Modern Supercritical Fluid Technology For Food Applications: Further

FO05CH11-King ARI 10 February 2014 13:4
ANNUAL
REVIEWS Further Modern Supercritical Fluid
Click here for quick links to
Annual Reviews content online,
including:
Technology for Food
• Other articles in this volume
• Top cited articles
Applications
Annu. Rev. Food Sci. Technol. 2014.5:215-238. Downloaded from www.annualreviews.org
• Top downloaded articles

• Our comprehensive search
Jerry W. King
Departments of Chemistry & Biochemistry and Food Science, University of Arkansas,
by Universidade de Brasilia on 05/02/14. For personal use only.
Fayetteville, Arkansas 72701; email: jwking1@uark.edu
Annu. Rev. Food Sci. Technol. 2014. 5:215–38 Keywords

First published online as a Review in Advance on carbon dioxide, extraction, high pressure, nutraceuticals, subcritical fluids
January 2, 2014
The Annual Review of Food Science and Technology is Abstract

online at http://food.annualreviews.org
This review provides an update on the use of supercritical fluid (SCF) tech-
This article’s doi: nology as applied to food-based materials. It advocates the use of the solubil-
10.1146/annurev-food-030713-092447
ity parameter theory (SPT) for rationalizing the results obtained when em-
Copyright c 2014 by Annual Reviews. ploying sub- and supercritical media to food and nutrient-bearing materials
All rights reserved
and for optimizing processing conditions. Total extraction and fractionation
of foodstuffs employing SCFs are compared and are illustrated by using mul-
tiple fluids and unit processes to obtain the desired food product. Some of
the additional prophylactic benefits of using carbon dioxide as the process-
ing fluid are explained and illustrated with multiple examples of commercial
products produced using SCF media. I emphasize the role of SCF technol-
ogy in the context of environmentally benign and sustainable processing,
as well as its integration into an overall biorefinery concept. Conclusions
are drawn in terms of current trends in the field and future research that is
needed to secure new applications of the SCF platform as applied in food
science and technology.
215
INTRODUCTION
The use of supercritical fluids (SCFs) as applied to the processing of food materials has been
ongoing since the late 1960s and represents probably the most successful application of SCFs and
related compressed fluids to date. This review focuses on assessing developments and trends in the
field since 2000, the current status of these developments and trends as applied to food materials
and supplements, and where new research and product developments are occurring.
Progress in SCF technology, the use of subcritical fluids, and mixed fluids under varying degrees
of compression has been recorded in many areas during the past 45 years. These developments
can be divided into approximate chronological eras in which they occurred, as summarized in
Table 1. Initial successes in the food industry for decaffeinating coffee (Zosel 1974) and the
universal use of SC-CO2 in isolating hops extracts for flavoring beer (Zekovic et al. 2007) highlight
this era and led to the construction of sizeable plants for these dedicated purposes. Recovery of
organic chemicals from fermentation media traditionally has been associated with the generation
of fuels or carbochemical moieties (Persson et al. 2002, Darani & Mozafari 2009), not flavors or
chemicals associated with the food industry. Supercritical fluid extraction (SFE) and supercritical
fluid chromatography (SFC) have been applied since the late 1970s for the analysis of foodstuffs
and for the determination of fat levels in food (Abbas et al. 2008, Brondz 2012) and trace levels
of toxicants (Herrero et al. 2009a). The use of SCFs for the fractionation (supercritical fluid
fractionation, SFF) and/or enrichment of specific components in foods has been recorded since the
1980s; however, commercial SCF extracts tend to contain, in general, both bioactive components
along with inert mixtures of coextracted compounds (King 2005, Brunner 2010).
Reaction chemistries that have had the most impact in food technology tend to be enzyme-
catalyzed reactions (Baig et al. 2011), hydrogenations designed to control particular trans isomers
occurring in lipid mixtures (Weidner et al. 2004, King & List 2011), and hydrolysis conducted
in the presence of enzymes or a medium such as subcritical water (SCW) (Turner et al. 2006,
Sereewatthanawut et al. 2008). Considerable activity in producing fine particles for use in the
pharmaceutical industry started in the late 1990s and has continued; however, in recent years,
there has been a focus on incorporating this technology platform into foods and nutraceutical
formulations (York et al. 2004, Weidner 2009). Also during this time, emphasis shifted back to SFE
Table 1 Developments in critical fluid technology according to the approximate year in which they
first appeared
1970—Supercritical Fluid Extraction (SFE—Foods)
1977—Energy Applications (Fermentation, Fuels, etc.)
1980—Analytical Applications (SFE + SFC)
1982—Supercritical Water Oxidation
1988—Supercritical Fluid Fractionation (SFF)
1993—Supercritical Fluid Reactions (SFR—Enzymatic, Hydrogenation)
1993—Applications in Material Science + Cleaning Technology
1996—Fine Particle Production and Encapsulation
1997—Renaissance of SFE/SFF (Nutraceuticals, Herbals, etc.)
1997—Green Chemistry/Engineering (Integrated Processing)
2000—Sustainability/Bioenergy/Biomass
2005—Use of Critical Fluids in Biorefineries
Abbreviations: SFC, supercritical fluid chromatography; SFE, supercritical fluid extraction; SFF, supercritical fluid
fractionation; SFR, supercritical fluid reaction.
216 King
and SFF techniques, which was largely catalyzed by consumer use of nutraceuticals, functional food
formulations, and herbal extracts for personal health enhancement (Martinez 2008, King 2012).
Using a green processing technology not only provided solvent-free products but also allayed food
consumer concern over environmental pollution and sustainability issues at the turn of the century
(Clark 2011). More recently, these same issues have become embedded in renewable bioenergy
production and the extraction of food-related chemicals, both before and after the production of
fuel chemicals such as bioethanol and biodiesel (Pandey et al. 2011, Bergeron et al. 2012). Indeed,
the biorefinery concept (Ramaswamy et al. 2013) seems to offer a solution to the food-versus-fuel
dilemma often quoted in both popular and technical publications (Thompson 2012).
With the timeline noted above and in Table 1, I attempt to provide for the reader a review of
the most recent developments in the application of SCFs and similar media to foods and related
substances in the twenty-first century. Solubility parameter theory (SPT) is used to rationalize
the choice of processing conditions and fluids as applied to food compounds (Rozzi & Singh
2002, Srinivas & King 2010), as well as to integrate with newer trends in the SFE and SFF of
food products/ingredients. Employing compressed fluids in the treatment of foodstuffs, such as
reduction of microbial contamination and enzymatic activity (Garcia-Gonzalez et al. 2007) in
food matrices, can result in additional benefits, such as extending product shelf life (Damar et al.
2009). Select actual applications will follow for the SCF processing of omega fatty acid–containing
oils, isolation of naturally occurring antioxidants from processing wastes, multiple applications to
rice-based food products, and juice preservation. Finally, I hope to convince the reader of the
merits of developing a critical-fluid green processing platform that embodies primarily CO2 from
diverse sources such as coal-fired energy plants, fermenters, and algae production schemes.
SOLUBILITY PARAMETER THEORY APPLIED TO SUPERCRITICAL

FLUID EXTRACTION AND SUPERCRITICAL FLUID FRACTIONATION
SFE and related processing methods continue to be characterized in terms of fundamental phase
equilibria and thermodynamic studies (Deiters & Kraska 2012, Brignole & Pereda 2013), kinetic
and mass transport parameters (Sovova 2010, Montes et al. 2011), optimization by statistical de-
sign methodology (Srinivas et al. 2011), and cost of production estimations (Prado et al. 2010,
Fernandez-Ronco et al. 2013). Thermodynamic and solute solubility data continue to be accu-
mulated for primarily SC-CO2 (Skerget et al. 2011) as well as subcritical liquid solvents under
pressure (Gupta & Shim 2007)—their correlation primarily done in terms of engineering models
based on solute fugacities (Ajchariyapagorn et al. 2008) and semiempirical equations that are ap-
plicable over specific ranges of pressure, temperature, and fluid density (Del Valle & de la Fuente
2006). Statistical design modeling (SDM) has become quite popular for optimizing the SFE of
natural products (Macias-Sanchez et al. 2008), although limited insight is provided in these cases
as to the underlying physicochemical interaction between the fluids and complex solutes which
constitute natural product and food matrices.
If properly applied, SPT overcomes some of the limitations of these methods in providing guid-
ance for evaluating the practicality and conditions that are optimal for both sub- and supercritical
fluid extraction. The molecular complexity of solutes in foodstuffs and natural products and the
paucity of physicochemical data on such solutes are indeed a challenge to the chemical or food
processing engineer. The concept of matching the solubility parameters (δ) of both solvent (fluid)
and solute may seem simplistic, given that the activity coefficient contribution to solution non-
ideality is primarily enthalpy driven and ignores solute-solvent size differences that are entropic
based. The latter contribution, of course, is of importance where there are appreciable molecular
size differences between the solute and the solvent medium; however, to a first approximation,
www.annualreviews.org • Supercritical Solvents for Food 217

SPT allows the food technologist to assess what can be accomplished via SFE and related SCF
methods and avoids choosing impractical conditions for pressure-based fluid extractions.
Improvements have been made in utilizing the SPT approach in terms of more accurately
calculating the δ of sub- and supercritical fluids as a function of pressure/temperature, as well as
estimating the δ of the constituent components associated with the lipid, carbohydrate, and protein
content of foods/natural products. Several equation-of-state (EOS) methods have been reported
recently that accurately predict the δ of the critical fluid over a range of reduced pressure and tem-
perature (Panayiotou 1997, Machida et al. 2011); additionally, these complement the traditional
semiempirical methods of estimating the δ of the critical fluid based on reduced state parameters
(Marcus 2006) and internal energy (Rai et al. 2007). Del Valle et al. (2011), Fornari et al. (2005),
and Tomberli et al. (2006), among others, discuss recent studies employing group contribution
methods coupled with estimation of the required critical parameters of solutes. Hence, when the
latter is coupled with accurate prediction of the δ dependence on both temperature and pressure
for both SCF and solutes, a fairly accurate picture emerges of what the conditions are when so-
lutes initially begin to dissolve in pressurized fluids, the pressure/temperature over which solute
solubility enhancement occurs in such fluids, as well as the often-ignored solubility maxima that
occur in such systems at higher fluid densities (Kraske et al. 2002). Therefore, I discuss how this
approach can be integrated to understand SFE operational parameters, as well as the choice of
fluids and conditions for extracting and enriching targeted solutes via SFE and SFF, in terms of
their respective solubility parameters.
Solubility/Extractability Related to Chemical Structure: A Tutorial

