
is the production of extracts with higher polyphenol content from
freeze-dried pomegranate peel compared to oven-dried and non-pre-
treated peels (Mphahlele, Fawole, Makunga, & Opara, 2016). The

∗
Corresponding author.
E-mail addresses: sess437@aucklanduni.ac.nz (S.O. Essien), b.young@auckland.ac.nz (B. Young), s.baroutian@auckland.ac.nz (S. Baroutian).

https://doi.org/10.1016/j.tifs.2020.01.014
Received 23 February 2019; Received in revised form 7 January 2020; Accepted 8 January 2020
Available online 16 January 2020
0924-2244/ © 2020 Elsevier Ltd. All rights reserved.
S.O. Essien, et al.
Abbreviation
C3RE Cyanidin-3-rutinoside equivalent
CAE Catechin equivalent
CE Chlorogenic acid equivalent
CO2 or CO2 Carbon dioxide
DES Deep eutectic solvents
dw dry weight
EAE Enzyme assisted extraction
EP Pyrogallol equivalent
EtOH Ethanol
GAE Gallic acid equivalent
GL Glycyrrhizic acid
H2O Water
solubility of target compounds in the selected solvents, the process
conditions, and measures to address co-extraction of undesirable com-
pounds all need to be considered during the process selection stage.
Traditionally, maceration, soxhlet extraction, and hydrodistillation
using organic or inorganic solvents are used. The extraction efficiency
depends solely on the extracting power of solvents which is also a factor
of the polarity of the targeted compounds (Azmir et al., 2013). These
methods are, frequently used to benchmark relatively new technique
with broad applicability. Poor selectivity, consumption of large vo-
lumes of organic solvent that can lead to generation of organic waste
are common drawbacks of these techniques. With growing awareness of
the need for environmentally friendly and cost-effective technique (or
for sustainability in production), a variety of alternatives have been
developed (Moreira, Alexandre, Pintado, & Saraiva, 2019). Table 1
briefly summarizes some of these emergent technologies and the pre-
mise for their application. “Subcritical and supercritical fluid extraction
technologies are among those methods that fulfil the criteria to be
considered suitable as green extraction technologies.” Both techniques
have been applied as effective tool for the recovery of plant bioactive.
Presently, these technologies are also used in the production of bioac-
tive film packaging (Zhao & Saldaña, 2019), for spray drying, as sol-
vents or anti-solvent for particle precipitation/encapsulation (Cheng,
Lu, Huang, & Wu, 2017), impregnation for development of anti-biofilms
(Zizovic et al., 2018), drugs, and wood dressing among others.
A fluid becomes supercritical when the temperature and pressure
are above the critical point. Under supercritical conditions, the prop-
erties of the fluid are intermediary between gases and liquids, thus
facilitates the extraction of compounds. SFE provides several ad-
vantages mainly due to their high diffusivities and low viscosity. These
properties can be modified by adjusting the pressure and temperature
to provide faster extraction yield. Carbon dioxide (either as a single
fluid or modified by co-solvents) is widely employed because of its mild
properties of carbon dioxide (CO2) favour these compounds. Besides
extraction, supercritical carbon dioxide has been used for pasteurisation
(Amaral et al., 2018) and encapsulation (Lee, Tan, Sulaiman, Hee, &
Chong, 2020). On the other hand, water is the most widely used for
subcritical fluid extraction. Other fluids, for instance, butane, dimethyl
ether, and propane have been employed in subcritical fluid extraction.
Subcritical propane was used to recover antioxidant compounds and
essential oil from mango leaves (Fernández-Ponce, Casas, Mantell,
Rodríguez, & Martínez de la Ossa, 2012) and sapucaia nuts (Teixeira,
Ghazani, Corazza, Marangoni, & Ribani, 2018), respectively. It showed
similar advantages to supercritical CO2, and its non-polar nature made
it suitable for lipophilic compounds like fatty acid. However, the idea of
SWE and SCCO2 is to promote the use of eco-friendly solvents during
extraction making for safe and high-quality extracts. This review will
focus on their application for selective extraction from plant material.
Publication on these subject areas continue to rise, as seen within
the last ten (10) years (Fig. 1). The trend for extraction of plants
157
Trends in Food Science & Technology 97 (2020) 156–169
HHP High Hydrostatic Pressure
IL Ionic liquids
MAE Microwave assisted extraction
PEF Pulsed-electric field
QE Quercetin equivalent
RE Rutin equivalent
ReE 20(S)-Ginsenoside;
SCCO2 Supercritical carbon dioxide extraction
SSR Solid-solvent ratio
SWE Subcritical water extraction
UAE Ultrasound assisted extraction
US-SCCO–2 Ultrasound assisted- SCCO–2
WoS Web of Science
bioactive using these two techniques was determined by using Scopus
and Clarivate Analytics Web of Science database search as per the cri-
teria stated in Fig. 1. Our search shows that these research outputs are
mostly focused on bioactive compounds, specifically those of plant
origin (Fig. 1c–d) for both extraction technique. Though out of the
scope for this project, it is important to note that interest in the utili-
sation of algae and seaweed have also increased in the last decade.
Other previous reviews have been published specifically on a particular
type of plant, for the extraction of specific and nonspecific compounds
from different plant materials or conducted on a broader view of green
technologies. Readers can refer to these some of these reviews for more
information (Belwal et al., 2018; Gallego et al., 2019; Plaza & Turner,
2015; Shitu, Izhar, & Tahir, 2015). This article provides a comprehen-
sive and updated overview of the current state of knowledge of SWE
and SCCO2 from different plant materials by discussing not only the
principles, mechanisms and limiting factors. But also, critically reviews
the latest advancements and perspectives in the application of these
two extraction techniques to obtaining bioactive compounds from
plants for analytical and industrial purposes, within the last decade. A
summary of the outcomes from various techno-economic studies is also
presented since this is essential for projects that are to attain com-
mercialisation. A case study on the industrial use of one of these
technologies is also presented.
2. Subcritical water extraction (SWE)
Subcritical water extraction is an eco-friendly technique that uses
the unique properties of subcritical water that is hot water above
boiling point to high temperature-pressure conditions just below its
critical point (374 °C, 220 bar). The use of SWE is based on temperature
and pressure range of (100–250 °C) and (1–8 MPa) respectively.
Subcritical water extraction is also called pressurised hot water or hot
liquid solvent extraction, but caution should be taken when using these
terms because, pressurised solvents are also used for liquids at sub-
boiling conditions (Srinivas & King, 2010). The knowledge of changes
in water with pressure and temperature is critical to understanding this
method. Of importance is the dielectric constant, which reduces to
values similar to organic solvent under subcritical conditions.
Several studies have shown that using SWE provided faster extrac-
tion time, low solvent consumption, high selectivity resulting in extract
fractions with diverse compositions and high biological activity. The
most recent and notable reports on SWE of plants bioactive compounds
are presented in Table 2. The primary target compounds, as can be
observed, are polar particularly antioxidants. The main shortcoming is
the degradation of the thermolabile bioactive compounds at very high
extraction temperatures.
S.O. Essien, et al. Trends in Food Science & Technology 97 (2020) 156–169

2.1. SWE process mechanism

Redondo, Venturini, Luengo,

Puri, Sharma, and Barrow

Raso, and Arias (2018).

Moreira et al. (2019) The mechanism of the SWE process involves a transfer of solutes

Bruno et al. (2019)

from the various active sites in the sample matrix to the extraction
medium by diffusion, partitioning equilibrium, and convection (Zakaria
& Kamal, 2015). The elution of the solutes from the matrix (that is,
References

external mass transfer through the liquid film) was said to be the pre-
(2012).

dominant mass transfer step for Khajenoori, Asl, and Hormozi (2009),
whereas the solute partitioning equilibrium between the solvent and
Inability to function under mild processing conditions in aqueous solutions.

possible release of metals because of corrosion and migration of electrode

Inability to monitor technical parameters in continuous-flow systems, and
chemical structure of target compounds which may alter bioactivity and the solid matrix was reported as the rate-limiting mechanism for SWE in
Non-uniform distribution of sound waves, and formation of free radicals

behaviour of enzymes under different environmental conditions such as

temperature, nutrient availability, and per cent dissolved oxygen may

Haghighi and Khajenoori (2013). To prevent oxidation during extrac-

The recovery of nonpolar compounds and ii) the modification of the
Relatively expensive enzymes for larger scale extraction. Changing

tion, nitrogen or another inert gas is used to purge the system. The
mechanism has been broken into a different number of sequential steps
by various authors all governed by mass transfer principles, the sample
materials leading to food contamination and adulteration.
and metal contamination, if an ultrasound probe is used

matrix, and solvent properties of water at the extraction conditions.

Extraction rate curves are now used to describe the importance of these
transport mechanisms in terms of yield, flow rates and time
(Nkurunziza, Pendleton, & Chun, 2019). Fig. 2 is the schematic of SWE
equipment for a static operation.

2.2. Important factors in subcritical water extraction

The most relevant properties of water are those modulated by the

hinder process scale-up

extraction process parameters. The main process parameters are pres-

limit further usage

sure, temperature, solvent ratio, particle size, extraction time, mixing

and flow rate. Choice of appropriate operating conditions becomes
Limitations

more evident when the nature of compounds to be extracted is known.

2.2.1. Pressure
The main role of pressure in SWE is to keep water above the boiling
Enzymes degrade the structural integrity of plant cell

Absorption and conversion of microwave to thermal

point, in its liquid form. This factor is also known to exert rupture ef-
Creation of temporary pores in the cell membrane

fects on the samples. Practically, SWE is weakly dependent on pressure,

walls depending on the catalytic specificity and

so any additional pressure has no significant influence on extraction

efficiency (Ko, Cheigh, & Chung, 2014). But with a substantial eleva-
tion, pressure could aid extraction by forcing water through sample
Acoustic cavitation for mass transfer

pores that were unreachable at ambient temperature. Cvetanović et al.

(2017) noted a 90% increase in apigenin yield and over a 100% in-
Summary of other novel extraction technologies applied in recovery of bioactive compounds.

crease in total phenolic content as pressure increased from 10 to 45 bar.

They, however, concluded that extra pressure is needless, especially
beyond 30–45 bar, if polyphenol is the target compound. There is still a
need for more studies in this area mainly to understand the mechanism
regioselectivity

in the various reaction systems for improved bioactivity.

