Supercritical Fluid Extraction From Vegetable Materials

Rev Chem Eng 27 (2011): 79156 2011 by Walter de Gruyter Berlin Boston. DOI 10.1515/REVCE.2011.
002
Supercritical fluid extraction from vegetable materials
Helena Sovov1,* and Roumiana P. Stateva2

1
Institute of Chemical Process Fundamentals

of the ASCR, v.v.i., Rozvojova 135, 16502 Prague,
Czech Republic, e-mail: sovova@icpf.cas.cz
2
Institute of Chemical Engineering, Bulgarian Academy of
Sciences, 1113 Sofia, Bulgaria
*Corresponding author
Abstract
In the 21st century, the mission of chemical engineering is
to promote innovative technologies that reduce or eliminate
the use or generation of hazardous materials in the design
and manufacture of chemical products. The sustainable use
of renewable resources, complying with consumer health and
environmental requirements, motivates the design, optimisation, and application of green benign processes. Supercritical
fluid extraction is a typical example of a novel technology for
the ecologically compatible production of natural substances
of high industrial potential from renewable resources such as
vegetable matrices that finds extended industrial application.
The present review is devoted to the stage of development of
supercritical fluid extraction from vegetable material in the
last 20 years. Without the ambition to be exhaustive, it offers
an extended, in comparison with previous reviews, enumeration of extracted plant materials, discusses the mathematical
modelling of the process, and advocates a choice for the appropriate model that is based on characteristic times of individual
extraction steps. Finally, the attention is focussed on the elements of a thermodynamic modelling framework designed to
predict and model robustly and efficiently the complex phase
equilibria of the systems solute+supercritical fluid.
Keywords: kinetic models; plants and herbs; supercritical
fluid extraction; thermodynamic models.
1. Introduction
A supercritical fluid (SCF) is a substance above its critical
pressure and temperature (Figure 1). Its properties range
between those of liquid and gas. The most important advantages of SCFs applied in extraction are the extreme variability of their solvent power with pressure and temperature, and
their low viscosity, enabling much faster mass transfer than
in liquids. No other extraction method can claim such flexibility. The main drawback of a large-scale SCF application
in comparison with conventional methods, namely the high
cost of the high-pressure equipment required, can often be
outweighed by superior product properties, lower operating

costs, and/or integration of several technological steps into
one.
SCF extraction (supercritical extraction, SFE) of natural
substances from plants is a relatively new process. The discovery of the solvent power of pressurised carbon dioxide
was made in the 19th century (Hannay and Hogarth 1879), but
its practical application for extraction of vegetable substances
was first studied in the 1960s when more sensitive analytical
methods indicated trace amounts of residual organic solvents
in food samples and initiated concern about their impact on
human health. It was realised that dense carbon dioxide in
its supercritical or liquid state (the term supercritical fluid
extraction often covers the extraction with both supercritical and liquid carbon dioxide) is a non-toxic solvent and thus
its traces left in extracts are not harmful. Its critical point
(Tc=31.1C, Pc=7.38 MPa) allows application of relatively
low operation temperatures so that thermally labile solutes
are protected and the extracts better resemble the natural
material than the products of steam distillation and conventional extraction where the solvent is usually separated from
the extract under increased temperature. Carbon dioxide
is non-flammable, non-explosive, cheap, and easily accessible in high purity. To also dissolve more polar substances,
supercritical carbon dioxide (SC-CO2) is usually modified by
addition of small amounts of polar liquids, such as methanol,
ethanol, water, and others.
Initially, the experiments with SC-CO2 extraction of natural products were conducted in a limited number of laboratories, most intensively in Germany (Zosel 1964) and in
Russia (Pekhov et al. 1965). Since then, many laboratories
in different countries have been equipped with SFE units
and extensive research has been done in the extraction of flavours, spices, essential oils, and other substances from herbs
and plants. The first pilot and full-scale plants were built for
SC-CO2 extraction of caffeine from coffee beans and tea
leaves, the extraction of acids from hops giving taste to bear,
and the extraction of taste and flavour compounds from spice.
The number and capacity of industrial units for supercritical
extraction and the variety of extracted substances are increasing, and today >200 industrial plants are operating all over
the world (Perrut 2007). The two most important commercial applications of SFE in the food industry still remain hop
extraction and coffee decaffeination (del Valle and Aguilera
1999); however, the production of extracts rich in biologically
active substances as antioxidants, lipid-soluble vitamins, and
others is fast increasing.
Small-scale SFE for analytical application was developed
in the mid-1980s in response to the desire to reduce the use of
organic solvents in the laboratory environment (King 1995).
Extraction equipment with extractor capacity of several
cubic centimetres or less enables a fast and efficient isolation
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H. Sovov and R.P. Stateva: SFE from vegetable materials
Pressure
(sc)
(l)
C
(s)
(g)
T
Temperature
Figure 1 Phase diagram with ternary point (T), critical point (C),
and solid (s), liquid (l), gaseous (g), and supercritical (sc) state.
of substances for chromatographic assay from bulk sample

matrix. To achieve complete extraction of analytes, high
pressures and temperatures are applied and SC-CO2 is usually modified to increase the solubility of more polar solutes
and/or to weaken solute-matrix interaction.
SC-CO2 and near-critical water (also known as subcritical
water, hot pressurised water, HPW) are regarded as the most
promising environmentally benign medium not only for the
extraction of natural substances but also for various chemical and related processes. The properties of HPW differ from
those of water at ambient conditions. Under pressure and high
temperature, it becomes an excellent solvent for not only polar
compounds but also non-polar substances. Nevertheless, its
critical point (22.1 MPa and 374C) is far above the critical point of CO2, and even though the operation temperature
of subcritical water is usually selected closer to the lower
limit of the range 100374C, the process is not appropriate for temperature-labile and easily hydrolysable substances.
Moreover, HPW is corrosive, in contrast to SC-CO2.
Although the focus of the research in SCF applications
is moving nowadays to new areas, such as particle design,
chemical reactions in supercritical solvents, polymer treatment with SCFs, and fractionation of liquid natural products
as edible oils in counter-current extraction columns, still the
most extended industrial application of SCFs remains the
SC-CO2 extraction from botanic materials. Concerns about
the cost and environmental dangers of waste disposal, and
the emission of hazardous solvents into the atmosphere motivate the design and application of a green technology such
as SFE.
Without the ambition to be exhaustive, we have limited the
reviewed literature sources almost entirely to original papers.
Moreover, during the last few years, several excellent review
papers on supercritical extraction from plants have been published, and there is no benefit from repetition. However, we
believe we can further elaborate several topics and present
new information. First, the table of extracted plants, extended
in comparison with previous reviews, should help exploit
the information contained in the literature. Further, as many
papers on mathematical modelling of SFE from plants have
been published recently, an attempt is made to review this literature and advocate a classification of the models in relation
with characteristic times of individual extraction steps.
We will also focus our attention on the thermodynamic

modelling of the complex systems solid solute+SCF. The
modelling of systems with an SCF has been comprehensively discussed in two books (McHugh and Krukonis 1994,
Prausnitz et al. 1999) and several reviews see, for example,
the contributions by Brennecke and Eckert (1989), Johnston
et al. (1989), and Ekart et al. (1991), to name just a few.
More recent papers and reviews devote particular attention to
modelling solid+SCF systems without and with a co-solvent
(Ashour et al. 2000, Escobedo-Alvarado et al. 2001, Higashi
et al. 2001, Gordillo et al. 2005a) and the main conclusion
of the authors can be briefly summarised as follows: (i) prediction of SFE is difficult even when experimental data are
available to refine the models used, (ii) theoretically based
models are forced to fit the data better by the introduction
of additional adjusted parameters. Needless to say that this
area of research is very competitive and fast moving, and we
believe there are still some points that need further attention
and elucidation.
2. SFE from plants

2.1. The process and the equipment
The extraction is usually carried out as a semicontinuous

process (Figure 2). Vegetable material, usually dry and disintegrated, is charged into an extraction vessel of cylindrical shape to obtain a fixed bed of particles. The supercritical
solvent, fed to the extractor continuously by a high-pressure
pump at a fixed flow rate, dissolves required substances. The
solution flows to a separator where the extracted substances
precipitate by temperature and/or pressure changes or by
applying a mass-separating agent, and the solvent is continuously regenerated and recirculated. More separation stages
are often used to achieve a partial fractionation of the extract
(Brunner 1987, Reverchon 1997).
The typical volume of extractors is from 0.1 to 2 dm3 on the
laboratory scale and from 2 to 5 dm3 on the pilot scale. MicroSFE devices are primarily designed for analytical purposes
and are frequently connected to an analyser such as gas chromatograph, gas chromatograph-mass spectrometer, or SCF
chromatograph. These instruments use extraction vessels that
Extractor
Separator
Solution
Mixture
CO2(g)
Condenser
80
CO2(sc)
CO2(l)
Figure 2 Simplified scheme of the extraction equipment with CO2

recycle.

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can range from 0.1 cm3 to several hundred cubic centimetres

(Reverchon 1997). In micro- and small-scale extraction, the
CO2 flow rate is low and therefore the equipment does not
require solvent recycle CO2 can be expanded to ambient
pressure in the separator and vented.
When the SFE plant is equipped with several separators in
series, fractionation of the extracts is possible, operating the
separators at different pressures and temperatures. The scope
of this operation is to induce the selective precipitation of different compound families as a function of their different saturation conditions in the solvent. This procedure has often been
applied in the SFE of essential oils to separate them from coextracted cuticular waxes (Reverchon and De Marco 2006).
High capital costs of SFE equipment are usually mentioned
among the drawbacks of the process. On the other hand, the
operating costs are usually lower than those of conventional
extraction. Thus, many large-scale units for the SFE of solid
natural materials, mainly for food ingredients and phytopharmaceuticals, are operated worldwide and are economically
competitive. Perrut (2000) published a correlation of the
investment cost of SFE units delivered on a turn-key basis
with the product of total volume of extractors and the design
flow rate, showing that the cost increases approximately with
the square root of the plant capacity. A chapter in a monograph
was devoted to the economic evaluation of high-pressure processes by Lack and Seidlitz (2001). The investment and operating costs were also discussed by Brunner (2005). del Valle
et al. (2005a) compiled costs of several production-scale SFE
plants of 0.68 m3 total extractor capacity and performed a
feasibility study of a plant for the extraction of wheat germ
oil. They showed how the break-even plant capacity would
vary in several countries in Latin America. Simultaneously,
Rosa and Meireles (2005a) described the methodology of
estimation of the manufacturing costs of SC-CO2 extracts and
used the procedure to estimate the costs of clove bud oil and
ginger oleoresin. This methodology was applied also in later
publications (Pereira and Meireles 2007, Pereira et al. 2007,
Prado et al. 2010, Mezzomo et al. 2011). Fiori (2010) performed a study on the possible use of exhausted grape marc
for obtaining grape seed oil by means of the SFE based on a
thorough analysis of the process, indicating that the proposed
industrial application could be economically interesting.
Specific costs and incomes linked to the supercritical technology are reported in details for the case study.
Perrut (2000) emphasised the importance of regular maintenance of the high-pressure equipment, necessary to eliminate hazards, and mentions the parts of the equipment that
must be inspected first. Cleaning of the equipment was also
discussed.
2.2. Review papers
Besides the monographs either devoted to the applications

of SCFs generally or directly to SFE (e.g., Stahl et al. 1987,
King and Bott 1993, Brunner 1994, Rizvi 1994, Koshevoi and
Bliagoz 2000), valuable information on the process has been
collected and reported in a number of review papers. From
those that are not only limited to supercritical extraction from
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plants but also examine other SCF applications, we mention

here only a few. Thus, the potential applications of SCFs in
bioprocessing (as non-aqueous media for enzymatic reactions, solvents or anti-solvents in production of micrometre
and submicrometre particles, solvents for extraction, rapidly
expanding fluid for disruption of cells) were reviewed by
Jarzebski and Malinowski (1995). The exceptional physical
properties of SCFs and their exploitation in environmentally benign separation and reaction processes, as well as
in other new kinds of materials processing are described by
Eckert et al. (1996). Hauthal (2001) reviewed the results on
SCF fundamentals and their applications. Marr and Gamse
(2000) reviewed developments in extraction, fractionation of
products, dyeing of fibres, treatment of contaminated soils,
production of powders in micron and submicron range, and
reactions in or with SCFs. Perrut (2000) considered the perspectives of production-scale applications of SCFs also in
respect to the economic competitiveness of these processes
with conventional ones. Beckman (2004) examined the use
of CO2 to create greener processes and products, with a focus
on research and commercialisation efforts since 1995. The literature on chemical and enzymatic reactions and formation of
micro- and nanoparticles revealed that careful application of
CO2 technology can result in cleaner and less expensive processes and products of higher quality. In the recent review of
Temelli (2009) on processing of fats and oils using SC-CO2,
it is shown that SFE of specialty oils has reached commercial
scale and that researchers focus on fractionation of complex
lipid mixtures, conducting reactions in supercritical fluid
media, and particle formation for the delivery of bioactive
lipid components. A bright future is predicted for new integrated processes to be developed, targeting ingredients for
both food and non-food industrial applications.
High-pressure fluid phase-equilibria, both experimental
methods and systems investigated, were reviewed by Fornari
et al. (1990) for data published in the period 19781987, Dohrn
and Brunner (1995) for the period 19881993, Christov and
Dohrn (2002) for the period 19941999, Dohrn et al. (2010)
for the period 20002004, and Fonseca et al. (2011) for the
period 20052008. The papers also contain solubility data for
many substances in supercritical solvents.
The reviews listed below focus directly on SFE.
2.2.1. Extraction for food, drug, and perfume industries The state of supercritical extraction of natural prod-
ucts in the middle of the 1980s was described by Brunner

(1987). Palmer and Ting (1995) discussed the actual and
potential applications of SCF technology and presented a
summary of commercial applications, patented processes,
and published research studies on utilisation of SCFs in food
processing. Starmans and Nijhuis (1996) compared different
methods, including SFE, for extraction of secondary metabolites from plant material. Sihvonen et al. (1999) summarised
some of the advances and the latest developments in the field
of SCF technology focusing on the use of SC-CO2 in food,
nutraceutical, and pharmaceutical applications. Wolski and
Ludwiczuk (2001) presented fundamentals of high-pressure
extraction and reviewed literature related to supercritical

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extraction in different branches of industry. Raventos et al.

(2002) focused their review on the applications and potential
of SC-CO2 in the food industry. Rozzi and Singh (2002) discussed the use of SCFs in different processes of food industry
and in food analysis. A review including general description
of SCFs, their physicochemical properties and particularly the
solvent power, effect of solid matrices on the extraction, and
application areas of SFE was published by Askin and Otles
(2005). Brunner (2005) reviewed the state of SCF applications to food processing. Besides other processes, industrialscale extraction from solid materials (decaffeination of green
coffee beans, production of hops extracts, recovery of aromas
and flavours from herbs and spices, extraction of edible oils,
and removal of contaminants) was discussed, including the
solvent power of SC-CO2, the course of the extraction process, design of commercial plants and modes of their operation, equipment size, and processing costs. Recent advances
in SFE were overviewed by Herrero et al. (2010).
Hierro and Santamaria (1992) reviewed the SFE techniques for extraction of vegetable and animal fats and particularly those containing polyunsaturated fatty acids, which
have important pharmacological applications. The paper written by Kerrola (1995) is focused particularly on the extraction
of essential oils and flavour compounds. Another excellent
review on SFE and fractionation of essential oils and related
products was published by Reverchon (1997). The paper presents experimental techniques for SFE from plants, solubility
in SC-CO2 of different essential oil components, and mathematical models for the process. Furthermore, the influence
of operating parameters on extraction rate and extract composition is discussed as well as pre-treatment of raw materials
and post-processing of the extracted essential oils. The applications of dense carbon dioxide for the extraction of pharmaceuticals from various matrices were reviewed by Dean and
Khundker (1997). The SFE process parameters required for
a preliminary analysis of the manufacturing costs were compiled from the literature published in 20012003 by Meireles
(2003). Brazilian research on SCFs and their application,
including the SFE from vegetable materials, was reviewed by
Rosa and Meireles (2005b). Herrero et al. (2006) reviewed
the SFE of functional ingredients from plants, food products,
algae, and microalgae with special attention to antioxidants,
both for SC-CO2 and subcritical water as solvents. DiazReinoso et al. (2006) published a comprehensive compilation
of data on the SFE of antioxidant compounds from vegetal
materials and their purification, with particular attention to
the substances of a phenolic nature. Wang and Weller (2006)
described and compared the conventional Soxhlet extraction with SFE and other alternative methods and summarised
potential uses of these methods for the extraction of nutraceuticals from plant materials. Reverchon and De Marco (2006)
critically analysed the research on supercritical extraction and
fractionation in the last decade, including the SFE of essential and seed oils, antioxidants, pharmaceuticals, colouring
matters and pesticides, as well as mathematical modelling of
SFE. Catchpole et al. (2009) reviewed the extraction and fractionation of specialty lipids (high-value seed oils, polyunsaturated fatty acid concentrates, carotenoids, and phospholipids)
with near-critical solvents. Pereira and Meireles (2010) published an extensive review on the SFE of bioactive compounds
(essential oils, phenolic compounds, carotenoids, tocopherols, and tocotrienols), taking into account extraction yields,
solubility, and manufacturing costs, and operation conditions
in the extraction and fractionation. Another overview focused
on the application of SFE in recovery of bioactive phenolic
compounds from natural sources and effects of extraction
conditions on the yield, composition, and antioxidant activity
of extracts was published by Marostica et al. (2010).
A review of transport properties and solubilities in SCFs,
particularly CO2, as well as other underlying factors that are
responsible for the kinetics and phase equilibrium in SFE processes, was presented by del Valle and Aguilera (1999). They
described the selective CO2 extraction of essential oils, pungent principles, carotenoid pigments, antioxidants, antimicrobials, and related substances to be used as ingredients for the
food, drug, and perfume industries from the point of view of
the potential applications of SFE in Latin America. Al-Jabari
(2002) considered models for various applications of SFE,
showed the importance of modelling the initial static extraction
(with no solvent flow) preceding the dynamic extraction, and
demonstrated the similarity between modelling SFE processes
and reversible adsorption/desorption processes. The paper of
del Valle et al. (2005a) summarises basic and applied research
on phase equilibrium and mass transfer kinetics involved in
high-pressure CO2 extraction from solid substrates and particularly the extraction of lipids and essential oils from native Latin
American plants. Mass transfer models for SFE of vegetable
oils from solid matrix were reviewed by del Valle and de la
Fuente (2006). A recent review paper published by Oliveira et
al. (2011) includes models for kinetics of SFE from solid particles and for SFE from liquids in counter-current columns.
Hawthorne
(1990) discussed SFE as a method for extraction of analytes
from a bulk sample matrix before their analysis. He considered SFE techniques and hardware and concluded that extraction time is reduced, generation of large volumes of waste
solvents is eliminated, and the step of concentration of the
extracted analytes is greatly simplified compared with conventional liquid solvent extraction techniques. Castioni et al.
(1995) focused attention on near-critical extraction of compounds of plant origin and its on-line coupling with chromatographic methods. Modey et al. (1996a) explored the
use of SCFs for analytical extraction of natural products and
highlighted applications where SFE might be advantageous.
Chester et al. (1996) published a review on SCF chromatography and extraction; 2 years later they continued their review
in a new contribution focusing on the most significant articles concerning the topics (Chester et al. 1998). According
to the authors, the enhanced performance characteristics of
SFE, such as greater selectivity compared with conventional
methods, reduced time, greater quantitative yields, lower cost
per extraction, and new capabilities, had driven the technology in the 1990s. The advances in SFE spurred the creation
of new extraction techniques known as accelerated solvent
extraction, hot (subcritical) water extraction, near-critical
2.2.2. Extraction for analytical purposes

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fluid extraction, enhanced-fluidity extraction, etc., which are

performed below the critical point of the solvent and can be
called pressurised fluid extraction. Smith (1999) reviewed the
development in SCF chromatography and SFE of analytes in
the last 20 years and showed that there is unity in separation
methods and that a continuum exists from gases to liquids. de
Castro and Jimnez-Carmona (2000) emphasised the advantages of SFE, such as preconcentration effect, cleaniness
and safety, quantitativeness, expeditiousness, and simplicity.
They discussed limitations of the method demonstrated when
extracting polar analytes, occurrence of matrix-analyte binding that often makes a complete extraction of analyte from
natural samples impossible, and mentioned different ways of
clean-up of fat-soluble analytes from unwanted matrix components. Chen and Ling (2000) presented a review on SFE in
Chinese herbal medicine. The paper contains lists of application examples of SFE of useful ingredients from herbs and
plants, including the operating parameters, concentrations of
modifiers in CO2, extraction yields, and analytical methods.
Similar data were given for SFE of pesticide residues from
different botanic materials. The authors concluded that SFE
had proven to be a practical and powerful method for the
extraction of useful ingredients and pesticide residues from
natural products and food plants. They regarded as promising
the possibility of extracting both types of solutes separately
using the same extraction medium at different operating conditions, and concluded that a systematic and effective means
to reach the optimal extraction conditions were yet to come.
Lang and Wai (2001) discussed practical aspects of SFE
applications in sample preparation, selection of modifiers,
collection methods, on-line coupling techniques, means for
avoiding mechanical problems, and approaches to optimisation of SFE conditions. King (2002) reviewed analytical
supercritical extraction with carbon dioxide as the extracting agent from a wide array of sample types. Zougagh et al.
(2004) underlined the great analytical potential of SFE, tried
to identify reasons for its rare implementation by routine
analytical laboratories, and proposed ways to overcome the
shortcomings behind them.
Several papers were focused on particular topics in analytical SFE. Extensive revue on the use of SFE in food analysis was published by Anklam et al. (1998). The application
of SFE and SCF chromatography in forensic investigations
was reviewed by Radcliffe et al. (2000). Turner et al. (2001)
reviewed the applications of SFE and chromatography for
fat-soluble vitamin analysis, and, in the next review paper,
Turner et al. (2002) focused on the modes and optimised conditions for the collection of extracted analytes. Smith (2002)
published a literature review on extraction with superheated
water where the extraction of essential oils, flavours, and fragrances from plant materials is mentioned besides other materials. Pourmortazavi and Hajimirsadeghi (2007) discussed the
developments, modes, and applications of SFE in the isolation
of essential oils from plant matrices; showed how the solubility of the solute in the fluid, diffusion through the matrix, and
collection process affect their extraction yield; and compared
the SFE with conventional extraction methods. Mendiola et
al. (2007) reviewed the applications of pressurised solvents,
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both supercritical and liquid, in sample preparation for food

analysis, and concluded that these extraction techniques could
be used for routine analysis as fast, reliable, clean, and cheap
methods. There is, however, a clear need for their validation
before they can be applied as official methods substituting the
most laborious, time-consuming, and classical procedures.
The application of SC-CO2 in SFE of lipids and in food processing generally was reviewed by Sahena et al. (2009).
3. Plants and extracts

A hypothetical list of herbs and other plants subjected to SFE in
laboratories is getting longer every week, being extended particularly by the plants growing in Asia and Latin America. Table
1 shows the large range of both plants and extracted substances.
To keep its size acceptable, we have excluded the extraction of
non-native components as pesticides and herbicides (Lehotay
1997, Motohashi et al. 2000, Aguilera et al. 2005), although
the research in this field is promising. Also the extraction with
subcritical water (see, e.g., Cacace and Mazza 2006) and with
other pressurised solvents than CO2 was not included. Thus,
the references concern the extraction of plant components with
dense CO2, either pure or modified. Even so, the table could
not cover all the papers published on the topic because of their
large number. It is based on the data collected in the Institute of
Chemical Process Fundamentals, the Czech Republic, for more
than two decades and therefore it is not restricted to a certain
period of publication or selected literature sources.
The knowledge collected in the literature should certainly
not be omitted in further research on SFE.
4. Thermodynamic modelling of systems

vegetable solute + SC-CO2 + entrainer
The advantages of using SCFs as solvents are numerous and
lead to environmental, health and safety, and chemical benefits. That is why they are referred to as the green solvents for
the future. Furthermore, as discussed previously, the thermophysical properties of SCFs (high diffusivity, low viscosity,
density, and dielectric constant) can be fine-tuned by changes
of operating pressure and/or temperature, and thus SFE has
a great potential as a promising, efficient, and clean alternative method compared with the conventional methods of
distillation and extraction. Thus, there is a clear-cut need for
obtaining detailed knowledge that will allow the design and
optimisation of the environmentally benign SFE processes.
Thermodynamics of the phase equilibria is a vital part of this
knowledge, as the objects of SFE are usually very complex,
and can exhibit intricate phase behaviour. To predict correctly
and calculate efficiently the equilibria, a robust and reliable
thermodynamic modelling framework (TMF) must be available. The TMF comprises three main elements: a library of
thermodynamic parameters pertaining to pure substances and
binary interactions; thermodynamic models for mixture properties; and methods, algorithms, and numerical techniques
for solving the equilibrium relations.

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Flavour compounds, polyphenols

Oil, -carotene
Apple (Malus domestica) fruit, peels, pomace

Apricot (Prunus armeniaca) kernels, shells, bagasse,
pomace
Artemisia herba-alba (Artemisia sieberi) herb
Assafoetida (Ferula assa-foetida)

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Blessed thistle (Cnicus benedictus) leaves, flowering

tops
Black oil plant (Celastrus paniculatus) seed

Blackberry (Rubus fruticosus) seed
Blackseed (Nigella sativa) fruit
Birch (Betula pendula) leaves

Black caraway (Bunium persicum) fruit
Amino acids
Volatile oil, oil, antioxidants thymoquinone
and carvacrol
Oil, sesquiterpenes
Oil
Oil, volatile oil: antioxidants thymoquinone
and carvacrol
Sesquiterpene lactone cnicin
Zhang et al. 1998a

Then et al. 1998
Turkay et al. 1996, Fullana et al. 1999, Machmudah et al. 2005, Rao et al. 2007,
Kokoska et al. 2008
Kery et al. 1998
Botha and McCrindle 1999

Wang et al. 2004a
Piantino et al. 2008
Monteiro et al. 1997
Mi et al. 2005
Lin et al. 1999, Chang et al. 2007
Colombo et al. 1998
Hawthorne et al. 1989, Reverchon et al. 1993a, 1994b, Reverchon and Sesti Osseo
1994b, Lachowicz et al. 1996, 1997, Ehlers et al. 2001, Diaz-Maroto et al. 2002,
Gainar et al. 2002, Menaker et al. 2004, Mazutti et al. 2006, Leal et al. 2008
Klejdus et al. 2008
Pourmortazavi et al. 2005
Antioxidants: -tocopherol
Oil, tocopherols, squalene
Alkaloids: phenanthridone class
Michellamines
Diterpene lactones: andrographolide, etc.
Alkaloids: hyoscyamine, scopolamine
Volatile oil: anethole
Antioxidants
Volatile oil
Pigments, carotenoid bixin
Aloe vera (Aloe barbadensis) leaf skin, pulp, rind

Amaranth (Amaranthus caudatus, A. cruentus) seed
Amaryllidaceae sp.
Ancistrocladus korupensis leaves
Andrographis paniculata herb, leaves
Angels trumpet (Datura candida D. aurea) roots
Anise (Pimpinella anisum) fruit
Anise hyssop (Lophantus anisatus)
Anise verbena (Lippia alba, L. sidoides)
Annatto (Bixa orellana) seed
Avocado (Persea americana) fruit

Babchi (Psoralea corylitolia) seed
Baccharis dracunculifolia leaves
Bacuri (Platonia insignis) fruit shells
Bai zi (Archangelica dahurica) root
Baical skullcap (Scutellaria baicalensis) root
Barley (Hordeum vulgare) fruit
Basil, sweet basil (Ocimum basilicum) leaves
Vargas et al. 2010

Bajer et al. 2007, Venskutonis et al. 2008
Khajeh et al. 2004
Core et al. 1994, 1996, Henning et al. 1994
Calame and Steiner 1982, Passey and Gros-Louis 1993, Lack and Seidlitz 1994,
Marrone et al. 1998, Femenia et al. 2001
Hu et al. 2005
Bruni et al. 2001, 2002, He et al. 2003, Westerman et al. 2006
Queckenberg and Frahm 1994
Ashraf-Khorassani and Taylor 1997
Bo et al. 2000, Kumoro and Hasan 2008
Brachet et al. 1999
Stahl and Gerard 1982a, Ondarza and Sanchez 1990, Rodrigues et al. 2003a
Dapkevicius et al. 1996
Sousa et al. 2002, Stashenko et al. 2004, Braga et al. 2005
Chao et al. 1991, Degnan et al. 1991, Anderson et al. 1997, Silva et al. 1999,
2008a, Nobre et al. 2006
Bundschuh et al. 1988, Adil et al. 2007
Niewoudt and Botha 1998, Doker et al. 2004, Sanal et al. 2004, 2005, Ozkal et al.
2005, 2005c
Ghasemi et al. 2007
Khajeh et al. 2005
Volatile oil, lupenol

Flavonoids
Volatile oil
Volatile compounds, repellents
Oil, volatile oil
Volatile oil: camphor, 1-8 cineol

E-1-propenyl sec-butyl disulfide,
germacrene B
Oil
Psoralen, isopsoralen
Phenolic compounds
Oleoresin
Volatile oil
Flavonoids: baicalin, baicalein, wogonin
Vitamin E: tocopherols, tocotrienols
Volatile oil, cuticular waxes, antioxidants
References
Extract components
Abajeru (Chrysobalanus icaco) leaves

Agrimony (Agrimonia eupatoria, A. procera) leaves
Ajowan (Carum copticum) fruit
Alfalfa (Medicago sativa) germ, leaf, stem
Almond (Prunus dulcis) fruit, seed
Plants extracted with pure or modified carbon dioxide.
Plant part
Table 1
84
Volatile oil
Oil, carotenoids, tocopherols
Sesquiterpenes as petasin, isopetasin,
pyrrolizidine alkaloids
Volatile oil: acorone, isoacorone, -asarone
Isoquinoline alkaloids
Nut shell liquid, cardanols

Oxindole alkaloids
Volatile oil, nepetolactone, waxes
Volatile oil
Alkaloids chelidonine, berberine, coptisine
Volatile oil, fatty oil, furanocoumarins,
fatty acids
Tocopherols, tocotrienols
Volatile oil, active components:
-bisabolol, matricine, chamazulene;
flavonoids
Oil: free fatty acids, sterol; phenolic
compounds
Cashew (Anacardium Occidentale) pericarp

Cats claw (Uncaria tormentosa) root
Catnip (Nepeta catari, N. transcaucasica)
Cedar (Cedrus) wood
Celandine (Chelidonium majus) aerial part
Celery (Apium graveolens) seed, leaf, root
Cereals
Chamomile (Matricaria chamomilla syn. Chamomilla
recutita) flowers
Cherry (Prunus avium) seed, pomace
Carqueja (Baccharis trimera) aerial part

Carrot (Daucus carota L.) root, fruit
Volatile oil, pigments, fatty acids,

antioxidants
Volatile oil
Oil, carotenes, volatile oil, biologically
active substances
Cardamom (Elettaria cardamomum) seed
Cape gooseberry (Physalis peruviana)

Capillary wormwood (Artemisia capillaris) aerial part
Caraway (Carum carvi) seed, fruit
Bioactive compounds
Volatile oil: germacrene d-4-ol, germacrene D, bicyclogermacrene, -cadinene
Antioxidants
Capillarisin
Volatile oil: limonene, carvone; fatty oil
Marongiu et al. 2007e

Franca et al. 1999a
Steiner et al. 1998, Bodensieck et al. 2007
-ecdysone, antioxidants
Brazilian ginseng (Pfaffia paniculata, P. glomerata)

root
Bulnesia sarmientoi wood
Buriti (Mauritia flexuosa) fruit
Butterbur (Petasites hybridus) rhizomes
Wu et al. 2006
Yang et al. 2007
Stahl and Gerard 1982a, Stahl et al. 1984, Kallio et al. 1994, Sovova et al. 1994b,
Then et al. 1998, Baysal and Starmans 1999, Gamse and Marr 2000, Ahro et al.
2001, Cabizza et al. 2001, Sedlakova et al. 2003a
Pekhov and Goncharenko 1968, Naik et al. 1989, Gopalakrishnan and Narayanan
1991, Illes et al. 1998, Marongiu et al. 2004a, Hamdan et al. 2008
Vargas et al. 2006, Silva et al. 2009
Subra et al. 1994, 1998, Barth et al. 1995, Vega et al. 1996, Chandra and Nair
1997, Ranalli et al. 2004, Sun and Temelli 2006, Glisic et al. 2007a, Maxia et al.
2009
Shobha and Ravindranath 1991, Smith et al. 2003, Patel et al. 2006
Lopez-Avila et al. 1997a
Dapkevicius et al. 1996, Barth et al. 1998, Chotratanadilok and Clifford 1998
Hawthorne et al. 1988
Sarkozi et al. 2000, Then et al. 2000b
Moyler 1993, Peplonski et al. 1994, Catchpole et al. 1996a, Jarvenpaa et al. 1997,
Nguyen et al. 1998, Della Porta et al. 1998b, Papamichail et al. 2000, Dauksas et
al. 2002a
Fratianni et al. 2002
Stahl and Schutz 1978, Vuorela et al. 1990, Reverchon and Senatore 1994, Smith
and Burford 1994, Pekic et al. 1995, Tolic et al. 1996, Scalia et al. 1999, Zekovic
2000, Povh et al. 2001, Hamburger et al. 2004, Kaiser et al. 2004, Bajer et al.
2007, Kotnik et al. 2007, Zizovic et al. 2007a
Bernardo-Gil et al. 2001, Adil et al. 2008
Sewram et al. 1998, 2000

Marongiu et al. 2006c
Stahl and Keller 1983, Marongiu et al. 2005c, Dai et al. 2008
Bugatti et al. 1993
Laroze et al. 2010

Sargenti and Lancas 1997b, del Valle et al. 2004b, 2005b
Illes et al. 1994, Sensidoni et al. 1994, Andujar et al. 1999, Dauksas et al. 2002b,
Gomez and de la Ossa 2002, Kotnik et al. 2006, Lu et al. 2007, Soto et al. 2008
Leal et al. 2010
Antioxidants
Volatile oil: antioxidants; alkaloid boldine
Oil, -linolenic acid
Blueberry (Vaccinium sp.) residue after pressing

Boldo (Peumus boldus) leaves, bark
Borage (Borago officinalis) seed
Calamus (Acorus calamus, A. graminei) rhizomes

California poppy (Eschscholtzia californica) aerial
part
Cape ash (Ekebergia capensis) wood
Cape gold (Helichrysum splendidum) leaves
References
Extract components
Plant part
(Table 1 continued)

Authenticated
85
Simandi et al. 1996

Modey et al. 1996b
Choi et al. 1998b
Liu et al. 2005a
Senatore et al. 2004, Marongiu et al. 2009
Stahl and Gerard 1982a, Hawthorne et al. 1988, Miller et al. 1995, Marongiu et al.
2007d
Volatile oil, methyl chavicol

Cedrelone, phytosterols
Podophyllotoxin
Alkaloid sinomenine
Volatile oil, pyrethrins
Volatile oil: cinnamaldehyde
Plant part
Chervil (Anthriscus cerefolium) herb

Chinese mahogany, cedrela, toon (Cedrela sinensis
syn. Toona sinensis) wood, bark
Chinese mayapple (Dysosma pleiantha) roots
Chinese moonseed (Sinomenium acutum) vine stem
Chrysanthemum (Chrysanthemum cinerariifolium,
C. coronarium, C. segetum, C. flosculosus) aerial part
Cinnamon (Cinnamomum zeylanicum) and cassia
(C. cassia) bark
Volatile oil
Isoflavones, volatile oil
Cocaine
Cocoa butter, theobromine, caffeine;
pyrazines from roasted beans
Oil
Clove basil (Ocimum gratissimum) leaves

Clover, red (Trifolium pratense) leaves, root
Coca (Erythroxylum coca) leaves
Cocoa (Theobroma cacao) beans/nibs

Authenticated
Coconut palm (Cocos nucifera) copra, meal
Tangor murcote Citrus sinensis (hybrid) peel

Yuzu (Citrus junos) seed
Clary sage (Salvia sclarea) herb
Clivia (Clivia miniata) root
Cloudberry (Rubus chamaemorus) seed
Clove (Syzygium aromaticum, Eugenia caryophyllata)
buds
Taiwan tangerine (Citrus depressa) peel
Volatile oil
Volatile oil, carotenoids, tocopherols
Volatile oil, perillyl alcohol, carotenoids,
tocopherols
-Cryptoxanthin
Coumarins imperatorin, meranzin,
meranzin hydrate
Polymethoxyflavones: nobiletin,
tangeretin
Volatile oil
Oil, -sitosterol, squalene
Volatile oil: sclareol
Bioactive compounds
Oil, -carotene, volatile oil, tocopherols
Volatile oil: eugenol, caryophyllene,
eugenyl acetate
Lime (Citrus aurantifolia, C. latifolia) peel

Mandarin (Citrus reticulata) peel
Orange (sweet orange) (Citrus sinensis), bitter orange
(C. aurantium) peel
Satsuma, tangerine (Citrus unshiu) press cake
Shaddock (Citrus maxima) peel
Sargenti and Lancas 1998b

Ueno et al. 2008
Ronyai et al. 1999a
Sewram et al. 1998, 2001
Manninen and Kallio 1997, Manninen et al. 1997b
Stahl and Gerard 1982a, Naik et al. 1989, Gopalakrishnan et al. 1990, Huston and
Hong 1991, Hauptschott and Lentz 1993, Moyler 1993, Kollmannsberger and Nitz
1994, Reverchon and Marrone 1997, Della Porta et al. 1998a, Clifford et al. 1999,
Rodrigues et al. 2002, Ruetsch et al. 2003, Geng et al. 2007, Guan et al. 2007,
Martinez et al. 2007, Takeuchi et al. 2008
Leal et al. 2006
Klejdus et al. 2005, Tapia et al. 2007
Brachet et al. 1999, 2000
Rossi et al. 1993, Li and Hartland 1996, Sanagi et al. 1997, Saldana et al. 2000b,c,
2002, 2002a, Skerget and Knez 2001, Mohamed et al. 2002
Asis et al. 2006
Lee at al. 2010
Poiana et al. 1994, 1999, Kondo et al. 2000

Poiana et al. 1998, Giannuzzo et al. 2003, Yu et al. 2007
Calame and Steiner 1982, Sugiyama and Saito 1988, Hawthorne et al. 1989,
Langenfeld et al. 1992
Hawthorne et al. 1989, Atti-Santos et al. 2005
Illes et al. 1999b
Hawthorne et al. 1988, Mira et al. 1996, 1999, Sargenti and Lancas 1998a, Illes
et al. 1999b, Berna et al. 2000, Lee et al. 2000, 2001
Lim et al. 2003
Teng et al. 2005
References
Extract components
(Table 1 continued)
Volatile oil: bergapten

Volatile oil, flavonoid naringin, limonoids
Volatile oil
Citruses
Bergamot (Citrus bergamia) peels, leaves, seed
Grapefruit (Citrus paradisi) flavedo, peel, seed
Lemon (Citrus limonum) peel
86
Sewram et al. 1998

Schneider et al. 1995
Sousa et al. 2005
Naik et al. 1989, Eikani et al. 1999a, Heikes et al. 2001
Eller et al. 2011
de Azevedo et al. 2003
Then et al. 1998a
Marongiu et al. 2003b, Poli et al. 2003
Vasudevan et al. 1997
Fuh et al. 1996
Peplonski et al. 1994, Gamse and Marr 1999, Simandi et al. 2002
Dean et al. 1998b, Wang et al. 2008a
DAndrea et al. 2007
Cao et al. 2007, Xiao et al. 2007
Gamse and Marr 2000
Liu et al. 1995
Sun et al. 2006
Vilegas et al. 1993
Volatile oil: biocides

Volatile oil
Oleoresin: -amyrin, -sitosterol
Tanshinones
Insecticide rotenone
Volatile oil
Volatile oil
Diosgenin
Ferulic acid
Pimpinelin, isobergapten, furocoumarins
psoralen, bergapten, isopimpinelin,
triterpenes
Wax
Volatile oil

Authenticated
Douglas-fir (Pseudotsuga menziesii) bark

Dragonhead (Dracocephalum moldavica) herb
Cranberry (Vacciniumk sp.) residue after pressing

Creeping spilanthes (Spilanthes americana) flowers,
leaves, and stems
Crossberry (Grewia occidentalis) wood
Croton matourensis bark
Croton zehntneri leaves
Cumin (Cuminum cyminum) seed
Cuphea (Cuphea viscosissmaC. lanceolata) seed
Cupuacu (Theobroma grandiflorum) seed
Currant, red and black (Ribes rubrum, R. nigrum) seed
Curry plant (immortelle) (Helichrysum italicum)
aerial part
Curry tree (Murraya koenigii syn. Chalcas koenigii)
leaves
Cypress, red (Taxodium distichum) sawdust
Dandelion (Taraxacum officinale) leaves, roots
Danshen (Salvia miltiorrhiza) root, rhizomes
Derris (Derris elliptica) root
Di qian (Marchantia convoluta) leaves
Dill (Anethum graveolens) seed
Dioscorea nipponica tuber
Dong quai (Archangelica sinensis) root
Dorstenia bryoniifolia rhizomes
McDonald et al. 1983

Hawthorne et al. 1993, Kakasy et al. 2006
Laroze et al. 2010

Stashenko et al. 1996b
List et al. 1983, 1984a, Snyder et al. 1984, Kuk and Hron 1994, Taylor et al. 1997,
Bhattacharjee et al. 2007
Calame and Steiner 1982, Cao et al. 2000
Ellington et al. 2003
Volatile oil
Alkaloids: colchicine, 3-dimethylcolchicine, colchicoside
Antioxidants
Volatile oil: sesquiterpenes, heavy hydrocarbons, amides, insecticide spilanthol
Bioactive compounds
Maravuic acid
Volatile oil
Volatile oil: cuminaldehyde, cymol
Fatty oil
Fat
Oil, linolenic acids
Volatile oil: neryl acetate, antioxidants
Cotton (Gossypium) seed
Cratoxylum prunifolium leaves

Crocus, autumn (Colchicum autumnale) seed
Volatile oil: -caryophyllene

Volatile oil, fatty oil, antioxidants: tocopherols, flavonoides
Cordia verbenacea leaves

Coriander (Coriandrum sativum) fruit, seed
Triterpenes: friedelin, betulin, -sitosterol,

sitost-4-en-3-one
Oil
Zosel 1978, Brunner 1984, Sugiyama et al. 1985, Peker et al. 1992, Roethe et al.
1992, Pietsch et al. 1998, Ramos et al. 1998, del Valle and Aguilera 1999, Oliveira
et al. 1999, 2001, Sarrazin et al. 2000, Araujo and Sandi 2006, de Azevedo et al.
2008a, 2008b,c
Quispe-Condori et al. 2008
Kallio and Kerrola 1992, Kerrola and Kallio 1993, Catchpole et al. 1994, 1996a,
1997, Anitescu et al. 1997, Ribeiro et al. 1998, Then et al. 1998a, Illes et al. 2000,
Yepez et al. 2002, Grosso et al. 2008
Castola et al. 2005
Caffeine, aroma, diterpenes cafestol and

kahweol, lipids, chlorogenic acids
Coffee (Coffea) beans
Cork oak (Quercus suber) bark
References
Extract components
Plant part
(Table 1 continued)
87

Authenticated
Ginseng (Panax ginseng) root hair, leaves, seed
Ginkgo, maidenhair tree (Ginkgo biloba) leaves
Garden angelica (Angelica archangelica, A. dahurica,

A. sinensis) root, fruit
Garlic (Allium sativum)
Geranium (Pelargonium graveolens) flowers, leaves,
stems, stalk
Giant fennel (Ferula communis) flowerheads
Ginger (Zingiber officinalis) Rhizomes
Frankincense (Boswellia thurifera, B. carterii) resin
Volatile oil, sesquiterpene lactone

parthenolide
Feverfew (Tanacetum parthenium syn.

Chrysanthemum partheniu, syn. Pyrethrum parthenium) flowers, seeds
Flax (Linum usitatissimum) seed, fibre
Terpene trilactones ginkgolides, bilobalide;

flavonoids
Oil, ginsenosides; saponins
Volatile oil: gurjunenes, selinenes

Volatile oil, gingerols, oleoresin, antioxidants, anticancer substances
Allicin
Volatile oil
Volatile oil: incensole acetate, octanol

acetate, incensole, phyllocladene
Volatile oil, furanocoumarins
Oil; wax: nutraceutical octacosanol
Volatile oil, evodiamine, rutaecarpine

Volatile oil
Volatile oil: anethol, estragol, fenchone;
fatty oil; flavonoids
Oil, -linolenic acid
Evodia (Evodia rutaecarpa) herb, fibre

Felty germander (Teucrium polium) leaves, flowers
Fennel (Foeniculum vulgare) seed
Eucalyptus (Eucalyptus globulus, E. camaldulensis,

E. citriodora, E. spathulata, E. microtheca) leaves,
wood
Evening primrose (Oenothera biennis) seed
Wang et al. 2001, Liu et al. 2005a, Wood et al. 2006, Zhang et al. 2006a,
Luo et al. 2007
Marongiu et al. 2005a

Pekhov and Goncharenko 1968, Krukonis 1985, Chen et al. 1986, Naik et al. 1989,
Kandiah and Spiro 1990, Moyler 1993, Bartley and Foley 1994, Bartley 1995,
Yonei et al. 1995a, Roy et al. 1996a, Badalyan et al. 1998, Monteiro et al. 1998,
Nguyen et al. 1998, Bartley and Jacobs 2000, Rodrigues et al. 2002, Zancan et
al. 2002, Catchpole et al. 2003, Leal et al. 2003, Martinez et al. 2003, Liu et al.
2005a, Balachandran et al. 2006, 2007
Choi et al. 2002c, Chiu et al. 2002, Yang et al. 2002, Mannila et al. 2003
Nykanen et al. 1991, Kerrola and Kallio 1994, Kerrola et al. 1994b, Gawdzik et al.
1996, Doneanu and Anitescu 1998, Paroul et al. 2002
Calvey et al. 1994, 1997, Rybak et al. 2004, del Valle et al. 2008
Reis Machado et al. 1993, Peterson et al. 2006, Gomes et al. 2007
Then et al. 1998a, Barthet and Daun 2002, Bozan and Temelli 2002, Morrison et
al. 2006
Ma et al. 1991, Marongiu et al. 2006e
Hawthorne et al. 1989, Garau and Pittau 1998, Della Porta et al. 1999, Fadel et
al. 1999, Gonzales-Vila et al. 2000, Francisco et al. 2001, Rodrigues et al. 2002,
Rozzi et al. 2002a, El-Ghorab et al. 2003, Ashtiani et al. 2007
Favati et al. 1991, Catchpole et al. 1994, King et al. 1997, Gawdzik et al. 1998,
Zizovic et al. 1998, Kotnik et al. 2006
Ma et al. 1991, Liu et al. 2010
Eikani et al. 1999b
Naik et al. 1989, Then et al. 1998a, Reverchon et al. 1999, Simandi et al. 1999,
Yamini et al. 2002, Coelho et al. 2003, Damjanovic et al. 2005, Diaz-Maroto et
al. 2005, Moura et al. 2005, Bajer et al. 2007, Zizovic et al. 2007a, Takeuchi et al.
2008
Smith and Burford 1992, 1994, Kery et al. 1998, 1999, Kaplan et al. 2002, Cretnik
et al. 2005
de Vasconcelos et al. 2000, Mossi et al. 2004, 2010
Volatile oil: -pinene

Oleoresin
Coumarin
Ephedrine and its derivatives, nonacosan10-ol
Triterpenes friedelan-3-ol, friedelin; phytol,
squalene, limonene, tocopherols, stigmasterol, dodecanoic acid, geranyl acetate
Volatile oil: 1,8-cineole; lipids, antioxidants
Eastern ferulago (Ferulago nodosa L.)

Elder (Sambucus nigra) fruit
Emburana (Torresea cearensis) seed
Ephedra (Ephedra sinica) aerial part
Espinheira santa (Maytenus aquifolium, M. ilicifolia)

leaves
References
Ruberto et al. 1999
Peplonski et al. 1994
Rodrigues et al. 2008
Choi et al. 1996, 1997, 1999b, Kim and Yoo 2000
Extract components
Plant part
(Table 1 continued)
88
Squalene, stigmasterol
Digoxin
Volatile oil
Coumarin, kaurenoic acid, lupeol kipeol
acetate
Caffeine, methylxanthines
Volatile oil
Oleoresin
Aucubin
Greater duckweed (Spirodela polyrhiza) entire plant

Grecian foxglove (Digitalis lanata) leaves
Greek sage (Salvia triloba, S. fruticosa)
Guaco (Mikania glomerata) leaves
King et al. 2001

Machmudah et al. 2009a
Takahashi et al. 2006
Raghuram Rao et al. 1992, Sastry and Mukhopadhyay 1994
Friedrich et al. 1984, Friedrich 1988, Salgin et al. 2004, 2007
Moyler 1993, Chatzopoulou 2002, Damjanovic et al. 2003, 2006,
Marongiu et al. 2003a, 2004c, 2006c, Park et al. 2004, Pourmortazavi et al. 2004,
Barjaktarovic et al. 2005, Glisic et al. 2007b, Medini et al. 2008
Carotenoids
Volatile oil
Oil
Volatile oil, bioactive compounds,
antimicrobials
Volatile oil
Hydrocarbons
Inula (Inula viscosa, I. graveolens) leaves

Iranian spurge (Euphorbia macroclada) leaves and
stalks (as petro-crops)
Ironweed (Vernonia galamensis) seed
Japanese pepper, Sichuan pepper (Xanthoxylum
piperitum)
Japanese persimmon (Diospyros kaki) peels
Jasmine (Jasminum officinalis, J. grandiflorum)
flowers
Jojoba (Simmondsia californica, S. chinensis) seed
Juniper (Juniperus communis, J. rigida, J. oxycedrus,
J. phoenica) fruit, leaves, wood
Oil, vernolic acid
Sanshool compounds
Oleoresin
Resveratrol, piceid, emodin, physcion
Volatile oil, antioxidants
Horsetail (Equisetum giganteum)

Hu zhang (Polygonum cuspidatum) herb, root
Hyssop (Hyssopus officinalis)
Hamburger et al. 2004

Bernardo-Gil et al. 2002, Ozkal et al. 2005b,c, Bernardo-Gil and Casquilho 2007
Holser and Bost 2004, Chan and Ismail 2009
Vasudevan et al. 1997
Pekhov and Goncharenko 1968, Hubert and Vitzthum 1978, Laws 1979, Sharpe
and Crabb 1980, Sharpe et al. 1980, Gardner 1982, Vollbrecht 1982, Langezaal et
al. 1990, Daoud and Kusinski 1992, Verschuere et al. 1992, Moyler 1993, Imbert
et al. 1998, del Valle and Aguilera 1999, del Valle et al. 2003b, Zekovic et al.
2007, Roj and Skowronski 2006
Michielin et al. 2005
Wenli et al. 2005, Yu et al. 2005, Lu et al. 2006, Machmudah et al. 2009b
Kerrola et al. 1994a, Dapkevicius et al. 1996, Langa et al. 2009, Kazazi et al.
2007, Babovi et al. 2010
Ozcan and Ozcan 2004
Lipophilic compounds
Oil, sterols, tocopherols
Oil, antioxidants
Volatile oil, biocides
Volatile oil, resins, bitter acids, waxes, and
lipids
Mehr et al. 1996, Saldana et al. 2000b,c, 2002b,c

Sagrero-Nieves et al. 1994a
Fernandez et al. 2006
Li et al. 2009
Sovova et al. 1994a, Gomez et al. 1996, Murga et al. 1998, 2000, Palma and
Taylor 1999, Palma et al. 1999, 2000, Arce et al. 2001, Pascual-Marti et al. 2001,
Palenzuela et al. 2002, 2004, Cao and Ito 2003, Ashraf-Khorassani and Taylor
2004, Louli et al. 2004b, Beveridge et al. 2005, Chafer et al. 2005, Bravi et al.
2007, Fiori 2007, Campos et al. 2008, da Silva et al. 2008a, Fiori et al. 2008,
Freitas et al. 2008a, 2008b
Choi et al. 1997
Moore and Taylor 1995, 1996, 1997
Ronyai et al. 1999b
Vilegas et al. 1997, Celeghini et al. 2001
Fatty oil, linoleic acid, tocopherols, tocotrienols, tannins, glycosides, polyphenols:

(+)-catechin, (-)-epicatechin, rutin, quercetin, resveratrol antioxidants
Grape (Vitis vinifera) seed, pulp, skin
Guaran (Paulinia cupana) seed

Guava (Psidium guajava) leaves
Guinea pepper (Aframomum melegueta) seed
Gutta-percha tree (hardy rubber tree) (Eucommia
ulmoides) seed
Hawthorn (Crataegus sp.)
Hazel (Corylus avellana) nut
Hibiscus (Hibiscus esculentus, H. different ssp.) seed
Holy basil, tulsi (Ocimum sanctum) leaves
Hop (Humulus lupulus) flowers
References
Extract components
Plant part
(Table 1 continued)

Authenticated
89
Pereira and Meireles 2007

Sovova et al. 2008
Ohira and Yatagai 1993
Ronyai et al. 1998b, Crabas et al. 2003, Baumann et al. 2004, Hamburger et al.
2004, Campos et al. 2005, Danielski et al. 2007, Petrovic et al. 2007, Zizovic et al.
2007a, Nagy et al. 2008
Reverchon 1992, Reverchon et al. 1993, Reverchon and Sesti Osseo 1994b,
Dapkevicius et al. 1996, Vagi et al. 2002, 2005a,b, Rodrigues et al. 2003a,
El-Ghorab et al. 2004
Caffeine
Flavonoids
Volatile oil, tocopherols, oil
Volatile oil, pasty products, antioxidants,
antimicrobials
Volatile oil, antioxidants
Volatile oil
Volatile oil
Volatile oil
Glycyrrhizin
Volatile oil, wax
Sesquiterpenoids
Oil, amygdalin, -sitosterol
Volatile oil: ligustilide
Oil, volatile oil
Sweeteners: mogrosides
Oil, alkaloids
Oil
Indole alkaloids vindoline, vinblastine
Sesquiterpene lactones pathenolide, costunolide, sesquiteprene cyclocolorenone,
antioxidants, neolignans honokiol, magnolol
Oil, sterols, ferulate-phytosterol esters,
phospholipids, beauvericin
Terpenoids, furocoumarins psoralen,
bergapten
Oleoresin
Ecdysterone, cynaropicrin
Maltol (antifungal activity)
Oleoresin, volatile oil, triterpenoids:
faradiol monoesters, monool taraxasterol,
lupeol, -amyrin; lutein
Volatile oil, cuticular waxes, pigments,
antimicrobials, antioxidants: ursolic acid,
carnosic acid, carnosol
Kola tree (Cola) nuts

Kudzu (Pueraria lobata) root
Laurel, daphne (Laurus nobilis) leaves, seed
Lavender (Lavandula intermedia, L. stoechas,

L. augustifolia) flowers
Lemon balm (Melissa officinalis)

Lemon beebalm (Monardia citriodora)
Lemon verbena (Aloysia triphylla) leaves
Lemongrass (Cymbopogon citratus) leaves, stems
Licorice (Glycyrrhiza glabra)

Lilac (Syringa) flowers
Lindera strychnifolia
Loquat (Eriobotrya japonica) seed
Lovage (Levisticum officinale) seed, leaves, and roots
Love-in-a-mist (Nigella damascena) seed
Luohan guo (Siraitia grosvenorii) fruit
Lupine (Lupinus)
Macadamia (Macadamia integrifolia) nuts
Madagascar periwinkle (Catharanthus roseus)
Magnolia (Magnolia grandiflora, M. virginiana,
M. officinalis) bar, root
Mama cadela (sweet cotton plant) (Brosimum gaudichaudii) bark, roots

Mango (Mangifera indica) leaves
Maral root (Leuzea carthamoides syn. Rhaponticum
carthamoides) root and leaves
Maries fir (Abies mariesii) leaves
Marigold (Calendula officinalis) flowers

Authenticated
Marjoram (Majorana hortensis syn. Origanum majorana L.) leaves
Christianson et al. 1984, List et al. 1984b, Wilp and Eggers 1991, Taylor et al.
1993, Fontan et al. 1994, Ronyai et al. 1998a, Taylor and King 2000, 2002,
Ambrosino et al. 2004, Nagy et al. 2008
Vilegas et al. 1993
Lopez-Avila and Benedicto 1997, Ashraf-Khorassani et al. 1999, Catchpole et al.