To better understand how to use SPT, I offer a tutorial here on how the basic SFE process works,
in terms of the variance in the δ of the fluid during SFE, as illustrated in Figure 1. The solubility
parameter, δ, is the square root of a substance’s internal energy, E, divided by its molecular volume,
V, or δ = (E/V)1/2 . The condition for maximum solubility between a solute and a solvent (fluid)
is given in Equation 1 below:
δsolute = δfluid . (1)
The condition for miscibility between the solute and the fluid can be approximated by Equation 2
as
(δsolute − δfluid ) ∼ 2.5 cal1/2 /cc3/2 or 5.11 MPa1/2 . (2)
1/2 3/2
Two units for δ are prevalent, the older Hildebrand unit (H) expressed in units of cal /cc or in
units of MPa1/2 , related by 1H = cal1/2 /cc3/2 = 2.0455 MPa1/2 . This is an important relationship,
given that there is considerable useful δ data expressed using both units (Barton 1991).
The solubility parameter of the fluid CO2 is calculated as a function of pressure/temperature,
as noted previously, and a graph showing this relationship is inserted below the simple schematic
of the SFE process shown in Figure 1 below the simplified process schematic given for SFE.
The extraction stage for SFE takes place typically under conditions in which the δfluid − δsolute is
≤2, conditions in which the solute has a high solubility in the SCF, and/or when some degree
of fractionation between the solutes is desired at 2 < δsolute − δfluid < 4. As the solute-containing
fluid passes out of the extraction vessel through the pressure reduction valve, its δ is lowered by
either reducing the pressure or increasing the temperature, thereby allowing capture of some of
the desired constituents contained in the SCF having a lowered δ in the first separator vessel (S1).
A second separation stage (S2) can be used to separate the solutes remaining in the fluid, which
results in precipitation of additional constituents, which then results in a crude fractionation of
the SCF-derived extract.
218 King
Cooling
Heating Heating
Pressure reduction Pressure reduction
Extraction
vessel
S1 S2
–U
δCO2 =
V
Extract #1 Extract #2 δsolute –δCO2 ≤ 2, highly soluble

Supercritical fluid
2 < δsolute–δCO2 < 4, extractable
16
δsolute–δCO2 > 4, not extractable
14 δ < 19, ‘lipophilic’; δ hexane = 15
δ > 25, ‘hydrophilic’, δ water = 48

12
Total solubility parameter, δ
Extraction
10
8 First stage
separation 312.8 K
318.0 K
6
323.5 K
2 Second stage
separation and recycle
0
0 5 10 15 20 25 30
Pressure/MPa
Figure 1
Supercritical fluid extraction (SFE) operating principles in terms of solubility parameters (δ) for CO2 as a function of pressure and
temperature relative to hypothetical solubility parameters for solutes and well-known liquid solvents. Thanks to Owen Catchpole of
Manuka Health New Zealand Limited, Mt. Wellington, Auckland, New Zealand, for permission to use this figure.
The variation in the solute solubility parameters that influence solute-fluid interactions can be
estimated using the three-dimensional Hansen solubility parameter (HSP) concept (Hansen 2007),
which quantifies, individually, the contributions of the dispersion (δd ), polar (δp ), and hydrogen-
bonding (δh ) interactions to the total solute solubility parameter, δsolute , given in Equation 3 below:

Ed Ep Eh
δ2solute = + + = δ2d + δ2p + δ2h .
V V V
HSP

35
30
Curcumin
Dihydrocapsaicin
Solubility parameter (MPa1/2)
25
Capsaicin
Capsanthin
Lutein
20 Lutein
β-Carotene Violaxanthin laureate ester
T = 25°C
T = 40°C Zeaxanthin laureate ester
15 T = 60°C
Capsanthin laureate ester
Carbon dioxide
Lutein stearate ester

Lutein stearate diester
10
Cryptoxanthin laureate ester
β-Carotene
0
0 10 20 30 40 50 60 70 80 90 100
Pressure (MPa)
Figure 2
The solubility parameter of carbon dioxide as a function of temperature and pressure relative to the computed solubility parameters for
various components found in natural products (on vertical axis), such as spice ingredients, pigments, and pigment esters.
The density dependence for these three-dimensional solubility parameters, δd , δp , and δh , as well
as the extraction fluid, can be calculated as
−1.25 −0.5
δd,ref V ref δp,ref V ref
= , = ,
δd V δp V
0.5
δh,ref −3 V ref
= exp −1.32 ∗ 10 (T ref − T ) − ln ,
δh V
where Vref is the molar volume at the reference reduced temperature, Tref , and V is the molar
volume at the particular temperature of extraction. These equations can be applied to the target
solutes and the extraction fluid (see Williams et al. 2004 for CO2 and Srinivas et al. 2009 for
water).
Figure 2 shows the δ trends for CO2 under pressure as a function of temperature up to
100 MPa (∼1,000 bar), as well as the δs of solutes commonly found in natural products as calculated
by the HSP method (see symbols on the y-axis). As previously noted, δfluid = δo is the optimal
extraction condition for a given target solute; however, SPT predicts that under the criterion given
in Equation 2, (δfluid − δo ) ∼ 5.11 MPa1/2 , solute-fluid miscibility and hence some solubilization
of the target solutes will occur at lower pressures, as indicated by the vertical arrows representing
β-carotene and lutein in Figure 2. Therefore, by applying this criterion in Figure 2 to the
solutes β-carotene and lutein, one sees a substantial extraction of β-carotene into CO2 between
the pressures of 10–30 MPa (Favati et al. 1988), whereas lutein requires higher CO2 pressures for
attaining both miscibility and solubility in SC-CO2 (∼30 MPa). However, what is most interesting
220 King
Nature
SFE
Extracts Products
SFF SFR
Fractions Products Products

SFR SFF
Products Fractions
Figure 3
Processing sequences for extracting, fractionating, and reacting naturally derived materials to desired end
products. Abbreviations: SFE, supercritical fluid extraction; SFF, supercritical fluid fractionation;
SFR, supercritical fluid reaction.
with regard to both β-carotene and lutein is that their extractability improves with pressure, and
their solubility can be optimized in SC-CO2 at pressures exceeding 60 MPa, where the δ for CO2
and the naturally occurring pigments become equal.
SUPERCRITICAL-BASED METHODS FOR PROCESSING

FOOD MATERIALS
SFE has historically been practiced to extract substances from “nature” to produce extracts or
products, as depicted by the schematic diagram in Figure 3. The classic SFE examples are the
decaffeination of coffee and the isolation of hops extract for flavoring beer. Today, literally all
hops extraction for the beer industry is done via SFE using SC-CO2 , whereas coffee decaffeina-
tion competes with other alternative “natural” extraction processes. Thus, SFE can be used for
extracting both desired, i.e., hops, and undesired components, i.e., caffeine, from food matrices.
Such extractions are accomplished using the basic approach described in Figure 1, with the ex-
ception that most commercial SFE plants consist of at least three extraction vessels to allow a
batch semicontinuous process to be realized.
Both solute solubility and diffusion in the SCF are important to achieve an optimal solute flux
during SFE. When using SFE to remove unwanted substances from foods and natural products,
such as pesticide removal from ginseng or desolventizing a vegetable oil, solute mass transfer from
the food matrix dominated by diffusive-based processes becomes very important. The onset of the
diffusion control region of an SFE (Favati et al. 1988) usually occurs after an optimal solvent/feed
ratio (S/F) has been determined. Below the optimal S/F, the extraction is thermodynamically driven
by the solute’s solubility in the SCF; hence, low S/F values are desired to minimize extraction
time and production costs.
Total Extraction versus Fractionation

In the 1980s, researchers developed methods using SCFs to fractionate extracted solutes, i.e., SFF.
Here the SFE-derived extract was fractionated to produce a desired composition or enrichment
of certain solutes relative to their concentration in the initial extraction, also known as folding
in the food industry. In theory and practice, a form of SFF can be employed by adjusting the ex-
traction conditions and separator pressure/temperature and using time-based fractionation while

performing SFE—the end result being fractions still containing a number of compounds—as noted
previously. There are two major options when performing SFF: columnar-based fractionation and
SFC. SFFs performed using packed columns are somewhat analogous to distillation, except that
the SCF under compression is circulated through a column, and usually contacts a liquid substrate
in the countercurrent mode (Brunner 1994, Reverchon & DeMarco 2006). A sectorial tempera-
ture gradient is also imposed to enhance the separation of components in the feed mixture; hence,
columnar-based separations are based on adjustment of the fluid density by both compression and
the temperature gradient, and produce a fluid density gradient longitudinally along the column.
Therefore, the extract (top of the column) and raffinate (bottom of the column) separate on the
basis of their relative solubilities in the dense fluid and their temperature-dependent volatilities.
Numerous food-related materials have been fractionated using the columnar approach, such
as marine-derived oils (Catchpole et al. 2000, Riha & Brunner 2000), mixed glycerides (Perrut
et al. 2001, Fornari et al. 2011), tocopherols (Brunner 2005), free fatty acids (Brunner &
Machado 2012), phytosterols (Dunford & King 2004), essential oil components (Reverchon &
DeMarco 2008), etc.; however, these folded concentrates are not prominent industrially marketed
extracts.
SFC on a preparative or production scale has not seen much commercial use despite several
studies on tocopherol- (King et al. 1996), phytosterol- (Sugihara et al. 2010), and phospholipid-
(Taylor et al. 2000) laden substrates. Isolation of function ingredients from rosemary has been
accomplished by preparative SFC (Ramirez et al. 2006), and SCF simulated moving bed (SMB)
chromatography has been applied for the separation of ethyl linoleate and ethyl oleate (Cristancho
et al. 2012). Recent reported studies (Montanes et al. 2013) on applying SFC to omega fatty acid–
containing fish or algae oils may further catalyze additional interest in this complex and expensive
SFF method. Interestingly, at the turn of the century, KD Pharma (http://www.kd-pharma.de)
developed a method in which SFC was applied on a good manufacturing practice (GMP) industrial
scale for enrichment of the ethyl esters of fish oils in Spain.
For the food technologist considering SFF techniques, the seminal question is the follow-
ing: For the food and nutraceutical marketplace, is there a need for fractionation in addition
to what can be accomplished with SFE alone? It would seem that extracts folded in concen-
tration of a specific bioactive solute would be welcomed; however, most SCF extracts that are
available to the consumer are products of the holistic SFE approach in which all ingredients are
extracted, active or inert, in the final extract. There is a profit-based motive to this approach;
examples include the SFE of the sawtooth palmetto berry (Gregg 2003), in which the resul-
tant extract has only a small percentage of the health-beneficial ingredients (sterols and sterol
esters—the rest of the extract is inert lipids), and fatty acids of marine-derived oils (Eltringham &
Catchpole 2008). In most cases, the levels of active ingredients are deemed sufficient to not require
further enrichment via SFF. King (2003) has noted that future SFE and SFF applications will no
longer be operated as single-step operations but as integrated unit operations (Temelli 2009, Goto
et al. 2012), either in combination with sequential unit operations, such as simultaneous parti-
cle formation upon precipitation of the extract, or by using ultrahigh-pressure SFE as discussed
below.
Extending the Range of Supercritical Fluid Extraction:

