Supercritical Fluid Chromatography and Extraction 1996

Anal. Chem.
1996, 68, 487R-514R
Supercritical Fluid Chromatography and Extraction

T. L. Chester,* J. D. Pinkston, and D. E. Raynie
The Procter & Gamble Company, P.O. Box 538707, Cincinnati, Ohio 45253-8707
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Publication Date (Web): June 15, 1996 | doi: 10.1021/a1960017i
Review Contents
Fluid Behavior and Physicochemical Measurements
Supercritical Fluid Chromatography
SFC Theory and Fundamental Measurements
Mobile Phases
(Achiral) Stationary Phases and Columns
SFC Instrumentation, Techniques, and Performance
Pumping
Sample Introduction
Other Instrumentation and Performance Issues
Detection
(Achiral) SFC Applications
Fats, Oils, and Other Lipids
Miscellaneous Food-Related Samples
Natural Products and Related Samples
Agrochemicals
Fossil Fuels, Polycyclic Aromatic Compounds, and
Synthetic Lubricants
Synthetic Polymers and Oligomers
(Achiral) Pharmaceutical Agents and Biologically
Important Mixtures
Organometallic Species and Miscellaneous
Applications
Chiral SFC
Supercritical Fluid Extraction
SFE Theory and Fundamental Measurements
SFE Instrumentation, Techniques, and
Performance
Solute Collection
Extracting Fluids
SFE-Coupled Techniques
SFE/Chromatography
Other SFE-Coupled Techniques
SFE Applications
Fossils Fuels and Environmental Samples
Pesticides and Herbicides
Foods and Fragrances
Polymers
Natural Products and Drugs
Miscellaneous Applications
Other Supercritical Fluid Measurements and Related
Techniques
Literature Cited
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We are happy to report continued growth in both research

and the application of supercritical fluid chromatography (SFC)
and extraction (SFE) techniques by analytical chemists. New
fundamental knowledge, new techniques, and many new applications herald further growth in the technical success of analytical
supercritical fluid techniques.
However, from the consumer-scientist perspective, one of the
big impediments in the growth of SFC and SFE techniques has
been the high price of commercial equipment. It has simply been
too expensive for many laboratories to consider a purchase unless
they had a specific, overwhelming need. Until recently, suppliers
have generally offered only high-capability instruments at high
S0003-2700(96)00017-0 CCC: $25.00
1996 American Chemical Society
prices. The apparent marketing strategy among the more

established vendors of SFE instruments has been to increase the
sophistication, automation level, and price. However, more simple
SFE instruments (with little automation and less expensive
pumping) are available and are attracting many new users. Buyers
of these entry-level instruments will no doubt return to the market
to meet their automation and capacity needs once they become
familiar and satisfied with the underlying technology. However,
at the time of this writing, there is still no commercial, entrylevel SFC instrument available in many large-market areas
including the United States. In addition, some manufacturers have
not significantly improved the technical capabilities of their
products for years, ignoring even the inexpensive advances freely
reported by independent researchers. Users find it impossible
to perform at levels described by researchers in the literature
without the cooperation of their instrument supplier.
This critical review resumes from our last review (1) and
covers the literature reported in Chemical Abstracts through
October 1995. We have limited our review to noteworthy articles
usually available in technical libraries worldwide.
We have reviewed supercritical fluid and related techniques.
Supercritical fluid techniques were originally distinguished from
conventional techniques by the use of temperatures and pressures
exceeding the critical values of the mobile or extracting phase.
Today we often think such a distinction is both arbitrary and
meaningless. There are no rigid boundaries separating hightemperature LC, enhanced-fluidity LC, subcritical fluid chromatography (SubFC), SFC, and high-pressure GC as we progress
down this list, although there are some practical differences,
particularly when comparing techniques not adjacent to each
other. Conventional LC and GC could, of course, be added to
their respective ends of the list. This would then seamlessly
connect all (partition) chromatography techniques. The only new
requirement for the intermediate techniques is simply the application of sufficient pressure at the column outlet to prevent
inadvertant boiling or phase separation of the mobile phase when
the temperature is raised or when a very volatile mobile phase is
chosen.
This is not really a new requirementsthe column outlet is
already pressurized (to 1 atm) in conventional techniques like LC.
Chromatography would have developed much differently if the
average temperature and pressure of our planet were somewhat
different. We should not limit ourselves to such default conditions
and to the classical techniques when better selectivity or faster
diffusion is available by making simple changes. We should also
point out that we can just as easily make a similar list for extraction
beginning with conventional liquid extraction techniques, ultrasonicenhanced liquid extraction (where the temperature and pressure
are raised in microscopic volumes of the sample), accelerated
solvent extraction (where the temperature and pressure are raised
uniformly in a way to keep the liquid phase from boiling), SFE,
steam distillation, and ordinary distillation.
Analytical Chemistry, Vol. 68, No. 12, June 15, 1996 487R
The critical point (or mixture critical point) of a fluid is very