2000, 2002
Ndiomu and Simpson 1988
Wang et al. 2008b
Ozek et al. 1998, Caredda et al. 2002, Gomez-Coronado et al. 2004, Beis and
Dunford 2006, Santoyo et al. 2006a, Marzouki et al. 2008
Simandi et al. 1993, Adasoglu et al. 1994, Walker et al. 1994b, Reverchon et al.
1995c, Dapkevicius et al. 1996, Fekete et al. 1996, Oszagyan et al. 1996, Akgun et
al. 2000, 2001, Flores et al. 2005, Zorca et al. 2006
Ribeiro et al. 2001, Rozzi et al. 2002a, Ziakova et al. 2002, Marongiu et al. 2004d
Rozzi et al. 2002a
Crabas et al. 2003, Pereira and Meireles 2007
Ndiomu and Simpson 1988, Sargenti and Lancas 1997a, Carlson et al. 2001, Rozzi
et al. 2002a, Marongiu et al. 2006a, Ha et al. 2008
Kim et al. 2004, 2005
Calame and Steiner 1982
Li et al. 2002
Kawahito et al. 2008, Machmudah et al. 2008b
Dauksas et al. 1998, 1999, 2002a, Menaker et al. 2004
Dauksas et al. 2002c
Xia et al. 2008
Stahl et al. 1981, Nossack et al. 2000
Silva et al. 2008a
Song et al. 1992, Choi et al. 2002a
Castaneda-Acosta et al. 1995, Chandra and Nair 1995, Suto et al. 1997, Dean et al.
1998a, Paltoo et al. 1999, Cheah et al. 2010
Oleoresin, kava lactones
Kava (Piper methysticum) herb, stems, root
Maize (corn) (Zea mays) bran, germ
References
Extract components
Plant part
(Table 1 continued)
90
Oil, -sitosterol, tocopherols

Oil, tocopherols, phenols, squalene
Oleoresin, flavour, sulphur, quercetin

Volatile oil
Okra (Abelmoschus esculentes syn. Hibiscus esculentes) seed

Olive tree (Olea europaea) leaves, husk, pomace
Onion (Allium cepa) bulb, skin
Orange jasmine (Murraya paniculata) flowers
Esquivel and Bernardo-Gil 1993, de Lucas et al. 1998, 2002a,b, 2003, Le Floch
et al. 1998, Esquivel et al. 1999b, Ibanez et al. 2000a, Stavroulias and Panayioutou
2005, del Valle et al. 2006
Calvey et al. 1994, 1997, Guyer and Sinha 1995, Dron et al. 1997, Sass-Kiss et al.
1998, Simandi et al. 2000, Martino and Guyer 2004
Marquina-Chidsey et al. 2000
Acorn oil, sterols, tocopherols, waxes

Oil, fatty acids, -tocopherol, - and
-carotene, squalene, sterols
Cernia et al. 1994, Johnson and Morgan 1997, Ambrosino et al. 1999,
Tonthubthimthong et al. 2001, 2004, Mongkholkhajornsilp et al. 2005
Wang et al. 2007, Suo and Wang 2010
Pekhov and Goncharenko 1968, Hubert and Vitzthum 1978, Moyler 1993, Nguyen
et al. 1998, Spricigo et al. 1999, 2001, Machmudah et al. 2006
Lopes et al. 1998, Lopes and Bernardo-Gil 2005, Bernardo-Gil et al. 2007
Birtigh et al. 1995, Franca and Meireles 2000, Hassan et al. 2000, Rahman et al.
2001, Norulaini et al. 2004a,b, 2008, Lau et al. 2006a,b, 2007, 2008, Zaidul et al.
2006a,b, 2007a,b
Andras et al. 2005
Barthet and Daun 2002

Ma et al. 1991, Marongiu et al. 2005c
Garau and Pittau 1998
Sun et al. 2002
del Valle and Aguilera 1989, Sakaki et al. 1990, Young and Games 1993, Abdulah
et al. 1994, Walker et al. 1999, Zhang et al. 2006a, Kitzberger et al. 2007, 2009
Dean and Liu 2000

Joo et al. 1994, Choi et al. 1997
Insecticides, pharmaceuticals: azadirachtin

A, nimbin, salannin, cuticular waxes
Oil: unsaturated fatty acids
Volatile oil, nutmeg butter
Hydrocarbons, antimicrobials, antioxidants

and fungicides
Paeonol
Triterpene -amyrin acetate, antioxidants
-carotene, -tocopherol
Oleoresin, oil, ergosterol, carboxylic and
fatty acids, antioxidants, substances of
antimicrobial activity, polysaccharides
Oil
Volatile oil
Volatile oil
Alkylamides
Oak (Quercus rotundifolia, Q. suber) fruit

Oil palm tree (Elaeis guineensis) kernel, leaves,
mesocarp fibres
Nitraria tangutorum seed

Nutmeg (Myristica fragrans) nutmeg, mace
Mustard (Brassica sp.) seed

Myrrh herb (Commiphora molmol, C. myrrha)
Myrtle (Myrtus communis) leaves
Narrow-leaf purple coneflower (Echinacea
angustifolia) aerial part
Neem tree (Azadirachta indica) seed, kernel
Mushrooms and fungi
Moutan (Paeonia suffruticosa) cortex

Mulberry tree (Morus alba) bark, leaves, root bark
Moso-bamboo (Phyllostachys heterocycla)
Senich et al. 1974, Barton et al. 1992, Goto et al. 1993, Hawthorne et al. 1993,
Simandi et al. 1993, Reverchon et al. 1994a, Roy et al. 1996c, Barth et al. 1998,
Aleksovski et al. 1999, Ammann et al. 1999, Pino et al. 1999, Reis-Vasco et al.
1999, 2000, Kim and Hong 2000, Qafisheh and Barth 2000, Kubatova et al. 2001,
Marongiu et al. 2001, Pop and Barth 2001, Diaz-Maroto et al. 2002, Aghel et al.
2004, Zizovic et al. 2005, Al-Marzouqi et al. 2007, Gomez-Prieto et al. 2007,
Zekovic et al. 2009
Quitain et al. 2004
Congiu et al. 2002

Ziemons et al. 2005, 2007
Sewram et al. 1998, Turner and McKeon 2002
Volatile oil, waxes

Volatile oil
Sesquiterpene lactone tagitinin C
Bioactive compounds; fatty oil, cis-vaccenic acid
Volatile oil, cuticular waxes, squalene,
carotenoids
Mastic (Pistacia lentiscus) leaves, berries

Medlar (Mespilus germanica) seed
Mexican sunflower (Tithonia diversifolia) aerial part
Milkweed (Asclepias fruticosa) root, seed
Mint (Mentha piperita, M. spicata, M. pulegium,

Romanian mint hybrid) leaves, flowers
References
Extract components
Plant part
(Table 1 continued)

Authenticated
91
Krukonis 1985, Pino et al. 1997, Marongiu et al. 2005b

McDonald et al. 1983, Orav et al. 1998, Ruivo et al. 2000, Duquesnoy et al. 2007,
Braga et al. 2008
Ahmad et al. 1994
Viana et al. 2003
Balaban et al. 1998, Palazoglu and Balaban 1998, Goli et al. 2005
Filho et al. 2008
Weinhold et al. 2008
Abbasi et al. 2008a,b
Stahl and Willing 1980, Ndiomu and Simpson 1988, Janicot et al. 1990, Then et
al. 2000, Bozan and Temelli 2003
Xanthones, flavanones, isoflavonoids:

osajin, pomiferin, lupeol, and butyrospermol esters
Ecdysterone
2-Acetyl-1-pyrroline, volatile oil
Oil, tocopherols, capsaicin alkaloids,
carotenoids
Volatile oil: estragole

Glycosylated flavonoids
Polyphenols
Oil
Oil
Oleoresin: volatile oil, piperine
Oil
Volatile oil: phellandrenes, limonene,
elemol, -eudesmol
Volatile oil: eugenol
Volatile oil, resin, fatty acids; manoyl
oxide; phenolic antioxidants
Oleoresin
Lapachol, lapachones
Lipids, antioxidants, volatile oil
Carotenoids lycopene, rubixanthin
Triterpenes, phytosterols, methyl salicylate
Volatile oil, fatty oil, phenolic compounds
Oil, tocol, opium alkaloids thebaine,
codeine, morphine
Osage orange tree (Maclura pomifera) root bark, fruit
Parsley (Petroselinum crispum, Apium petroselinum)

seed, leaves
Passion (Passiflora edulis) fruit, leaves
Peach (Prunus persica) pomace
Peanut (Arachis hyprogaea)
Pecan (Carya illinoensis) kernels, halves

Pepper, black (Piper nigrum) fruit
Physic nut (Jatropha curcas) seed

Pepper tree (Schinus molle)
Pimento, allspice, Jamaica pepper (Pimenta dioica)

berries, leaves
Pine (Pinus palustris, P. sylvestris, P. pinaster,
P. nigra) wood, needles, bark
Pinecone ginger (Zingiber zerumbet)
Pink trumpet tree (Tabebuia avellanedae) wood
Pistacia (Pistacia vera, P. lentiscus) nuts, hull
Pitanga (Eugenia uniflora) fruit pulp
Polygala cyparissias root, stems, leaves
Pomegranate (Punica granatum) seed
Poppy (Papaver bracteatum) seed, straw
Moraes et al. 1997

Adil et al. 2007
Snyder et al. 1984, Goodrum and Kilgo 1987, King and Catchpole 1993, Lancas et
al. 1994, Santerre et al. 1994, Goodrum et al. 1996
Maness et al. 1995, Zhang et al. 1995a, Alexander et al. 1997, Li et al. 1999
Hubert and Vitzthum 1978, Calame and Steiner 1982, Vidal and Richard 1987,
Ferreira et al. 1993, 1999, Sovova et al. 1995, Nguyen et al. 1998, Skerget and
Knez 2001, Ferreira and Meireles 2002, Catchpole et al. 2003, Perakis et al. 2005,
Izadifar and Abdolahi 2006, Li et al. 2006
Machmudah et al. 2008b
Marongiu et al. 2004b
Zheng et al. 2008

Laohakunjit and Noomhorm 2004, Bhattacharjee et al. 2005
Hubert and Vitzthum 1978, Coenen 1983, Coenen and Kriegel 1984, Yao et al.
1994, Peusch et al. 1997, Nguyen et al. 1998, Skerget et al. 1998, Illes et al. 1999a,
Jaren-Galan et al. 1999, Sato et al. 1999, Weathers et al. 1999, Gnayfeed et al.
2001, Skerget and Knez 2001, Ambrogi et al. 2002, Daood et al. 2002, Catchpole
et al. 2003, del Valle et al. 2003a, 2003c, Duarte et al. 2004, Perva-Uzunalic et al.
2004, Uquiche et al. 2004, 2005, Fernandez-Trujillo 2008, Nagy et al. 2008, Nagy
and Simandi 2008, Tepic et al. 2009, Richins et al. 2010, Li et al. 2011
Naik et al. 1989, Della Porta et al. 1998b, Then et al. 1998a, Louli et al. 2004a
Ondarza and Sanchez 1990, Dapkevicius et al. 1996, Gaspar et al. 1998, 2000,
2001, 2003, Simandi et al. 1998, Diaz-Maroto et al. 2002, Gaspar 2002, Leeke et
al. 2002, Menaker et al. 2004, Rodrigues et al. 2004, Lu et al. 2005, Cavero et al.
2006, Santoyo et al. 2006a
Djarmati et al. 1998, da Costa et al. 1999
Volatile oil, cuticular waxes, resinoid compounds, antioxidants
Oregano, wild marjoram (Origanum vulgare, O.

virens) leaves, bracts
Ox knee (Achyranthes bidentata) root

Pandan (Pandanus amaryllifolius) leaves
Paprika, red pepper (Capsicum annuum), and chillies
(Capsicum frutescens) fruit
References
Extract components
Plant part
(Table 1 continued)
92

Authenticated
Volatile oil
Volatile oil, waxes
Volatile oil: p-cymene, -phellandrene,
-terpinene, thymol methyl ether, dill apiole
Oil, carotenoids, tocopherols
Ridolfia (Ridolfia segetum) different aerial parts

Rock rose (Cistus ladanifer) leaves
Rock samphire (Crithmum maritimum) aerial part

Authenticated
Alkaloids
Volatile oil
Rue (Ruta graveolens) aerial part, root

Russian sage (Perovskia atriplicifolia) aerial part
Rosemary (Rosmarinus officinalis) leaves
Hexadecanoic acid, 9,12-octadecadienoic

acid, heneicosane, heptacosane
Volatile oil, phenolic diterpene antioxidants: carnosic acid, carnosol, favonoids,
cuticular waxes, antimicrobials
Rose of Jericho (Anastatica hierochuntica) aerial part
Rose: wild dog rose and sweet briar rose (Rosa canina,
R. rubiginosa) fruit, seed and peel
Oil, antioxidants
Oil (bioactive agent)
Oil, triacylglycerols, free fatty acids,
oryzanols, tocopherols, sterols, waxes;
aroma
Raspberry (Rubus idaeus) seed, residue after pressing

Red cedar (Juniperus virginiana) wood chips
Rice (Oryza sativum) bran, corn
Rape, canola (Brasica napus, B. campestris) seed
Rain daisy (Dimorphotheca pluvialis) seed
Hawthorne et al. 1988, Reverchon and Senatore 1992, Reverchon et al. 1993,
Reverchon and Sesti Osseo 1994b, Walker et al. 1994b, Mendes et al. 1995,
Coelho et al. 1997, Tena et al. 1997, Lopez-Sebastian et al. 1998, Bauman et al.
1999, Ibanez et al. 1999, 2000b, Bicchi et al. 2000, Senorans et al. 2000, Leal et
al. 2003, Ramirez et al. 2004, Carvalho et al. 2005, Presti et al. 2005, Santoyo et
al. 2005, Bajer et al. 2007, Celiktas et al. 2007, Babovi et al. 2010
Stashenko et al. 2000
Illes et al. 1997, del Valle et al. 2000a, 2004, 2006, Eggers et al. 2000, Reverchon
et al. 2000, del Valle and Uquiche 2002, Szentmihalyi et al. 2002, Hegel et al.
2007, Machmudah et al. 2007, 2008a,b, Tozzi et al. 2008
Norulaini et al. 2009
Stahl et al. 1980, Bunzenberger et al. 1983, Brunner 1984, Bulley et al. 1984,
Eggers et al. 1985, Lee et al. 1986, King et al. 1987, Fattori et al. 1988, Temelli
1992, Taylor et al. 1993, 1997, Walker et al. 1994a, Dunford and Temelli 1995,
1997, Goodrum et al. 1996, Montanari et al. 1996, Bruhl and Matthaus 1999,
Matthaus and Bruhl 1999, 2001, Barthet and Daun 2002, Luque-Garcia and de
Castro 2004, Germain et al. 2005, del Valle et al. 2006, Jenab et al. 2006, Dong
and Walker 2008, Sun et al. 2008
Then et al. 1998a, Laroze et al. 2010
Eller and King 2000, Eller and Taylor 2004
Ramsay et al. 1991, Saito et al. 1991, Garcia et al. 1996, King et al. 1996, Shen
et al. 1996, 1997, Kuk and Dowd 1998, Kim et al. 1999a, Xu and Godber 2000,
Bhattacharjee et al. 2003, Perretti et al. 2003, Danielski et al. 2005, Sarmento et
al. 2006, Sparks et al. 2006, Balachandran et al. 2008, Chen et al. 2008a,b, Wang
et al. 2008a
de Lucas et al. 1999, Rincon et al. 2000
Muuse et al. 1994, Cuperus et al. 1996
Araujo et al. 2000

Catchpole et al. 2000, 2002
Stahl and Schutz 1980b, Bunzenberger et al. 1983, Pan et al. 1995, Otterbach and
Wenclawiak 1999, Kiriamiti et al. 2003a,b, OMahony et al. 2003
Bicchi et al. 1991
Oil
Alkylamides
Insecticides pyrethrins
Pyrrolizidine alkaloids: senecionine,
seneciphylline
Oil, tocopherols, dimorphecolic acid,
tri- and di-dimorphecolin
Oil, polyunsaturated fatty acids, phospholipids, phenolic acids
Devittori et al. 2000

Bernardo-Gil and Lopes 2004, Yu et al. 2004, Seo et al. 2005, Nagy et al. 2008
Oil
Oil, carotenoids
Proso millet (Panicum miliaceum) bran

Pumpkin (Cucurbita ficifolia, C. moschata) flesh,
seed
Pupunha (Guilielma speciosa) fruit
Purple coneflower (Echinacea purpurea) aerial part
Pyrethrum (Chrysanthemum cinerariaefolium) flowers
Ragwort (Senecio inaequidens, S. cordatus)
References
Extract components
Plant part
(Table 1 continued)
93
Oil, -tocopherol, antioxidants, lignans

Volatile oil
Alkaloid: monocrotaline
Sapogenins
Oil, tocopherols, phospholipids, isoflavones
daidzein, genistein, phytosterols, phenolic
compounds
Volatile oil
Spiked thyme (Thymbra spicata)
Tropane alkaloids: hyoscamine, scopolamine salts

Oil, polyunsaturated fatty acids, waxes,
carotenoids, tocopherols, phytosterols
Sesame (Sesamum indicum) seed

Seseli bocconi leaves
Showy rattlebox (Crotalaria spectabilis) seed
Smilax, China (Smilax china) tubers
Soya (Glycine maximus) beans, flakes, flour, hypocotyle, cake, pulp
Sea buckthorn (Hippophae rhamnoides) fruit, seed,

pulp
Scopolia parviflora, Sc. japonica roots, aerial parts
Lignans, cinnamic acid
Fatty acids, -sitosterol, nutraceuticals
Saw palmetto (Serenoa serrulata syn. S. repens syn.

Sabal serrulata) berries
Schizandra (Schisandra chinensis) fruit, seed, stems,
leaves
Sassafras (Sassafras albidum) root, bark

Savory (Satureja hortensis), shrubby savory
(S. fruticosa), S. montana leaves
Volatile oil
Volatile oil: sesquiterpenes santalol, bisabolol, farnesol, nuciferol
Volatile oil, waxes, cytotoxic and antimicrobial substances
Allylbenzenes: safrole
Volatile oil, antioxidants, insecticides
Salvia mirzayanii aerial part

Sandalwood (Santalum album, S. spicatum) stems,
wood
Santolina insularis
Francisco et al. 2005

Follegatti-Romero et al. 2009
Alkylresorcinols
Fatty oil: linoleic acid, linolenic acid,
- and -tocopherol
Diterpenoids: cis-abienol
Oil
Safranal
Volatile oil, antioxidants, cuticular waxes
Rye (Secale cereale) bran

Sacha inchi (Plukenetia
volubilis) seed
Sachalin fir (Abies sachalinensis) bark
Safflower (Carthamus tinctorius) seed
Saffron (Crocus sativus) flowers
Sage (Salvia officinalis, S. desoleana) leaves
Shaftan et al. 1986, Stastova et al. 1996, Manninen et al. 1997a, Yin et al. 2003,
2005a,b, Derevich and Shindyapkin 2004, Yakimishen et al. 2005, Arimboor et al.
2006, Vlase et al. 2006, Cossuta et al. 2007, Li et al. 2007, Olah et al. 2007, Xu et
al. 2008a,b, Sajfrtova et al. 2010
Namiki et al. 2002, Odabasi and Balaban 2002, Hu et al. 2004, Xu et al. 2005
Schaeffer et al. 1988, 1989, 1989a
Shu et al. 2004
Stahl et al. 1980, Friedrich et al. 1982, Snyder et al. 1984, Eggers et al. 1985,
Taylor et al. 1993, Lancas et al. 1994, 1995, Reverchon and Sesti Osseo 1994a,
Chandra and Nair 1996, King et al. 1996, Montanari et al. 1996, 1999, Taylor et
al. 1997, 2000, Sievers 1998, Bruhl and Matthaus 1999, Matthaus and Bruhl 1999,
2001, Nodar et al. 2002, Rostagno et al. 2002, Luque-Garcia and de Castro 2004,
Klejdus et al. 2005, Armando et al. 2006, Quitain et al. 2006, Araujo et al. 2007,
Hegel et al. 2007, Kao et al. 2008, Rochova et al. 2008
Sonsuzer et al. 2004
Lojkova et al. 1997, Slanina et al. 1997, Choi et al. 1998a, Kim et al. 1999b, Dean
and Liu 2000, Bartlova et al. 2002, Huyke et al. 2007, Sovova et al. 2007b, Wang
et al. 2008a
Joo et al. 1994, Choi et al. 1999
Heikes 1994
Hawthorne et al. 1993, Ribeiro et al. 1998, Esquivel et al. 1999a, Kubatova et al.
2001, 2002, Coelho et al. 2007, Zorca et al. 2007, Pavela et al. 2008, Grosso et al.
2009
Marentis 1998, Catchpole et al. 2000, 2002
Cherchi et al. 2001
Ohira and Yatagai 1994

Taylor et al. 1997
Semiond et al. 1996, Lozano et al. 2000
Reverchon et al. 1995c, Catchpole et al. 1996a, 1997, Reverchon 1996,
Lemberkovics et al. 1998, Bauman et al. 1999, Dauksas et al. 2001, Marongiu et
al. 2001, Menaker et al. 2004, Aleksovski and Sovova 2007, Micic et al. 2008,
Babovi et al. 2010
Yamini et al. 2008
Naik et al. 1989, Piggott et al. 1997, Marongiu et al. 2006e
References
Extract components
Plant part
(Table 1 continued)
94

Authenticated

Authenticated
Tea tree (Melaleuca alternifolia) leaves, terminal

branchlets
Tabernaemontana catharinensis branches and leaves

Tagetes, marigold (Tagetes lucida, T. erecta, T. patula,
T. minuta) flower petals
Taiwan plum yew (Cephalotaxus wilsoniana) leaves
Tamarind (Tamarindus indica) fruit, pulp, seed coat
Tansy (Tanacetum vulgare) flowers
Tea (Camellia sinensis, C. sasanqua) seed, leaves
Sweet iris (Dalmatian iris) (Iris pallida) rhizomes

Sweet olive (Osmanthus fragrans) flowers
Sweet potatoes (Ipomea batatas) root
Sweet wormwood (Artemisia annua) aerial part
Sweet gale (Myrica gale) fruit

Sweet grass (Hierochloe odorata)
Stonebreaker (Phyllanthus niruri) stems, aerial part

Strawberry (Fragaria) fruit
Sugar cane (Saccharum officinarum) leaves, rind
Sunflower (Helianthus annuus L.) seed
Stinging nettle (Urtica dioica) leaves, root
Stevia (Stevia rebaudiana) leaves
Volatile oil: terpinen-4-ol
Cephalotaxine
Volatile oil, antioxidants: epicatechin
Volatile oil
Oil, volatile oil, catechins, caffeine, gallic
acid
Volatile oil
Antioxidants 5,8-dihydroxycoumarin,
5-hydroxy-8-O--d-glucopyranosylbenzopyranone
Irones, iridals
Essential oil
Carotenoids, -tocopherol
Artemisinin (antimalaric compound),
artemisinic acid, scopoletin
Indole alkaloids, antioxidants
Volatile oil: insecticides; lutein
Oleoresin: sesquiterpenes, fatty acids,

aliphatic hydrocarbons, steroids, triterpenes; glycosides: stevioside, rebaudioside A
Oil, oleoresin: pigments, -sitosterol,
scopoletin
Gallic acid, ellagic acid, corilagin
Aroma
Wax, oil, resin
Oil, bioactive compounds
Bicchi et al. 1993

Yao et al. 1998
Spanos et al. 1993, Okuno et al. 2002
Kohler et al. 1997a,b, Hao et al. 2002, Quispe-Condori et al. 2005, Tzeng et al.
2007
Pereira et al. 2004, 2005, 2007
Wells et al. 1992, Vasudevan et al. 1997, Bicchi et al. 1999, Ma et al. 2008, Gao et
al. 2009, 2010, Skerget et al. 2010
Choi et al. 2000
Sagrero et al. 1994, Tsuda et al. 1995, Luengthanaphol et al. 2004
Smith and Burford 1994
Swift et al. 1994, Braren and Kurzhals 1998, Chang et al. 1999, 2000, Rajaei et
al. 2005, Huang et al. 2007, Kim et al. 2007, 2008, Lee et al. 2007, Park et al.
2007a,b, Shalmashi et al. 2008
Garau and Pittau 1998, Wong et al. 2001
Rafajlovska et al. 2001, Sovova et al. 2004, Sajfrtova et al. 2005, Hojnik et al.
2007
Markom et al. 2007
Polesello et al. 1993
Garcia et al. 1994, de Lucas et al. 2007
Stahl et al. 1980, Calvo et al. 1994, 1998, Favati et al. 1994, Lancas et al. 1994,
Cocero and Calvo 1996, Perrut et al. 1997, Taylor et al. 1997, Bruhl and Matthaus
1999, Matthaus and Bruhl 1999, 2001, Royer and Barth 2000, Andrich et al. 2001,
Cocero and Garcia 2001, Bravi et al. 2002, Kiriamiti et al. 2002, Luque-Garcia
and de Castro 2004, Salgin et al. 2006, Casas et al. 2007, 2008, Hegel et al. 2007
Sokolova et al. 2005
Grigonis et al. 2005
Hawthorne et al. 1988, Orav et al. 1998, Sedlakova et al. 2003b

Catchpole et al. 2000, 2002, Cui and Ang 2002, Mannila et al. 2002, 2003,
Dimitrieska-Stojkovic and Zdravkovski 2003, Rompp et al. 2004, Seger et al.
2004, Smelcerovic et al. 2004, Wang et al. 2004, Glisic et al. 2008
Szentmihalyi et al. 1998, Gamse and Marr 1999, Skerget et al. 2000, Hadolin et al.
2001, Skerget and Knez 2001
Stahl and Gerard 1982a, Liu 1996, Tuan and Ilangantileke 1997, Della Porta et al.
1998a
Liu et al. 1997, Pasquel et al. 1999, 2000, Choi et al. 2002b, Yoda et al. 2003
Volatile oil
Volatile oil, alkanes, fatty acids, waxes,
phytosterols, phloroglucinols hyperforin,
adhyperforin; quercetin, rutin
Oil, silymarin, pigments, tocopherols,
metals
Volatile oil: anethole
Spruce (Picea abies, P. omorica, P. pungens) needle

St Johns wort (hyperici herba) (Hypericum perforatum L.) aerial part, flowers
St Marys thistle, milk thistle (Silybum marianum)

fruit, seed
Star anise (Illicium verum) fruit
References
Extract components
Plant part
(Table 1 continued)
95
Volatile oil, fatty acids, hydrocarbons

Tar precursors, nicotine, N-nitrosamines,
volatile oil, tetra-acyl sucrose esters
Oil, carotenoids: lycopene, -carotene;
tocopherols, sitosterols
Lipophilic top phase, crystalline base

phase, coumarin
Volatile oil: trans-thujone, camphor,
chamazulene
Wax: fatty acids, primary alcohols,
alkanes, sterols, diketones
Volatile oil, antioxidants, antimutagens
Oil, carotenoids
Volatile oil, curcuminoids, turmerones
Tirphal (Zanthoxylum rhesta) fruit

Tobacco (Nicotiana tabacum)
Tomato (Solanum lycopersicum, syn. Lycopersicon

esculentum) seed, fruit pulp, skin
Tonka bean tree (Dipteryx odorata, Coumarouna

odorata) beans
Tree wormwood (Artemisia arborescens) aerial part
Triticale (Triticosecale) straw

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Oleoresin
Volatile oil
- and -Carotene
Volatile oil: khusinol, khusilal
Oil
Lycopene
Volatile oil: biocides, antibacterial and
antifungal substances
Fatty oil: non-polar lipids, glycolipids,
phospholipids, tocopherols
Vanilla (Vanilla planifolia) beans

Vassoura (Baccharis dracunculifolia)
Vegetables various
Vetiver (Vernonia zizanioides) root
Walnut tree (Juglans nigra) nuts
Watermelon (Citrullus lanatus) fruit

West Indian lantana (Lantana camara)
Wheat (Triticum vulgare, T. aestivum) germ, flour,

plumule
Volatile oil, valepotriates, valerenic acid,

sesquiterpenes
Valerian (Valeriana wallichii, V. officinalis) root
Tropical almond (Terminalia catappa) leaves, seed

Tucuma palm (Astrocaryum vulgare) pulp
Turmeric (Curcuma longa, C. zedoaria) rhizomes
Bestmann et al. 1985, Hawthorne et al. 1988, Hartonen et al. 1992, Dapkevicius et
al. 1996, Fekete et al. 1996, Oszagyan et al. 1996, Ribeiro et al. 1998, de Melo et
al. 2000, Moldao-Martins et al. 2000, 2002, Zekovic et al. 2000, 2001, 2003, De
Gioannis et al. 2001, Simandi et al. 2001, Diaz-Maroto et al. 2005, Dawidowicz et
al. 2009, Babovi et al. 2010
Rout et al. 2007
Hubert and Vitzthum 1978, Donsi et al. 1990, Prokopczyk et al. 1992, 1995,
Uematsu et al. 1994, Yonei et al. 1995b, Fischer and Jefferies 1996, Rincon et al.
1998, Stojanovic et al. 2000, Palic et al. 2002, Ashraf-Khorassani et al. 2005
Roy et al. 1994a, 1996a, Favati et al. 1997, Inakuma et al. 1998, Baysal et al. 2000,
Cadoni et al. 2000, Ollanketo et al. 2001, Gomez-Prieto et al. 2002, 2003, Rozzi
et al. 2002b, del Castillo et al. 2003, Sabio et al. 2003, Vasapollo 2004, Topal et al.
2006, Blanch et al. 2007, Vagi et al. 2007, Kassama et al. 2008, Nobre et al. 2009
Ehlers et al. 1996
Volatile oil: thymol, pasty products,

antioxidants
Thyme (Thymus vulgaris, T. zygis, T. herba-barona)

leaves, flowering tops
Taniguchi et al. 1985, Saito et al. 1989, Artz and Sauer 1992, Lancas et al. 1994,
King et al. 1996, Gomez et al. 1997, Zhang et al. 1998a, Munoz et al. 1999, Gomez
and de la Ossa 2000, Ge at al. 2002a,b, Panfili et al. 2003, Hubbard et al. 2004,
Eisenmerger et al. 2006, Zacchi et al. 2006, Lucas et al. 2007, Eisenmerger and
Dunford 2008, Shao et al. 2008, Piras et al. 2009
Ko et al. 2002, 2003, Mau et al. 2003

Franca et al. 1999b
Sanagi et al. 1993, Ma et al. 1995, Baumann et al. 2000, Began et al. 2000,
Chassagnez-Mendez et al. 2000a,b, Gopalan et al. 2000, Machado et al. 2000,
Braga et al. 2003, Leal et al. 2003, Chang et al. 2006, Kao et al. 2007
Muravlev and Smetanin 1974, Stahl and Schutz 1980a, Gamse and Marr 1999,
Shohet and Wills 2006, Zizovic et al. 2007b, Safaralie et al. 2008, 2010, Salimi et
al. 2008, Huang et al. 2009
Vitzthum and Hubert 1971, Nguyen et al. 1991, Anklam and Muller 1995
Cassel et al. 2000
Marsili and Callahan 1993
Naik et al. 1989, Blatt and Ciola 1991, Martinez et al. 2004, 2007, Takeuchi et al.
2008, Talansier et al. 2008
Crowe et al. 2002, Oliveira et al. 2002, Crowe and White 2003, Salgin and Salgin
2006, Bernardo-Gil and Casquilho 2007
Vaughn et al. 2008
Vasudevan et al. 1997, Marongiu et al. 2007a
Athukorala and Mazza 2010
References
Extract components
Plant part
(Table 1 continued)
96
Yew (Taxus brevifolia, T. cuspidata, T. baccata)

needles, bark
Ylang-ylang (Cananga odorata) flowers
Zataria multiflora
Yerba mate (Ilex paraguarensis) herbs, leaves
Volatile oil
Volatile oil
Jennings et al. 1992, Heaton et al. 1993, Chun et al. 1994, 1996, Vandana and Teja
1995, Vandana et al. 1996
Stashenko et al. 1996a
Ebrahimzadeh et al. 2003
Stahl and Gerard 1982b, 1983

Peplonski et al. 1994, Gamse and Marr 1999, Bocevska and Sovova 2007,
Barghamadi et al. 2009
Saldana et al. 1999, 2000a,b,c, 2002b, Esmelindro et al. 2004, Cardozo et al.
2007, Jacques et al. 2007
Volatile oil: -thujone, artabsin, absinthin
Volatile oil, oleoresin
Purine alkaloids: caffeine, xanthines,

squalene, tocopherols, sterols, fatty acids,
hydrocarbons, alcohols
Paclitaxel (Taxol), taxicin, baccatin III
References
Extract components
Wormwood (Artemisia absinthium)

Yarrow (Achillea millefolium) aerial part, flowers
Plant part
(Table 1 continued)
97
In the particular case of designing and development of

supercritical processes for extraction of valuable botanic substances, the TMF should be able to model and predict mainly
the solubility of solid solutes in supercritical solvents, and to
a lesser extent the solubility of liquids. However, as discussed
in detail by Fornari et al. (2010), this is not a simple task
because the modelling of the solubility of condensed nonvolatile solutes in supercritical solvents involves a number
of difficulties not usually encountered in other phase equilibrium calculations. In particular
(i) The vapour pressure is the most important indicator
of solubility: However, together with additional purecomponent data, it is often unavailable and cannot be
measured experimentally for relatively non-volatile complex solids, which are most of the solutes of interest.
(ii) The proximity to the critical point: The rapid density
changes and the anomalous behaviour displayed in the
critical region is a challenge to any model applied near
the critical point, which is mathematically singular.
(iii) SCF solutions are often highly asymmetric: The solute
and solvent molecules generally differ greatly in molecular size and in their interaction strengths, leading
to highly non-ideal mixtures. As a result, binary interaction constants must be correlated from data using
conventional corresponding states theory based on
critical properties.
(iv) SCF solutions are highly compressible: This leads to
solvent condensation or clustering about the solute even
in non-polar systems.
In what follows we will briefly outline the thermodynamics
of the phase equilibria exhibited by the systems SCF+botanic
substance without/with an entrainer, followed by a concise
description of the different elements of a TMF: namely thermodynamic mixture models; the methods that are used to
estimate the properties of the extracts when they are not available; and the methods, algorithms, and numerical techniques
to calculate the phase equilibria.
4.1. The thermodynamics of phase equilibria of
SCF+botanic substances systems
4.1.1. Vapour-liquid equilibria The extraction with
SC-CO2 of valuable vegetable oils consisting mainly of triglycerides, with a low fraction of diglycerides, free fatty acids,
and a number of minor components (sterols, tocopherols,
phospholipids, etc.) that have added value as pharmaceuticals
and food additives, and the extraction and fractionation of
essential oils with SC-CO2 requires detailed knowledge of the
of the vapour-liquid (and vapour-liquid-liquid) equilibria of
the systems under consideration (Franceschi et al. 2004).
For vapour-liquid equilibrium, the general equilibrium
relation is
fi L = fi V
(1)
where fi L and fi V are the fugacities of component i in the liquid and vapour phases, respectively.

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98
Fugacities are related as

fi L = xi iL P
fi V = yi iV P
(2)
where P is the pressure, and xi and yi are mole fractions, and

iL and iV are fugacity coefficients of the i-th component in
the liquid and vapour phase, respectively.
Thus, the solubility (mole fraction) of component i in the
vapour (SC fluid) phase can be expressed as follows:
yi =
xi iL
iV
(3)
Thus, the problem is how to calculate the fugacity coefficient of the i-th component in the liquid and vapour phases.
The majority of the systems that we focus
on involve medium- and large-sized solutes at ambient or
slightly elevated temperatures where they are typically pure
solids. Four different modelling approaches are typically used
to describe the solubility of solids in SCFs. These approaches
are density based, dense gas, expanded liquid, and solubility
parameter.
The density-based approach is an empirical or semiempirical modelling approach that relies on developing a relationship between the solubility and the density of the SCF. The
dense gas and expanded liquid approaches are both equationof-state (EoS) approaches that differ in the way in which the
SCF phase is treated. At high pressures and liquid-like densities common in SFE, the distinction between a gas and a
liquid is difficult. SCFs can therefore be treated either as a gas
or as a liquid (McHugh et al. 1988, McHugh and Krukonis
1994). The dense gas approach treats the SCF as a gas while
the expanded liquid approach treats the SCF as a liquid. The
solubility parameter approach is an expanded liquid approach
that uses the regular solution theory and the solubility parameter concept to develop a model for the solubility of solids
in SCFs.
The density-based approach for modelling solubilities of solids in SCFs attempts to explain the common observation that the
logarithm of the solubility is linearly dependent on the density
or the logarithm of the density of the SCFs (Kumar and Johnston
1988). This approach has been studied by many authors, including Chrastil (1982), Schmitt and Reid (1985), Kumar and
Johnston (1988), Harvey (1990), Bartle et al. (1991a), Mitra and
Wilson (1991), and Liu and Nagahama (1996).
Chrastil (1982) proposed the following relationship
between the solubility and the density:
4.1.2. Solid-SCF
a
c = k exp + b
T
(4)
where c is the concentration of the solid in the SCF in g l-1,

is the SCF density, T is the temperature, k is the association
number, and a and b are empirical constants. The parameters
k, a, and b are obtained performing a multiple linear regression on the experimental solubility data.
Chrastil (1982) identified the constant a with the heat of

reaction as the solute associates with the solvent and the constant b with a relationship between the molecular weights
of the solute and solvent, and used Eq. (4) to successfully
correlate solubilities of a variety of different compounds in
SC-CO2.
Adachi and Lu (1983) used Chrastils equation to correlate the solubilities of 37 systems. To obtain reasonable performance, they made the parameter k density dependent and
added two additional parameters. Yun et al. (1991) correlated
cholesterol solubilities in SC-CO2 using Chrastils equation
and obtained a performance ranging from 1.5% to 9%.
Skerget et al. (1995) correlated solubilities of carotene,
oleic acid, and capsaicin in SC-CO2 using Chrastils equation.
The performance of the correlation for these compounds varied from 10% to 34%. Kumar and Johnston (1988) proposed
two new relationships to relate the solubility to the SCF density. The relationships were derived using a dense gas-type
approach, expressing the fugacity coefficient of the supercritical phase in terms of density rather than pressure.
Chrastils equation was used to describe the solubility
behaviour of fatty acids; mono-, di-, and triglycerides; and
fatty acid esters in SC-CO2 (Guclu-Ustundag and Temelli
2000). The authors point out that mono- and diglycerides are
the least studied classes of lipids, although information on
their phase behaviour is essential for the design of processes
such as fractionation of glyceride mixtures or refining of vegetable oils, which are of great commercial importance.
Brennecke and Eckert (1989) state that Chrastils equation
has been the most successful density-based model, but due to
its empirical nature, it is unable to predict phase equilibria.
Additional detailed enumeration of the empirical models most
often applied for modelling of the solubilities of solids in SCFs
can be found in the recent review by Skerget et al. (2011).
4.1.3. The dense gas approach The dense gas approach
for modelling solute solubilities in SCFs begins with equating the fugacities of the solid and SCF phase and the standard formulation of this problem is based on the equi-fugacity
condition for the solute; that is, assuming an EoS model for
the fluid phase and denoting by the superscript S the solid
solute and by the superscript F the fluid phase:
f S(T, P) = f F(T, P, y, V)
(5)
where f S is the fugacity of the solute in the pure solid phase,

f F is fugacity of the solute in the fluid-phase solution, y=(y1,
y2, ,yNc)T is the vector of fluid-phase mole fractions, and V is
the molar volume of the fluid from an EoS model. Additional
relationships that must be satisfied are the summation to one
of the fluid-phase mole fractions.
As discussed by Fornari et al. (2010), there have been a
number of efforts at introducing mathematical artifices for
solid-phase fugacity within traditional fluid-phase equilibrium EoS descriptions. Some investigators have attempted
to modify the EoS so that it may predict the existence of a
solid phase. However, it has been more common to take a
popular EoS and use it directly in solid-fluid equilibrium

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calculations by introducing a solid-phase fugacity function

defined in terms of a fluid-phase reference state. Two different approaches are popular.
According to the first approach, originally proposed by
McHugh et al. (1988), the solid vapour pressure is used as
the reference fugacity of the solid. Thus, for the simple case
of binary solid-gas equilibria, and if the solid solute in the
system is denoted by subscript 2, then:
P
v2SdP
RT
Ps
f2S = P2s s2 exp
(6)
where P2s (T) is the sublimation (vapour) pressure of the pure

solid, S2 is the fugacity coefficient at sublimation pressure, and
v2S is the molar volume of the solid, all at temperature T.
The fugacity of the solute in the supercritical phase is
f2G = y2 PG2
(7)
G
where 2 is the fugacity coefficient and y2 is the solubility
(mole fraction) of the solute in the SCF.
For phase equilibrium between a high-boiling compound
and a SCF whose critical temperature is low, the following
three assumptions are usually introduced: (i) the solid solute
remains pure since the size and shape of solute and solvent
molecules are ordinarily sufficiently different and hence
solid solutions do not form; (ii) the molar volume of the
solid solute can be treated as a constant with respect to pressure; and (iii) the saturated vapour of the solid solute-vapour
(pure) system behaves as an ideal gas. The fugacity coefficient takes into account deviations of the saturated vapour
from ideal gas behaviour and the Poynting factor (the exponential term) takes into account the effect of pressure.
Furthermore, since the solid phase is pure (assumption 1),
the fugacity of the solute in the solid state is equal to the pure
solid fugacity and Eq. (6) can be rewritten as follows:
S
vS P -Psub1
(T )
S
S
f2S = Psubl
(T )subl
exp
RT
(6a)
Applying further assumption 2 and the thermodynamic

equilibrium condition [Eq. (5)], the mole fraction of the solid
component in the supercritical phase can be expressed as
y2 =
P2s
E
P
(8)
where
v P -P
v2SdP
s2 exp
RT
RT
P2s
=
G2
G2
P
s2 exp
S
2
s
2
(9)
The enhancement factor E contains three correction terms:

s2 , which takes into account non-ideality of the pure saturated vapour; the Poynting correction, which gives the effect
99
of pressure on the fugacity of the pure solid; and G2. Of all

three correction terms, the last one is by far the most important. In most practical cases, the sublimation pressure of
the solid is quite small and thus s2 is nearly equal to unity
(assumption 3). The Poynting correction is not negligible,
but it generally accounts for an enhancement factor <2 or
3. However, G2 is always far removed from unity and can
produce very large enhancement factors. The solubility in an
Ps
ideal gas is y2 = 2 ; hence, the large solubility enhancements
P
in SCFs relative to an ideal gas are due to exceptionally
small values of G2. The above equation represents the basis
for the dense gas approach for modelling solubilities in SCFs.
G
This equation relies on the adequate evaluation of 2 , at the
specified conditions of P and T.
Therefore, the solute solubility is primarily a function of
the solid solute pure compound physical properties, the system temperature and pressure, and the fugacity coefficient
of the solid solute in the SCF. The fugacity coefficient is the
property calculated by a thermodynamic model.
The second approach, introduced originally by Kikic et al.
(1997), implements the fugacity of a hypothetical subcooled
liquid phase, as the reference of the solid phase fugacity.
Thus, the solid-phase fugacity function, for a pure solute solid
phase at temperature T and pressure P, defined in terms of a
hypothetical liquid-phase fugacity as a reference state, and
disregarding the change in specific heat because of its negligible effect, is given as follows:
P V S -V SCL
Hfus 1 1
dP +
f S = f SCL ( P, T )exp
-
R Tm T
RT
s
Psubl
(10)
Implicitly assuming that there are no solid-solid phase

transitions and provided the solid specific volume at the subcooled liquid state V SCL is weakly dependent on pressure,
Eq. (10) can be written as follows:
f S = f SCL ( P, T )exp
)(
V S -V SCL
H 1 1
S
P -Psubl
(T ) + fus -
RT
R Tm T
(10a)
In Eq. (10), f SCL is the fugacity of the pure subcooled liquid,

Hfus is the enthalpy of fusion, Vfus=V S-V SCL is the change in
volume, all taken for the solute at its triple point.
Often the second approach should be preferred because of
the following reasons:
(i) With the use of Eq. (6a) for the calculation of solid fugacity, it is not usually possible to fit the normal melting
point (Tfus) of the solid compound. On the other hand,
use of Eq. (10a) reproduces the normal melting point of
the solid compound since it is an input parameter for this
approach.
(ii) The first part of the exponential term in Eq. (10a),
Vfus=V S-V SCL, is important at higher pressures and
should not be eliminated.

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100 H. Sovov and R.P. Stateva: SFE from vegetable materials
In Eq. (10a), the data that are required for calculating the
fugacity of the pure solid phase are as follows: the fugacity of
the pure solute in the subcooled liquid phase (calculated from
a thermodynamic model), the enthalpy of fusion at the triple
point (HTP), the triple point temperature (TTP), the triple point
pressure (PTP), and the change in molar volume assumed to be
a constant upon fusion (VTP).
The theory behind lattice gas
models is based on the fact that the molecules are distributed
over a three-dimensional lattice (Brennecke and Eckert 1989)
and that these molecules interact with a mean-field-type intermolecular potential (McHugh and Krukonis 1994). A number
of holes are placed at specific lattice sites to obtain the correct density (McHugh and Krukonis 1994). Lattice gas models are reviewed by Johnston et al. (1989), Brennecke and
Eckert (1989) and McHugh and Krukonis (1994). Brennecke
and Eckert (1989) conclude in their review that, although
the lattice gas equations are theoretically based, their performance in terms of modelling solubilities is poorer than the
performance of cubic and perturbed EoSs.
4.1.4. Lattice gas models
4.1.5. Expanded liquid approach The expanded liquid

approach for modelling solute solubilities in SCFs begins with
equating the fugacities of the solid and SCF phase. Assuming
the solid is pure, the fugacity of the solid is calculated using the
same equation as in the dense gas approach. The fugacity of the
SCF phase, treated as an expanded liquid, is written as follows:
SCF
f2SCF = y2 2 f pure
(11)
where 2 is the activity coefficient of the solute in the liquid

phase.
The expanded liquid approach has an advantage over the
dense gas approach in that it does not require integration
through the critical region. The expanded liquid approach,
however, requires the evaluation of two parameters, the activity coefficient and the partial molar volume of the solute at infinite dilution, versus one parameter in the dense gas approach.
Mackay and Paulaitis (1979) found that the expanded liquid
approach did not provide better solubility correlation performance than the dense gas approach and therefore the introduction of a second parameter is not warranted.
The solubility
parameter approach is an expanded liquid approach that uses
the regular solution theory to determine the solubility and
activity coefficient, according to the following relations:
4.1.6. Solubility parameter approaches
ln y2 = -
H fus Tm2
RT T
m2
ln 2 =
-1 - ln 2
V2 2
( - )2
RT 1 1 2
(12)
(13)
where V2 is the solute molar volume in a hypothetical liquid state, 1=(x1V1)/(x1V1+x2V2) is the volume fraction of the
solvent, V1 is the molar volume of the liquid solvent, and

1 and 2 are, respectively, the solvent and solute solubility
parameters, defined by:
1/ 2
U
i = i
Vi
i =1, 2
(14)
where Ui is the vapourisation energy and Vi is the liquid

molar volume. Thus, Eqs. (12) and (13) represent the functional form of the RST, using solubility parameters to calculate the solubility.
Ekart et al. (1991) and Brennecke and Eckert (1989), in
summarising the efforts that have been made to use the RST
in correlating solubilities in SCFs, point out that semiempirical modifications of the theory have been required.
4.2. Thermodynamic models
Reliable thermodynamics mixture models that are able to

describe the extremely complex phase behaviour of the systems studied are a vital element of the TMF. An ideal thermodynamic model is a model that uses easily measured physical
properties to predict phase equilibria at all conditions and is
theoretically based. Still, up to the present time, no current
model fits these criteria. Existing correlations of phase equilibria data contain many regressed parameters, are semiempirical at best, and may succeed in fitting the data in portions
of the phase diagram with some accuracy (Ekart et al. 1991).
The dense gas approach is an EoS approach that treats the
supercritical phase as a gas and is currently the most widely
used for representing the phase equilibria of asymmetric systems at high pressures. It requires the evaluation of the fugacity coefficient using an EoS valid over the entire density range
studied, and hence an adequate relationship to describe the
P-V-T behaviour of the SCF phase.
The dense gas approach requires the evaluation of the
fugacity coefficient and hence a variety of different relationships exist to describe this relationship. The most commonly
used are the cubic equations of state.
4.2.1. Equations of state Both cubic and noncubic EoSs
have been used to model the solubility of solids in SCFs, and a
summary of the models and methods used can be found inAshour
et al. (2000).
Cubic EoSs are derived from the equation, which takes
attractive and repulsive forces into account, and was proposed for the first time by van der Waals. Currently, cubic
EoSs, in combination with different mixing rules, are the
most widely used models for the calculation of solubilities
of solid solutes in SCF. The recent contribution of Fornari et
al. (2010) is devoted entirely to the application of cubic EoSs
to correlating the solubility of solid compounds in SCFs. The
authors offer a detailed critical analysis of the cubic EoSs
advantages and shortcomings in fulfilling the above tasks and
stress that to model adequately SC fluid-solid phase equilibria
or SCF+liquid equilibria using an EoS approach, the EoSs
employed must be able to describe both the fluid-phase and

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the solid (liquid) phase behaviour reliably. To realize that, two

avenues are usually pursued improvement of mixing rules
and improvement of the existing EoS and development of
new models and Fornari et al. (2010) present an analysis of
van der Waals one-fluid mixing rule and its modifications.
Haselow et al. (1986) evaluated seven cubic EoSs and two
non-cubic EoSs for the prediction of SFE. They suggested
that there is a need to develop new mixing rules, otherwise no
existing cubic EoS with the traditional van der Waals mixing
rules can yield good predictions. Yamamoto et al. (1987) evaluated two EoSs, namely the perturbed hard sphere (PHS) EoS
that comprises the Carnahan-Starling equation repulsive term
and the Soave attractive term, and the Soave-Redlich-Kwong
(SRK) EoS (Soave 1972) for the prediction of the solubilities
of high-boiling compounds in SCFs. They reported that the
performance of the SRK-EoS seems slightly better than that
of the PHS-EoS, and it was pointed out that the selection of
mixing rules is more important than the equation itself. Lee
et al. (1989) conducted a similar study to examine three cubic
EoSs for the prediction of solid solubilities in SCFs with
co-solvent. Weber et al. (1999) modelled the solubility of
tristearin, tripalmitin, and triolein with the Redlich-KwongAspen EoS and the Mathias-Klotz-Prausnitz mixing rule: the
relative deviation of calculated and experimental solubility
in the gas-phase was high, whereas the absolute deviation
was considerably small. Yamamoto et al. (2000) correlated
solubilities and entrainer effects for fatty acids and higher
alcohols in SC-CO2 using SRK EoS with association model.
Ismadji and Bhatia (2003) demonstrated that the one- or twoparameter van der Waals mixing rule with the Peng-Robinson
(PR) EoS model failed to predict the solubility of some esters
in SC-CO2, but the Stryjek-Vera mixing rules were able to
correlate the experimental data fairly well.
One empirical approach to eliminate the shortcomings of
the van der Waals one-fluid model for a cubic EoS has been to
provide additional composition dependence by adding parameters to the combining rule for the parameter amix, generally leaving the mixing rule for the parameter bmix unchanged.
Some examples are the combining rules of Panagiotopoulos
et al. (1986), Adachi and Sugie (1986), Sandoval et al. (1989)
and Schwartzentruber and Renon (1989a,b). However,
there are several problems associated with this multiparameter combining rules that limit their use. One is that
because of added composition dependence in the parameter
amix, this group of combining rules fails to satisfy the theoretical quadratic composition dependence of the second virial
coefficient.
Ashour et al. (2000) have shown that incorporating additional parameters in the cubic EoS does not significantly
improve the prediction of the solubility of the solid in the
SCF. However, this study did not take into account the dependence of the interaction EoS parameters with respect to temperature. Nicolas et al. (2005) considered different mixing
rules associated with the Sanchez-Lacombe EoS, and the
results were compared with those obtained with the PR equation. For this purpose, binary mixtures of solids with SC-CO2,
ethane, ethylene, and xenon were investigated. Several mixing rules were considered, among which classical kij and lij
101
and the generalised composition-dependent mixing rule originally proposed by Adachi and Sugie (1986) and generalised
by Hernandez-Garduza et al. (2001), to avoid the invariance
problem pointed out by Michelsen and Kistenmacher (1990).
With Sanchez-Lacombe EoS, two versions were studied: kij( 0 ) ,
kij(1) mixing rule associated with a linear co-volume b, and kij( 0 ),
kij(1), lij mixing rule where b is a quadratic function of molar
fractions. It was shown that, in many cases, the range of solubility data was too narrow to allow estimating meaningful kij( 0 ),
kij(1) values. The correlation of data in a large range of temperatures by means of classical mixing rules requires taking
into account a temperature dependence of binary interaction
parameters. It was observed that, with the proposed temperature function, only three parameters associated with the
kij (T) and lij, or kij and lij(T) mixing rules allow to predict
solubility data with an accuracy comparable to that of isothermal correlation. The PR-EoS results at the same conditions
were of the same accuracy, provided a temperature dependence of EoS parameters was considered.
Another interesting approach was advocated by Ruckenshtein and Shulgin (2001) who suggested a family of mixing
rules for the cubic EoS in which the empirical binary interaction parameter k12 in the van der Waals mixing rule was
replaced by a physically more meaningful parameter. In the
new mixing rules, some mole fractions in the expressions of
parameters amix and bmix in the van der Waals mixing rules were
replaced with various expressions for the local mole fractions.
The family of the new mixing rules can contain one, two, or
even three parameters, and thus they are quite flexible regarding the number of adjustable parameters. In particular, it was
shown that the new mixing rules with two or three adjustable
parameters provided better correlations of the experimental
data for the solubilities of the antibiotic penicillin in SCF CO2
than the conventional mixing rules or the empirical expressions containing many more parameters.
To avoid the two principal limitations of the dense-gas/
cubic EoS approach and in an attempt to improve the modelling success that is, in some cases, only semiquantitative,
researchers have focused on developing more sophisticated
mixing rules and EoS (Colussi et al. 1992), e.g., Rao and
Mukhopadhyay (1989), Sheng et al. (1992), Bartle et al.
(1992a) and Carleson et al. (1993). Rao and Mukhopadhyay
(1989) and Sheng et al. (1992) proposed new mixing rules
to attempt to improve correlation results. Nishiumi et al.
(1988), Bartle et al. (1992a), and Carleson et al. (1993) developed new relationships for the binary interaction parameter
that avoid the need for experimental data. Schmitt and Reid
(1986) therefore adopt a new approach that still remains a
dense gas approach, which uses the PR-EoS to evaluate the
fugacity coefficient but the EoS parameters of the mixture are
not calculated in the conventional manner.
Another alternative to van der Waals one-fluid mixing
rules and a very attractive route to developing better mixing
rules is to combine EoS with activity coefficient models thus
combining the advantages of successful cubic EoS and GE
models, such as the Universal Functional Activity Coefficient
(UNIFAC) model (Fornari et al. 2010). A number of models

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that are essentially all mixing rules for the energy parameter
of cubic EoS has appeared (see, e.g., Huron and Vidal 1979,
Mollerup 1986, Dahl and Michelsen 1990, Michelsen 1990a,
Dahl et al. 1991, Holderbaum and Gmehling 1991, Wong and
Sandler 1992).
EoS/GE models have been applied mainly to modelling
vapour-liquid systems and only to a limited extent to solidgas systems (see, e.g., Sheng et al. 1992, Spiliotis et al. 1994,
Chen et al. 1995, Escobedo-Alvarado et al. 2001, Huang et
al. 2001, Sovova et al. 2001a, to name a few). Tochigi et al.
(1998) applied the PR-EoS with the analytical solutions of
group (PRASOG) method to estimate solid solubilities in
SC-CO2 and indicated its applicability. Coutsikos et al. (2003)
evaluate the linear combination of Vidal and Michelsen mixing rules (LCVM) EoS model (Boukouvalas et al. 1994,
Voutsas et al. 1996), which combines the PR-EoS with original UNIFAC using an EoS/GE type mixing rule, for solid-gas
equilibria applications including systems with co-solvents, and
studied the influence of using vapor-liquid equilibria (VLE)based parameters for making SGE predictions. The LCVM
model has a large parameter table including gases and it has
been shown to yield quantitatively satisfactory predictions for
binary solid+gas systems involving aromatic hydrocarbons,
aliphatic acids, and some alcohols. Poor results were obtained,
however, for complex solids, e.g., naproxen and cholesterol.
Another model that can be used successfully to calculate and
predict the solubility of a solid solute in SCFs is the predictive
SRK (PSRK) EoS (Holderbaum and Gmehling 1991). PSRK
has also a large parameter table available enabling the representation of a wide variety of complex natural products.
Jaubert et al. (1999) performed phase equilibria calculations
of mixtures involving SC-CO2 and fatty acid esters (FAE) by
combining at a constant packing fraction the PR-EoS and the
Van Laar GE model. A new group O=C-O was added, and the
fully predictive model thus obtained was used to predict the
phase behaviour of a real fish oil containing 30 different fatty
acid ethyl esters. In a further study, Jaubert et al. (2001) compared the phase equilibria predictions for systems of carbon
dioxide and two different fatty acid ethyl esters eicosapentaenoic acid and docosahexaenoic acid ethyl esters of the
Jaubert et al. (1999) model with that developed by Coniglio
et al. (1995), namely the MHV1-QB approach. The MHV1-QB
approach combines the SRK-EoS with a quadratic expression for the mixture b parameter, and a constant value for
the binary interaction parameter lij = 0.3, with the first order
modified Huron-Vidal mixing rule (MHV1) proposed by
Michelsen (1990b). It was demonstrated that the MHV1-QB
model lead to very good results at low pressures but overestimated the bubble point pressures in the vicinity of the critical
point and all the dew point pressures. Jaubert et al. (1999)
model performed better in the vicinity of the critical point and
for the dew point prediction, which was explained by some
intrinsic features of the two models.
Araujo and Meireles (2000) applied the PR equation with
van der Waals mixing rules and combining rules with two
parameters and three binary parameters of Kwak and Mansoori
(1986) and Park et al. (1987) to the systems containing fatand oil-related compounds in SC-CO2. Preference was given
to correlating experimental data for both phases, which is perhaps the most difficult form of correlating vapour-liquid equilibrium data with cubic EoS considering the importance of
this information for the design of supercritical fractionation
systems. On the basis of the absolute mean deviation for mole
fractions, it was concluded that the PR equation with van der
Waals mixing rules for the three different combining rules
described qualitatively all the important characteristics of the
vapour-liquid equilibrium of the systems studied. The differences among the results obtained with the analysed combining rules were not significant. On the other hand, the absolute
mean deviations for the vapour phase obtained were smaller
compared with the Soave equation and the mixing rules of
MHV1 and MHV2, and the LCVM model for the majority of
the binary and ternary systems studied. Therefore, concluded
the authors, if experimental data are available, a simple model
as the one discussed predicts the phase equilibrium of complex system within the required accuracy for project design.
On the other hand, in the absence of experimental data, the
entirely predictive EoS/GE models are very useful.
Huang et al. (2001) applied the PR-EoS and a modified
Huron-Vidal type mixing model with a volume correction
term to calculate the solid solubilities of aromatic, fatty acid,
and heavy alcohol compounds in SC-CO2. The UNIFAC
activity coefficient model with its optimally fitted binary
interaction parameters was used and a volume correction term
was employed, and its parameters were correlated as functions of the solid molar volume for both non-polar and polar
systems.
Escobedo-Alvarado et al. (2001) used the Wong-Sandler
mixing rule and the PR-EoS to model the solubility of solid
phases in SCFs. More recently, Vieira de Melo et al. (2005)
applied the PR-LCVM-UNIFAC model to model the solubility of caffeic acid and l-dopa in the SC-CO2-rich phase.
Gracin et al. (2002) examined the ability of the original
UNIFAC method to predict solubilities of very different solid
organic fine and specialty chemicals, organic intermediates,
and pharmaceutically important compounds in 15 industrially
important solvents.
Valderrama et al. (2003) proposed a model that includes
an EoS and an excess Gibbs free energy model and applied
it to the correlation of phase equilibria in gas+solid systems
containing SC-CO2. A modified regular solution model for
the excess Gibbs free energy that considers nonpolar, polar,
and hydrogen-bonding contributions and a generalised threeconstant EoS was advocated. The mixing rule derived for the
model includes a concentration-dependent interaction parameter and an interaction parameter into one of the volume
constants of the EoS. Literature data for nine binary gas+solid
systems containing SC-CO2 were used for testing the proposed model.
Espinosa et al. (2002) applied the group contribution (GC)
EoS proposed by Skjold-Jorgensen (1988) to model highpressure phase equilibria in mixtures of fatty oils and acid
alkyl esters with SCFs. The GC-EoS is based on the generalised van der Waals partition function and a group contribution principle. The repulsive term is a Carnahan-Starling-type
expression, which is characterised by the critical hard-sphere

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diameter, and it is considered a function of the molecular size

of the pure component. The attractive term is calculated using
the non-random two liquid (NRTL) model with density-dependent mixing rules. Espinosa et al. (2002) represented the
fatty oil by a pseudo-triacylglyceride with the same molecular weight and degree of unsaturation of the natural oil. The
critical hard sphere diameter of the oil, i.e., the size-related
parameter, was determined from the correlation of infinite
dilution activity coefficients of n-alkanes in high molecular
weight triacylglycerides and hydrocarbons. Good predictions of vapour-liquid, liquid-liquid, and vapour-liquid-liquid
equilibria in mixtures of supercritical solvents (propane, ethane, and CO2) with pure triacylglycerides, natural vegetable
oils, and fatty acid alkyl esters were obtained. The authors
conclude that the results obtained show the capability of the
GC-EoS model to describe the phase equilibria of size-asymmetric mixtures and its potential for modelling supercritical
processes involving oils and derivatives.
In new developments, Chafer et al. (2004, 2005) and de
la Fuente et al. (2005) also applied the GC-EoS to model the
solubility of quercetin and carnosic acid, and capsaicin in
SC-CO2 and compared its capabilities with those of SRK.
Still, the use of this group contribution approach can be
considered to be quite demanding while dealing with the
amount of necessary regressed parameters and with the calculation of the association contributions for multiple associating groups.
At this stage, we feel that the following should be underlined: the key assumption of all group contribution approaches
such as UNIFAC is that molecules can be broken down into
functional groups that can be treated as being independent
of the rest of the molecule. Interaction parameters between
groups are determined by correlation of the model to experimental data. For UNIFAC parameters, for example, more than
60 different functional groups are determined simultaneously
in an extensive optimisation where the total deviation between
the UNIFAC model and huge amounts of experimental data
is minimised. Because of the complexity of this optimisation,
parameter values are primarily correlation values rather than
describing the actual physics in each particular interaction,
and of course this limits the possibility to extrapolate the use
into new situations. Furthermore, the values of the UNIFAC
parameters to be used have been determined from vapour-liquid equilibrium data because these are the most extensive data
that are available. From a physical point of view these interaction parameters should be equally useful for solid-liquid equilibria. However, because of deviations from the underlying
assumptions and because of the complexity of the parameter
determination, the extrapolation to solid-liquid systems is not
necessarily valid.
The practical problems associated with the application of
the UNIFAC-based mixing rules are that many solid solute
compound molecules extracted from natural matrices are
more complex than the molecules normally encountered in
gas-liquid equilibria. In addition, these molecules sometimes
contain functional groups for which UNIFAC parameters are
unavailable. Also, even if all group definitions exist, a subset
of the relevant parameters is unavailable. These problems can
103
be eliminated with sufficient and accurate experimental data.