Premise

energy

2.2.2. Temperature
Among the many effects of temperature, the most important is its
ability to alter physiochemical properties of water. Increase in extrac-
Enzymes (cellulase, hemicellulase,

Electric fields (0.5–10 kV/cm) for

tion temperature leads to decrease in viscosity and surface tension of

water, reduces adhesive (solute-matrix) and cohesive (solute-solute)
micro- to millisecond periods
Propagation of sound waves

intermolecular interactions, and weakens hydrogen bonds (Zhao et al.,

Electromagnetic radiation

2019). These changes reduce the dielectric constant of water to similar

values like those of ethanol and methanol (Shitu et al., 2015) resulting
Mode of operation

in higher solubility of solutes in water. Past research has shown a re-

(0.3–300 GHz)
and pectinase)

markable increase in mass transfer rate and high solubility of a wide

(> 20 kHz)

range of bioactive compounds, including the water-insoluble sub-

stances, due to these changes. Studies have also shown that elevated
temperature causes a decrease in the concentration of target com-
pounds because of mainly solute degradation or molecular transfor-
assisted extraction (PEF)

mation (Munir, Kheirkhah, Baroutian, Quek, & Young, 2018). These

Pulsed Electric Field-
Ultrasound-Assisted

Microwave-assisted

degradation of analytes or formation of new compounds are unavoid-

extraction (MAE)
Extraction (UAE)

extraction (EAE)
Enzyme-assisted

able at very high temperature (Plaza & Turner, 2015) but are sometimes
desirable as seen in Ko, Nam, and Chung (2019). It proves that the type
Technique

of target compounds influences the range of temperature selected. This

fact was confirmed by Belwal et al. (2018); Gallego et al. (2019); Plaza
and Turner (2015); Shitu et al. (2015). The acceptability of some of the
Table 1

S/N

new products, for instance, furan compounds, is still being disputed

1

(Moreira et al., 2018). Defining the optimal extraction temperature in

158
S.O. Essien, et al.
Fig. 1. Progress in number of publications featuring (a) “Subcritical water extraction”, (b) “Supercritical carbon dioxide extraction” in Elsevier Scopus and Clarivate
Web of Science (WoS). (c) “Subcritical water extraction of plant bioactive”, and (d) “Supercritical carbon dioxide extraction of plant bioactive” in Scopus database.
SWE for different target compounds in plant material is also very im-
portant.
2.2.3. Solvent-to-sample ratio
Solvent-to-sample ratio affects the solubility and partition-equili-
brium constant of the SWE process (Ko et al., 2014). An increase in this
parameter increases the concentration gradient of the solutes allowing
for a higher extraction rate (Cvetanović et al., 2017). Certain factors
like extraction time, quality of extract and economic factors are con-
sidered when determining the optimal solvent ratio. An optimum sol-
vent ratio maintains just the right concentration gradient between the
sample matrix and the bulk of the solvent during extraction.
2.2.4. Time
The effect of time can be described using Sarfarazi, Jafari,
Rajabzadeh, and Feizi (2019). Rapid dissolution rates of picrocrocin,
safranal and crocin content occurred at the beginning of extraction and
progress with time, but this rate decreased subsequently with prolonged
extraction time. This trend depends strongly on the extraction tem-
perature, modifiers used, the nature of plant and target compounds, and
the mode of extraction (Fan, Xiang, Li, Jiang, & Gao, 2016). It occurs
either because the process has reached its solubility limit, or due to
decomposition of already extracted compounds. The latter is the most
common reason because of the thermal stability of these bioactive
compounds at high temperature. At this point, minor concentration
changes in chemical composition are noted as reported for garlic in
(Tomšik et al., 2017). Subsequently, the yield begins to decrease with
longer extraction time due to decomposition of already extracted
compounds (Fan et al., 2016). Sampling at fixed intervals should assist
in monitoring variation in the composition of the extract with time. The
point of compromise for effective extraction will now depend on the
overall production cost.
159
Trends in Food Science & Technology 97 (2020) 156–169
2.2.5. Flowrate
SWE is mostly operated as a static mode process. For continuous
SWE system, flow rate impacts positively on extraction rate by shifting
the equilibrium and allowing for greater solvent flux through the plant
materials. By this, faster extractions are achieved, and the residence
time of compounds in the solvent is reduced. The influence of flow rate
is controlled by the stage at which SWE kinetics is. Therefore, de-
pending on the operating range, the opposing effect of time can cause
the influence of flow rate on extraction yield to become insignificant.
Lachos-Perez et al. (2018) obtained the best yield of flavonones at their
lowest flow rate (10 mL/min) and stated that a high flow rate prevented
the formation of degradation products. The downside of too high flow
rate is the production of diluted extracts, thus requiring extra con-
centration steps which directly translates to additional production cost
and time. These two conditions must be considered when deciding the
best flow rate.
2.2.6. Particle size
It is well known that smaller particle size increases the contact
surface area between the solvent and the sample. The polyphenol
content of subcritical water extract from onion skin increased with a
decrease in particle size (Munir et al., 2018), meaning smaller particle
size led to higher extraction yields. According to Munir et al. (2018),
the influence of particle size on radical scavenging activity in the sub-
critical water onion skins extract was controlled by temperature. The
optimal particle size should be such that it increases the yield of pro-
ducts while avoiding the chance of particle agglomeration.
2.2.7. Mixing rate
Mixing is incorporated to reduce low-temperature regions within
the system. Increasing mixing speed leads to enhanced mass transfer by
improving the convective mass transfer rates of solutes between the
 S.O. Essien, et al.

Table 2
Selected publication involving application of SWE for bioactive compounds from plant materials between the period 2010–2019.
Compound Plant Source Operating Conditions Yield References

Temperature (°C) Pressure Time (min) Solid: liquid ratio Others

(MPa)

Lycopene and β-carotene Watermelon: rind and 100–30 – 10–60 – – Rind (0.15–7.53 mg GAE/g), flesh (0.16–3.7 mg GAE/g Kim et al. (2014)
flesh extract)
Phenolic compounds Pomegranate seeds 80–280 6 15–120 1:10–1:50, m/v – 4854.7 mg CAE/100 g DW He et al. (2012)
Polyphenols Grape skins and seeds 80–120 10 20–120 2–5 mL/min 77 ± 3 mg GAE/g; 124 ± 1 mg GAE/g Duba et al. (2015)
Hayward kiwifruit 170–225 5 10–180 1:100 g/mL – 26.16 ± 0.08–86.26 Kheirkhah, Baroutian,
pomace ± 0.06 mg CAE/g dw; and Quek (2019)
Betulinic acid Birch bark 140–220 1.5–3.5 10–50 40–60 mL/g – 16.03–26.54 mg/10 g dw Liu et al. (2015)
Antimicrobial and Green coffee bean 180–220 3–6 ~30–40 – – 20.4–144.4 mg GAE/g Getachew and Chun
antihypertensive compounds 5–43 mg CAE/g (2016)
Fucoidan Saccharina japonica 100–180 2–8 5–15 0.04–0.09 g/mL 0.1% sodium 0.1–12.89% (w/w) Saravana et al. (2018)
hydroxide
Withanosides and withanolides Ashwagandha 100–200 10 10–30 – – 51.9 ± 1.2–82.5 ± 1.08 mg GAE/g Nile, Nile, Gansukh,
Baskar, and Kai (2019)

160
Rutin Buckwheat 80–120 5 20 – 1–3 mL/min 54.9 ± 1.1–91.0 ± 1.2%
β-glucan-enriched fractions Shiitake mushroom 200 11.7 15–60 1:8 (w/w) – 5.92 ± 0.67–15.54 ± 2.18 g/100 g Morales et al. (2019)
(Lentinula
Edodes)
Isoflavones Okra 100–200 2–5 30–275 10–30 g/mL – 64.61 ± 1.1–109.27 ± 0.14 mg/100 g Nkurunziza et al. (2019)
Apigenin Chamomile ligulate 115 4.5 30 – – 100–158 mg CAE/g dry material; 15–37 mg RE/g dry Cvetanović et al. (2017)
flowers material; Apigenin (3–11 mg/g)
Ginsenosides, maltol Ginseng roots (Panax 150–200 100 5–30 – – 49.6 mg GAE/g red ginseng; (1.59 mg, 1.19 mg)/g red Lee, Ko, and Chung
ginseng C.A. Meyer ginseng (2018)
Phenols, flavonoids and Licorice 80–320 7 2–100 1:30 (w/v) – (1.2–2 mg GAE; 1.9–2.7 mg RE; 0.008–1.851 mg GL)/g dry Fan et al. (2016)
glycyrrhizic acid weight
Flavonoid Onion skin 170–230 3 30 – – (200 mg GAE and 90 mg QE)/g dw Munir et al. (2018)
Green tea leaves 110–190 5–10 5–15 – – 71.36 ± 4.23 mg/g green tea leaves Ko et al. (2014)
Kaempferol derivatives Wild garlic 120–200 – 10–30 – acidifier (HCl P: 4 mg GAE/g dry weight F: 0.71 mg CE/g dw Tomšik et al. (2017)
0–1.5%)
Phenolic compounds Potato peel 100–240 6 30–120 – 2 mL/min 81.83 mg/100 g potato peal; wet basis Singh and Saldaña
(2011)

CAE-catechin equivalent; CE: chlorogenic acid equivalent; GAE-gallic acid equivalent; GL–Glycyrrhizic acid; ReE- 20(S)-ginsenoside; RE-rutin equivalent; QE-quercetin equivalent; dw – dry weight.
Trends in Food Science & Technology 97 (2020) 156–169
S.O. Essien, et al.
Fig. 2. Schematic of the apparatus used for SWE studies.
plant matrix and solvent. Lin et al. (2015) recorded an increase in re-
ducing sugar yield with increasing mixing rate. Similarly, Saravana
et al. (2018) also noted an increase in fucoidan content in their Sac-
charina japonica extract even though it was also dependent on extrac-
tion time. But in Cvetanović et al. (2017), the apigenin yield decreased
from 2.36 to 1.30 mg/g when they increased the rate from 120 rpm to
360 rpm. Previous reports have demonstrated that too high mixing
speed may lead to the reduction of extraction yield by agglomeration of
sample particles on the wall which can enhance degradation pathway
resulting in the production of artefacts (Lin et al., 2015). Agitation is
provided through centrifugal, vibratory or rotational forces and phy-
sical limitation of the process such as vessel geometry, and splashes
should be taken into consideration.
2.3. Recent practices in SWE applications
Some inclusions have been made to improve the extractability of a
wide range of target compounds, and the biological activity of extracts
obtain by subcritical water extraction. Regarding biomass pre-treat-
ment, recent SWE practices involve co-solvents to modify water po-
larity. Ethanol was used as co-solvent during SWE of antioxidants from
pistachio nuts (Bodoira et al., 2019). The maximum yield of total
phenolics, which was parallel with the highest antioxidant activity, was
recovered with 50% ethanol at 220 °C and 6.5 MPa. Klinchongkon,
Chanthong, Ruchain, Khuwijitjaru, and Adachi (2017) showed that
adding ethanol in their case, increased the antioxidant activity of pectic
polysaccharides from passion fruit peel due to co-extraction of phenolic
compounds. More results on co-solvent addition in SWE can be read
from (Zullaikah et al., 2019).
Interest is rising with respect to combining SWE with alternative
green solvents such as ionic liquids and even with other novel tech-
nologies for separation of plant-based bioactive. The alternative sol-
vents have wide solvating range, strong miscibility with aqueous
Fig. 3. Number of publications combining other techniques with subcritical water and supercritical carbon dioxide extraction.
161
Trends in Food Science & Technology 97 (2020) 156–169
substance, low volatility, high thermal and electrochemical stability,
are recyclable, and do not need high energy cost for synthesis. The
combination of ionic liquids (IL) with subcritical water was used to
recover phenolic-rich extracts from brown seaweed (Vo Dinh, Saravana,
Woo, & Chun, 2018). Ionic liquids, consisting of large cations and an-
ions, are salts with great thermal stability (Ramos, Jiménez, & Garrigós,
2019). The addition of IL improved recovery of phenolics such that the
antioxidant activity of brown seaweed was higher for IL + SWE brown
seaweed extract than SWE extract (Vo Dinh et al., 2018). The de-
gradation rate of phenolics also reduced by approximately 50% in
IL + SWE, when temperature increased from 175 to 250 °C. The
common issue for IL-SWE has to do with the increase in IL concentra-
tion which is ascribed to the increase in viscosity of the entire solution
(Ramos et al., 2019). Another type of solvent used to enhance the se-
lectivity and efficiency of SWE is deep eutectic solvents (DES). These
are binary mixtures of organic compounds which interact with each
other forming intermolecular hydrogen bonds. Xanthone, a phenolic
compound with anti-inflammatory, anticancer, and antibacterial ac-
tivity, was extracted from mangosteen pericarp by DES-assisted SWE
(Machmudah et al., 2018). In that study, the amount of xanthone
produced increased with increasing concentration of DES. Products of
thermal degradation were also absent in the extracts, which means that
DES can increase SWE efficiency. However, they did not attempt to
recover these solvents afterwards. Other instances of assisted-SWE use
microwave-assisted, ultrasound-assisted, as well as pulsed-electric field
(PEF). Publications continue to grow and mostly targeted at ultrasound-
assisted extraction (Fig. 3).
Further processing, like drying of SWE extracts, may expose the
extracts to physical factors like light, heat that can lead to degradation
of bioactive compounds. An online process to obtain dried powders of
subcritical water extracts, with intact antioxidant activity, from plant
material in a single operation was developed to overcome this issue.
This process combines dynamic SWE with continuous drying of the
 S.O. Essien, et al.