Ultrahigh-Pressure Extraction
Optimization of the conditions for SFE is critical to obtaining extracts that contain the desired
compounds, particularly when extracting physiologically active ingredients intended for use in
the food and nutraceutical industrial sectors. Historically, most SFEs have been conducted in the
222 King
pressure regime of 100–450 bar (10–45 MPa) due to the attendant cost of processing equipment
capable of operating at higher pressures (Mohamed & Mansoori 2002). However, SFE done with
any set of chosen conditions of pressure and temperature discriminates with respect to components
contained within the food or natural matrix—even exhaustive extraction at very high pressures
may enrich or deplete certain components contained in the starting material.
Recently, the use of high extraction pressures (≥1,000 bar) has been advocated to enhance
certain components within a natural product matrix that are marginally soluble in SC-CO2 at
lower extraction pressures (Igl-Schmid & Wuzik 2012, http://www.nateco2.de). For example,
for the extraction of pigment moieties from some natural products, a higher extraction yield of
polar pigments such as xanthophylls can be obtained. For these compounds exhibiting marginal
solubility in SC-CO2 , the application of such ultrahigh-pressure extraction has provided not only
a better recovery from the natural product matrix but also perhaps a more authentic extract that is
comparable to that obtained using organic solvent extraction (Minatelli et al. 2011). Although this
might seem insignificant, one must consider the importance of these small amounts of compounds
in a natural product extract and the properties they confer, such as their sensory and antioxidant
properties and their color.
There are numerous examples of foodstuffs and natural products extracted on a laboratory
scale using the higher SC-CO2 pressures: algae oil and pigments at 750 bar, argun nuts at 700
bar, chamomile at 750 bar, caraway at 700 bar, celandine root at 700 bar, chili pepper at 700 bar,
cocoa polyphenols including press cake at 700 bar, the spice coriander at 850 bar, dill seed at 700
bar, lecithin de-oiling at 700 bar, as well as numerous other food-related matrices. Luetge et al.
(2007) report a slight increase in the maximum yield from sage at 1,300 bar and 100◦ C with an
S/F of 60. A two-stage separator such as that shown in Figure 1 (the first separator being held
at 150–250 bar between 40 and 80◦ C) allowed an extract to be obtained that contained a higher
carnosolic acid content than could be obtained with a single-separator system. Similarly, for the
extraction of rosemary at 1,000 or 1,500 bars and 60–80◦ C at S/Fs of 20–60, a tenfold extract
could be obtained with respect to carnosolic acid content, by using a two-vessel separator system
held at 100–300 bar between 40 and 60◦ C.
Extraction of carotenoids and their oxygenated analogs can be achieved faster at higher extrac-
tion pressures and equivalent temperatures. This is because the respective δs for beta-carotene
and lutein are 8.71 H and 10.0 H, which is why lutein is not as easily extracted from the natural
product matrix as beta-carotene (Figure 2). This trend has been confirmed in SFE studies involv-
ing pigments, such as those of Steinhagen et al. (2010), who reported SFE of carotenoids between
700 and 1,500 bar between 40 and 60◦ C using a two-separator system at an S/F of 40. Similarly,
Luetge et al. (2009) studied the SFE of nut kernels at 40◦ C, over a pressure range of 300–1,500
bar, and demonstrated a decreasing S/F with an increasing extraction pressure. For example, the
maximum nut oil yield extraction occurs at S/F ∼ 80 at 300 bar, and at 1,500 bar the S/F was 20.
This has implications for processing costs—at least a one-quarter reduction in production costs
can be realized by extracting at pressures of 300 to 1,500 bar.
King (2013) has recently noted that distinct solubility maxima of solutes in SC-CO2 and other
SCFs occur between 650 and 1,000-bar pressure and that solute mole fraction solubility in such flu-
ids exhibits a parabolic dependence on extraction pressure. This is due to the decrease in the relative
solubility parameter differences between the solute and extraction fluid with increasing extraction
pressure. These solubility maxima occur at reduced extraction densities between 2.00 and 2.50,
corresponding to solute solubility parameters between 17.0 and 21.0 MPa1/2 (King 2013). SFE
embracing this range of conditions is now being utilized industrially; for example, the Valensa Cor-
poration in the United States currently produces Deep Extract platform products using ultrahigh-
pressure SFE to achieve a more complete natural extract (http://www.valensa.com).

Overcoming the Limitations of Carbon Dioxide (CO2 )

The solubility of food-related solutes in SC-CO2 has been extensively studied, and a recent tome
provides considerable solubility data (Skerget et al. 2011). Likewise there is a fair understanding
as to the choice of a suitable cosolvent to pair with SC-CO2 to enhance the solubility of more
polar solutes in the compressed CO2 medium—although binary phase equilibria data are not
always available over the desired range of pressure/temperature for such systems. This can be
critical to operating in the one-phase SCF region, with respect to the main fluid and cosolvent
components, as noted by several investigators (Nobre et al. 2006, Beckman 2012). Ethanol, which
is frequently the preferred cosolvent in SFE applications due to its GRAS (generally regarded
as safe) status, is miscible with SC-CO2 over a select range of pressures/temperatures with mole
fractions of 0.1–0.2. However, end users would prefer to avoid the use of this cosolvent because
government regulatory rules require strict accounting of ethanol use. This is also true in the case
of applying hydroethanolic solvents for food and natural product extraction. Despite this concern,
SC-CO2 /ethanol mixtures are used to extract and fractionate polar lipids, such as phospholipids
(Carvalho et al. 2012), which are not soluble to any appreciable extent in neat SC-CO2 . Several
studies have been reported that use copious amounts of cosolvents, even in the two-stage phase
region (Durling et al. 2007). This can produce the desired result but defeats the purpose of using
SC-CO2 . The question then becomes whether another compressed fluid might be better for the
extraction/fractionation of these more polar solutes.
The use of sub- or near-critical fluids is one alternative. So-called subcritical fluids can range
from liquid CO2 to SCW for extracting and fractionating food-related solutes. SCW has been
extensively studied since the 1990s (Basile et al. 1998) as a suitable alternative to SC-CO2 and
complements the use of CO2 , allowing one to use an all-natural processing platform. The solvent
features of SCW have been characterized in terms of its dielectric constant (Kubatova et al. 2001,
Ibanez et al. 2003) and more recently by Srinivas (2010) in terms of its temperature-dependent
δ. As shown in Figure 4, the hydrogen-bonding component (δh ) of water’s δ is most affected by
an increase in temperature, thereby permitting water to solubilize polar to eventually nonpolar
solutes as its temperature is increased. For the extraction of foodstuffs and natural products,
SCW is used at reduced temperatures in the range of 0.50–0.80, which requires only very low
reduced pressures (Pr = 0.02–0.35) to keep it in its hot liquid state. Under such conditions, SCW
becomes a very effective extraction medium for very polar solutes, such as flavonoids, sugars, and
polyphenolic compounds, which occur in natural products ( Ju & Howard 2005, Shi et al. 2012). By
contrast, there is a considerable amount of literature in the application of SC-CO2 for extracting
grape- and berry-derived oils (Kagliwala et al. 2011, Prado et al. 2012); however, these SC-CO2 -
based methods almost always require the use of methanol or ethanol as cosolvents (Seabra et al.
2012).
Table 2 compares extractions using SC-CO2 and SCW. Extraction with SCW does not require
drying of food or natural products, and the attendant equipment costs are much cheaper than
the construction of an SFE plant. However, the aqueous-derived extracts from subcritical water
extraction (SWE) will often require removal of water unless the SWE can be performed quickly, as
noted by King (2006). This is often the case because the residence time in the extraction vessel of
the material undergoing SWE must be minimized to avoid any thermal degradation of substrate
as well as the resultant extract. SCW is an extremely versatile medium and has been used for
the hydrolysis of vegetable oils to produce fatty acids (Eller et al. 2011); for the extraction of
flavors, spices (Khuwijitjaru et al. 2012), and essential oils (Ozel et al. 2003); and the degradation
of cellulosic and lignin-containing natural polymers to oligomeric carbohydrate mixtures, as well
as polyphenolic compounds (Cacace & Mazza 2006).
224 King
50
45 δD
δP
40
δH
Solubility Parameter (MPa1/2)
35 δT
30
δ2T = δ2D + δ2P + δ2H
25
20
15
10
5
0
0 50 100 150 200 250 300 350
Temperature (C)
Figure 4
The component three-dimensional Hansen solubility parameters for subcritical water as a function of
temperature.
It is also possible to carry out extractions and fractionations using liquefied fluids such as
CO2 (Compton et al. 2012), propane (Ahangari & Sargolzaei 2012), and dimethyl ether (DME)
(Catchpole et al. 2008, 2009). The solute selectivity exhibited by these subcritical fluids is primarily
controlled by temperature, and they are inferior to their SCF analog with respect to mass transport
of the target solutes out of a food matrix. DME, in particular, is an interesting fluid based on
research and development at Industrial Research Limited (now Callaghan Innovation) in New
Zealand. This is largely due to DME’s mutual miscibility with water (∼10–20 mole%) and the
solubility of DME in water (∼20–30 mole%) (Tallon & Fenton 2010). Hence, in the case of
SC-CO2 , water can serve as an alternative cosolvent to alcohol-based cosolvents when extracting
more polar solutes.
Table 2 Contrast between SFE using SC-CO2 and SCW for subcritical water extraction (SWE)
SC-CO2 (SFE) versus SCW (SWE)
Aspect SC-CO2 (SFE) SCW (SWE)
Drying Yes No
Ext. of Waxes Yes No
Installation Cost High Low - Medium
Ext. Cond. Mild Medium
Conc. Effect Yes No
Environmental Yes Yes
Residual Matter Yes Yes
Abbreviations: Conc., concentration; Ext., extraction; SCW, subcritical water; SFE, supercritical fluid extraction;
SWE, subcritical water extraction.

The merits of using neat DME alone and in conjunction with CO2 have been described in a
review by Catchpole et al. (2010). Of particular interest to food technologists are the recorded
high solubilities of polar lipids such as soybean phospholipids in DME (∼20 wt.%), as well as in
DME-water mixtures using water as a cosolvent (∼30 wt.%). This is because DME-water mix-
tures under compression have a higher δ relative to SC-CO2 , which overlaps with the calculated
δs for phospholipids, such as phosphatidylcholine (18.3 MPa1/2 ), phosphatidic acid (18.8 MPa1/2 ),
phosphatidylethanolamine (19.1 MPa1/2 ), and phosphatidylinositol (22.3 MPa1/2 ). Catchpole et al.
(2006) describe a continuous process for the extraction of egg yolks and aqueous whey protein
concentrate streams in which a liquid feed stream is contacted continuously with DME through
an in-line static mixer. Lipid extraction ranged from 60% to ≥90% recovery, depending on the
feed material and processing conditions. Although DME has some of the same disadvantages
as exhibited by propane, namely high flammability, this can be partly suppressed by using mix-
tures of DME and CO2. The ability of DME and its mixture with water to extract wet biomass such
as algae, dairy products, and fermentation-derived solutes such as natural pigments at lower pres-
sures relative to those required for SC-CO2 warrants its use in the processing of foodstuffs and
natural products.
Particle Formation and Encapsulation for Food Products