meaningful in terms of fluid properties, but any single-phase fluid
can be used successfully as a mobile or extracting phase.
Therefore, we strongly recommend that the term supercritical be
ignored, or at least discounted, and it should certainly not be
interpreted as limiting in any way.
FLUID BEHAVIOR AND PHYSICOCHEMICAL
MEASUREMENTS
In SFC, it is necessary to operate the mobile phase under
conditions where phase separation does not occur from the time
the sample components reach the column until all the peaks are
recorded by the detector, even as pressure, temperature, or
composition are changed either spatially or temporally, on purpose
or by default. When a liquid sample is injected into an SFC
instrument, the phase behavior and mass transfer of the new
mixture of sample plus mobile phase must be considered. In SFE,
it is essential that separate matrix and extracting fluid phases
always be maintained. Thus, understanding phase transitions in
fluid mixtures is necessary for success.
Although most phase-behavior studies are done using view
cells and will not be reviewed, SFC and SFE techniques can also
be used in these studies. Meier et al. directly coupled an SFC
instrument to a variable-volume cell to determine the composition
of mixtures of CO2 and R-tocopherol and compared the results to
those obtained using near-IR and gravimetric sampling methods
(2). Kordikowski and Schneider, through a phase-behavior
investigation, determined the effect of quinoxaline and octanediol
modifiers on the extraction separation of decanol and decanoic
acid using CO2 (3). Stadler used SFC measurements to predict
CO2/hydrocarbon phase behavior (4). And Ziegler et al. used a
flow injection procedure, essentially open-tubular SFC without a
stationary phase, to map the critical loci of binary mixtures of CO2
with 13 common solvents (5).
Other thermophysical properties can be measured by SFC and
SFE. Cortesi, Spicka, et al. reviewed the use of SFC for measuring
partial molar quantities, interaction parameters, and diffusion
coefficients (6, 7). Cortesi et al. also determined the partial molar
volume of alcohols in CO2 using SFC. They showed that the
relationship between partial molar volumes at infinite dilution and
retention, which is strictly true at the mobile-phase critical point,
is useful away from the critical point (8). Lee and Holder
measured mass-transfer coefficients of solutes from packed beds
using SFC (9). Zhao et al. reported their use of a microsupercritical fluid extraction coupled to SFC to measure the solubilities
of materials in CO2 (10). Coutsikos et al. used SFE-LC to measure
the solubility of phenols in CO2 (11). Johannsen and Brunner
described an SFC system to determine solubilities in CO2 and
measured the solubilities of theophylline and theobromine in CO2
(12, 13). Hansen and Bruno measured solubilities in supercritical
fluids by injecting saturated solutions into a liquid chromatograph
(14).
Hitchen and Dean reviewed the properties of supercritical
fluids and their use in extraction and chromatography (15).
Brunner covers the fundamentals of supercritical fluids and their
use in separations in a new book (16).
SUPERCRITICAL FLUID CHROMATOGRAPHY
The most exciting and rapidly growing area in SFC is chiral
separations. In organizing the SFC section we have grouped all
the chiral references together rather than mixing them through
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Analytical Chemistry, Vol. 68, No. 12, June 15, 1996
the sections on stationary phases, applications, etc. We will begin