Frequently, however, this involves a rather large number of
parameters compared with the amount of data available.
Finally, all group contribution methods discussed thus
far treat the light gases, such as CO2, as individual groups,
and hence the volume and surface area parameters for these
groups must be determined. In some cases, as pointed out by
Fornari et al. (2010), these structural parameters are estimated
using semitheoretical methods like those of Bondi (1964) and
Apostolou et al. (1995) but their values are essentially arbitrary and differ from those given by Dahl et al. (1991), the
size parameters of the latter being about twice the size of the
gases of Apostolou et al. (1995). There has not been a thorough analysis of which values are the best. In addition, these
values must be set before the optimum values of the group
interaction parameters of the UNIFAC model can be found,
and hence any deficiency that exists in the selection of these
structural parameters will inevitably affect the group interaction parameters (Orbey and Sandler 1998).
4.2.2. Other models Cubic EoSs are exceedingly simple
and have been remarkably successful in modelling SCFphase behaviour and are probably the most widely used in
analysing experimental data. Moreover, the cubic EoS must
be the equation of choice for process design of any complex
system because the interactions are too involved to justify the
use of a more fundamentally based equation. However, all
of the cubic EoSs were originally developed to characterise
hydrocarbons, and they embody a very wrong component of
the corresponding state theory. This theory assumes similarity of molecular size and force constant an assumption that
does not work for the highly asymmetric in force constant
and size SC systems. Furthermore, cubic EoSs are least precise in the region near the critical point, and are completely
inapplicable right at the critical point, which is mathematically singular. This is because many cubic EoSs predict common value for the critical compressibility factor for all fluids,
Zc = 0.303, while real values vary from 0.2 to 0.5 (Valderrama
2003, Valderrama and Alvarez 2004).
Furthermore, the rapid density changes and the anomalous
behaviour displayed in the critical region are a further challenge for EoS models. Thus, attempts to modify mixing rules,
making them variable in density, temperature, or composition
may be useful, but are stopgap solutions. The real need is to
develop better EoSs. One response to this challenge is the
application of the statistical associating fluid theory (SAFT)
to model SFE.
To overcome the use of empirical corrections to cubic EoSs
or G E mixing rules, the breakthrough in the modelling of polar
and highly non-ideal systems came with the development of
more rigorous explicit association models. A semiempirical
EoS that was developed in the late 1980s and has gained considerable popularity in both the academic and industrial communities is the SAFT. SAFT is derived from the first-order
thermodynamic perturbation theory of Wertheim (1984a,b,
1986a,b), where the reference fluid is a hard sphere and the
perturbation consists of the relatively weak dispersive attractions. In SAFT, the Helmholtz free energy is written as the

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sum of contributions due to hard-sphere repulsive interactions, due to chain formation through bonding of a number
of hard spheres, and due to association and dispersion. From
the several successful modifications of SAFT that have been
advocated, the one suggested by Huang and Radosz (1990,
1991) should be mentioned in particular.
Although the approach is very successful in modelling the
phase equilibria of complex systems, research dealing with
its application to the modelling of the solubility of solids in
SCFs is rather scarce (Muller and Gubbins 2001). Economou
et al. (1992) used the SAFT EoS to correlate the solubility
of polynuclear aromatics in supercritical ethylene and ethane,
where a total of six systems were adopted and the correlated
results showed that good agreement with experimental data
can be obtained with the SAFT EoS.
Zhong and Yang (2002) carried out a comprehensive investigation of the capability of the SAFT approach for modelling
the solubility of solids in SCFs. They adopted an extended
SAFT EoS combined with eight mixing rules to evaluate the
capability of the SAFT approach. The results show that the
SAFT approach gives good correlative accuracy in general,
and that it can be used to model solid-SCF equilibria, which
gives slightly better correlative accuracy than the cubic EoSs.
In their further work, the authors apply the SAFT approach
to model the solubility of solid aromatic compounds in SCFs
with co-solvents (Yang and Zhong 2005).
Efforts to develop new models and improve the existing ones
with the view to represent in a more comprehensive manner the
complex interaction between the solid+SCF are continuing. We
will briefly discuss some of them without either the ambition to
be exhaustive or that all new models are covered.
Vetere (1998) presented an empirical correlation with two
parameters, namely molecular weight and melting point for
the prediction of solid solubility. In a similar development,
Mendez-Santiago and Teja (1999) showed that a simple linear
expression, based on the theory of dilute solutions, can be used
to correlate solid solubility data. The linear relationship may
also be used to check the consistency of experimental data. The
proposed equation for solid solubility requires knowledge of
the sublimation pressure of the solid of interest, and the authors
advocated another relationship for the solid solubility that
incorporates a Clausius-Clapeyron equation for the sublimation pressure. Although the resulting expression contains three
parameters, it was demonstrated that these parameters are independent of temperature and pressure. The proposed expression may therefore be used to extrapolate data to temperatures
where experimental information may not be available.
The molecular interactions near the critical point and high
pressures have recently been studied intensively. The solutesolvent interactions near the critical point are strong. The
studies that show these phenomena observed clusters in solutions aggregates of solvent around solute of dilute organics in SCFs (see, e.g., Walsh et al. 1987, Eckert and Knutson
1993, Zhang et al. 1995a). Cheng et al. (2003) calculated solid
solubility by applying the equilibrium criteria for the cluster
formation process. The simplified cluster-solvation model
has two temperature-independent binary parameters, and it
was observed that the overall deviation in solid solubility
calculations from this model is comparable to that from other

semiempirical models with more optimally fitted parameters.
Solute-solute interactions are also important, as observed
by Kurnik and Reid (1982) and Kwiatkowski et al. (1984).
Brennecke and Eckert (1989) presented evidence for both
solute-solvent and solute-solute interactions, due to the formation of dimers, even at very low concentrations using
spectroscopic studies. They recommended using solute-solute
interactions to develop EoSs.
Zhong et al. (1998) suggested a model for correlating the solubility of solids in SCFs. This model is based on the fact that the
free solute molecules, the solvent molecules, and the solventsolute clusters in such solid-SCF systems are in chemical equilibrium. The local density of the solvent surrounding a solute is
used as a one parameter. The model can correlate the solubility
data that are not in immediate region to the critical point of the
solvent. Jiang et al. (1998) presented an equation for solubility
behaviour representation derived from the solvation concept.
Cheng et al. (2002) also explored the application of a modified regular solution model as an alternative method without the need of critical constants to the modelling of solid
solubility of complex biological compounds, including steroids, antioxidants, xanthines, drugs, and heavy aromatic in
SC-CO2. They compared their results with those obtained
using semiempirical equations and EoS approaches. It was
demonstrated that with two or with a single parameter in the
solution model, satisfactory results are obtained that are comparable to those from other methods with more parameters.
The optimally fitted parameters in the solution model method
are presented and the generalisation of the solution model
parameters as a function of pure solid property is illustrated.
Ruckenstein and Shulgin (2002) developed a predictive
method for the solubility of a solid in a SCF containing an
entrainer at any concentration. They presented a method
based on the Kirkwood-Buff formalism, and expressions for
the derivatives of the fugacity coefficient of the solute in a ternary mixture with respect to the mole fractions were obtained.
On the basis of these expressions, an algebraic equation,
which allowed one to predict the solubility of a solid solute
in terms of its solubilities in the SCF and in the entrainer, was
derived. The equation was compared with the experimental
results available in the literature regarding the solubility in a
mixture of SCFs and good agreement was obtained.
Li et al. (2003) studied the solubility of solids in SCFs by
chemical association reaction method, and both cases of with
and without co-solvent were considered. On the basis of the
thermodynamic and association reaction equilibrium theories,
a model for the solubility of solids in SCFs under association
reactions was developed. It reduces to normal solubility calculation model when there are no co-solvent and association
reactions. The model was tested with the experimental data
collected from the literature, and the results show that it is
more accurate than other models.
4.3. Solute properties estimation
The systems that we focus on involve medium- and largesized solutes at ambient or slightly elevated temperatures

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where they are typically pure solids. Such substances usually

have the following characteristics: molar mass >100 g mol-1;
polyfunctionality (two or more functional groups); multiple
molecular conformations; complex molecular interactions,
such as large dipoles, high polarisability, hydrogen bonding,
and charge-transfer complexes; and, very importantly, limited
amounts of reliable measured data, as their critical parameters
and/or melting properties cannot be determined experimentally (Fornari et al. 2010).
Correlation of solubility requires not only robust thermodynamic models but reliable methods to estimate the values of
the solid compounds thermophysical properties (e.g., critical
and melting properties) because inaccuracy in the properties
plays a major role in the quality of the SFE predictions. This
is a very challenging task on its own, moreover that there are
very big deviations between the values estimated and reported
by the different authors applying different methods. In view
of this, a range of effective methods to estimate the solute
properties should be available within the TMF.
The two groups of properties of the pure solid solute
required for modelling its solubility in SCF are its critical
parameters and melting properties. For a liquid solute (such
as essential oils, and di- and triglycerides), only critical parameters are required, while for a solid solute both the critical
and the melting properties are needed.
For most of the solutes
extracted from vegetable material, the critical properties may
not be experimentally accessible because of thermal cracking below their critical temperature. Hence, the values of the
critical parameters and normal boiling temperatures should
be considered as hypothetical quantities rather than properties
with any physical meaning, which have to be estimated either
by correlations or group contribution methods.
A concise but critical analysis of the methods applied to
estimate the critical parameters of solid solutes can be found
in Fornari et al. (2010), and we will not further pursue this
topic here. Still, it should be noted that usually there are no
experimental data available with which to compare the estimated values. In view of this, it is recommendable to apply
as an assessment tool of the reliability of the properties estimated the generalised semitheoretical expression advocated
by Zbogar et al. (2006):
4.3.1. Critical parameters
Tc/Pc = 9.0673 + 0.43309 (Qw1.3+Qw1.95)
(15)
where Tc is in Kelvin and Pc is in bar. The dimensionless

parameter Qw is a measure of the van der Waals molecular
surface area and is calculated as the sum of the group area
parameters, Qk:
Qw = kQk
k
(16)
where k is the number of times group k appears in the molecule. The group area parameters Qk are available in the
UNIFAC tables.
The influence of the uncertainties in the values of the critical parameters is explored in detail by Gordillo et al. (2005b)
105
although for a different type of solid solutes, namely dyes.

The authors employ several methods to estimate the critical parameters of blue 14, a disperse anthraquinone dye, and
demonstrate that the choice of a particular group contribution method was more important than the choice of the EoS;
for example, for the SRK cubic EoS, the Lydersen (1955)
method, combined with Meissner group contribution method,
leads to a better value for the AARD of the dye solubility than
Joback and Reids (1987) method. The latter is not surprising
taking into consideration that the former gives an excellent
approximation to the theoretically calculated Tc/Pc ratio for
blue 14 (31.56), namely 32.11 versus 42.85 for the latter.
It has been demonstrated that
the sublimation pressure plays a dominant role in the correlation of solubility data and that, in many cases, the only way to
obtain a reasonable calculation of these data is to consider the
sublimation pressure as an adjustable parameter (Reverchon
et al. 1995a, Neau et al. 1996). It has also been shown that,
in the case of high molar mass compounds for which sublimation pressures cannot be measured, the safest way to estimate them is to correlate experimental vapour pressure data
through an analytical relation and to use normal fusion properties in order to settle the sublimation pressure equation with
respect to temperature (Neau et al. 1999).
Thus, a possible route to estimate the sublimation pressure
of a solid compound is to integrate the Clapeyron relation
from the triple-point temperature Tt and pressure Pt, assuming a negligible dependence of the sublimation enthalpy with
respect to temperature (Neau et al. 1999):
4.3.2. Melting properties
P s H s 1 1
ln = R T Tt
Pt
(17)
where H s is the sublimation enthalpy at the triple point of

the pure component, which can be expressed with respect to
the fusion and vapourisation enthalpies as
H s = H fus + H vap
(18)
The practical interest of this method is thus to require,

besides an EoS, fusion property data that can be either measured, found in the literature, or estimated (Garnier et al.
1999).
In most cases the triple-point conditions (the temperature
and pressure at the triple point) for the solute are unknown
experimentally. However, for almost all heavy compounds,
there is little difference between the triple-point temperature
and the normal melting temperature. Indeed, this difference is
usually <0.1 K, which is less than the scattering of experimental values of transition temperatures found in the literature.
Furthermore, the difference in the heats of fusion at these two
temperatures is also often negligible (Perry and Green 1999).
Under this assumption, the enthalpy of fusion in Eq. (17) can
be estimated with the fusion enthalpy measured at the normal
melting temperature. Hence, if the melting temperature of the
compound of interest is known it is possible to calculate Pt
and H vap from an EoS.

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Coniglio (1993), Trassy (1998), and more recently Neau

et al. (1999) and Crampon et al. (2004) discuss in detail the
reliable methods, among the numerous ones devoted to this
subject. We would like, however, to mention also the contribution of Valderrama and Zavaleta (2005) who propose
to calculate the sublimation pressures of pure solids from
high-pressure solubility data using genetic algorithms. The
sublimation pressure is considered as a parameter to be determined by regression analysis of experimental solubility data,
and hence an optimisation problem, in which the difference
between the correlated and experimental data of solubility is
to be minimised, is solved using a method that applies biologically derived techniques such as inheritance, mutation,
natural selection, and recombination to find the optimum
solution.
In the case of compounds that may decompose before the
melting point, all fusion properties have to be estimated.
For example, Jain et al. (2004) advocate a combination of
additive group contributions and non-additive molecular
parameters to estimate the normal melting points of 1215
organic compounds. The melting points are calculated from
the ratio of the total phase change enthalpy and entropy of
melting. The total phase change enthalpy of melting is calculated from the enthalpic group contributions, whereas the
total phase change entropy of melting is estimated using a
semiempirical equation based on only two non-additive
molecular parameters.
If, however, the melting temperature is known, then it
is possible to estimate H fus from the following empirical
equation:
H fus = 4.184kT fus
(19)
where k is an empirical parameter related to the properties

of the solute, and for organic compounds it is usually in the
range 1016 (Chen and Ma 2004). Yet another possibility is
to estimate the sublimation enthalpy solely on the basis of the
value for Hvap, taking into consideration that H fus is usually
less than one quarter of the sum given by Eq. (16) (Prausnitz
et al. 1999).
Another route to pursue is presented by Coutsikos et al.
(2003) who advocate a group contribution method for the prediction of the vapour pressures of organic solids, based on the
concept of the hypothetical liquid:
S Tm
1R T
fus
ln P S = ln P L +
(20)
The vapour pressure of the hypothetical liquid is obtained

using the Abrams-Massaldi-Prausnitz equation developed
for liquids (Abrams et al. 1974), and the entropy of fusion is
estimated applying a group contribution method. Coutsikos
et al. (2003) underline that experimental values for the
entropy of fusion for most of the compounds are not available and reliable predictions of these values are extremely
difficult and the few available correlations are cumbersome
to use (e.g., Chickos et al. 1990, 1991, Dannenfelser and
Yalkowsky 1996). Thus, the authors advocate a group contribution method to predict values for the entropy of fusion
with typical deviations from the experimental ones, where

available, of about 10% to 25%. Taking into consideration
the simplicity of the proposed method for such a difficult
task, it appears sufficient for the needs for sublimation pressure predictions. The overall error for the families of organic
compounds considered (hydrocarbons, halogenated aromatics, nitro-aromatics, alkanols, phenols, acids, ketones, and
multifunctional ones) is in the range of 1040%, and the error
for the total of about 2650 data points exceeds one order of
magnitude in very few cases.
Finally, if no experimental data for the solid molar volume
is available, a value can be estimated according to the following extended relationship (Goodman et al. 2004), which
allows including temperature dependence for solid density
from Tt to substantially lower temperatures:
T
solid (T ) = 1.28-0.16 liquid (Tt )
Tt
(21)
where solid is the solid density and liquid (Tt) is the liquid density at the triple point, which is calculated from an EoS.
Needless to say that the lack of reliable experimental data
for most of the solutes extracted from vegetable matrices
forces the application of correlations and estimation methods.
The latter, of course, inevitably leads to uncertainties in the
values obtained.
The uncertainties in the values of the parameters of the
pure components can seriously influence the quality of SFE
predictions. Sovova et al. (2001a) show on the example of
the triolein+CO2 binary that the uncertainties in the values of the critical parameters might have a dramatic effect
on the phase behaviour calculations and on the predicted
extent of the VL region. Thus, applying some of the estimations of triolein critical parameters, the system was erroneously predicted to be homogeneous at very low values of
the pressure.
However, it should be underlined that to perform a detailed
analysis of the influence of the thermophysical properties
uncertainties on the phase behaviour predictions and calculations of a solute+SC solvent binary is a very complex task and
must be explored from many different angles.
4.4. Computational techniques to solve the
equilibrium relations
The third vital element of a TMF comprises methods, algorithms, and numerical routines to model the complex phase
behaviour of the solid+SCF (+entrainer) systems solve the
equilibrium relations and calculate the solubility.
Fornari et al. (2010) point out that correlating the solubility
even for the simplest cases can be a very challenging task as
the weakness of phase equilibrium predictions using an EoS
are resulting not only from the weakness of the equation itself
but also from the computational techniques applied. Xu et
al. (2000) underline that when calculating the solubility of a
solid at new conditions using a particular EoS model, there
are two computational pitfalls that can be encountered in the
calculation of solid-fluid equilibrium:

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(i) Solid solubilities in SCFs are usually computed by locating a mole fraction, which satisfies the equi-fugacity
equation relating the solute fugacity in the SCF, as predicted by the EoS, and the fugacity of the pure solid
[see Eq. (5)]. However, at certain values of temperature,
pressure, and kij, there can exist multiple solutions to the
equi-fugacity condition. A common method for solving
the equi-fugacity equation is successive substitution or
some similar approach, using some small value of the
solid solubility in the fluid phase as the initial guess. In
general, this strategy will only find the smallest solubility root and may miss any larger values, if present, that
satisfy the equi-fugacity equation. Thus, what is needed
is a completely reliable method to determine all the roots
to the equi-fugacity equation.
(ii) Equi-fugacity is a necessary but not sufficient condition for stable solid-fluid equilibrium. Solutions to the
equi-fugacity equation must be tested for global thermodynamic phase stability.
The problem can become even more complex, because a
molecularly dissimilar system (different molecular size and
force interactions) can exhibit very complex phase behaviour in the PT thermodynamic phase space. For example,
the onset of liquid-liquid immiscibility can occur either as a
break in the critical point locus or can outgrow from the
solid-liquid-gas (SLG) locus. This outgrowth of the liquidliquid-gas (LLG) behaviour changes the nature of the SLG
locus from a continuous one to one of two branches (with different composition of the liquid phases), and is accompanied
by the formation of a quadruple point (solid-liquid-liquidgas, SLLG), from which four three phase loci originate. As
molecular differences between the pure components become
more pronounced, and the melting temperature of the heavier
component is higher than the critical temperature of the solvent, the l = g critical point locus becomes discontinuous.
Further molecular dissimilarities will cause the pure component phase equilibria in the PT space to draw further apart
and the LLG will be replaced by two separate liquid-vapour
regions, and the two disconnected SLG loci, terminating at
an upper critical end point and at a lower critical end point,
respectively, will have markedly different compositions. The
PT diagram of the latter phase behaviour is usually referred
to as typical for a solid+solute binary (Garcia and Luks 1999,
Labadie et al. 2000).
Moreover, in the presence of the solvent, the melting curve
of the solute can be depressed, lowering its melting point.
There are cases known of up to 70C depression of the melting point of a solute (Lemert and Johnston 1989). If this fact
is not taken into consideration, and particularly when there
is no optical view cell to observe the sample, then there is a
strong possibility to mistakenly accept and report the experimental data as solid-fluid equilibrium, while in reality it is
vapour-liquid, and there is no solid present.
Furthermore, for solid+SCF binaries, for which the difference between the melting temperature of the solute is not
much higher than the critical temperature of the solvent CO2
(304.2 K), any of the PT diagrams discussed above is feasible
107
and the possibility to mistakenly interpret the solubility data

measured is even stronger. For example, the solubility measurements for naphthalene (melting temperature 353.65 K)
and biphenyl (melting temperature 344.15 K) in SC-CO2
were initially reported as representing solid-fluid equilibrium
because it was not realised that the experiments were carried
out at temperatures in the vapour-liquid region (at temperatures above the upper critical end point). It was only later
acknowledged that these measurements were actually representing the composition of a vapour phase in equilibrium
with a liquid and that there was no solid present (McHugh and
Paulaitis 1980, Xu et al. 2000).
Thus, to have a viable and detailed description of the phase
behaviour of a solid+SCF system in the thermodynamic phase
space, and to correlate reliably the solid solubility, in addition
to solute physical properties and a thermodynamic model, a
variety of robust, effective, and efficient flash routines (SLG,
LLG, LG, etc.), algorithms, and numerical procedures are
required.
When three phases, namely solid, liquid, and vapour, are in
equilibrium, the following equations must be satisfied:
T S= T L = T V
(22)
PS = PL = PV
(23)
f = f =f
S
i
L
i
V
i
i = 1, 2
(24)
The liquid-vapour equilibrium conditions for the CO2+solid

solute binary system, applying the above equations, are
1L x1 = 1V y1
(25)
2L x2 = 2V y2
(26)
where the subscript 1 corresponds to SC-CO2 and subscript 2

to the solid solute. Furthermore, it is assumed that the solid
phase is pure solute, and hence for the solid-liquid equilibrium the following holds:
S2 = 2L x2
(27)
The following constraints also apply for the liquid and

vapour phases:
2
x =1
(28)
i =1
y =1
(28a)
i =1
The fugacity coefficient of the solid solute is calculated

according to (Prausnitz et al. 1999):
ln S2 = ln 2PSL +
H TP 1 1 VTP
- +
(P -PTP )
R TTP T RT
(29)
Equation (29) relates the fugacity coefficient of the solid

solute to the fugacity coefficient of the pure solute in the

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subcooled liquid phase at temperature T and pressure P ( 2PSL ),

and it is assumed implicitly that there are no solid-solid phase
transitions and that the solid phase is incompressible.
The above system of equations is strongly non-linear and
may have several solutions. The non-uniqueness is a particular problem and is a result of the mathematical presence of
local minima and maxima in the Gibbs energy surface. This,
in turn, relates to convergence to a local rather than global
minimum, and to the impossibility to distinguish among
thermodynamically stable and unstable equilibrium states.
As pointed out previously, the equality of chemical potentials represents a necessary but not a sufficient condition for
equilibrium, and hence a stability analysis routine and a phase
identification procedure must be employed at each step to find
with guarantee the phase configuration with the minimum
Gibbs energy, which is particularly important in regions of
the thermodynamic phase space where the EoS has multiple
roots as is the case around the SLG locus.
Somewhat surprisingly, the practice of searching for all
roots to the equi-fugacity condition and testing for phase stability appears not to be widespread among those who measure, model, and compute high-pressure solid-fluid equilibria
(Xu et al. 2000).
Still, the need to test for stability and its influence on phase
diagrams has been an area of interest to some researchers.
We will like to mention particularly the works of Xu et al.
(2000) and Scurto et al. (2003) who described a new method
for reliably computing solid-fluid equilibrium without and
with co-solvents at constant temperature and pressure based
on interval analysis, in particular, an interval Newton/generalised bisection algorithm; Marcilla et al. (1997), who focused
on low-pressure solid-liquid equilibrium and the need for
stability analysis and were able to carefully map out the full
phase diagrams for their selected systems, as well as the contributions by Corazza et al. (2004) and Sovova et al. (2007a).
However, as pointed out by Fornari et al. (2010), it is only fair
to say that some of the above-mentioned researchers applied
local, initialisation-dependent solvers, which in general neither provide guarantee that all equi-fugacity roots are found
nor that phase stability analysis is done correctly, while Xu
et al. (2000) and Scurto et al. (2003) were the first to present a technique that provides a mathematical and computational guarantee that all roots to the equi-fugacity equation are
enclosed and that phase stability analysis is performed correctly and thus the stable solution to the solid-fluid problem is
determined with certainty.
5. Mathematical models for SFE kinetics

Mathematical models that effectively describe the extraction
kinetics of solid substrates in packed beds operating with SCFs
are useful tools for the design and scale-up of SFE processes,
with predictive models being of special interest to assess process feasibility preliminarily, and/or to validate experimental data for process scale-up (del Valle et al. 2006). Several
aspects distinguish the SFE from plants from the extraction
with conventional solvents. First, the external mass transfer
from plant surface to bulk fluid is much faster due to the

excellent transport properties of SCFs. Thus, as long as there
is enough solute near the plant surface, the solution flowing
out of the extractor is saturated or near saturated. Second, a
dry solvent such as pure carbon dioxide gradually removes
from the plant the moisture remaining there after drying usually in the concentration of 810 wt.%. The permeability of
an overdried plant tissue is extremely low, the diffusion of a
solute through the plant surface is very slow, and thus it is
easy to distinguish between the initial period of fast extraction of easily accessible solute and the final period with much
slower extraction. Brunner (1994) explains the sensitivity of
cell walls to the moisture by the properties of an elementary
membrane. The membrane consists, according to Danielli, of
three bimolecular lipid layers with pores that can be passed by
water and by lipids. If there is not enough water in the system,
the pores are closed and the membrane becomes impermeable. Third, the low kinematic viscosity makes SCFs prone
to natural convection induced by even small density gradients related to the differences in concentration (due to the
extraction) or in temperature (due to the heat transfer through
the wall of extractor). As a result, the flow pattern could differ significantly from the plug flow, which ensures the best
extractor performance.
The most easily available experimental data on extraction
kinetics are the extraction curves, the dependence of extraction yield on either extraction time, or the solvent-to-feed
ratio, directly proportional to the time. These curves are
compared with a mathematical model to adjust its parameters and to check whether it corresponds to the reality. To
distinguish better between different models, del Valle et al.
(2000b) recommend a multiobjective fitting strategy when
both experimental extraction curves and experimental residual concentration profiles in solid phase should be fitted by
the models.
A phenomenological model for SFE from plant materials is
a mathematical description of extraction kinetics in the form
of equation or a set of equations defining the solute concentrations in the extractor in dependence on extraction time and
spatial coordinates. The extraction yield is then calculated
from the outlet concentration. The models are usually not predictive; some of their parameters can be estimated according
to literature correlations but at least one parameter is adjusted
to fit experimental data.
The extraction process comprises phase equilibrium or
adsorption/desorption kinetics, diffusion through the plant
particles to their surface, external mass transfer from particle
surface to the bulk fluid, and displacement with the flowing
solvent. Different types of models are obtained combining
different expressions for these steps. Probably the most thorough overview was published by del Valle and de la Fuente
(2006), who focus on the extraction of vegetable oils but also
mention the models for other types of solutes. The paper also
contains a valuable survey of published correlations used to
estimate some model parameters: binary diffusion coefficient
of extracted substance in supercritical solvent, external mass
transfer coefficient, coefficient of axial dispersion, effective
internal diffusion coefficient, and also the relationships for

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the extract solubility in SCF and/or for its adsorption isotherm, when it is adsorbed on vegetable matrix. del Valle and
de la Fuente (2006) started with a complex model and showed
different possibilities for its simplification.
Al-Jabari (2002) regarded the models as sets of blocks
describing individual extraction steps; one or more blocks
could be deleted when the corresponding step was marginal
under given conditions. In the present paper, we follow the
scenario advocated by Al-Jabari (2002) and judge on the
importance of individual steps according to their characteristic times. Where possible, the relationships are presented
in dimensionless form to facilitate comparison of the results
from the papers using different notation.
5.1. Mass balance for solute
The basis for phenomenological SFE models is a differential

mass balance equation for the solute in the packed bed (del
Valle and de la Fuente 2006). On the assumption of plug flow,
the mass balance equation for the fluid phase is
c
c
+ u = J , c(h = 0) = 0,
t
h
c(t = 0) = c0
(30)
where is the free void of extraction bed, c is the fluid phase

concentration (kg m-3), t is the extraction time, u is the interstitial velocity, h is the axial co-ordinate, J is the mass transfer
rate per unit volume of bed, and the subscript 0 denotes the
state at t = 0. The mass balance equation for the solute in the
solid phase is
(1-)
cs
= -J , cs (t = 0) = cs 0
t
(31)
where cs is the average solid phase concentration (kg m-3).

Time-dependent concentration profiles for fluid and solid
phase are obtained by integration of these equations. The
extraction yield is calculated from the fluid phase concentration at the extractor outlet:
t
e=
q
c (h = H ) dt ,
f 0
e(t = 0) = 0
(32)
where e is the extraction yield in terms of mass of extract

over the mass of plant inserted into extractor, q is the specific flow rate in terms of the solvent mass flow rate over the
mass of plant, f is the solvent density, and H is the height of
the packed bed. Eqs. (30) and (31) contain the mass transfer
rate per unit volume of the extractor, J, which is given by the
equation for external mass transfer:
J = k f a (c+-c)
(33)
where the superscript+indicates the surface of a plant particle, kf is the fluid phase (external) mass transfer coefficient,
and a is the specific surface area. The concentrations at the
particle surface are usually assumed to satisfy an equilibrium
relationship:
( )
c + = c* cs+
109
(34)
where cs is the local concentration within the particles and

the superscript * denotes equilibrium. The solid phase
concentration at particle surface, cs+ , is related through an
internal mass transfer relationship to the average particle
concentration. For example, the mass balance for a spherical particle of radius R and effective internal diffusion coefficient De is
cs 3De cs
=
t
R r
=
r=R
J
1-
(35)
where r is the radial co-ordinate (Esquvel et al. 1999, del

Valle et al. 2000b).
The initial concentrations at t = 0 when the outlet valve
opens and the solution begins flowing out of the extractor are
related to the content of the solute in the plant put into the
extractor, cu (kg m-3):
cu -cs 0 =
c0 .
1-
(36)
They are usually chosen either on the assumption that no

mass transfer has taken place until t = 0, it is c0 = 0 and cs0 = cu,
or, on the opposite, on the assumption that phase equilibrium
has been established during the static extraction before the
solvent starts flowing out of the extractor. The real initial
concentrations may be between these limits and depend on
the rate of mass transfer during the period of static extraction
before t = 0. The models for the mass transfer during static
extraction were published by Al-Jabari (2002) and Steffani
et al. (2006).
The content of solute in the plant loaded into the extractor is primarily expressed in mass fraction xu, (kg solute)
(kg plant)-1, which can be converted to units (kg solute)(kg
matrix)-1, where matrix is the insoluble part of the plant.
Similarly, the contents of solute in both phases in the extractor
are often expressed in mass ratio y (kg solute)(kg solvent)-1
and either mass fraction or mass ratio x, x expressed as (kg
solute)(kg plant)-1 or (kg solute)(kg matrix)-1, respectively.
The conversion between the volume-related and mass-related
quantities is via densities f and s, where s is the density of
plant particles calculated as either mass of plant or the mass
of matrix over the volume of plant:
c = f y,
cs = s x,
cs = s x .
(37)
(The solute, the volume of solid phase, and also the specific
flow rate are related to the mass of matrix when the initial
content of solute in the plant is high and thus the mass of
the plant varies considerably during the extraction.) The
alternative form of the model equations expressed in y and
x is
y
y
f + u = J ,
t
h
y(h = 0) = 0,

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y(t = 0) = y0
(30a)
110
(1-) s
x
= -J ,
t
x ( t = 0 ) = x0
(31a)
e = q yout dt , e (t =0) = 0
(32a)
J = kf a f ( y+-y)
(33a)
y+ = y*(x+)
(34a)
x 3De x
=
t R r r = R
(35a)
xu -x0 =
s (1-)
y0 = y0 .
(36a)
5.2. Extraction steps and their characteristic times
For any flow

pattern, the characteristic time of washing out is equal to the
mean residence time, tr = H/u. The course of washing out of a
solute from the extractor is, however, not only a function of
the dimensionless extraction time = t/tr but is also closely
related to the flow pattern, as shown in Figure 3. Plug flow is
an idealisation. In reality, axial dispersion is always present
in the extractor, at least the dispersion by molecular diffusion
and small-scale mixing due to the flow between the particles.
The mass balance for the fluid phase with the coefficient of
axial dispersion Dax, combined with the Danckwerts boundary
conditions, is
5.2.1. Washing out (fluid displacement)
c c
2c
+ u -Dax 2 = J ,
h
h
t
uc-Dax
c
=0
h
(30b)
for h = 0,
c
= 0 for h = H.
h
1.2
1.0
e/x, g/g
0.8
0.6
0.4
0.2
0
0
, -
Figure 3 The effect of flow pattern on washing out of the solute

from the extractor: () plug flow, ( + + ) ideal mixer.
The value of Dax for SFE from plants is usually estimated

from literature correlations for Peclet number, such as those
developed by Tan and Liou (1989), Catchpole et al. (1996b),
Funazukuri et al. (1998), or Yu et al. (1999).
It seems, however, that these correlations based on the data
measured without mass transfer may not be always valid in
the situation of mass transfer in the extractor because the mass
transfer causes concentration gradients leading to density gradients, which can invoke or suppress mixing, as mentioned
below in Section 5.2.3. Reis-Vasco et al. (2000) extracted
with CO2 the essential oil from leaves and observed that the
axial dispersion coefficient was by one order of magnitude
larger than according to the correlations and still the effect of
axial dispersion on extraction kinetics was quite small. On the
other hand, Zwiefelhofer and Brunner (1993), who extracted
theobromine from cocoa shells, found a stronger dependence
of the coefficient of axial dispersion on Reynolds number
than according to the correlations.
Another form of the fluid phase mass balance frequently used
for short (small) extractors is the lumped parameter model:
dc c
+ = J ,
dt tr
c(t = 0) = c0.
(30c)
Mathematically, this model is identical to the model for

continuous stirred tank extractor (ideal mixer).
The axial mixing can also be expressed by a series of n
ideal mixers into which the extractor is divided along its
height (Clavier et al. 1995, Reverchon 1996, Sovova 2005).
The model is identical to the lumped parameter model for
n = 1 and approaches the model with plug flow for a high
number of mixers.
Another flow pattern was used in a model for extractor
divided on its cross section into zones with parallel plug flows
of different rates. When the extractor is scaled-up, attention
should be paid to flow patterns because the flow in the packed
vessels of larger diameter becomes less homogeneous.
Brunner (1994) showed that the local degree of extraction
depends also on the radial coordinate of extractor. Particularly
at small flow velocities, the local velocity and mass transfer
are higher near the wall and thus the residual concentration
in the particles is higher close to the axis of the extractor.
Brunner (1994) suggests using the model with axial dispersion separately for the centre and the rim, with the amount of
solvent for each section as an additional parameter, to simulate the radial distribution. A similar solution with the extractor divided into up to six parallel sections with plug flow of
different flow rates was proposed by Sovova et al. (1994a) to
fit experimental extraction curves affected by natural convection in the extractor where the SC-CO2 dissolving vegetable
oil flowed from the bottom to the top. When del Valle et al.
(2004a) extracted oil from milled seeds in a laboratory-scale
extractor of 20 mm inner diameter and in a pilot extractor
with a sample holder of 90 mm inner diameter, they found
that the plug flow pattern was adequate for the smaller extractor (the axial dispersion was too low to affect the extraction
rate), while the simulation of extraction rate in the larger
extractor required dividing the extractor into inner and outer

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zones of different flow rates. A review of the literature on the

scale-up of pressurised fluid extractors was recently published
by Pronyk and Mazza (2009).
Catchpole et al. (1996a) investigated the effect of extractor geometry on the extraction rate, comparing the extraction
curves measured in the standard extractor with axial flow and
in an extractor with radial horizontal flow through the bed of
particles. When the extraction was controlled by external mass
transfer, the extraction with the horizontal solvent flow was
much slower than with the axial flow. The residual oil content
in the particles was significantly higher at the bottom than at
the top of the bed, indicating that the bottom was bypassed.
5.2.2. Phase equilibrium With respect to the extraction
from plants, it is necessary to mention that phase equilibrium,
in addition to its dependence on pressure and temperature,
is often affected also by the solute interaction with the plant
matrix, particularly when the content of the solute in the plant
is low a few weight per cent or less. The equilibrium fluid
phase concentration then decreases during the extraction, as
sketched in Figure 4. The solubility, csat, as a characteristic of
solute-solvent equilibrium can be applied particularly in the
extraction of oils from seeds where the initial content of solute
is expressed in tens of per cent. A widely accepted correlation
for the solubility of common vegetable oils composed mostly
of C18 fatty acids in dense CO2 was published by del Valle
and Aguilera (1988):
csat =
10.742
f
18708 2186840
exp -26.810+
T
T 2
(38)
where T is the temperature in kelvins and both csat and f are

in kg m-3. The equation is valid for pressures from 15.2 to
89.2 MPa, temperatures from 20C to 80C, and oil solubility
below 100 kg m-3.
If there is no solute-matrix interaction, the equilibrium
fluid phase concentration remains constant as long as there is
still any solute in the solid phase:
c* = csat for cs* > 0,
y* = ysat for x* > 0,
c* = 0 for cs* = 0, or
y* = 0 for x* = 0.
(39)
Such discontinuous relationship could complicate numerical solution of differential equations of SFE models. Lee
c*
c*
csat
csat
111
et al. (1986) proved experimentally that the fluid phase concentration of canola oil extracted from seed flakes with SC-CO2
was constant and in agreement with Eq. (38) in the range of
initial oil content, 0.20.7 g (g oil-free seed)-1. However, a
decrease of equilibrium oil concentration was described in
other works after the oil content in seeds decreased below
approximately 25% (Bulley et al. 1984) or 15% (King et al.
1987), as depicted in the review of del Valle and de la Fuente
(2006). This phenomenon was observed also by Perrut et al.
(1997) who extracted sunflower seed oil. They proposed a
simple equilibrium relationship combining the oil solubility
ysat for oil content in seed higher than a transition value xt and
a linear equilibrium corresponding to oil-matrix interaction
for lower oil content in seed, with a mass-related partition
coefficient Km:
y* = ysat for x* > xt,
y* = Kmx for x xt,
Kmxt < ysat (40)
Equation (40) can be readily converted to the relationship

of volumetric concentrations c, cs. The more general Eq. (40)
is reduced to Eq. (39) when the transition concentration xt is
set to zero.
The most frequently used relationship in the case of solutematrix interaction is a linear sorption isotherm with a constant
partition coefficient K:
K m = K s f .
c*= Kcs or y* = K m x,
(41)
More complicated equilibrium relationships in the models

for SFE are different adsorption isotherms such as Langmuir
isotherm applied by Clavier et al. (1995) and Subra et al. (1998),
Freundlich isotherm applied in the VTII model (Zwiefelhofer
and Brunner 1993, Brunner 1994) and later, e.g., by Ghoreishi
and Sharifi (2001), or the BET isotherm applied by Goto et
al. (1998). Different equilibrium relationships were mutually
compared (Salimi et al. 2008). Araus et al. (2009) propose that
the sorption isotherms should be experimentally determined
when modelling a given extraction process instead of selecting
a certain equilibrium relationship in advance.
5.2.2.1. Equilibrium extraction The equilibrium extraction
is an extraction with negligible mass transfer resistance. The
characteristic time of equilibrium extraction is based on the
assumption that the extraction rate is limited only by the initial
fluid phase equilibrium concentration established at t = 0 when
c0 = c*(cs0). Thus, the characteristic time teq and the dimensionless time of equilibrium extraction eq are, respectively
teq =
1- cs 0
tr ,
c0
eq =
teq
tr
(42)
Particularly, for the two cases without solute-matrix interaction and with linear equilibrium:
cs
ct
cs
Figure 4 Equilibrium relationships: () no solute-matrix interaction, Eq. (10); (---) transition to linear equilibrium, Eq. (11); ( + + )
solute-matrix interaction with linear equilibrium, Eq. (12).
eq =
1- cu
-1
csat
eq =
1-
K
when c* = csat,
when c* = Kcs.

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(43)
The expression eq for linear equilibrium is a reciprocal

value of the dimensionless parameter introduced by Poletto
and Reverchon (1996) in their parametric analysis of a model
for the SFE with plug flow, internal or external mass transfer
resistance, and linear equilibrium. The paper contains also
the analytical solution of equilibrium extraction equations for
plug flow, which is valid for both equilibrium relationships
from Eq. (40). The concentration profile in the extractor is
a discontinuous function of dimensionless axial co-ordinate
z = h/H:
where is the characteristic dimension of a particle equal to

its volume-to-surface ratio ( = R/3 for a spherical particle of
radius R). The models for the extraction from particle surface
(or from the particles with negligible internal mass transfer
resistance) are obtained combining mass balance equations
for both phases, Eq. (33) for the external mass transfer, and
phase equilibrium relationship. As the internal mass transfer
resistance is neglected, the concentration is assumed to be
uniform across the particle and Eq. (34) is modified to the
relationship
c cs
= = 1 for z
and <1+ eq ,
1+ eq
c0 cs 0
c + = c*(cs ) .
(44)
c cs
= = 0 else,
c0 cs 0
and the extraction yield increases linearly until the extraction
is complete:
e
=
for <1+ eq ,
xu 1+ eq
e = xu else.
(45)
On the other hand, the analytical solution of equilibrium

extraction with linear equilibrium described by the lumped
parameter model is

e
=1- exp
xu
1+ eq
(46)
(Goto et al. 1993, Al-Jabari 2002). Both extraction curves are

compared in Figure 5. Evidently, the shape of the equilibrium
extraction curve is determined by flow pattern in the same
way as in the case of a simple washing out of a solute.
5.2.3. External mass transfer and extraction from
particle surface It follows from Eqs. (30) and (33)
that the characteristic external mass transfer time and the

dimensionless external resistance are, respectively:
tf =

=
,
k f a k f 1-
f =
tf
tr
,
k f atr
(47)
1.2
1.0
e/x, g/g
0.8
0.6
0.4
(34b)
5.2.3.1. Model for plug flow + no solute-matrix interaction Brunner (1984) introduced into the modelling of SFE
from plants a relationship valid for plug flow and no solutematrix interaction (when the equilibrium fluid phase concentration equals the solubility of solute in the solvent, csat),
which reads in the nomenclature of the present paper
1
z e

c
=
1- exp - .
=1- exp - ,
f
csat
f xu 1+ eq
(48)
Brunner (1984) used this relationship to describe the

initial period of oil extraction from pre-pressed seed.
According to Eq. (48), the extraction rate is constant and
the corresponding section of extraction curve is a straight
line. This equation is valid as long as all particles contain
the solute. Lee et al. (1986) solved the mass balance equations numerically for both the initial period and the second
extraction period, when the solute is exhausted first at the
extractor inlet and then the region free of solute extends
until it reaches the extractor outlet. The model was fitted
to both experimental extraction curves and experimental
solid phase concentration profiles cs(h, t). The experiments
with oil extracted from crushed seed with SC-CO2 were
conducted in a wide range of flow rates and the evaluated
external mass transfer coefficient was found to be directly
proportional to u0.54.
Although the extraction rate of oil from seed usually agrees
with Eq. (48), S-shaped extraction curves were sometimes
observed (Cocero and Garca 2001). This could be related to
the mixing in the empty volume between the extractor and the
separator. When a basket with the plant particles was placed
into the extractor and a large empty space remained behind the
basket in the flow direction, the outlet concentration was much
lower than the oil solubility, although the residence time in the
basket was sufficient to saturate the solution (Fiori 2007). This
again could be explained by mixing of the saturated solution
with pure solvent filling initially the empty place.
5.2.3.2. Model for plug flow + partial solute-matrix
interaction Perrut et al. (1997) extracted sunflower oil
0.2
0
0
1+eq
, -
Figure 5 Equilibrium extraction with linear equilibrium: () plug

flow, ( + + ) ideal mixer.
from seeds and observed that the slower extraction in the

second period, following the first constant rate period, was
still controlled by phase equilibrium. They used therefore
in the model for SFE the equilibrium relationship given by
Eq. (40). The numerical solution of the model was compared

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113
Table 2 CO2 extraction from plants: external mass transfer coefficients based on experimental data for different solutes, particle sizes,
pressures and temperatures, and flow velocities.
Solute/plant
Substrate
k f 105 m s-1
k f a 0 102 s-1
References
Fatty oil
Fatty oil
Fatty oil
Fatty oil
Fatty oil
Fatty oil
Fatty oil
Essential oil
Oleoresin
Oleoresin
Flaked canola seed

Milled tomato seed
Milled grape seed
Milled sea buckthorn berries
Milled sunflower seed
Milled wheat germ
Crushed sunflower seed
Ground clove buds
Milled black pepper berries
Milled black pepper berries
0.21.4
0.40.6
2.2
0.251.6
0.67
410
0.051
19
0.31
0.32
0.030.08
Lee et al. 1986

Roy et al. 1994
Sovova et al. 1994a
Stastova et al. 1996
Cocero and Garcia 2001
Lucas et al. 2007
Perrut et al. 1997
Reverchon and Marrone 1997
Sovova et al. 1995
Ferreira et al. 1999
with experimental curves, and the equilibrium parameters and

kf were adjusted.
5.2.3.3. Model for plug flow + linear equilibrium Cocero
and Garca (2001) adapted a model for desorption from particle surface to simulate the extraction of oil from seed with
SC-CO2 modified with alcohols. The mass balance equations
were integrated numerically. The analytical solution of the
model equations, which evaluation however requires numerical methods, was published by Lucas et al. (2007).
5.2.3.4. Model for mixer + linear equilibrium Neglecting
the accumulation term in Eq. (30c) and using the equilibrium
relationship according to Eq. (41), Papamichail et al. (2000)
obtained analytical solution of the ordinary differential equations (in the present nomenclature):
cout =
Kcu
exp , =1- exp

1+ f
eq 1+ f xu
eq 1+ f
(49)
5.2.3.5. Model for mixer + partial solute-matrix interaction Moreover, Papamichail et al. (2000) solved the SFE
model for the conditions of negligible internal mass resistance, lumped parameters, and the equilibrium relationship
given by Eq. (40). The accumulation term in mass balance for
the fluid phase, Eq. (30c), was again neglected to obtain the
approximate analytical solution:
extraction curves measured once at a given flow rate and once

at a very low flow rate, when the solution at the extractor outlet is saturated. Several results of kf evaluation from experimental extraction curves are shown in Table 2. The kf values
are usually of the order of magnitude 10-6 m s-1, the volumetric
mass transfer coefficient is not far from 1 min-1, and the characteristic time of external mass transfer in SC-CO2, tf , is usually close to 1 min or even less. It is a common practice to use
Eq. (48) to evaluate kf via f . Nevertheless, it is evident from
Eqs. (48)(50) that the effect of external mass transfer resistance on the outlet concentration depends on the flow pattern,
as illustrated also in Figure 6 and discussed in the literature
(Sovova 2005). Thus, Eq. (48) should be used to evaluate kf
only when the flow pattern is close to plug flow. The lower
values of kf a obtained by Ferreira et al. (1999) are based on
experiments in a horizontal extractor where the flow pattern
was most probably different, as indicated by the results on
SFE in a horizontal extractor published by Catchpole et al.
(1996a).
Channelling is an exception from the rule that the characteristic time of external mass transfer in the SFE from plants
is only a few minutes or even tenths of minutes. When the
particles forming the extraction bed stick closely together,
the solvent breaks several channels in the bed and passes
through them with a high velocity. As the specific interfacial
1.2
yout
e y
1
, = sat
for t = 1+ f ( xu -xt ) ( ysat ),
=
ysat 1+ f xu xu 1+ f
K ( - t )
xK
yout = t m exp - m
,
1+ f
1+ f
(50)
K ( - t )
x
e
=1- t exp - m
for > t .
xu
xu
1+ f
where is the solvent-to-matrix mass ratio in the extraction
bed, = f /[(1-)s]. The models for SFE from particle surface enable, among others, calculation of kf from experimental extraction curves. The initial y(h = H)/ysat or c(h = H)/csat
ratio can be determined experimentally from initial slopes of
1.0
0.8
cout/cO, -
0.6
0.4
0.2
0
0
f, -
Figure 6 Extraction from particle surface: the dependence of outlet concentration on dimensionless external mass transfer resistance:
() plug flow, ( + + ) ideal mixer.

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114
area is extremely small, the external volumetric mass transfer

coefficient kf a decreases and tf increases by several orders of
magnitude against usual values. So it was for example in the
extraction of essential oil from sticky particles in a large-scale
extractor (Berna et al. 2000).
The external mass transfer coefficient in packed beds was
correlated with the physical properties of solute and solvent, flow velocity, and particle size d in terms of Sherwood,
Reynolds, and Schmidt numbers. The most frequently used
correlations to estimate kf in SFE models are listed in Table 3
together with references to some of their applications; more
extensive reviews of kf correlations together with ranges of
their validity are offered by del Valle and de la Fuente (2006)
and particularly by Puiggene et al. (1997). The last lines of
Table 3 indicate the correlations that include also the Grashoff
number, Gr, which is proportional to the density differences
in the fluid phase which induce natural convection. The natural (free) convection can enter the models for SFE either by
changing flow pattern, as mentioned above in Section 5.2.1,
or by changing kf as proposed in a series of papers by Stuber et
al. (1996), Puigenne et al. (1997), and Germain et al. (2005).
In the calculation of Sherwood number, the term containing
Gr is either added to the term for the forced convection in the
case of gravity assisted mass transfer (usually solvent downflow) or subtracted from it in the case of gravity opposed mass
transfer (usually solvent up-flow).
The numbers Sh and Sc include the binary diffusion coefficient of a solute in supercritical solvent, D. Although D
depends on pressure, temperature, and chemical composition, its value does not vary substantially under the conditions
of SFE. Its order of magnitude is usually 10-9 m2 s-1 or close
to this value. For example, D of essential oils in CO2 under
pressure of 910 MPa and at temperature 40C was found in
the range 110-8210-8 m2 s-1, and D of fatty oils in CO2 at
2830 MPa and 40C was 310-9 m2 s-1 (Germain et al. 2005).
Typical kf values under the conditions of SFE from plants,
calculated from the correlations, are then of the order of magnitude 10-6 or 10-5 m s-1.
The internal
mass transfer is characterised in the models by either effective
diffusion coefficient, De, or solid phase (internal) mass transfer
coefficient, ks, the later one in analogy to the external mass
transfer coefficient.
5.2.4. Internal and overall mass transfer
Table 3
5.2.4.1. Effective diffusivity According to Ficks second

law, the equation for symmetrical diffusion in a spherical particle of radius R is
c
cs De 2 cs cs
= 0 for r = 0, J = -De a s
=
r
,
r
t r 2 r r r
(51)
r =R
Bartle et al. (1990) simulated the SFE controlled by internal diffusion using this equation with initial and boundary conditions cs = cu for t = 0, cs = 0 for r = R. The solution
was taken from an analogical case of heat transfer from a
sphere:
e xu =1- x xu =1- cs cu ,
D t
e
6 1
=1- 2 2 exp -n2 2 e2
xu
n =1 n
R
(52)
The model is therefore called the hot ball model. The

higher terms of the infinite series become negligible after a
short time and the extraction curve is then
D t
e
6
=1- 2 exp - 2 e2 .
xu
R
(53a)
Thus, the effective diffusivity can be estimated from the

slope of a plot of ln(1-e/xu) against the extraction time at sufficiently high extraction times. The solution of a model for
mass transfer from a slab-like particle (Bartle et al. 1991b) is
of a similar form as Eq. (52).
The next step was made by Reverchon et al. (1993, 1994b)
who adapted for the SFE of essential oils a mathematical
description of heat transfer from a sphere that takes into
account also the external mass transfer. No interface was
assumed at particle surface as the internal diffusion was
assumed to take place in the pores of a porous particle that
are filled with solvent. The solution of model equations shows
that the external mass transfer resistance is important only in
the very beginning of the extraction and later it does not affect
the extraction kinetics because it is negligible in comparison
with increasing internal mass transfer resistance.
In their third paper on the hot ball model, Bartle et al.
(1992b) extended Eq. (52) by an expression including the
solubility of solute in the solvent, respecting the fact that
the fluid phase concentration is limited by the solubility. It
is evident, however, that the models where mass transfer and
Correlations for the external mass transfer coefficient (Sh = kf d/D, Re = udf /(), Sc = /f D).
Correlation
Published by
Applied by
Sh=2+1.1 Re0.6Sc1/3
Wakao and Funazkri 1978,

Wakao and Kaguei 1982
Tan et al. 1988
Brunner 1984, Recasens et al. 1989, Peker et al. 1992, Goto et al. 1993, 1996,
Ghoreishi and Sharifi 2001, Skerget and Knez 2001, Vedaraman et al. 2005
Reverchon et al. 1993, 1994a, Reverchon and Sesti Osseo 1994a, Goodarznia
and Eikani 1998, del Valle et al. 2004a, Perakis et al. 2005
Gaspar et al. 2003, Lu et al. 2007
Sh=0.38 Re0.83 Sc1/3

Sh=0.839 Re0.667 Sc1/3
Sh=0.206 Re0.8Sc1/3
Sh=Sh(Re, Sc, Gr)
Sh=Sh(Re, Sc, Gr)
Catchpole 1991 (PhD thesis),

cited in Brunner 1994, p. 160
Puiggen et al. 1997
Lim et al. 1990
Puiggen et al. 1997
del Valle et al. 2006, Araus et al. 2009

Roethe et al. 1992
Germain et al. 2005

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phase equilibrium are expressed independently, such as those

discussed below in Sections 5.35.6, correspond better to the
situation where both steps control the extraction kinetics.
5.2.4.2. Mass transfer coefficient The internal mass
transfer rate is often approximated by a function of the average solid phase concentration:
J = ks a s x -x + = ks a cs -cs+ .
(53)
The solution of Eq. (53) together with Eq. (31) and with
initial and boundary conditions cs = cu for t = 0, cs+ = 0 is
t
t
e
=1- exp - , ti = , i = i
xu
ks
tr
ti
(54)
where ti is the characteristic time of internal mass transfer.

The dimensionless internal mass transfer resistance i was
used, e.g., by Poletto and Reverchon (1996) in the analysis
of extraction kinetics. It can be shown that a formally identical result is obtained when a parabolic concentration profile
is assumed in the particles. After the parabolic concentration
profile substitution into Eq. (51) for spherical particle, into
analogous equations for diffusion in a long cylindrical particle, and in a slab-like particle, and after integration of these
equations with the above-mentioned initial and boundary
conditions one obtains
t
e
2
=1- exp - , ti =
xu
De
ti
(54a)
where is equal to 3/5 for a sphere, 1/2 for a cylinder, and 1/3
for a slab (Catchpole et al. 1996a, Reverchon 1996). Thus, a
conversion between the estimates of De and ks is possible:
De
; k = 5De/R for a sphere,
s
ks = 3De/R for a slab of thickness 2R.
ks =
(55)
The internal-to-external mass transfer resistance ratio is

often expressed in terms of Biot number Bi = kf R/De:
Bi = 5kf /ks for a sphere,
Bi = 3kf /ks for a slab of thickness 2R.
(56)
5.2.4.3. Applications The internal mass transfer was

a controlling step in the extraction of caffeine with nitrous
oxide from water-soaked coffee beans, where De in the pores
filled with water was as high as 110-10 m2 s-1 (Brunner 1984).
When essential oil is extracted with CO2 from dry plants, the
mass transfer resistance is by orders of magnitude higher.
Thus, the effective diffusivity of vanilla essential oil extracted
from chopped beans was estimated to 310-13 m2 s-1 (Nguyen
et al. 1991), essential oils from basil, marjoram, and rosemary leaves were extracted with De 1.210-132.810-13 m2
s-1 (Reverchon et al. 1993, 1994a), and De of essential oils
from sage and celery aerial parts and from coriander seed was
1.410-125.110-12 m2 s-1 (Catchpole et al. 1996a).
115
5.2.4.4. Overall mass transfer resistance and linear

driving force When linear equilibrium and parabolic con-
centration profiles in particles are assumed, the two driving

forces represented by the concentration differences between
the average solid phase concentration and the solid phase concentration at particle surface, Eq. (53), and between the fluid
phase concentrations at particle surface and in bulk fluid, Eq.
(33), are combined into a linear driving force and multiplied
by the combined mass transfer coefficient, kcomb, to calculate
the mass transfer rate:
J = kcomb a (Kcs -c),
kcomb =
kcomb =
kf
1+ KBi 5
1
kcomb
1 K
+ ,
k f ks
for a sphere,
kf
(57)
for a slab
1+ KBi 3
(Recasens et al. 1989, Goto et al. 1990, Peker et al. 1992).