Table 3
Selected applications involving SCCO2 for recovery of bioactive compounds from plant materials between the period 2010–2019.
Compound Plant source Operating conditions Yield References

Pressure Temperature (°C) Flow rate (g/ Co-solvent Time (min)

(MPa) min)

Aromatic (ar-) Curcuma longa Linn 10–35 40–60 8.6 – – 0.07–1.14 mg/g turmeric, dw Carvalho et al. (2015)
turmerones
Carotenoids Carrot peel 15–35 50–70 15 5–15% EtOH 80 0.31–5.7 wt% of ~0.21–0.35 mg/g peels de Andrade Lima et al. (2018)
Yuzu ichandrin 20–30 40–50 27 – 120 1.952 mg/g oil Ndayishimiye and Chun (2017)
Tocopherols Rosmarinus eriocalyx 45 70 3.96 – 180 Leaves (8.9 mg/g dw) flowers (1.45 mg/g dw) Bendif et al. (2018)
leaves and flowers
Flavonoid Spearmint 10–30 40–60 15 EtOH (3 g/min) 30–60 40.28 ± 3.45–51.07 ± 3.21 mg/g Bimakr et al. (2011)
α,β-amyrin triterpene rosemary leaves 180 50 1 – – 45.22% Bensebia, Bensebia, Allia, and Barth
(2016)
Eugenol oil Clove leaves 15–22 10–60 1.99 – 80 22.85–29.84%
Essential oil Eucalyptus leaves 10–50 40–80 3.96 EtOH (5–15% w/w) 30–150 0.99–4.78% w/w Zhao and Zhang (2014)

162
Protocatechuic acid Scutellaria barbata D. Don 16.2–30 45–80 1.6–5.4 × 10−3 Water (0–15.6%) 10–100 64.094 ± 2.756 μg/g Yang et al. (2013)
Peach palm pulp (Bactris 10–30 40–60 5.9–17.8 – – 2.01 mg/g extract Espinosa-Pardo, Martinez, and
gasipaes) Martinez-Correa (2014)
Phenolic compounds Dry and fermented 15–35 40–60 16.02 EtOH 6% (w/w) – 36–57 mg GAE/100 g raw material Espinosa-Pardo, Nakajima, Macedo,
orange pomace Macedo, and Martínez (2017)
Flavonoids, phytosterol Clinacanthus nutans 35 60 150 – 120 (7.01 mg GAE, 5.88 mg QE, 1.35 mg BS)/g dry Mustapa, Martin, Mato, and Cocero
lindau material (2015)
Cannabinoids Cannabis sativa L. 17–34 55 200 EtOH – 82.99 ± 1.87 g Rovetto and Aieta (2017)
Phenolic compounds Oak tree galls 20–30 50–70.6 – 3.654 × 10−3 120 –
Phenolic compounds Apple peel 25 50 – 25 mol % EtOH 180 26.7–34.7 mg/g extract (0.55–0.8 mg/g dry peel) Massias, Boisard, Baccaunaud, Leal
Calderon, and Subra-Paternault (2015)
α-tocopherol rich oil Eugenia involucrate leaves 15–200 40–60 3.96–7.92 × – 80 30.93 ± 1.8–87.91 ± 4.98 mg/100 g leaves Barzotto et al. (2019)
10-3
β-carotene Pumpkin sees 18–22 20–60 – – 180 1.5–171.6 mg/100 g oil Cuco, Cardozo-Filho, and Silva (2019)