with general SFC.
Several noteworthy reviews of SFC have recently appeared
(17-20). Saito et al. edited a new book on SFC and SFE (21).
Chapters of particular interest to new readers include fundamental
properties of supercritical fluids (22) and fundamentals of SFE
and of packed-column SFC (23).
Revillion looked at SFC along with several other methods to
overcome shortcomings of size exclusion chromatography (24).
We should point out that size exclusion chromatography can be
performed with supercritical mobile phases in some situations.
We reported last time of Ettres leadership in creating a new
IUPAC nomenclature standard for chromatography (25). Smith
produced a supplement to the IUPAC standard adding additional
terms necessary to describe SFC (26).
SFC Theory and Fundamental Measurements. Shang et
al. reported measuring enthalpies and entropies of transfer on SFC
columns as a function of mobile-phase density and showed that a
point of intersection of extrapolated Vant Hoff plots is characteristic of the stationary phase (27). Hagege et al. studied the
retention of alkanes, alkylbenzenes, and chloroalkanes, relating
retention with various enthalpies. They concluded hydrophobic
interactions mainly control retention when using pure CO2 mobile
phase and also described interactions between polar functional
groups (28).
Yun et al. showed the importance of measuring the void
volume in chromatographic systems (including SFC) in which a
mobile-phase component may become part of the stationary phase
through adsorption. This work defines different types of void
volumes and adsorbed-phase volume, discusses excess and total
adsorption, and reviews experimental methods (29). Liu et al.
used tracer pulse chromatography to measure the decrease in
void volume caused by four different mobile phases adsorbed to
a stationary phase of a chromatographic column at 77 K (30).
Volumetric isotherms were generated, and the values of the van
der Waals b constants for four mobile phases were estimated and
found in agreement with accepted values. While the experimental
temperatures were much lower than what is used in SFC, the
mobile-phase densities are similar. This work certainly makes
us reconsider the stationary phase and how it might change when
the density of the mobile phase is varied. Berger reported that
plots of log of the retention factor vs density in packed-column
SFC, combined with van Deemter curves, suggest the formation
of a thick film of adsorbed mobile phase on the stationary-phase
surface (31). Afrane and Chimowitz used the Bragg-Williams
approximation for molecular interaction and correlated and
predicted the adsorption of high-pressure supercritcal CO2 in
contact with various chromatographic stationary phases (32).
Retention and Selectivity. Lesellier et al. characterized 29 ODS
stationary phases with carotenoids and PAHs and determined the
mechanism of carotenoid retention in LC and SubFC. This work
illuminates retention differences in planar and nonplanar compounds and shows the similarity between LC and SubFC (33).
We already know from numerous studies that there is no
discontinuous transition between SubFC and SFC. Wang et al.
studied the retention of homologs in SFC (34). Hadj-Mahammed
et al. studied the retention of flavones on open-tubular SFC
columns (35). Larkins and Olesik studied the effect of solute
shape for stilbene and stilbene-like solutes on retention by a glassy
carbon stationary phase. They concluded the extent of -
interactions between the solutes and the stationary-phase surface

were controlled by solute shape (36).
Gonenc et al. investigated the effects of temperature, pressure,
and mobile-phase density on solute solubility and retention in SFC.
Mobile-phase partial molar volumes of solutes were determined
and linked to pressure dependence of retention. This work, in
turn, indicates solute/stationary-phase interactions (37). Ibanez
et al. studied the effects of temperature and density on micropacked columns in SFC. Their use of column diameters less than
1 mm, combined with highly porous, large-diameter (greater than
100 m) packings, results in columns with very high permeability
(38). Heaton et al. developed a packed-column SFC retention
model based on solubility parameters. The model treated phenylsubstituted solutes, five different stationary phases, and methanol
modifier up to 20% in CO2 (39). Hagege et al. compared the
retention of cyanoalkanes and cyanoalkylbenzenes to alkane
retention on alkyl and cyanoalkyl-bonded stationary phases. They
found silanophilic interactions with the underlying silica to be
important in the retention mechanism (40). Jones et al. investigated the effect of temperature (at 80 and 150 C) on selectivity
for a variety of probes on eight stationary phases in open-tubular
SFC. Selectivities for polar stationary phases were highly temperature dependent, but nonpolar phases showed only small
temperature dependence (41). Kot et al. demonstrated selectivity
tuning in packed-column SFC and developed a method to separate
16 polycyclic aromatic hydrocarbons (PAHs) in under 7 min (42).
Hanson found much larger selectivity shifts using polar packings
than using nonpolar packings with variations of pressure, temperature, and modifier. This resulted in a loss in resolution at
low densities with polar stationary phases for the particular
steroids used as model solutes combined with the particular
stationary phase used (43). This work further emphasizes that
selectivity can be easily and widely tuned in SFC.
Lee and Olesik found that elevating the temperature in
enhanced-fluidity LC results in large increases in solute diffusion
coefficients which improve separation efficiency and shorten
analysis time. However, they also found that selectivity (among
PAHs) decreased as the temperature was raised. They showed
that an isocratic enhanced-fluidity separation could produce the
same quality separation of PAHs in about the same time as
gradient-elution LC (44).
Unified Chromatography. This technique bridges all partition
chromatography, essentially combining the characteristics of LC,
SFC and the other intermediate techniques, and GC together.
Martire et al. continued their development of a unified theory of
chromatography (45, 46). Robinson et al. built a unified chromatograph to perform GC followed by SFC on the same column.
This allowed the elution by SFC of sample components retained
throughout the GC conditions (47). Shen et al. examined the
retention behavior of carboxylic acid methyl esters in SFC and
found that the results fit well with a theory of unified chromatographic retention (48). Tong and Bartle found that band broadening can occur during the mobile-phase change in unified chromatography and showed how to minimize this through optimization
(49).
Pressure Drop and Efficiency. There continues to be a variety
of conclusions regarding the effect of column pressure drop in
open-tubular and packed-column SFC. Cramers et al. numerically
described efficiency in packed and open-tubular SFC columns.
Density gradients over the length of the column result in changes
in the retention factor, but velocity and diffusion coefficient