A combined mass transfer resistance in terms of characteristic times can be introduced as
tcomb = t f +
K
t = t + t , comb = f + s eq .
1- s f s eq
(58)
It is evident from Eq. (58) that when the partition coefficient K is low, the external mass transfer resistance may affect
the overall mass transfer rate more than the internal mass
transfer resistance, although tf is much smaller than ts, or in
other words, although the external mass transfer coefficient is
considerably bigger than the internal mass transfer coefficient
(Peker et al. 1992). The dependence of extraction rate on both
mass transfer resistances was evident also in the extraction
of theobromine from cocoa shells, where the equilibrium is
described by Freundlich isotherm (Zwiefelhofer and Brunner
1993, Brunner 1994).
A good approximation of extraction curves calculated
with linear driving force and lumped parameter model offers
Eq. (49) when comb is substituted for f:
e
=1- exp .
eq 1+ f + s
xu
(49a)
5.3. One-stage models

5.3.1. Diffusion model
5.3.1.1. Model equations The model includes the internal
diffusion in a homogeneous and usually non-porous solid,
phase equilibrium at particle surface characterised by a partition coefficient, external mass transfer to bulk fluid, and flow
with the fluid to the extractor outlet.
Goodarznia and Eikani (1998) solved model equations
for linear equilibrium and flow with axial dispersion, using
the method of finite differences for the three independent
variables: time, axial coordinate of the extractor, and radial

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coordinate of spherical particles. del Valle et al. (2000b)

assumed a plug flow pattern in the extractor, divided the
extraction bed and the substrate particles into several discand spherical-shell-shaped volume elements, respectively,
and integrated the obtained ordinary differential equations in
time using a fourth-order Runge-Kutta method. This numerical solution technique was used also by Araus et al. (2009) to
integrate model equations for the flow with axial dispersion.
5.3.1.2. Simplified forms The diffusion model equations are
simplified using the assumption of parabolic concentration profile in the particles, enabling further combining the internal and
external mass transfer resistances using the linear driving force.
The concentration in the solid phase is then characterised by
the average solid phase concentration and the number of independent variables is reduced to two, the time and the axial coordinate. Brunner (1994) presented the VTII model with linear
driving force, Freundlich isotherm, and flow with axial dispersion. Catchpole et al. (1996a) published analytical solution of
equations of the diffusion model with linear driving force and
plug flow. The dimensionless fluid phase concentration profile is a function of two dimensionless variables, z/comb and
(t/tr-z)/(eqcomb). Its approximations are presented, too, and it
is shown that the extraction curve is reduced to Eq. (54a) when
the extraction is controlled solely by the internal mass transfer
and thus the flow pattern does not affect the extraction rate.
The model with plug flow, linear equilibrium, and neglected
external mass transfer resistance was derived by Reverchon
(1996) to simulate the extraction of sage; the model equations were solved using the method of characteristics or, alternatively, dividing the extractor axially into a series of mixed
extractors and integrating the set of ordinary differential equations by a fourth-order Runge-Kutta method. This model with
linear equilibrium, neglected external mass transfer resistance,
and plug flow pattern was analysed by Poletto and Reverchon
(1996) who evaluated the concentration profiles and extraction curves for different values of two dimensionless parameters = 1/eq and s. They concluded that the mass transfer
resistance can be neglected and equilibrium model can be used
when s/eq 0.02. When s/eq 2, the mass transfer resistance prevails, the concentration profiles in the extractor are
flat, and therefore the flow pattern has little effect on the overall
extraction rate; the mathematically simpler lumped parameter
model is then recommended. When s / eq is between 0.02 and
2, both equilibrium and mass transfer resistance must be taken
into account. These results are easily generalised to overall
mass transfer resistance when s is substituted by eqcomb.
The lumped parameter model has analytical solution
dependent on initial conditions. The extraction curve for zero
fluid phase concentration at t = 0 is
p exp ( p2 ) -p2 exp ( p1 )

e
where
=1- 1
xu
p1 -p2
1
p1 = -b + b2 -4 B ,
2
b =1+
1
comb
+ B, B =
1
p2 = -b- b2 -4 B ,
2
1
combeq
The dimensionless parameter used in the paper of Peker

et al. (1992) where this analytical solution was published is
equal to 1/[comb(1-)] in the present notation.
The adjustable model parameter is the effective internal diffusivity De, which is evaluated
by fitting the calculated extraction curves to experimental data.
The other model parameters are usually estimated from correlations (the external mass transfer coefficient and the axial
dispersion coefficient) or from an experimental extraction
curve, where the initial equilibrium fluid phase concentration
is read from its initial slope and the content of extractable solute from its horizontal asymptote; these two values are used
to estimate the partition coefficient. Alternatively, the partition coefficient is taken from the literature (Reverchon 1996,
Goodarznia and Eikani 1998).
5.3.1.3. Model parameters
5.3.1.4. Applications del Valle et al. (2000b) examined

two modifications of the model neglecting either the external
mass transfer resistance or the internal mass transfer resistance (for the extraction from particle surface). The sensitivity analysis of the effect of f and s resulted in finding that
the extraction curves are almost identical for different internal
and external mass transfer characteristic times as long as the
combined characteristic time is constant, but the solid phase
concentration profile in the axial direction is flatter when the
contribution of external resistance increases. Thus, a multiobjective fit to both experimental extraction curves and experimental solid phase concentration profiles was recommended
to identify the major mass transfer resistance.
The results of application of the model on the extraction
of different essential oils are listed in Table 4. It is interesting
to compare the different De values obtained from the same
slightly scattered experimental data, in one instance assuming slab-like particles and in another spherical particles (see
the first two lines of the table). Evidently, the assumption of
spherical particles is not correct when pieces of leaves or
flowers of size larger than about 0.5 mm are extracted. When
the result calculated for inadequate particle shape is skipped,
the values of De are in the range 210-13710-13 m2 s-1.
The diffusion model was successfully applied also to the
extraction of theobromine from cocoa seed shells (Brunner
1994) or the extraction of caffeine from water-soaked coffee
beans (Peker et al. 1992).
To sum up, the diffusion model is appropriate when the
mass transfer resistance is mainly inside the plant particles
and the equilibrium is characterised by partition coefficient.
The model, however, does not fit the broken extraction curves
of the SFE of fatty oils (triglycerides) from seeds where the
equilibrium fluid phase concentration is equal to the oil solubility in the solvent, at least in the first extraction period, while
the diffusion model is based on the proportionality between
the equilibrium solid and fluid phase concentrations.
5.3.2. Desorption model
The desorption model, also

called DDD (desorption-dissolution-diffusion) model, is a
model for porous particles with pores filled with the solvent.
5.3.2.1. Model equations
(59)

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117
Table 4 Effective diffusion coefficients of volatile oils extracted with SC-CO2, evaluated from experimental extraction curves using the
diffusion model.
Herb
Particle size
(mm)
Pressure/temperature
(MPa/C)
De 1012
(m2 s-1)
References
Sage leaves
0.253.1
9/50
0.6a
Reverchon 1996
Sage leaves
0.253.1
9/50
8.5
Araus et al. 2009
Pennyroyal leaves
0.30.7
10/50
58.2
Araus et al. 2009
Basil leaves
0.17
10/40
0.2
del Valle et al. 2000a
Basil and marjoram leaves
0.17
10/40
0.2
Goodarznia and Eikani 1998
Caraway seed
0.5
910/40
0.50.7
Goodarznia and Eikani 1998
a
Slab-like particles were assumed, in contrast to spherical particles in other calculations.
It consists of solute desorption on the pore walls, its internal

diffusion to particle surface, external mass transfer, and displacement with bulk fluid. With respect to the solute transport, there is no interface at particle surface, and therefore
K = 1 is substituted into the formula for linear driving force,
Eq. (57). Two mass balance equations are written for the particles, one for the pores and one for the solid matrix. Recasens
et al. (1989) formulated a general model for SCF regeneration
of a porous adsorbent in a packed bed of spherical particles
where the solvent flows with axial dispersion. A nonlinear
Langmuir-type kinetics of adsorbate desorption from the pore
walls was assumed. [The Langmuir-type kinetics on particle
surface was later considered by Al-Jabari (2003) in a model
for SFE.] Recasens et al. (1989) derived also two simplified
versions of the general model, based on linear driving force
and plug flow: the model with instantaneously established
equilibrium and the model with irreversible desorption, and
derived their analytical solutions. These models have only
two parameters, the overall mass transfer coefficient and
either partition coefficient or desorption rate constant. The
linear equilibrium between the solid phase and the fluid filling the pores enables a reduction of two mass balances for
particles to one equation.
Srinivasan et al. (1990) proved that a first-order, reversible
adsorption model (containing both equilibrium constant and
desorption rate constant) successfully fits the detailed experimental data on desorption of ethyl acetate from activated carbon with SC-CO2.
Numerical solution of model equations is described in more
details in several papers. For the flow with axial dispersion,
Ghoreishi and Sharifi (2001) assumed the Freundlich adsorption isotherm and used the technique of orthogonal collocation on finite elements, and Meireles et al. (2009) assumed the
linear equilibrium and applied the finite difference method.
The lumped parameter model is usually combined with linear
driving force, which leads to an analytical solution formally
identical with the solution for the diffusion model, Eq. (59),
where comb is given by Eq. (58) and eq by Eq. (43); however, the partition coefficient K in Eq. (43) that was written
for the interface at particle surface must be substituted by Kpp
for a porous particle:
K pp =
K
1- + K
(60)
Source of data
Reverchon 1996
Reverchon 1996
Reis-Vasco et al. 2000
Reverchon et al. 1993
Reverchon et al. 1993
Sovova et al. 1994b
where K is the partition coefficient on the pore walls (inversed

adsorption equilibrium constant) and is the porosity of the
particle (Peker et al. 1992, Goto et al. 1994). When a more
complex phase equilibrium relationship such as the BET isotherm applied by Goto et al. (1998) is used, the ordinary differential equations of the lumped parameter model are solved
numerically.
The axial dispersion coefficient is calculated from literature correlations. The effective
internal diffusivity De in the particles of porosity and tortuosity ltor is estimated as
5.3.2.2. Model parameters
De =
D
ltor
(61)
(del Valle et al. 2006). The estimation of De is even simpler

when the tortuosity is assumed to be equal to 1/:
De = 2D
(61a)
(Goto et al. 1993, Skerget and Knez 2001, Meireles et al.

2009). The resulting internal mass transfer resistance is even
smaller than the external resistance based on the external
mass transfer coefficient kf calculated from literature correlations. Thus, the overall mass transfer resistance is low and the
extraction kinetics is close to that of equilibrium extraction.
The most important model parameter, the partition coefficient,
is determined by fitting the experimental extraction curves.
The model with irreversible
desorption rate was tested in the study on SFE of -carotene
from carrots published by Subra et al. (1998) with the conclusion that the model based on adsorption equilibrium would
be more adequate. The model with adsorption equilibrium
corresponds better to experimental data measured for different flow rates, is applied most frequently, and only this
model will be discussed below. Goto et al. (1993) simulated
the extraction of peppermint volatile oil with SC-CO2. The
peppermint leaves were regarded as slabs. The process could
be simulated as equilibrium extraction due to the negligible
effect of mass transfer resistance. The only model parameter,
the equilibrium constant of the linear equilibrium relationship,
was evaluated in dependence on extraction pressure and temperature. A more general equilibrium relationship, the BET
isotherm, was introduced into the model by Goto et al. (1998)
5.3.2.3. Applications to SFE

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and applied on the same set of experimental data. Adjusting

the equilibrium parameters, the volatile oil extraction could
be simulated as desorption while only a weak solute-matrix
interaction was assumed for the initial period of the extraction
of cuticular wax.
Meireles et al. (2009) used the desorption model with linear equilibrium and axial dispersion to simulate the extraction
of vetiver oil from particles as small as 0.18 mm. The effect of
mass transfer resistance was almost negligible according to the
model. The experimental data, however, showed a decrease
in the extraction rate after about 80% of solute had been
extracted. The model ability to predict the effects of scale-up
was proved by fitting the partition coefficient to experimental
data from a smaller extractor, prediction of extraction kinetics in a larger equipment, and comparison of the results with
experimental extraction curves in this equipment.
Skerget and Knez (2001) applied the desorption model
to evaluate extraction curves measured for different plants:
cocoa, paprika, pepper, and Silybum mariannum; the solvents
used were CO2 and propane. The effect of pressure and temperature on the extraction kinetics was investigated. More
details on the extraction of S. mariannum and its model can be
found in the paper published by Hadolin et al. (2001). Again,
the controlling factor in the model was the equilibrium. The
model simulates tightly the initial sections of extraction
curves but the agreement is not as good in the following section of some of the curves.
Mongkholkhajornsilp et al. (2005) matched the model
to experimental extraction curves of nimbin extracted from
neem seeds with CO2. The seed was ground to different particle sizes ranging from 0.575 to 1.85 mm. The extraction rate
decreased with increasing particle size but the model could not
simulate this behaviour as long as the mass transfer resistance
[based on the correlations of Wakao and Funazkri (1978) and
Tan et al. (1988), and on De according to Eq. (61a)] was negligible. Instead of considering a larger internal mass transfer
resistance, the authors decided to decrease the external mass
transfer coefficient and developed a new correlation for kf .
5.3.2.4. Comment The porous and tortuous structure of different pre-pressed vegetable substrates was evidenced by del
Valle et al. (2006). Generally, however, natural materials have
cellular structure and thus diffusion across the cell walls may
be slower than through the pores of a porous substrate (Roy
et al. 1996a). Roethe et al. (1992) proposed a detailed model
for parallel mass transfer through the pores and through the
cells, each of them characterised by its own effective diffusivity. On the basis of a comparison between scanning electron
microscope (SEM) images of the substrate structure and the
results of Hg-porosity measurement, they drew a conclusion
about the volumetric fraction of pores open for mass transfer
in green coffee beans.
5.3.3. Shrinking core model
5.3.3.1. Model equations The shrinking core model
assumes a sharp boundary within a porous spherical particle
between extracted part and inner non-extracted part, the core.
The pores in the core are filled with condensed solute up to
the boundary, where the solute dissolves in the solvent and

diffuses then through the external shell to the particle surface.
The core initially fills the whole particle; as the extraction
proceeds, the core boundary moves to the centre. Equilibrium
is assumed at the core boundary; the fluid phase concentration is equal to csat. The internal mass transfer resistance is
located in the shell surrounding the core and increases as the
core shrinks. The complete model consists of the description
of internal diffusion, external mass transfer, mass balance for
fluid, and mass balance for the particles, which is limited on
the core. Zero concentration in the fluid phase outside particles is assumed at t = 0. The model was formulated for the
flow with axial dispersion and the partial differential equations were solved numerically by Crank Nicholsons method
(Goto et al. 1996, Roy et al. 1996a). The equations of the
model for plug flow were integrated in time using a modified Rosembrock formula after the spatial derivatives had
been substituted by finite differences (Germain et al. 2005,
del Valle et al. 2006).
5.3.3.2. Simplified form When some slow changes of the
core radius are neglected in the equations of the model for
plug flow, a quasi-steady-state analytical solution is obtained
as a dependence of the core radius rc on extraction time and
axial coordinate (King and Catchpole 1993, p. 184, Goto et
al. 1996):
3c =
z
1
x
-z
r
where c = c ,
=1exp com 1+ eq
xu
R
comb
eq =
1
cs 0 1-
, comb = f + 5 s -1 .
1- c
csat
(62)
5.3.3.3. Model parameters Goto et al. (1996) analysed

the effects of internal and external mass transfer resistance
and of axial dispersion on extraction kinetics. As expected, the
extraction is slower and occurs similarly in the whole extractor when s is large. The effect of axial dispersion is therefore
observed only when the mass transfer resistance is low, as
shown for s = 0.67 (parameter a in the paper equals to 15s)
and for Peclet number <100. The extraction rate according to
the quasi-steady state solution is higher than the rate calculated with the complete model; the agreement of both models
increases with decreasing Bi. For large Bi, the sudden initial
change of the concentration at the particle surface contradicts
to the assumption for quasi-steady solution.
The model parameters are usually obtained from the literature except for the effective internal diffusivity De, which
is determined by fitting the calculated extraction curves to
experimental data (Goto et al. 1996).
5.3.3.4. Applications Goto et al. (1996) simulated with the
model the literature data published by Brunner (1984) on the
SFE of rapeseed oil from pre-pressed seeds. The values of
model parameters were taken from the paper together with the
data, except for Dax, which was estimated according to other
literature sources and the only adjusted model parameter, De,
which was found to be 0.7510-101.510-10 m2 s-1. The complete model equations were solved numerically because the

Authenticated
corresponding s in the range 0.330.47 was too small for the

simplified analytical solution.
The shrinking core model was found suitable to describe
the extraction of lipids from pre-pressed or flaked seeds also
by del Valle et al. (2006). The solubility of vegetable oils
in CO2 at given pressure and temperature, csat or ysat, which
can be obtained from a literature correlation, really fits the
experimental extraction curves and gives evidence that the
equilibrium is, at least in the initial extraction period, independent of the substrate. The model was used to predict De
from the particle microstructure and binary diffusion coefficient D according to Eq. (60) for both new experimental data
and data from the literature. The extraction kinetics was not
far from the equilibrium extraction because of high values
of De between 1.810-11 and 8.610-10 m2 s-1. The amount of
extractable oil varied according to the technique of seed pretreatment. The agreement of predicted extraction curves with
experimental ones was very good.
Germain et al. (2005) simulated the extraction of oil from
pre-pressed rapeseeds with the shrinking core model to examine the effect of solvent flow direction in the extractor on the
extraction kinetics. The topic is related to natural convection
occurring at low fluid velocities, when the mass transfer could
be either assisted by gravity (under solvent down-flow for solutions denser than pure solvent) or opposed by gravity (usually
under solvent up-flow). They fitted the model for plug flow to
experimental extraction curves and evaluated the decrease in
the external mass transfer coefficient when the solvent flow
direction was changed to the up-flow. The decrease was from
7.410-6 to 210-6 m s-1 for the superficial velocity as small as
0.17 mm s-1 but no change was observed at the velocity 1.5
mm s-1 when kf was 1.910-5 m s-1 for both flow directions.
The model was applied also to other vegetable substrates
and solutes, mostly volatile oils. Roy et al. (1996a) simulated
the SFE of volatile oil from freeze-dried ginger root with CO2
at 24.5 MPa and 40C. The particles of ginger were sieved
into size fractions from 0.35 to 2.56 mm; the initial content of
oil in the root was 3.8 wt.% and the porosity of the particles
was 0.81. The parameters determined by fitting the model to
experimental extraction curves were De = 2.510-10 m2 s-1 and
csat = 1.23 kg m-3 (ysat = 1.38 g kg-1). The authors observed that
the experimental data for smaller particle size could not be
simulated with this model as the final part of extraction was
much slower than predicted. Akgun et al. (2000) integrated
the equations of the model for plug flow numerically to simulate the extraction of volatile oil from lavender flowers frozen in liquid nitrogen before being crushed. The agreement
of experimental extraction curves and the curves calculated
with adjusted model parameter De = 1.210-11 m s-2 was satisfactory. Spricigo et al. (2001) used the shrinking core model
to represent the nutmeg essential oil extraction with liquid
CO2. The adjusted effective diffusion coefficient varied from
1.510-12 to 2.510-11 m2 s-1.
An unusual form of the shrinking core model where the
solute is initially present in both pores and solid part of a particle was described by Doker et al. (2004) and applied later
by Salgin et al. (2006). Some model equations were probably
distorted by typographical errors. The adjusted De was of the
119
order 10-11 to 10-10 m2 s-1 in the first paper and 10-10 m2 s-1 or
even 10-9 m2 s-1 in the second study, and thus the internal diffusion had little effect on the extraction kinetics. Steffani et al.
(2006) simulated the extraction of volatile oil from the leaves
of ho-sho, a tree native in East Asia, using two models: the
shrinking core model and a model of porous particles where
the rate of diffusion from the pore wall into the bulk pore is
proportional to a kinetic parameter and no volatile oil-matrix
interaction is assumed.
To sum up, the shrinking core model appropriately simulates the extraction from porous substrates rich in solute, such
as vegetable oils from pre-pressed seeds or essential oils filling glandular ducts of leaves or flowers. The effective diffusivity is usually of the order of 10-11 to 10-10 m2 s-1 and thus
ts < teq and the extraction is governed by equilibrium, except
for extremely large particles where the effect of internal mass
transfer prevails. Although the equilibrium in the shrinking
core model is characterised by solubility, the model is applied
also to the extraction of essential oils where it is known that
solute-matrix interaction exists.
5.4. Models based on complex structure of plant
particles
5.4.1. Broken and intact cell models Vegetable oil is
extracted from seed particles obtained by milling. The SEM
images of a surface of particles after the extraction shows a layer
of broken cells, the cavities from where the oil was removed
(Marrone et al. 1998, Reverchon and Marrone 2001). The SFE
begins as the extraction from particle surface (see Section 5.2.3),
it means from the mechanically damaged cells with broken
walls, which may be in several layers below particle surface, and
then it continues from intact cells in the particle core where the
oil diffuses through low permeable cell walls and the extraction
is therefore slower. The broken and intact cell (BIC) models
describe this process. An important parameter of BIC models is
the initial fraction of easily accessible solute, G, which is equal
to the solute in broken cells over the solute in broken and intact
cells and which value is therefore between 0 and 1.
The observed extraction periods correspond to characteristic
times of extraction steps. As the relation of characteristic times
is usually tf < tr < teq and teq < ti , the extraction in the first period
of extraction from broken cells is governed by equilibrium and
the controlling step in the second period is the internal mass
transfer. (An exception is the extraction from extremely small
particles or from the particles with low mass transfer resistance;
in such case, teq > ti , the effect of internal diffusion is marginal,
and a simple one-stage model should be applied.)
When this mass transfer mechanism is built into a SFE
model for plug flow, the extraction curves calculated using
the model consist of three parts, denoted by Povh et al. (2001)
as the constant extraction rate period, when all particles in the
extractor contain easily accessible solute, the falling extraction rate period, when the particles near to the solvent inlet are
already free of easily accessible solute which is still present
near the solvent outlet, and the diffusion controlled extraction
period, where the mass transfer is governed solely by internal
diffusion.

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The BIC models were developed gradually. Semi-empirical

models (Goodrum et al. 1996, Hong et al. 1990, Yoo and Hong
1996) described extraction curves composed of two sections,
the first one given by Eq. (48) for the extraction from particle surface and the second section by Eq. (54) or (54a)
for internal diffusion. Alternatively, Cygnarowicz-Provost
(1996) introduced into the model an empirical mass transfer
coefficient, the initial value of which is equal to kf and, in
dependence on the solute content in particles, was monotonously decreasing. Lack (1985) under supervision of Prof.
Marr utilised the analogy of SFE with a drying process and
modified the relevant equations for drying. In the SFE model
written for plug flow, J according to Eq. (33) is multiplied
by a function of average solute concentration in the particles,
x, which is equal to unity until the easily accessible solute is
depleted and then it monotonously decreases with decreasing
x. The shape of the function can be adjusted to fit different
experimental extraction curves; when J in the second period
is directly proportional to x and when the accumulation term
in the mass balance for the fluid phase with plug flow pattern
is neglected, the model has analytical solution.
Sovova (1994) modified the term J so that it after the depletion of free oil describes the internal mass transfer, on the
condition that ti >> tf and therefore cs+ can be set equal to zero,
and used this analytical solution. This approximate model
for SFE, more consistently described later (Stastova et al.
1996), is frequently used to evaluate model parameters from
experimental extraction curves. It yields good results when
applied to the SFE of vegetable oil from seeds; however, with
respect to the conditions used in its derivation, it should not
be applied when the solubility of the solute is high or when a
solute-matrix interaction exists.
Gaspar et al. (2003) derived a simple and efficient version
of the BIC model for the SFE of essential oil from oregano
bracts, where the easily accessible solute from disrupted
glands dissolves completely before t = 0 and then the solute
from intact cells diffuses to the interface with a rate derived
by Bartle et al. (1991b) in the version of hot ball model for
slabs. No equilibrium relationship is necessary in this model
as the first period is a simple washing out and the second part
is controlled by internal diffusion. The fraction of free solute was G = 0.51, the effective diffusivity was De = 210-14
410-14 m2 s-1.
Reis-Vasco et al. (2000) applied the BIC model to the
extraction of essential oil from pennyroyal leaves where two
kinds of trichomes contain the essential oil: peltate trichomes
that are on the surface, assumed to be broken, and capitate
trichomes protected by cell wall and cuticle, representing
the intact cells. Extraction curves e(q) measured at different
flow rates overlapped until 70% essential oil were extracted;
moreover, the curves measured for different particle sizes
overlapped up to this point. Thus it was assumed that the
extraction of 70% of essential oil was the equilibrium extraction. The model was written for the flow with axial dispersion
and for the linear equilibrium. When the easily accessible
essential oil was depleted, the extraction from the capitate
trichomes was controlled by internal mass transfer resistance.
The only adjusted model parameter, ks, was 1.410-7 m s-1 for
average particle diameters 0.3, 0.5, and 0.7 mm. The De range,
estimated from these values, is 410-12810-12 m2 s-1.
In their versatile software for numerical simulation of SFE,
most probably of the BIC type, Clavier et al. (1995) used
the linear driving force. The equilibrium was represented by
either solubility (no solute-matrix interaction) or Langmuirtype adsorption isotherm, and the fluid flow was simulated by
a series of mixers, allowing taking into account the length of
the bed (for an extremely short laboratory extractor the number of mixers is reduced to one).
To describe the mass transfer inside the particles in more
detail, three mass balance equations are integrated: for the
fluid phase, for the region of broken cells, and for the region
of intact cells. The solute from intact cells diffuses to the
region of broken cells, and from broken cells to bulk fluid
(Sovova et al. 1994b). The mass transfer resistance in the
region of broken cells can be neglected and equilibrium is
established between the concentration in broken cells and the
fluid phase concentration at particle surface. When essential
oil is extracted from seed, it is partitioned between the liquid
vegetable oil in seed and the supercritical solvent (Sovova et
al. 2001b).
Perrut et al. (1997) observed a solute-matrix interaction
in the second period of SFE of vegetable oil from seed with
SC-CO2. The slope of the extraction curves was first determined by oil solubility in CO2, and when the free oil was
depleted, it decreased to a value corresponding to the equilibrium fluid phase concentration of oil adsorbed on matrix.
The solution flowing out of the extractor was saturated in
both extraction periods, as indicated by the extraction experiments, when the extraction curves e(q) measured under the
conditions of different residence times of the solvent in the
extractor overlapped in both periods. It seems probable that
the solute-matrix interaction exists also in the SFE of vegetable oils, such as in the extraction of other solutes, at least
for a part of oil initially present in the seed. A versatile BIC
model could therefore incorporate the equilibrium relationship given by Eq. (40), which allows simulating the transition
from the extraction of free solute to the extraction of bound
solute, and includes the simpler case when the bound solute
is extracted from the very beginning. Such BIC model was
derived for different flow patterns, analysed, and simplified
relationships for calculation of approximate extraction curves
were derived (Sovova 2005). The analysis of the model for
plug flow shows that the existing solute-matrix interaction
practically is not visible on the shape of extraction curve
when the characteristic time of its equilibrium extraction is
smaller than the characteristic time of equilibrium extraction
calculated on the basis of solubility. According to Eq. (43),
the condition is Kcs0 > csat.
Marrone et al. (1998) modified the BIC model with three
mass balance equations assuming that the oil inside the intact
cells is adsorbed on the matrix (with linear equilibrium), in
contrast to the free oil in broken cells, and diffuses directly to
the SCF. The number of adjustable parameters was reduced
estimating G from SEM images of extracted particles. The
free easily accessible oil was assumed to fill the surface layer
of broken cells which depth was determined from the shape

Authenticated
and size of oil-bearing cells, which was typically 2030 m

according to the species. This approach was applied by
Reverchon and Marrone (2001) to evaluate the internal mass
transfer resistance from experimental data measured in their
laboratory and also different sets of extraction curves available in the literature. The resulting De values were relatively
high. The reason could be that when G is fixed at a lower
value than the real fraction of free oil is, the effective diffusivity is automatically adjusted to a value ensuring that the
extraction will not be slowed down after depletion of free solute (in terms of characteristic times, tf << teq and ti << teq) and
the extraction is controlled by equilibrium in both periods.
This BIC model was further applied and analysed by Fiori
and colleagues (Fiori 2007, Fiori et al. 2007) who found that
the depth of the region with easily accessible oil is approximately two layers of cells. They also improved the accuracy
of modelling, simulating simultaneous extraction from the
particles of a wide size distribution (Fiori et al. 2008). Finally
they developed and further applied a new model for SFE of oil
from seed where, after the oil from broken cells is removed,
the oil from the first layer of intact cells diffusing through one
cell wall is extracted. After its depletion, the oil from the second intact layer diffusing through two cell walls is extracted,
etc. Thus the model combines the feature of BIC model and
shrinking core model (Fiori et al. 2009, Fiori 2010).
5.4.2. Models for SFE of essential oils tailored to plant
microstructure iovi and co-workers linked the models
for SFE of essential oils with the shape, structure, and location
of secretory structures from where they are extracted and with
behaviour of these structures during the extraction, studied
on SEM images. Thus, a model including the mechanism
of breakage of peltate glandular trichomes on the surface of
leaves of Lamiaceae family plants was derived and adjusted
to experimental data (iovic et al. 2005). The next extracted
plants were those from Asteraceae family where the essential
oil is extracted from secretory ducts and the mass transfer
resistance is relatively low (iovic et al. 2007) and, in
contrast, the valerian root where the secretory cells have a
thick cuticularised lining and the extraction rate depends on
its breakage (iovic et al. 2007a). The results for different
types of secretory structures are summarised and the models
are further developed in the last paper (Stamenic et al. 2008).
5.5. Models for SFE of mixtures
All extracts from plants are mixtures of many substances.

When mixture components are similar, such as triglycerides
in vegetable oils, the mixture can be regarded as a pseudocomponent and the above-described models can be applied
directly. When, however, the major components of extract are
of very different solubilities, the overall extraction curve will
be composed of several extraction curves of different shapes
and the first decrease in extraction rate may correspond to the
point when the more soluble component was depleted but the
extraction of easily accessible less soluble components continues. Moreover, the extracted components can affect each
121
other, for example, when the more soluble component acts as

entrainer for the less soluble component.
The gradual changes in extract composition are denoted as
fractionation in time. The fractionation in time was observed
for example during CO2 extraction of sage essential oil consisting of monoterpenes, oxygenated monoterpenes, sesquiterpenes, and oxygenated sesquiterpenes (Reverchon et al.
1995b), while the extraction of three oxygenated monoterpenes, the major components of peppermint oil, was simultaneous (Goto et al. 1993). Also the extraction of savory
oleoresin with subcritical water showed a strong fractionation in time among individual components of essential oil
(Kubatova et al. 2001).
One group of models for multicomponent SFE from
plants includes the models that describe the extraction of
each selected component or each group of components as
not affected by co-extracted substances. The BIC model was
applied to simulate CO2 extraction of essential oil, piperine,
and lipids from black pepper seed, each component with
its own model parameters (Sovova et al. 1995). Franca and
Meireles (2000) used an empirical expression with different
parameters for extraction curves of free fatty acids, triglycerides, and -carotene to simulate time fractionation of vegetable oil extracted from pressed palm oil fibres. This approach
was applied also by Martinez et al. (2003) to simulate the
extraction of oleoresin from ginger rhizome, composed of
monoterpenes, sesquiterpenes, and other hydrocarbons. Goto
et al. (1994) proposed a modification of the lumped parameter
desorption model with linear driving force, where a continuous mixture is extracted instead of one extracted substance.
The concept of the continuous mixture simulates a mixture of
groups of a large number of components as continuous functions of some mixture property, in this case as the Gaussian
function of molecular mass. The partition coefficient defined
in the paper as K = cs/c was assumed to be directly proportional to the molecular mass and the kinetics of the extraction
of two groups of components was predicted.
In the second group of models, the equilibrium of a mixture of extracted substances with the solvent is taken into
account. The initial extraction of easily accessible extract is
simulated as the equilibrium extraction based on separation
factors known from the models for SFE of liquids in countercurrent columns. Shen et al. (1997), who extracted oil from
rice bran with SC-CO2, recognised that the rate of extraction
of minor oil components was related to the rate of extraction of major component and evaluated their separation factors towards triglycerides from the ratio of initial slopes of
extraction curves. Gaspar (2002) studied the CO2 extraction
of volatile oil from oregano bracts under different extraction
conditions and evaluated the selectivity of individual essential
oil components. Sovova et al. (2010) implemented the separation factor of -sitosterol to triglycerides into a model for the
extraction of sea buckthorn oil from particle surface.
Another possibility is to link the different rates of extraction of different extract components with their diffusion coefficients. Machmudah et al. (2006) applied the shrinking core
model to the CO2 extraction of nutmeg oil, distinguishing
between components with lower molecular weight (terpene

Authenticated
hydrocarbons) and components with higher molecular weight

(oxygenated terpenes and myristicin), the effective diffusivity
of which was adjusted to approximately 2.5 lower value than
the diffusivity of the hydrocarbons, to fit experimental data
on overall extraction yield and on the changes in extract composition. The ability of the shrinking core model to simulate
the fractionation in time was studied in detail by Tezel et al.
(2000) who assumed that the components differ in both solubility and effective diffusivity. They also took into account
that due to the different rates of extraction of two components, there are two shrinking cores in the spherical particles
the inner core containing both condensed components and
the outer core where only the slower extracted component
is condensed. The faster extracted component must diffuse
through the outer core before it is dissolved in the solvent
filling the pores outside the outer core. Moreover, Tezel et
al. (2000) adapted for the extraction of mixtures the desorption model with a Langmuir-like adsorption isotherm where
several extract components compete for active sites; the
components differ in both adsorption isotherm constants and
effective diffusivities.
6. Conclusions
Large-scale SFE from plant materials is considered nowadays
a standard process. It has extended from the first applications
extraction of flavour and aroma from hops, extraction of
caffeine from raw coffee beans, and the extraction of spices
to other branches as, for example, the extraction of biologically active substances from medical plants and the extraction of herbicides from rice. More and more plant materials
are tested for extraction with SC-CO2 in laboratories around
the world. SFE with SC-CO2 modified with entrainers is finding application as a fast and easy to be automated technique
for the extraction of analytes from plant matrix prior to their
chromatographic analysis.
As the SFE from plants is more and more widely applied in
practice, its theory is often regarded as more or less complete,
and its further research superfluous (redundant) and marginal.
The contemporary research is finding new and fascinating
applications of supercritical solvents in formation of micro- and
nanoparticles, in chemical and enzymatic reactions as reaction
medium, in the production and treatment of polymers, and others. Nevertheless, new tasks arise with practical applications of
SFE from plants, as the optimisation of operating conditions
and of plant pre-treatment with the aim to increase the extraction yield, reduce the extraction time or the solvent consumption, and/or to increase the concentration of efficient substances
in the extract or maintain their level constant extract despite of
changing quality of the extracted plant material.
While in other chemical engineering branches with longer history, the engineers and technicians can solve such
tasks using a set of equations and formulae that are based on
a comprehensive theory, supercritical extraction from plants
still lacks such widely accepted theory and recommended
mathematical relationships. Moreover, there is a lack of such
theory in the extraction of valuable substances from plant
materials generally, even for the extraction with liquid solvents at atmospheric pressure despite of its long tradition. As
shown in the present review, extensive experimental and theoretical research has been carried out by tremendous number of
researchers and a large amount of knowledge on supercritical
extraction from plants has been collected. It is, thus, probably
time to synthesise the knowledge and formulate practically
applicable mathematical relationships describing the process
generally. Phase equilibrium has been measured for many substances and can be understood with the help of thermodynamic
modelling. There are correlations enabling estimation of the
mass transfer resistance in SCF, and the internal mass transfer
resistance has been evaluated from the course of extraction.
Attention is being paid also to the effect of flow pattern on the
extraction rate, which is important especially in the scale-up
process. However, the most intriguing features concerning the
extract composition, such as mutual interactions of the components of extracted mixtures or solute-to-matrix interaction
in dependence on extraction conditions, have not yet been
studied sufficiently to be included into the theory to make it
complete. Although the representation of botanical materials
by mathematical relationships applicable in engineering practice requires severe simplifications, the authors believe that the
chemical engineering approach to the extraction of plants will
enable its rational optimisation and development of new efficient procedures and new products of high quality.
Acknowledgements
Financial support by the Ministry of Education, Youth and Sports of
the Czech Republic (projects 2B06024 and 2B06049) is gratefully
acknowledged.
References
Abbasi H, Rezaei K, Rashidi K. Extraction of essential oils from
the seeds of pomegranate using organic solvents and supercritical
CO2. J Am Oil Chem Soc 2008a; 85: 8389.
Abbasi H, Rezaei K, Emamdjomeh Z, Mousavi SME. Effect of various extraction conditions on the phenolic contents of pomegranate seed oil. Eur J Lipid Sci Technol 2008b; 110: 435440.
Abdullah MI, Young JC, Games DE. Supercritical fluid extraction
of carboxylic and fatty acids from Agaricus spp. mushrooms. J
Agric Food Chem 1994; 42: 718722.
Abrams DS, Massaldi HA, Prausnitz JM. Vapor pressures of liquids
as a function of temperature. Two-parameter equation based on
kinetic theory of fluids. Ind Eng Chem Fund 1974; 13: 259
262.
Adachi Y, Lu BCY. Supercritical fluid extraction with carbon dioxide
and ethylene. Fluid Phase Equilib 1983; 14: 147156.
Adachi Y, Sugie H. A new mixing rule modified conventional mixing rule. Fluid Phase Equilib 1986; 28: 103118.
Adasoglu N, Dincer S, Bolat E. Supercritical-fluid extraction of
essential oil from Turkish lavender flowers. J Supercrit Fluids
1994; 7: 9399.
Adil IH, Cetin HI, Yener ME, Bayindirli A. Subcritical (carbon
dioxide+ethanol) extraction of polyphenols from apple and
peach pomaces, and determination of the antioxidant activities of
the extracts. J Supercrit Fluids 2007; 43: 5563.

Authenticated
Adil IH, Yener ME, Bayindirli A. Extraction of total phenolics of

sour cherry pomace by high pressure solvent and subcritical fluid
and determination of the antioxidant activities of the extracts.
Sep Sci Technol 2008; 43: 10911110.
Aghel N, Yamini Y, Hadjiakhoondi A, Pourmortazavi SM.
Supercritical carbon dioxide extraction of Mentha pulegium L.
essential oil. Talanta 2004; 62: 407411.
Aguilera A, Rodriguez M, Brotons M, Boulaid M, Valverde A.
Evaluation of supercritical fluid extraction/aminopropyl solidphase In-line cleanup for analysis of pesticide residues in rice.
J Agric Food Chem 2005; 53: 93749382.
Ahmad UK, Sirat HM, Sanagi MM, Smith RM. Supercritical fluid
extraction and capillary gas chromatography of the rhizomes of
Z. zerumbet. J Microcolumn Sep 1994; 6: 2732.
Ahro M, Hakala M, Sihvonen J, Kauppinen J, Kallio H. Lowresolution gas-phase FT-IR method for the determination of the
limonene/carvone ratio in supercritical CO2-extracted caraway
fruit oils. J Agric Food Chem 2001; 49: 31403144.
Akgun M, Akgun NA, Dincer S. Extraction and modeling of lavender flower essential oil using supercritical carbon dioxide. Ind
Eng Chem Res 2000; 39: 473477.
Akgun M, Akgun NA, Dincer S, Akgerman A. Supercritical fluid
extraction of Lavandula stoechas L. ssp. cariensis (Boiss.)
Rozeira. J Essent Oil Res 2001; 13: 143148.
Al-Jabari M. Kinetic models of supercritical fluid extraction. J Sep
Sci 2002; 25: 477489.
Al-Jabari M. Modeling analytical tests of supercritical fluid extraction from solids with Langmuir kinetics. Chem Eng Commun
2003; 190: 16201640.
Al-Marzouqi AH, Rao MV, Jobe B. Comparative evaluation of SFE
and steam distillation methods on the yield and composition of
essential oil extracted from spearmint (Mentha spicata). J Liquid
Chromatogr Rel Technol 2007; 30: 463475.
Aleksovski S, Sovova H. Supercritical CO2 extraction of Salvia officinalis L. J Supercrit Fluids 2007; 40: 239245.
Aleksovski S, Sovova H, Poposka FA, Kulevanova S, Ristic M.
Comparison of essential oils obtained from Mentha piperita L.
using supercritical carbon dioxide extraction and hydrodistillation. Acta Pharm (Zagreb) 1999; 19: 5157.
Alexander WS, Brusewitz GH, Maness NO. Pecan oil recovery and
composition as affected by temperature, pressure, and supercritical CO2 flow rate. J Food Sci 1997; 62: 762766.
Ambrogi A, Cardarelli DA, Eggers R. Fractional extraction of paprika
using supercritical carbon dioxide and on-line determination of
carotenoids. J Food Sci 2002; 67: 32363241.
Ambrosino P, Fresa R, Fogliano V, Monti SM, Ritieni A. Extraction
of azadirachtin a from neem seed kernels by supercritical fluid
and its evaluation by HPLC and LC/MS. J Agric Food Chem
1999; 47: 52525256.
Ambrosino P, Galvano F, Fogliano V, Logrieco A, Fresa R, Ritieni A.
Supercritical fluid extraction of Beauvericin from maize. Talanta
2004; 62: 523530.
Ammann A, Hinz DC, Addleman RS, Wai CM, Wenclawiak
BW. Superheated water extraction, steam distillation and
SFE of peppermint oil. Fresen J Anal Chem 1999; 364:
650653.
Anderson SG, Nair MG, Chandra A, Morrison E. Supercritical fluid
carbon dioxide extraction of annatto seeds and quantification
oftrans-bixin by high pressure liquid chromatography. Phytochem
Anal 1997; 8: 247249.
Andras CD, Simandi B, Orsi F, Lambrou C, Missopolinou-Tatala
D, Panayiotou C, Domokos J, Doleschall F. Supercritical carbon
dioxide extraction of okra (Hibiscus esculentus L) seeds. J Sci
Food Agric 2005; 85: 14151419.
123
Andrich G, Balzini S, Zinnai A, De Vitis V, Silvestri S, Venturi F,

Fiorentini R. Supercritical fluid extraction in sunflower seed
technology. Eur J Lipid Sci Technol 2001; 103: 151157.
Andujar AD, Gomez AM, de la Ossa EM. Caracterizacin del aceite
de semilla de borraja extrado con dixido de carbono supercrtico. Grasas Aceites 1999; 50: 283288.
Anitescu G, Doneanu C, Radulescu V. Isolation of coriander oil:
comparison between steam distillation and supercritical CO2
extraction. Flavour Fragr J 1997; 12: 173176.
Anklam E, Muller A. Extraction of caffeine and vanillin from drugs
by supercritical carbon dioxide. Pharmazie 1995; 50: 364365.
Anklam E, Berg H, Mathiasson L, Sharman M, Ulberth F.
Supercritical fluid extraction (SFE) in food analysis: a review.
Food Addit Contam 1998; 15: 729750.
Apostolou DA, Kalospiros NS, Tassios DP. Prediction of gas solubilities using the LCVM equation of state/excess gibbs energy
model. Ind Eng Chem Res 1995; 34: 948957.
Araujo ME, Meireles MAA. Improving phase equilibrium calculation with the PengRobinson EOS for fats and oils related
compounds/supercritical CO2 systems. Fluid Phase Equilib 2000;
169: 4964.
Araujo JMA, Sandi D. Extraction of coffee diterpenes and coffee
oil using supercritical carbon dioxide. Food Chem 2006; 101:
10871094.
Araujo ME, Machado NT, Franca LF, Meireles MAA. Supercritical
extraction of pupunha (Guilielma speciosa) oil in a fixed bed
using carbon dioxide. Braz J Chem Eng 2000; 17: 297306.
Araujo ME, Silva MV, Chaves JBP. Supercritical fluid extraction of
daidzein and genistein isoflavones from soybean hypocotyl after
hydrolysis with endogenous -glucosidases. Food Chem 2007;
105: 266272.
Araus K, Uquiche E, del Valle JM. Matrix effects in supercritical
CO2 extraction of essential oils from plant material. J Food Eng
2009; 92: 438447.
Arce L, Lista AG, Rios A, Valcarcel M. Screening of polyphenols
in grape marc by on-line supercritical fluid extraction flow
through sensor. Anal Lett 2001; 34: 14611476.
Arimboor R, Venugopalan VV, Sarinkumar K, Arumughan C,
Sawhney RC. Integrated processing of fresh Indian sea buckthorn (Hippophae rhamnoides) berries and chemical evaluation
of products. J Sci Food Agric 2006; 86: 23452353.
Armando TQ, Oro K, Katoh S, Moriyoshi T. Recovery of oil components of okara by ethanol-modified supercritical carbon dioxide
extraction. Biores Technol 2006; 97: 15091514.
Artz WE, Sauer RM. An improved micro-extraction cell for supercritical fluid extraction and chromatography of fatty acids. J Am
Oil Chem Soc 1992; 69: 309313.
Ashour I, Almehaideb R, Fateen SE, Aly G. Representation of solidsupercritical fluid phase equilibria using cubic equations of state.
Fluid Phase Equilib 2000; 167: 4161.
Ashraf-Khorassani M, Taylor LT. Supercritical fluid extraction of
michellamines A and B from ancistrocladus korupensis leaves.
Anal Chim Acta 1997; 347: 305311.
Ashraf-Khorassani M, Taylor LT. Sequential fractionation of grape
seeds into oils, polyphenols, and procyanidins via a single system employing CO2-based fluids. J Agric Food Chem 2004; 52:
24402444.
Ashraf-Khorassani M, Taylor LT, Martin M. Supercritical fluid
extraction of Kava lactones from Kava root and their separation
via supercritical fluid chromatography. Chromatographia 1999;
50: 287292.
Ashraf-Khorassani M, Taylor LT, Nazem N, Coleman WA. Isolation of
tetra-acyl sucrose esters from turkish tobacco using supercritical

Authenticated
fluid CO2 and comparison with conventional solvent extraction. J

Agric Food Chem 2005; 53: 18661872.
Ashtiani F, Sefidkon F, Yamini Y, Khajeh K. Supercritical carbon
dioxide extraction of volatile components from two eucalyptus
species (E-spathulata and E-microtheca). J Essent Oil Bearing
Plants 2007; 10: 198208.
Asis C, Baroy R, Bendijo S, Hansen SL, Nacion V, Tolimao J.
Supercritical fluid extraction to determine the oil content in
copra and extracted meal. J Am Oil Chem Soc 2006; 83:
1114.
Askin R, Otles S. Supercritical fluids. Acta Sci Pol Technol Aliment
2005; 4: 316.
Athukorala Y, Mazza G. Supercritical carbon dioxide and hexane
extraction of wax from triticale straw: content, composition and
thermal properties. Ind Crops Prod 2010; 31: 550556.
Atti-Santos AC, Rossato M, Serafini LA, Cassel E, Moyna P.
Extraction of essential oils from lime (Citrus latifolia Tanaka)
by hydrodistillation and supercritical carbon dioxide. Braz Arch
Biol Technol 2005; 48: 155160.
Babovi N, Djilas S, Jadranin M, Vajs V, Ivanovic J, Petrovic S,
Zizovic I. Supercritical carbon dioxide extraction of antioxidant fractions from selected Lamiaceae herbs and their antioxidant capacity. Innov Food Sci Emerg Technol 2010; 11:
98107.
Badalyan AG, Wilkinson GT, Chun BS. Extraction of Australian ginger root with carbon dioxide and ethanol entrainer. J Supercrit
Fluids 1998; 13: 319324.
Bajer T, Adam M, Galla L, Ventura K. Comparison of various extraction techniques for isolation and determination of isoflavonoids
in plants. J Sep Sci 2007; 30: 122127.
Balaban MO, Palazoglu TK, OKeefe S. Supercritical CO2 extraction of lipids from roasted pistachio nuts and evaluation of the
remaining meal. Proc. 5th Meeting on Supercritical Fluids/2,
Nice, France, 1998: 633.
Balachandran S, Kentish SE, Mawson R. The effects of both preparation method and season on the supercritical extraction of ginger.
Sep Purif Technol 2006; 48: 94105.
Balachandran S, Kentish SE, Mawson R, Ashokkumar M. Ultrasonic
enhancement of the supercritical extraction from ginger. Ultrason
Sonochem 2007; 13: 471479.
Balachandran C, Mayamol PN, Thomas S, Sukumar D, Sundaresan
A, Arumughan C. An ecofriendly approach to process rice bran
for high quality rice bran oil using supercritical carbon dioxide for nutraceutical applications. Biores Technol 2008; 99:
29052912.
Barghamadi A, Mehrdad M, Sefidkon F, Yamini Y, Khajeh M.
Comparison of the volatiles of Achillea millefolium L. obtained
by supercritical carbon dioxide extraction and hydrodistillation
methods. J Essent Oil Res 2009; 21: 259263.
Barjaktarovic B, Sovilj M, Knez Z. Chemical composition of
Juniperus communism. Fruits supercritical CO2 extracts: dependence on pressure and extraction time. J Agric Food Chem 2005;
53: 26302636.
Barth MM, Zhou C, Kute KM, Rosenthal GA. Determination of optimum conditions for supercritical fluid extraction of carotenoids
from carrot (Daucus carota L.) tissue. J Agric Food Chem 1995;
43: 28762878.
Barth D, Pop E, Hubert N, Mihaiescu D, Gainar I. Supercritical CO2
extraction from some Romanian Lamiaceae. Proc. 5th Meeting
on Supercritical Fluids/2, Nice, France, 1998: 655660.
Barthet VJ, Daun JK. An evaluation of supercritical fluid extraction
as an analytical tool to determine fat in canola, flax, solin, and
mustard. J Am Oil Chem Soc 2002; 79: 245251.
Bartle KD, Clifford AA, Hawthorne SB, Langenfeld JJ, Miller DJ,
Robinson R. A model for dynamic extraction using a supercritical fluid. J Supercrit Fluids 1990; 3: 143149.
Bartle KD, Clifford AA, Jafar SA, Shilstone GF. Solubilities of solids and liquids of low volatility in supercritical carbon dioxide.
J Phys Chem Ref Data 1991a; 20: 713756.
Bartle KD, Boddington T, Clifford AA, Cotton NJ, Dowle CJ.
Supercritical fluid extraction and chromatography for the determination of oligomers in poly(ethylene terephthalate) films. Anal
Chem 1991b; 63: 23712377.
Bartle KD, Clifford AA, Shilstone GF. Estimation of solubilities in
supercritical carbon dioxide: a correlation for the Peng-Robinson
interaction parameters. J Supercrit Fluids 1992a; 5: 220225.
Bartle KD, Boddington T, Clifford AA, Hawthorne SB. The effect of
solubility on the kinetics of dynamic supercritical-fluid extraction. J Supercrit Fluids 1992b; 5: 207212.
Bartley JP. A new method for the determination of pungent compounds in ginger (Zingiber officinale). J Sci Food Agric 1995;
68: 215222.
Bartley JP, Foley P. Supercritical fluid extraction of Australiangrown ginger (Zingiber officinale). J Sci Food Agric 1994; 66:
365371.
Bartley JP, Jacobs AL. Effects of drying on flavour compounds in
Australian-grown ginger (Zingiber officinale). J Sci Food Agric
2000; 80: 209215.
Bartlova M, Opletal L, Chobot V, Sovova H. Liquid chromatographic
analysis of supercritical carbon dioxide extracts of Schizandra
chinensis. J Chromatogr B 2002; 770: 283289.
Barton P, Hughes RE, Hussein MM. Supercritical carbon dioxide
extraction of peppermint and spearmint. J Supercrit Fluids 1992;
5: 157162.
Bauman D, Hadolin M, Rizner-Hras A, Knez Z. Supercritical fluid
extraction of rosemary and sage antioxidants. Acta Aliment Hung
1999; 28: 1528.
Baumann W, Rodrigues SV, Viana LM. Pigments and their solubility
in and extractability by supercritical CO2 I: the case of curcumin. Braz J Chem Eng 2000; 17: 323328.
Baumann D, Adler S, Gruner S, Otto F, Weinreich B, Hamburger
M. Supercritical carbon dioxide extraction of marigold at high
pressures: comparison of analytical and pilot-scale extraction.
Phytochem Anal 2004; 15: 226230.
Baysal T, Starmans DAJ. Supercritical carbon dioxide extraction
of carvone and limonene from caraway seed. J Supercrit Fluids
1999; 14: 225234.
Baysal T, Ersus S, Starmans DAJ. Supercritical CO2 extraction of
-carotene and lycopene from tomato paste waste. J Agric Food
Chem 2000; 48: 55075511.
Beckman EJ. Supercritical and near-critical CO2 in green chemical
synthesis and processing. J Supercrit Fluids 2004; 28: 121191.
Began G, Goto M, Kodama A, Hirose T. Response surfaces of total
oil yield of turmeric (Curcuma longa) in supercritical carbon
dioxide. Food Res Int 2000; 33: 341345.
Beis SH, Dunford NT. Supercritical fluid extraction of daphne (Laurus
nobilis L.) seed oil. J Am Oil Chem Soc 2006; 83: 953957.
Berna A, Tarrega A, Blasco M, Subirats S. Supercritical CO2 extraction of essential oil from orange peel; effect of the height of the
bed. J Supercrit Fluids 2000; 18: 227237.
Bernardo-Gil MG, Casquilho M. Modeling the supercritical fluid
extraction of hazelnut and walnut oils. AICHE J 2007; 53:
29802985.
Bernardo-Gil MG, Lopes LMC. Supercritical fluid extraction of
Cucurbita ficifolia seed oil. Eur Food Res Technol 2004; 219:
593597.

Authenticated
Bernardo-Gil G, Oneto C, Antunes P, Rodrigues MF, Empis JM.

Extraction of lipids from cherry seed oil using supercritical carbon dioxide. Eur Food Res Technol 2001; 212: 170174.
Bernardo-Gil MG, Grenha J, Santos J, Cardoso P. Supercritical fluid
extraction and characterisation of oil from hazelnut. Eur J Lipid
Sci Technol 2002; 104: 402409.
Bernardo-Gil MG, Lopes IMG, Casquilho M, Ribeiro MA, Esquivel
MM, Empis J. Supercritical carbon dioxide extraction of acorn
oil. J Supercrit Fluids 2007; 40: 344348.
Bestmann HJ, Erler J, Vostrowsky O. Extraktion von Thymian mit
flssigem CO2 im Labormastab. Z Lebensm Forsch 1985; 180:
491493.
Beveridge THJ, Girard B, Kopp T, Drover JCG. Yield and composition of grape seed oils extracted by supercritical carbon dioxide
and petroleum ether: varietal effects. J Agric Food Chem 2005;
53: 17991804.
Bhattacharjee P, Ranganathan TV, Singhal RS, Kulkarni PR.
Comparative aroma profiles using supercritical carbon dioxide
and Likens-Nickerson extraction from a commercial brand of
Basmati rice. J Sci Food Agric 2003; 83: 880883.
Bhattacharjee P, Kshirsagar A, Singhal RS. Supercritical carbon
dioxide extraction of 2-acetyl-1-pyrroline from Pandanus amaryllifolius Roxb. Food Chem 2005; 91: 255259.
Bhattacharjee P, Singhal RS, Tiwari SR. Supercritical carbon
dioxide extraction of cottonseed oil. J Food Eng 2007; 79:
892898.
Bicchi C, Rubiolo P, Frattini C, Sandra P, David F. Off-line supercritical fluid extraction and capillary gas chromatography of
pyrrolizidine alkaloids in senecio species. J Nat Prod 1991; 54:
941945.
Bicchi C, Rubiolo P, Rovida C. Analysis of constituents of Iris rhizomes. Part II. Simultaneous SFE of irones and iridals from Iris
pallida L. rhizomes. Flavour Fragr J 1993; 8: 261267.
Bicchi C, Binello A, Rubiolo P. Supercritical carbon dioxide in combination with silica gel to fractionate essential oils. Phytochem
Anal 1999; 10: 1721.
Bicchi C, Binello A, Rubiolo P. Determination of phenolic diterpene
antioxidants in rosemary (Rosmarinus officinalis L.) with different methods of extraction and analysis. Phytochem Anal 2000;
11: 236242.
Birtigh A, Johannsen M, Brunner G. Supercritical-fluid extraction of
oil-palm components. J Supercrit Fluids 1995; 8: 4650.
Blanch GP, del Castillo MLR, del Mar Caja M, Perez-Mendez M,
Sanchez-Cortes S. Stabilization of all-trans-lycopene from
tomato by encapsulation using cyclodextrins. Food Chem 2007;
105: 13351341.
Blatt CR, Ciola R. Analysis of vetiver essential oil by supercritical
fluid extraction and on-line capillary gas chromatography. HRC-J
High Res Chromatogr 1991; 14: 775777.
Bo J, Yudong Y, Zhimin X, Hancha L. Study on extracting the active
ingredients from common andrographis herb by using supercritical carbon dioxide. Proc. 7th Meeting on Supercritical Fluids/2,
Antibes/Juan-les-Pins, France, 2000: 649654.
Bocevska M, Sovova H. Supercritical CO2 extraction of essential oil
from yarrow. J Supercrit Fluids 2007; 40: 360367.
Bodensieck A, Kunert O, Haslinger E, Bauer R. New eremophilane
sesquiterpenes from a rhizome extract of Petasites hybridus.
Helvet Chim Acta 2007; 90: 183195.
Bondi A. van der Waals volumes and radii. J Phys Chem 1964; 68:
441451.
Botha BM, McCrindle RI. Supercritical carbon dioxide extraction of avocado oil. Proc. 6th Meeting on Supercritical Fluids,
Nottingham, UK, 1999: 605610.
125
Boukouvalas C, Spiliotis N, Coutsikos P, Tzouvaras N, Tassios D.

Prediction of vapor-liquid equilibrium with the LCVM model:
a linear combination of the Vidal and Michelsen mixing rules
coupled with the original UNIF. Fluid Phase Equilib 1994; 92:
75106.
Bozan B, Temelli F. Supercritical CO2 extraction of flaxseed. J Am
Oil Chem Soc 2002; 79: 231235.
Bozan B, Temelli F. Extraction of poppy seed oil using supercritical
CO2. J Food Sci 2003; 68: 422426.
Brachet A, Mateus L, Cherkaoui S, Christen P, Gauvrit JY, Lanteri
P, Veuthey JL. Application of central composite designs in the
supercritical fluid extraction of tropane alkaloids in plant extracts.
Analusis 1999; 27: 772779.
Brachet A, Christen P, Gauvrit JY, Longeray R, Lanteri P, Veuthey
JL. Experimental design in supercritical fluid extraction of
cocaine from coca leaves. J Biochem Biophys Methods 2000;
43: 353366.
Braga MEM, Leal PF, Carvalho J, Meireles MAA. Comparison
of yield, composition, and antioxidant activity of turmeric
(Curcuma longa L.) extracts obtained using various techniques.
J Agric Food Chem 2003; 51: 66046611.
Braga MEM, Ehlert PAD, Ming LC, Meireles MAA. Supercritical
fluid extraction from Lippia alba: global yields, kinetic data,
and extract chemical composition. J Supercrit Fluids 2005; 34:
149156.
Braga MEM, Santos RMS, Seabra IJ, Facanali R, Marques MOM, de
Sousa HC. Fractioned SFE of antioxidants from maritime pine
bark. J Supercrit Fluids 2008; 47: 3748.
Braren M, Kurzhals HA. Supercritical extraction of black tea producing a cold-water soluble tea extract with natural flavour.
Proc. 5th Meeting on Supercritical Fluids/2, Nice, France, 1998:
501506.
Bravi M, Bubbico R, Manna F, Verdone N. Process optimisation
in sunflower oil extraction by supercritical CO2. Chem Eng Sci
2002; 57: 27532764.
Bravi M, Spinoglio F, Verdone N, Adami M, Aliboni A, DAndrea A,
De Santis A, Ferri D. Improving the extraction of -tocopherolenriched oil from grape seeds by supercritical CO2. Optimisation
of the extraction conditions. J Food Eng 2007; 78: 488493.
Brennecke JF, Eckert CA. Phase equilibria for supercritical fluid
process design. AIChE J 1989; 35: 14091427.
Bruhl L, Matthaus B. Extraction of oilseeds by SFE a comparison with other methods for the determination of the oil content.
Fresenius J Anal Chem 1999; 364: 631634.
Bruni R, Medici A, Guerrini A, Scalia S, Poli F, Muzzoli M,
Saccheti G. Wild Amaranthus caudatus seed oil, a nutraceutical
resource from Ecuadorian flora. J Agric Food Chem 2001; 49:
54555460.
Bruni R, Guerrini A, Scalia S, Romagnoli C, Sacchetti G. Rapid techniques for the extraction of vitamin E isomers from Amaranthus
caudatus seeds: ultrasonic and supercritical fluid extraction.
Brunner G. Mass-transfer from solid material in gas extraction. Ber
Bunsenges Phys Chem 1984; 88: 887891.
Brunner G. Stofftrennung mit berkritischen Gasen (Gasextraktion).
Chem Ing Tech 1987; 59: 1222.
Brunner G. Gas extraction an introduction to fundamentals of
supercritical fluid and the application to separation processes.
Berlin, Springer, 1994.
Brunner G. Supercritical fluids: technology and application to food
processing. J Food Eng 2005; 67: 2133.
Bugatti C, Colombo ML, Mossa A. Application of supercritical
carbon dioxide to the extraction of isoquinoline alkaloids from
Eschscholtzia californica. Planta Med 1993; 59: A626A627.