SCF processes for the generation of micron-sized and submicron-sized particles having distinct
morphologies and compositions have been reported in the literature over the past two decades
(York et al. 2004). Even as early as 1996, Wagner & Eggers (1996) had shown that a powdered
form of lecithin could be generated from an oilseed concentrate by mixing the oil-laden lecithin
extract with SC-CO2 in a jet-type device. Initially, the focus was on producing materials for the
pharmaceutical industry that would either accelerate the dissolution of drugs or sustain their
release into the body. Research developed by Peter York’s group at Bradford University in the
United Kingdom catalyzed considerable interest in the pharmaceutical industry in the late 1990s;
however, adoption and transfer of these processes to this industry have not been very successful
to date. A myriad of techniques have been developed bearing acronyms such as RESS (rapid
expansion of supercritical solutions), GAS (gas antisolvent), PGSS (particles from gas-saturated
solutions), CPF (concentrated powder form), DELOS (depressurization from expanded liquid
organic solution), and PCA (precipitated with compressed antisolvent) as well as others based on
either dissolution in an SCF or use of the medium to precipitate the targeted material as fine
particles or encapsulates having usually very narrow particle-size distributions.
These methods have also been applied in the past decade to food and nutraceutical materials,
the most successful being the PGSS and CPF methods. There are numerous reviews of these
techniques, some of which cite food and nutraceutical applications (Kappler et al. 2003, Weidner
2003), including two summaries by King (2002, 2004). The PGSS process involves dissolving
the bioactive compound in a suitable solvent that is then conveyed for mixing with SC-CO2 or
another suitable fluid in a capillary-like mixing chamber. CPF, however, involves contacting the
liquid form of the bioactive material with the compressed fluid, and then expanding the mixture
through a nozzle onto a solid carrier material. These two processes find favor in part due to the
ability to operate them continuously, their GMP compatibility, and their low consumption of
compressed fluid.
Food components that have proven amenable to processing with PGSS and CPF include com-
pounds that are degraded when exposed to oxygen or light or are extremely volatile. Hence, their
adsorption on a solid carrier, such as starches, sugars, silicic acid, or the encapsulation of such
moieties via the PGSS or CPF processes, impart an extended shelf life or controlled release of the
226 King
bioactive ingredients via encapsulation. Depending on the primary mechanisms responsible for
achieving successful particle production, namely adsorption, aggregation, impregnation, or com-
binations thereof, it is possible to produce particulates in which water in lipid, or vice versa, exists.
Such particle engineering (PGSS) can stabilize aroma components in either medium depending
on their chemical nature, allowing for sustained retention of the odoriferous compounds. It is pos-
sible by selection of the right carrier material to produce an array of morphological forms ranging
from fibers, foams, porous particles, porous spheres, and solid spheres, as has been demonstrated
using polyethylene glycol (PEG) polymers. SCF-based particle engineering can also be used to
produce microemulsions or liposomes (Zhong & Dai 2011), thereby allowing delivery of essential
oils or enhancing the stability of the fish oil–based emulsions. There is an excellent review of
SCF-based particle formation of bioactive compounds by Thereza et al. (2012), which includes a
discussion of nanoemulsions and SCF extraction of emulsions.
The PGSS process has in one case been scaled up to produce more than 300 kg of partic-
ulate product per hour (Lack et al. 2005). Further scale-up of the PGSS process to 1,500 kg/h
has a projected production cost for powders in the range of $0.25–1.33, depending on the per-
annum production time and CO2 /powder ratio. In their review, Weidner & Petermann (2008)
provide further economic rationale for the PGSS process versus the antisolvent-based particu-
late processes, such as the implementation of the alternative processes being plagued by high
capitalization costs and copious fluid consumption. These are similar to production cost figures
generated by the Natex Corporation in Austria.
Table 3 lists some specific food-related products produced by critical fluid–based particulate
technology. Santos & Meireles (2010) provide a summary of carotenoid encapsulation technology,
including the merits of SCF-particulate generation. Similarly, Martin et al. (2010) have summa-
rized encapsulation of essential oil moieties using SCFs and have compared this method with
alternative encapsulation options. Seifried & Temelli (2012) demonstrated recently the drying of
β-glucan and gum Arabic particulates containing β-carotene. Encapsulation of marine- or algae-
derived oils, even if derived via SFE, is still largely done by traditional methods; however, this
could change in the near future.
Coupling of these particulate-generation technologies embracing SCFs with SFE would be
welcomed to produce the food-related product in a form for direct application after SCF process-
ing. This is one form of multiple unit processing using sub- and supercritical fluids advocated by
King & Srinivas (2009). Similarly, Catchpole et al. (2012) advocate a similar philosophy in situ in
critical fluid media. The potential reaction of CO2 with food-related materials also should be fur-
ther investigated, given that the encapsulation of carbonated food products in a particulate format
would prove useful in the commercial marketplace. However, despite considerable promise over
the past one-and-a-half decades, SCF particulate technology and related techniques must move
Table 3 Food-related products produced by critical fluid–based particulate technology

Food product Benefit
Chocolate—Kirsch Composites Aroma Retention
Powdered Green Tea Extract Antioxidant Retention
Spice Extractives (Ginger, Thyme) Adsorption of Flavor Components
Paprika Extract Dispersion of Extract in Water
β-carotene Encapsulation via Biodegradable Polymers
Astaxanthin from Shrimp Residues Microemulsion for Encapsulation
Powdered Tomato Soup Ease of Handling—Food Preparation

out of the “academic” laboratory and be commercially utilized to remain a viable option for the
food industry.
PROTECTION OF FOOD-DERIVED PRODUCTS USING

SUPERCRITICAL FLUIDS
The use of ultrahigh pressures for pasteurization of foods (Hendrickx & Knoor 2002) is a topic
in itself, and space limitations do not permit a thorough discussion of its merits and industrial
implementation. The use of gas-fluid sterilization, such as can be accomplished with SC-CO2 , is
an alternative to this technique; however, with the advent of ultrahigh-pressure SFE utilizing SC-
CO2 , there appears, perhaps, to be a synergistic benefit from the application of high hydrostatic
pressures for microbial reduction, extended shelf-life protection of the treated foodstuff, as well
as the merits associated with using SFE. Several recent reviews on the subject of sterilization and
pasteurization using SCF media (see, e.g., Damar & Balaban 2006, Bertucco & Spilimbergo 2007)
and the recent book edited by Balaban & Ferrentino (2012) are essential for those interested in a
more in-depth understanding of the subject, a state-of-the art evaluation of the patent literature,
and details of the processing technique.

Both SCF microbial and enzymatic deactivation have been demonstrated on liquid food sub-
strates, such as fruit juices, milk, and alcoholic beverages. Spilimbergo et al. (2011) have compiled
a list of these food substrates and the microorganisms of concern, primarily for CO2 -treated
substrates. Solid food substrates such as oysters, fish, ginseng, kimchi, and meats have also been
CO2 treated. Sensory panel evaluation of CO2 -pasteurized substrates indicates that there is little
perceivable difference from those foodstuffs treated via retorting.
Microbial Reduction and Pasteurization of Foods with Supercritical Fluids

Successful exposure of bacterial cells and their subsequent deactivation can be accomplished if
three criteria are met: (a) SC-CO2 must dissolve and diffuse in the supporting media in which the
cells are contained; (b) the CO2 must permeate the cell wall to gain access to the cell interior; and
(c) the microorganism must be deactivated by the fluid via one or a combination of mechanisms,
such as a pH change (in the case of CO2 ), denaturing of the constituent proteins, and physi-
cal disruption of the cells’ morphologies. The latter may permanently or reversibly disrupt the
microorganism and can be promoted by cycling the applied fluid pressure.
It is well known that carbon dioxide can influence the pH of aqueous media at various pres-
sures and temperatures, and that this secondary equilibrium can exert a specific control over
extraction using SC-CO2 , the activity profile of specific proteins/enzymes, as well as act as a bac-
teriostat. Using high-pressure carbon dioxide to reduce microbial counts in foodstuffs is attractive
because it represents a benign pasteurization technique relative to thermal retorting, thereby al-
lowing retention of the original properties of the food matrix with respect to flavor, color, etc.
Garcia-Gonzalez et al. (2007) have provided a critical updated review. Relative to high-pressure
food processing, the requisite pressures of CO2 are much lower (20 MPa versus 300–600 MPa).
SC-CO2 is somewhat unique relative to other high-pressure fluids, such as nitrogen, nitrous oxide,
etc., in reducing microbial counts, partly due to the presence of carbonic acid in the aqueous fluid,
as previously mentioned. Depending on the type of bacterial cells being exposed to pressurized
CO2 , there are a range of log reductions that have been reported. These are summarized in a
tabular form for Gram-positive cells, Gram-negative cells, fungal species, and bacterial spores.
These log reductions range from slightly above zero to 8 log in magnitude, depending on the
resistance of the microorganism (Erkmen 2012).
228 King
The versatility of microbial deactivation with supercritical carbon dioxide is facilitated by using
moist foodstuffs facilitating the formation of carbonic acid, and the rate—particularly of CO2
depressurization—if abrupt, can rupture cell walls. These benefits suggest that, as mentioned
previously, SWE slightly above 100◦ C could be a very effective method for sterilizing an aqueous
extract in situ, an effect that has not yet been confirmed. If a high rate of microbial deactivation
were to occur during SWE, it would probably be due to a combination of thermal deactivation
and carbonic acid lowering of the microbial count. For example, the results of Del Pozo-Insfran
et al. (2006), who compared dense CO2 -treated grape juice with grape juice treated with heat
pasteurization, provide some support for the dual benefit of carbonated SWE, in terms of its shelf
life, anthocyanin content, total phenolics, and antioxidant capacity.
The thermodynamic basis of aqueous SC-CO2 treatment of fruit and vegetable products is
based, once again, in CO2 ’s solubility in water as a function of CO2 pressure, temperature, and
the CO2 partial pressure above the liquid being treated. The Balaban group (Calix et al. 2008) has
reported additional data on high-pressure CO2 solubility in neat water and juices (Ferrentino et al.
2009) based on a stirred autoclave solubility device and measurements taken of CO2 sorption into
neat water, real orange or apple juice, and model solutions simulating the fruit juices. In general,
CO2 solubility is suppressed slightly in the real and simulated juice matrices.
Regulation of Enzymatic Activity in the Food Matrix

Unlike synthetic enzymatic-initiated reactions in the presence of SC-CO2 , where the emphasis
is on enzyme survival under SCF conditions (Wimmer & Zarevúcka 2010), the deactivation of
enzymes using CO2 at elevated pressures is intended to nullify their activity in order to preserve
attributes of the foodstuff that contribute to consumer acceptance and extension of shelf life.
Some examples are the deactivation of polyphenol oxidases that cause browning in fruits and
vegetables, lipoxygenase activity reduction due to its off-flavor inducing activity, pectinesterase-
induced clouding in fruit juices, and peroxidase discoloration in foods.
Food enzyme deactivation in the presence of an SCF can be due to a change in the fluid pH
surrounding the enzyme, alteration in the isoelectric point of the constituent protein, as well
as conformational effects that render the enzyme inactive. Concerns about the effect of pH on
certain food types, such as dairy products, and the vitamin content of the food substrate have
made a case for the substitution of supercritical nitrous oxide, SC-N2 O, in place of CO2 .
With respect to the treatment of subcellular moieties such as viruses, prions, and toxic phages,
ultrahigh-pressure food processing is probably a better choice, although it requires pressures
in the range of 300–600 MPa. However, the previously noted ultrahigh-pressure SFE may also
impart some prophylactic action with respect to microbe and enzyme deactivation, and hence also
enhance the shelf life of the extract intended for food use. Certainly, the benefits of combining
exposure to CO2 during SFE on the sterilization and shelf life of extracts, such as antioxidants,
could be considered a prerequisite in post-extraction testing of a resultant extract. This is similar
to the requirement of doing a mandatory life cycle and/or economic analysis of SCF-based
processes, as advocated in the literature (Rodriguez-Meizoso et al. 2012).
Isolation of Natural Antioxidants from Sustainable Sources

Currently, considerable research interest has been focused on obtaining antioxidant-laden extracts
from natural products and industrial food waste streams using SWE and SC-CO2 , both with and
without cosolvents. The notable studies of Turner & Ibanez (2012) and many other groups (see,
e.g., Diaz-Reinoso et al. 2006) have demonstrated that pressurized fluid extraction and/or SFE

can produce extracts exhibiting high ORAC (oxygen radical absorbance capacity) values, among
them procyanidins and anthocyanins from waste grape pomace and rosemary extracts. A nice
review by Parajo et al. (2009) of SFE applied to the extraction of antioxidants includes a consid-
erable list of additional substrates to which both SFE and SWE have been applied. Their sum-
mary table tabulates the application of antioxidant tests that have been applied on SWE extracts,
thereby illustrating that assays such as bioassays can be used to test the efficacy of an extraction
technology.
BENEFITS OF SUPERCRITICAL FLUID TECHNOLOGY