SSR: solid-solvent ratio; H2O – water; EtOH-Ethanol; MeOH – Methanol; BS- β-sitosterol; GAE-gallic acid equivalent; C3RE: Cyanidin-3-rutinoside equivalent; EP - pyrogallol equivalent; QE-quercetin equivalent; RE-rutin
equivalent; dw – dry weight.
Trends in Food Science & Technology 97 (2020) 156–169
S.O. Essien, et al.
Fig. 4. Kinetics of SCCO2 represented by different shapes of overall extraction
curves according to Sovova's model (Mouahid et al., 2017).
extract produced using hot N2 (70 °C) as the drying agent and super-
critical carbon dioxide as the dispersion medium (Ibáñez et al., 2009).
This process is known as water extraction and particle formation on-line
(WEPO) and has been patented by Ibáñez et al. (2009). Only a few
reports are available on this subject; with rosemary leaves as the plant
material (Rodríguez-Meizoso et al., 2012). One limitation in this pro-
cess is the chamber design which made particle collection lower and
more difficult compared to freeze-dried extractors; however, the pro-
cess is still under development.
Furthermore, the integration of SWE as a form of pre-treatment for
extraction of bioactive compounds has been preliminarily explored.
SWE was favoured as a pre-treatment for enzyme hydrolysis compared
to a methanol-HCl method due to shorter extraction time, and lower
environmental impact (Lindahl et al., 2010). Process optimisation is
usually performed using Response Surface Methodology (RSM). Several
mathematical models for SWE have been proposed and tested (Duba,
Casazza, Mohamed, Perego, & Fiori, 2015).
3. Supercritical carbon dioxide extraction (SCCO2)
Supercritical CO2 extraction is an environmentally friendly process
that ensures minimal alteration of the bioactive compounds. Much of
Fig. 5. Schematic of experimental setup for supercritical carbon-dioxide extraction.
163
Trends in Food Science & Technology 97 (2020) 156–169
these advantages result from properties of carbon dioxide, precisely the
mild critical temperature (31.1 °C), and the non-oxidative medium
which favours extraction of thermally unstable and easily oxidised
compounds. SCCO2 extracts have shown potency as antibacterial, anti-
proliferative, and antioxidant agents compared to their counterpart
obtained using organic solvents (Zizovic et al., 2018).
The chief advantage of this technique is the ability to alter the CO2
density, which controls solubility, by changing pressure or temperature.
Another benefit of SCCO2 as an extraction technique is the production
of solvent-free extracts. Removal of CO2 is achieved by depressurizing
the system once the extraction is completed since CO2 is a gas at am-
bient temperature. This step is also potentially cost and energy saving
because it eliminates the energy-intensive procedures required to re-
move solvents. Most studies evaluating the capacity of SCCO2 to re-
cover high-added value compounds from many different plant materials
focus on non-polar to mid-polar compounds like essential oil. Moreover,
SCCO2 has limited capacity for extracting more polar compounds, so co-
solvents (or modifiers) are added in low quantities to improve the ex-
traction efficiency. An understanding of thermodynamics and kinetics
of SCCO2 is vital to ensuring high extraction selectivity and reduce the
possibility of co-extraction of non-target compounds such as waxes.
Finally, high capital investment is required because of the high energy
consumption for compression and decompression (Moncada, Tamayo,
& Cardona, 2014). Implementation of recycling measures, especially at
industrial scale, can reduce energy cost very often associated with the
method. A selection of recent application of SCCO2 in extraction of
plant bioactive is listed in Table 3.
3.1. SCCO2 process mechanism
The performance of SCCO2 relies on the significant variation in the
solvating power of CO2 achieved through heating and pressurisation.
Phase equilibrium, mass transfer by convection and diffusion, and
displacement of solution via expansion are what makes up the me-
chanism of this process. The low viscosity and high diffusivity allow the
fluid to diffuse easily through the plant matrix, like gas and helps to
dissolve the solute like liquid (Bruno, Ekorong, Karkal, Cathrine, &
Kudre, 2019). How efficient this process can be is dependent on pres-
sure, temperature, extraction time, density, flow rate, co-solvents. A
graph of accumulated extracted mass as a function of time, flow rate or
solvent to feed mass ratio is often used as a kinetic representation of
SCCO2 from solid matrices (Confortin et al., 2017). These extraction
curves are useful for scaling-up processes and calculating manu-
facturing costs. According to Sovová (2005), the overall extraction
S.O. Essien, et al.
curves (OEC) can be divided up to three periods based on different mass
transfer mechanisms. They are (1) the constant extraction rate (CER)
period where convective mass transfer is the dominant mechanism, and
the extraction process is limited by the thermodynamic equilibrium of
the easily accessible solute; (2) the falling extraction rate (FER) period
where the diffusion mechanism begins to be combined with convection,
which is much slower; and (3) the diffusion-controlled (DC) period
when all the extractable solutes are removed, and the dominant me-
chanism is the effective diffusion of the remaining solute from the solid
particle to the CO2 medium. Four types of these curves were defined by
(Mouahid, Bouanga, Crampon, & Badens, 2017) as represented in
Fig. 4. The slope of these curves depends on solubility and solute-matrix
interaction which are further controlled extraction conditions, the in-
itial composition of solid and fluid phases (Mouahid et al., 2017).
Several researchers have adopted this outlook (de Andrade Lima,
Charalampopoulos, & Chatzifragkou, 2018; Mouahid et al., 2017).
A back pressure regulator is employed to maintain the CO2 fluid at
supercritical conditions and control the pressure at a collection or se-
paration vessel, thereby preventing loss of product to the rapid ex-
pansion of CO2·SCCO2 can be performed as a simple system or as a
complex multistage separation process by incorporating additional ex-
traction and/or collection vessels (Rovetto & Aieta, 2017). Fig. 5 shows
the schematic of a simple SCCO2 system.
3.2. Important factors in SCCO2
Unlike SWE, where the temperature is the critical factor, here
pressure is of supreme importance and offers a considerably wider
margin for adjustment than temperature.
3.2.1. Pressure
Variation in pressure has significant effects for SCCO2. For any given
temperature, an increase in pressure increases SCCO2 density which is
directly proportional to the solubility of target solutes, thus higher
extraction yield. Ndayishimiye and Chun (2017) observed an increase
in the carotenoid content of their citrus by-products extracts with
pressure. Similarly, the total yield of bioactive compounds from feijoa
leaves along with their antioxidant capacity also increased in Bimakr,
Ghoreishi Seyyed, Ganjloo, and Mousavi (2019). However, as pressure
in both studies increased towards 30 MPa (300 bar), a decrease in ex-
traction yield was observed for both studies. This decrease was attrib-
uted to the lower recovery of target compounds as a result of co-ex-
traction of non-target compounds at elevated pressures depending on
volatility. This effect is, however, dependent on the type of plant as well
as the target compounds because Özkal and Yener (2016) recovered
more oil from flaxseed with an increase in pressure up to 60 MPa.
3.2.2. Temperature
An increase in temperature for an isobaric process lowers the sol-
vation power of SCCO2, thus, reduces extraction rates (Yang, Wei,
Huang, & Lee, 2013). Temperature exerts a dual effect on SCCO2 be-
cause, by increasing temperature, the vapour pressure of solutes in-
creases while the density of CO2 decreases. The phenomenon, called
retrogradation, is controlled by pressure and progressively overlaps
each other as temperature increases. The pressure at that point is
termed “cross-over or inversion pressure”. With pressure below the
inversion pressure, low temperature allows density to dominate,
leading to increase in extraction yield as seen in the study on Lupines
albescens extracts by Confortin et al. (2017). However, if the pressure is
above the inversion pressure, increasing temperature favours extraction
rate due to the dominating influence of solute vapour pressure (Sovilj,
Nikolovski, & Spasojevic, 2011). A proper selection of an optimal
temperature for high extraction yield will require a trade-off between
these two opposing effects.
164
Trends in Food Science & Technology 97 (2020) 156–169
3.2.3. Co-solvent addition
Addition of co-solvent is mostly done to boost extraction yield by
tuning the affinity of CO2 to substances with poor solubility in the fluid,
mainly polar compounds. Lima, Ribeiro, Cardozo-Filho, Vedoy, and
Alves (2019) discovered that the addition of 5% methanol gave a 40%
increase in yield of pipercallosidine from pepper leaves compared to
using CO2 alone. According to Srinivas and King (2010), co-solvents
with volatility in-between supercritical fluid and the compound to be
extracted will benefit the process. Ethanol mostly used due to its low
miscibility in CO2, lower toxicity, and ease to eliminate relative to other
solvents. Concentration and pH of co-solvent are additional parameters
that may influence the yield and purity of target compounds, yet there
are no publications available on the influence of pH of co-solvents.
Overall, the selection of the best co-solvent should be per the properties
of the sample and the chemical nature of target compounds.
3.2.4. Time
Generally, the extraction yield increases with more extended con-
tact period between the solvent and solutes in SCCO2. Yang et al. (2013)
found a significant increase in procatechuic acid when the time
changed from 10 to 100 min. Same with (Ekinci Mustafa & Gürü, 2019)
for phytosterols extraction from melon seeds were they recovered 97%
of the compound for dynamic extraction time from 1 to 3 h. The effect
of change in time was insignificant after then because the solubility had
reached its limit. Another reason maybe because of the flow rate used.
Herzi et al. (2013) observed that while 30 min was sufficient for a flow
rate of 20 g/min, 60 min was not enough to complete extraction at a
flow rate of 5 g/min.
3.2.5. Solvent flow rate
The flow rate of CO2 solvent directly influences the contact time and
convective mass transfer coefficient. Like SWE, an increase in solvent
flow rate increases the extraction capacity by reducing the external
mass transfer resistance. Ruslan, Idham, Nian Yian, Ahmad Zaini, and
Che Yunus (2018) recovered the highest catechin (34 mg/g betel nuts)
at the highest flow rate studied (4 mL/min). However, very high solvent
flow rates decrease the yield because of the insufficient contact time
between the solute and the solvent (Ekinci Mustafa & Gürü, 2019).
3.2.6. Particle size
Particle size is another factor to be considered when optimising
SCCO2. Smaller particle size can increase extraction rate of solutes by
increasing the specific interfacial area, and a reduction in the diffusion
path of solute. Using peanut skin, Putra et al. (2018) got a high oil yield
as particle size increased. But, Herzi et al. (2013) in the past found no
difference in yield of antioxidant compounds with changes in particle
size under the same extraction period of 30 min. This low effect of
particle size is said to be typical for herbaceous plants (Zizovic et al.,
2018). Similar to SWE, the drawback of smaller particle size is the
tendency to channelling or clumping of the particles. This effect de-
creases fluidised bed velocity and clogs the filters, which can cause a
significant reduction in extraction efficiency (Putra et al., 2018).