Authenticated
Bulley NR, Fattori M, Meisen A, Moyls L. Supercritical fluid

extraction of vegetable oil seeds. J Am Oil Chem Soc 1984; 61:
13621365.
Bundschuh E, Baumann G, Gierschner K. Investigations of the isolation of flavor compounds from apple peels by CO2-high pressure
extraction. Deut Lebensm-Rundsch 1988; 84: 205210.
Bunzenberger G, Lack E, Marr R. CO2-Extraktion Vergleich
der berkritischen Fluid-Extraktion mit der unterkritischen
Betriebsweise anhand von Problemen der Naturstoff-Extraktion.
Chem Ing Tech 1983; 55: 320.
Cabizza M, Cherchi G, Marongiu B, Porcedda S. Isolation of a volatile concentrate of caraway seed. J Essent Oil Res 2001; 13:
371375.
Cacace JE, Mazza G. Pressurized low polarity water extraction of
biologically active compounds from plant products. In: Shi J,
editor. Functional food ingredients and nutraceuticals: processing technologies. Boca Raton, FL: CRC Taylor & Francis, 2006:
135155.
Cadoni E, De Giorgi MR, Medda E, Poma G. Supercritical CO2
extraction of lycopene and -carotene from ripe tomatoes. Dyes
Pigm 2000; 44: 2732.
Calame JP, Steiner R. CO2 extraction in the flavor and perfumery
industries. Chem Ind 1982; 19: 399402.
Calvey EM, Matusik JE, White KD, Betz JM, Block E, Littlejohn
MH, Naganathan S, Putman D. Off-line supercritical fluid extraction of thiosulfinates from garlic and onion. J Agric Food Chem
1994; 42: 13351341.
Calvey EM, Matusik JE, White KD, DeOrazio R, Shy DY, Block E.
Allium chemistry: supercritical fluid extraction and LCAPCI
MS of thiosulfinates and related compounds from homogenates
of garlic, onion, and ramp. Identification in garlic and ramp and
synthesis of 1-propanesulfinothioic acid S-allyl ester. J Agric
Food Chem 1997; 45: 44064413.
Calvo L, Cocero MJ, Diez JM. Oxidative stability of sunflower oil
extracted with supercritical carbon dioxide. J Am Oil Chem Soc
1994; 71: 12511254.
Calvo L, Ramirez AI, Cocero MJ. Effect of the addition of butanol
to SC-CO2 on solubility and selectivity of the extraction of sunflower oil. Proc. 5th Meeting on Supercritical Fluids/2, Nice,
France, 1998: 699703.
Campos LMAS, Michielin EMZ, Danielski L, Ferreira SRS.
Experimental data and modeling the supercritical fluid extraction
of marigold (Calendula officinalis) oleoresin. J Supercrit Fluids
2005; 34: 163170.
Campos LMAS, Leimann FV, Pedrosa RC, Ferreira SRS. Free radical scavenging of grape pomace extracts from Cabernet sauvingnon (Vitis vinifera). Biores Technol 2008; 99: 84138420.
Cao XL, Ito YC. Supercritical fluid extraction of grape seed oil
and subsequent separation of free fatty acids by high-speed
counter-current chromatography. J Chromatogr A 2003; 1021:
117124.
Cao XL, Tian Y, Zhang TY, Ito Y. Supercritical fluid extraction of
catechins from Cratoxylum prunifolium dyer and subsequent
purification by high-speed counter-current chromatography. J
Chromatogr A 2000; 898: 7581.
Cao H, Xiao JB, Xu M. Comparison of volatile components of
Marchantia convoluta obtained by supercritical carbon dioxide
extraction and petrol ether extraction. J Food Comp Anal 2007;
20: 4551.
Cardozo EL, Cardozo L, Ferrarese O, Zanoelo EF. Selective liquid
CO2 extraction of purine alkaloids in different Ilex paraguariensis progenies grown under environmental influences. J Agric
Food Chem 2007; 55: 68356841.
Caredda A, Marongiu B, Porcedda S, Soro C. Supercritical carbon

dioxide extraction and characterization of Laurus nobilis essential oil. J Agric Food Chem 2002; 50: 14921496.
Carleson TE, Chandra S, Wai C, Wai L, Huang SS. Group contribution method for estimating the solubility of selected hydrocarbon
solutes in supercritical carbon dioxide. ACS Symp Series 1993;
514: 6673.
Carlson LHC, Machado RAF, Spricigo CB, Pereira LK, Bolzan A.
Extraction of lemongrass essential oil with dense carbon dioxide.
J Supercrit Fluids 2001; 21: 3339.
Carvalho RN, Moura LS, Rosa PTV, Meireles MAA. Supercritical
fluid extraction from rosemary (Rosmarinus officinalis): kinetic
data, extracts global yield, composition, and antioxidant activity.
Casas L, Mantell C, Rodriguez M, Torres A, Macias FA, Martinez de
la Ossa E. Effect of the addition of cosolvent on the supercritical
fluid extraction of bioactive compounds from Helianthus annuus
L. J Supercrit Fluids 2007; 41: 4349.
Casas L, Mantell C, Rodriguez M, Torres A, Macias FA, Martinez de
la Ossa EJ. Supercritical fluid extraction of bioactive compounds
from sunflower leaves with carbon dioxide and water on a pilot
plant scale. J Supercrit Fluids 2008; 45: 3742.
Cassel E, Frizzo CD, Vanderlinde R, Atti-Serafini L, Lorenzo D,
Dellacassa E. Extraction of baccharis oil by supercritical CO2.
Ind Eng Chem Res 2000; 39: 48034805.
Castaneda-Acosta J, Cain AV, Fischer NH, Knopf FC. Extraction of
bioactive sesquiterpene lactones from magnolia grandiflora using
supercritical carbon dioxide and near-critical propane. J Agric
Food Chem 1995; 43: 6368.
Castioni P, Christen P, Veuthey JL. Supercritical fluid extraction of
compounds from plant origin. Analusis 1995; 23: 95106.
Castola V, Marongiu B, Bighelli A, Floris C, Lai A, Casanova
J. Extractives of cork (L.): chemical composition of dichloromethane and supercritical CO extracts. Ind Crops Products
2005; 21: 6569.
Catchpole OJ. Packed bed mass transfer using a near critical solvent.
Ph.D. thesis, University of Birmingham, UK, 1991.
Catchpole OJ, Andrews EW, Toikka GN, Wilkinson GT. Mathematical
models for the extraction of oils from plant matrices using a nearcritical solvent. Proc 3rd Int Symp Supercrit Fluids/2, Strasbourg,
France, 1994: 4752.
Catchpole OJ, Grey JB, Smallfield BM. Near-critical extraction of
sage, celery, and coriander seed. J Supercrit Fluids 1996a; 9:
273279.
Catchpole OJ, Bernig R, King MB. Measurement and correlation of
packed-bed axial dispersion coefficients in supercritical carbon
dioxide. Ind Eng Chem Res 1996b; 35: 824828.
Catchpole OJ, Grey JB, Smallfield BM. Extraction of sage and coriander seed using near-critical carbon dioxide. ACS Symp Ser
1997; 670: 7689.
Catchpole OJ, Perry NB, da Silva BMT, Grey JB, Smallfield BM.
Extraction of medicinal herbs using supercritical CO2 and CO2
+ ethanol mixtures. Proc. 7th Meeting on Supercritical Fluids/2,
Antibes/Juan-les-Pins, France, 2000: 665670.
Catchpole OJ, Perry NB, da Silva BMT, Grey JB, Smallfield BM.
Supercritical extraction of herbs I: Saw Palmetto, St Johns
Wort, Kava Root, and Echinacea. J Supercrit Fluids 2002; 22:
129138.
Catchpole OJ, Grey JB, Perry NB, Burgess EJ, Redmond WA, Porter
NG. Extraction of chili, black pepper, and ginger with nearcritical CO2, propane, and dimethyl ether: analysis of the extracts
by quantitative nuclear magnetic resonance. J Agric Food Chem
2003; 51: 48534860.

Authenticated
Catchpole OJ, Tallon SJ, Eltringham WE, Grey JB, Fenton KA, Vagi
EM, Vyssotski MV, MacKenzie AN, Ryan J, Zhu Y. The extraction and fractionation of specialty lipids using near critical fluids.
Cavero S, Garcia-Risco MR, Marin FR, Jaime L, Santoyo S,
Senorans FJ, Reglero G, Ibanez E. Supercritical fluid extraction
of antioxidant compounds from oregano. J Supercrit Fluids 2006;
38: 6269.
Celeghini RMS, Vilegas JHY, Lancas FM. Extraction and quantitative HPLC analysis of coumarin in hydroalcoholic extracts of
Mikania glomerata Spreng: (guaco) leaves. J Braz Chem Soc
2001; 12: 706709.
Celiktas OY, Bedir E, Sukan FV. In vitro antioxidant activities of
Rosmarinus officinalis extracts treated with supercritical carbon
dioxide. Food Chem 2007; 101: 14571464.
Cernia E, Palocci C, DAndrea A, Ferri D, Maccioni O, van der Esch
SA, Vitali F. Fractionation by SFE of active substances from
Azadirachta indica (A.Juss) seeds. Proc 3rd Int Symp Supercrit
Fluids/2, Strasbourg, France, 1994: 317322.
Chafer A, Fornari T, Berna A, Stateva RP. Solubility of quercetin in
supercritical CO2+ethanol as a modifier: measurements and thermodynamic modelling. J Supercrit Fluids 2004; 32: 8996.
Chafer A, Fornari T, Berna A, Ibanez E, Reglero G. Solubility of
solid carnosic acid in supercritical CO2 with ethanol as a cosolvent. J Supercrit Fluids 2005; 34: 323329.
Chan KW, Ismail M. Supercritical carbon dioxide fluid extraction
of Hibiscus cannabinus L. seed oil: a potential solvent-free
and high antioxidative edible oil. Food Chem 2009; 114: 970
975.
Chandra A, Nair MG. Supercritical carbon dioxide extraction and
quantification of bioactive neolignans from Magnolia virginiana
flowers. Planta Med 1995; 61: 192195.
Chandra A, Nair MG. Supercritical carbon dioxide extraction of
daidzein and genistein from soybean products. Phytochem Anal
1996; 7: 259262.
Chandra A, Nair MG. Supercritical fluid carbon dioxide extraction
of -and -carotene from carrot (Daucus carota L.). Phytochem
Anal 1997; 8: 244246.
Chang CJ, Chiu KL, Chen YL, Chang CY. High-pressure carbon dioxide extraction of polyphenols from green tea. Proc. 6th Meeting
on Supercritical Fluids, Nottingham, UK, 1999: 543548.
Chang CMJ, Chiu KL, Chen YL, Chang CY. Separation of catechins
from green tea using carbon dioxide extraction. Food Chem
2000; 68: 109113.
Chang LH, Jong TT, Huang HS, Nien YF, Chang CMJ. Supercritical
carbon dioxide extraction of turmeric oil from Curcuma longa
Linn and purification of turmerones. Sep Purif Technol 2006; 47:
119125.
Chang Y, Liu B, Shen B. Orthogonal array design for the optimization of supercritical fluid extraction of baicalin from roots
of Scutellaria baicalensis Georgi. J Sep Sci 2007; 30: 1568
1574.
Chao RR, Mulvaney SJ, Sanson DR, Hsieh FH, Tempest MS.
Supercritical CO2 extraction of annatto (Bixa orellana) pigments
and some characteristics of the color extracts. J Food Sci 1991;
56: 8083.
Chassagnez-Mendez AL, Machado NT, Araujo ME, Maia JG,
Meireles MAA. Supercritical CO2 extraction of curcumins and
essential oil from the rhizomes of turmeric (Curcuma longa L.).
Ind Eng Chem Res 2000a; 39: 47294733.
Chassagnez-Mendez AL, Correa NCF, Franca LF, Machado NT,
Araujo ME. A mass transfer model applied to the supercritical extraction with CO2 of curcumins from turmeric
127
rhizomes (Curcuma longa L). Braz J Chem Eng 2000b; 17: 315
322.
Chatzopoulou P, de Haan A, Katsiotis ST. Investigation on the supercritical CO2 extraction of the volatile constituents from Juniperus
communis obtained under different treatments of the berries
(cones). Planta Med 2002; 68: 827831.
Cheah ELC, Heng PWS, Chan LW. Optimization of supercritical
fluid extraction and pressurized liquid extraction of active principles from Magnolia officinalis using the Taguchi design. Sep
Purif Technol 2010; 71: 293301.
Chen YT, Ling YC. An overview of supercritical fluid extraction in
chinese herbal medicine: from preparation to analysis. J Food
Drug Analysis 2000; 8: 235247.
Chen MM, Ma PS. Solid-liquid equilibria of several systems containing acetic acid. J Chem Eng Data 2004; 49: 756759.
Chen CC, Kuo MC, Wu CM, Ho CT. Pungent compounds of ginger
(Zingiber officinale roscoe) extracted by liquid carbon dioxide.
J Agric Food Chem 1986; 34: 477480.
Chen PC, Tang M, Chen YP. Calculations of the solubilities of solids in supercritical fluids using the Peng-Robinson equation of
state and a modified mixing model. Ind Eng Chem Res 1995;
34: 332339.
Chen CR, Wang CH, Wang LY, Hong ZH, Chen SH, Ho WJ, Chang
CMJ. Supercritical carbon dioxide extraction and deacidification
of rice bran oil. J Supercrit Fluids 2008a; 45: 322331.
Chen CR, Wang LY, Wang CH, Ho WJ, Chang CMJ. Supercritical
carbon dioxide extraction of rice bran oil and column partition fractionation of -oryzanols. Sep Purif Technol 2008b; 61:
358365.
Cheng JS, Tang M, Chen YP. Correlation of solid solubility for biological compounds in supercritical carbon dioxide: comparative
study using solution model and other approaches. Fluid Phase
Equilib 2002; 194197: 483491.
Cheng KW, Tang M, Chen YP. Calculations of solid solubility in
supercritical fluids using a simplified cluster solvation model.
Cherchi G, Deidda D, De Gioannis B, Marongiu B, Pompei R,
Porcedda S. Extraction of Santolina insularis essential oil by
supercritical carbon dioxide: influence of some process parameters and biological activity. Flavour Fragr J 2001; 16:
3543.
Chester TL, Pinkston JD, Raynie DE. Supercritical-fluid chromatography and extraction. Anal Chem 1996; 70: R106R130.
Chester TL, Pinkston JD, Raynie DE. Supercritical fluid chromatography and extraction. Anal Chem 1998; 70: 301R319R.
Chickos JS, Hesse DG, Liebman JF. Estimating entropies and
enthalpies of fusion of hydrocarbons. J Org Chem 1990; 55:
38333840.
Chickos JS, Braton CM, Hesse DG, Liebman JF. Estimating entropies and enthalpies of fusion of organic compounds. J Org Chem
1991; 56: 927938.
Chiu KL, Cheng YC, Chen JH, Chang CMJ, Yang PW. Supercritical
fluids extraction of Ginkgo ginkgolides and flavonoids. J
Supercrit Fluids 2002; 24: 7787.
Choi YH, Kim JW, Noh MJ, Park EM, Yoo KP. Extraction of epicuticular wax and nonacosan-10-OL from Ephedra herb utilizing supercritical carbon dioxide. Korean J Chem Eng 1996; 13:
216219.
Choi YH, Kim JW, Noh MJ, Choi FS, Yoo KP. Comparison of supercritical carbon dioxide extraction with solvent extraction of nonacosan-10-ol, -amyrin acetate, squalene and stigmasterol from
medicinal plants. Phytochem Anal 1997; 8: 233237.

Authenticated
Choi YH, Kim J, Jeon SH, Yoo KP, Lee HK. Optimum SFE condition for lignans of Schisandra chinensis fruits. Chromatographia
1998a; 48: 695699.
Choi YH, Kim JY, Ryu JH, Yoo KP, Chang YS, Kim JW. Optimum
SFE condition for lignans of Schisandra chinensis fruits. Planta
Med 1998b; 64: 482483.
Choi YH, Chin YW, Kim J, Jeon SH, Yoo KP. Strategies for supercritical fluid extraction of hyoscyamine and scopolamine salts
using basified modifiers. J Chromatogr A 1999a; 863: 4755.
Choi YH, Kim J, Kim YC, Yoo KP. Selective extraction of ephedrine
from Ephedra sinica using mixtures of CO2, diethylamine, and
methanol. Chromatographia 1999b; 50: 673679.
Choi YH, Kim J, Kim JY, Joung SN, Yoo KP, Chang YS. Modifier
effects on supercritical CO2 extraction efficiency of cephalotaxine from Cephalotaxus wilsoniana leaves. Arch Pharm Res 2000;
23: 163166.
Choi YH, Yoo KP, Kim J. Supercritical fluid extraction and liquid
chromatography-electrospray mass analysis of vinblastine from
Catharanthus roseus. Chem Pharm Bull 2002a; 50: 1294
1296.
Choi YH, Kim I, Yoon KD, Lee SJ, Kim CY, Yoo KP, Choi YH,
Kim J. Supercritical fluid extraction and liquid chromatographicelectrospray mass spectrometric analysis of stevioside from
Stevia rebaudiana leaves. Chromatographia 2002b; 55: 617
620.
Choi YH, Kim J, Yoo KP. Supercritical-fluid extraction of bilobalide
and ginkgolides from Ginkgo biloba leaves by use of a mixture
of carbon dioxide, methanol, and water. Chromatographia 2002c;
56: 753757.
Chotratanadilok C, Clifford AA. Extraction of nepetlactone from
Nepeta cataria using supercritical fluids. Proc. 5th Meeting on
Supercritical Fluids/2, Nice, France, 1998: 647650.
Chrastil J. Solubility of solids and liquids in supercritical gases. J
Phys Chem 1982; 86: 30163021.
Christianson DD, Friedrich JP, List GR, Warner K, Bagley EB,
Stringfellow AC, Inglett GE. Supercritical fluid extraction of
dry-milled corn germ with carbon dioxide. J Food Sci 1984; 49:
229232.
Christov M, Dohrn R. High-pressure fluid phase equilibria experimental methods and systems investigated (19941999). Fluid
Phase Equilib 2002; 202: 153218.
Chun MK, Shin HY, Lee H, Liu JR. Supercritical fluid extraction of taxol and baccatin III from needles of Taxus cuspidata.
Biotechnol Tech 1994; 8: 547550.
Chun MK, Shin HW, Lee H. Supercritical fluid extraction of paclitaxel and baccatin III from needles of Taxus cuspidata. J Supercrit
Fluids 1996; 9: 192198.
Clavier JY, Majewski W, Perrut M. Extrapolation from pilot plant to
industrial scale SFE: a case study. Proc. I fluidi supercritici a le
loro applicazioni, Grignano (Trieste), Italy, 1995: 107114.
Clifford AA, Basile A, Al-Saidi SHR. A comparison of the extraction
of clove buds with supercritical carbon dioxide and superheated
water. Fresen J Anal Chem 1999; 364: 635637.
Cocero MJ, Calvo L. Supercritical fluid extraction of sunflower seed
oil with CO2-ethanol mixtures. J Am Oil Chem Soc 1996; 73:
15731578.
Cocero MJ, Garcia J. Mathematical model of supercritical extraction applied to oil seed extraction by CO2+saturated alcohol I.
Desorption model. J Supercrit Fluids 2001; 20: 229243.
Coelho LAF, Oliveira JV, dAvila SG, Vilegas JHY, Lancas FM. SFE
of rosemary oil: assessment of the influence of process variables
and extract characterization. J High Res Chromatogr 1997; 20:
431436.
Coelho JAP, Pereira AP, Mendes RL, Palavra AMF. Supercritical

carbon dioxide extraction of Foeniculum vulgare volatile oil.
Flavour Fragr J 2003; 18: 316319.
Coelho JA, Grosso C, Pereira AP, Burillo J, Urieta JS, Figuiredo
AC, Barroso JG, Mendes RL, Palavra AMF. Supercritical carbon
dioxide extraction of volatiles from Satureja fruticosa Bguinot.
Flavour Fragr J 2007; 22: 438442.
Coenen H. Anwendungen der Extraktion mit berkritischen Gasen
in der Nahrungsmittel-Industrie. Chem Ing Tech 1983; 55:
816817.
Coenen H, Kriegel E. Use of supercritical gas extraction in the foodindustry. Ger Chem Eng 1984; 7: 335344.
Colombo ML, Corsini A, Mossa A, Sala L, Stanca M. Supercritical
carbon dioxide extraction, fluorimetric and electrochemical high
performance liquid chromatrographic detection of vitamin E
from Hordeum vulgare L. Phytochem Anal 1998; 9: 192195.
Colussi LE, Fermeglia M, Gallo V, Kikic I. Supercritical multistaged
multicomponent separation: process simulation. Comp Chem
Eng 1992; l6: 211224.
Congiu R, Falconieri D, Marongiu B, Piras A, Porcedda S. Extraction
and isolation of Pistacia lentiscus L. essential oil by supercritical
CO2. Flavour Fragr J 2002; 17: 239244.
Coniglio L. Estimation des proprietes thermophysiques des hydrocarbures lourds. Thesis, Universite dAix-Marseille III, 1993.
Coniglio L, Knudsen K, Gani R. Model prediction of supercritical
fluid-liquid equilibria for carbon dioxide and fish oil related compounds. Ind Eng Chem Res 1995; 34: 24732484.
Corazza ML, Filho LC, Oliveira JV, Dariva C. A robust strategy
for SVL equilibrium calculations at high pressures. Fluid Phase
Equilib 2004; 221: 113126.
Core RJ, Henning JA, Gardea-Torresdey J. Volatile compounds from
medicago spp. as potential signals for alfalfa weevil response. J
Agric Food Chem 1994; 42: 29322936.
Core RJ, Henning JA, Gardea-Torresdey J, Mostafavi R. Quantitative
comparison of volatile compounds among seven Medicago spp.
accessions. J Chem Ecol 1996; 22: 16211627.
Cossuta D, Simandi B, Hohmann J, Doleshall F, Keve T. Supercritical
carbon dioxide extraction of sea buckthorn (Hippophae rhamnoides L.) pomace. J Sci Food Agric 2007; 87: 24722481.
Coutsikos P, Magoulas K, Kontogeorgis GM. Prediction of solid-gas
equilibria with the Peng-Robinson equation of state. J Supercrit
Fluids 2003; 25: 197212.
Crabas N, Marongiu B, Piras A, Pivetta T, Porcedda S. Porcedda S.
Extraction, separation and isolation of volatiles and dyes from
Calendula officinalis L. and Aloysia triphylla (L'Her.) Britton
by supercritical CO2. J Essent Oil Res 2003; 15: 272277;
350355.
Crampon C, Trassy L, Avaullee L, Neau E, Coniglio L.
Simplification and extension of a predictive group contribution method for estimating heavy organic pure compound
vapor pressures I. Hydrocarbons. Fluid Phase Equilib 2004;
216: 95109.
Cretnik L, Skerget M, Knez Z. Separation of parthenolide from
feverfew: performance of conventional and high-pressure extraction techniques. Sep Purif Technol 2005; 41: 1320.
Crowe TD, White PD. Impact of extraction method on yield of lipid
oxidation products from oxidized and unoxidized walnuts. J Am
Oil Chem Soc 2003; 80: 569578.
Crowe TD, Crowe TW, Johnson LA, White PD. Oxidation, flavor,
and texture of walnuts reduced in fat content by supercritical carbon dioxide. J Am Oil Chem Soc 2002; 79: 453456.
Cui YY, Ang CYW. Supercritical fluid extraction and high-performance liquid chromatographic determination of phloroglucinols

Authenticated
in St. Johns wort (Hypericum perforatum L.). J Agric Food

Chem 2002; 50: 27552759.
Cuperus FP, Boswinkel G, Muuse BG, Derksen JTP. Supercritical
carbon dioxide extraction of Dimorphotheca pluvialis oil seeds.
J Am Oil Cem Soc 1996; 73: 16751679.
Cygnarowicz-Provost M. Design and economic analysis of supercritical fluid extraction processes. In: King JW, List GR, editors. Supercritical fluid technology in oil and lipid chemistry.
Champaign, IL: AOCS Press, 1996: 155179.
DAndrea A, Aliboni A, De Santis A, Mariani S, Gorgoglione D,
Ritieni A. SFE of Derris elliptica (Wallich) Benth. roots: influence of process parameters on yield and purity of rotenone.
da Costa CT, Margolis SA, Benner BA, Horton D. Comparison of
methods for extraction of flavanones and xanthones from the
root bark of the osage orange tree using liquid chromatography.
J Chromatogr A 1999; 831: 167178.
da Silva TL, Bernardo EC, Nobre B, Mendes RL, Reis A. Extraction
of victoria and red globe grape seed oils using supercritical carbon dioxide with and without ethanol. J Food Lipids 2008; 15:
356369.
Dahl S, Michelsen ML. High-pressure vapor-liquid equilibrium
with a UNIFAC-based equation of state. AIChE J 1990; 36:
18291836.
Dahl S, Fredenslund A, Rasmussen P. The MHV2 model: a UNIFACbased equation of state model for prediction of gas solubility and
vapor-liquid equilibria at low and high pressures. Ind Eng Chem
Res 1991; 30: 19361945.
Dai J, Ha C, Shen M. Systematic study of -asarone-rich volatile
oil from Acori graminei rhizoma by off-line supercritical CO2
extractiongas chromatographymass spectrometry. J Sep Sci
2008; 31: 714720.
Damjanovic BM, Skala D, Petrovic-Djakov D, Baras J. A comparison between the oil, hexane extract and supercritical carbon
dioxide extract of Juniperus communis L. J Essent Oil Res 2003;
15: 9092.
Damjanovic B, Lepojevic Z, Zivkovic V, Tolic A. Extraction of fennel (Mill.) seeds with supercritical CO: comparison with hydrodistillation. Food Chem 2005; 92: 143149.
Damjanovic B, Skala D, Baras J, Petrovic-Djakov D. Isolation of
essential oil and supercritical carbon dioxide extract of Juniperus
communis L. fruits from Montenegro. Flavour Fragr J 2006; 21:
875880.
Danielski L, Zetzl C, Hense H, Brunner G. A process line for the
production of raffinated rice oil from rice bran. J Supercrit Fluids
2005; 34: 133141.
Danielski L, Campos LMAS, Bresciani LFV, Hense H, Yunes RA,
Ferreira SRS. Marigold (Calendula officinalis L.) oleoresin:
solubility in SC-CO2 and composition profile. Chem Eng Proc
2007; 46: 99106.
Dannenfelser RM, Yalkowsky SH. Estimation of entropy of melting
from molecular structure: a non-group contribution method. Ind
Eng Chem Res 1996; 35: 14831486.
Daood HG, Illes V, Gnayfeed MH, Meszaros B, Horvath G, Biacs
PA. Extraction of pungent spice paprika by supercritical carbon
dioxide and subcritical propane. J Supercrit Fluids 2002; 23:
143152.
Daoud IS, Kusinski S. Liquid CO2 and ethanol extraction of hops.
1. Effect of hop deterioration on extraction efficiency and extract
quality. J Inst Brewing 1992; 98: 3741.
Dapkevicius A, Venskutonis R, van Beek TA, Linssen JPH.
Antioxidant activity of extracts obtained by different isolation
procedures from some aromatic herbs grown in Lithuania. J Sci
Food Agric 1996; 77: 140146.
129
Dauksas E, Venskutonis PR, Sivik B. Extraction of lovage (Levisticum

officinale Koch.) roots by carbon dioxide. 1. Effect of CO2 parameters on the yield of the extract. J Agric Food Chem 1998; 46:
43474351.
Dauksas E, Venskutonis PR, Sivik B. Supercritical CO2 extraction
of the main constituents of lovage (Levisticum officinale Koch.)
essential oil in model systems and overground botanical parts of
the plant. J Supercrit Fluids 1999; 15: 5162.
Dauksas E, Venskutonis PR, Povilaityte V, Sivik B. Rapid screening of antioxidant activity of sage (Salvia officinalis L.) extracts
obtained by supercritical carbon dioxide at different extraction
conditions. Nahrung 2001; 45: 338341.
Dauksas E, Venskutonis PR, Sivik B, Nilsson T. Effect of fast CO2
pressure changes on the yield of lovage (Levisticum officinale
Koch.) and celery (Apium graveolens L.) extracts. J Supercrit
Fluids 2002a; 22: 201210.
Dauksas E, Venskutonis PR, Sivik B. Supercritical fluid extraction
of borage (Borago officinalis L.) seeds with pure CO2 and its
mixture with caprylic acid methyl ester. J Supercrit Fluids 2002b;
22: 211219.
Dauksas E, Venskutonis PR, Sivik B. Comparison of oil from Nigella
damascena seed recovered by pressing, conventional solvent
extraction and carbon dioxide extraction. J Food Sci 2002c; 67:
10211024.
Dawidowicz AL, Rado E, Wianowska D, Mardarowicz M, Gawdzik
J. Application of PLE for the determination of essential oil components from Thymus vulgaris L. Talanta 2009; 76: 878884.
de Azevedo ABA, Kopcak U, Mohamed RS. Extraction of fat from
fermented Cupuau seeds with supercritical solvents. J Supercrit
Fluids 2003; 27: 223237.
de Azevedo ABA, Kieckbush TG, Tashima AK, Mohamed RS,
Mazzafera P, de Melo SABV. Extraction of green coffee oil
using supercritical carbon dioxide. J Supercrit Fluids 2008a; 44:
186192.
de Azevedo ABA, Mazzafera P, Mohamed RS, de Melo SABV,
Kieckbush TG. Extraction of caffeine, chlorogenic acids and lipids from green coffee beans using supercritical carbon dioxide
and co-solvents. Braz J Chem Eng 2008b; 25: 543552.
de Azevedo ABA, Kieckbush TG, Tashima AK, Mohamed RS,
Mazzafera P, de Melo SABV. Supercritical CO2 recovery of caffeine from green coffee oil: new experimental solubility data and
modeling. Quimica Nova 2008c; 31: 13191323.
de Castro MDL, Jimnez-Carmona MM. Where is supercritical fluid
extraction going? Trends Anal Chem 2000; 19: 223228.
De Gioannis B, Marongiu B, Porcedda S. Isolation of Thymus herbabarona volatiles by supercritical fluid extraction. J Essent Oil Res
2001; 13: 240244.
de la Fuente JC, Valderrama JO, Bottini SB, del Valle JM.
Measurement and modeling of solubilities of capsaicin in highpressure CO2. J Supercrit Fluids 2005; 34: 195201.
de Lucas A, Rincon J, Gracia I. Supercritical extraction of husk oil.
711714.
de Lucas A, Rincon J, Gracia I. Investigation of biologically active
compounds in plant oils extracted by different extraction methods. Proc. 6th Meeting on Supercritical Fluids, Nottingham, UK,
1999: 555560.
de Lucas A, de la Ossa EM, Rincon J, Blanco MA, Gracia I.
Supercritical fluid extraction of tocopherol concentrates from
olive tree leaves. J Supercrit Fluids 2002a; 22: 221228.
de Lucas A, Rincon J, Gracia I. Influence of operating variables on
yield and quality parameters of olive husk oil extracted with
supercritical carbon dioxide. J Am Oil Chem Soc 2002b; 79:
237243.

Authenticated
de Lucas A, Rincon J, Gracia I. Influence of operation variables on

quality parameters of olive husk oil extracted with CO2: threestep sequential extraction. J Am Oil Chem Soc 2003; 80: 181
188.
de Lucas A, Garcia A, Alvarez A, Gracia I. Supercritical extraction
of long chain n-alcohols from sugar cane crude wax. J Supercrit
Fluids 2007; 41: 267271.
de Melo SABV, Costa GMN, Garau R, Casula A, Pittau B. Supercritical
CO2 extraction of essential oils from Thymus vulgaris.
Braz J Chem Eng 2000; 17: 367371.
de Vasconcelos EC, Vilegas JHY, Lancas FM. Comparison of
extraction and clean-up methods for the analysis of friedelan3-ol and friedelin from leaves of Maytenus aquifolium Martius
(Celastraceae). Phytochem Anal 2000; 11: 247250.
Dean JR, Khundker S. Extraction of pharmaceuticals using pressurised carbon dioxide. J Pharm Biomed Anal 1997; 15: 875
886.
Dean JR, Liu B. Supercritical fluid extraction of Chinese herbal
medicines: investigation of extraction kinetics. Phytochem Anal
2000; 11: 16.
Dean JR, Liu B, Price R. Extraction of magnolol from Magnolia officinalis using supercritical fluid extraction and phytosol solvent
extraction. Phytochem Anal 1998a; 9: 248252.
Dean JR, Liu B, Price R. Extraction of Tanshinone IIA from Salvia
miltiorrhiza bunge using supercritical fluid extraction and a new
extraction technique, phytosol solvent extraction. J Chromatogr
A 1998b; 799: 343348.
Degnan AJ, von Elbe JH, Hartel RW. Extraction of annatto seed
pigment by supercritical carbon dioxide. J Food Sci 1991; 56:
1655.
del Castillo MLR, Gomez-Prieto MS, Herraiz M, Santa-Maria G.
Lipid composition in tomato skin supercritical fluid extracts
with high lycopene content. J Am Oil Chem Soc 2003; 80:
271274.
del Valle JM, Aguilera JM. An improved equation for predicting the
solubility of vegetable oils in supercritical carbon dioxide. Ind
Eng Chem Res 1988; 27: 15511553.
del Valle JM, Aguilera JM. Effects of substrate densification and CO2
conditions on supercritical extraction of mushroom oleoresins.
J Food Sci 1989; 54: 135141.
del Valle JM, Aguilera JM. Revision: extraccion con CO2 a alta presion. Fundamentos y aplicaciones en la industria de alimentos/
Review: high pressure CO2 extraction. Fundamentals and applications in the food industry. Food Sci Technol Int 1999; 5: 124.
del Valle JM, Uquiche E. Particle size effects on supercritical CO2
extraction of oil-containing seeds. J Am Oil Chem Soc 2002; 79:
12611266.
del Valle JM, de la Fuente JC. Supercritical CO2 extraction of oilseeds: review of kinetic and equilibrium models. Crit Rev Food
Sci Nutr 2006; 46: 131160.
del Valle JM, Bello S, Thiel J, Allen A, Chordia L. Comparision of
conventional and supercritical CO2-extracted rosehip oil. Braz J
Chem Eng 2000a; 17: 335348.
del Valle JM, Napolitano P, Fuentes N. Estimation of relevant
mass transfer parameters for the extraction of packed substrate
beds using supercritical fluids. Ind Eng Chem Res 2000b; 39:
47204728.
del Valle JM, Jimenez M, Napolitano P, Zetzl C, Brunner G.
Supercritical carbon dioxide extraction of pelletized Jalapeo
peppers. J Sci Food Agric 2003a; 83: 550556.
del Valle JM, Rivera O, Mattea M, Ruetsch L, Daghero J, Flores A.
Supercritical CO2 extraction of Chilean hop (Humulus lupulus)
ecotypes. J Sci Food Agric 2003b; 83: 13491356.
del Valle JM, Jimenez M, de la Fuente JC. Extraction kinetics of prepelletized Jalapeo peppers with supercritical CO2. J Supercrit
Fluids 2003c; 25: 3344.
del Valle JM, Rivera O, Mattea M, Ruetsch L, Daghero J, Flores A.
Supercritical CO2 processing of pretreated rosehip seeds: effect
of process scale on oil extraction kinetics. J Supercrit Fluids
2004a; 31: 159174.
del Valle JM, Godoy C, Asencio M, Aguilera JM. Recovery of antioxidants from boldo (Peumus boldus M.) by conventional and
supercritical CO2 extraction. Food Res Int 2004b; 37: 695
702.
del Valle JM, de la Fuente JC, Cardarelli DA. Contributions to
supercritical extraction of vegetable substrates in Latin America.
J Food Eng 2005a; 67: 3557.
del Valle JM, Rogalinski T, Zetzl C, Brunner G. Extraction of boldo
(Peumus boldus M.) leaves with supercritical CO2 and hot pressurized water. Food Res Int 2005b; 38: 203213.
del Valle JM, Germain JC, Uquiche E, Zetzl C, Brunner G.
Microstructural effects on internal mass transfer of lipids in prepressed and flaked vegetable substrates. J Supercrit Fluids 2006;
37: 178190.
del Valle JM, Mena C, Budinich M. Extraction of garlic with supercritical CO2 and conventional organic solvents. Braz J Chem Eng
2008; 25: 535542.
Della Porta G, Taddeo R, DUrso E, Reverchon E. Isolation of clove
bud and star anise essential oil by supercritical CO2 extraction. J
Food Sci Technol (LWT) 1998a; 31: 454460.
Della Porta G, Reverchon E, Ambruosi A. Pilot plant isolation of
celery and parsley essential oil by supercritical CO2. Proc.
5th Meeting on Supercritical Fluids/2, Nice, France, 1998b:
613618.
Della Porta C, Porcedda S, Marongiu B, Reverchon E. Isolation of
eucalyptus oil by supercritical fluid extraction. Flavour Fragr J
1999; 14: 214218.
Derevich IV, Shindyapkin AA. Extraction of organic oil from sea
buckthorn seeds with supercritical carbon dioxide. Theor Found
Chem Eng 2004; 38: 274283.
Devittori C, Gumy D, Kusy A, Colarow L, Bertoli C, Lambelet P.
Supercritical fluid extraction of oil from millet bran. J Am Oil
Chem Soc 2000; 77: 573579.
Diaz-Maroto MC, Perez-Coello MS, Cabezudo MD. Supercritical
carbon dioxide extraction of volatiles from spices: comparison
with simultaneous distillationextraction. J Chromatogr A 2002;
947: 2329.
Diaz-Maroto MC, Diaz-Maroto IJ, Sanchez-Palomo E, PerezCoello MS. Volatile components and key odorants of fennel
(Foeniculum vulgaremil L.) and thyme (Thymus vulgaris L.)
oil extracts obtained by simultaneous distillationextraction and
supercritical fluid extraction. J Agric Food Chem 2005; 53: 5385
5389.
Diaz-Reinoso B, Moure A, Dominguez H, Parajo C. Supercritical
CO2 extraction and purification of compounds with antioxidant
activity. J Agric Food Chem 2006; 54: 24412469.
Dimitrieska-Stojkovic E, Zdravkovski Z. Supercritical fluid extraction of quercetin and rutin from Hyperici herba. J Liquid
Chromatogr Relat Technol 2003; 26: 25172533.
Djarmati Z, Csanadi J, Filip S, Dinya Z, Najdenova V, Jankov RM.
High antioxidant activity of extract obtained from Osage orange
with aid of supercritical CO2 extraction. Proc. 5th Meeting on
Dohrn R, Brunner G. High-pressure fluid-phase equilibria: experimental methods and systems investigated (19881993). Fluid
Phase Equilib 1995; 106: 213282.

Authenticated
Dohrn R, Peper S, Fonseca JMS. High-pressure fluid-phase equilibria: experimental methods and systems investigated (20002004).
Doker O, Salgin U, Sanal I, Mehmetoglu U, Calimli A. Modeling of
extraction of -carotene from apricot bagasse using supercritical
CO2 in packed bed extractor. J Supercrit Fluids 2004; 28: 1119.
Doneanu C, Anitescu G. Supercritical carbon dioxide extraction of
Angelica archangelica L. root oil. J Supercrit Fluids 1998; 12:
5967.
Dong M, Walker TH. Production and recovery of polyunsaturated
fatty acids-added lipids from fermented canola. Biores Technol
2008; 99: 85048506.
Donsi G, Reverchon E, Salatino P, Tufano V. Supercritical extraction
from solid matrices: a preliminary study on cut tobaccos. Chem
Biochem Eng Q 1990; 4: 2124.
Dron A, Guyer DE, Gage DA, Lira CT. Yield and quality of onion
flavor oil obtained by supercritical fluid extraction and other
methods. J Food Process Eng 1997; 20: 107124.
Duarte C, Moldao-Martins M, Gouveia AF, da Costa SB, Leitao AE,
Bernardo-Gil MG. Supercritical fluid extraction of red pepper
(Capsicum frutescens L.). J Supercrit Fluids 2004; 30: 155161.
Dunford NT, Temelli F. Extraction of phospholipids from canola
with supercritical carbon dioxide and ethanol. J Am Oil Chem
Soc 1995; 72: 10091015.
Dunford NT, Temelli F. Extraction conditions and moisture content
of canola flakes as related to lipid composition of supercritical
CO2 extracts. J Food Sci 1997; 62: 155159.
Duquesnoy E, Marongiu B, Castola V, Piras A, Porcedda S, Casanova
J. Supercritical CO2 extract from needles of Pinus nigra ssp.laricio: combined analysis by GC, GC-MS and13C NMR. Nat Prod
Res 2007; 21: 834837.
Ebrahimzadeh H, Yamini Y, Sefidkon F, Chakloosi D, Pourmortazavi
SM. Chemical composition of the essential oil and supercritical
CO2 extracts of Zataria multiflora Boiss. Food Chem 2003; 83:
357361.
Eckert CA, Knutson BL. Molecular charisma in supercritical fluids.
Eckert CA, Knutson BL, Debenedetti PG. Supercritical fluids as
solvents for chemical and materials processing. Nature 1996;
383: 313318.
Economou IG, Gregg CJ, Radosz M. Solubilities of solid polynuclear aromatics (PNAs) in supercritical ethylene and ethane from
statistical associating fluid theory (SAFT): toward separating
PNAs by size and structure. Ind Eng Chem Res 1992; 31: 2620
2624.
Eggers R, Sievers U, Stein W. High-pressure extraction of oil seed. J
Am Oil Chem Soc 1985; 62: 12221230.
Eggers R, Ambrogi A, von Schnitzler J. Special features of scf
solid extraction of natural products: deoiling of wheat gluten and extraction of rose hip oil. Braz J Chem Eng 2000; 17:
329334.
Ehlers D, Pfister M, Gerard D, Quirin KW, Bork WR, Toffel Nadolny
P. Reducing the coumarin content of tonka bean extracts using
supercritical CO2. Int J Food Sci Technol 1996; 31: 9195.
Ehlers D, Nguyen T, Gerard D, Quirin KW. Analysis of essential basil
oils CO2 extracts and steam-distilled oils. Dtsch LebensmittRundsch 2001; 97: 245250.
Eikani MH, Goodarznia I, Mirza M. Supercritical carbon dioxide
extraction of cumin seeds (Cuminum cyminum L.). Flavour Fragr
J 1999a; 14: 2931.
Eikani MH, Goodarznia I, Mirza M. Comparison between the essential oil and supercritical carbon dioxide extract of Teucrium
polium L. J Essent Oil Res 1999b; 11: 470472.
131
Eisenmerger M, Dunford NT. Bioactive components of commercial

and supercritical carbon dioxide processed wheat germ oil. J Am
Oil Chem Soc 2008; 85: 5561.
Eisenmerger M, Dunford NT, Eller F, Taylor S, Martinez J. Pilotscale supercritical carbon dioxide extraction and fractionation of
wheat germ oil. J Am Oil Chem Soc 2006; 83: 863868.
Ekart MP, Brennecke JF, Eckert CA. Molecular analysis of phase
equilibria in supercritical fluids. In: Bruno TJ, Ely JF, editors.
Supercritical fluid technology: reviews in modern theory and applications (Chap 3). Boca Raton, FL: CRC Press, 1991: 163193.
El-Ghorab AH, El-Massry KF, Marx F, Fadel HM. Antioxidant activity of Egyptian Eucalyptus camaldulensis var. brevirostris leaf
extracts. Nahrung-Food 2003; 47: 4145.
El-Ghorab AH, Mansour AF, El-Massry KF. Effect of extraction
methods on the chemical composition and antioxidant activity
of Egyptian marjoram (Majorana hortensis Moench). Flavour
Fragr J 2004; 19: 5461.
Eller FJ, King JW. Supercritical carbon dioxide extraction of cedarwood oil: a study of extraction parameters and oil characteristics.
Eller FJ, Taylor SL. Pressurized fluids for extraction of cedarwood
oil from Juniperus virginianna. J Agric Food Chem 2004; 52:
23352338.
Eller FJ, Cermak SC, Taylor SL. Supercritical carbon dioxide extraction of cuphea seed oil. Ind Crops Prod 2011; 33: 554557.
Ellington E, Bastida J, Viladomat F, Codina C. Supercritical carbon dioxide extraction of colchicine and related alkaloids from
seeds of Colchicum autumnale L. Phytochem Anal 2003; 14:
164169.
Escobedo-Alvarado GN, Sandler SI, Scurto AM. Modeling of solidsupercritical fluid phase equilibria with a cubic equation of stateGex model. J Supercrit Fluids 2001; 21: 123134.
Esmelindro AA, Girardi JD, Mossi A, Jacques RA, Dariva C.
Influence of agronomic variables on the composition of mate
tea leaves (Ilex paraguariensis) extracts obtained from CO2
extraction at 30C and 175 bar. J Agric Food Chem 2004; 52:
19901995.
Espinosa S, Fornari T, Bottini SB, Brignole EA. Phase equilibria in mixtures of fatty oils and derivatives with near critical
fluids using the GC-EOS model. J Supercrit Fluids 2002; 23:
91102.
Esquivel MM, Bernardo-Gil G. Extraction of olive husk oil with
compressed carbon dioxide. J Supercrit Fluids 1993; 6: 9194.
Esquivel MM, Ribeiro MA, Bernardo-Gil MG. Supercritical extraction of savory oil: study of antioxidant activity and extract characterization. J Supercrit Fluids 1999a; 14: 129138.
Esquivel MM, Bernardo-Gil MG, King MB. Mathematical models
for supercritical extraction of olive husk oil. J Supercrit Fluids
1999b; 16: 4358.
Fadel H, Marx F, El-Sawy A, El-Ghorab A. Effect of extraction techniques on the chemical composition and antioxidant activity of
Eucalyptus camaldulensis var. brevirostris leaf oils. Z Lebensm
Unters F A 1999; 208: 212216.
Fattori M, Bulley NR, Meisen A. Carbon dioxide extraction of canola
seed: oil solubility and effect of seed treatment. J Am Oil Chem
Soc 1988; 65: 968974.
Favati F, King JW, Mazzanti M. Supercritical carbon dioxide extraction of evening primrose oil. J Am Oil Chem Soc 1991; 68:
422427.
Favati F, Fiorentini R, De Vitis V. Supercritical fluid extraction of
sunflower oil: extraction dynamics and process optimization.
Proc 3rd Int Symp Supercrit Fluids/2, Strasbourg, France, 1994:
305310.

Authenticated
Favati F, Galgano F, Damiano N, Lanzarini G. Supercritical CO2

extraction of lycopene and beta-carotene from by-products
of the tomato industry. Proc. 4th Italian Conf Supercrit Fluids
Applications, Capri, Italy, 1997: 121128.
Fekete J, Kery A, Lemberkovics E, Oszagyan M, Sawinsky J,
Simandi B. Supercritical fluid extraction of volatile compounds
from lavandin and thyme. Flavour Fragr J 1996; 11: 157165.
Femenia A, Garcia-Marin M, Simal S, Rossello C, Blasco M. Effects
of supercritical carbon dioxide (SC-CO2) oil extraction on the
cell wall composition of almond fruits. J Agric Food Chem 2001;
49: 58285834.
Fernandez X, Pintaric C, Lizzani-Cuvelier L, Loiseau AM, Morello
A, Pellerin P. Chemical composition of absolute and supercritical
carbon dioxide extract of Aframomum melegueta. Flavour Fragr
J 2006; 21: 162165.
Fernandez-Trujillo JP. Supercritical CO2 extraction of sweet and hot
paprika. Grasas Aceites 2008; 59: 715.
Ferreira SRS, Meireles MAA. Modeling the supercritical fluid
extraction of black pepper (Piper nigrum L.) essential oil. J Food
Eng 2002; 54: 263269.
Ferreira SRS, Meireles MAA, Cabral FA. Supercritical CO2 extraction of carotenoids from pitanga fruits (Eugenia uniflora L.).
J Food Eng 1993; 20: 121133.
Ferreira SRS, Nikolov ZL, Doraiswamy LK, Meireles MAA,
Petenate AJ. Supercritical fluid extraction of black pepper (Piper
nigrun L.) essential oil. J Supercrit Fluids 1999; 14: 235245.
Filho GL, De Rosso VV, Meireles MAA, Rosa PTV, Oliveira AL,
Mercadante AZ, Cabral FA. Supercritical CO2 extraction of carotenoids from pitanga fruits (Eugenia uniflora L.). J Supercrit
Fluids 2008; 46: 3339.
Fiori L. Grape seed oil supercritical extraction kinetic and solubility
data: critical approach and modeling. J Supercrit Fluids 2007;
43: 4354.
Fiori L. Supercritical extraction of sunflower seed oil: experimental
data and model validation. J Supercrit Fluids 2009; 50: 218224.
Fiori L. Supercritical extraction of grape seed oil at industrial-scale:
plant and process design, modeling, economic feasibility. Chem
Eng Proc 2010; 49: 866872.
Fiori L, Calcagno D, Costa P. Sensitivity analysis and operative conditions of a supercritical fluid extractor. J Supercrit Fluids 2007;
41: 3142.
Fiori L, Basso D, Costa P. Seed oil supercritical extraction: particle
size distribution of the milled seeds and modeling. J Supercrit
Fluids 2008; 47: 174181.
Fiori L, Basso D, Costa P. Supercritical extraction kinetics of seed
oil: a new model bridging the broken and intact cells and the
shrinking-core models. J Supercrit Fluids 2009; 48: 131138.
Fischer M, Jefferies TM. Optimization of nicotine extraction from
tobacco using supercritical fluid technology with dynamic extraction modeling. J Agric Food Chem 1996; 44: 12581264.
Flores G, Blanch GP, del Castillo MLR, Herraiz M. Enantiomeric
composition studies in Lavandula species using supercritical fluids. J Sep Sci 2005; 28: 23332338.
Follegatti-Romero LA, Piantino CR, Grimaldi R, Cabral FA.
Supercritical CO2 extraction of omega-3 rich oil from Sacha
inchi (Plukenetia volubilis L.) seeds. J Supercrit Fluids 2009; 49:
323329.
Fonseca JMS, Dohrn R, Peper S. High-pressure fluid-phase equilibria: experimental methods and systems investigated (20052008).
Fontan IM, Esquivel MM, Bernardo-Gil MG. Supercritical extraction of corn germ oil. Proc. 3rd Int Symp Supercrit Fluids/2,
Strasbourg, France, 1994: 423428.
Fornari RE, Alessi P, Kikic I. High pressure fluid phase equilibria:

experimental methods and systems investigated (19781987).
Fornari T, Luna P, Stateva RP. The vdW EoS hundred years later, yet
younger than before. Application to the phase equilibria modeling of food-type systems for a green technology. J Supercrit
Fluids 2010; 55, 579593.
Franca LF, Meireles MAA. Modeling the extraction of carotene
and lipids from pressed palm oil (Elaes guineensis) fibers using
supercritical CO2. J Supercrit Fluids 2000; 18: 3547.
Franca LF, Reber G, Meireles MAA, Machado NT, Brunner G.
Supercritical extraction of carotenoids and lipids from buriti
(Mauritia flexuosa), a fruit from the Amazon region. J Supercrit
Fluids 1999a; 14: 247256.
Franca LF, Christensen T, Brunner G. High Pressure Chemical
Engineering, Book Series: Forschungszentrum Karlsruhe
Technik und Umwelt, Wissenschaftliche Berichte (FZKA)
1999b; 6271: 215219.
Franceschi E, Grings MB, Frizzo CD, Oliveira JV, Dariva C. Phase
behavior of lemon and bergamot peel oils in supercritical CO.
Francisco JD, Jarvenpaa EP, Huopalahti R, Sivik B. Comparison
of Eucalyptus camaldulensis Dehn. Oils from Mozambique as
obtained by hydrodistillation and supercritical carbon dioxide
extraction. J Agric Food Chem 2001; 49: 23392342.
Francisco JDC, Danielsson B, Kozubek A, Dey ES. Application of
supercritical carbon dioxide for the extraction of alkylresorcinols
from rye bran. J Supercrit Fluids 2005; 35: 220226.
Fratianni A, Caboni MF, Irano M, Panfili G. A critical comparison
between traditional methods and supercritical carbon dioxide
extraction for the determination of tocochromanols in cereals.
Eur Food Res Technol 2002; 215: 353358.
Freitas LDS, De Oliveira JV, Dariva C, Jacques RA, Caramao EB.
Extraction of grape seed oil using compressed carbon dioxide
and propane: extraction yields and characterization of free glycerol compounds. J Agric Food Chem 2008a; 56: 25582564.
Freitas LDS, Jacques RA, Richter MF, da Silva AL, Caramao EB.
Pressurized liquid extraction of vitamin E from Brazilian grape
seed oil. J Chromatogr A 2008b; 1200: 8083.
Friedrich JP. Semicontinuous supercritical CO2 system for rapid
extraction of jojoba and other oilseeds. J Am Oil Chem Soc 1988;
65: 3030.
Friedrich JP, List GR, Heakin AJ. Petroleum-free extraction of oil
from soybeans with supercritical CO2. J Assoc Oil Chem Soc
1982; 59: 288292.
Friedrich JP, List GR, Spencer GF. Supercritical CO2 extraction of
lipid-bearing materials and characterization of the products. J
Am Oil Chem Soc 1984; 61: 698698.
Fuh SM, Lue GT, Ke SH, Pan WHT. Supercritical carbon dioxide
extraction of red cypress sawdust: a comparison of solvent
extraction vs. steam distillation methods. J Food Drug Anal
1996; 4: 203214.
Fullana M, Trabelsi F, Recasens F. Use of neural net computing for
statistical and kinetic modelling and simulation of supercritical
fluid extractors. Chem Eng Sci 1999; 54: 58455862.
Funazukuri T, Kong C, Kagei S. Effective axial dispersion coefficients in packed beds under supercritical conditions. J Supercrit
Fluids 1998; 13: 169175.
Gainar L, Vilcu R, Mocan M. Supercritical fluid extraction of basil
essential oil. Influence of the process parameters and chemical characterization of extracts. Rev Roumaine Chim 2002; 47: 2932.
Gamse T, Marr R. Supercritical CO2-extraction for production of
extracts from plant materials containing cholagoga substances.

Authenticated
In: Dahmen N, Dinjus E, editors. High pressure chemical engineering. Book series: Forschungszentrum Karlsruhe Technik
und Umwelt, Wissenschaftliche Berichte (FZKA) 1999; 6271:
201204.
Gamse T, Marr R. Supercritical CO2-extraction for producing secondary metabolites from dill and caraway. Proc. 7th Meeting
on Supercritical Fluids/2, Antibes/Juan-les-Pins, France, 2000:
635640.
Gao YX, Nagy B, Liu X, Simandi B, Wang Q. Supercritical CO2
extraction of lutein esters from marigold (Tagetes erecta L.)
enhanced by ultrasound. J Supercrit Fluids 2009; 49: 345350.
Gao YX, Liu X, Xu HG, Zhao J, Wang Q, Liu GM, Hao QF.
Optimization of supercritical carbon dioxide extraction of lutein
esters from marigold (Tagetes erecta L.) with vegetable oils as
continuous co-solvents. Sep Purif Technol 2010; 71: 214219.
Garau R, Pittau B. Essential oils contained in the Myrtaceae family.
Extraction and fractionation. Proc. 5th Meeting on Supercritical
Fluids/2, Nice, France, 1998: 621626.
Garcia A, Alvarez A, Canete R, Sovova H. Supercritical extraction of
lipids from sugar cane by products. Proc. 3rd Int Symp Supercrit
Garcia A, deLucas A, Rincon J, Alvarez A, Gracia I, Garcia MA.
Supercritical carbon dioxide extraction of fatty and waxy material from rice bran. J Am Oil Chem Soc 1996; 73: 11271131.
Garcia DC, Luks KD. Patterns of solid-fluid phase equilibria: new
possibilities? Fluid Phase Equilib 1999; 161: 91106.
Gardner DS. Industrial scale hop extraction with liquid CO2. Chem
Ind 1982; 19: 402405.
Garnier S, Neau E, Alessi P, Cortesi A, Kikic I. Modelling solubility of solids in supercritical fluids using fusion properties. Fluid
Phase Equilib 1999; 158160: 491500.
Gaspar F. Extraction of essential oils and cuticular waxes with compressed CO2: effect of extraction pressure and temperature. Ind
Eng Chem Res 2002; 41: 24972503.
Gaspar F, Guibert D, Santos R, King MB. Extraction of essential oils
from Origanum virens L.: a comparative study of hydrodistillation with supercritical CO2. Proc. 5th Meeting on Supercritical
Gaspar F, Santos R, King MB. Extraction of essential oils and cuticular waxes with compressed CO2: effect of matrix pretreatment.
Ind Eng Chem Res 2000; 39: 46034608.
Gaspar F, Santos R, King MB. Disruption of glandular trichomes
with compressed CO2: alternative matrix pre-treatment for CO2
extraction of essential oils. J Supercrit Fluids 2001; 21: 1122.
Gaspar F, Lu T, Santos R, Al-Duri B. Modelling the extraction of
essential oils with compressed carbon dioxide. J Supercrit Fluids
2003; 25: 247260.
Gawdzik J, Mardarowicz M, Suprynowicz Z, Kawka S, Wolski T.
Supercritical fluid extraction of essential oils from the fruits of
Archangelica off. Hoffm. and their characterization by GC/MS.
HRC-J High Res Chromatogr 1996; 19: 237240.
Gawdzik J, Suprynowicz Z, Mardarowicz M, Poszytek J, Lodkowski
R, Pilorz K. Supercritical fluid extraction of oil from evening
primrose (Oenothera paradoxa H.) seeds. Chem Analityczna
1998; 43: 695702.
Ge Y, Ni Y, Yan H, Chen Y, Cai T. Optimization of the supercritical fluid extraction of natural vitamin E from wheat germ using
response surface methodology. J Food Sci 2002a; 67: 239243.
Ge YQ, Yan H, Hui BD, Ni YY, Wang SX, Cai TY. Extraction of
natural vitamin E from wheat germ by supercritical carbon dioxide. J Agric Food Chem 2002b; 50: 685689.
Geng Y, Liu J, Lv R, Yuan J, Lin Y, Wang X. An efficient method for
extraction, separation and purification of eugenol from Eugenia
133
caryophyllata by supercritical fluid extraction and high-speed

counter-current chromatography. Sep Purif Technol 2007; 57: 237
241.
Germain JC, del Valle JM, de la Fuente JC. Natural convection retards
supercritical CO2 extraction of essential oils and lipids from vegetable substrates. Ind Eng Chem Res 2005; 44: 28792886.
Ghasemi E, Yamini Y, Bahramifar N, Sefidkon F. Comparative analysis of the oil and supercritical CO2 extract of Artemisia sieberi.
J Food Eng 2007; 79: 306311.
Ghoreishi SM, Sharifi S. Modeling of supercritical extraction of
mannitol from plane tree leaf. J Pharm Biomed Anal 2001; 24:
10371048.
Giannuzzo AN, Boggetti HJ, Nazareno MA, Mishima HT.
Supercritical fluid extraction of naringin from the peel of Citrus
paradisi. Phytochem Anal 2003; 14: 221223.
Glisic SB, Misic DR, Stamenic MD, Zizovic IT, Asanin RM, Skala
DU. Supercritical carbon dioxide extraction of carrot fruit essential oil: chemical composition and antimicrobial activity. Food
Chem 2007a; 105: 346352.
Glisic SB, Milojevic SZ, Dimitrijevic SI, Orlovic AM, Skala DU.
Antimicrobial activity of the essential oil and different fractions
of Juniperus communis L. and a comparison with some commercial antibiotics. J Serb Chem Soc 2007b; 72: 311320.
Glisic S, Smelcerovic A, Zuehlke S, Spiteller M, Skala D. Extraction
of hyperforin and adhyperforin from St. Johns Wort (Hypericum
perforatum L.) by supercritical carbon dioxide. J Supercrit Fluids
2008; 45: 332337.
Gnayfeed MH, Daood HG, Illes V, Biacs PA. Supercritical CO2 and
subcritical propane extraction of pungent paprika and quantification of carotenoids, tocopherols, and capsaicinoids. J Agric Food
Chem 2001; 49: 27612766.
Goli AH, Barzegar M, Sahari M. Antioxidant activity and total phenolic compounds of pistachio (Pistachia vera) hull extracts. Food
Chem 2005; 92: 521525.
Gomes PB, Mata VG, Rodrigues AE. Production of rose geranium
oil using supercritical fluid extraction. J Supercrit Fluids 2007;
41: 5060.
Gomez AM, de la Ossa EM. Quality of wheat germ oil extracted
by liquid and supercritical carbon dioxide. J Am Oil Chem Soc
2000; 77: 969974.
Gomez AM, de la Ossa EM. Quality of borage seed oil extracted by
liquid and supercritical carbon dioxide. Chem Eng J 2002; 88:
103109.
Gomez AM, Lopez CP, de la Ossa EM. Recovery of grape seed oil
by liquid and supercritical carbon dioxide extraction: a comparison with conventional solvent extraction. Chem Eng J Bioch Eng
1996; 61: 227231.
Gomez AM, Romero MDG, de la Ossa EM. Caracterizacin del
aceite de germen de trigo extrado con dixido de carbono lquido
y supercrtico. Grasas Aceites 1997; 48: 8792.
Gomez-Coronado DJM, Ibanez E, Ruperez FJ, Barbas C. Tocopherol
measurement in edible products of vegetable origin. J Chromatogr
A 2004; 1054: 227233.
Gomez-Prieto MS, Caja MM, Santa-Maria G. Solubility in supercritical carbon dioxide of the predominant carotenes of tomato
skin. J Am Oil Chem Soc 2002; 79: 897902.
Gomez-Prieto MS, Caja MM, Herraiz M, Santa-Maria G. Supercritical
fluid extraction of all-trans-lycopene from tomato. J Agric Food
Chem 2003; 51: 37.
Gomez-Prieto MS, Ruiz del Castillo ML, Flores G, Santa-Maria G,
Blanch GP. Application of Chrastils model to the extraction in
SC-CO2 of -carotene and lutein in Mentha spicata L. J Supercrit
Fluids 2007; 43: 3236.