IN A BROADER CONTEXT
There are now more than 150 SFE plants with a total extraction volume of more than 500 L
that now exist throughout the world. Many of these production plants are generally dedicated to
the SFE of natural products, leading to the recovery of higher-value products. Today, processes
such as SFE and SFF are currently oriented toward extracts or products with much higher added
value than those developed using SCF technology in the past 40 years. These include targeted
products for the nutraceutical industry or for incorporation into functional foods. Examples of
this trend are the SFE and SFF of specialty lipids from high-value seed oils and microalgae that
contain polyunsaturated fatty acids. Finally, future SFE and SFF applications will no longer be
operated as single-step operations but as integrated unit operations (Leboeuf & Deschamps 2010),
in combination with additional separation processes such as membrane separations, high-pressure
reactors, or integrated particulate formation.
A Supercritical Fluid–Based Food Processing Platform for

Supporting Sustainability
The application of SCFs and related media to obtain food-related chemicals from renewable and
sustainable resources, such as starch-containing materials, crops, lignocellulosic biomass feed-
stocks, vegetable oils, and microalgae, is well under way, and the resultant extracts—which often
require additional purification—will provide interesting options for use in the food industry. Of
these renewable materials, microalgae-derived compounds seem amenable to SFE and SWE,
primarily because of their economic value. Mantell et al. (2013) summarize these possibilities
to include the following: carotenoids, ω-fatty-acid-containing oils, oxygen-containing pigments
such as astaxanthin and lutein esters, and tocopherols, among others.
King & Srinivas (2009) have advocated that SFE or SWE be inserted initially into processing
schemes involving renewal biomass or biofuel feedstocks, so as to remove food-related and bioac-
tive compounds prior to the feedstock treatment for conversion to a fuel-related substrate. The
use of SFE and SWE on agriculturally derived processing wastes continues to be explored and has
elicited considerable interest from industries interested in achieving additional profits. Examples
of such residues include grape and olive waste, tomato and onion skins, spent brewers’ yeast, and
citrus substrates such as mango. The antioxidant and pigment contents of many of these waste
products are being extracted for the nutraceutical and food markets.
Hence, it appears that if we can design our biomass fractionation processes properly, we
can achieve benefit for both the food and bioenergy sectors that are often viewed as competing
for the same agriculturally derived feedstock materials. An excellent example of this processing
philosophy is depicted in Figure 5, where a hypothetical biorefinery for rice feedstock has been
envisioned. Here, physical fractionation of the components of rice is shown to have the potential
for providing rice in several forms for food use, energy use (biodiesel), phytochemical isolation
230 King
Energy
scPropane
1,3-propylenediol Glycerol Biodiesel Fatty alcohol Surfactants
sc MeOH
PTT Ferrulic acid IP6 (Phytic acid)
Poly(trimethylene
terephthalate) γ-Oryzanol Inositol
Tocopherol Calcium phosphates
sc CO2
Hull
Bran Brown Rice sc CO2 Defatted

Deffated Milling
White rice rice bran rice bran
Germ
scCO2
Powdered
defatted
rice bran
White sc CO2
Hull rice
SCW
CO2-treated white rice
Bio-PET
Bio-nylon
Bio-PC
scCO2-treated
brown rice
Figure 5
A rice-based biorefinery illustrating fractionation of rice into food, fuel, and chemical components with the aid of supercritical fluid
technology. Abbreviation: SCW, subcritical water. Figure reprinted with permission from Professor Yuan Woo Lee, Seoul National
University.
(rice bran oil), as well as chemicals as intermediates in oleochemical and polymer production.
Treatment using SC-CO2 can assist in extending the shelf lives of certain types of rice, removing
unwanted substances from rice, and defatting rice-based substrates, as pictured in Figure 5. This
processing theme incorporating pressurized CO2 to some extent has been implemented in several
Asian countries such as Taiwan, South Korea, and China.
The integration of multi-fluid and unit operation processes utilizing critical fluid technology
has been summarized by King et al. (2011) and has been shown to be applicable to rice bran
processing, cashew nut shells, and palm oil constituents. These make use of extractions using mixed
critical fluids in sequence and together (SC-CO2 + SCW); columnar fractionation; SFC; and, in
some cases, reaction chemistry embracing enzymes, hydrogenation, and hydrolysis under SCW
conditions. As already noted in the discussion of particulate formation using SCFs, the addition
of SC-CO2 can provide an antisolvent effect, and this principle has been used to demonstrate the
separation of lipid species, fruit-derived acids, and carotenoids. Thiering et al.’s (2000) studies
have demonstrated the salting-out properties of SC-CO2 related to protein fractionation, and a
similar theme has been extensively investigated by Bonnaillie & Tomasula (2012) for milk and
cheese-related food products. In one particular case, extraction with pressurized water has been

used to produce micron-sized particulates from rosemary and oregano extracts (Herrero et al.
2009b).
Coupling Supercritical Fluid Extraction for Food Use

with Bioenergy Production
Over the past 20 years, I have been, on more than one occasion, questioned about the possibility
of constructing an SFE plant in close proximity to an alcohol fermentation facility that produces
high-purity CO2 as a by-product. This would seem logical given that the opportunity to apply
SFE for vegetable or specialty oil extraction could be facilitated with this source of CO2 , as well as
any of the above-mentioned CO2 -based unit processes. The production of ethanol at such a site
facilitates its use as a preferred cosolvent for coupling with SC-CO2 or for use in forming fatty
acid ethyl esters for biodiesel use, or for improving the SFF of lipid compounds.
In the renewable bioenergy field today, it is envisioned as ideal to build coexisting bioethanol
and biodiesel production capabilities at the same site. Hence, on the basis of our discussion above,
this suggests the possibility of extending the application of the critical fluids platform for the
production of these two renewable fuels. Similarly, it was noted above that SC-CO2 could be mixed
advantageously with pressurized water (SCW) for potential extraction and reaction chemistries.
Such a critical fluid–based processing concept supports the use of bio-based renewable resources
and a sustainability platform, and does so in a green, environmentally benign manner.
SUMMARY POINTS
1. Antioxidant folding using supercritical fluid technology has been commercially-
implemented and will receive continual emphasis because of its importance in nutraceu-
tical and functional food science.
2. The application of SFE to algae and related marine-derived products is and will continue
to be an application focus area. The use of these health-beneficial food products versus
their use as renewable fuel resources in fuel is a point of considerable controversy.
3. The use of multiple fluids and unit processes based on critical fluid processing technology
is seeing increased use in producing food-based materials and supplements.
4. Numerous processing facilities continue to be implanted worldwide, resulting in many
food and nutraceutical supplements that proclaim the use of SFE and SC-CO2 on their
labels.
FUTURE ISSUES
1. Optimizing continuous SCF processing systems—such as expellers, extruders, and other
countercurrent-based systems—will be important in terms of increasing production.
2. Removal of residual solvents and toxicants from food and nutraceutical products using
SFE employing SC-CO2 needs to be studied further with respect to new regulatory
requirements.
3. Cost and life-cycle analysis for SCF technologies versus competitive technologies will be
a future requirement and will complement research and development in this field.
232 King
4. Production-scale SFC needs further development in terms of its application to producing

bioactive concentrates for the nutraceutical or functional food marketplace.
5. Extraction versus reaction conditions to produce functional food ingredients using sub-
critical fluids such as water needs further investigation in terms of deriving bioactive
components.
DISCLOSURE STATEMENT
The author is not aware of any affiliations, memberships, funding, or financial holdings that might
be perceived as affecting the objectivity of this review.
LITERATURE CITED
Abbas KA, Mohamed A, Abdulamir AS, Abas HA. 2008. A review on supercritical fluid extraction as new
analytical method. Am. J. Biochem. Biotechnol. 4:345–53
Ahangari B, Sargolzaei J. 2012. Extraction of pomegranate seed oil using subcritical propane and supercritical
carbon dioxide. Theor. Found. Chem. Eng. 46:258–65
Ajchariyapagorn A, Douglas PL, Douglas S, Pongamphai S, Teppaitoon W. 2008. Prediction of solubility
of solid biomolecules in supercritical solvents using group contribution methods and equations of state.
Am. J. Food Technol. 3:275–93
Baig MN, Santos RCD, Zetzl C, King J, Pioch D, Bowra S. 2011. Evaluation and modeling the utility of
SCCO2 to support efficient lipase mediated esterification. Enzyme Microb. Technol. 49:420–26
Balaban MO, Ferrentino G, eds. 2012. Dense Phase Carbon Dioxide – Food and Pharmaceutical Applications. Ames,
IA: Wiley. 316 pp.
Barton AFM. 1991. Handbook of Solubility Parameters and Other Cohesional Parameters. Boca Raton, FL: CRC
Press. 739 pp. 2nd ed.
Basile A, Jimenez-Carmona MM, Clifford AA. 1998. Extraction of rosemary by superheated water. J. Agric.
Food Chem. 46:5204–9
Beckman EJ. 2012. Supercritical and near-critical CO2 processing. In Green Technologies in Food Production and
Processing, ed. JI Boye, Y Arcand, pp. 239–71. New York: Springer
Bergeron C, Carrier DJ, Ramaswamy S, eds. 2012. Biorefinery Co-Products Phytochemicals, Primary Metabolites
and Value-Added Biomasss Processing. West Sussex, UK: Wiley. 361 pp.
Bertucco A, Spilimbergo S. 2007. Food pasteurization and sterilization with high pressure. In Functional Food
Ingredients and Nutraceuticals, ed. J Shi, pp. 269–95. Boca Raton, FL: Taylor & Francis
Bonnaillie LM, Tomasula PM. 2012. Sequential fractionation of milk and whey proteins with supercritical
carbon dioxide for new health-promoting food ingredients. In ISSF-2012: 10th Int. Symp. Supercrit. Fluids,
San Francisco, May 13–16. Proc. L-227, pp. 647–52
Brignole E, Pereda S. 2013. Phase Equilibrium Engineering. Amsterdam: Elsevier. 331 pp.
Brondz I. 2012. Supercritical fluids: supercritical fluid extraction (SFE) and supercritical fluid chromatography.
Special issue. Am. J. Anal. Chem. 3(12A):867–69
Brunner G. 1994. Gas Extraction. An Introduction to Fundamentals of Supercritical Fluids and the Application to
Separation Processes. Darmstadt: Steinkopff/New York: Springer. 387 pp.
Brunner G. 2005. Supercritical fluids: technology and applications to food processing. J. Food Eng. 67:21–33
Brunner G. 2010. Applications of supercritical fluids. Annu. Rev. Chem. Biomol. Eng. 1:321–42
Brunner G, Machado NT. 2012. Process design methodology for fractionation of fatty acids from palm fatty
acid distillates in countercurrent packed columns with supercritical CO2 . J. Supercrit. Fluids 66:96–110
Cacace JE, Mazza G. 2006. Pressurized low polarity water extraction of lignans from whole flaxseed. J. Food
Eng. 77:1087–95
Calix TF, Ferrentino G, Balaban MO. 2008. Measurement of high pressure carbon dioxide solubility in orange
juice, apple juice, and model liquid foods. J. Food Sci. 73:E439–45