3.3. Recent advances in SCCO2 applications
Various strategies have been considered effective in the quest to
improve SCCO2 efficiency via enhancement of selectivity and yield.
From biomass pre-treatment and solvent modification to combination
with other eco-friendly technologies.
The practice of sample pre-treatment now involves multi-unit pro-
cessing as a new approach to sample preparation. By that, we mean
coupling SCCO2 extraction with other environmentally-benign tech-
nologies to boost SCCO2 of a final product (Srinivas & King, 2010).
Optimum extraction conditions here depend on the target molecule and
the properties of the plant material. Addition of these extra processing
steps improves the accessibility of the supercritical solvent to the solute
S.O. Essien, et al.
by mechanistic disruption of the plant cell wall resulting in increased
extraction yield and efficiency (Srinivas & King, 2010). It is interesting
to see that ultrasounds also hold the record of most research in this
regard, Fig. 3. Ultrasound-assisted SCCO2 (US–SCCO2) provides an ef-
ficient way to produce deep agitation in the medium for mass transfer
processes (Koubaa, Mhemdi, & Fages, 2018). It has been used to remove
caffeine from green tea, applied in the recovery of anthocyanins from
blackberry begasses (Pasquel Reátegui, Machado, Barbero, Rezende, &
Martínez, 2014), capsaicinoid from pepper (Santos, Aguiar, Barbero,
Rezende, & Martínez, 2015), luteolin and apigenin from shiso leaves.
All authors indicated an increase in extraction rate and yield at a
shorter time with US-assistance. A review of this approach, its appli-
cation and challenges, especially if it is to become a common practice, is
given in Koubaa et al. (2018).
Another example is the use of enzymatic mixture to pre-treat tomato
samples before SCCO2 of lycopene (Lenucci et al., 2015). The result was
a remarkable increase in the lycopene yield for enzyme-treated tomato
sample, over 3-times higher than the non-treated sample. Similarly,
Torres-Ossandón et al. (2018) combined high hydrostatic pressure
(HHP) with SCCO2 to recover bioactive compounds from Cape goose-
berry while Reyes, Mendiola, Suárez-Alvarez, Ibañez, and del Valle
(2016) utilised adsorbent-assisted SCCO2 to improve carotenoid yield,
however from algae. Although the amount of extract was low in both
cases, the adsorbent-assisted extracts had the highest carotenoid con-
tent while the antioxidant capacity of the HHP-assisted extracts re-
mained high even after 60 days of storage.
As previously stated, reported data in the literature suggests that
polar modifiers can enhance SCCO2 extraction efficiency. The drawback
for this strategy, in some cases, is the need for subsequent processing to
eliminate the co-solvent collected together with the extract. Rovetto
and Aieta (2017) recently explored the idea of delivering ethanol in
pulses as a strategy to reduce co-solvent consumption without nega-
tively affecting the extraction rate. They found that this regime im-
proved performance compared to the standard practice of adding co-
solvent at a constant concentration in the flow. The same extraction
efficiency was obtained within a shorter time, using 33% of the pro-
jected ethanol consumption.
Nowadays, fractionation operations are applied to the extraction or
separation step to improve extraction selectivity. The concept is espe-
cially useful when there are numerous compounds to be recovered from
the plant. Compounds of higher molecular weight are separated from
lightweight compounds, like volatile oil. Fractionation is approached in
two ways: (1) involving stepwise multiple extractions where the first
extraction occurs at a lower density than the next; (2) a single-stage
extraction with sequential separation steps. The second approach is
more common, where a cascade of multiple separators at different
Table 4
Difference between the influence of similar factors on SWE and SCCO2 with respect to solubility of analytes and extraction yield.
Operating parameter SWE
Temperature Main controlling factor.
Increases the solvation power of subcritical water by reducing
dielectric constant hence, the solute solubility is enhanced.
Too high temperature may cause decomposition of thermally
unstable compound.
Temperature range: > 100 °C
Pressure Maintains the liquid state of water.
No significant effect on the solvent or extraction except on
substantial elevation.
Range between 3 and 20 MPa
Time If prolonged, will lead to reduction in yield and target
compounds.
Dependent temperature and concentration gradient.
Flow rate Increase in flow rate increases yield. Dependent on time and
operating range
Particle size Small sizes increase yield. Too small size can cause clogging
165
Trends in Food Science & Technology 97 (2020) 156–169
conditions are used to carry out the sequential extraction (Rovetto &
Aieta, 2017). The critical question here focuses on the best temperature
and pressure combination to achieve the desired extract composition.
Studies to probe the nature of solute-solvent interactions and SCCO2
kinetics have also experienced some progressions in the last few years.
A number of proposed mass transfer models have been applied, or
improved on, by several authors to represent the kinetic behaviour of
the SCCO2 from plants like marigold (López-Padilla, Ruiz-Rodriguez,
Reglero, & Fornari, 2017), Jatropha curcas (Mouahid et al., 2017), po-
megranate seed (Natolino & Da Porto, 2019). These models include a
logistic model, a desorption model, a simple single plate model, a
shrinking core model, a diffusion models, an empirical model, and a
broken and intact cell model (de Andrade Lima et al., 2018;
Machmudah, Martin, Sasaki, & Goto, 2012; Sovová, 2005). Of these, the
most widely used is the model proposed by Sovova, which assumes that
the extractable materials are contained in a structure made up of
broken cells (on the outer layer) and intact cells. It is derived from
Lack's plug flow model adapted from a model for drying. These ex-
traction curve and kinetic models are typically used for SCCO2 of nat-
ural products using only one solvent. Recently, Machmudah et al.
(2012) modelled and numerically simulated extraction of coffee beans
using SCCO2 and water in a counter-current system. The aim was to
improve fractionation between polar and non-polar materials in the
water and CO2 phases. Recently, Schuster et al. (2018) developed an
approach for measuring, in real-time, the amount of extract and es-
sential substances in the extract from SCCO2 of two different hop
varieties. The online monitoring was achieved via an in situ Raman
measurement system based on an inelastic scattering mechanism be-
tween the incident laser light and the investigated substance (Bumbrah
& Sharma, 2016). They found that the major drawback of the inter-
fering fluorescence signals was also effectively eliminated using the
shifted excitation Raman differential spectroscopy (SERDs) technique.
4. Sequential SWE and SCCO2
Subcritical water and supercritical carbon dioxide extraction share
some similar operating parameter which influences their efficiency
differently. A summary of the distinction of influence of each factor is
presented can be found in Table 4. The potential of arranging SWE and
SCCO2 in a tandem manner to achieve full-spectrum extraction from
plants and other natural products has been realised through laboratory
investigations. The integrated step-wise extraction is mostly conducted
at lower conditions of temperatures and pressures than when running
each technique independently. Some advantages include overcoming
limitations of one or all the extraction methods used, recovery of any
remaining valuable compounds from the unextracted matrix,
SCCO2
Influence depends on pressure.
At constant pressure extraction, increasing temperature decreases the solvation power
of supercritical carbon dioxide due to decrease in density but increases solute solubility
due to increase in vapour pressure.
Temperature range: 40–80 °C
Main controlling factor.
At constant temperature, increase of the pressure will increase the solvation power of
supercritical carbon dioxide by increasing density hence, the solubility of solute is
enhanced.
Range between 30 and 80 MPa
Prolonging extraction time increases yield till equilibrium is attained.
Same with SWE, increases extraction yield.
Same with SWE, small particle size increases extraction yield.
S.O. Essien, et al.
differential extraction of target compounds, and reduction in annual
operating cost (Zabot, Moraes, Carvalho, & Meireles, 2015).
By following SWE with SCCO2, beta-carotene and linoleic acids
were enriched in extracts of Eucheuma cottonii and Gracilaria sp.
(Machmudah, Widiyastuti, Wahyudiono, & Goto, 2017). In another
study by Garmus, Paviani, Queiroga, and Cabral (2015), the best global
yield of polyphenol from pepper-rosmarin leaves was obtained by ap-
plying SCCO2 sequentially with ethanolic extraction and finally frac-
tionating with pressurised hot water. A similar approach was used to
recover anthocyanins from the cob and pericarp of purple corn.
5. Techno-economic evaluation
Techno-economic assessment is a cost-benefit comparison that
gauges the feasibility and establishes benchmarks for investment pro-
cesses. It is a driving force of process development because it shows the
gaps, needs, and opportunities for research that can advance efficient
and economically competitive processes. The main issue associated
with this tool is data availability; consequently, assumptions are made
as a solution. However, these assumptions must be practical and will
require knowledge of the process, process objectives, the vegetal matrix
and products, and market trends, to avoid making the wrong conclu-
sions. Technical analysis is commonly the first step followed by an
economic assessment to evaluate the market potential of products based
on current trends in prices. Afterwards, the influence of vital process
factors on economic indicators, also known as sensitivity analysis, is
conducted to give an idea of the profits. Environmental assessment is
conducted especially for novel processes, to assess the carbon footprint
and environmental impact (Moncada et al., 2014).
A case study on SCCO2 and other extraction methods by Moncada
et al. (2014) suggested the addition of energy integration as a value-
added strategy to drive a reduction in production cost. They found that
using the pinch method saved not only energy (58% for SCCO2) but also
decreased potential environmental impact. On the other hand, product
characterisation provided a baseline for the purity of the extract which,
together with extraction time, primarily influenced the cost and profit
of the process (Patel, Bandyopadhyay, & Ganesh, 2006). The effect of
process parameters on the yield and composition of products can assist
in the selection of the best extraction conditions. This information is
vital for optimisation, modelling, and scale-up activities.
Research has shown that the cost of raw materials is almost entirely
responsible for cost of manufacturing (COM) (Zabot et al., 2015), at the
beginning of the process. This is because the amount of raw material
needed to obtain a reasonable amount of solute is significant (Patel
et al., 2006; Todd & Baroutian, 2017). However, as time progresses, the
value of COM becomes dependent on the extraction rate (Carvalho,
Osorio-Tobón, Rostagno, Petenate, & Meireles, 2015). The extraction
time is directly proportional to labour and utility cost. The cost of
utilities depends mainly on energy consumption; as such re-use or re-
cycle of waste and by-products generated can offset this cost. Overall,
economic studies over a fixed period can provide information on total
investment, capital recovery, and profit.