Authenticated
Gonzalez-Vila FJ, Bautista JM, Gutierrez A, Del Rio JC, Gonzalez

AG. Supercritical carbon dioxide extraction of lipids from
Eucalyptus globulus wood. J Biochem Biophys Methods 2000;
43: 345351.
Goodarznia I, Eikani MH. Supercritical carbon dioxide extraction
of essential oils Modeling and simulation. Chem Eng Sci 1998;
53: 13871395.
Goodman BT, Wilding W, Oscarson JL, Rowley R. A note on the
relationship between organic solid density and liquid density at
the triple point. J Chem Eng Data 2004; 49: 15121514.
Goodrum JW, Kilgo MB. Peanut oil extraction with sc-CO2 solubility
and kinetic functions. Trans ASAE 1987; 30: 18651868.
Goodrum JW, Kilgo MK, Santerre CR. Oilseed solubility and extraction modeling. In: King JW, List GR, editors. Supercritical fluid
technology in oil and lipid chemistry. Champaign, IL: AOCS
Press, 1996: 101131.
Gopalakrishnan N, Narayanan CS. Supercritical carbon dioxide
extraction of cardamom. J Agric Food Chem 1991; 39: 1976
1978.
Gopalakrishnan N, Shanti PPV, Narayanan CS. Composition of clove
(Syzygium aromaticum) bud oil extracted using carbon dioxide.
J Sci Food Agric 1990; 50: 111117.
Gopalan B, Goto M, Kodama A, Hirose T. Supercritical carbon dioxide extraction of turmeric (Curcuma longa). J Agric Food Chem
2000; 48: 21892192.
Gordillo MD, Blanco MA, Pereyra C, Martinez de la Ossa EJ.
Thermodynamic modelling of supercritical fluid-solid phase
equilibrium data. Comp Chem Eng 2005a; 29: 18851890.
Gordillo MD, Pereyra C, Martinez de la Ossa EJ. Solubility estimations for disperse blue 14 in supercritical carbon dioxide. Dyes
Pigm 2005b; 67: 167173.
Goto M, Smith JM, McCoy BJ. Parabolic profile approximation (linear driving-force model) for chemical reactions. Chem Eng Sci
1990; 45: 443448.
Goto M, Sato M, Hirose T. Extraction of peppermint oil by supercritical carbon dioxide. J Chem Eng 1993; 26: 401407.
Goto M, Hirose T, McCoy BJ. Continuous-mixture model of extraction processes. J Supercrit Fluids 1994; 7: 6166.
Goto M, Roy BC, Hirose T. Shrinking-core leaching model for supercritical-fluid extraction. J Supercrit Fluids 1996; 9: 128133.
Goto M, Roy BC, Kodama A, Hirose T. Modeling supercritical fluid
extraction process involving solute-solid interaction. J Chem Eng
Jpn 1998; 31: 171177.
Gracin S, Brinck T, Rasmuson AC. Prediction of solubility of solid
organic compounds in solvents by UNIFAC. Ind Eng Chem Res
2002; 41: 51145124.
Grigonis D, Venskutonis PR, Sivik B, Sandahl M, Eskilsson CS.
Comparison of different extraction techniques for isolation of
antioxidants from sweet grass (Hierochlo odorata). J Supercrit
Fluids 2005; 33: 225235.
Grosso C, Ferraro V, Figueiredo AC, Barroso JG, Coelho JA, Palavra
AM. Supercritical carbon dioxide extraction of volatile oil from
Italian coriander seeds. Food Chem 2008; 111: 197203.
Grosso C, Figueiredo AC, Burillo J, Mainar AM, Urieta JS, Barroso
JG, Coelho JA, Palavra AMF. Enrichment of the thymoquinone
content in volatile oil from Satureja montana using supercritical
fluid extraction. J Sep Sci 2009; 32: 328334.
Guan WQ, Li SF, Yan RX, Tang SK, Quan C. Comparison of essential oils of clove buds extracted with supercritical carbon dioxide
and other three traditional extraction methods. Food Chem 2007;
101: 15581564.
Guclu-Ustundag O, Temelli F. Correlating the solubility behavior
of fatty acids, mono-, di-, and triglycerides, and fatty acid esters
in supercritical carbon dioxide. Ind Eng Chem Res 2000; 39:

47564766.
Guyer DE, Sinha NK. Supercritical carbon dioxide extraction of
onion flavours relationship of onion pyruvate content on flavour yield. J Sci Food Agric 1995; 69: 457460.
Ha HKP, Maridable J, Gaspillo P, Hasika M, Malaluan R, Kawasaki
J. Essential oil from lemongrass extracted by supercritical carbon
dioxide and steam distillation. Philipp Agric Scientist 2008; 91:
3641.
Hadolin M, Skerget M, Knez Z, Bauman D. High pressure extraction
of vitamin E-rich oil from Silybum marianum. Food Chem 2001;
74: 355364.
Hamburger M, Baumann D, Adler S. Supercritical carbon dioxide
extraction of selected medicinal plants effects of high pressure
and added ethanol on yield of extracted substances. Phytochem
Anal 2004; 15: 4654.
Hamdan S, Daood HG, Toth-Markus M, Illes V. Extraction of cardamom oil by supercritical carbon dioxide and sub-critical propane.
Hannay JB, Hogarth J. On the solubility of solids in gases. Proc R
Soc London A 1879; 29: 324.
Hao J, Han W, Huang S, Xue B, Deng X. Microwave-assisted extraction of artemisinin from Artemisia annua L. Sep Purif Technol
2002; 28: 191196.
Hartonen K, Jussila M, Manninen P, Riekkola ML. Volatile oil
analysis of Thymus vulgaris L. by directly coupled SFE/GC.
J Microcolumn Sep 1992; 4: 37.
Harvey AH. Supercritical solubility of solids from near-critical
dilute-mixture theory. J Phys Chem 1990; 94: 84038406.
Haselow JS, Han SJ, Greenkorn RA, Chao KC. Equation of state for
supercritical extraction. ACS Symp Ser 1986; 300: 156178.
Hassan MN, Rahman NNA, Ibrahim MH, Omar AKM. Simple fractionation through the supercritical carbon dioxide extraction of
palm kernel oil. Sep Purif Technol 2000; 19: 113120.
Hauptschott J, Lentz H. Kopplung einer einfachen sub- oder superkritischen Extraktion mit normalen Analysenmethoden. Monatsh
Chem 1993; 124: 10831087.
Hauthal WH. Advances with supercritical fluids [review].
Chemosphere 2001; 43: 123135.
Hawthorne SB. Analytical-scale supercritical fluid extraction. Anal
Chem 1990; 62: 633A642A.
Hawthorne SB, Krieger MS, Miller DJ. Analysis of flavor and
fragrance compounds using supercritical fluid extraction coupled
with gas chromatography. Anal Chem 1988; 60: 472477.
Hawthorne SB, Miller DJ, Krieger MS. Coupled SFE-GC a rapid
and simple technique for extracting, identifying, and quantitating
organic analytes from solids and sorbent resins. J Chromatogr Sci
1989; 27: 347354.
Hawthorne SB, Riekkola ML, Serenius K, Holm Y, Hiltunen R,
Hartonen K. Comparison of hydrodistillation and supercritical
fluid extraction for the determination of essential oils in aromatic
plants. J Chromatogr 1993; 634: 297308.
He HP, Corke H, Cai JG. Supercritical carbon dioxide extraction of
oil and squalene from Amaranthus grain. J Agric Food Chem
2003; 51: 79217925.
Heaton DM, Bartle KD, Rayner CD, Clifford AA. Application of
supercritical fluid extraction and supercritical fluid chromatography to the production of taxanes as anti-cancer drugs. J High
Resolut Chromatogr 1993; 16: 666670.
Hegel PE, Zabaloy MS, Mabe GDB, Pereda S, Brignole EA. Phase
equilibrium engineering of the extraction of oils from seeds using
carbon dioxide+propane solvent mixtures. J Supercrit Fluids
2007; 42: 318324.

Authenticated
Heikes DL. SFE with GC and MS determination of safrole and

related allylbenzenes in sassafras teas. J Chromatogr Sci 1994;
32: 253258.
Heikes DL, Scott B, Gorzovalitis NA. Quantitation of volatile oils
in ground cumin by supercritical fluid extraction and gas chromatography with flame ionization detection. J AOAC Int 2001;
84: 11301134.
Henning JA, Core RJ, Gardea-Torresdey JL. Extracting volatile compounds from single plants using supercritical fluid extraction.
Crop Sci 1994; 34: 11201122.
Hernandez-Garduza O, Garcia-Sanchez F, Neau E. Generalization
of composition-dependent mixing rules for multicomponent
systems: prediction of vaporliquid and liquidliquid equilibria.
Chem Eng J 2001; 84: 283294.
Herrero M, Cifuentes A, Ibanez E. Sub- and supercritical fluid extraction of functional ingredients from different natural sources:
plants, food-by-products, algae and microalgae: a review. Food
Chem 2006; 98: 136148.
Herrero M, Mendiola JA, Cifuentes A, Ibanez E. Supercritical fluid
extraction: recent advances and applications. J Chromatogr A
2010; 1217: 24952511.
Hierro MTG, Santamaria G. Supercritical fluid extraction of vegetable and animal fats with CO2 a mini review. Food Chem
1992; 45: 189192.
Higashi H, Iwai Y, Arai Y. Solubilities and diffusion coefficients of
high boiling compounds in supercritical carbon dioxide. Chem
Eng Sci 2001; 56: 30273044.
Hojnik M, Skerget M, Knez Z. Concentrating the chlorophylls in
extract by pretreatment of stinging nettle leaves with nonpolar
organic solvents and supercritical carbon dioxide. J Food Process
Eng 2007; 30: 701716.
Holderbaum T, Gmehling J. PSRK: a group contribution equation of
state based on UNIFAC. Fluid Phase Equilib 1991; 70: 251265.
Holser RA, Bost G. Hybrid hibiscus seed oil compositions. J Am Oil
Chem Soc 2004; 81: 795797.
Hong IK, Rho SW, Lee KS, Lee WH, Yoo KP. Modeling of soybean
oil bed extraction with supercritical carbon dioxide. Korean J
Chem Eng 1990; 7: 4046.
Hu QH, Xu J, Chen SB, Yang FM. Antioxidant activity of extracts of
black sesame seed (Sesamum indicum L.) by supercritical carbon
dioxide extraction. J Agric Food Chem 2004; 52: 943947.
Hu QH, Hu Y, Xu J. Free radical-scavenging activity of Aloe vera
(Aloe barbadensis Miller) extracts by supercritical carbon dioxide extraction. Food Chem 2005; 91: 8590.
Huang SH, Radosz M. Equation of state for small, large, polydisperse, and associating molecules. Ind Eng Chem Res 1990; 29:
22842294.
Huang SH, Radosz M. Equation of state for small, large, polydisperse, and associating molecules: extension to fluid mixtures. Ind
Eng Chem Res 1991; 30: 19942005.
Huang CC, Tang M, Tao WH, Chen YP. Calculation of the solid solubilities in supercritical carbon dioxide using a modified mixing
model. Fluid Phase Equilib 2001; 179: 6784.
Huang KJ, Wu JJ, Chiu YH, Lai CY, Chang CMJ. Designed polar
cosolvent-modified supercritical CO2 removing caffeine from
and retaining catechins in green tea powder using response
surface methodology. J Agric Food Chem 2007; 55: 9014
9020.
Huang BK, Qin LP, Chu QC, Zhang QY, Gao LH, Zheng HC.
Comparison of headspace SPME with hydrodistillation and SFE
for analysis of the volatile components of the roots of Valeriana
officinalis var. latifolia. Chromatographia 2009; 69: 489496.
135
Hubbard JD, Downing JM, Ram MS, Chung OK. Lipid extraction
from wheat flour using supercritical fluid extraction. Cereal
Chem 2004; 81: 693698.
Hubert P, Vitzthum OG. Fluid extraction of hops, spices, and
tobacco with supercritical gases. Angew Chem Int Ed 1978; 17:
710715.
Huron MJ, Vidal J. New mixing rules in simple equations of state for
representing vapour-liquid equilibria of strongly non-ideal mixtures. Fluid Phase Equilib 1979; 3: 255271.
Huston CK, Hong J. Optimization of the analytical supercritical fluid
extraction of cloves via an on-column interface to an ion trap
GC/MS system. J Agric Food Chem 1991; 39: 12291233.
Huyke C, Engel K, Simon-Haarhaus B, Quirin W, Schempp CM.
Composition and biological activity of different extracts from
Schisandra sphenanthera and Schisandra chinensis. Planta Med
2007; 73: 11161126.
Ibanez E, Oca A, de Murga G, Lopez-Sebastian S, Tabera J, Reglero G.
Supercritical fluid extraction and fractionation of different preprocessed rosemary plants. J Agric Food Chem 1999; 47: 14001404.
Ibanez E, Palacios J, Senorans FJ, Santa-Maria G, Tabera J, Reglero
G. Isolation and separation of tocopherols from olive by-products with supercritical fluids. J Am Oil Chem Soc 2000a; 77:
187190.
Ibanez E, Cifuentes A, Crego AL, Senorans FJ, Cavero S, Reglero
G. Combined use of supercritical fluid extraction, micellar electrokinetic chromatography, and reverse phase high performance
liquid chromatography for the analysis of antioxidants from rosemary (Rosmarinus officinalis L.). J Agric Food Chem 2000b; 48:
40604065.
Illes V, Szalai O, Szebenyi NI, Grosz M, Hethelyi I. Oil recovery
from borage seed with carbon dioxide and propane solvents.
Proc. 3rd Int Symp Supercrit Fluids/2, Strasbourg, France, 1994:
511516.
Illes V, Szalai O, Then M, Daood H, Perneczki S. Extraction of
hiprose fruit by supercritical CO2 and propane. J Supercrit Fluids
1997; 10: 209218.
Illes V, Daood H, Karsai E, Szalai O. Oil extraction from cardamom crop by sub- and supercritical carbon dioxide and propane.
533538.
Illes V, Daood HG, Biacs PA, Gnayfeed MH, Meszaros B.
Supercritical CO2 and subcritical propane extraction of spice red
pepper oil with special regard to carotenoid and tocopherol content. J Chromatogr Sci 1999a; 37: 345352.
Illes V, Hamdan S, Daood H. Supercritical fluid extraction of oil
from mixtures of citrus peel and carrot. Proc. 6th Meeting on
Supercritical Fluids, Nottingham, UK, 1999b: 537542.
Illes V, Daood HG, Perneczki S, Szokonya L, Then M. Extraction of
coriander seed oil by CO2 and propane at super- and subcritical
conditions. J Supercrit Fluids 2000; 17: 177186.
Imbert R, Mathe M, Abbe P, Vandermander J. Supercritical CO2
extraction of aromatic hop for use in perfumery. Proc. 5th Meeting
on Supercritical Fluids/2, Nice, France, 1998: 651654.
Inakuma T, Yasumoto M, Koguchi M, Kobayashi T. Effect of drying
methods on extraction of lycopene in tomato skin with supercritical carbon dioxide. J Jpn Soc Food Sci 1998; 45: 740743.
Ismadji S, Bhatia SK. Solubility of selected esters in supercritical
carbon dioxide. J Supercrit Fluids 2003; 27: 111.
Izadifar M, Abdolahi F. Comparison between neural network and
mathematical modeling of supercritical CO2 extraction of black
pepper essential oil. J Supercrit Fluids 2006; 38: 3743.

Authenticated
Jacques RA, Santos JG, Dariva C, Oliveira JV, Caramao EB. GC/MS
characterization of mate tea leaves extracts obtained from highpressure CO2 extraction. J Supercrit Fluids 2007; 41: 354359.
Jain A, Yang G, Yalkowsky SH. Estimation of total entropy of
melting of organic compounds. Ind Eng Chem Res 2004; 43:
43764379.
Janicot JL, Caude M, Rosset R. Extraction of major alkaloids from
poppy straw with near-critical mixtures of carbon dioxide and
polar modifiers. J Chromatogr 1990; 505: 247256.
Jaren-Galan M, Nienaber U, Schwartz SJ. Paprika (Capsicum annuum) oleoresin extraction with supercritical carbon dioxide.
J Agric Food Chem 1999; 47: 35583564.
Jarvenpaa EP, Jestoi MN, Huopalahti R. Quantitative determination
of phototoxic furocoumarins in celeriac (Apium graveolens L. var.
rapeceum) using supercritical fluid extraction and high performance
liquid chromatography. Phytochem Anal 1997; 8: 250256.
Jarzebski AB, Malinowski JJ. Potentials and prospects for application of supercritical fluid technology in bioprocessing. Proc
Biochem 1995; 30: 343352.
Jaubert JN, Coniglio L. The group contribution concept: a useful tool
to correlate binary systems and to predict the phase behavior of
multicomponent systems involving supercritical CO2 and fatty
acids. Ind Eng Chem Res 1999; 38: 50115018.
Jaubert JN, Coniglio L, Denet F. From the correlation of binary
systems involving supercritical CO2 and fatty acid esters to the
prediction of (CO2fish oils) phase behavior. Ind Eng Chem Res
1999; 38: 31623171.
Jaubert JN, Borg P, Coniglio L, Barth D. Phase equilibria measurements and modeling of EPA and DHA ethyl esters in supercritical
Jenab E, Rezaei K, Emam-Djomeh Z. Canola oil extracted by supercritical carbon dioxide and a commercial organic solvent. Eur J
Lipid Sci Technol 2006; 108: 488492; 794794.
Jennings DW, Deutsch HM, Zalkow LH, Teja AS. Supercritical
extraction of taxol from the bark of Taxus brevifolia. J Supercrit
Fluids 1992; 5: 16.
Jiang C, Pan Q, Pan Z. Solubility behavior of solids and liquids in
compressed gases. J Supercrit Fluids 1998; 12: 19.
Joback KG, Reid RC. Estimation of pure-component properties from
group-contributions. Chem Eng Commun 1987; 57: 233243.
Johnson S, Morgan ED. Supercritical fluid extraction of oil and triterpenoids from neem seeds. Phytochem Anal 1997; 8: 228232.
Johnston KP, Peck DG, Kim S. Modeling supercritical mixtures: how
predictive is it? Ind Eng Chem Res 1989; 28: 11151125.
Joo SJ, Choi YH, Kim JW, Noh MJ, Park EM, Yoo KP. Supercritical
carbon dioxide extraction of pharmaceutical agents from plant
materials in Korea. Proc. 3rd Int Symp Supercrit Fluids/2,
Strasbourg, France, 1994: 407412.
Kaiser CS, Rompp H, Schmidt PC. Supercritical carbon dioxide
extraction of chamomile flowers: extraction efficiency, stability,
and in-line inclusion of chamomile carbon dioxide extract in
-cyclodextrin. Phytochem Anal 2004; 15: 249256.
Kakasy AZ, Lemberkovics E, Simandi B, Lelik L, Hethelyi E, Antal I,
Szoke E. Comparative study of traditional essential oil and supercritical fluid extracts of Moldavian dragonhead (Dracocephalum
moldavica L.). Flavour Fragr J 2006; 21: 598603.
Kallio H, Kerrola K. Application of liquid carbon dioxide to the
extraction of essential oil of coriander (Coriandrum sativum L.)
fruits. Z Lebensm Unters Forsch 1992; 195: 545549.
Kallio H, Kerrola K, Alhonmaeki P. Carvone and limonene in caraway fruits (Carum carvi L.) analyzed by supercritical carbon
dioxide extraction-gas chromatography. J Agric Food Chem
1994; 42: 24782485.
Kandiah M, Spiro M. Extraction of ginger rhizome: kinetic studies

with supercritical carbon dioxide. Int J Food Sci Technol 1990;
25: 328338.
Kao L, Chen CR, Chang CMJ. Supercritical CO2 extraction of turmerones from turmeric and high-pressure phase equilibrium of
CO2+turmerones. J Supercrit Fluids 2007; 43: 276282.
Kao TH, Chien JT, Chen BH. Extraction yield of isoflavones from
soybean cake as affected by solvent and supercritical carbon
dioxide. Food Chem 2008; 107: 17281736.
Kaplan M, Simmonds MR, Davidson G. Comparison of supercritical
fluid and solvent extraction of feverfew (Tanacetum parthenium).
Turk J Chem 2002; 26: 473480.
Kassama LS, Shi J, Mittal GS. Optimization of supercritical fluid
extraction of lycopene from tomato skin with central composite
rotatable design model. Sep Purif Technol 2008; 60: 278284.
Kawahito Y, Kondo M, Machmudah S, Sibano K, Sasaki M, Goto
M. Supercritical CO2 extraction of biological active compounds
from loquat seed. Sep Purif Technol 2008; 61: 130135.
Kazazi H, Rezaei K, Ghotb-Sarif SJ, Emam-Djomeh Z, Yamini Y.
Supercriticial fluid extraction of flavors and fragrances from
Hyssopus officinalis L. cultivated in Iran. Food Chem 2007; 105:
805811.
Kerrola K. Literature review: isolation of essential oils and flavor
compounds by dense carbon dioxide. Food Rev Int 1995; 11:
547573.
Kerrola K, Kallio H. Volatile compounds and odor characteristics of
carbon dioxide extracts of coriander (Coriandrum sativum L.)
fruits. J Agric Food Chem 1993; 41: 785790.
Kerrola KM, Kallio HP. Extraction of volatile compounds of angelica (Angelica archangelica L.) root by liquid carbon dioxide.
J Agric Food Chem 1994; 42: 22352245.
Kerrola K, Galambosi B, Kallio H. Volatile components and odor
intensity of four phenotypes of hyssop (Hyssopus officinalis L.).
J Agric Food Chem 1994a; 42: 776781.
Kerrola K, Galambosi B, Kallio H. Characterization of volatile composition and odor of angelica (Angelica archangelica subsp.
archangelica L.) root extracts. J Agric Food Chem 1994b; 42:
19791988.
Kery A, Simandi B, Ronyai E, Lemberkovics E. Supercritical fluid
extraction of some non-volatile bioactive terpenoids. Proc. 5th
Meeting on Supercritical Fluids/2, Nice, France, 1998: 561566.
Kery A, Ronyai E, Simandi B, Keve T, Deak A, Kemeny S. Recovery
of a bioactive sesquiterpene lactone from Tanacetum parthenium
by extraction with supercritical carbon dioxide. Chromatographia
1999; 49: 503508.
Khajeh M, Yamini Y, Sefidkon F, Bahramifar N. Comparison of
essential oil composition of Carum copticum obtained by supercritical carbon dioxide extraction and hydrodistillation methods.
Food Chem 2004; 86: 587591.
Khajeh M, Yamini Y, Bahramifar N, Sefidkon F, Pirmoradei MR.
Comparison of essential oils compositions of Ferula assa-foetida
obtained by supercritical carbon dioxide extraction and hydrodistillation methods. Food Chem 2005; 91: 639644.
Kikic I, Lora M, Bertucco A. A thermodynamic analysis of threephase equilibria in binary and ternary systems for applications
in rapid expansion of a supercritical solution (RESS), particles
from gas-saturated solutions (PGSS), and supercritical antisolvent (SAS). Ind Eng Chem Res 1997; 36: 55075515.
Kim KH, Hong JA. Dynamic extraction of spearmint oil components
by using supercritical CO2. Sep Sci Technol 2000; 35: 315322.
Kim JY, Yoo KP. Effects of basic modifiers on sfe efficiencies of
ephedrine derivatives from plant matrix. Korean J Chem Eng
2000; 17: 672677.

Authenticated
Kim HL, Lee SB, Park KA, Hong IK. Characterization of extraction
and separation of rice bran oil rich in EFA using SFE process.
Sep Purif Technol 1999a; 15: 18.
Kim Y, Choi YH, Chin YW, Jang YP, Kim YC, Kim J, Kim JY, Joung
SN, Noh MJ, Yoo KP. Effect of plant matrix and fluid ethanol
concentration on supercritical fluid extraction efficiency of
schisandrin derivatives. J Chromatogr Sci 1999b; 37: 457461.
Kim HS, Lee SY, Kim BY, Lee EK, Lim BG. Effects of modifiers
on the supercritical CO2 extraction of glycyrrhizin from licorice
and the morphology of licorice tissue after extraction. Biotech
Bioproc Eng 2004; 9: 447453.
Kim HS, Lim BG, Kim BY. Effects of modifiers on the supercritical
CO2 extraction of licorice (Glycyrrhiza glabra) and the morphology of licorice tissue. Food Sci Biotechnol 2005; 14: 610.
Kim WJ, Kim JD, Oh SG. Supercritical carbon dioxide extraction
of caffeine from Korean green tea. Sep Sci Technol 2007; 42:
32293242.
Kim WJ, Kim JD, Kim J, Oh SG, Lee YW. Selective caffeine removal
from green tea using supercritical carbon dioxide extraction.
J Food Eng 2008; 89: 303309.
King JW. Analytical-process supercritical fluid extraction: a synergistic combination for solving analytical and laboratory scale
problems. Trends Anal Chem 1995; 14: 474481.
King JW. Supercritical fluid extraction: present status and prospects.
Grasas Aceites 2002; 53: 821.
King MB, Catchpole OJ. Physicochemical data for the design of
near-critical fluid extraction processes. In: King MB, Bott TR,
editors. Extraction of natural products using near-critical solvents. Glasgow: Blackie A&P, 1993: 184231.
King MB, Catchpole OJ. In: King MB, Bott TR, editors. Extraction
of natural products using near-critical solvents. Glasgow: Blackie
A&P, 1993.
King MB, Bott TR, Barr MJ, Mahmud RS, Sanders N. Equilibrium
and rate data for the extraction of lipids using compressed carbon
dioxide. Sep Sci Technol 1987; 22: 11031120.
King JW, Favati F, Taylor SL. Production of tocopherol concentrates
by supercritical fluid extraction and chromatography. Sep Sci
Technol 1996; 31: 18431857.
King JW, Cygnarowicz-Provost M, Favati F. Supercritical fluid
extraction of evening primrose oil kinetic and mass transfer
effects. Ital J Food Sci 1997; 9: 193204.
King JW, Mohamed A, Taylor SW, Mebrahtu T, Paul C. Supercritical
fluid extraction of Vernonia galamensis seeds. Ind Crops Prod
2001; 14: 241249.
Kiriamiti HK, Rascol E, Marty H, Condoret JS. Extraction rates of
oil from high oleic sunflower seeds with supercritical carbon
dioxide. Chem Eng Proc 2002; 41: 711718.
Kiriamiti HK, Camy S, Gourdon C, Condoret JS. Pyrethrin exraction
from pyrethrum flowers using carbon dioxide. J Supercrit Fluids
2003a; 26: 193200.
Kiriamiti HK, Camy S, Gourdon C, Condoret JS. Supercritical carbon dioxide processing of pyrethrum oleoresin and pale. J Agric
Food Chem 2003b; 51: 880884.
Kitzberger CSG, Smania A, Pedrosa RC, Ferreira SRS. Antioxidant
and antimicrobial activities of shiitake (Lentinula edodes)
extracts obtained by organic solvents and supercritical fluids.
J Food Eng 2007; 80: 631638.
Kitzberger CSG, Lomonaco RH, Michielin EMZ, Danielski L,
Correia J, Ferreira SRS. Supercritical fluid extraction of shiitake
oil: curve modeling and extract composition. J Food Eng 2009;
90: 3543.
Klejdus B, Lojkova L, Lapcik O, Koblovska R, Moravcova J, Kuban
V. Supercritical fluid extraction of isoflavones from biological
137
samples with ultra-fast high-performance liquid chromatography/

mass spectrometry. J Sep Sci 2005; 28: 13341346.
Klejdus B, Lojkova L, Kula E, Buchta I, Hrdlicka P, Kuban V.
Supercritical fluid extraction of amino acids from birch (Betula
pendula Roth) leaves and their liquid chromatographic determination with fluorimetric detection. J Sep Sci 2008; 31:
13631373.
Ko TF, Weng YM, Chiou RYY. Squalene content and antioxidant
activity of Terminalia catappa leaves and seeds. J Agric Food
Chem 2002; 50: 53435348.
Ko TF, Weng YM, Lin SB, Chiou RYY. Antimutagenicity of supercritical CO2 extracts of Terminalia catappa leaves and cytotoxicity of the extracts to human hepatoma cells. J Agric Food Chem
2003; 51: 35643567.
Kohler M, Haerdi W, Christen P, Veuthey JL. Supercritical fluid
extraction and chromatography of artemisinin and artemisinic
acid. An improved method for the analysis of Artemisia annua
samples. Phytochem Anal 1997a; 8: 223227.
Kohler M, Haerdi W, Christen P, Veuthey JL. Extraction of artemisinin and artemisinic acid from Artemisia annua L. using supercritical carbon dioxide. J Chromatogr A 1997b; 785: 353360.
Kokoska L, Havlik J, Valterova I, Sovova H, Sajfrtova M, Jankovska
I. Comparison of chemical composition and antibacterial activity
of Nigella sativa seed essential oils obtained by different extraction methods. J Food Protect 2008; 71: 24752480.
Kollmannsberger H, Nitz S. ber die Aromastoffzusammensetzung
von Hoch-Druck-Extrakten: 3. Gewurznelken (Syzygium
aromaticum). Chem Mikrobiol Technol Lebensm 1994; 16:
112123.
Kondo M, Goto M, Kodama A, Hirose T. Fractional extraction by
supercritical carbon dioxide for the deterpenation of bergamot
oil. Ind Eng Chem Res 2000; 39: 47454748.
Koshevoi EP, Bliagoz CR. Ekstrakciia dvuokosiu ugleroda v pishchevoi tekhnologii. Maikop, Russia: MGTI, 2000.
Kotnik P, Skerget M, Knez Z. Kinetics of supercritical carbon dioxide extraction of borage and evening primrose seed oil. Eur J
Lipid Sci Technol 2006; 108: 569576.
Kotnik P, Skerget M, Knez Z. Supercritical fluid extraction of chamomile flower heads: comparison with conventional extraction,
kinetics and scale-up. J Supercrit Fluids 2007; 43: 192198.
Krukonis VJ. Supercritical fluid extraction in flavor applications.
ACS Symp Series 1985; 289: 154175.
Kubatova A, Lagadec AJM, Miller DJ, Hawthorne SB. Selective
extraction of oxygenates from savory and peppermint using subcritical water. Flavour Fragr J 2001; 16: 6473.
Kubatova A, Jansen B, Vaudoisot JF, Hawthorne SB. Thermodynamic
and kinetic models for the extraction of essential oil from savory
and polycyclic aromatic hydrocarbons from soil with hot (subcritical) water and supercritical CO2. J Chromatogr A 2002; 975:
175188.
Kuk MS, Dowd MK. Supercritical CO2 extraction of rice bran. J Am
Oil Chem Soc 1998; 75: 623628.
Kuk MS, Hron RJ. Supercritical carbon dioxide extraction of cottonseed with co-solvents. J Am Oil Chem Soc 1994; 71:
13531356.
Kumar SK, Johnston KP. Modelling the solubility of solids in supercritical fluids with density as the independent variable. J Supercrit
Fluids 1988; 1: 1522.
Kumoro AC, Hasan M. Modeling of supercritical carbon dioxide
extraction of andrographolide from Andrographis paniculata
leaves. Chem Eng Commun 2008; 195: 7280.
Kurnik RT, Reid RC. Solubility of solid mixtures in supercritical fluids. Fluid Phase Equilib 1982; 8: 93105.

Authenticated
Kwak TY, Mansoori GA. Van der Waals mixing rules for cubic equations of state. Applications for supercritical fluid extraction modelling. Chem Eng Sci 1986; 41: 13031309.
Kwiatkowski J, Lisicki Z, Majewski W. An experimental method
for measuring solubilities of solids in supercritical fluids. Ber
Bunsenges Phys Chem 1984; 88: 865869.
Labadie JA, Garcia DC, Luks KD. Patterns of solidfluid phase equilibria II. Interplay with fluid phase criticality and stability. Fluid
Phase Equilib 2000; 171: 1126.
Lachowicz KJ, Jones GP, Briggs DR, Bienvenu FE, Palmer MV,
Ting SST, Hunter MM. Characteristics of essential oil from basil
(Ocimum basilicum L.) grown in Australia. J Agric Food Chem
1996; 44: 877881.
Lachowicz KJ, Jones GP, Briggs DR, Bienvenu FE, Palmer MV,
Mishra V, Hunter MM. Characteristics of plants and plant extracts
from five varieties of basil (Ocimum basilicum L.) grown in
Australia. J Agric Food Chem 1997; 45: 26602665.
Lack EA. Kriterien zur Auslegung von Anlagen fr die
Hochdruckextraktion von Naturstoffen. PhD Thesis, TU Graz,
Austria 1985.
Lack E, Seidlitz H. Extraction of food ingredients by means of
fluid CO2 at pressures higher than 500 bar. Proc. 3rd Int Symp
Supercrit Fluids/2, Strasbourg, France, 1994: 235239.
Lack E, Seidlitz H. Economics of high pressure processes. In:
Bertucco A, Vetter G, editors. High pressure process technology,
Amsterdam: Elsevier, 2001: 437471.
Lancas FM, Queiroz MEC, DaSilva ICE. Seed oil extraction
with supercritical carbon dioxide modified with pentane.
Chromatographia 1994; 39: 687692.
Lancas FM, Queiroz MEC, DaSilva ICE. Simplex optimization of extraction of soybean oil by supercritical pentane.
Chromatographia 1995; 40: 421424.
Lang QY, Wai CM. Supercritical fluid extraction in herbal and natural
product studies a practical review. Talanta 2001; 53: 771782.
Langa E, Cacho J, Palavra AMF, Burillo J, Mainar AM, Urieta
JS. The evolution of hyssop oil composition in the supercritical extraction curve. Modelling of the oil extraction process. J
Langenfeld JJ, Burford MD, Hawthorne SB, Miller DJ. Effects of
collection solvent parameters and extraction cell geometry on
supercritical fluid extraction efficiencies. J Chromatogr 1992;
594: 297307.
Langezaal CR, Chandra A, Scheffer JJC. Analysis of supercritical
carbon dioxide extracts from cones and leaves of Ahumulus lupulus cultivar. Planta Med 1990; 56: 593593.
Laohakunjit N, Noomhorm A. Supercritical carbon dioxide extraction of 2-acetyl-1-pyrroline and volatile components from pandan leaves. Flavour Flagr J 2004; 19: 251259.
Laroze LE, Diaz-Reinoso B, Moure A, Zuniga ME, Dominguez H.
Extraction of antioxidants from several berries pressing wastes
using conventional and supercritical solvents. Eur Food Res
Technol 2010; 231: 669677.
Lau HLN, Choo YM, Ma AN, Chuah CH. Characterization and supercritical carbon dioxide extraction of palm oil (Elaeis guineensis).
J Food Lipids 2006a; 13: 210221.
Lau HLN, Choo YM, Ma AN, Chuah CH. Quality of residual oil
from palm-pressed mesocarp fiber (Elaeis guineensis) using
supercritical CO2 with and without ethanol. J Am Oil Chem Soc
2006b; 83: 893898.
Lau HLN, Choo YM, Ma AN, Chuah CH. Production of refined
carotene-rich palm oil from palm mesocarp (Elaeis guineensis) using supercritical carbon dioxide. J Food Lipids 2007; 14:
396410.
Lau HLN, Choo YM, Ma AN, Chuah CH. Selective extraction of

palm carotene and vitamin E from fresh palm-pressed mesocarp
fiber (Elaeis guineensis) using supercritical CO2. J Food Eng
2008; 84: 289296.
Laws DRJ. Extraction of hops with liquid carbon-dioxide. J Inst
Brewing 1979; 85: 306306.
Le Floch F, Tena MT, Rios A, Valcarcel M. Supercritical fluid extraction of phenol compounds from olive leaves. Talanta 1998; 46:
11231130.
Leal PF, Braga MEM, Sato DN, Carvalho JE, Marques MOM,
Meireles MAA. Functional properties of spice extracts obtained
via supercritical fluid extraction. J Agric Food Chem 2003; 51:
25202525.
Leal PF, Chaves FCM, Ming LC, Petenate AJ, Meireles MAA. Global
yields, chemical compositions and antioxidant activities of clove
basil (Ocimum gratissimum L.) extracts obtained by supercritical
fluid extraction. J Food Process Eng 2006; 29: 547559.
Leal PF, Maia NB, Carmello QAC, Catharino RR, Eberlin MN,
Meireles MAA. Sweet basil (Ocimum basilicum) extracts obtained
by supercritical fluid extraction (SFE): global yields, chemical
composition, antioxidant activity, and estimation of the cost of
manufacturing. Food Bioprocess Technol 2008; 1: 326338.
Leal PF, Kfouri MB, Alexandre FC, Fagundes FHR, Prado JM, Toyama
MH, Meireles MAA. Brazilian Ginseng extraction via LPSE and
SFE: global yields, extraction kinetics, chemical composition and
antioxidant activity. J Supercrit Fluids 2010; 54: 3845.
Lee AKK, Bulley NR, Fattori M, Meisen A. Modelling of supercritical carbon dioxide extraction of canola oilseed in fixed beds.
J Am Oil Chem Soc 1986; 63: 921925.
Lee YY, Kim H, Lee H, Hong VH. One-fluid mixing rules for cubic
equations of state: III. Solubility of pure solids in supercritical
mixed solvents. Korean J Chem Eng 1989; 6: 131137.
Lee YW, Lee CH, Kim JD, Lee YY, Row KH. Extraction of perillyl alcohol in Korean orange peel by supercritical CO2. Sep Sci
Technol 2000; 35: 10691076.
Lee CH, Row KH, Lee YW, Kim JD, Lee YY. Supercritical fluid
extraction of perillyl alcohol in Korean orange peel. J Liq
Chromatogr Relat Technol 2001; 13: 19871996.
Lee S, Park MK, Kim KH, Kim YS. Effect of supercritical carbon
dioxide decaffeination on volatile components of green teas.
J Food Sci 2007; 72: S497S502.
Lee YH, Charles AL, Kung HF, Ho CT, Huang TC. Extraction of
nobiletin and tangeretin from Citrus depressa Hayata by supercritical carbon dioxide with ethanol as modifier. Ind Crops Prod
2010; 31: 5964.
Leeke G, Gaspar F, Santos R. Influence of water on the extraction
of essential oils from a model herb using supercritical carbon
dioxide. Ind Eng Chem Res 2002; 41: 20332039.
Lehotay SJ. Supercritical fluid extraction of pesticides in foods.
J Chromatogr A 1997; 785: 289312.
Lemberkovics E, Kery A, Simandi B, Marczal G, Then M. Then
M. Influence of supercritical fluid extraction and other facts on
composition of volatile oils. Proc. 5th Meeting on Supercritical
Lemert RM, Johnston KP. Solid-liquid-gas equilibria in multicomponent supercritical fluid systems. Fluid Phase Equilib 1989; 45:
265286.
Li SF, Hartland S. A new industrial process for extracting cocoa butter and xanthines with supercritical carbon dioxide. J Am Oil
Chem Soc 1996; 73: 423429.
Li M, Bellmer DD, Brusewitz GH. Pecan kernel breakage and oil
extracted by supercritical CO2 as affected by moisture content.
J Food Sci 1999; 64: 10841088.

Authenticated
Li JB, Ding Y, Li WM. A new sesquiterpene from the roots of Lindera

strychnifolia. Chin Chem Lett 2002; 13: 965967.
Li Q, Zhong C, Zhang Z, Liu Y, Zhou Q. An equilibrium model for
the correlation of the solubility of solids in supercritical fluids
with cosolvent. Sep Sci Technol 2003; 38: 17051719.
Li ZY, Liu XW, Chen SH, Zhang XD, Xia YJ, Wei Y, Xiao F. An
experimental and simulating study of supercritical CO2 extraction for pepper oil. Chem Eng Proc 2006; 45: 264267.
Li TSC, Beveridge THJ, Drover JCG. Phytosterol content of sea
buckthorn (Hippophae rhamnoides L.) seed oil: extraction and
identification. Food Chem 2007; 101: 16331639.
Li H, Hu JY, Ouyang H, Li YN, Shi H, Ma CJ, Zhang YK. Extraction
of aucubin from seeds of Eucommia ulmoides Oliv. using supercritical carbon dioxide. J AOAC Int 2009; 92: 103110.
Li GL, Song CH, You JM, Sun ZW, Xia LA, Suo YR. Optimisation
of red pepper seed oil extraction using supercritical CO2 and
analysis of the composition by reversed-phase HPLC-FLDMS/MS. Int J Food Sci Technol 2011; 46: 4451.
Lim GB, Holder GD, Shah YT. Mass transfer in gas-solid systems at
supercritical conditions. J Supercrit Fluids 1990; 3: 186197.
Lim S, Jung SK, Jwa MK. Extraction of carotenoids from Citrus
unshiu press cake by supercritical carbon dioxide. Food Sci
Biotechnol 2003; 12: 513520.
Lin MC, Tsai MJ, Wen KC. Supercritical fluid extraction of flavonoids from Scutellariae Radix. J Chromatogr A 1999; 830:
387395.
List GR, Friedrich JP, Pominski J. Processing of cottonseed oil
obtained by extraction with supercritical carbon dioxide. J Am
Oil Chem Soc 1983; 60: 719720.
List GR, Friedrich JP, Pominski DD. Characterization and processing
of cottonseed oil obtained by extraction with supercritical carbon
dioxide. J Am Oil Chem Soc 1984a; 61: 18471849.
List GR, Friedrich JP, Christianson DD. Properties and processing of
corn oils obtained by extraction with supercritical carbon dioxide. J Am Oil Chem Soc 1984b; 61: 18491851.
Liu LK. Selective isolation of anethole from fructus anisi stellati
(star anise) by supercritical fluid extraction. Anal Commun 1996;
33: 175176.
Liu G, Nagahama K. Solubility of organic solid mixture in supercritical fluids. J Supercrit Fluids 1996; 9: 152160.
Liu B, Lockwood GB, Gifford LA. Supercritical fluid extraction of
diosgenin from tubers of Dioscorea nipponica. J Chromatogr A
1995; 690: 250253.
Liu J, Ong C, Li SFY. Subcritical fluid extraction of stevia sweeteners from Stevia rebaudiana. J Chrom Sci 1997; 35: 446450.
Liu B, Jiang HL, Shen B, Chang YL. Supercritical fluid extraction
of sinomenine from Sinomenium acutum (Thumb) Rehd et Wils.
J Chromatogr A 2005a; 1075: 213215.
Liu CM, Zhao XL, Li HM, Liu ZQ, Xing JP. Supercritical fluid
extraction of saponins from ginseng. Chem Res Chin Univ
2005b; 21: 757760.
Liu XW, Li ZY, Chen SH, Zhan SP, Xia YJ, Wei Y. Experimental
and simulating study of supercritical CO2 extraction of ginger
essential oil. Chin J Chem Eng 2005c; 13: 572576.
Liu B, Guo F, Chang YL, Jiang HL, Wang QA. Optimization of
extraction of evodiamine and rutaecarpine from fruit of Evodia
rutaecarpa using modified supercritical CO2. J Chromatogr A
2010; 1217: 78337839.
Lojkova L, Slanina J, Mikesova M, Taborska E, Vejrosta J.
Supercritical fluid extraction of lignans from seeds and leaves of
Schizandra chinensis. Phytochem Anal 1997; 8: 261265.
Lopes I, Bernardo-Gil MG, Beirao-da-Costa ML, Simao L.
Supercritical carbon dioxide extraction and lipid composition of
139
Quercus rotundifolia acorn oil. Proc. 5th Meeting on Supercritical

Lopes IMG, Bernardo-Gil MG. Characterisation of acorn oils
extracted by hexane and by supercritical carbon dioxide. Eur J
Lipid Sci Technol 2005; 107: 1219.
Lopez-Avila V, Benedicto J. Supercritical fluid extraction of kava
lactones from Piper methysticum (kava) herb. HRC-J High Res
Chromatogr 1997; 20: 555559.
Lopez-Avila V, Benedicto J, Robaugh D. Supercritical fluid extraction of oxindole alkaloids from Uncaria tormentosa. HRC-J
Lopez-Sebastian S, Ramos E, Ibanez E, Bueno JM, Ballester M,
Tabera J, Reglero G. Dearomatization of antioxidant rosemary
extracts by treatment with supercritical carbon dioxide. J Agric
Food Chem 1998; 46: 1319.
Louli V, Folas G, Voutsas E, Magoulas K. Extraction of parsley seed
oil by supercritical CO2. J Supercrit Fluids 2004a; 30: 163174.
Louli V, Ragoussis N, Magoulas K. Recovery of phenolic antioxidants from wine industry by-products. Biores Technol 2004b; 92:
201208.
Lozano P, Delgado D, Gomez D, Rubio M, Iborra JL. A non-destructive method to determine the safranal content of saffron (Crocus
sativus L.) by supercritical carbon dioxide extraction combined
with high-performance liquid chromatography and gas chromatography. J Biochem Bioph Methods 2000; 43: 367378.
Lu TJ, Gaspar F, Leeke G. Effect of flow rate on the extraction of volatile concentrates and resinoid compounds from Origanum vulgare L. ssp.virens (Hoffm. et Link) letswaart using compressed
CO2. J Essent Oil Res 2005; 17: 8993.
Lu HM, Ni WD, Liang YZ, Man RL. Supercritical CO2 extraction
of emodin and physcion from Polygonum cuspidatum and subsequent isolation by semipreparative chromatography. J Sep Sci
2006; 29: 21362142.
Lu TJ, Gaspar F, Marriott F, Mellor S, Watkinson C, Al-Duri B,
Seville J, Santos R. Extraction of borage seed oil by compressed
CO2: effect of extraction parameters and modelling. J Supercrit
Fluids 2007; 41: 6873.
Lucas S, Calvo MP, Garcia-Serna J, Palencia C, Cocero MJ. Twoparameter model for mass transfer processes between solid
matrixes and supercritical fluids: analytical solution. J Supercrit
Fluids 2007; 41: 257266.
Luengthanaphol S, Mongkholkharjornsilp D, Douglas S, Douglas
PL, Pengsopa LI, Pongamphai S. Extraction of antioxidants from
sweet Thai tamarind seed coat preliminary experiments. J Food
Eng 2004; 63: 247252.
Luo DL, Qiu TQ, Lu Q. Ultrasound-assisted extraction of ginsenosides in supercritical CO2 reverse microemulsions. J Sci Food
Agric 2007; 87: 431436.
Luque-Garcia JL, de Castro MDL. Ultrasound-assisted Soxhlet
extraction: an expeditive approach for solid sample treatment:
application to the extraction of total fat from oleaginous seeds.
J Chromatogr A 2004; 1034: 237242.
Lydersen AL. Estimation of critical properties of organic compounds.
Madison, WI: University of Wisconsin College of Engineering,
1955.
Ma X, Yu X, Zheng Z, Mao J. Analytical supercritical fluid extraction
of Chinese herbal medicines. Chromatographia 1991; 32: 4044.
Ma XZ, Yu XB, Han J. Application of off-line supercritical fluid
extraction gas chromatography for the investigation of chemical constituents in Curcuma zedoaria. Phytochem Anal 1995; 6:
292296.
Ma QX, Xu X, Gao YX, Wang Q, Zhao J. Optimisation of supercritical carbon dioxide extraction of lutein esters from marigold

Authenticated
140
(Tagetes erect L.) with soybean oil as a co-solvent. Int J Food Sci
Technol 2008; 43: 17631769.
Machado NT, Meireles MAA, Chassagnez-Mendez AL, Arajuo ME.
Supercritical CO2 extraction of curcumins and essential oil from
the rhizomes of turmeric (Curcuma longa L.). Ind Eng Chem Res
2000; 39: 47294733.
Machmudah S, Shiramizu Y, Goto M, Sasaki M, Hirose T. Extraction
of Nigella sativa L. using supercritical CO2: a study of antioxidant activity of the extract. Sep Sci Technol 2005; 40: 1267
1275.
Machmudah S, Sulaswatty A, Sasaki M, Goto M, Hirose T.
Supercritical CO2 extraction of nutmeg oil: experiments and
modeling. J Supercrit Fluids 2006; 39: 3039.
Machmudah S, Kawahito Y, Sasaki M, Goto M. Supercritical CO2
extraction of rosehip seed oil: fatty acids composition and process optimization. J Supercrit Fluids 2007; 41: 421428.
Machmudah S, Kawahito Y, Sasaki M, Goto M. Process optimization and extraction rate analysis of carotenoids extraction from
rosehip fruit using supercritical CO2. J Supercrit Fluids 2008a;
44: 308314.
Machmudah S, Kondo M, Sasaki M, Goto M, Munemasa J, Yamagata
M. Pressure effect in supercritical CO2 extraction of plant seeds.
J Supercrit Fluids 2008b; 44: 301307.
Machmudah S, Izumi T, Sasaki M, Goto M. Extraction of pungent
components from Japanese pepper (Xanthoxylum piperitum
DC.) using supercritical CO2. Sep Purif Technol 2009a; 68:
159164.
Machmudah S, Kamogawa T, Sasaki M, Goto M. Supercritical
CO2 and hydrothermal extraction of phytochemical compounds
from Polygonum cuspidatum roots. J Biosci Bioeng 2009b; 108:
S138S138.
Mackay ME, Paulaitis ME. Solid solubilities of heavy hydrocarbons in supercritical solvents. Ind Eng Chem Fundam 1979; 16:
149153.
Maness NO, Chrz D, Pierce T, Brusewitz GH. Quantitative extraction of pecan oil from small samples with supercritical carbon
dioxide. J Am Oil Chem Soc 1995; 72: 665669.
Mannila M, Kim H, Isaacson C, Wai CM. Optimization of supercritical fluid extraction for the separation of hyperforin and adhyperforin in St. Johns wort (Hypericum perforatum L.). Green Chem
2002; 4: 331336.
Mannila M, Lang QY, Wai CM, Cui YY, Ang CYW. Supercritical
fluid extraction of bioactive components from St. Johns Wort
(Hypericum perforatum L.) and Ginkgo biloba. ACS Symp
Series 2003; 860: 130144.
Manninen P, Kallio H. Supercritical fluid chromatography-gas chromatography of volatiles in cloudberry (Rubus chamaemorus)
oil extracted with supercritical carbon dioxide. J Chromatogr A
1997; 787: 276282.
Manninen P, Haivala E, Sarimo S, Kallio H. Distribution of microbes
in supercritical CO2 extraction of sea buckthorn (Hippopha
rhamnoides) oils. Z Lebensm Unters Forsch A 1997a; 204:
202205.
Manninen P, Pakarinen J, Kallio H. Large-scale supercritical carbon
dioxide extraction and supercritical carbon dioxide countercurrent extraction of cloudberry seed oil. J Agric Food Chem 1997b;
45: 25332538.
Marcilla A, Conesa JA, Olaya MM. Comments on the problematic
nature of the calculation of solid-liquid equilibrium. Fluid Phase
Equilib 1997; 135: 169178.
Marentis R. The extraction of Serenoa serulata with carbon dioxide
for use as a therapeutic agent in prostrate drugs. Proc. 5th Meeting
on Supercritical Fluids/2: 675679, Nice, France, 1998.
Markom M, Hasan M, Daud WRW, Singh H, Jahim JM. Extraction

of hydrolysable tannins from Phyllanthus niruri Linn.: effects
of solvents and extraction methods. Sep Purif Technol 2007; 52:
487496.
Marongiu B, Porcedda S, Della Porta G, Reverchon E. Extraction
and isolation of Salvia desoleana and Mentha spicata subsp.
insularis essential oils by supercritical CO2. Flavour Fragr
J 2001; 16: 384388.
Marongiu B, Porcedda S, Caredda A, De Gioannis B, Vargiu L, La Colla
P. Extraction of Juniperus oxycedrus ssp. oxycedrus essential oil by
supercritical carbon dioxide: influence of some process parameters
and biological activity. Flavour Fragr J 2003a; 18: 390397.
Marongiu B, Piras A, Desogus E, Porcedda S, Ballero M. Analysis of
the volatile concentrate of the leaves and flowers of Helichrysum
italicum (Roth) Don ssp. microphyllum (Willd.) Nyman
(Asteraceae) by supercritical fluid extraction and their essential
oils. J Essent Oil Res 2003b; 15: 120126.
Marongiu B, Piras A, Pani F, Porcedda S, Ballero M. Extraction,
separation and isolation of essential oils from natural matrices by
supercritical CO2. Flavour Fragr J 2003c; 18: 505509.
Marongiu B, Piras A, Porcedda S. Comparative analysis of the oil and
supercritical CO2 extract of Elettaria cardamomum(L.) maton.
J Agric Food Chem 2004a; 52: 62786282.
Marongiu B, Porcedda APS, Casu R, Pierucci P. Chemical composition of the oil and supercritical CO2 extract of Schinus molle L.
Flavour Fragr J 2004b; 19: 554558.
Marongiu B, Porcedda S, Caredda A, Piras A, Mascia V, Cadeddu A,
Loddo R. Isolation of Juniperus phoenicea volatiles by supercritical carbon dioxide extraction and bioactivity assays. J Essent
Oil Res 2004c; 16: 256261.
Marongiu B, Porcedda S, Piras A, Rosa A, Deiana M, Dessi MA.
Antioxidant activity of supercritical extract of Melissa officinalis subsp. officinalis and Melissa officinalis subsp. inodora.
Phytotherapy Res 2004d; 18: 789792.
Marongiu B, Piras A, Porcedda S. Comparative analysis of the oil
and supercritical CO2 extract of Ferula communis L. J Essent Oil
Res 2005a; 17: 150152.
Marongiu B, Piras A, Porcedda S, Casu R, Pierucci P. Comparative
analysis of supercritical CO2 extract and oil of Pimenta dioica
leaves. J Essent Oil Res 2005b; 17: 530532.
Marongiu B, Piras A, Porcedda S, Scorciapino A. Chemical composition of the essential oil and supercritical CO2 extract of
Commiphora myrrha (Nees) Engl. and of Acorus calamus L.
J Agric Food Chem 2005c; 53: 79397943.
Marongiu B, Piras A, Porcedda S, Tuveri E. Comparative analysis
of the oil and supercritical CO2 extract of Cymbopogon citratus
Stapf. Nat Prod Res 2006a; 20: 455459.
Marongiu B, Piras A, Porcedda S, Tuveri E, Maxia A. Isolation of
Seseli bocconi Guss., subsp. praecox Gamisans (Apiaceae) volatile oil by supercritical carbon dioxide extraction. Nat Prod Res
2006b; 20: 820826.
Marongiu B, Piras A, Porcedda S. Comparative analysis of the oil
and supercritical CO2 extract of Artemisia arborescens L. and
Helichrysum splendidum (Thunb.) Less. Nat Prod Res 2006c; 20:
421428.
Marongiu B, Porcedda S, Piras A, Sanna G, Murreddu M, Loddo R.
Extraction of Juniperus communis L. ssp. nana Willd. essential
oil by supercritical carbon dioxide. Flavour Fragr J 2006d; 21:
148154.
Marongiu B, Piras A, Porcedda S, Tuveri E. Extraction of Santalum
album and Boswellia carterii Birdw. volatile oil by supercritical
carbon dioxide: influence of some process parameters. Flavour
Fragr J 2006e; 21: 718724.

Authenticated
Marongiu B, Piras A, Porcedda S, Tuveri E, Deriu A, Zanetti S.

Extraction of Lantana camara essential oil by supercritical carbon dioxide: influence of the grinding and biological activity. Nat
Prod Res 2007a; 21: 3336.
Marongiu B, Piras A, Porcedda S, Tuveri E, Maxia A. Comparative
analysis of the oil and supercritical CO2 extract of Ridolfia segetum (L.) Moris. Nat Prod Res 2007b; 21: 412417.
Marongiu B, Maxia A, Piras A, Porcedda S, Tuveri E, Goncalves
MJ, Cavaleiro C, Salgueiro L. Isolation of Crithmum maritimum
L. volatile oil by supercritical carbon dioxide extraction and biological assays. Nat Prod Res 2007c; 21: 11451150.
Marongiu B, Piras A, Porcedda S, Tuveri E, Sanjust E, Meli M,
Sollai F, Zucca P, Rescigno A. Supercritical CO2 extract of
Cinnamomum zeylanicum: chemical characterization and antityrosinase activity. J Agric Food Chem 2007d; 24: 1002210027.
Marongiu B, Piras A, Porcedda S, Tuveri E. Isolation of Guaiacum
bulnesia volatile oil by supercritical carbon dioxide extraction. J
Essent Oil Bearing Plants 2007e; 10: 221228.
Marongiu B, Piras A, Porcedda S, Tuveri E, Laconi S, Deidda D,
Maxia A. Chemical and biological comparisons on supercritical
extracts of Tanacetum cinerariifolium (Trevir) Sch. Bip. with
three related species of chrysanthemums of Sardinia (Italy). Nat
Prod Res 2009; 23: 190199.
Marostica MR Jr, Leite AV, Dragano NRV. Supercritical fluid extraction and stabilization of phenolic compounds from natural
sources review (supercritical extraction and stabilization of
phenolic compounds). Open Chem Eng J 2010; 4: 5160.
Marquina-Chidsey G, Palencia RG, Figueroa Y, Martinez JL.
Supercritical carbon dioxide extraction and characterization of Murraya paniculata essential oil. Proc. 7th Meeting on
Supercritical Fluids/2, Antibes/Juan-les-Pins, France, 2000:
677680.
Marr R, Gamse T. Use of supercritical fluids for different processes
including new developments a review. Chem Eng Proc 2000;
39: 1928.
Marrone C, Poletto M, Reverchon E, Stassi A. Almond oil extraction
by supercritical CO2: experiments and modelling. Chem Eng Sci
1998; 53: 37113718.
Marsili R, Callahan D. Comparison of a liquid solvent-extraction
technique and supercritical-fluid extraction for the determination
of alpha-carotene and beta-carotene in vegetables. J Chrom Sci
1993; 31: 422428.
Martinez J, Monteiro AR, Rosa PTV, Marques MOM, Meireles
MAA. Multicomponent model to describe extraction of ginger
oleoresin with supercritical carbon dioxide. Ind Eng Chem Res
2003; 42: 10571063.
Martinez J, Rosa PTV, Menut C, Leydet A, Brat, Pallet D, Meireles
MAA. Valorization of Brazilian Vetiver (Vetiveria zizanioides (L.)
Nash ex Small) oil. J Agric Food Chem 2004; 52: 65786584.
Martinez J, Rosa PTV, Meireles MAA. Extraction of clove and
vetiver oils with supercritical carbon dioxide: modeling and simulation. Open Chem Eng J 2007; 1: 17.
Martino KG, Guyer D. Supercritical fluid extraction of quercetin
from onion skins. J Food Proc Eng 2004; 27: 1728.
Marzouki H, Piras A, Marongiu B, Rosa A, Dessi MA. Extraction
and separation of volatile and fixed oils from berries of Laurus
nobilis L. by supercritical CO2. Molecules 2008; 13: 702711.
Matthaus B, Bruhl L. Comparison of a supercritical fluid extraction
method for the extraction of oilseeds with the DGF standard
method B-I 5. Fett-Lipid 1999; 101: 203206.
Matthaus B, Bruhl L. Comparison of different methods for the determination of the oil content in oilseeds. J Am Oil Chem Soc 2001;
78: 95102.
141
Mau JL, Ko PT, Chyau CC. Aroma characterization and antioxidant

activity of supercritical carbon dioxide extracts from Terminalia
catappa leaves. Food Res Int 2003; 36: 97104.
Maxia A, Marongiu B, Piras A, Porcedda S, Tuveri E, Goncalves MJ,
Cavaleiro C, Salgueiro L. Chemical characterization and biological activity of essential oils from Daucus carota L. subsp. carota
growing wild on the Mediterranean coast and on the Atlantic
coast. Fitoterapia 2009; 80: 5761.
Mazutti M, Beledelli B, Mossi AJ, Cansian RL, Dariva C, de
Oliveira JV, Paroul N. Caracterizao qumica de extratos de
Ocimum basilicum L. obtidos atravs de extrao com CO2 a
altas presso es. Quimica Nova 2006; 29: 11981202.
McDonald EC, Howard J, Bennett B. Chemicals from forest products by supercritical fluid extraction. Fluid Phase Equilib 1983;
10: 337341.
McHugh MA, Krukonis VJ. Supercritical fluid extraction: principles
and practice, 2nd ed. Boston, MA: Butterworth-Heine, 1994.
McHugh M, Paulaitis ME. Solid solubilities of naphthalene and
biphenyl in supercritical carbon dioxide. J Chem Eng Data 1980;
25: 326329.
McHugh MA, Watkins JJ, Doyle BT, Krukonis VJ. High-pressure
naphthalene-xenon phase behavior. Ind Eng Chem Res 1988; 27:
10251033.
Medini H, Marzouki H, Chemli R, Marongiu B, Piras A, Porcedda
S, Tuveri E. Chemical characterization and evaluation of biological activity of essential oil of Juniperus phoenicea of Tunisia. J
Essent Oil Bearing Plants 2008; 11: 233241.
Mehr CB, Biswal RN, Collins JL, Cochran HD. Supercritical carbon
dioxide extraction of caffeine from guaran. J Supercrit Fluids
1996; 9: 185191.
Meireles MAA. Supercritical extraction from solid: process design
data (20012003). Curr Opinion Solid State Mat Sci 2003; 7:
321330.
Meireles MAA, Zahedi G, Hatami T. Mathematical modeling of
supercritical fluid extraction for obtaining extracts from vetiver
root. J Supercrit Fluids 2009; 23: 2331.
Menaker A, Kravets M, Koel M, Orav A. Identification and characterization of supercritical fluid extracts from herbs. Comptes
Rendus Chimie 2004; 7: 629633.
Mendes RL, Coelho JP, Fernandes HL, Marrucho IJ, Cabral JMS,
Novais JM, Palavra AF. Applications of supercritical CO2 extraction to microalgae and plants. J Chem Technol Biotechnol 1995;
62: 5359.
Mendez-Santiago J, Teja AS. The solubility of solids in supercritical
fluids. Fluid Phase Equilib 1999; 158160: 501510.
Mendiola JA, Herrero B, Cifuentes A, Ibanez E. Use of compressed
fluids for sample preparation: food applications. J Chromatogr A
2007; 1152: 234246.
Mendiola JA, Garcia-Martinez D, Ruperez FJ, Martin-Alvarez
PJ, Reglero G, Cifuentes A, Barbas C, Ibanez E, Senorans FJ.
Enrichment of vitamin E from Spirulina platensis microalga by
SFE. J Supercrit Fluids 2008; 43: 484489.
Mezzomo N, Martinez J, Ferreira SRS. Economical viability of SFE
from peach almond, spearmint and marigold. J Food Eng 2011;
103: 473479.
Mi H, Qu LL, Ren YL, Xing JP, Liu ZQ, Jia YQ. Analysis of volatile components in essential oil of radix Angelicae dahuricae of
supercritical fluid extraction by gas chromatography/mass spectrometry. Chin J Anal Chem 2005; 33: 366370.
Michelsen ML. A method for incorporating excess Gibbs energy models in equations of state. Fluid Phase Equilib 1990a; 60: 4758.
Michelsen ML. A modified Huron-Vidal mixing rule for cubic equations of state. Fluid Phase Equilib 1990b; 60: 213219.