Carvalho RHR, Galvão EL, Barros JAC, Conceição MM, Sousa EMBD. 2012. Extraction, fatty acid profile
and antioxidant activity of sesame extract (Sesamum Indicum L.). Braz. J. Chem. Eng. 29:409–20
Catchpole OJ, Durling NE, Grey JB. 2006. Improvements in or relating to separation technology. NZ Patent
Appl. No. 545146, World Patent No. WO2007091901
Catchpole OJ, Grey JB, Noermark KA. 2000. Fractionation of fish oils using supercritical CO2 and CO2 +
ethanol mixtures. J. Supercrit. Fluids 19:25–37
Catchpole OJ, Ryan J, Zhu Y, Fenton K, Grey J, et al. 2010. Extraction of lipids from fermentation biomass
using near-critical dimethyl ether. J. Supercrit. Fluids 53:34–41
Catchpole OJ, Tallon S, Dyer P, Montanes F, Moreno T, et al. 2012. Integrated supercritical fluid extraction
and bioprocessing. Am. J. Biochem. Biotechnol. 8:263–87
Catchpole OJ, Tallon SJ, Eltringham WE, Grey JB, Fenton KA, et al. 2009. The extraction and fractionation
of specialty lipids using near critical fluids. J. Supercrit. Fluids 47:591–97
Catchpole OJ, Tallon SJ, Grey JB, Fletcher K, Fletcher AJ. 2008. Extraction of lipids from a specialist dairy
stream. J. Supercrit. Fluids 45:314–21
Clark JH. 2011. Introduction to green chemistry. In Alternatives to Conventional Food Processing, ed. A Proctor,
pp. 1–10. Cambridge, UK: RSC
Compton DL, Eller FJ, Laszlo JA, Evans KO. 2012. Purification of 2-monoacylglycerols using liquid CO2
extraction. J. Am. Oil Chem. Soc. 89:1529–36
Cristancho CAM, Peper S, Johannsen M. 2012. Supercritical fluid simulated moving bed chromatography
for the separation of ethyl linoleate and ethyl oleate. J. Supercrit. Fluids 66:129–36
Damar S, Balaban M. 2006. Review of dense phase CO2 technology: Microbial and enzyme inactivation, and
effects on food quality. J. Food Sci. 71:R1–11
Damar S, Balaban MO, Sims CA. 2009. Continuous dense-phase CO2 processing of a coconut water beverage.
Int. J. Food Sci. Technol. 44:666–73
Darani K-K, Mozafari MR. 2009. Supercritical fluids technology in bioprocess industries: A review. J. Biochem.
Technol. 2:144–52
Deiters UK, Kraska T. 2012. High-Pressure Fluid Phase Equilibria. Amsterdam: Elsevier. 342 pp.
del Pozo-Insfran D, Balaban MO, Talcott ST. 2006. Microbial stability, phytochemical retention, and
organoleptic attributes of dense phase CO2 processed muscadine grape juice. J. Agric. Food Chem. 54:5468–
73
del Valle JM, de la Fuente JC. 2006. Supercritical CO2 extraction of oilseeds: review of the kinetic and
equilibrium models. Crit. Rev. Food Sci. Nutr. 46:131–60
del Valle JM, de la Fuente JC, Srinivas K, King JW. 2011. Correlation for the variations with temperature of
solute solubilities in high temperature water. Fluid Phase Equilib. 301:206–16
Diaz-Reinoso B, Moure A, Dominguez H, Parajo JC. 2006. Supercritical CO2 extraction and purification of
compounds with antioxidant activity. J. Agric. Food Chem. 54:2441–69
Dunford NT, King JW. 2004. Supercritical fluid fractionation process for phytosterol ester enrichment in
vegetable oils. US Patent No. 6677469 B1
Durling NE, Catchpole OJ, Tallon SJ, Grey JB. 2007. Measurement and modeling of the ternary phase
equilibria for high pressure carbon dioxide-ethanol-water mixtures. Fluid Phase Equilib. 252:103–13
Eller FJ, Teel JA, Palmquist DE. 2011. Continuous hydrolysis of cuphea seed oil in subcritical water. J. Am.
Oil Chem. Soc. 88:1455–61
Eltringham W, Catchpole O. 2008. Processing of fish oils by supercritical fluids. See Martinez 2008, pp. 141–88
Erkmen O. 2012. Effects of dense phase carbon dioxide on vegetative cells. See Balaban & Ferrentino 2012,
pp. 67–97
Favati F, King JW, Friedrich JP, Eskins K. 1988. Supercritical CO2 extraction of carotene and lutein from
leaf protein concentrates. J. Food Sci. 53:1532–36
Fernandez-Ronco MP, de Lucas A, Rodriguez JF, Garcia MT, Gracia I. 2013. New consideration in the
economic evaluation of supercritical processes: Separation of bioactive compounds from multicomponent
mixtures. J. Supercrit. Fluids 79:345–55
Ferrentino G, Plaza ML, Ramirez-Rodrigues M, Ferrari G, Balaban MO. 2009. Effects of dense phase carbon
dioxide pasteurization on the physical and quality attributes of a red grapefruit juice. J. Food Sci. 74:E333–
41
234 King
Fornari T, Chafer A, Stateva RP, Reglero G. 2005. A new development in the application of the group
contribution associating equation of state to model solid solubilities of phenolic compounds in SC-CO2 .
Ind. Eng. Chem. Res. 44:8147–56
Fornari T, Tenllado D, Torres C, Reglero G. 2011. Supercritical phase equilibria modeling of glyceride
mixtures and carbon dioxide using the group contribution EoS. J. Thermodyn. 2011:730960
Garcia-Gonzalez L, Geeraerd AH, Spilimbergo S, Elst K, Van Ginneken L, et al. 2007. High pressure carbon
dioxide inactivation of microorganisms in foods: The past, the present and the future. Int. J. Food Microbiol.
117:1–28
Goto M, Tanaka M, Quitain AT, Sasaki M, Fukuzato R. 2012. Recovery of phytochemicals by hybrid
extraction process using supercritical CO2 and water. In ISSF-2012: 10th Int. Symp. Supercrit. Fluids,
San Francisco, May 13–16, pp. 626–32
Gregg FB Jr. 2003. Saw palmetto composition and associated methods. US Patent No. 6669968 B2
Gupta RB, Shim J-J. 2007. Solubility in Supercritical Carbon Dioxide. Boca Raton, FL: CRC Press. 909 pp.
Hansen CM. 2007. Hansen Solubility Parameters – A User’s Handbook. Boca Raton, FL: CRC Press. 519 pp. 2nd
ed.
Hendrickx MEG, Knoor D, eds. 2002. Ultra High Pressure Treatments of Foods. New York: Kluwer
Acad./Plenum. 340 pp.
Herrero M, Mendiola JA, Cifuentes A, Ibanez E. 2009a. Supercritical fluid extraction: recent advances and
applications. J. Chromatogr. A 1217:2495–511
Herrero M, Plaza M, Cifuentes A, Ibáñez E. 2009b. Green processes for extraction of bioactives from rose-
mary. Chemical and functional characterization via UPLC-MS/MS and in-vitro assays. J. Chromatogr. A
1217:2512–20
Ibanez E, Kubatova A, Senorans FJ, Cavero S, Reglero G, Hawthorne SB. 2003. Subcritical water extraction
of antioxidant compounds from rosemary plants. J. Agric. Food Chem. 51:375–82
Igl-Schmid N, Wuzik A. 2012. Extraction of natural products for industrial applications. In ISSF-2012: 10th
Int. Symp. Supercrit. Fluids, San Francisco, May 13–16, pp. 122–24
Ju ZY, Howard LR. 2005. Subcritical water and sulfured water extraction of anthocyanins and other phenolics
from dried red grape skin. J. Food Sci. 70:S270–76
Kagliwala LD, Patilb SC, Polb AS, Singhala RS, Patravaleb VB. 2011. Separation of bioactives from seabuck-
thorn seeds by supercritical carbon dioxide extraction methodology through solubility parameter ap-
proach. Sep. Purif. Technol. 80:533–40
Kappler P, Leiner W, Petermann M, Weidner E. 2003. Size and morphology of particles generated by spraying
polymer-melts with carbon dioxide. In ISSF-2003: 6th Int. Symp. Supercrit. Fluids, Versailles, Fr., April
28–30
Khuwijitjaru P, Sayputikasikorn N, Samuhasaneetoo S, Penroj P, Siriwongwilaichat P, Adachi S. 2012. Subcrit-
ical water extraction of flavoring and phenolic compounds from cinnamon bark (Cinnamomum zeylanicum).
J. Oleo Sci. 61:349–55
King JW. 2002. Critical fluid technology options for isolating and processing agricultural and natural products.
In Proc. 1st Int. Symp. Supercrit. Fluid Technol. Energy Environ. Appl. (Super Green 2002), Suwon, South
Korea, Nov. 3–6, pp. 61–66
King JW. 2003. Coupled processing options for agricultural materials using supercritical fluid carbon dioxide.
In Supercritical Carbon Dioxide – Separations and Process, ed. AS Gopalan, CM Wai, HK Jacobs, pp. 104–29.
Washington, DC: Am. Chem. Soc.
King JW. 2004. Development and potential of critical fluid technology in the nutraceutical industry. In
Supercritical Fluids Technology for Drug Product Development, ed. P York, UB Kompella, BY Shekunov,
pp. 579–614. New York: Marcel Dekker
King JW. 2005. Supercritical fluid processing of nutritionally functional lipids. In Healthful Lipids, ed. CC
Akoh, O-M Lai, pp. 99–126. Champaign, IL: AOCS Press
King JW. 2006. Pressurized water extraction: resources and techniques for optimizing analytical applications.
In Modern Extraction Techniques: Food and Agricultural Samples, ed. C Turner, pp. 79–95. Washington,
DC: Am. Chem. Soc.
King JW. 2012. Supercritical fluid-based extraction/processing: then and now. INFORM 23:122–25

King JW. 2013. Supercritical fluid extraction at high pressures (>700 bar): theoretical considerations and
practical applications. In Proc. 3rd Iberoam. Conf. Supercrit. Fluids (Prosciba 2013), Cartagena, Colomb.,
April 1–5. Proceeding K-2, pp. 1–14
King JW, Favati F, Taylor SL. 1996. Production of tocopherol concentrates by supercritical fluid extraction
and chromatography. Sep. Sci. Technol. 31:1843–57
King JW, List GR. 2011. Hydrogenation using critical fluids. In Hydrogenation of Fats and Oils: Theory and
Practice, ed. GR List, JW King, pp. 49–109. Champaign, IL: AOCS Press. 2nd ed.
King JW, Srinivas K. 2009. Multiple unit processing using sub- and supercritical fluids. J. Supercrit. Fluids
47:508–610
King JW, Srinivas K, Zhang D. 2011. Advances in critical fluid processing. In Alternatives to Conventional Food
Processing, ed. A Proctor, pp. 93–144. Cambridge, UK: RSC
Kraske T, Leonhard KO, Tuma D, Schneider GM. 2002. Correlation of the solubility of low-volatile or-
ganic compounds in near- and supercritical fluids. Part I: Applications to adamantine and β-carotene.
J. Supercrit. Fluids 23:209–24
Kubatova A, Lagadec AJM, Miller DJ, Hawthorne SB. 2001. Selective extraction of oxygenates from savory
and peppermint using subcritical water. Flavour Fragr. J. 16:64–73
Lack E, Weidner E, Knez Z, Grüner S, Weinreich B, Seiditz H. 2005. Particle generation with supercrit-
ical CO2 . Proc. 1st Vienna Int. Conf.: Micro- Nano-Technol., Vienna, Austria. The Austrian Tribol. Soc.,
March 9–11. http://www.natex.at/download/CPF-PGSS-article.pdf