changes also occur. The net effect is that open tubes have fairly
uniform efficiency and packed columns have increasing plate
height along the column (50). Blomberg et al. reviewed the
performance of open-tubular and packed-column SFC (51). They
mentioned using evaporative light scattering as a means of
universal detection with modified mobile phases and showed
examples of mobile-phase composition programming. They
concluded that open-tubular columns are preferred for separating
complex mixtures and isomers and for applications requiring neat
CO2 as mobile phase. Open-tubular columns can produce high
plate counts, but analysis times are relatively long in such cases.
Packed columns can produce much faster separations, but, they
report, pressure drop prevents the generation of high plate
numbers. This is contrasted by Berger and Blumberg, who report
that under practical conditions efficiency losses do not occur in
packed-column SFC (52). Koehler et al. examined the influence
of mobile-phase velocity, column length, and pressure drop in
packed-column SFC. They found that there was no detrimental
effect caused by pressure drop and that efficiency can be increased
without significant penalty by using longer columns (53, 54). One
way to minimize pressure drop in packed columns is to prepare
columns with large particles and low packing densities. This is
the approach reported by Ibanez et al. (38, 55, 56). They have
made micropacked columns with pressure drops near that of
typical open-tubular columns. Karlsson et al. investigated how
retention data from single open-tubular (OT) SFC columns could
be used to predict retention on coupled columns. Good agreement resulted without the need to correct for pressure drop (57).
Jaermo et al. also investigated the effects of pressure drop on
serially coupled OT-SFC columns (58).
Mobile Phases. CO2 and modified CO2 mobile phases for
SFC have always had the disadvantage of poorly dissolving many
polar solutes, particularly those having high water solubility.
However, the diffusion rate benefits of SFC can be approached
with enhanced-fluidity chromatography, where CO2 or another
viscosity-reducing modifier is added to a liquid mobile phase. The
required instrumentation is identical to SFC instrumentation,
mainly because of the requirement of elevating the pressure at
the outlet to keep the mobile phase from phase separating. Cui
and Olesik have recently applied this approach to reversed-phase
LC with methanol/water/CO2 mobile phase resulting in significant
efficiency and analysis time improvements (59). This approach
requires knowledge of the phase behavior of the mobile phase in
order to appropriately specify pressure and temperature limits.
Blackwell and Schallinger investigated the eluotropic strength
and selectivity of fluoroform compared to CO2 and CO2/methanol
for the analysis of naphthalene derivatives. They found that
fluoroform is much stronger than the other mobile phases at the
same temperature and pressure but is weaker under the same
reduced conditions (60). These authors also investigated hydrofluorocarbon and perfluorocarbon mobile phases. They found the
perfluorocarbons studied to be much stronger than CO2, CO2/
methanol, and fluoroform (61).
It is common to see binary mixtures, such as CO2/methanol,
offered premixed in cylinders for use as SFC mobile phase or
SFE fluid. Via et al., however, showed that the composition of
the fluid delivered changes as the cylinder contents are consumed.
The modifier concentration in the delivered fluid more than
doubled over the use life of the cylinder (62). This suggests that
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work requiring accurate (or precise) fluid compositions may