The sensitivity analysis by Todd and Baroutian (2017) showed that
SWE and SCCO2 had their percentage yield above the assumed average
but required higher amounts of products to match the COM per kg
product for solvent extraction. Discount factors were assumed based on
the novelty of the method; this means that an already commercialised
method will have a lower value compared to a new and unproven
method. Techno-economic evaluations are mainly conducted for up-
scaling purposes, the last step of a research path. The goal of scale-up is
to reproduce the same overall extraction curve in vessels of different
shapes and capacity. Most of such studies for SCCO2 and SWE assume
the same conditions and efficiency for both laboratory and industrial
scale (Carvalho et al., 2015; Patel et al., 2006), but for López-Padilla
et al. (2017) the residence time and velocity were adjusted to suit the
bed geometry in the different scale system. The few available studies
166
Trends in Food Science & Technology 97 (2020) 156–169
have shown that some phenomenon considered negligible at laboratory
scale may become significant at industrial scale. For instance, the cost
of raw material increased (from 3.6% to 38%) with scale-up whereas
labour, utilities, and investment decreased. These cost reductions de-
creased the COM by 8% after upscaling (Carvalho et al., 2015).
Therefore, scale-up criteria must be made according to rules that govern
the processing mechanism to ensure accuracy when comparing results.
From the techno-economic studies reviewed, SCCO2 and SWE were
feasible, both technically and economically, however, very energy in-
tensive. It is pertinent to note that although the technologies may be
capital intensive, the bioactive products can attract higher revenues in
the market which may offset some of the cost. Besides, the use of green
solvent and re-use of solvents, like CO2, can save energy thereby re-
ducing operating cost. However, more techno-economic studies are
needed especially for SWE, which is yet to achieve commercial status.
6. Current status and challenges for SWE and SCCO2
The number of research outputs on the SWE of bioactive compounds
from plant sources has increased in recent years. However, very few
pilot-scale and industrial applications exist even though the equipment
is easy to construct (Haghighi & Khajenoori, 2013). The reasons may be
attributed to the range of operating temperatures and pressures, and the
mode of operation. SWE is a novel technology that has shown to be
highly competitive with solvent extraction (Todd & Baroutian, 2017).
Advancing SWE will require pilot-scale research to elucidate reaction
pathways and mechanisms of operation in various reaction systems.
Moreover, data on raw material handling and storage, extraction
parameters, and other limiting factors will aid optimisation and profit
maximisation.
On the other hand, SCCO2 has been utilised by many companies for
many applications for almost four decades. One of these companies is
Pharmalink Extracts Ltd. Their services include SCCO2 of essential oil
and nutraceuticals from unique NZ marine and terrestrial biomass such
as totara wood and green shell mussel. Pharmalink Extracts uses SCCO2
as a closed loop process thereby promoting the reuse of CO2 gas. Their
process has a co-solvent capability that has helped in broadening their
range of commercial possibilities like adding a 33% increase in capa-
city. Accordingly, their products have received zero resistance from
consumers because they pose no food safety issues and retain biological
activity. The only potential risk associated with the use of this tech-
nique is the risk of elevated CO2 retention in the blood of process op-
erators. Installation of leak detection and alarm systems are some of the
management strategies that Pharmalink has adopted to prevent such a
situation. Other risks are typical of high-pressure industrial facilities
and are minimised by observing good manufacturing practices. From
this case study, SCCO2 has several advantages compared to extraction
with classical solvents for many applications. Nonetheless, some world
regions still see it as not fully competitive despite its industrial appli-
cation, probably due to its high capital cost that may need a long
payback period.
The ability to estimate the mechanism and yield at the design stage,
through simulations and modelling, can aid future development of
these technologies. However, modelling of extraction of these high-
value compounds from plant matrixes has been difficult. This difficulty
is attributed to the variation in the structures of plants. One suggestion
that has helped simplify model development is to make assumptions
about the plant matrix and mass-transfer kinetics. Knowledge of mass-
transfer principles and physiochemical properties of such materials is
required. Some examples of models in this area are a mathematical
model for extraction from real matrixes as mentioned previously and
computer simulation that uses mass transfer kinetics/principles to study
the economics of SCCO2 from plants (del Valle, 2015). Several other
authors have also taken up this approach mainly for optimisation
purposes, active control, and economic analysis (Haghayegh, Zabihi,
Eikani, Kamya Moghadas, & Vaziri Yazdi, 2015; Shrirame et al., 2018).
S.O. Essien, et al.
7. Conclusions
SCCO2 and SWE are two eco-friendly extraction methods that can be
used to obtain various bioactive compounds from plant material. A
review of research output over the last ten years has revealed the
progress of both techniques mostly on the improvement of extraction
efficiency. Application of SCCO2 is a well-established method from lab-
scale, pilot-scale up to commercialisation. Conversely, use of SWE is
still at the laboratory-scale and mostly operated as a batch process, but
it has been shown that it is practically competitive with traditional
methods. Pilot to large-scale operations, especially as a continuous
process, would be welcomed by researchers for SWE of natural and
food-related products. Suggestions to integrate SWE and SCCO2 have
been made to increase process efficiency, improve the quality of the
final product, or even to obtain various products from a unique in-
tegrated processing line. The scientific literature reviewed has shown
that SCCO2 is predictable and scalable from a bench-top process to a
large-scale application. On the other hand, SWE still requires scale-up
operations to determine yield, process parameters and economic eva-
luation for industrial set-ups. These operations will require standar-
dised research and development facilities. An understanding of the
nature of the plant matrix and chemistry of the target bioactive com-
pound is also needed for optimisation of these extraction processes.
Modelling of these technologies is essential for the provision of online
process monitoring and control as well as prediction of process beha-
viour. However, this will depend on the bioactive compound, and plant
material studied. Nonetheless, a modelling approach that can be ap-
plied to a wide range of compounds is crucial for effective optimisation.
Declaration of competing interest
The authors declare no conflict of interest in the publication of this
study.
References
Amaral, G. V., Silva, E. K., Cavalcanti, R. N., Martins, C. P. C., Andrade, L. G. Z. S.,
Moraes, J., et al. (2018). Whey-grape juice drink processed by supercritical carbon
dioxide technology: Physicochemical characteristics, bioactive compounds and vo-
latile profile. Food Chemistry, 239, 697–703. https://doi.org/10.1016/j.foodchem.
2017.07.003.
de Andrade Lima, M., Charalampopoulos, D., & Chatzifragkou, A. (2018). Optimisation
and modelling of supercritical CO 2 extraction process of carotenoids from carrot
peels. The Journal of Supercritical Fluids, 133, 94–102. https://doi.org/10.1016/j.
supflu.2017.09.028.
Azmir, J., Zaidul, I. S. M., Rahman, M. M., Sharif, K. M., Mohamed, A., Sahena, F., et al.
(2013). Techniques for extraction of bioactive compounds from plant materials: A
review. Journal of Food Engineering, 117(4), 426–436. https://doi.org/10.1016/j.
jfoodeng.2013.01.014.
Barzotto, I. L. M., Santos, K. A., da Silva, E. A., Sene, A. C., da Silva, N. S., & Vieira, L.
(2019). Supercritical extraction of Eugenia involucrata leaves: Influence of operating
conditions on yield and Α-tocopherol content. The Journal of Supercritical Fluids, 143,
55–63. https://doi.org/10.1016/j.supflu.2018.08.003.
Belwal, T., Ezzat, S. M., Rastrelli, L., Bhatt, I. D., Daglia, M., Baldi, A., et al. (2018). A
critical analysis of extraction techniques used for botanicals: Trends, priorities, in-
dustrial uses and optimization strategies. Trends in Analytical Chemistry (Reference
Ed.), 100, 82–102. https://doi.org/10.1016/j.trac.2017.12.018.
Bendif, H., Miara, M. D., Kalboussi, Z., Grauzdytė, D., Povilaitis, D., Venskutonis, P. R.,
et al. (2018). Supercritical CO2 extraction of Rosmarinus eriocalyx growing in
Algeria: Chemical composition and antioxidant activity of extracts and their solid
plant materials. Industrial Crops and Products, 111, 768–774. https://doi.org/10.
1016/j.indcrop.2017.11.056.
Bensebia, O., Bensebia, B., Allia, K., & Barth, D. (2016). Supercritical CO2 extraction of
triterpenes from rosemary leaves: Kinetics and modelling. Separation Science and
Technology, 51(13), 2174–2182. https://doi.org/10.1080/01496395.2016.1202977.
Bimakr, M., Ghoreishi Seyyed, M., Ganjloo, A., & Mousavi, M. (2019). Modified super-
critical carbon dioxide extraction of biologically active compounds from feijoa sell-
owiana leaves. International Journal of food Engineering, 15.
Bimakr, M., Rahman, R. A., Taip, F. S., Ganjloo, A., Salleh, L. M., Selamat, J., et al. (2011).
Comparison of different extraction methods for the extraction of major bioactive
flavonoid compounds from spearmint (Mentha spicata L.) leaves. Food and
Bioproducts Processing, 89(1), 67–72. https://doi.org/10.1016/j.fbp.2010.03.002.
Bodoira, R., Velez, A., Rovetto, L., Ribotta, P., Maestri, D., & Martinez, M. (2019).
Subcritical fluid extraction of antioxidant phenolic compounds from pistachio (pis-
tacia vera L.) nuts: Experiments, modeling, and optimization. Journal of Food Science,
167
Trends in Food Science & Technology 97 (2020) 156–169
84(5), 963–970. https://doi.org/10.1111/1750-3841.14507.
Bruno, S. F., Ekorong, F. J. A. A., Karkal, S. S., Cathrine, M. S. B., & Kudre, T. G. (2019).
Green and innovative techniques for recovery of valuable compounds from seafood
by-products and discards: A review. Trends in Food Science & Technology, 85, 10–22.
https://doi.org/10.1016/j.tifs.2018.12.004.
Bumbrah, G. S., & Sharma, R. M. (2016). Raman spectroscopy – basic principle, in-
strumentation and selected applications for the characterization of drugs of abuse.
Egyptian Journal of Food Science, 6(3), 209–215. https://doi.org/10.1016/j.ejfs.2015.
06.001.
Carvalho, P. I. N., Osorio-Tobón, J. F., Rostagno, M. A., Petenate, A. J., & Meireles, M. A.
A. (2015). Techno-economic evaluation of the extraction of turmeric (Curcuma longa
L.) oil and ar-turmerone using supercritical carbon dioxide. The Journal of
Supercritical Fluids, 105, 44–54. https://doi.org/10.1016/j.supflu.2015.03.020.
Cheng, Y.-S., Lu, P.-M., Huang, C.-Y., & Wu, J.-J. (2017). Encapsulation of lycopene with
lecithin and α-tocopherol by supercritical antisolvent process for stability enhance-
ment. The Journal of Supercritical Fluids, 130, 246–252. https://doi.org/10.1016/j.
supflu.2016.12.021.
Confortin, T. C., Todero, I., Soares, J. F., Brun, T., Luft, L., Ugalde, G. A., et al. (2017).
Extraction and composition of extracts obtained from Lupinus albescens using su-
percritical carbon dioxide and compressed liquefied petroleum gas. The Journal of
Supercritical Fluids, 128, 395–403. https://doi.org/10.1016/j.supflu.2017.06.006.