Leboeuf F, Deschamps F. 2010. Supercritical fluid processing in food and pharmaceutical industries: Scale-up
issues. In Current Trends of Supercritical Fluid Technology in Pharmaceutical, Nutraceutical and Food Processing
Industries, ed. ARC Duarte, CMM Duarte, pp. 97–115. Sharjah, UAE: Bentham Sci.
Luetge C, Bork M, Knez Z, Kreiner M. 2007. Ultra high pressure dense gas extraction and fractionation. In
Proc. 5th Int. Symp. High Press. Process. Technol. Chem. Eng., Segovia, Spain. June 24–27
Luetge C, Steinhagen V, Bork M, Knez Z. 2009. Supercritical carbon dioxide extraction of plant materials at
ultrahigh pressure. In ISSF-2009: 9th Int. Symp. Supercrit. Fluids, Arcachon, Fr., May 18–20
Machida H, Takesue M, Smith RL. 2011. Green chemical processes with supercritical fluids: Properties,
materials, separation and energy. J. Supercrit. Fluids 60:2–15
Macias-Sanchez MD, Mantell C, Rodriguez M, Martinez de la Ossa EJ, Lubian E, Montero O. 2008. Extraction
of carotenoids and chlorophyll from microalgae with supercritical carbon dioxide and ethanol as cosolvent.
J. Sep. Sci. 31:1352–62
Mantell C, Casas L, Rodriguez M, Martinez de la Ossa E. 2013. Supercritical fluid extraction. In Separation
and Purification Technologies in Biorefineries, ed. S Ramaswamy, H-J Huang, BV Ramarao, pp. 79–100.
West Sussex, UK: Wiley
Marcus Y. 2006. Are solubility parameters relevant to supercritical fluids? J. Supercrit. Fluids 38:7–12
Martin A, Varona S, Navarrete A, Cocero MJ. 2010. Encapsulation and co-precipitation processes with su-
percritical fluids: Applications with essential oils. Open Chem. Eng. J. 4:31–40
Martinez JL, ed. 2008. Supercritical Fluid Extraction of Nutraceuticals and Bioactive Compounds. Boca Raton, FL:
CRC Press. 402 pp.
Minatelli J, Hill S, Meorck R, Nguyen U. 2011. Plant derived seed extract rich in essential fatty acids
derived from perilla seed: composition of matter, manufacturing process and use. World Patent No.
WO2013039537 A1, US Patent No. 2012/027787 A1
Mohamed RS, Mansoori GA. 2002. The use of supercritical fluid extraction in food processing. Food Technol.
Mag., June
Montanes F, Catchpole OJ, Tallon S, Mitchell K, Lagutin K. 2013. Semi-preparative supercritical chromatog-
raphy scale plant polyunsaturated fatty acids purification. J. Supercrit. Fluids 79:46–54
Montes A, Gordillo MD, Pereyra C, Martinez de la Ossa EJ. 2011. Particles formation using supercritical
fluids. In Mass Transfer – Advanced Aspects, ed. H Nakajima, pp. 461–80. Rijeka, Crotia: InTech.
http://www.intechopen.com/books/mass-transfer-advanced-aspects/particles-formation-using-
supercritical-fluids
Nobre B, Marcelo F, Passos R, Beirao L, Palavra A, et al. 2006. Supercritical carbon dioxide extraction of
astaxanthin and other carotenoids from the microalga Haematococcus pluvialis. Eur. Food Res. Technol.
223:787–90
236 King
Ozel MZ, Gogus F, Lewis AC. 2003. Subcritical water extraction of essential oil from Thymbra spicata. Food
Chem. 82:381–86
Panayiotou C. 1997. Solubility parameter revisited: an equation-of-state approach for its estimation. Fluid
Phase Equilib. 131:21–35
Pandey A, Larroche C, Ricke SC, Dussap C-G, Gnansounou E, eds. 2011. Biofuels – Alternative Feedstocks and
Conversion Processes. Amsterdam: Elsevier. 629 pp.
Parajo JC, Dominguez H, Moure A, Diaz-Reinoso B. 2009. Obtaining antioxidants by supercritical fluid
extraction. In Extracting Bioactive Compounds for Food Products, ed. MAA Meireles, pp. 288–327. Boca
Raton, FL: CRC Press
Perrut M, Majewski W, Breivik H. 2001. Purifying polyunsaturated fatty acid glycerides. US Patent
No. 6204401 B1
Persson P, Larsson S, Jönsson LJ, Nilvebrant NO, Sivik B, et al. 2002. Supercritical fluid extraction of a
lignocellulosic hydrolysate of spruce for detoxificationand to facilitate analysis of inhibitors. Biotechnol.
Bioeng. 79:694–700
Prado JM, Assis A, Marostica MR, Meireles MAA. 2010. Manufacturing cost of of supercritical-extracted oils
and carotenoids from Amazonian plants. J. Food Process Eng. 33:348–69
Prado JM, Dalmolin I, Carareto NDD, Basso RC, Meirelles AJ. 2012. Supercritical fluid extraction of grape
seed: process scale-up, extract chemical composition and economic evaluation. J. Food Eng. 109:249–57
Rai N, Siepmann JI, Schultz NE, Ross RB. 2007. Pressure dependence of the Hildebrand solubility parameter
and the internal pressure: Monte Carlo simulations for external pressures up to 300 MPa. J. Phys. Chem.
C 111:15634–41
Ramaswamy S, Huang H-J, Ramarao BV. 2013. Separation and Purification Technologies in Biorefineries. West
Sussex, UK: Wiley. 584 pp.
Ramirez P, Garcia-Risco MR, Santoyo S, Senorans FJ, Ibanez E, Reglero G. 2006. Isolation of functional
ingredients from rosemary by preparative supercritical fluid chromatography (SFC). J. Pharm. Biomed.
Anal. 41:1606–13
Reverchon E, DeMarco I. 2006. Supercritical fluid extraction and fractionation of natural matter. J. Supercrit.
Fluids 38:146–66
Reverchon E, DeMarco I. 2008. Essential oils extraction and fractionation using supercritical fluids. See
Martinez 2008, pp. 305–35
Riha V, Brunner G. 2000. Separation of fish oil ethyl esters with supercritical carbon dioxide. J. Supercrit.
Fluids 17:55–64
Rodriguez-Meizoso I, Castro-Puyana M, Borjesson P, Mendiola JA, Turner C, Ibanez E. 2012. Life cycle
assessment of green pilot-scale extraction processes to obtain potent antioxidants from rosemary leaves.
J. Supercrit. Fluids 72:205–12
Rozzi NL, Singh RK. 2002. Supercritical fluids and the food industry. Comp. Rev. Food Sci. Food Saf. 1:33–44
Santos DT, Meireles MAA. 2010. Carotenoid pigments encapsulation: Fundamentals, techniques and recent
trends. Open Chem. Eng. J. 4:42–50
Seabra IJ, Braga MEM, Batista MTP, de Sousa HC. 2012. Fractionated high pressure extraction of antho-
cyanins from elderberry (Sambucus nigra L.) pomace. Food Bioprocess Technol. 3:674–83
Seifried B, Temelli F. 2012. Supercritical fluid drying of high molecular weight biopolymers for particle
formation and delivery of bioactives. In ISSF-2012: 10th Int. Symp. Supercrit. Fluids, San Francisco,
May 13–16, Proc. L-315, pp. 816–23
Sereewatthanawut I, Prapintip S, Watchiraruji K, Goto M, Sasaki M, Shotipruk A. 2008. Extraction of protein
and amino acids from deoiled rice bran by subcritical water hydrolysis. Bioresour. Technol. 99:555–61
Shi J, Xue SJ, Ma Y, Jiang Y, Ye X, Yu D. 2012. Green separation technologies in food processing: supercritical-
CO2 fluid and subcritical water extraction. In Green Technologies in Food Production and Processing, ed. JI
Boye, Y Arcand, pp. 273–94. New York: Springer
Skerget M, Knez Z, Knez-Hrncic M. 2011. Solubility of solids in sub- and supercritical fluids: a review.
J. Chem. Eng. Data 56:694–719
Sovova H. 2010. Mathematical modeling of supercritical fluid extraction. In Current Trends of Supercritical
Fluid Technology in Pharmaceutical, Nutraceutical and Food Processing Industries, ed. ARC Duarte, CMM
Duarte, pp. 80–96. Sharjah, UAE: Bentham Sci.

Spilimbergo S, Matthews MA, Cinquemani C. 2011. Supercritical fluid pasteurization and food safety. In
Alternatives to Conventional Food Processing, ed. A Proctor, pp. 145–83. Cambridge, UK: RSC
Srinivas K. 2010. Determination of thermodynamic and mass transfer parameters for subcritical water extraction of
flavonoids from grape pomace. PhD Thesis, Univ. Ark., Fayetteville
Srinivas K, King JW. 2010. Supercritical carbon dioxide and subcritical water: Complimentary agents in the
processing of functional foods. In Functional Food Product Development, ed. J Smith, E Charter, pp. 39–78.
New York: Wiley-Blackwell
Srinivas K, King JW, Howard LR, Monrad JK, Zhang D. 2011. Pressurized solvent extraction of flavonoids
from grape pomace utilizing organic acid additives. Ital. J. Food Sci. 23:90–105
Srinivas K, King JW, Monrad J, Howard L, Hansen CM. 2009. Optimization of subcritical fluid extraction
of bioactive compounds using Hansen solubility parameters. J. Food Sci. 74:E342–54
Steinhagen V, Luetge C, Knez Z. 2010. Multi-stage separation during ultra high pressure extraction processes.
In Proc. 2nd Iberoam. Conf. Supercrit. Fluids (Prosciba 2010), Natal, Braz., April 5–9
Sugihara N, Kanda A, Nakano T, Nakamura T, Igusa H, Hara S. 2010. Novel fractionation method for
squalene and phytosterols contained in the deodorizer distillate of rice bran oil. J. Oleo Sci. 59:65–70
Tallon S, Fenton K. 2010. The solubility of water in mixtures of dimethyl ether and carbon dioxide. Fluid
Phase Equilib. 298:60–66
Taylor SL, King JW, Montanari L, Fantozzi P, Blanco MA. 2000. Enrichment and fractionation of phospho-
lipid concentrates by supercritical fluid extraction and chromatography. Ital. J. Food Sci. 12:65–76
Temelli F. 2009. Perspectives on supercritical fluid processing of fats and oils. J. Supercrit. Fluids 47:583–90
Thereza M, Gomes MS, Santos DT, Meireles MAA. 2012. Trends in particle formation of bioactive com-
pounds using supercritical fluids and nanoemulsions. Food Public Health 2:142–52
Thiering R, Dehghani F, Dillow A, Foster NR. 2000. The influence of operating conditions on the dense gas
precipiation of model proteins. J. Chem. Technol. Biotechnol. 75:29–41
Thompson PB. 2012. The agricultural ethics of biofuels: The food versus fuel debate. Agriculture 2:339–58
Tomberli B, Goldman S, Gray CG, Saldaña MDA, Temelli F. 2006. Using solute structure to predict solubility
of organic molecules in supercritical carbon dioxide. J. Supercrit. Fluids 37:333–41
Turner C, Ibanez E. 2012. Pressurized hot water extraction and processing. In Enhanced Extraction Processes in
the Food Industry, ed. N Lebovka, E Vorobiev, F Chemat, pp. 223–53. Boca Raton, FL: CRC Press
Turner C, Jacobson G, Almgren K, Waldeback M, Sjoberg PJR, et al. 2006. Subcritical water extraction and
β-glucosidase-catalyzed hydrolysis of quercetin glycosides in onion waste. Green Chem. 8:949–59
Wagner H, Eggers R. 1996. Extraction of spray particles with supercritical fluids in a two-phase flow. AIChE
J. 42:1901–10
Weidner E. 2003. Powderous composites by high pressure spray processes. In ISSF-2003: 6th Int. Symp.
Supercrit. Fluids, April 28–30, Versailles, Fr.
Weidner E. 2009. High pressure micronization for food applications. J. Supercrit. Fluids 47:556–65
Weidner E, Brake C, Richter D. 2004. Thermo-and fluid-dynamic aspects of the hydrogenation of triglycerides
and esters in the presence of supercritical fluids. In Supercritical Fluids as Solvents and Reaction Media, ed.
G Brunner, pp. 269–94. Amsterdam: Elsevier
Weidner E, Petermann M. 2008. Preparation and processing of micro- and nano-scale materials by supercrit-
ical fluid technology. See Martinez 2008, pp. 367–89
Williams LL, Rubin JB, Edwards HW. 2004. Calculation of Hansen solubility parameter values for a range
of pressure and temperature conditions, including the supercritical fluid region. Ind. Eng. Chem. Res.
43:4967–72
Wimmer Z, Zarevúcka M. 2010. A review on the effects of supercritical carbon dioxide on enzyme activity.
Int. J. Mol. Sci. 11:233–53
York P, Kompelle UB, Shekunov BY. 2004. Supercritical Fluid Technology for Drug Product Development. New
York: Marcel Dekker. 666 pp.
Zekovic Z, Pfaf-Sovljanski I, Grujic O. 2007. Supercritical fluid extraction of hops. J. Serb. Chem. Soc. 72:81–87
Zhong J, Dai LC. 2011. Liposomal preparation by supercritical fluids technology. Afr. J. Biotechnol. 10:16406–
13
Zosel K. 1974. Process for recovering caffeine. US Patent No. 3806619
238 King
FO05-FrontMatter ARI 13 February 2014 9:39
Annual Review
of Food Science
and Technology
Contents Volume 5, 2014
From Tomato King to World Food Prize Laureate