require dynamic mixing in a two-pump system or careful mixing
of each charge individually when a single syringe pump is used.
Raynie et al., used ammonia as the mobile phase in investigating the chromatographic performance of an (ethylvinyl)benzenedivinylbenzene polymeric stationary phase (see the next section)
(63).
(Achiral) Stationary Phases and Columns. Much work
has been done developing and evaluating chiral stationary phases.
Please look at the Chiral SFC section for a summary of this
information.
Steenackers and Sandra reported coating 25- and 50-m-i.d.
columns with films of SE-54 up to 2 m thick (64). Such thick
films add needed sample capacity to narrow columns but, of
course, increase retention and increase pressure requirements
of the SFC instrument. Solute retention factors would be 10
times larger than with columns having more conventional 0.10.25-m film thicknesses used at the same temperature and
pressure. Thus, thick-film columns will hardly be practical until
significantly higher pressures are made available on commercial
OT-SFC instruments.
SFC has long been successfully used for the analysis of fats
and other lipids. Additional information on double-bond number
and position requires stationary phases with increased selectivity
for those features. Dobson et al. published a general review of
argentation methods, including SFC (65). Blomberg and Demibuker used argentation SFC to separate triacylglycerols of samples
like rapeseed and fish oil (66). Tanaka et al. described a stationary
phase of silver-loaded ceramic for SFC. They successfully used
this to purify docosahexaneoic acid ethyl ester from tuna oil by
semipreparative SFC (67).
Raynie et al., using ammonia as the mobile phase, investigated
the chromatographic performance of an (ethylvinyl)benzenedivinylbenzene polymeric stationary phase. Although there was
some loss in efficiency after exposure to ammonia, this polymeric
phase was much more stable than conventional silica-based
packings (63).
Engle et al. used a low-temperature method to generate glassy
carbon on fused-silica tubes and evaluated them using SFC (68).
Micropacked Columns. There has been considerable interest
in developing SFC columns that overcome the complaints of fairly
long analysis time and low sample capacity characteristic of opentubular SFC columns. Packed capillary columns promise big
improvements in these features if packings can be developed with
the same degree of inertness as typical OT-SFC stationary phases.
Malik et al. described packed fused-silica columns for SFC in the
range of 0.5-10 m in length. They compared conventional
packing methods with a supercritical CO2 slurry method which
produced columns both more stable and with better chromatographic performance. Efficiencies of over 240 000 theoretical
plates were realized (69, 70). Tong et al. described a similar
method to produce packed-capillary columns for SFC and LC (71).
Haegglund et al. packed a capillary with 8-quinolinol-modified silica
particles. This stationary phase performed well when a polar
modifier was used in the mobile phase. Selectivity could be
further improved by loading the stationary phase with metal ions
(72).
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SFC INSTRUMENTATION, TECHNIQUES, AND