Cuco, R. P., Cardozo-Filho, L., & Silva, C. D. (2019). Simultaneous extraction of seed oil
and active compounds from peel of pumpkin (Cucurbita maxima) using pressurized
carbon dioxide as solvent. The Journal of Supercritical Fluids, 143, 8–15. https://doi.
org/10.1016/j.supflu.2018.08.002.
Cvetanović, A., Švarc-Gajić, J., Gašić, U., Tešić, Ž., Zengin, G., Zeković, Z., et al. (2017).
Isolation of apigenin from subcritical water extracts: Optimization of the process. The
Journal of Supercritical Fluids, 120, 32–42. https://doi.org/10.1016/j.supflu.2016.10.
012.
Duba, K. S., Casazza, A. A., Mohamed, H. B., Perego, P., & Fiori, L. (2015). Extraction of
polyphenols from grape skins and defatted grape seeds using subcritical water:
Experiments and modeling. Food and Bioproducts Processing, 94, 29–38. https://doi.
org/10.1016/j.fbp.2015.01.001.
Ekinci Mustafa, S., & Gürü, M. (2019). Extraction of phytosterols from melon (Cucumis
melo) seeds by supercritical CO2 as a clean technology. Green processing and synthesis:
Vol. 8, (pp. 677–). .
Espinosa-Pardo, F. A., Martinez, J., & Martinez-Correa, H. A. (2014). Extraction of
bioactive compounds from peach palm pulp (Bactris gasipaes) using supercritical
CO2. The Journal of Supercritical Fluids, 93, 2–6. https://doi.org/10.1016/j.supflu.
2014.05.010.
Espinosa-Pardo, F. A., Nakajima, V. M., Macedo, G. A., Macedo, J. A., & Martínez, J.
(2017). Extraction of phenolic compounds from dry and fermented orange pomace
using supercritical CO2 and cosolvents. Food and Bioproducts Processing, 101, 1–10.
https://doi.org/10.1016/j.fbp.2016.10.002.
Fan, R., Xiang, J., Li, N., Jiang, X., & Gao, Y. (2016). Impact of extraction parameters on
chemical composition and antioxidant activity of bioactive compounds from Chinese
licorice (Glycyrrhiza uralensisFisch.) by subcritical water. Separation Science and
Technology, 51(4), 609–621. https://doi.org/10.1080/01496395.2015.1117103.
Fernández-Ponce, M. T., Casas, L., Mantell, C., Rodríguez, M., & Martínez de la Ossa, E.
(2012). Extraction of antioxidant compounds from different varieties of Mangifera
indica leaves using green technologies. The Journal of Supercritical Fluids, 72,
168–175. https://doi.org/10.1016/j.supflu.2012.07.016.
Gallego, R., Bueno, M., & Herrero, M. (2019). Sub- and supercritical fluid extraction of
bioactive compounds from plants, food-by-products, seaweeds and microalgae – an
update. Trends in Analytical Chemistry (Reference Ed.), 116, 198–213. https://doi.org/
10.1016/j.trac.2019.04.030.
Garmus, T. T., Paviani, L. C., Queiroga, C. L., & Cabral, F. A. (2015). Extraction of phe-
nolic compounds from pepper-rosmarin (Lippia sidoides Cham.) leaves by sequential
extraction in fixed bed extractor using supercritical CO2, ethanol and water as sol-
vents. The Journal of Supercritical Fluids, 99, 68–75. https://doi.org/10.1016/j.supflu.
2015.01.016.
Getachew, A. T., & Chun, B. S. (2016). Influence of hydrothermal process on bioactive
compounds extraction from green coffee bean. Innovative Food Science & Emerging
Technologies, 38, 24–31. https://doi.org/10.1016/j.ifset.2016.09.006.
Haghayegh, M., Zabihi, F., Eikani, M. H., Kamya Moghadas, B., & Vaziri Yazdi, S. A.
(2015). Supercritical fluid extraction of flavonoids and terpenoids from herbal
compounds: Experiments and mathematical modeling. Journal of Essential Oil Bearing
Plants, 18(5), 1253–1265. https://doi.org/10.1080/0972060X.2014.961037.
Haghighi, A., & Khajenoori, M. (2013). Subcritical water extraction. Mass transfer - ad-
vances in sustainable energy and environment oriented numerical modeling.
Herzi, N., Camy, S., Bouajila, J., Destrac, P., Romdhane, M., & Condoret, J.-S. (2013).
Supercritical CO2 extraction of Tetraclinis articulata: Chemical composition, anti-
oxidant activity and mathematical modeling. The Journal of Supercritical Fluids, 82,
72–82. https://doi.org/10.1016/j.supflu.2013.06.007.
He, L., Zhang, X., Xu, H., Xu, C., Yuan, F., Knez, Ž., et al. (2012). Subcritical water ex-
traction of phenolic compounds from pomegranate (Punica granatum L.) seed re-
sidues and investigation into their antioxidant activities with HPLC–ABTS+ assay.
Food and Bioproducts Processing, 90(2), 215–223. https://doi.org/10.1016/j.fbp.2011.
03.003.
Ibáñez, E., Cifuentes, A., Rodriguez, I., Mendiola, J. A., Reglero, G., Señoráns, F. J., et al.
(2009). Spanish patent P200900164.
Khajenoori, M., Asl, A. H., & Hormozi, F. (2009). Proposed models for subcritical water
extraction of essential oils. Chinese Journal of Chemical Engineering, 17(3), 359–365.
https://doi.org/10.1016/S1004-9541(08)60217-7.
Kheirkhah, H., Baroutian, S., & Quek, S. Y. (2019). Evaluation of bioactive compounds
extracted from Hayward kiwifruit pomace by subcritical water extraction. Food and
S.O. Essien, et al.
Bioproducts Processing, 115, 143–153. https://doi.org/10.1016/j.fbp.2019.03.007.
Kim, S.-J., Matsushita, Y., Fukushima, K., Aoki, D., Yagami, S., Yuk, H.-G., et al. (2014).
Antioxidant activity of a hydrothermal extract from watermelons. Lebensmittel-
Wissenschaft und -Technologie- Food Science and Technology, 59(1), 361–368. https://
doi.org/10.1016/j.lwt.2014.04.041.
Klinchongkon, K., Chanthong, N., Ruchain, K., Khuwijitjaru, P., & Adachi, S. (2017).
Effect of ethanol addition on subcritical water extraction of pectic polysaccharides
from passion fruit peel. Journal of Food Processing and Preservation, 41(5), e13138.
https://doi.org/10.1111/jfpp.13138.
Ko, M. J., Cheigh, C. I., & Chung, M. S. (2014). Optimization of subcritical water ex-
traction of flavanols from green tea leaves. Journal of Agricultural and Food Chemistry,
62(28), 6828–6833. https://doi.org/10.1021/jf5012006.
Ko, M. J., Nam, H.-H., & Chung, M.-S. (2019). Conversion of 6-gingerol to 6-shogaol in
ginger (Zingiber officinale) pulp and peel during subcritical water extraction. Food
Chemistry, 270, 149–155. https://doi.org/10.1016/j.foodchem.2018.07.078.
Koubaa, M., Mhemdi, H., & Fages, J. (2018). Recovery of valuable components and in-
activating microorganisms in the agro-food industry with ultrasound-assisted super-
critical fluid technology. The Journal of Supercritical Fluids, 134, 71–79. https://doi.
org/10.1016/j.supflu.2017.12.012.
Lachos-Perez, D., Baseggio, A. M., Mayanga-Torres, P. C., Maróstica, M. R., Rostagno, M.
A., Martínez, J., et al. (2018). Subcritical water extraction of flavanones from de-
fatted orange peel. The Journal of Supercritical Fluids, 138, 7–16. https://doi.org/10.
1016/j.supflu.2018.03.015.
Lee, J.-H., Ko, M.-J., & Chung, M.-S. (2018). Subcritical water extraction of bioactive
components from red ginseng (Panax ginseng C.A. Meyer). The Journal of Supercritical
Fluids, 133, 177–183. https://doi.org/10.1016/j.supflu.2017.09.029.
Lee, W. J., Tan, C. P., Sulaiman, R., Hee, Y. Y., & Chong, G. H. (2020). Storage stability
and degradation kinetics of bioactive compounds in red palm oil microcapsules
produced with solution-enhanced dispersion by supercritical carbon dioxide: A
comparison with the spray-drying method. Food Chemistry, 304. https://doi.org/10.
1016/j.foodchem.2019.125427.
Lenucci, M. S., De Caroli, M., Marrese, P. P., Iurlaro, A., Rescio, L., Böhm, V., et al. (2015).
Enzyme-aided extraction of lycopene from high-pigment tomato cultivars by super-
critical carbon dioxide. Food Chemistry, 170, 193–202. https://doi.org/10.1016/j.
foodchem.2014.08.081.
Lima, R. N., Ribeiro, A. S., Cardozo-Filho, L., Vedoy, D., & Alves, P. B. (2019). Extraction
from leaves of piper klotzschianum using supercritical carbon dioxide and Co-sol-
vents. The Journal of Supercritical Fluids, 147, 205–212. https://doi.org/10.1016/j.
supflu.2018.11.006.
Lin, R., Cheng, J., Ding, L., Song, W., Qi, F., Zhou, J., et al. (2015). Subcritical water
hydrolysis of rice straw for reducing sugar production with focus on degradation by-
products and kinetic analysis. Bioresource Technology, 186, 8–14. https://doi.org/10.
1016/j.biortech.2015.03.047.
Lindahl, S., Ekman, A., Khan, S., Wennerberg, C., Börjesson, P., Sjöberg, P. J. R., et al.
(2010). Exploring the possibility of using a thermostable mutant of β-glucosidase for
rapid hydrolysis of quercetin glucosides in hot water. Green Chemistry, 12(1),
159–168. https://doi.org/10.1039/b920195p.
Liu, J., Chen, P., Yao, W., Wang, J., Wang, L., Deng, L., et al. (2015). Subcritical water
extraction of betulinic acid from birch bark. Industrial Crops and Products, 74,
557–565. https://doi.org/10.1016/j.indcrop.2015.05.064.
López-Padilla, A., Ruiz-Rodriguez, A., Reglero, G., & Fornari, T. (2017). Supercritical
carbon dioxide extraction of Calendula officinalis : Kinetic modeling and scaling up
study. The Journal of Supercritical Fluids, 130, 292–300. https://doi.org/10.1016/j.
supflu.2017.03.033.
Machmudah, S., Lestari, S. D., Widiyastuti, W., Kanda, H., Winardi, S., & Goto, M. (2018).
Subcritical water extraction enhancement by adding deep eutectic solvent for ex-
tracting xanthone from mangosteen pericarps. The Journal of Supercritical Fluids, 133,
615–624. https://doi.org/10.1016/j.supflu.2017.06.012.
Machmudah, S., Martin, A., Sasaki, M., & Goto, M. (2012). Mathematical modeling for
simultaneous extraction and fractionation process of coffee beans with supercritical
CO2 and water. The Journal of Supercritical Fluids, 66, 111–119. https://doi.org/10.
1016/j.supflu.2011.11.011.
Machmudah, S., Widiyastuti, S. W., Wahyudiono, H. K., & Goto, M. (2017). Sub- and
supercritical fluids extraction of phytochemical compounds from Eucheuma cottonii
and Gracilaria sp. Chemical Engineering Transactions, 56, 1291–1296. https://doi.org/
10.3303/CET1756216.
Massias, A., Boisard, S., Baccaunaud, M., Leal Calderon, F., & Subra-Paternault, P. (2015).
Recovery of phenolics from apple peels using CO2+ethanol extraction: Kinetics and
antioxidant activity of extracts. The Journal of Supercritical Fluids, 98, 172–182.
https://doi.org/10.1016/j.supflu.2014.12.007.
Moncada, J., Tamayo, J. A., & Cardona, C. A. (2014). Techno-economic and environ-
mental assessment of essential oil extraction from citronella (cymbopogon win-
teriana) and lemongrass (cymbopogon citrus): A Colombian case to evaluate different
extraction technologies. Industrial Crops and Products, 54, 175–184. https://doi.org/
10.1016/j.indcrop.2014.01.035.
Morales, D., Smiderle, F. R., Villalva, M., Abreu, H., Rico, C., Santoyo, S., et al. (2019).
Testing the effect of combining innovative extraction technologies on the biological
activities of obtained β-glucan-enriched fractions from Lentinula edodes. Journal of
Functional Foods, 60. https://doi.org/10.1016/j.jff.2019.103446.
Moreira, S. A., Alexandre, E. M. C., Pintado, M., & Saraiva, J. A. (2019). Effect of
emergent non-thermal extraction technologies on bioactive individual compounds
profile from different plant materials. Food Research International, 115, 177–190.
https://doi.org/10.1016/j.foodres.2018.08.046.
Moreira, M. M., Barroso, M. F., Porto, J. V., Ramalhosa, M. J., Švarc-Gajić, J., Estevinho,
L., et al. (2018). Potential of Portuguese vine shoot wastes as natural resources of
bioactive compounds. The Science of the Total Environment, 634, 831–842. https://doi.
168
Trends in Food Science & Technology 97 (2020) 156–169
org/10.1016/j.scitotenv.2018.04.035.
Mouahid, A., Bouanga, H., Crampon, C., & Badens, E. (2017). Supercritical CO 2 ex-
traction of oil from Jatropha curcas : An experimental and modelling study. The
Journal of Supercritical Fluids. https://doi.org/10.1016/j.supflu.2017.11.014.
Mphahlele, R. R., Fawole, O. A., Makunga, N. P., & Opara, U. L. (2016). Effect of drying
on the bioactive compounds, antioxidant, antibacterial and antityrosinase activities
of pomegranate peel. BMC Complementary and Alternative Medicine, 16(1), 143.
https://doi.org/10.1186/s12906-016-1132-y.