Philip E. Nelson p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Opportunities and Progress

John H. Litchfield p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p23
Body Weight Regulation and Obesity: Dietary Strategies to Improve

the Metabolic Profile
M.J.M. Munsters and W.H.M. Saris p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p39
Delivery of Lipophilic Bioactives: Assembly, Disassembly,
and Reassembly of Lipid Nanoparticles
Mingfei Yao, Hang Xiao, and David Julian McClements p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p53
Extraction, Evolution, and Sensory Impact of Phenolic Compounds
During Red Wine Maceration
L. Federico Casassa and James F. Harbertson p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p83
Gastric Digestion In Vivo and In Vitro: How the Structural Aspects
of Food Influence the Digestion Process
Gail M. Bornhorst and R. Paul Singh p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 111
New Developments on the Role of Intramuscular Connective Tissue
in Meat Toughness
Peter P. Purslow p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 133
Strategies to Mitigate Peanut Allergy: Production, Processing,
Utilization, and Immunotherapy Considerations
Brittany L. White, Xiaolei Shi, Caitlin M. Burk, Michael Kulis,
A. Wesley Burks, Timothy H. Sanders, and Jack P. Davis p p p p p p p p p p p p p p p p p p p p p p p p p p p 155
Designing Food Structures for Nutrition and Health Benefits
Jennifer E. Norton, Gareth A. Wallis, Fotis Spyropoulos, Peter J. Lillford,
and Ian T. Norton p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 177
Nanodelivery of Bioactive Components for Food Applications:
Types of Delivery Systems, Properties, and Their Effect on ADME
Profiles and Toxicity of Nanoparticles
T. Borel and C.M. Sabliov p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 197
v
FO05-FrontMatter ARI 13 February 2014 9:39
Modern Supercritical Fluid Technology for Food Applications

Jerry W. King p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 215
Impact of Diet on Human Intestinal Microbiota and Health
Anne Salonen and Willem M. de Vos p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 239
Applications of Power Ultrasound in Food Processing
Sandra Kentish and Hao Feng p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 263
Nondestructive Measurement of Fruit and Vegetable Quality
Bart M. Nicolaı̈, Thijs Defraeye, Bart De Ketelaere, Els Herremans,
Maarten L.A.T.M. Hertog, Wouter Saeys, Alessandro Torricelli,
Thomas Vandendriessche, and Pieter Verboven p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 285
Production of Aroma Compounds in Lactic Fermentations

E.J. Smid and M. Kleerebezem p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 313
Phage Therapy in the Food Industry
Lorraine Endersen, Jim O’Mahony, Colin Hill, R. Paul Ross, Olivia McAuliffe,
and Aidan Coffey p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 327
Public Health Impacts of Foodborne Mycotoxins
Felicia Wu, John D. Groopman, and James J. Pestka p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 351
Soft Materials Deformation, Flow, and Lubrication Between
Compliant Substrates: Impact on Flow Behavior, Mouthfeel,
Stability, and Flavor
Nichola Selway and Jason R. Stokes p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 373
Metabolic Stimulation of Plant Phenolics for Food Preservation
and Health
Dipayan Sarkar and Kalidas Shetty p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 395
Indexes
Cumulative Index of Contributing Authors, Volumes 1–5 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 415

Cumulative Index of Article Titles, Volumes 1–5 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 418
Errata
An online log of corrections to Annual Review of Food Science and Technology articles may
be found at http://www.annualreviews.org/errata/food
vi Contents
Annual Reviews
It’s about time. Your time. It’s time well spent.
New From Annual Reviews:

Annual Review of Statistics and Its Application
Volume 1 • Online January 2014 • http://statistics.annualreviews.org
Editor: Stephen E. Fienberg, Carnegie Mellon University

Associate Editors: Nancy Reid, University of Toronto
Stephen M. Stigler, University of Chicago
The Annual Review of Statistics and Its Application aims to inform statisticians and quantitative methodologists, as
well as all scientists and users of statistics about major methodological advances and the computational tools that
allow for their implementation. It will include developments in the field of statistics, including theoretical statistical
underpinnings of new methodology, as well as developments in specific application domains such as biostatistics
and bioinformatics, economics, machine learning, psychology, sociology, and aspects of the physical sciences.
Complimentary online access to the first volume will be available until January 2015.
table of contents:
• What Is Statistics? Stephen E. Fienberg • High-Dimensional Statistics with a View Toward Applications
• A Systematic Statistical Approach to Evaluating Evidence in Biology, Peter Bühlmann, Markus Kalisch, Lukas Meier
from Observational Studies, David Madigan, Paul E. Stang, • Next-Generation Statistical Genetics: Modeling, Penalization,
Jesse A. Berlin, Martijn Schuemie, J. Marc Overhage, and Optimization in High-Dimensional Data, Kenneth Lange,
Marc A. Suchard, Bill Dumouchel, Abraham G. Hartzema, Jeanette C. Papp, Janet S. Sinsheimer, Eric M. Sobel
Patrick B. Ryan • Breaking Bad: Two Decades of Life-Course Data Analysis
• The Role of Statistics in the Discovery of a Higgs Boson, in Criminology, Developmental Psychology, and Beyond,
David A. van Dyk Elena A. Erosheva, Ross L. Matsueda, Donatello Telesca
• Brain Imaging Analysis, F. DuBois Bowman • Event History Analysis, Niels Keiding
• Statistics and Climate, Peter Guttorp • Statistical Evaluation of Forensic DNA Profile Evidence,
• Climate Simulators and Climate Projections, Christopher D. Steele, David J. Balding
Jonathan Rougier, Michael Goldstein • Using League Table Rankings in Public Policy Formation:
• Probabilistic Forecasting, Tilmann Gneiting, Statistical Issues, Harvey Goldstein
Matthias Katzfuss • Statistical Ecology, Ruth King
• Bayesian Computational Tools, Christian P. Robert • Estimating the Number of Species in Microbial Diversity
• Bayesian Computation Via Markov Chain Monte Carlo, Studies, John Bunge, Amy Willis, Fiona Walsh
Radu V. Craiu, Jeffrey S. Rosenthal • Dynamic Treatment Regimes, Bibhas Chakraborty,
• Build, Compute, Critique, Repeat: Data Analysis with Latent Susan A. Murphy
Variable Models, David M. Blei • Statistics and Related Topics in Single-Molecule Biophysics,
• Structured Regularizers for High-Dimensional Problems: Hong Qian, S.C. Kou
Statistical and Computational Issues, Martin J. Wainwright • Statistics and Quantitative Risk Management for Banking
and Insurance, Paul Embrechts, Marius Hofert
Access this and all other Annual Reviews journals via your institution at www.annualreviews.org.
Annual Reviews | Connect With Our Experts

Tel: 800.523.8635 (us/can) | Tel: 650.493.4400 | Fax: 650.424.0910 | Email: service@annualreviews.org

Modern Supercritical Fluid Technology For Food Applications: Further

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Modern Supercritical Fluid Technology For Food Applications: Further

Uploaded by

Copyright:

Available Formats

FO05CH11-King ARI 10 February 2014 13:4

• Top downloaded articles

Fayetteville, Arkansas 72701; email: jwking1@uark.edu

Annu. Rev. Food Sci. Technol. 2014. 5:215–38 Keywords

The Annual Review of Food Science and Technology is Abstract

SOLUBILITY PARAMETER THEORY APPLIED TO SUPERCRITICAL

www.annualreviews.org • Supercritical Solvents for Food 217

Solubility/Extractability Related to Chemical Structure: A Tutorial

Extract #1 Extract #2 δsolute –δCO2 ≤ 2, highly soluble

14 δ < 19, ‘lipophilic’; δ hexane = 15

δ > 25, ‘hydrophilic’, δ water = 48

www.annualreviews.org • Supercritical Solvents for Food 219

Lutein stearate ester

Fractions Products Products

SUPERCRITICAL-BASED METHODS FOR PROCESSING

Total Extraction versus Fractionation

www.annualreviews.org • Supercritical Solvents for Food 221

Extending the Range of Supercritical Fluid Extraction:

www.annualreviews.org • Supercritical Solvents for Food 223

Overcoming the Limitations of Carbon Dioxide (CO2 )

www.annualreviews.org • Supercritical Solvents for Food 225

Particle Formation and Encapsulation for Food Products

Table 3 Food-related products produced by critical fluid–based particulate technology

www.annualreviews.org • Supercritical Solvents for Food 227

PROTECTION OF FOOD-DERIVED PRODUCTS USING

and details of the processing technique.

Microbial Reduction and Pasteurization of Foods with Supercritical Fluids

Regulation of Enzymatic Activity in the Food Matrix

Isolation of Natural Antioxidants from Sustainable Sources

www.annualreviews.org • Supercritical Solvents for Food 229

BENEFITS OF SUPERCRITICAL FLUID TECHNOLOGY

A Supercritical Fluid–Based Food Processing Platform for

Tocopherol Calcium phosphates

Bran Brown Rice sc CO2 Defatted

www.annualreviews.org • Supercritical Solvents for Food 231

Coupling Supercritical Fluid Extraction for Food Use

4. Production-scale SFC needs further development in terms of its application to producing

www.annualreviews.org • Supercritical Solvents for Food 233

www.annualreviews.org • Supercritical Solvents for Food 235

March 9–11. http://www.natex.at/download/CPF-PGSS-article.pdf

www.annualreviews.org • Supercritical Solvents for Food 237

Contents Volume 5, 2014

From Tomato King to World Food Prize Laureate

Opportunities and Progress

Body Weight Regulation and Obesity: Dietary Strategies to Improve

Modern Supercritical Fluid Technology for Food Applications

Production of Aroma Compounds in Lactic Fermentations

Cumulative Index of Contributing Authors, Volumes 1–5 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 415

New From Annual Reviews:

Editor: Stephen E. Fienberg, Carnegie Mellon University

Annual Reviews | Connect With Our Experts

You might also like

Editor: Stephen E. Fienberg, Carnegie Mellon University