Authenticated
142
Michelsen ML, Kistenmacher H. On composition-dependent interaction coefficeints. Fluid Phase Equilib 1990; 58: 229230.
Michielin EMZ, Bresciani LFV, Danielski L, Yunes RA, Ferreira
SRS. Composition profile of horsetail (Equisetum giganteum
L.) oleoresin: comparing SFE and organic solvents extraction.
Micic V, Lepojevic Z, Mandic B, Jotanovic M, Tadic G, Tolic A.
Influence of pressure and time on extraction process using supercritical CO2. J Min Metall B-Metall 2008; 44: 125131.
Miller KG, Poole CF, Chichila TMP. Solvent-assisted supercritical
fluid extraction for the isolation of semivolatile flavor compounds
from the cinnamons of commerce and their separation by seriescoupled column gas chromatography. J High Res Chromatogr
1995; 18: 461 471.
Mira B, Blasco M, Subirats S, Berna A. Supercritical CO2 extraction
of essential oils from orange peel. J Supercrit Fluids 1996; 9:
238243.
Mira B, Blasco M, Berna A, Subirats S. Supercritical CO2 extraction
of essential oil from orange peel. Effect of operation conditions
on the extract composition. J Supercrit Fluids 1999; 14: 95104.
Mitra S, Wilson NK. An empirical-method to predict solubility in
supercritical fluids. J Chrom Sci 1991; 29: 305309.
Modey WK, Mulholland DA, Raynor MW. Analytical supercritical
fluid extraction of natural products. Phytochem Anal 1996a; 7:
115.
Modey WK, Mulholland DA, Mahomed H, Raynor MW. Analysis
of extracts from Cedrela toona (meliaceae) by on-line and offline supercritical fluid extraction-capillary gas chromatography.
J Microcolumn Sep 1996b; 8: 6774.
Mohamed RS, Saldana MDA, Mazzafera P, Zetzl C, Brunner G.
Extraction of caffeine, theobromine, and cocoa butter from
Brazilian cocoa beans using supercritical CO2 and ethane. Ind
Eng Chem Res 2002; 41: 67516758.
Moldao-Martins M, Palavra A, da Costa MLB, Bernardo-Gil MG.
Supercritical CO2 extraction of Thymus zygis L. subsp. sylvestris
aroma. J Supercrit Fluids 2000; 18: 2534.
Moldao-Martins M, Bernardo-Gil MG, da Costa MLB. Sensory
and chemical evaluation of Thymus zygis L. essential oil and
compressed CO2 extracts. Eur Food Res Technol 2002; 214:
207211.
Mollerup J. A note on the derivation of mixing rules from excess
Gibbs energy models. Fluid Phase Equilib 1986; 25: 323327.
Mongkholkhajornsilp D, Douglas S, Douglas PL, Elkamel A,
Teppaitoon W, Pongamphai S. Supercritical CO extraction of
nimbin from neem seeds a modelling study. J Food Eng 2005;
71: 331340.
Montanari L, King JW, List GR, Rennick KA. Selective extraction of
phospholipid mixtures by supercritical carbon dioxide and cosolvents. J Food Sci 1996; 61: 12301234.
Montanari L, Fantozzi P, Snyder J, King JW. Selective extraction of
phospholipids from soybeans with supercritical carbon dioxide
and ethanol. J Supercrit Fluids 1999; 14: 8793.
Monteiro AR, Meireles MAA, Marques MOM, Petenate AJ.
Extraction of the soluble material from the shells of the bacuri
fruit (Platonia insignis Mart) with pressurized CO2 and other solvents. J Supercrit Fluids 1997; 11: 91102.
Monteiro AR, Meireles MAA, Marques MOM. Ginger (Zingiber
officinalis) essential oil and oleoresin extraction with pressurized
CO2: an evaluation of pretreatment and process variables in oil
composition. Proc. 5th Meeting on Supercritical Fluids/2, Nice,
France, 1998: 515520.
Moore WN, Taylor LT. Solid phase trapping mechanisms involved
in the supercritical fluid extraction of digitalis glycosides
with modified carbon dioxide. Anal Chem 1995; 67: 2030

2036.
Moore WN, Taylor LT. Extraction and quantitation of digoxin and
acetyldigoxin from the Digitalis lanata leaf via near-supercritical
methanol-modified carbon dioxide. J Nat Prod 1996; 59: 690693.
Moore WN, Taylor LT. Gaining greater selectivity in the supercritical fluid extraction of digoxin from Digitalis lanata leaves.
Moraes MDLL, Vilegas JHY, Lancas FM. Supercritical fluid
extraction of glycosylated flavonoids from Passiflora leaves.
Morrison WH, Holser R, Akin DE. Cuticular wax from flax processing waste with hexane and super critical carbon dioxide extractions. Ind Crops Prod 2006; 24: 119122.
Mossi AJ, Cansian RL, Carvalho AZ, Dariva C, Oliveira JV, Mazutti
M, Filho IN, Echeverrigaray S. Extraction and characterization
of volatile compounds in Maytenus ilicifolia, using high-pressure
CO2. Fitoterapia 2004; 75: 168178.
Mossi AJ, Mazutti MA, Cansian RL, de Oliveira D, de Oliveira JV,
Dallago R, Leontiev-Orlov O, Treichel H, Echeverrigaray S, do
Nascimento I. Variabilidade qumica de compostos orgnicos
volteis e semivolteis de populaes nativas de Maytenus ilicifolia. Quim Nova 2010; 33: 10671070.
Motohashi M, Nagashima H, Parkanyi C. Supercritical fluid extraction for the analysis of pesticide residues in miscellaneous samples. J Biochem Biophys Methods 2000; 43: 313328.
Moura LS, Carvalho RN, Stefanini MB, Ming LC, Meireles MAA.
Supercritical fluid extraction from fennel (Foeniculum vulgare):
global yield, composition and kinetic data. J Supercrit Fluids
2005; 35: 212219.
Moyler DA. Extraction of essential oils with carbon dioxide. Flavour
Fragr J 1993; 8: 235247.
Muller EA, Gubbins KE. Molecular-based equations of state for
associating fluids: a review of SAFT and related approaches. Ind
Eng Chem Res 2001; 40: 21932211.
Munoz MAB, Gomez AM, de la Ossa EM. Optimizacin del proceso
de extraccin de tocoferol de germen de trigo con dixido de carbono lquido y supercrtico. Grasas Aceites 1999; 50: 275279.
Muravlev IA, Smetanin YI. Aktualnye voprosy farmacii 1974; 2: 244.
Murga R, Ruiz R, Beltran S, Cabezas JL. Study of the extraction of
natural polyphenols from grape seeds by using supercritical carbon dioxide. Proc. 5th Meeting on Supercritical Fluids/2, Nice,
France, 1998: 529532.
Murga R, Ruiz R, Beltran S, Cabezas JL. Extraction of natural complex phenols and tannins from grape seeds by using supercritical mixtures of carbon dioxide and alcohol. J Agric Food Chem
2000; 48: 34083412.
Muuse BG, Cuperus FP, Derksen JTP. Extraction and characterization of Dimorphotheca pluvialis seed oil. J Am Oil Chem Soc
1994; 71: 313317.
Nagy B, Simandi B. Effects of particle size distribution, moisture
content, and initial oil content on the supercritical fluid extraction
of paprika. J Supercrit Fluids 2008; 46: 293298.
Nagy B, Simandi B, Andras CD. Characterization of packed beds of
plant materials processed by supercritical fluid extraction. J Food
Eng 2008; 88: 104113.
Naik SN, Lentz H, Maheshwari RC. Extraction of perfumes and
flavours from plant materials with liquid carbon dioxide under
liquidvapor equilibrium conditions. Fluid Phase Equilib 1989;
49: 115126.
Namiki M, Fukuda Y, Takei Y, Namiki K, Koizumi Y. Changes in
functional factors of sesame seed and oil during various types of
processing. ACS Symp Series 2002; 816: 85104.

Authenticated
Ndiomu DP, Simpson CF. Some applications of supercritical fluid

extraction. Anal Chim Acta 1988; 213: 237243.
Neau E, Garnier S, Alessi P, Cortesi, Kikic I. Modeling solubility
of biological compounds in supercritical fluids. In: von Rohr
PR, Trepp C, editors. High pressure chemical engineering.
Amsterdam: Elsevier, 1996: 265270.
Neau E, Garnier S, Avaullee SL. A consistent estimation of sublimation pressures using a cubic equation of state and fusion properties. Fluid Phase Equilib 1999; 164: 173186.
Nguyen K, Barton P, Spencer JS. Supercritical carbon dioxide extraction of vanilla. J Supercrit Fluids 1991; 4: 4046.
Nguyen U, Anstee M, Evans DA. Extraction and fractionation
of spices using supercritical fluid carbon dioxide. Proc. 5th
Meeting on Supercritical Fluids/2, Nice, France, 1998: 523
528.
Nicolas C, Neau E, Meradji S, Raspo I. The SanchezLacombe lattice fluid model for the modeling of solids in supercritical fluids.
Niewoudt L, Botha KE. The utilization of apricot kernels and shells.
583588.
Nishiumi H, Arai T, Takeuchi K. Generalization of the binary interaction parameter of the Peng-Robinson equation of state by component family. Fluid Phase Equilib 1988; 42: 4362.
Nobre BP, Mendes RL, Queiroz EM, Pessoa FLP, Coelho JP, Palavra
AF. Supercritical carbon dioxide extraction of pigments from
Bixa orellana seeds (experiments and modeling). Braz J Chem
Eng 2006; 23: 251258.
Nobre BP, Palavra AF, Pessoa FLP, Mendes RL. Supercritical CO2
extraction of trans-lycopene from Portuguese tomato industrial
waste. Food Chem 2009; 116: 680685.
Nodar MD, Gomez AM, de la Ossa EM. Characterisation and process development of supercritical fluid extraction of soybean oil.
Food Sci Technol Int 2002; 8: 337342.
Norulaini NAN, Zaidul ISM, Anuar O, Omar AKM. Supercritical
enhancement for separation of lauric acid and oleic acid in palm
kernel oil (PKO). Sep Purif Technol 2004a; 35: 5560.
Norulaini NAN, Zaidul ISM, Anuar O, Omar AKM. Supercritical
reduction of lauric acid in palm kernel oil (PKO) to produce
cocoa butter equivalent (CBE) fat. J Chem Eng Jpn 2004b; 37
(Sp Iss): 194203.
Norulaini NAN, Ahmad A, Omar FM, Banana AAS, Zaidul ISM,
Kadir MOA. Sterilization and extraction of palm oil from screw
pressed palm fruit fiber using supercritical carbon dioxide. Sep
Purif Technol 2008; 60: 272277.
Norulaini NAN, Anuar O, Abbas FMA, Fatehah MO, Omar AKM,
Sahena F, Zaidul ISM. Optimization of supercritical CO2 extraction of Anastatica hierochuntica. Food Bioprod Proc 2009; 87:
152158.
Nossack AC, Vilegas JHY, von Baer D, Lancas FM. Supercritical
fluid extraction and chromatographic analysis (HRGC-FID and
HRGC-MS) of Lupinus spp. alkaloids. J Braz Chem Soc 2000;
11: 495501.
Nykanen I, Nykanen L, Alkio M. Composition of angelica root oils
obtained by supercritical CO2 extraction and steam distillation.
J Essent Oil Res 1991; 3: 229236.
Odabasi AZ, Balaban MO. Supercritical CO2 extraction of sesame
oil from raw seeds. J Food Sci Technol-Mysore 2002; 39:
496501.
Ohira T, Yatagai M. Extractives of Abies mariesii Masters. 2. The
efficient extraction of maltol using supercritical-fluid, and its antifungal and plant-growth regulation effects. Mokuzai Gakkaishi
1993; 39: 237242.
143
Ohira T, Yatagai M. Extractives from the bark of Abies sachalinensis. 1. The efficient extraction of cis-abienol using supercritical
carbon-dioxide. Mokuzai Gakkaishi 1994; 40: 751757.
Okuno S, Yoshinaga M, Nakatani M, Ishiguro K, Yoshimoto M,
Morishita T, Uehara T, Kawano M. Extraction of antioxidants
in sweetpotato waste powder with supercritical carbon dioxide.
Food Sci Technol Res 2002; 8: 154157.
Olah N, Vlase L, Marculescu A. The study of tocopherols from
different sea buckthorn and wheat germ extracts. Rev Chim
Bucharest 2007; 58: 365368.
Oliveira AL, Vasconcellos VR, Eberlin MN, Cabral FA. Characteristic
smell and yield of coffee essential oil from supercritical extraction. Proc. 6th Meeting on Supercritical Fluids, Nottingham, UK,
1999: 639644.
Oliveira AL, Silva SS, da Silva MAP, Eberlin MN, Cabral FA.
Sensory and yield response surface analysis of supercritical CO2
extracted aromatic oil from roasted coffee. J Food Sci Technol
Mysore 2001; 38: 3842.
Oliveira R, Rodrigues MF, Bernardo-Gil MG. Characterization and
supercritical carbon dioxide extraction of walnut oil. J Am Oil
Chem Soc 2002; 79: 225230.
Oliveira ELG, Silvestre AJD, Silva CM. Review of kinetic models
for supercritical fluid extraction. Chem Eng Res Des 2011; 89:
11041117.
Ollanketo M, Hartonen K, Riekkola ML, Holm Y, Hiltunen R.
Supercritical carbon dioxide extraction of lycopene in tomato
skins. Eur Food Res Technol 2001; 212: 561565.
OMahony T, Moore S, Brosnan B, Glennon JD. Monitoring the
supercritical fluid extraction of pyrethroid pesticides using capillary electrochromatography. Int J Environ Anal Chem 2003; 83:
681691.
Ondarza M, Sanchez A. Steam distillation and supercritical fluid
extraction of some Mexican spices. Chromatographia 1990; 30:
1618.
Orav A, Kailas T, Koel M. Simultaneous distillation, extraction and
supercritical fluid extraction for isolating volatiles and other materials from conifer needles. J Essent Oil Res 1998; 10: 387393.
Orbey H, Sandler SI. Modeling vapor-liquid equilibria: cubic equations of state and their mixing rules. Cambridge: Cambridge
University Press, 1998.
Oszagyan M, Simandi B, Sawinsky J, Kery A, Lemberkovics E,
Fekete J. Supercritical fluid extraction of volatile compounds
from lavandin and thyme. Flavour Fragr J 1996; 11: 157165.
Otterbach A, Wenclawiak BW. Ultrasonic/Soxhlet/supercritical fluid
extraction kinetics of pyrethrins from flowers and allethrin from
paper strips. Fresenius J Anal Chem 1999; 365: 472474.
Ozcan A, Ozcan AS. Comparison of supercritical fluid and Soxhlet
extractions for the quantification of hydrocarbons from Euphorbia
macroclada. Talanta 2004; 64: 491495.
Ozek T, Bozan B, Baser KHC. Supercritical CO2 extraction of
volatile components from leaves of Laurus nobilis L. Khimiya.
Prirodnykh Soedinenii 1998; 746750.
Ozkal SG, Yener MG, Bayindirli L. Response surfaces of apricot
kernel oil yield in supercritical carbon dioxide. LWT-Food Sci
Technol 2005a; 38: 611616.
Ozkal SG, Salgin U, Yener MG. Supercritical carbon dioxide extraction of hazelnut oil. J Food Eng 2005b; 69: 217223.
Ozkal SG, Yener MG, Salgin U, Mehmetglu U. Response surfaces of
hazelnut oil yield in supercritical carbon dioxide. Eur Food Res
Technol 2005c; 220: 7478.
Ozkal SG, Yener ME, Bayindirli L. Mass transfer modeling of
apricot kernel oil extraction with supercritical carbon dioxide.
J Supercrit Fluids 2005d; 35: 119127.

Authenticated
144
Palazoglu TK, Balaban MO. Supercritical CO2 extraction of lipids

from roasted pistachio nuts. Trans ASAE 1998; 41: 679684.
Palenzuela B, Rodriguez-Amaro R, Rios A, Valcarcel M. Screening
of polyphenols in grape marc by on-line supercritical fluid extraction amperometric detection with a PVC-graphite composite
electrode. Electroanalysis 2002; 14: 14271432.
Palenzuela B, Arce L, Macho A, Munoz E, Rios A, Valcarcel M.
Bioguided extraction of polyphenols from grape marc by using
an alternative supercritical-fluid extraction method based on a
liquid solvent trap. Anal Bioanal Chem 2004; 378: 20212027.
Palic R, Stojanovic G, Alagic S, Nikolic M, Lepojevic Z. Chemical
composition and antimicrobial activity of the essential oil and
CO2 extracts of the oriental tobacco, Prilep. Flavour Fragr J
2002; 17: 323326.
Palma M, Taylor LT. Extraction of polyphenolic compounds from
grape seeds with near critical carbon dioxide. J Chromatogr A
1999; 849: 117124.
Palma M, Taylor LT, Varela RM, Cutler SJ, Cutler HG. Fractional
extraction of compounds from grape seeds by supercritical fluid
extraction and analysis for antimicrobial and agrochemical activities. J Agric Food Chem 1999; 47: 50445048.
Palma M, Taylor LT, Zoecklein BW, Douglas LS. Supercritical fluid
extraction of grape glycosides. J Agric Food Chem 2000; 48:
775779.
Palmer MV, Ting SST. Applications for supercritical fluid technology in food processing. Food Chemistry 1995; 52: 345352.
Paltoo V, McGaw D, Yen IC, Edwards V. Supercritical carbon dioxide extraction of nutmegs parameters and modeling. Proc.
6th Meeting on Supercritical Fluids, Nottingham, UK, 1999:
531536.
Pan WHT, Chang CC, Su TT, Lee F, Fuh MRS. Preparative supercritical fluid extraction of pyrethrin I and II from pyrethrum flower.
Talanta 1995; 42: 17451749.
Panagiotopoulos AZ, Reid RC, Watanasiri S. Multiphase high pressure equilibria in ternary aqueous systems. Fluid Phase Equilib
1986; 29: 525534.
Panfili G, Cinquanta L, Fratianni A, Cubadda R. Extraction of wheat
germ oil by supercritical CO2: oil and defatted cake characterization. J Am Oil Chem Soc 2003; 80: 157161.
Papamichail I, Louli V, Magoulas K. Supercritical fluid extraction of
celery seed oil. J Supercrit Fluids 2000; 18: 213226.
Park SJ, Kwak TY, Mansoori GA. Statistical mechanical description
of supercritical fluid extraction and retrograde condensation. Int
J Thermophys 1987; 8: 449471.
Park YS, You JE, Kim JD, Chung BH, Lee SH, Lee MK, Lee HY,
Hwang B, Kim JH, Pakr YB, Lee HJ. The effect of the oil and
supercritical fluid CO2 extract of Juniperus rigida Sieb. on the
growth performance of rat adrenal nerve cells. J Essent Oil Res
2004; 16: 151156.
Park HS, Choi HK, Lee SJ, Park KW, Choi SG, Kim KH. Effect of
mass transfer on the removal of caffeine from green tea by supercritical carbon dioxide. J Supercrit Fluids 2007a; 42: 205211.
Park HS, Lee HJ, Shin MH, Lee KW, Lee H, Kim YS, Kim KO,
Kim KH. Effects of cosolvents on the decaffeination of green tea
by supercritical carbon dioxide. Food Chem 2007b; 105: 1011
1017.
Paroul N, Rota L, Frizzo C, dos Santos ACA, Moyna P, Gower AE,
Serafini LA, Cassel E. Chemical composition of the volatiles of
angelica root obtained by hydrodistillation and supercritical CO2
extraction. J Essent Oil Res 2002; 14: 282285.
Pascual-Marti MC, Salvador A, Chafer A, Berna A. Supercritical
fluid extraction of resveratrol from grape skin of Vitis vinifera
and determination by HPLC. Talanta 2001; 54: 735740.
Pasquel A, Marques MOM, Meireles MAA. Stevia (Stevia rebaundiana Bertoni) leaves pretreatment with pressurized CO2: an
evaluation of the extract composition. Proc. 6th Meeting on
Supercritical Fluids, Nottingham, UK, 1999: 501506.
Pasquel A, Meireles MAA, Marques MOM, Petenate AJ. Extraction
of stevia glycosides with CO2+water, CO2+ethanol, and
CO2+water+ethanol. Braz J Chem Eng 2000; 17: 271282.
Passey CA, Gros-Louis M. Production of calorie-reduced almonds by
supercritical extraction. J Supercrit Fluids 1993; 6: 255261.
Patel RL, Bandyopadhyay S, Ganesh A. Extraction of cashew
(Anacardium occidentale) nut shell liquid using supercritical
carbon dioxide. Biores Technol 2006; 97: 847853.
Pavela R, Sajfrtova M, Sovova H, Barnet M. The insecticidal activity
of Satureja hortensis L. extracts obtained by supercritical fluid
extraction and traditional extraction techniques. Appl Entom
Zool 2008; 43: 377382.
Peker H, Srinivasan MP, Smith JM, McCoy BJ. Caffeine extraction rates from coffee beans with supercritical carbon dioxide.
AICHE J 1992; 38: 761770.
Pekhov AV, Goncharenko GK. Ekstrakcija prjanogo rastitelnogo
syrja szhizhennymi gazami. Maslo-zhirovaja promyshlennostj
1968; 34: 2629.
Pekhov AV, Ponomarenko IJ, Prokopchuk AF. Patent USSR No.
167798, 1965.
Pekic B, Zekovic Z, Petrovic L, Tolic A. Behavior of (-)--bisabolol
and (-)--bisabololoxides A and B in camomile flower extraction with supercritical carbon dioxide. Sep Sci Technol 1995; 30:
35673576.
Peplonski R, Kwiatkowski J, Jarosz M, Lisicki Z. Extraction of some
components for flavouring, colouring and preservation of food
using supercritical carbon dioxide. Proc. 3rd Int Symp Supercrit
Perakis C, Louli V, Magoulas K. Supercritical fluid extraction of
black pepper oil. J Food Eng 2005; 71: 386393.
Pereira CG, Meireles MAA. Economic analysis of rosemary, fennel
and anise essential oils obtained by supercritical fluid extraction.
Flavour Fragr J 2007; 22: 407413.
Pereira CG, Meireles MAA. Supercritical fluid extraction of bioactive compounds: fundamentals, applications and economic perspectives. Food Bioprocess Technol 2010; 3: 340372.
Pereira CG, Marques MOM, Barreto AS, Siani AC, Fernandes
EC, Meireles MAA. Extraction of indole alkaloids from
Tabernaemontana catharinensis using supercritical CO2+ethanol:
an evaluation of the process variables and the raw material origin. J Supercrit Fluids 2004; 30: 5161.
Pereira CG, Leal PF, Sato DN, Meireles MA. Antioxidant and antimycobacterial activities of Tabernaemontana catharinensis
extracts obtained by supercritical CO2+cosolvent. J Med Food
2005; 8: 533538.
Pereira CG, Rosa PTV, Meireles MAA. Extraction and isolation of
indole alkaloids from Tabernaemontana catharinensis A.DC:
technical and economical analysis. J Supercrit Fluids 2007; 40:
232238.
Perretti G, Miniati E, Montanari L, Fantozzi P. Improving the
value of rice by-products by SFE. J Supercrit Fluids 2003; 26:
6371.
Perrut M. Supercritical fluid applications: industrial developments
and economic issues. Ind Eng Chem Res 2000; 39: 45314535.
Perrut M. Proc. 1st Iberoamerican Conf on Supercritical Fluids,
Iguassu Falls, Brazil, 2007.
Perrut M, Clavier JY, Poletto M, Reverchon E. Mathematical modeling of sunflower seed extraction by supercritical CO2. Ind Eng
Chem Res 1997; 36: 430435.

Authenticated
Perry RH, Green DW, editors. Perrys Chemical Engineers

Handbook. New York: McGraw Hill, 1999: 361.
Perva-Uzunalic A, Skerget M, Weinreich B, Knez Z. Extraction of
chilli pepper (var. Byedige) with supercritical CO2: effect of
pressure and temperature on capsaicinoid and colour extraction
efficiency. Food Chem 2004; 87: 5158.
Peterson A, Machmudah S, Roy BC, Goto M, Sasaki M, Hirose T.
Extraction of essential oil from geranium (Pelargonium graveolens) with supercritical carbon dioxide. J Chem Technol
Biotechnol 2006; 81: 167172.
Petrovic L, Lepojevic Z, Sovilj V, Adamovic D, Tesevic V. An investigation of CO2 extraction of marigold (Calendula officinalis L.).
J Serb Chem Soc 2007; 72: 407413.
Peusch M, MullerSeitz E, Petz M, Muller A, Anklam E. Extraction
of capsaicinoids from chillies (Capsicum frutescens L.) and
paprika (Capsicum annuum L.) using supercritical fluids and
organic solvents. Z Lebensm Unters Forsch A 1997; 204: 351
355.
Piantino CR, Aquino FWB, Follegatti-Romero LA, Cabral FA.
Supercritical CO2 extraction of phenolic compounds from
Baccharis dracunculifolia. J Supercrit Fluids 2008; 47:
209214.
Pietsch A, Hilgendorff W, Thom O, Eggers R. Basic investigation
of integrating a membrane unit into high-pressure decaffeination
processing. Sep Purif Technol 1998; 14: 107115.
Piggott MJ, Ghisalberti EL, Trengove RD. Western Australian sandalwood oil: extraction by different techniques and variations
of the major components in different sections of a single tree.
Flavour Fragr J 1997; 12: 4346.
Pino JA, Garcia J, Martinez MA. Solvent extraction and supercritical carbon dioxide extraction of Pimenta dioica Merrill. leaf. J
Essent Oil Res 1997; 9: 689691.
Pino JA, Garcia J, Martinez MA. Comparison of solvent extract and
supercritical carbon dioxide extract of spearmint leaf. J Essent
Oil Res 1999; 11: 191193.
Piras A, Rosa A, Falconieri D, Porcedda S, Dessi MA, Marongiu
B. Extraction of oil from wheat germ by supercritical CO2.
Molecules 2009; 14: 25732581.
Poiana M, Sicari V, Tramontana A, Mincione B, Crispo F. Application
of supercritical carbon dioxide to the citrus product extraction.
Proc. 3rd Int Symp Supercrit Fluids/2, Strasbourg, France, 1994:
395400.
Poiana M, Sicari V, Mincione B. Supercritical carbon dioxide
(SC-CO2) extraction of grapefruit flavedo. Flavour Fragr J 1998;
13: 125130.
Poiana M, Fresa R, Mincione B. Supercritical carbon dioxide extraction of bergamot peels. Extraction kinetics of oil and its components. Flavour Fragr J 1999; 14: 358366.
Polesello S, Lovati F, Rizzolo A, Rovida C. Supercritical fluid extraction as a preparative tool for strawberry aroma analysis. HRC-J
Poletto M, Reverchon E. Comparison of models for supercritical
fluid extraction of seed and essential oils in relation to the masstransfer rate. Ind Eng Chem Res 1996; 35: 36803686.
Poli F, Muzzoli M, Sacchetti G, Tassinato G, Lazzarin R, Bruni A.
Antioxidant activity of supercritical CO2 extracts of Helichrysum
italicum. Pharm Biol 2003; 41: 379383.
Pop EG, Barth D. Supercritical fluid extraction of Z-sabinene
hydrate-rich essential oils from Romanian Mentha hybrids. Pure
Appl Chem 2001; 73: 12871291.
Pourmortazavi SM, Hajimirsadeghi SS. Supercritical fluid extraction
in plant essential and volatile oil analysis. J Chromatogr A 2007;
1163: 224.
145
Pourmortazavi SM, Sefidkon F, Hosseini SG. Supercritical carbon

dioxide extraction of essential oils from Perovskia atriplicifolia
Benth. J Agric Food Chem 2003; 51: 54145419.
Pourmortazavi SM, Baghaee P, Mirhosseini MA. Extraction of volatile compounds from Juniperus communis L. leaves with supercritical fluid carbon dioxide: comparison with hydrodistillation.
Flavour Fragr J 2004; 19: 417420.
Pourmortazavi SM, Ghadiri M, Hajimirsadeghi SS. Supercritical
fluid extraction of volatile components from Bunium persicum
Boiss. (black cumin) and Mespilus germanica L. (medlar) seeds.
J Food Comp Anal 2005; 18: 439446.
Povh NP, Marques MOM, Meireles MAA. Supercritical CO2 extraction of essential oil and oleoresin from chamomile (Chamomilla
recutita [L.] Rauschert). J Supercrit Fluids 2001; 21: 245256.
Prado JM, Assis AR, Marostica MR, Meireles MAA. Manufacturing
cost of supercritical-extracted oils and carotenoids from amazonian plants. J Food Proc Eng 2010; 33: 348369.
Prausnitz JM, Lichtenthaler RN, de Azevedo EG. Molecular thermodynamics of fluid-phase equilibria. Upper Saddle River, NJ:
Prentice Hall, 1999: 671749.
Presti ML, Ragusa S, Trozzi A, Dugo P, Visinoni F, Fazio A, Dugo G,
Mondello L. A comparison between different techniques for the
isolation of rosemary essential oil. J Sep Sci 2005; 28: 273280.
Prokopczyk B, Hoffmann D, Cox JE, Djordjevic MV, Brunnemann
KD. Supercritical fluid extraction in the determination of tobacco-specific N-nitrosamines in smokeless tobacco. Chem Res
Toxicol 1992; 5: 336340.
Prokopczyk B, Wu M, Cox JE, Amin S, Desai D, Idris AM, Hoffmann
D. Improved methodology for the quantitative assessment of
tobacco-specific N-nitrosamines in tobacco by supercritical fluid
Pronyk C, Mazza G. Design and scale-up of pressurized fluid extractors for food and bioproducts. J Food Eng 2009; 95: 215226.
Puiggene R, Larrayoz MA, Recasens F. Free liquid-to-supercritical fluid
mass transfer in packed beds. Chem Eng Sci 1997; 52: 195212.
Qafisheh N, Barth D. The effects of process parameters on the supercritical CO2 extraction of mint hybrid oils. Proc. 7th Meeting
on Supercritical Fluids/2, Antibes/Juan-les-Pins, France, 2000:
605610.
Queckenberg OR, Frahm AW. Supercritical-fluid extraction quickness and selectivity in the analysis of natural products. Pharmazie
1994; 49: 159166.
Quispe-Condori S, Sanchez D, Foglio MA, Rosa PTV, Zetzl C,
Brunner G, Meireles MAA. Global yield isotherms and kinetic
of artemisinin extraction from Artemisia annua L leaves using
supercritical carbon dioxide. J Supercrit Fluids 2005; 36: 4048.
Quispe-Condori S, Foglio MA, Rosa PTV, Meireles MAA. Obtaining
-caryophyllene from Cordia verbenacea de Candolle by supercritical fluid extraction. J Supercrit Fluids 2008; 46: 2732.
Quitain AT, Katoh S, Moriyoshi T. Isolation of antimicrobials and
antioxidants from Moso-Bamboo (Phyllostachys heterocycla) by
supercritical CO2 extraction and subsequent hydrothermal treatment of the residues. Ind Eng Chem Res 2004; 43: 10561060.
Quitain AT, Oro K, Katoh S, Moriyoshi T. Recovery of oil components of okara by ethanol-modified supercritical carbon dioxide
extraction. Biores Technol 2006; 97: 15091514.
Radcliffe C, Maguire K, Lockwood B. Applications of supercritical fluid extraction and chromatography in forensic science.
J Biochem Biophys Methods 2000; 43: 261272.
Rafajlovska V, Rizova V, Djarmati Z, Tesevic V, Cvetkov L. Contents
of fatty acids in stinging nettle extracts (Urtica dioica L.)
obtained with supercritical carbon dioxide. Acta Pharm (Zagreb)
2001; 51: 4551.

Authenticated
146
Raghuram Rao GV, Srinivas P, Sastry SVGK, Mukhopadhyay M.

Modeling solute-co-solvent interactions for supercritical-fluid
extraction of fragrances. J Supercrit Fluids 1992; 5: 1923.
Rahman NNA, Hassan MN, Omar A, Ibrahim MH, Kadir MOA.
Dehulling and its effect on supercritical extraction of palm kernel
oil. J Chem Eng Jpn 2001; 34: 407410.
Rajaei A, Barzegar M, Yamini Y. Supercritical fluid extraction of tea
seed oil and its comparison with solvent extraction. Eur Food Res
Technol 2005; 220: 401405.
Ramirez P, Senorans FJ, Ibanez E, Reglero G. Separation of rosemary antioxidant compounds by supercritical fluid chromatography on coated packed capillary columns. J Chromatogr A 2004;
1057: 241245.
Ramos E, Valero E, Ibanez E, Reglero G, Tabera J. Obtention of a
brewed coffee aroma extract by an optimized supercritical CO2based process. J Agric Food Chem 1998; 46: 40114016.
Ramsay ME, Hsu JT, Novak RA, Reighter WJ. Processing rice bran
by supercritical fluid extraction. Food Technol (Nov.) 1991;
98104.
Ranalli A, Contento S, Lucera L, Pavone G, Di Giacomo G, Aloisio
L, Di Gregorio C, Mucci A, Kourtikakis I. Characterization of
carrot root oil arising from supercritical fluid carbon dioxide
Rao VSG, Mukhopadhyay M. Effect of covolume dependency of
the energy parameter on the predictability of SCFE data using
the Peng-Robinson equation of state. J Supercrit Fluids 1989; 2:
2229.
Rao MV, Al-Marzouqi AH, Kaneez FS, Ashraf SS, Adem A.
Comparative evaluation of SFE and solvent extraction methods
on the yield and composition of black seeds (Nigella sativa).
J Liquid Chromatogr Rel Technol 2007; 30: 25452555.
Raventos M, Duarte S, Alarcon R. Application and possibilities of
supercritical CO2 extraction in food processing industry: an overview. Food Sci Technol Int 2002; 8: 269284.
Recasens F, McCoy BJ, Smith JM. Desorption processes: supercritical fluid regeneration of activated carbon. AICHE J 1989; 35:
951958.
Reis Machado AS, Gomes de Azevedo E, Sardinha RMA, Nunes da
Ponte M. High pressure CO2 extraction from geranium plants. J.
Essent Oil Res 1993; 5: 185189.
Reis-Vasco EMC, Coelho JAP, Palavra AMF. Comparison of pennyroyal oils obtained by supercritical CO2 extraction and hydrodistillation. Flavour Fragr J 1999; 14: 156160.
Reis-Vasco EMC, Coelho JAP, Palavra AMF, Marrone C, Reverchon
E. Mathematical modelling and simulation of pennyroyal
essential oil supercritical extraction. Chem Eng Sci 2000; 55:
29172922.
Reverchon E. Fractional separation of SCF extracts from marjoram
leaves: mass transfer and optimization. J Supercrit Fluids 1992;
5: 256261.
Reverchon E. Mathematical modeling of supercritical extraction of
sage oil. AICHE J 1996; 42: 17651771.
Reverchon E. Supercritical fluid extraction and fractionation of
essential oils and related products. J Supercrit Fluids 1997; 10:
137.
Reverchon E, De Marco I. Supercritical fluid extraction and fractionation of natural matter. J Supercrit Fluids 2006; 38: 146166.
Reverchon E, Marrone C. Supercritical extraction of clove bud
essential oil: isolation and mathematical modeling. Chem Eng
Sci 1997; 52: 34213428.
Reverchon E, Marrone C. Modeling and simulation of the supercritical CO2 extraction of vegetable oils. J Supercrit Fluids 2001; 19:
161175.
Reverchon E, Senatore F. Isolation of rosemary oil: comparison

between hydrodistillation and supercritical CO2 extraction.
Flavour Fragr J 1992; 7: 227230.
Reverchon E, Senatore F. Supercritical carbon dioxide extraction of
chamomile essential oil and its analysis by gas chromatographymass spectrometry. J Agric Food Chem 1994; 42: 154158.
Reverchon E, Sesti Osseo L. Comparison of processes for the supercritical carbon dioxide extraction of oil from soybean seeds.
J Am Oil Chem Soc 1994a; 71: 10071012.
Reverchon E, Sesti Osseo L. Supercritical CO2 extraction: model
evaluation of the processing time. Chem Biochem Eng Q 1994b;
8: 3134.
Reverchon E, Donsi G, Sesti Osseo L. Modeling of supercritical fluid
extraction from herbaceous matrices. Ind Eng Chem Res 1993;
32: 27212726.
Reverchon E, Ambruosi A, Senatore F. Isolation of peppermint oil using
supercritical CO2 extraction. Flavour Fragr J 1994a; 9: 1923.
Reverchon E, Sesti Osseo L, Gorgoglione D. Supercritical CO2
extraction of basil oil: characterization of products and process
modeling. J Supercrit Fluids 1994b; 7: 185190.
Reverchon E, Della Porta G, Taddeo R, Pallado P, Stassi A. Solubility
and micronization of griseofulvin in supercritical CHF3. Ind Eng
Chem Res 1995a; 34: 40874091.
Reverchon E, Della Porta G, Senatore F. Supercritical CO2 extraction and fractionation of lavender essential oil and waxes. J Agric
Food Chem 1995b; 43: 16541658.
Reverchon E, Taddeo R, Della Porta G. Extraction of sage oil by
supercritical CO2: influence of some process parameters.
J Supercrit Fluids 1995c; 8: 302309.
Reverchon E, Daghero J, Marrone C, Mattea M, Poletto M.
Supercritical fractional extraction of fennel seed oil and essential
oil: experiments and mathematical modeling. Ind Eng Chem Res
1999; 38: 30693075.
Reverchon E, Kaziunas A, Marrone C. Supercritical CO2 extraction
of hiprose seed oil: experiments and mathematical modelling.
Chem Eng Sci 2000; 55: 21952201.
Ribeiro MA, Lopes I, Esquivel MM, Bernardo-Gil MG. Comparison
of antioxidant activity of plant extracts obtained using supercritical extraction and classical methods. Proc. 5th Meeting on
Ribeiro MA, Bernardo-Gil MG, Esquivel MM. Melissa officinalis, L:
study of antioxidant activity in supercritical residues. J Supercrit
Fluids 2001; 21: 5160.
Richins RD, Hernandez L, Dungan B, Hambly S, Holguin FO,
OConnell MA. A green extraction protocol to recover red
pigments from hot Capsicum fruit. Hortscience 2010; 45:
10841087.
Rincon J, De Lucas A, Garcia MA, Garcia A, Alvarez A, Carnicer A.
Preliminary study on the supercritical carbon dioxide extraction of
nicotine from tobacco wastes. Sep Sci Technol 1998; 33: 411423.
Rincon J, De Lucas A, Garcia I. Isolation of rock rose essential oil
using supercritical CO2 extraction. Sep Sci Technol 2000; 35:
27452763.
Rizvi SSH. Supercritical fluid processing of food and biomaterials.
London: Blackie A&P, 1994.
Rochova K, Sovova H, Sobolik V, Allaf K. Impact of seed structure modification on the rate of supercritical CO2 extraction.
Rodrigues VM, Sousa EMBD, Monteiro AR, Chiavone-Filho
O, Marques MOM, Meireles MAA. Determination of the
solubility of extracts from vegetable raw material in pressurized CO2: a pseudo-ternary mixture formed by cellulosic
structure+solute+solvent. J Supercrit Fluids 2002; 22: 2136.

Authenticated
Rodrigues MRA, Caramao EB, dos Santos JG, Dariva C, Oliveira

JV. The effects of temperature and pressure on the characteristics
of the extracts from high-pressure CO2 extraction of Majorana
hortensis Moench. J Agric Food Chem 2003a; 51: 453456.
Rodrigues VM, Rosa PTM, Marques MOM, Petenate AJ, Meireles
MAA. Supercritical extraction of essential oil from aniseed
(Pimpinella anisum L) using CO2: solubility, kinetics, and composition data. J Agric Food Chem 2003b; 51: 15181523.
Rodrigues MRA, Krause LC, Caramao EB, dos Santos JG, Dariva C,
de Oliveira JV. Chemical composition and extraction yield of the
extract of Origanum vulgare obtained from sub- and supercritical
CO2. J Agric Food Chem 2004; 52: 30423047.
Rodrigues RF, Tashima AK, Pereira RMS, Mohamed RS, Cabral FA.
Coumarin solubility and extraction from emburana (Torresea
cearensis) seeds with supercritical carbon dioxide. J Supercrit
Fluids 2008; 43: 375382.
Roethe A, Rosahl B, Suckow M, Roethe KP. Physikalish-chemisch
begrndete Beschreibung von Hochdruck-Extraktionsvorgngen.
Chem Tech-Leipzig 1992; 44: 243249.
Roj E, Skowronski B. Modeling of hop extraction under supercritical
conditions. Przem Chem 2006; 85: 11401141.
Rompp H, Seger C, Kaiser CS, Haslinger E, Schmidt PC. Enrichment
of hyperforin from St. Johns Wort (Hypericum perforatum) by
pilot-scale supercritical carbon dioxide extraction. Eur J Pharm
Sci 2004; 21: 443451.
Ronyai E, Simandi B, Tomoskozi S, Deak A, Vigh L, Weinbrenner
Z. Supercritical fluid extraction of corn germ with carbon dioxide
ethyl alcohol mixture. J Supercrit Fluids 1998a; 14: 7581.
Ronyai E, Simandi B, Deak A, Kery A, Lemberkovics E, Keve T,
Lack E. Production of marigold extracts with carbon dioxide
supercritical fluid extraction. Proc. 5th Meeting on Supercritical
Fluids/2, Nice, France, 1998b: 607612.
Ronyai E, Simandi B, Lemberkovics E, Veress T, Patiaka D.
Comparison of the volatile composition of clary sage oil obtained
by hydrodistillation and supercritical fluid extraction. J Essent
Oil Res 1999a; 11: 6971.
Ronyai E, Simandi B, Veress T, Lemberkovics E, Patiaka D.
Comparison between the essential oil and supercritical carbon
dioxide extract of Salvia fruticosa Mill. J Essent Oil Res 1999b;
11: 499502.
Rosa PTV, Meireles MAA. Rapid estimation of the manufacturing
cost of extracts obtained by supercritical fluid extraction. J Food
Eng 2005a; 67: 235240.
Rosa PTV, Meireless MAA. Supercritical technology in Brazil: system
investigated (19942003). J Supercrit Fluids 2005b; 34: 109117.
Rossi M, Arnoldi C, Antoniazzi F, Schiraldi A. Supercritical-fluid
extraction of cocoa lipid with carbon-dioxide. Ind Aliment-Italy
1993; Suppl. S: 2833.
Rostagno MA, Araujo JMA, Sandi D. Supercritical fluid extraction of
isoflavones from soybean flour. Food Chem 2002; 78: 111117.
Rout PK, Naik SN, Rao YR, Jadeja G, Maheshwari RC. Extraction
and composition of volatiles from Zanthoxylum rhesta: comparison of subcritical CO2 and traditional processes. J Supercrit
Fluids 2007; 42: 334341.
Roy BC, Goto M, Hirose T, Navaro O, Hortacsu O. Extraction rates
of oil from tomato seeds with supercritical carbon dioxide.
J Chem Eng Jpn 1994; 27: 768772.
Roy BC, Goto M, Hirose T. Extraction of ginger oil with supercritical carbon dioxide: experiments and modeling. Ind Eng Chem
Res 1996a; 35: 607612.
Roy BC, Goto M, Hirose T. Temperature and pressure effects on
supercritical CO2 extraction of tomato seed oil. Int J Food Sci
Technol 1996b; 31: 137141.
147
Roy BC, Goto M, Kodama A, Hirose T. Supercritical CO2 extraction

of essential oils and cuticular waxes from peppermint leaves. J
Chem Technol Biotechnol 1996c; 67: 2126.
Royer F, Barth D. Supercritical carbon dioxide extraction of sunflower seeds oils and characterisation of the products. Proc. 7th
Meeting on Supercritical Fluids/2, Antibes/Juan-les-Pins, France,
2000: 611616.
Rozzi NL, Singh RK. Supercritical fluids and the food industry.
Compr Rev Food Sci Food Saf 2002; 1: 3444.
Rozzi NL, Phippen W, Simon JE, Singh RK. Supercritical fluid
extraction of essential oil components from lemon-scented
botanicals. Lebensm-Wiss Technol 2002a; 35: 319324.
Rozzi NL, Singh RK, Vierling RA, Watkins BA. Supercritical fluid
extraction of lycopene from tomato processing byproducts.
J Agric Food Chem 2002b; 50: 26382643.
Ruberto G, Biondi D, Renda A. The composition of the volatile oil of
Ferulago nodosa obtained by steam distillation and supercritical
carbon dioxide extraction. Phytochem Anal 1999; 10: 241246.
Ruckenstein E, Shulgin I. Cubic equation of state and local composition mixing rules: correlations and predictions. Application to the
solubility of solids in supercritical solvents. Ind Eng Chem Res
2001; 40: 25442549.
Ruckenstein E, Shulgin I. The solubility of solids in mixtures composed of a supercritical fluid and an entrainer. Fluid Phase Equilib
2002; 200: 5367.
Ruetsch L, Daghero J, Mattea M. Supercritical extraction of solid
matrices. Model formulation and experiments. Lat Am Appl Res
2003; 33: 103107.
Ruivo R, Ribero N, Casimiro T, Vital J, Simoes P. Supercritical fluid
extraction of natural compounds from the Pinus pinaster Ait.
needles. Proc. 7th Meeting on Supercritical Fluids/2, Antibes/
Juan-les-Pins, France, 2000: 623628.
Rybak ME, Calvey EM, Harnly JM. Quantitative determination of
allicin in garlic: supercritical fluid extraction and standard addition of alliin. J Agric Food Chem 2004; 52: 682687.
Sabio E, Lozano M, de Espinosa VM, Mendes RL, Pereira AP,
Palavra AF, Coelho JA. Lycopene and -carotene extraction from
tomato processing waste using supercritical CO2. Ind Eng Chem
Res 2003; 42: 66416646.
Safaralie A, Fatemi S, Sefidkon F. Essential oil composition of
Valeriana officinalis L. roots cultivated in Iran: comparative
analysis between supercritical CO2 extraction and hydrodistillation. J Chromatogr A 2008; 1180: 159164.
Safaralie A, Fatemi S, Salimi A. Experimental design on supercritical extraction of essential oil from valerian roots and study of
optimal conditions. Food Bioprod Proc 2010; 88: 312318.
Sagrero L, Bartley JP, Provis-Schwede A. Supercritical fluid extraction of the volatile constituents from tamarind (Tamarindus
indica L.). J Essent Oil Res 1994; 6: 547548.
Sagrero-Nieves L, Bartley JP, Provis-Schwede A. Supercritical fluid
extraction of the volatile components from the leaves of psidium
guajava l. (guava). Flavour Fragr J 1994; 9: 135137.
Sahena F, Zaidul ISM, Jinap S, Karim AA, Abbas KA, Norulaini
NAN, Omar AKM. Application of supercritical CO2 in lipid
extraction A review. J Food Eng 2009; 95: 240253.
Saito M, Yamauchi Y, Inomata K, Kottkamp W. Enrichment of
tocopherols in wheat-germ by directly coupled supercritical fluid
extraction with semipreparative supercritical fluid chromatography. J Chromatogr Sci 1989; 27: 7985.
Saito N, Ikushima Y, Hatakeda K, Ito S, Goto T. Fractional extraction
of rice bran oil and their ester with supercritical carbon-dioxide.
Nippon Nogeik Kaishi-J Jap Soc Biosci Biotechnol Agrochem
1991; 65: 153161.

Authenticated
148
Sajfrtova M, Sovova H, Opletal L, Bartlova M. Near-critical extraction of -sitosterol and scopoletin from stinging nettle roots.
Sajfrtova M, Lickova I, Wimmerova M, Sovova H, Wimmer Z.
-sitosterol: supercritical carbon dioxide extraction from sea
buckthorn (Hippophae rhamnoides L.) seeds. Int J Mol Sci 2010;
11: 18421850.
Sakaki K, Yokochi T, Suzuki O, Hakuta T. Supercritical fluid extraction of fungal oil using CO2, N2O, CHF3 and SF6. J Am Oil Chem
Soc 1990; 67: 553557.
Saldana MDA, Mohamed RS, Baer MG, Mazzafera P. Extraction of
purine alkaloids from mat (Ilex paraguariensis) using supercritical CO2. J Agric Food Chem 1999; 47: 38043808.
Saldana MDA, Mohamed RS, Mazzafera P. Supercritical carbon
dioxide extraction of methylxanthines from mat tea leaves. Braz
J Chem Eng 2000a; 17: 251259.
Saldana MDA, Zetzl C, Mohamed RS, Brunner G. The extraction
of methylxanthines from natural products in a microextraction
column using supercritical CO2 and ethanol. Proc. 7th Meeting
on Supercritical Fluids/2, Antibes/Juan-les-Pins, France, 2000b:
787792.
Saldana MDA, Zetzl C, Mohamed RS, Brunner G. Extraction of
methylxanthines from guaran seeds, mat tea leaves and sosoa
nibs in a microextraction column using supercritical CO2. Proc.
7th Meeting on Supercritical Fluids/2, Antibes/Juan-les-Pins,
France, 2000c: 793798.
Saldana MDA, Mohamed RS, Mazzafera P. Extraction of cocoa butter from Brazilian cocoa beans using supercritical CO2 and ethane. Fluid Phase Equilib 2002a; 194: 885894.
Saldana MDA, Zetzl C, Mohamed RS, Brunner G. Extraction of
methylxanthines from guaran seeds, mat leaves, and cocoa
beans using supercritical carbon dioxide and ethanol. J Agric
Food Chem 2002b; 50: 48204826.
Saldana MDA, Zetzl C, Mohamed RS, Brunner G. Decaffeination of
guaran seeds in a microextraction column using water-saturated
CO2. J Supercrit Fluids 2002c; 22: 119127.
Salgin U. Extraction of jojoba seed oil using supercritical CO2+ethanol
mixture in green and high-tech separation process. J Supercrit
Fluids 2007; 39: 330337.
Salgin S, Salgin U. Supercritical fluid extraction of walnut kernel oil.
Eur J Lipid Sci Technol 2006; 108: 577582.
Salgin U, Calimli A, Uysal BZ. Supercritical fluid extraction of
jojoba oil. J Am Oil Chem Soc 2004; 81: 293296.
Salgin U, Doker O, Calimli A. Extraction of sunflower oil with
supercritical CO2: experiments and modeling. J Supercrit Fluids
2006; 38: 326331.
Salimi A, Fatemi S, Nei HZN, Safaralie A. Mathematical modeling
of supercritical extraction of valerenic acid from Valeriana officinalis L. Chem Eng Technol 2008; 31: 14701480.
Sanagi MM, Ahmad UK, Smith RM. Application of supercritical
fluid extraction and chromatography to the analysis of turmeric.
J Chromatogr Sci 1993; 31: 2025.
Sanagi MM, Hung WP, Yasir SM. Supercritical fluid extraction of
pyrazines in roasted cocoa beans effect of pod storage period.
J Chromatogr A 1997; 785: 361367.
Sanal IS, Guvenc A, Salgin U, Mehmetoglu U, Calimli A. Recycling
of apricot pomace by supercritical CO2 extraction. J Supercrit
Fluids 2004; 32: 221230.
Sanal IS, Bayraktar E, Mehmetoglu U, Calimli A. Determination
of optimum conditions for SC-(CO2+ethanol) extraction of
-carotene from apricot pomace using response surface methodology. J Supercrit Fluids 2005; 34: 331338.
Sandoval R, Wilczek-Vera G, Vera JH. Prediction of ternary vaporliquid equilibria with the PRSV equation of state. Fluid Phase
Equilib 1989; 52: 119126.
Santerre CR, Goodrum JW, Kee JM. Roasted peanuts and peanut
butter quality are affected by supercritical fluid extraction. J Food
Sci 1994; 59: 382386.
Santoyo S, Cavero S, Jaime L, Ibanez E, Senorans FJ, Reglero G.
Chemical composition and antimicrobial activity of Rosmarinus
officinalis L. essential oil obtained via supercritical fluid extraction. J Food Protect 2005; 68: 790795.
Santoyo S, Cavero S, Jaime L, Ibanez E, Senorans FJ, Reglero G.
Supercritical carbon dioxide extraction of compounds with
antimicrobial activity from Origanum vulgare L.: determination of optimal extraction parameters. J Food Protect 2006a; 69:
369375.
Santoyo S, Lloria R, Jaime L, Ibanez E, Senorans FJ, Reglero G.
Supercritical fluid extraction of antioxidant and antimicrobial
compounds from Laurus nobilis L. Chemical and functional
characterization. Eur Food Res Technol Protect 2006b; 222:
565571.
Sargenti SR, Lancas FM. Supercritical fluid extraction of Cymbopogon
citratus (DC.) Stapf. Chromatographia 1997a; 46: 285290.
Sargenti SR, Lancas FM. Supercritical fluid extraction of Peumus
boldus (Molina). HRC-J High Res Chromatogr 1997b; 20:
511515.
Sargenti SR, Lancas FM. Influence of extraction mode and temperature in the supercritical fluid extraction of Citrus sinensis
(Osbeck). J Chromatogr Sci 1998a; 36: 169174.
Sargenti SR, Lancas FM. Influence of the extraction mode and temperature in the supercritical fluid extraction of Tangor murcote
(Blanco)Citrus sinensis (Osbeck). J Microcolumn Sep 1998b;
10: 213.
Sarkozi A, Then M, Illes V, Szentmihalyi K. Comparative study in
the supercritical fluid and microwave extraction of greater celandine (Chelidonium majus L.) Proc. 7th Meeting on Supercritical
Fluids/2, Antibes/Juan-les-Pins, France, 2000: 687692.
Sarmento CMP, Ferreira SRS, Hense H. Supercritical fluid extraction (SFE) of rice bran oil to obtain fractions enriched with
tocopherols and tocotrienols. Braz J Chem Eng 2006; 23:
243249.
Sarrazin C, Le Quere JL, Gretsch C, Liardon R. Representativeness
of coffee aroma extracts. Food Chem 2000; 70: 99106.
Sass-Kiss A, Simandi B, Gao YX, Boross F, Vamos-Falusi Z. Study
on the pilot-scale extraction of onion oleoresin using supercritical CO2. J Sci Food Agric 1998; 76: 320326.
Sastry SVGK, Mukhopadhyay M. Substrate hindrance in supercritical extraction of fragrance from jasmine flowers. Proc. 3rd Int
Symp Supercrit Fluids/2, Strasbourg, France, 1994: 341348.
Sato K, Sasaki SS, Goda Y, Yamada T, Nunomura O, Ishikawa K,
Maitani T. Direct connection of supercritical fluid extraction and
supercritical fluid chromatography as a rapid quantitative method
for capsaicinoids in placentas of Capsicum. J Agric Food Chem
1999; 47: 46654668.
Scalia S, Giuffreda L, Pallado P. Analytical and preparative supercritical fluid extraction of Chamomile flowers and its comparison with conventional methods. J Pharmaceut Biomed 1999; 21:
549558.
Schaeffer ST, Zalkow LH, Teja AS. Supercritical extraction of crotalaria spectabilis in the cross-over region. AICHE J 1988; 34:
17401742.
Schaeffer ST, Zalkow LH, Teja AS. Supercritical fluid isolation of
monocrotaline from Crotalaria spectabilis using ion-exchange
resins. Ind Eng Chem Res 1989a; 28: 10171020.