Munir, M. T., Kheirkhah, H., Baroutian, S., Quek, S. Y., & Young, B. R. (2018). Subcritical
water extraction of bioactive compounds from waste onion skin. Journal of Cleaner
Production, 183, 487–494. https://doi.org/10.1016/j.jclepro.2018.02.166.
Mustapa, A. N., Martin, Á., Mato, R. B., & Cocero, M. J. (2015). Extraction of phyto-
compounds from the medicinal plant Clinacanthus nutans Lindau by microwave-as-
sisted extraction and supercritical carbon dioxide extraction. Industrial Crops and
Products, 74, 83–94. https://doi.org/10.1016/j.indcrop.2015.04.035.
Natolino, A., & Da Porto, C. (2019). Supercritical carbon dioxide extraction of pome-
granate (Punica granatum L.) seed oil: Kinetic modelling and solubility evaluation.
The Journal of Supercritical Fluids, 151, 30–39. https://doi.org/10.1016/j.supflu.2019.
05.002.
Ndayishimiye, J., & Chun, B. S. (2017). Optimization of carotenoids and antioxidant
activity of oils obtained from a co-extraction of citrus (Yuzu ichandrin) by-products
using supercritical carbon dioxide. Biomass and Bioenergy, 106, 1–7. https://doi.org/
10.1016/j.biombioe.2017.08.014.
Nile, S. H., Nile, A., Gansukh, E., Baskar, V., & Kai, G. (2019). Subcritical water extraction
of withanosides and withanolides from ashwagandha (Withania somnifera L) and
their biological activities. Food and Chemical Toxicology, 132, 110659. https://doi.
org/10.1016/j.fct.2019.110659.
Nkurunziza, D., Pendleton, P., & Chun, B. S. (2019). Optimization and kinetics modeling
of okara isoflavones extraction using subcritical water. Food Chemistry, 295, 613–621.
https://doi.org/10.1016/j.foodchem.2019.05.129.
Özkal, S. G., & Yener, M. E. (2016). Supercritical carbon dioxide extraction of flaxseed oil:
Effect of extraction parameters and mass transfer modeling. The Journal of
Supercritical Fluids, 112, 76–80. https://doi.org/10.1016/j.supflu.2016.02.013.
Pasquel Reátegui, J. L., Machado, A. P.d. F., Barbero, G. F., Rezende, C. A., & Martínez, J.
(2014). Extraction of antioxidant compounds from blackberry (Rubus sp.) bagasse
using supercritical CO2 assisted by ultrasound. The Journal of Supercritical Fluids, 94,
223–233. https://doi.org/10.1016/j.supflu.2014.07.019.
Patel, R. N., Bandyopadhyay, S., & Ganesh, A. (2006). Economic appraisal of supercritical
fluid extraction of refined cashew nut shell liquid. Journal of Chromatography A,
1124(1), 130–138. https://doi.org/10.1016/j.chroma.2006.06.015.
Plaza, M., & Turner, C. (2015). Pressurized hot water extraction of bioactives. Trends in
Analytical Chemistry (Reference Ed.), 71, 39–54. https://doi.org/10.1016/j.trac.2015.
02.022.
Puri, M., Sharma, D., & Barrow, C. J. (2012). Enzyme-assisted extraction of bioactives
from plants. Trends in Biotechnology, 30(1), 37–44. https://doi.org/10.1016/j.tibtech.
2011.06.014.
Putra, N. R., Rizkiyah, D. N., Zaini, A. S., Yunus, M. A. C., Machmudah, S., Idham, Z.b.,
et al. (2018). Effect of particle size on yield extract and antioxidant activity of peanut
skin using modified supercritical carbon dioxide and soxhlet extraction. Journal of
Food Processing and Preservation, 42(8), e13689. https://doi.org/10.1111/jfpp.13689.
Ramos, M., Jiménez, A., & Garrigós, M. C. (2019). Il-based advanced techniques for the
extraction of value-added compounds from natural sources and food by-products.
Trends in Analytical Chemistry (Reference Ed.), 119. https://doi.org/10.1016/j.trac.
2019.07.027.
Redondo, D., Venturini, M. E., Luengo, E., Raso, J., & Arias, E. (2018). Pulsed electric
fields as a green technology for the extraction of bioactive compounds from thinned
peach by-products. Innovative Food Science & Emerging Technologies, 45, 335–343.
https://doi.org/10.1016/j.ifset.2017.12.004.
Reyes, F. A., Mendiola, J. A., Suárez-Alvarez, S., Ibañez, E., & del Valle, J. M. (2016).
Adsorbent-assisted supercritical CO2 extraction of carotenoids from Neochloris
oleoabundans paste. The Journal of Supercritical Fluids, 112, 7–13. https://doi.org/10.
1016/j.supflu.2016.02.005.
Rodríguez-Meizoso, I., Castro-Puyana, M., Börjesson, P., Mendiola, J. A., Turner, C., &
Ibáñez, E. (2012). Life cycle assessment of green pilot-scale extraction processes to
obtain potent antioxidants from rosemary leaves. The Journal of Supercritical Fluids,
72, 205–212. https://doi.org/10.1016/j.supflu.2012.09.005.
Rovetto, L. J., & Aieta, N. V. (2017). Supercritical carbon dioxide extraction of canna-
binoids from Cannabis sativa L. The Journal of Supercritical Fluids, 129, 16–27.
https://doi.org/10.1016/j.supflu.2017.03.014.
Ruslan, M. S. H., Idham, Z., Nian Yian, L., Ahmad Zaini, M. A., & Che Yunus, M. A. (2018).
Effect of operating conditions on catechin extraction from betel nuts using super-
critical CO2-methanol extraction. Separation Science and Technology, 53(4), 662–670.
https://doi.org/10.1080/01496395.2017.1406947.
Santos, P., Aguiar, A. C., Barbero, G. F., Rezende, C. A., & Martínez, J. (2015).
Supercritical carbon dioxide extraction of capsaicinoids from malagueta pepper
(Capsicum frutescens L.) assisted by ultrasound. Ultrasonics Sonochemistry, 22, 78–88.
https://doi.org/10.1016/j.ultsonch.2014.05.001.
Saravana, P. S., Tilahun, A., Gerenew, C., Tri, V. D., Kim, N. H., Kim, G.-D., et al. (2018).
Subcritical water extraction of fucoidan from Saccharina japonica: Optimization,
characterization and biological studies. Journal of Applied Phycology, 30(1), 579–590.
https://doi.org/10.1007/s10811-017-1245-9.
Sarfarazi, M., Jafari, S. M., Rajabzadeh, G., & Feizi, J. (2019). Development of an en-
vironmentally-friendly solvent-free extraction of saffron bioactives using subcritical
water. Lebensmittel-Wissenschaft & Technologie, 114. https://doi.org/10.1016/j.lwt.
2019.108428.
Schuster, J. J., Bahr, L. A., Fehr, L., Tippelt, M., Schulmeyr, J., Wuzik, A., et al. (2018).
S.O. Essien, et al.
Online monitoring of the supercritical CO2 extraction of hop. The Journal of
Supercritical Fluids, 133, 139–145. https://doi.org/10.1016/j.supflu.2017.10.006.
Semprini, A., Singer, J., Shortt, N., Braithwaite, I., & Beasley, R. (2017). Protocol for a
randomised controlled trial of 90% kānuka honey versus 5% aciclovir for the treat-
ment of herpes simplex labialis in the community setting. British Medical Journal
Open, 7(8), https://doi.org/10.1136/bmjopen-2017-017766.
Shitu, A., Izhar, S., & Tahir, T. M. (2015). Sub-critical water as a green solvent for pro-
duction of valuable materials from agricultural waste biomass: A review of recent
work. Global Journal of Environmental Science and Management, 1(3), 255–264.
https://doi.org/10.7508/gjesm.2015.03.008.
Shrirame, B. S., Geed, S. R., Raj, A., Prasad, S., Rai, M. K., Singh, A. K., et al. (2018).
Optimization of supercritical extraction of coriander (coriandrum sativum L.) seed
and characterization of essential ingredients. Journal of Essential Oil Bearing Plants,
21(2), 330–344. https://doi.org/10.1080/0972060X.2018.1470943.
Singh, P. P., & Saldaña, M. D. A. (2011). Subcritical water extraction of phenolic com-
pounds from potato peel. Food Research International, 44(8), 2452–2458. https://doi.
org/10.1016/j.foodres.2011.02.006.
Sovilj, M., Nikolovski, B., & Spasojevic, M. (2011). Critical review of supercritical fluid
extraction of selected spice plant materials, Vol. 30, 197–220.
Sovová, H. (2005). Mathematical model for supercritical fluid extraction of natural pro-
ducts and extraction curve evaluation. The Journal of Supercritical Fluids, 33(1),
35–52. https://doi.org/10.1016/j.supflu.2004.03.005.
Srinivas, K., & King, J. W. (2010). Supercritical carbon dioxide and subcritical water:
Complementary agents in the processing of functional foods. In J. Smith, & E. Charter
(Eds.). Functional food products development (pp. 39–78). Blackwell Publishing Ltd.
Teixeira, G. L., Ghazani, S. M., Corazza, M. L., Marangoni, A. G., & Ribani, R. H. (2018).
Assessment of subcritical propane, supercritical CO2 and Soxhlet extraction of oil
from sapucaia (Lecythis pisonis) nuts. The Journal of Supercritical Fluids, 133,
122–132. https://doi.org/10.1016/j.supflu.2017.10.003.
Todd, R., & Baroutian, S. (2017). A techno-economic comparison of subcritical water,
supercritical CO 2 and organic solvent extraction of bioactives from grape marc.
Journal of Cleaner Production, 158, 349–358. https://doi.org/10.1016/j.jclepro.2017.
05.043.
Tomšik, A., Pavlić, B., Vladić, J., Cindrić, M., Jovanov, P., Sakač, M., et al. (2017).
Subcritical water extraction of wild garlic (Allium ursinum L.) and process optimi-
zation by response surface methodology. The Journal of Supercritical Fluids, 128,
79–88. https://doi.org/10.1016/j.supflu.2017.05.012.
Torres-Ossandón, M. J., Vega-Gálvez, A., López, J., Stucken, K., Romero, J., & Di Scala, K.
(2018). Effects of high hydrostatic pressure processing and supercritical fluid ex-
traction on bioactive compounds and antioxidant capacity of Cape gooseberry pulp (
169
Trends in Food Science & Technology 97 (2020) 156–169
Physalis peruviana L.). The Journal of Supercritical Fluids, 138, 215–220. https://doi.
org/10.1016/j.supflu.2018.05.005.
del Valle, J. M. (2015). Extraction of natural compounds using supercritical CO2: Going
from the laboratory to the industrial application. The Journal of Supercritical Fluids,
96, 180–199. https://doi.org/10.1016/j.supflu.2014.10.001.
Vo Dinh, T., Saravana, P. S., Woo, H. C., & Chun, B. S. (2018). Ionic liquid-assisted
subcritical water enhances the extraction of phenolics from brown seaweed and its
antioxidant activity. Separation and Purification Technology, 196, 287–299. https://
doi.org/10.1016/j.seppur.2017.06.009.
Yang, Y.-C., Wei, M.-C., Huang, T.-C., & Lee, S.-Z. (2013). Extraction of protocatechuic
acid from Scutellaria barbata D. Don using supercritical carbon dioxide. The Journal
of Supercritical Fluids, 81, 55–66. https://doi.org/10.1016/j.supflu.2013.04.007.
Zabot, G. L., Moraes, M. N., Carvalho, P. I. N., & Meireles, M. A. A. (2015). New proposal
for extracting rosemary compounds: Process intensification and economic evaluation.
Industrial Crops and Products, 77, 758–771. https://doi.org/10.1016/j.indcrop.2015.
09.053.
Zakaria, S. M., & Kamal, S. M. M. (2015). Subcritical water extraction of bioactive
compounds from plants and algae: Applications in pharmaceutical and food in-
gredients. Food Engineering Reviews, 8(1), 23–34. https://doi.org/10.1007/s12393-
015-9119-x.
Zhao, T., Luo, Y., Zhang, X., Zhang, W., Qu, H., Mao, G., et al. (2019). Subcritical water
extraction of bioactive compounds from Radix Puerariae and optimization study
using response surface methodology. Chemical Engineering Communications, 206(9),
1218–1227. https://doi.org/10.1080/00986445.2018.1555529.
Zhao, Y., & Saldaña, M. D. A. (2019). Use of potato by-products and gallic acid for de-
velopment of bioactive film packaging by subcritical water technology. The Journal of
Supercritical Fluids, 143, 97–106. https://doi.org/10.1016/j.supflu.2018.07.025.
Zhao, S., & Zhang, D. (2014). Supercritical CO2 extraction of Eucalyptus leaves oil and
comparison with Soxhlet extraction and hydro-distillation methods. Separation and
Purification Technology, 133, 443–451. https://doi.org/10.1016/j.seppur.2014.07.
018.
Zizovic, I., Senerovic, L., Moric, I., Adamovic, T., Jovanovic, M., Krusic, M. K., et al.
(2018). Utilization of supercritical carbon dioxide in fabrication of cellulose acetate
films with anti-biofilm effects against Pseudomonas aeruginosa and Staphylococcus
aureus. The Journal of Supercritical Fluids, 140, 11–20. https://doi.org/10.1016/j.
supflu.2018.05.025.
Zullaikah, S., Naulina, R. Y., Meinawati, P., Fauziyah, K., Rachimoellah, M., Rachmaniah,
O., et al. (2019). Enhanced extraction of phenolic compounds from moringa oleifera
leaves using subcritical water ethanol mixture. IOP Conference Series: Materials Science
and Engineering, 543. https://doi.org/10.1088/1757-899x/543/1/012021.