Authenticated
Schaeffer ST, Zalkow LH, Teja AS. Extraction of monocrotaline

from Crotalaria spectabilis using supercritical carbon dioxide
and carbon dioxide-ethanol mixtures. Biotechnol Bioeng 1989a;
34: 13571365.
Schmitt WJ, Reid RC. The Influence of the solvent gas on solubility and selectivity in supercritical extraction. In: Penninger JML,
Radosz M, McHugh M, Krukonis VJ, editors. Supercritical fluid
technology. Amsterdam: Elsevier, 1985: 123154.
Schmitt WJ, Reid RC. Solubility of monofunctional organic solids in
chemically diverse supercritical fluids. J Chem Eng Data 1986;
31: 204212.
Schneider C, Breitmaier E, Bayma JD, de Franca JF, Kneifel H,
Krebs HC. Maravuic acid, a new seco-labdane diterpene from
Croton matourensis. Liebigs Ann 1995; 4: 709710.
Schwartzentruber J, Renon H. Development of a new cubic equation
of state for phase equilibrium calculations. Fluid Phase Equilib
1989a; 52: 127134.
Schwartzentruber J, Renon H. Extension of UNIFAC to high pressures and temperatures by the use of a cubic equation of state. Ind
Eng Chem Res 1989b; 28: 10491055.
Scurto AM, Xu G, Brennecke JF, Stadtherr MA. Phase behavior and
reliable computation of high-pressure solid-fluid equilibrium
with cosolvents. Ind Eng Chem Res 2003; 42: 64646475.
Sedlakova J, Kocourkova B, Lojkova L, Kuban V. Determination
of essential oil content in caraway (Carum carvi L.) species by
means of supercritical fluid extraction. Plant Soil Environ 2003a;
49: 277282.
Sedlakova J, Lojkova L, Kuban V. Gas chromatographic determination of monoterpenes in spruce needles (Picea abies, P-omorica,
and P-pungens) after supercritical fluid extraction. Chem Pap
2003b; 57: 359363.
Seger C, Rompp H, Sturm S, Haslinger E, Schmidt PC, Hadacek F.
Characterization of supercritical fluid extracts of St. Johns Wort
(Hypericum perforatum L.) by HPLC-MS and GC-MS. Eur J
Pharm Sci 2004; 21: 453463.
Semiond D, Dautraix S, Desage M, Majdalani R, Casabianca H,
Brazier JL. Identification and isotopic analysis of safranal from
supercritical fluid extraction and alcoholic extracts of saffron.
Anal Lett 1996; 29: 10271039.
Senatore F, Rigano D, De Fusco R, Bruno M. Composition of the
essential oil from flowerheads of Chrysanthemum coronarium
L.(Asteraceae) growing wild in Southern Italy. Flavour Fragr J
2004; 19: 149152.
Senich VJ, Shishkov GE, Poliakov AF. Sostav uglekislotnogo ekstrakta
mjaty perechnoj. Izv VUZ Pishch Tekh 1974 (4): 8587.
Senorans FJ, Ibanez E, Cavero S, Tabera J, Reglero G. Liquid
chromatographicmass spectrometric analysis of supercriticalfluid extracts of rosemary plants. J Chromatogr A 2000; 870:
491499.
Sensidoni A, Bortolussi G, Orlando C, Lognay G, Santi R, Fantozzi
P. Borage oil (Borago officinalis L) an important source of
gamma-linolenic acid. Note 1 compositive characteristics and
oxidative stability of oils extracted by different techniques and
mixed with extra-virgin olive oil. Ind Aliment Italy 1994; 33:
11211127.
Seo JS, Burri BJ, Quan ZJ, Neidlingen TR. Extraction and chromatography of carotenoids from pumpkin. J Chromatogr A 2005;
1073: 371375.
Sewram V, Raynor MW, Raidoo DM, Mulholland DA. Coupling SFE
to uterotonic bioassay: an on-line approach to analysing medicinal plants. J Pharm Biomed Anal 1998; 18: 305318.
Sewram V, Raynor MW, Mulholland DA, Raidoo DM. The uterotonic activity of compounds isolated from the supercritical fluid
149
extract of Ekebergia capensis. J Pharm Biomed Anal 2000; 24:

133145.
Sewram V, Raynor MW, Mulholland DA, Raidoo DM. Supercritical
fluid extraction and analysis of compounds from Clivia miniata
for uterotonic activity. Planta Med 2001; 67: 451455.
Shaftan EA, Mikhailova NS, Pekhov AV, Dyubankova NF.
Sravnitelnoe izuchenie khladonovogo i uglekislotnogo ekstraktov
iz vozdushno-sukhogo zhoma plodov Hippophae Rhamnoides L.
kavkazskogo i sibirskogo proiskhozhdenia. Rast Resursy 1986;
22: 6066.
Shalmashi A, Golmohammad F, Eikani MH. Subcritical water extraction of caffeine from black tea leaf of Iran. J Food Process Eng
2008; 31: 330338.
Shao P, Sun P, Ying Y. Response surface optimization of wheat germ
oil yield by supercritical carbon dioxide extraction. Food Bioprod
Proc 2008; 86: 227231.
Sharpe FR, Crabb D. Pilot-plant extraction of hops with liquid carbon-dioxide and the use of these extracts in pilot and production
scale brewing. J Inst Brewing 1980; 86: 6064.
Sharpe FR, Grimmet CM, Laws DRJ, Bett G. Preparation of hop
extracts rich in particular constituents. J Inst Brewing 1980; 86:
234241.
Shen Z, Palmer MV, Ting SST, Fairclough RJ. Pilot scale extraction
of rice bran oil with dense carbon dioxide. J Agric Food Chem
1996; 44: 30333039.
Shen ZP, Palmer MV, Ting SST, Fairclough RJ. Pilot scale extraction and fractionation of rice bran oil using supercritical carbon
dioxide. J Agric Food Chem 1997; 45: 45404544.
Sheng J, Chen PC, Chen YP, Wong DSH. Calculations of solubilities
of aromatic compounds in supercritical carbon dioxide. Ind Eng
Chem Res 1992; 31: 967973.
Shobha SV, Ravindranath B. Supercritical carbon dioxide and solvent extraction of the phenolic lipids of cashew nut (Anacardium
occidentale) shells. J Agric Food Chem 1991; 39: 22142217.
Shohet D, Wills RBH. Characteristics of extracted valerenic acids
from valerian (Valeriana Officinalis) root by supercritical fluid
extraction using carbon dioxide. Int J Food Properties 2006; 9:
325329.
Shu XS, Gao ZH, Yang XL. Supercritical fluid extraction of sapogenins from tubers of Smilax china. Fitoterapia 2004; 75: 656661.
Sievers U. Energy optimization of supercritical fluid extraction processes with separation at supercritical pressure. Chem Eng Proc
1998; 37: 451460.
Sihvonen M, Jarvenpaa E, Hietaniemi V, Huopalahti R. Advances
in supercritical carbon dioxide technologies. Trends Food Sci
Technol 1999; 10: 217222.
Silva GF, Vasconcellos VR, Cabral FA. Optimization of a system
for extraction of annatto pigments with supercritical carbon dioxide. Proc. 6th Meeting on Supercritical Fluids, Nottingham, UK,
1999: 631636.
Silva CF, Mendes MF, Pessoa FLP, Queiroz EM. Supercritical carbon
dioxide extraction of macadamia (Macadamia integrifolia) nut oil:
experiments and modeling. Braz J Chem Eng 2008a; 25: 175181.
Silva GF, Gamarra FMC, Oliveira AL, Cabral FA. Extraction of
bixin from annatto seeds using supercritical carbon dioxide. Braz
J Chem Eng 2008b; 25: 419426.
Silva DCMN, Bresciani LFV, Dalagnol RL, Danielski L, Yunes RA,
Ferreira SRS. Supercritical fluid extraction of carqueja (Baccharis
trimera) oil: process parameters and composition profiles. Food
Bioprod Proc 2009; 87: 317326.
Simandi B, Kery A, Lemberkovics E, Oszagyan M, Hethely E.
Supercritical fluid extraction of essential oils from Mentha piperita and Lavandula intermedia. Planta Med 1993; 59: A626.

Authenticated
Simandi B, Oszagyan M, Lemberkovics E, Petri G, Kery A, Feejes

S. Comparison of the volatile composition of chervil oil obtained
by hydrodistillation and supercritical fluid extraction. J Essent
Oil Res 1996; 8: 305306.
Simandi B, Oszagyan M, Lemberkovics E, Kery A, Kaszacs J,
Thyrion F, Matyas T. Supercritical carbon dioxide extraction
and fractionation of oregano oleoresin. Food Res Int 1998; 31:
723728.
Simandi B, Deak A, Ronyai E, Gao YX, Veress T, Lemberkovics
E, Then M. Supercritical carbon dioxide extraction and fractionation of fennel oil. J Agric Food Chem 1999; 47: 16351640.
Simandi B, Sass-Kiss A, Czukor B, Deak A, Prechl A, Csordas A,
Sawinsky J. Pilot-scale extraction and fractional separation of
onion oleoresin using supercritical carbon dioxide. J Food Eng
2000; 46: 183188.
Simandi B, Hajdu V, Peredi K, Czukor B, Nobik-Kovacs A, Kery
A. Antioxidant activity of pilot-plant alcoholic and supercritical
carbon dioxide extracts of thyme. Eur J Lipid Sci Technol 2001;
103: 355358.
Simandi B, Kristo ST, Key A, Selmeczi LK, Kmecz I, Kemeny S.
Supercritical fluid extraction of dandelion leaves. J Supercrit
Fluids 2002; 23: 135142.
Skerget M, Knez Z. Modelling high pressure extraction processes.
Comp Chem Eng 2001; 20: 879886.
Skerget M, Knez Z, Habulin M. Solubility of -carotene and oleic
acid in dense CO2 and data correlation by a density based model.
Skerget M, Knez Z, Novak Z, Bauman D. Separation of paprika components using dense CO2. Acta Alimentaria 1998; 27: 149160.
Skerget M, Knez Z, Hadolin M, Hedorez SS. Phase equilibria and
extraction of vitamin E rich oil from Silybum marianum using
dense CO2 and propane. Proc. 7th Meeting on Supercritical
Fluids/2, Antibes/Juan-les-Pins, France, 2000: 593598.
Skerget M, Bezjak M, Makovsek K, Knez Z. Extraction of lutein
diesters from Tagetes erecta using supercritical CO2 and liquid
propane. Acta Chim Sloven 2010; 57: 6065.
Skerget M, Knez Z, Knez-Hrncic M. Solubility of solids in suband supercritical fluids: a review. J Chem Eng Data 2011; 56:
694719.
Skjold-Jorgensen S. Group contribution equation of state (GC-EOS):
a predictive method for phase equilibrium computations over
wide ranges of temperature and pressures up to 30 MPa. Ind Eng
Chem Res 1988; 27: 110118.
Slanina J, Taborska E, Lojkova L. Lignans in the seeds and fruits of
Schisandra chinensis cultured in Europe. Planta Med 1997; 63:
277280.
Smelcerovic A, Lepojevic Z, Djordjevic S. Sub-and supercritical
CO2-extraction of Hypericum perforatum L. Chem Eng Technol
2004; 27: 13271329.
Smith RM. Supercritical fluids in separation science the dreams,
the reality and the future. J Chromatogr A 1999; 856: 83115.
Smith RM. Extractions with superheated water. J Chromatogr A
2002; 975: 3146.
Smith RM, Burford MD. Supercritical fluid extraction and gas chromatographic determination of the sesquiterpene lactone parthenolide in the medicinal herb feverfew (Tanacetum parthenium).
J Chromatogr 1992; 627: 255261.
Smith RM, Burford MD. GLC of subvertically fluid extracts of essential oils from the medicinal herbs, feverfew, tansy, and German
chamomile. J Chromatogr Sci 1994; 32: 265269.
Smith RL, Malaluan RM, Setianto WB, Inomata H, Arai K. Separation
of cashew (Anacardium occidentale L.) nut shell liquid with
supercritical carbon dioxide. Biores Technol 2003; 88: 17.
Snyder JM, Friedrich JP, Christianson DD. Effect of moisture and

particle size on the extractability of oils from seeds with supercritical CO2. J Am Oil Chem Soc 1984; 61: 18511856.
Soave G. Equilibrium constants from a modified Redlich-Kwong
equation of state. Chem Eng Sci 1972; 27: 11971203.
Sokolova M, Orav A, Koel M, Kailas T, Muurisepp M. Composition
of the oil and supercritical fluid CO2 extract of sweet gale (Myrica
gale L.) fruits. J Essent Oil Res 2005; 17: 188191.
Song KM, Park SW, Hong WH, Lee H, Kwak SS, Liu JR. Isolation
of vindoline from Catharanthus roseus by supercritical fluid
extraction. Biotechnol Progr 1992; 8: 583586.
Sonsuzer S, Sahin S, Yilmaz L. Optimization of supercritical CO2
extraction of Thymbra spicata oil. J Supercrit Fluids 2004; 30:
189199.
Soto C, Conde E, Moure A, Zuniga ME, Dominguez H. Supercritical
extraction of borage seed oil coupled to conventional solvent
extraction of antioxidants. Eur J Lipid Sci Technol 2008; 110:
10351044.
Sousa EMBD, Chiavone O, Moreno MT, Silva DN, Marques MOM,
Meireles MAA. Experimental results for the extraction of essential oil from Lippia sidoides cham. Using pressurized carbon
dioxide. Braz J Chem Eng 2002; 19: 229241.
Sousa EMBD, Martinez J, Chiavone O, Rosa PTV, Domingos T,
Meireles MAA. Extraction of volatile oil from Pax et Hoff with
pressurized CO: solubility, composition and kinetics. J Food Eng
2005; 69: 325333.
Sovova H. Rate of the vegetable oil extraction with supercritical CO2I.
Modelling of extraction curves. Chem Eng Sci 1994; 49: 409414.
Sovova H. Mathematical model for supercritical fluid extraction
of natural products and extraction curve evaluation. J Supercrit
Fluids 2005; 33: 3552.
Sovova H, Kucera J, Jez J. Rate of the vegetable oil extraction with
supercritical CO2II. Extraction of grape oil. Chem Eng Sci
1994a; 49: 415420.
Sovova H, Komers R, Kucera J, Jez J. Supercritical carbon dioxide
extraction of caraway essential oil. Chem Eng Sci 1994b; 49:
24992505.
Sovova H, Jez J, Bartlova M, Stastova J. Supercritical carbon dioxide
extraction of black pepper. J Supercrit Fluids 1995; 8: 295301.
Sovova H, Stateva RP, Galushko A. Solubility of -carotene in supercritical CO2 and the effect of entrainers. J Supercrit Fluids 2001a;
21: 195203.
Sovova H, Stateva RP, Galushko AA. Essential oils from seeds: solubility of limonene in supercritical CO2 and how it is affected by
fatty oil. J Supercrit Fluids 2001b; 20: 113129.
Sovova H, Sajfrtova M, Bartlova M, Opletal L. Near-critical extraction of pigments and oleoresin from stinging nettle leaves.
Sovova H, Stateva RP, Galushko A. High-pressure equilibrium of
menthol+CO2. J Supercrit Fluids 2007a; 41: 19.
Sovova H, Opletal L, Bartlova M, Sajfrtova M, Krenkova M.
Supercritical fluid extraction of lignans and cinnamic acid from
Schisandra chinensis. J Supercrit Fluids 2007b; 42: 8895.
Sovova H, Opletal L, Sajfrtova M, Bartlova M. Supercritical fluid
extraction of cynaropicrin and 20-hydroxyecdysone from Leuzea
carthamoides DC. J Sep Sci 2008; 31: 13871392.
Sovova H, Galushko AA, Stateva RP, Rochova K, Sajfrtova M,
Bartlova M. Supercritical fluid extraction of minor components of vegetable oils: -sitosterol. J Food Eng 2010; 101:
201209.
Spanos GA, Chen H, Schwartz SJ. Supercritical CO2 extraction of -carotene from sweet potatoes. J Food Sci 1993; 58:
817820.

Authenticated
Sparks D, Hernandez R, Zappi M, Blackwell D, Fleming T. Extraction

of rice brain oil using supercritical carbon dioxide and propane.
J Am Oil Chem Soc 2006; 83: 885891.
Spiliotis N, Magoulas K, Tassios DP. Prediction of the solubility of
aromatic hydrocarbons in supercritical CO2 with EoSGE models.
Spricigo CB, Pinto LT, Bolzan A, Novais AF. Extraction of essential
oil and lipids from nutmeg by liquid carbon dioxide. J Supercrit
Fluids 1999; 15: 253259.
Spricigo CB, Bolzan A, Pinto LT. Mathematical modeling of nutmeg
essential oil extraction by liquid carbon dioxide. Lat Am Appl
Res 2001; 31: 397401.
Srinivasan MP, Smith JM, McCoy BJ. Supercritical fluid desorption
from activated carbon. Chem Eng Sci 1990; 45: 18851895.
Stahl E, Schutz E. Extraktion der Kamillenblten mit berkritischen
Gasen. Arch Pharm (Weinheim) 1978; 311: 9921001.
Stahl E, Willing E. Extraktion labiler Naturstoffe mit berkritischen
Gasen. 5. Mitt.: Prparative Gasextraktion von Thebain
aus Papaver bracteatum Lindl. Pharm Ind 1980; 42: 1136
1139.
Stahl E, Schutz E. Extraction of labile natural substances using
supercritical gases. 4. Extraction of valepotriates from Valerianawallichii. Planta Med 1980a; 40: 262270.
Stahl E, Schutz E. Extraction of natural compounds with supercritical gases. 3. Pyrethrum extracts with liquefied and supercritical
carbon-dioxide. Planta Med 1980b; 40: 1221.
Stahl E, Gerard D. Hochdruck-Extraktion von Naturstoffen mit berkritischen und verflssigten Gasen 9. Mitteilung: Verfahren zur
schonenden Gewinnung etherischen le. Parfum Kosmet 1982a;
63: 117125.
Stahl E, Gerard D. Entgiftung von Absinthkraut durch CO2Hochdruckextraktion. Planta Med 1982b; 45: 147147.
Stahl E, Gerard D. Hochdruck-Extraktion von Naturstoffen mit berkritischen und verflssigten Gasen. Z Lebensm Unters Forsch
1983; 176: 14.
Stahl E, Keller K. Extraktion labiler Naturstoffe mit berkritischen
Gasen. Planta Med 1983; 47: 7578.
Stahl E, Schutz E, Mangold H. Extraction of seed oils with liquid
and supercritical carbon dioxide. J Agric Food Chem 1980; 28:
11531157.
Stahl E, Quirin KW, Mangold HK. Extraktion von Lupinenl mit
berkritischem Kohlendioxid. Fette Seifen Anstrichmittel 1981;
83: 472474.
Stahl E, Quirin K, Blagrove R. Extraction of seed oils with supercritical carbon dioxide: effect on residual proteins. J Agric Food
Chem 1984; 32: 938940.
Stahl E, Quirin KW, Gerard D. Verdichtete Gase zur Extraktion und
Raffination. Berlin: Springer-Verlag, 1987. [Dense Gases for
Extraction and Refining. Berlin: Springer-Verlag, 1988.].
Stamenic M, Zizovic I, Orlovic A, Skala D. Mathematical modelling
of essential oil SFE on the micro-scale classification of plant
material. J Supercrit Fluids 2008; 46: 285292.
Starmans DAJ, Nijhuis HH. Extraction of secondary metabolites
from plant material: a review. Trends Food Sci Technol 1996;
7: 191197.
Stashenko EE, Prada NQ, Martinez JR. HRGC/FID/NPD and
HRGGC/MSD study of Colombian ylang-ylang (Cananga odorata) oils obtained by different extraction techniques. HRC-J
High Res Chromatogr 1996a; 19: 353358.
Stashenko EE, Puertas MA, Combariza MY. Volatile secondary
metabolites from Spilanthes americana obtained by simultaneous steam distillation-solvent extraction and supercritical fluid
extraction. J Chroma A 1996b; 752: 223232.
151
Stashenko EE, Acosta R, Martinez JR. High-resolution gas-chromatographic analysis of the secondary metabolites obtained by
subcritical-fluid extraction from Colombian rue (Ruta graveolens
L.). J Biochem Biophys Meth 2000; 43: 379390.
Stashenko EE, Jaramillo BE, Martinez JR. Comparison of different
extraction methods for the analysis of volatile secondary metabolites of Lippia alba (Mill.) N.E. Brown, grown in Colombia,
and evaluation of its in vitro antioxidant activity. J Chromatogr A
2004; 1025: 93103.
Stastova J, Jez J, Bartlova M, Sovova H. Rate of the vegetable oil
extraction with supercritical CO2III. Extraction from sea buckthorn. Chem Eng Sci 1996; 51: 43474352.
Stavroulias S, Panayioutou C. Determination of optimum conditions
for the extraction of squalene from olive pomace with supercritical CO2. Chem Biochem Eng Q 2005; 19: 373381.
Steffani E, Atti-Santos AC, Atti-Serafini L, Pinto LT. Extraction of hosho (Cinnamomum camphora nees and eberm var. Linaloolifera
fujita) essential oil with supercritical CO2: experiments and modeling. Braz J Chem Eng 2006; 23: 259266.
Steiner R, Tratz W, Brattstrom A, Debrunner B. Proc. 5th Meeting on
Stojanovic G, Palic R, Alagic S, Zekovic Z. Chemical composition
and antimicrobial activity of the essential oil and CO2 extracts
of semi-oriental tobacco, Otlja. Flavour Fragr J 2000; 15:
335338.
Stuber F, Vazquez AM, Larrayoz MA, Recasens F. Supercritical
fluid extraction of packed beds: external mass transfer in
upflow and downflow operation. Ind Eng Chem Res 1996; 35:
36183628.
Subra P, Castellani S, Garrabos Y. Supercritical carbon dioxide
extraction of carotenoids from carrots. Proc. 3rd Int Symp
Supercrit Fluids/2, Strasbourg, France, 1994: 447452.
Subra P, Castellani S, Jestin P, Aoufi A. Extraction of -carotene with
supercritical fluids. J Supercrit Fluids 1998; 12: 261269.
Sugiyama K, Saito M. Simple microscale supercritical fluid extraction system and its application to gas chromatography-mass spectrometry of lemon peel oil. J Chromatogr 1988; 442: 121131.
Sugiyama K, Saito M, Hondo T, Senda M. New double-stage
separation analysis method: directly coupled laboratory-scale
supercritical fluid extraction supercritical fluid chromatography, monitored with a multiwavelength ultraviolet detector.
J Chromatogr 1985; 332: 107116.
Sun L, Temelli F. Supercritical carbon dioxide extraction of carotenoids from carrot using canola oil as a continuous co-solvent.
Sun L, Rezaei KA, Temelli F, Ooraikul B. Supercritical fluid extraction of alkylamides from Echinacea angustifolia. J Agric Food
Chem 2002; 50: 39473953.
Sun Y, Li S, Song H, Tian S. Extraction of ferulic acid from
Angelica sinensis with supercritical CO2. Nat Prod Res 2006; 20:
835841.
Sun M, Xu L, Saldana MDA, Temelli F. Comparison of canola
meals obtained with conventional methods and supercritical
CO2 with and without ethanol. J Am Oil Chem Soc 2008; 85:
667675.
Suo YR, Wang LY. Extraction of Nitraria tangutorum seed lipid
using different extraction methods and analysis of its fatty acids
by HPLC fluorescence detection and on-line MS identification.
Eur J Lipid Sci Technol 2010; 112: 390399.
Suto K, Ito Y, Sagara K, Itokawa H. Determination of magnolol and
honokiol in Magnoliae Cortex using supercritical fluid chromatography on-line coupled with supercritical fluid extraction by
on-column trapping. J Chromatogr A 1997; 786: 366370.

Authenticated
Swift DA, Kallis SG, Longmore RB, Smith TN, Trengrove RD.
Supercritical carbon dioxide extraction of oils from Camellia sinensis. Proc 3rd Int Symp Supercrit Fluids/2, Strasbourg, France,
1994: 487490.
Szentmihalyi K, Then M, Illes V, Perneczky S, Sandor Z, Lakatos B,
Vinkler P. Phytochemical examination of oils obtained from the
fruit of mille thistle (Silybum marianum L. Gaertner) by supercritical fluid extraction. Z Naturforsch C 1998; 53: 779784.
Szentmihalyi K, Vinkler P, Lakatos B, Illes V, Then M. Rose hip
(Rosa canina L.) oil obtained from waste hip seeds by different
extraction methods. Biores Technol 2002; 82: 195201.
Takahashi M, Watanabe H, Kikkawa J, Ota M, Watanabe M, Sato Y,
Inomata H, Sato N. Carotenoids extraction from Japanese persimmon (hachiya-kaki) peels by supercritical CO2 with ethanol.
Anal Sci 2006; 22: 14411447.
Takeuchi TM, Leal PF, Favareto R, Cardozo-Filho L, Corazza ML,
Rosa PTV, Meireles MAA. Study of the phase equilibrium formed
inside the flash tank used at the separation step of a supercritical
fluid extraction unit. J Supercrit Fluids 2008; 43: 447459.
Talansier E, Braga MEM, Rosa PTV, Paolucci-Jeanjean D, Meireles
MAA. Supercritical fluid extraction of vetiver roots: a study of
SFE kinetics. J Supercrit Fluids 2008; 47: 200208.
Tan CS, Liou DC. Axial dispersion of supercritical carbon dioxide in
packed beds. Ind Eng Chem Res 1989; 28: 12461250.
Tan CS, Liang SK, Liou DC. Fluidsolid mass transfer in a supercritical fluid extractor. Chem Eng J 1988; 38: 1722.
Taniguchi M, Tsuji T, Shibata M, Kobayashi T. Extraction of oils
from wheat germ with supercritical carbon dioxide. Agr Biol
Chem Tokyo 1985; 49: 23672372.
Tapia T, Perich F, Pardo F, Palma G, Quiroz A. Identification of
volatiles from differently aged red clover (Trifolium pratense)
root extracts and behavioural responses of clover root borer
(Hylastinus obscurus) (Marsham) (Coleoptera: Scolytidae) to
them. Biochem Syst Ecol 2007; 35: 6167.
Taylor SL, King JW. Optimization of the extraction and fractionation
of corn bran oil using analytical supercritical fluid instrumentation. J Chrom Sci 2000; 38: 9194.
Taylor SL, King JW. Preparative-scale supercritical fluid extraction/
supercritical fluid chromatography of corn bran. J Am Oil Chem
Soc 2002; 79: 11331136.
Taylor SL, King JW, List GR. Determination of oil content in oilseeds by analytical supercritical fluid extraction. J Am Oil Chem.
Soc 1993; 70: 437439.
Taylor SL, Eller FJ, King JW. A comparison of oil and fat content
in oilseeds and ground beef using supercritical fluid extraction and related analytical techniques. Food Res Int 1997; 30:
365370.
Taylor SL, King JW, Montanari L, Fantozzi P, Blanco MA.
Enrichment and fractionation of phospholipid concentrates by
supercritical fluid extraction and chromatography. Ital J Food Sci
2000; 12: 6576.
Temelli F. Extraction of triglycerides and phospholipids from canola
with supercritical carbon dioxide and ethanol. J Food Sci 1992;
57: 440.
Temelli F. Perspectives on supercritical fluid processing of fats and
oils. J Supercrit Fluids 2009; 47: 583590.
Tena MT, Valcarcel M, Hidalgo PJ, Ubera JL. Supercritical fluid
extraction of natural antioxidants from rosemary: comparison
with liquid solvent sonication. Anal Chem 1997; 69: 521526.
Teng WY, Chen CC, Chung RS. HPLC comparison of supercritical
fluid extraction and solvent extraction of coumarins from the
peel of Citrus maxima fruit. Phytochem Anal 2005; 16: 459
462.
Tepic A, Zekovic Z, Kravic S, Kravic S, Mandic A. Pigment content

and fatty acid composition of paprika oleoresins obtained by conventional and supercritical carbon dioxide extraction. CYTA-J
Food 2009; 7: 95102.
Tezel A, Hortacsu A, Hortacsu O. Multi-component models for seed
and essential oil extractions. J Supercrit Fluids 2000; 19: 317.
Then M, Daood H, Illes V, Simandi B, Szentmihalyi K, Pernetczki
S, Bertalan L. Investigation of biologically active compounds
in plant oils extracted by different extraction methods. Proc.
5th Meeting on Supercritical Fluids/2, Nice, France, 1998:
555559.
Then M, Illes V, Daood H, Szentmihalyi K. Supercritical fluid,
Soxhlet and microwave extraction of poppy plant (Papaver somniferum L., Papaveraceae) and mixtures of poppy seed with different medicinal plant drugs. Proc. 7th Meeting on Supercritical
Fluids/2, Antibes/Juan-les-Pins, France, 2000a: 641648.
Then M, Szentmihalyi K, Sarkozi A, Illes V, Forgacz E. Effect of
sample handling on alkaloid and mineral content of aqueous
extracts of greater celandine (Chelidonium majus L.). J Chrom
A 2000b; 889: 6974.
Tochigi K, Iizumi T, Sekikawa H, Kurihara K, Kojima K. Highpressure vaporliquid and solidgas equilibria using a Peng
Robinson group contribution method. Ind Eng Chem Res 1998;
37: 37313740.
Tolic A, Zekovic Z, Pekic B. Dependence of camomile flower solubility on carbon dioxide density at supercritical extraction. Sep
Sci Technol 1996; 31: 18891892.
Tonthubthimthong P, Chuaprasert S, Douglas P, Luewisutthichat W.
Supercritical CO2 extraction of nimbin from neem seeds an
experimental study. J Food Eng 2001; 47: 289293.
Tonthubthimthong P, Douglas PL, Douglas S, Luewisutthichat W,
Teppaitoon W, Pengsopa L. Extraction of nimbin from neem
seeds using supercritical CO2 and a supercritical CO2 methanol
mixture. J Supercrit Fluids 2004; 30: 287301.
Topal U, Sasaki M, Goto M, Hayakawa K. Extraction of lycopene
from tomato skin with supercritical carbon dioxide: effect of
operating conditions and solubility analysis. J Agric Food Chem
2006; 54: 56045610.
Tozzi R, Mulinacci N, Storlikken K, Pasquali I, Vincieri FF, Bettini
R. Supercritical extraction of carotenoids from Rosa canina L.
hips and their formulation with -cyclodextrin. AAPS Pharm Sci
Tech 2008; 9: 693700.
Trassy L. Thermodynamics of petroleum fluids. Thesis, Universite
de la Mediterranee, 1998.
Tsuda T, Mizuno K, Oshima K, Kawakishi S, Osawa T. Supercritical
carbon dioxide extraction of antioxidative components from
tamarind (Tamarindus indica L.) seed coat. J Agric Food Chem
1995; 43: 28032806.
Tuan DQ, Ilangantileke SG. Liquid CO2 extraction of essential oil from
Star anise fruits (Illicium verum H.). J Food Eng 1997; 31: 4757.
Turkay S, Burford MD, Sangun MK, Ekinci E, Bartle KD, Clifford
AA. Deacidification of black cumin seed oil by selective supercritical carbon dioxide extraction. J Am Oil Chem Soc 1996; 73:
12651270.
Turner C, McKeon T. The use of immobilized Candida antarctica
lipase for simultaneous supercritical fluid extraction and in-situ
methanolysis of cis-vaccenic acid in milkweed seeds. J Am Oil
Chem Soc 2002; 79: 473478.
Turner C, King JW, Mathiasson L. Supercritical fluid extraction and
chromatography for fat-soluble vitamin analysis. J Chromatogr
A 2001; 936: 215237.
Turner C, Eskilsson CS, Bjorklund E. Collection in analytical-scale
supercritical fluid extraction. J Chromatogr A 2002; 947: 122.

Authenticated
Tzeng TC, Lin YL, Jong TT, Chang CMJ. Ethanol modified supercritical fluids extraction of scopoletin and artemisinin from
Artemisia annua L. Sep Purif Technol 2007; 56: 1824.
Uematsu H, Itoh J, Takeuchi M, Yonei Y. Selective separation of nicotine from tobacco with supercritical carbon dioxide. Proc. 3rd Int
Symp Supercrit Fluids/2, Strasbourg, France, 1994: 335339.
Ueno H, Tanaka M, Machmudah S, Sasaki M, Goto M. Supercritical
carbon dioxide extraction of valuable compounds from citrus
junos seed. Food Bioprocess Technol 2008; 1: 357363.
Uquiche E, del Valle JM, Ortiz J. Supercritical carbon dioxide extraction of red pepper (Capsicum annuum L.) oleoresin. J Food Eng
2004; 65: 5566.
Uquiche E, del Valle JM, Ihl M. Microstructure-extractability relationships in the extraction of prepelletized jalapeo peppers
with supercritical carbon dioxide. J Food Sci 2005; 70: E379
E386.
Vagi E, Simandi B, Daood HG, Deak A, Sawinsky J. Recovery of pigments from Origanum majorana L. by extraction with supercritical carbon dioxide. J Agric Food Chem 2002; 50: 22972301.
Vagi E, Simandi B, Suhajda A, Hethelyi E. Essential oil composition and antimicrobial activity of L. extracts obtained with ethyl
alcohol and supercritical carbon dioxide. Food Res Int 2005a;
38: 5157.
Vagi E, Rapavi E, Hadolin M, Peredi KV, Balazs A, Blazovics
A, Simandi B. Phenolic and triterpenoid antioxidants from
Origanum majorana L. herb and extracts obtained with different
solvents. J Agric Food Chem 2005b; 53: 1721.
Vagi E, Simandi B, Vasarhelyine KP, Daood H, Kery A, Doleschall F,
Nagy B. J. Supercritical carbon dioxide extraction of carotenoids,
tocopherols and sitosterols from industrial tomato by-products.
Valderrama JO. The state of the cubic equations of state. Ind Eng
Chem Res 2003; 42: 16031618.
Valderrama JO, Alvarez VH. Temperature independent mixing rules
to correlate the solubility of solids in supercritical carbon dioxide. J Supercrit Fluids 2004; 32: 3746.
Valderrama JO, Zavaleta J. Sublimation pressure calculated from
high-pressure gassolid equilibrium data using genetic algorithms. Ind Eng Chem Res 2005; 44: 48244833.
Valderrama JO, Gonzalez NA, Alvarez VH. Gas-solid equilibrium in
mixtures containing supercritical CO2 using a modified regular
solution model. Ind Eng Chem Res 2003; 42: 38573864.
Vandana V, Teja AS. Supercritical extraction of paclitaxel using
CO2 and CO2-ethanol mixtures. ACS Symp Series 1995; 608:
429443.
Vandana V, Teja AS, Zalkow LH. Supercritical extraction and HPLC
analysis of taxol from Taxus brevifolia using nitrous oxide and
nitrous oxide+ethanol mixtures. Fluid Phase Equilib 1996; 116:
162169.
Vargas RMF, Cassel E, Gomes GMF, Longhi LGS, Atti-Serafini
L, Atti-Santos AC. Supercritical extraction of carqueja essential oil: experiments and modeling. Braz J Chem Eng 2006; 23:
375382.
Vargas CE, Mendes MF, Azevedo DA, Pessoa FLP, Uller AC.
Extraction of the essential oil of abajeru (Chrysobalanus icaco)
using supercritical CO2. J Supercrit Fluids 2010; 54: 171177.
Vasapollo G, Longo L, Rescio L, Ciurlia L. Innovative supercritical
CO2 extraction of lycopene from tomato in the presence of vegetable oil as co-solvent. J Supercrit Fluids 2004; 29: 8796.
Vasudevan P, Tandon M, Pathak N, Nuennerich P, Mueller F, Mele
A, Lentz H. Fluid CO2 extraction and hydrodistillation of certain
biocidal essential oils and their constituents. J Sci Ind Res India
1997; 56: 662672.
153
Vaughn KLS, Clausen EC, King JW, Luke HR, Carrier DJ. Extraction
conditions affecting supercritical fluid extraction (SFE) of lycopene from watermelon. Biores Technol 2008; 99: 78357841.
Vedaraman N, Srinivasakannan C, Brunner G, Ramabrahmam BV,
Rao PG. Experimental and modeling studies on extraction of
cholesterol from cow brain using supercritical carbon dioxide.
Vega PJ, Balaban MO, Sims CA, OKeefe SF, Cornell JA. Supercritical
carbon dioxide extraction efficiency for carotenes from carrots
by RSM. J Food Sci 1996; 61: 757759.
Venskutonis PR, Skemaite M, Sivik B. Assessment of radical scavenging capacity of Agrimonia extracts isolated by supercritical
Verschuere M, Sandra P, David F. Fractionation by SFE and microcolumn analysis of the essential oil and the bitter principles of
hops. J Chromatogr Sci 1992; 30: 388391.
Vetere A. A short-cut method to predict the solubilities of solids in
supercritical carbon dioxide. Fluid Phase Equilib 1998; 148:
8393.
Viana LM, Freitas RL, Rodrigues SV, Baumann W. Extraction of
lapachol from Tabebuia avellanedae wood with supercritical
CO2: an alternative to Soxhlet extraction? Braz J Chem Eng
2003; 20: 317325.
Vidal JP, Richard H. Production of a black pepper oleoresin by dense
carbon-dioxide or carbon dioxide-ethanol extraction. Sci Aliment
1987; 7: 481498.
Vieira de Melo SAB, Vieira de Melo RLF, Costa GMN, Alves TLM.
Solubility of l-Dopa in supercritical carbon dioxide: prediction
using a cubic equation of state. J Supercrit Fluids 2005; 34:
231236.
Vilegas JHY, Lancas FM, Vilegas W, Pozetti GL. Off-line supercritical fluid extraction high resolution gas chromatography
applied to the study of moraceae species. Phytochem Anal 1993;
4: 230234.
Vilegas JHY, deMarchi E, Lancas FM. Extraction of low-polarity
compounds (with emphasis on coumarin and kaurenoic acid)
from Mikania glomerata (guaco) leaves. Phytochem Anal
1997; 8: 266270.
Vitzthum O, Hubert P. German Patent 21 27 611, 1971.
Vlase L, Olah N, Marculescu A. The study of tocopherols from different sea buckthorn and wheat germ extracts. Rev Chim-Bucharest
2006; 57: 320322.
Vollbrecht R. Extraction of hops with supercritical CO2. Chem Ind
1982; 19: 397399.
Voutsas EC, Boukouvalas C, Kalospiros N, Tassios D. The performance of EoS/GE models in the prediction of vapor-liquid equilibria in asymmetric systems. Fluid Phase Equilib 1996; 116:
480487.
Vuorela H, Holm Y, Hiltunen R, Harvala T, Laitinen A. Extraction
of the volatile oil in chamomile flowerheads using supercritical
carbon dioxide. Flavour Fragr J 1990; 5: 8184.
Wakao N, Funazkri T. Effect of fluid dispersion coefficients on particle-to-fluid mass transfer coefficients in packed beds correlation
of sherwood numbers. Chem Eng Sci 1978; 33: 13751384.
Wakao N, Kaguei S. Heat and mass transfer in packed beds. New
York: Gordon and Breach Sci, 1982.
Walker DFG, Bartle KD, Clifford AA. Determination of the oil content of rapeseed by supercritical fluid extraction. Analyst 1994a;
119: 14711474.
Walker DFG, Bartle KD, Breen DGPA, Clifford AA, Costiou S.
Quantitative method for the analysis of flavour and fragrance components from lavender and rosemary by studying the kinetics of their
supercritical fluid extraction. Analyst 1994b; 119: 27892793.

Authenticated
Walker TH, Cochran HD, Hulbert GJ. Supercritical carbon dioxide

extraction of lipids from Pythium irregulare. J Am Oil Chem Soc
1999; 76: 595602.
Walsh JM, Ikonomou GD, Donohue MD. Supercritical phase
behavior: the entrainer effect. Fluid Phase Equilib 1987; 33:
295314.
Wang L, Weller CL. Recent advances in extraction of nutraceuticals
from plants. Trends Food Sci Technol 2006; 17: 300312.
Wang HC, Chen CR, Chang CJ. Carbon dioxide extraction of ginseng
root hair oil and ginsenosides. Food Chem 2001; 72: 505509.
Wang X, Wang YQ, Yuan JP, Sun QL, Liu JH, Zheng CC. An efficient new method for extraction, separation and purification of
psoralen and isopsoralen from Fructus Psoraleae by supercritical
fluid extraction and high-speed counter-current chromatography.
J Chromatogr A 2004a; 1055: 135140.
Wang ZY, Ashraf-Khorassani M, Taylor LT. Air/light-free hyphenated extraction/analysis system: supercritical fluid extraction
on-line coupled with liquid chromatography-UV absorbance/
electrospray mass spectrometry for the determination of hyperforin and its degradation products inhypericum pertoratum. Anal
Chem 2004b; 76: 67716776.
Wang H, Suo Y, Wang X, Li Y, Yu J, Zhao X. Extraction of Nitraria
tangutorum seed oil by supercritical carbon dioxide and determination of free fatty acids by HPLC/APCI/MS with fluorescence
detection. Sep Purif Technol 2007; 56: 371377.
Wang CH, Chen CR, Wu JJ, Wang LY, Chang CMJ, Ho WJ.
Designing supercritical carbon dioxide extraction of rice bran
oil that contain oryzanols using response surface methodology.
J Sep Sci 2008a; 31: 13991407.
Wang L, Song Y, Cheng Y, Liu X. Orthogonal array design for the
optimization of supercritical fluid extraction of tanshinones from
Danshen. J Sep Sci 2008b; 31: 321328.
Wang L, Yang B, Du X, Yi C. Optimisation of supercritical fluid
extraction of flavonoids from Pueraria lobata. Food Chem 2008c;
108: 737741.
Wang MC, Lai YC, Chang CL. High throughput screening and antioxidant assay of dibenzo[a,c]cyclooctadiene lignans in modifiedultrasonic and supercritical fluid extracts of Schisandra chinensis
Baill by liquid chromatography mass spectrometry and a free
radical-scavenging method. J Sep Sci 2008d; 31: 13221332.
Weathers RM, Beckholt DA, Lavella AL, Danielson ND. Comparison
of acetals as in situ modifiers for the supercritical fluid extraction
of -carotene from paprika with carbon dioxide. J Liq Chrom Rel
Technol 1999; 22: 241252.
Weber W, Petkov S, Brunner G. Vapourliquid-equilibria and calculations using the RedlichKwong-Aspen-equation of state
for tristearin, tripalmitin, and triolein in CO2 and propane. Fluid
Phase Equilib 1999; 158160: 695706.
Weinhold TD, Bresciani LFV, Tridapalli CW, Yunes RA, Hense H,
Ferreira SRS. Polygala cyparissias oleoresin: comparing CO2
and classical organic solvent extractions. Chem Eng Proc 2008;
47: 109117.
Wells C, Bertsch W, Perich M. Isolation of volatiles with insecticidal
properties from the genus Tagetes (Marigold). Chromatographia
1992; 34: 241248.
Wenli Y, Bo S, Yaping Z. Supercritical CO2 extraction of resveratrol
and its glycoside piceid from Chinese traditional medicinal herb
Polygonum cuspidatum. J Sci Food Agric 2005; 85: 489492.
Wertheim MS. Fluids with highly directional attractive forces. I.
Statistical thermodynamics. J Stat Phys 1984a; 35: 1934.
Wertheim MS. Fluids with highly directional attractive forces. II.
Thermodynamic perturbation theory and integral equations.
J Stat Phys 1984b; 35: 3547.
Wertheim MS. Fluids with highly directional attractive forces. III.

Multiple attraction sites. J Stat Phys 1986a; 42: 459476.
Wertheim MS. Fluids with highly directional attractive forces. IV.
Equilibrium polymerization. J Stat Phys 1986b; 42: 477492.
Westerman D, Santos RCD, Bosley JA, Rogers JS, Al-Duri B.
Extraction of Amaranth seed oil by supercritical carbon dioxide.
Wilp C, Eggers R. High-pressure extraction by multistage fractionated separation for gentle production of corn germ oils with
highly compressed carbon-dioxide. Fett Wiss Technol 1991; 93:
348354.
Wolski T, Ludwiczuk A. Natural products extraction with supercritical gases. Przemysl Chem 2001; 80: 286289.
Wong DSH, Sandler SI. A theoretically correct mixing rule for cubic
equations of state. AIChE J 1992; 38: 671680.
Wong V, Wyllie SG, Cornwell CP, Tronson D. Supercritical fluid
extraction (SFE) of monoterpenes from the leaves of melaleuca
alternifolia (Tea Tree). Molecules 2001; 6: 92103.
Wood JA, Bernards MA, Wan WK, Charpentier PA. Extraction
of ginsenosides from North American ginseng using modified supercritical carbon dioxide. J Supercrit Fluids 2006; 39:
4047.
Wu SJ, Tsai JY, Chang SP, Lin DL, Wang SS, Huang SN, Ng LT.
Supercritical carbon dioxide extract exhibits enhanced antioxidant and anti-inflammatory activities of Physalis peruviana.
J Ethnopharm 2006; 108: 407413.
Xia Y, Rivero-Huguet ME, Hughes BH, Marshall WD. Isolation of
the sweet components from Siraitia grosvenorii. Food Chem
2008; 107: 10221028.
Xiao JB, Chen JW, Xu M. Supercritical fluid CO2 extraction of essential oil from Marchantia convoluta: global yields and extract
chemical composition. Electronic J Biotech 2007; 10: 141
148.
Xu ZM, Godber JS. Comparison of supercritical fluid and solvent
extraction methods in extracting -oryzanol from rice bran. J Am
Oil Chem Soc 2000; 77: 547551.
Xu G, Scurto AM, Castier M, Brennecke JF, Stadtherr MA. Reliable
computation of high-pressure solid-fluid equilibrium. Ind Eng
Chem Res 2000; 39: 16241636.
Xu J, Chen S, Hu Q. Antioxidant activity of brown pigment and
extracts from black sesame seed (Sesamum indicum L.). Food
Chem 2005; 91: 7983.
Xu X, Gao YX, Liu GM, Wang Q, Zhao H. Optimization of supercritical carbon dioxide extraction of sea buckthorn (Hippophae
rhamnoides L.) oil using response surface methodology. LWTFood Sci Technol 2008a; 41: 12231231.
Xu X, Gao YX, Liu GM, Zheng YY, Zhao J. Supercritical CO2
extraction of whole berry oil from sea buckthorn (Hippophae
rhamnoides var. sp) fruit. Food Sci Biotechnol 2008b; 17: 470
474.
Yakimishen R, Cenkowski S, Muir WE. Oil recoveries from sea
buckthorn seeds and pulp. Appl Eng Agric 2005; 21: 1047
1055.
Yamamoto H, Kanegae F, Mishima K, Iwai Y, Arai Y. Correlation
of solubilities of coal liquefaction products in supercritical gases
by equations of state. Mem Fac Eng, Kyushu Univ 1987; 47:
95113.
Yamamoto M, Iwai Y, Nakajima T, Tanabe D, Arai Y. Correlation of
solubilities and entrainer effects for fatty acids and higher alcohols in supercritical carbon dioxide using SRK equation of state
with association model. J Chem Eng Jpn 2000; 33: 538544.
Yamini Y, Sefidkon F, Pourmortazavi SM. Comparison of essential
oil composition of Iranian fennel (Foeniculum vulgare) obtained

Authenticated
by supercritical carbon dioxide extraction and hydrodistillation

methods. Flavour Fragr J 2002; 17: 345348.
Yamini Y, Khajeh M, Ghasemi E, Mirza M, Javidnia K. Comparison
of essential oil compositions of Salvia mirzayanii obtained by
supercritical carbon dioxide extraction and hydrodistillation
methods. Food Chem 2008; 108: 341346.
Yang H, Zhong C. Modeling of the solubility of aromatic compounds
in supercritical carbon dioxide-cosolvent systems using SAFT
equation of state. J Supercrit Fluids 2005; 33: 99106.
Yang C, Xu YR, Yao WX. Extraction of pharmaceutical components
from Ginkgo biloba Leaves using supercritical carbon dioxide.
J Agric Food Chem 2002; 50: 846849.
Yang CC, Lee MR, Hsu SL, Chang CMJ. Supercritical fluids extraction
of capillarisin from Artemisia capillaris and its inhibition of in vitro
growth of hepatoma cells. J Supercrit Fluids 2007; 42: 96103.
Yao JP, Nair MG, Chandra A. Supercritical carbon dioxide extraction of scotch bonnet (capsicum annuum) and quantification of
capsaicin and dihydrocapsaicin. J Agric Food Chem 1994; 42:
13031305.
Yao W, Xu Y, Chun Y, Qin Y. Extraction of the Osmanthus fragrans lour by supercritical carbon dioxide. Proc. 5th Meeting on
Yepez B, Espinosa M, Lopez S, Bolanos G. Producing antioxidant
fractions from herbaceous matrices by supercritical fluid extraction. Fluid Phase Equilib 2002; 194: 879884.
Yin JZ, Sun XW, Ding XW, Liang HH. Modeling of supercritical
fluid extraction from Hippophae rhamnoides L. seeds. Sep Sci
Technol 2003; 38: 40414055.
Yin JZ, Wang AQ, Wei W, Liu Y, Shi WH. Analysis of the operation
conditions for supercritical fluid extraction of seed oil. Sep Purif
Technol 2005a; 43: 163167.
Yin JZ, Xu QQ, Wei W, Wang AQ. Experiments and numerical
simulations of supercritical fluid extraction for Hippophae rhamnoides L seed oil based on artificial neural networks. Ind Eng
Chem Res 2005b; 44: 74207427.
Yoda SK, Marques MOM, Petenate AJ, Meireles MAA. Supercritical
fluid extraction from Stevia rebaudiana Bertoni using CO2 and
CO2+water: extraction kinetics and identification of extracted
components. J Food Eng 2003; 57: 125134.
Yonei Y, Ohinata H, Yoshida R, Shimizu Y, Yokoyama C. Extraction
of ginger flavor with liquid or supercritical carbon dioxide.
J Supercrit Fluids 1995a; 8: 156161.
Yonei Y, Kobari M, Yokoyama C, Arai K. A search for optimum
extraction conditions of flavor from tobacco leaves by high
pressure carbon dioxide. Kagaku Kogaku Ronbun 1995b; 21:
674682.
Yoo KP, Hong IK. Modeling of the supercritical fluid extraction of
oilseeds. In: King JW, List GR, editors. Supercritical fluid technology in oil and lipid chemistry. Champaign, IL: AOCS Press,
1996: 132154.
Young JC, Games DE. Supercritical fluid extraction and supercritical
fluid chromatography of the fungal metabolite ergosterol. J Agric
Food Chem 1993; 41: 577581.
Yu D, Jackson K, Harmon TC. Dispersion and diffusion in porous
media under supercritical conditions. Chem Eng Sci 1999; 54:
357367.
Yu WL, Zhao YP, Chen JJ, Shu B. Comparison of two kinds of
pumpkin seed oils obtained by supercritical CO2 extraction. Eur
J Lipid Sci Technol 2004; 106: 355358.
Yu WL, Shu B, Zhao YP. Supercritical CO2 extraction of resveratrol and its glycoside piceid from Chinese traditional medicinal
herb Polygonum cuspidatum. J Sci Food Agric 2005; 85: 489
492.
155
Yu J, Dandekar DV, Toledo RT, Singh RK, Patil BS. Supercritical

fluid extraction of limonoids and naringin from grapefruit (Citrus paradisi Macf.) seeds. Food Chem 2007; 105:
10261031.
Yun SLJ, Liong KK, Gurdial GS, Foster NR. Solubility of cholesterol in supercritical carbon dioxide. Ind Eng Chem Res 1991;
30: 24762482.
Zacchi P, Daghero J, Jaeger P, Eggers R. Extraction/fractionation and
deacidification of wheat germ oil using supercritical carbon dioxide. Braz J Chem Eng 2006; 23: 105110.
Zaidul ISM, Norulaini NAN, Omar AKM, Smith RL. Supercritical
carbon dioxide (SC-CO2) extraction of palm kernel oil from palm
kernel. J Food Eng 2006a; 73: 210216.
Zaidul ISM, Norulaini NAN, Omar AKM. Separation/fractionation
of triglycerides in terms of fatty acid constituents in palm kernel oil using supercritical CO2. J Sci Food Agric 2006b; 86:
11381145.
Zaidul ISM, Norulaini NAN, Omar AKM, Smith RL. Supercritical
carbon dioxide (SC-CO2) extraction of palm kernel oil from palm
kernel. J Food Eng 2007a; 79: 10071014.
Zaidul ISM, Norulaini NAN, Omar AKM, Sato Y, Smith RL.
Separation of palm kernel oil from palm kernel with supercritical carbon dioxide using pressure swing technique. J Food Eng
2007b; 81: 419428.
Zancan KC, Marques MOM, Petenate AJ, Meireles MAA. Extraction
of ginger (Zingiber officinale Roscoe) oleoresin with CO2 and
co-solvents: a study of the antioxidant action of the extracts. J
Zbogar A, Lopes FVD, Kontogeorgis GM. Approach suitable for
screening estimation methods for critical properties of heavy
compounds. Ind Eng Chem Res 2006; 45: 476480.
Zekovic Z. Chamomile ligulate flowers in supercritical CO2extraction. J Essent Oil Res 2000; 12: 8593.
Zekovic Z, Lepojevic Z, Vujic D. Effect of oregano (Origanum
vulgare L.) and thyme (Thymus vulgaris L.) essential oils on
Trypanosoma cruzi (Protozoa: Kinetoplastida) growth and ultrastructure. Chromatographia 2000; 51: 175179.
Zekovic Z, Lepojevic Z, Tolic A. Modeling of the thyme-supercritical carbon dioxide extraction system. 1. The influence of carbon
dioxide flow rate and grinding degree of thyme. Sep Sci Technol
2001; 36: 34593472.
Zekovic Z, Lepojevic Z, Tolic A. Modeling of the thyme-supercritical carbon-dioxide extraction system. II. The influence of extraction time and carbon dioxide pressure. Sep Sci Technol 2003;
38: 541552.
Zekovic Z, Pfaf-Sovljanski I, Grujic O. Supercritical fluid extraction
of hops. J Serb Chem Soc 2007; 72: 8187.
Zekovic Z, Lepojevic Z, Milic S, Adamovic D, Mujic I.
Supercritical CO2 extraction of mentha (Mentha piperita L.)
at different solvent densities. J Serb Chem Soc 2009; 74: 417
425.
Zhang J, Lee LL, Brennecke JF. Fluorescence spectroscopy and
integral equation studies of preferential solvation in supercritical
fluid mixtures. J Phys Chem 1995a; 99: 92689277.
Zhang C, Brusewitz GH, Maness NO, Gasem KAM. Feasibility of
using supercritical carbon dioxide for extracting oil from whole
pecans. Trans ASAE 1995b; 38: 17631767.
Zhang K, Wang YH, Chen YZ, Tu YQ, Jing H, Huang HM, Huang
XF, Fan JS. Sesquiterpenes from celastrus paniculatus subsp.
Paniculatus. Phytochemistry 1998a; 48: 10671069.
Zhang XW, Sun T, Sun ZY, Liu X, Gu DX, Zeng XY. Supercritical
carbon dioxide extraction of wheat plumule oil. J Food Eng
1998b; 37: 103110.

Authenticated
Zhang J, Zhang L, Duan J, Liang Z, Zhang W, Huo Y, Zhang Y. On-line

hyphenation of supercritical fluid extraction and two-dimensional
high performance liquid chromatography-atmospheric pressure
chemical ionization tandem mass spectrometer for the analysis of
Ganoderma lucidum. J Sep Sci 2006a; 29: 25142522.
Zhang SQ, Chen RZ, Wu H, Wang CZ. Ginsenoside extraction
from Panax quinquefolium L. (American ginseng) root by
using ultrahigh pressure. J Pharm Biomed Anal 2006b; 41:
5763.
Zheng Y, Liu B, Chen M, Chen T. Supercritical fluid extraction of
ecdysterone from the roots of Achyranthes bidentata BL. J Sep
Sci 2008; 31: 13931398.
Zhong M, Han B, Ke J, Yan H, Peng DY. A model for correlating
the solubility of solids in supercritical CO2. Fluid Phase Equilib
1998; 146: 93102.
Zhong C, Yang H. Representation of the solubility of solids in supercritical fluids using the SAFT equation of state. Ind Eng Chem
Res 2002; 41: 48994905.
Ziakova A, Brandsteterova E. Application of different preparation
techniques for extraction of phenolic antioxidants from lemon
balm (Melissa officinalis) before HPLC analysis. J Liquid
Chromatogr Rel Technol 2002; 25: 30173032.
Ziemons E, Goffin E, Lejeune R, da Cunha AP, Angenot L,
Thunus L. Supercritical carbon dioxide extraction of tagitinin C from Tithonia diversifolia. J Supercrit Fluids 2005; 33:
5359.
Ziemons E, Mbakop NW, Rozet E, Lejeune R, Angenot L, Thunus
L, Hubert P. Optimisation of SFE method on-line coupled to
FT-IR spectroscopy for the real-time monitoring of the extraction of tagitinin C in T. diversifolia. J Supercrit Fluids 2007; 40:
368375.
Zizovic I, Skala D, Ristic M. Extraction of Oenothera biennis seed

oil with supercritical carbon dioxide - determination of the content of gamma linolenic acid in seed oil. J Serbian Chem Soc
1998; 63: 883889.
Zizovic I, Stamenic M, Orlovic A, Skala D. Supercritical carbon
dioxide essential oil extraction of Lamiaceae family species:
mathematical modelling on the micro-scale and process optimization. Chem Eng Sci 2005; 60: 67476756.
Zizovic I, Stamenic M, Orlovic A, Skala D. Supercritical carbon
dioxide extraction of essential oils from plants with secretory
ducts: mathematical modelling on the micro-scale. J Supercritic
Fluids 2007a; 39: 338346.
Zizovic I, Stamenic M, Ivanovic J, Orlovic A, Ristic M, Djordjevic
S, Petrovic SD, Skala D. Supercritical carbon dioxide extraction
of sesquiterpenes from valerian root. J Supercritic Fluids 2007b;
43: 249258.
Zorca M, Gainar I, Bala D. Comparative study of essential oils of
lavender obtained by hydrodistillation and supercritical fluid
extraction. Rev Chim-Bucharest 2006; 57: 361363.
Zorca M, Gainar I, Bala D. Pressure effect on the savory essential
oil obtained by extraction with supercritical carbon dioxide. Rev
Chim-Bucharest 2007; 58: 11221125.
Zosel K. German patent no. 14 93 190, 1964.
Zosel K. Separation with supercritical gases: practical applications.
Angew Chem Int Ed 1978; 17: 702.
Zougagh M, Valcarcel M, Rios A. Supercritical fluid extraction: a
critical review of its analytical usefulness. Trends Anal Chem
2004; 23: 399405.
Zwiefelhofer U, Brunner G. Stoffbergang in Festbetten bei der
Extraktion mit berkritischem Kohlendioxid. Chem Ing Tech
1993; 65: 1128.
Helena Sovov is a scientist in the field of supercritical fluid extraction at the

Institute of Chemical Process
Fundamentals (ICPF) in
Prague, CR. Her primary
research interest is in the
modelling and simulation
of kinetics of extractions.
She studied at the Institute
of Chemical Technology in
Prague where she received a
Masters degree in 1970, and
at the ICPF where she received a CSc (PhD) degree in chemical engineering in 1975. She
is a member of the working party of High Pressure Technology
of the European Federation of Chemical Engineering.
Roumiana P. Stateva is a
professor at the Institute
of Chemical Engineering,
Bulgarian
Academy
of
Sciences. She has an MSc
in chemical cybernetics and
a PhD in chemical engineering from the Mendeleev
University of Chemical
Technology, Moscow, Russia.
Her research is devoted to the
modelling and efficient calculation of phase equilibria of complex systems, and to the
development of original methods for the prediction of properties from the chemical structure of pure substances.

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Supercritical Fluid Extraction From Vegetable Materials

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Rev Chem Eng 27 (2011): 79156 2011 by Walter de Gruyter Berlin Boston. DOI 10.1515/REVCE.2011.

Supercritical fluid extraction from vegetable materials

Helena Sovov1,* and Roumiana P. Stateva2

Institute of Chemical Process Fundamentals

outweighed by superior product properties, lower operating

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H. Sovov and R.P. Stateva: SFE from vegetable materials

of substances for chromatographic assay from bulk sample

We will also focus our attention on the thermodynamic

2. SFE from plants

The extraction is usually carried out as a semicontinuous

Figure 2 Simplified scheme of the extraction equipment with CO2

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H. Sovov and R.P. Stateva: SFE from vegetable materials

can range from 0.1 cm3 to several hundred cubic centimetres

Besides the monographs either devoted to the applications

plants but also examine other SCF applications, we mention

ucts in the middle of the 1980s was described by Brunner

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H. Sovov and R.P. Stateva: SFE from vegetable materials

extraction in different branches of industry. Raventos et al.

2.2.2. Extraction for analytical purposes

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H. Sovov and R.P. Stateva: SFE from vegetable materials

fluid extraction, enhanced-fluidity extraction, etc., which are

both supercritical and liquid, in sample preparation for food

3. Plants and extracts

4. Thermodynamic modelling of systems

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Flavour compounds, polyphenols

Apple (Malus domestica) fruit, peels, pomace

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Blessed thistle (Cnicus benedictus) leaves, flowering

Black oil plant (Celastrus paniculatus) seed

Birch (Betula pendula) leaves

Zhang et al. 1998a

Botha and McCrindle 1999

Aloe vera (Aloe barbadensis) leaf skin, pulp, rind

Avocado (Persea americana) fruit

Vargas et al. 2010

Volatile oil, lupenol

Volatile oil: camphor, 1-8 cineol

Abajeru (Chrysobalanus icaco) leaves

Plants extracted with pure or modified carbon dioxide.

Nut shell liquid, cardanols

Cashew (Anacardium Occidentale) pericarp

Cherry (Prunus avium) seed, pomace

Carqueja (Baccharis trimera) aerial part

Volatile oil, pigments, fatty acids,

Cardamom (Elettaria cardamomum) seed

Cape gooseberry (Physalis peruviana)

Marongiu et al. 2007e

Brazilian ginseng (Pfaffia paniculata, P. glomerata)

Sewram et al. 1998, 2000

Laroze et al. 2010

Blueberry (Vaccinium sp.) residue after pressing

Calamus (Acorus calamus, A. graminei) rhizomes

H. Sovov and R.P. Stateva: SFE from vegetable materials

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Simandi et al. 1996

Volatile oil, methyl chavicol

Chervil (Anthriscus cerefolium) herb

Clove basil (Ocimum gratissimum) leaves