PERFORMANCE
Pumping. Early SFC systems usually used syringe pumps
for delivering mobile phase. Most open-tubular SFC systems still
do. When flow splitting was required for sample introduction,
90% or more of the mobile phase was vented to waste in the
injector. This required high-pressure pumps of 100-250-mL
volume to contain enough mobile phase for a few hours of work
without refilling.
These pumps are expensive, so effort was justified in exploring
ways of controlling modifier addition that do not require a second
pump. Saturator devices are one approach that has been tried
by several researchers. Goerner et al. recently reported a simple
device to prepare binary mobile phases based on achieving
equilibrium in a saturator (73). Pyo and Ju used HPLC filters to
dynamically add water or methanol to CO2 (74-76). They
reported a Teflon high-capacity filter could sustain a constant water
addition much longer than a saturator column (75). Page et al.
used a saturator column to add water to CO2 and produced a water
gradient by thermostating the saturator and programming the
density of the CO2 at the saturator inlet (77).
Ashraf-Khorassani and Levy used a low-cost microbore reciprocating pump to introduce modifier (78). Francis et al. used a
high-pressure pulsed valve to introduce methanol modifier into a
CO2 mobile-phase stream. The entire apparatus required only one
pump (79). Many HPLC pumps can pump CO2 adequately for
research purposes if the heads are cooled. Workers often simply
put an aluminum pie pan under the pump heads and apply ice.
Hancock showed that a Peltier cooling device also works well (80).
Packed-column SFC is usually done today with HPLC-like
reciprocating or diaphram pumps. Modifier is simply added
volumetrically with a second pump. These pumps are not
inexpensive, but users coming to SFC from previous HPLC
experience do not seem to mind a two-pump system. OT-SFC
no longer requires the big and expensive syringe pumps if
injection is performed without flow splitting. Several suitable
injection options are described later. Without flow splitting, a
syringe pump with just a 10- or 20-mL volume would operate many
hours without requiring refilling. Thousands of dollars could be
removed from the price of an OT-SFC instrument, and the
capabilities improved significantly, if a low-volume pump with
higher pressure capability than todays offerings were made
available on turnkey OT-SFC systems.
Sample Introduction. We hinted earlier that flow-splitting
injection is no longer often used. Many workers also consider
timed-split injection obsolete, although it is still practiced widely
in OT-SFC. Both of these sample introduction techniques limit
initial band spreading by keeping the effective injection volume
in the low-nanoliter range. Such small sample volumes make trace
analysis impossible with typical detectors. So, work in OT-SFC
sample introduction has been aimed primarily at increasing the
effective sample volume, and perhaps secondarily at avoiding the
quantitation uncertainties introduced by the older sample-splitting
techniques.
Greibrokk et al. have led in the development of solvent-venting
injection for OT-SFC. Their techniques allow automated injections
of microliter volumes (81-83). Cortes et al. have developed a
very powerful injection technique for OT-SFC in which the sample
solvent is eliminated in a venting arrangement; then the solutes
are transferred with CO2 and pressure focused near the analytical
column inlet. This technique accommodates injection volumes

up to 100 L with excellent precision. Unfortunately, this
technique is not commercially available and is described in a
recent patent, leaving the possibilities for widespread adoption
uncertain (84). Chester and Innis demonstrated an inexpensive
(virtually free) direct injection technique using a retention gap.
By paying attention to the phase behavior of the sample solvent/
mobile-phase mixture, a flooded zone is created within the
retention gap. The solvent is then evaporated and removed
through the column, the solutes refocused at the column inlet,
and the chromatography performed as usual. Sample volumes
up to 0.5 L were demonstrated without splitting, achieving peak
height and area relative standard deviations of 0.6-1.8% (85).
Daimon and Hirata developed an on-line SFE/OT-SFC system
involving trapping of the solutes in the interface (86). Hirata and
Pawliszyn described an injection procedure in which a polymercoated fiber is exposed to liquid sample to absorb solutes. The
fiber is then removed and placed in a piece of tubing for desorption
to an OT-SFC column to accomplish a solvent-free solute transfer
(87). Ullsten and Markides combined solid-phase extraction and
SFE to introduce samples dissolved in polar solvents onto an SFC
column. Sample volumes were 10 L (88).
Packed-column SFC injection is still practiced fairly straightforwardly by most users. Injection volumes in the tens of
microliters or more can be routinely accommodated by 4.6-mmi.d. columns. Arnold and Kleiboehmer described an injection
system using a solid-phase extraction cartridge to receive up to
100 L of sample. The sample solvent was evaporated with
nitrogen and vented. Then the solutes were transferred to the
SFC column with mobile phase (89). Zegers et al. used a similar
approach in which a precolumn is loaded with aqueous sample
and dried with a nitrogen flow. The precolumn was next desorbed
with SFC mobile phase and the solutes were focused at an SFC
packed-capillary column inlet. The largest sample injection
reported was 47 mL, resulting in a detection limit of 0.1 ng/L for
a pesticide using thermionic detection (90). Games et al. also
described a solute-focusing sample introduction technique for
packed-column SFC (91).
Gretier et al. (92) and Hirata et al. (93) described solvent
evaporation techniques for large-volume sample injection in
preparative SFC. Bruno described the use of a vortex tube for
cryofocusing and cryotrapping of sample components in SFE and
SFC applications (94, 95).
Other Instrumentation and Performance Issues. Changes
in the practice of SFC are slowly rendering the older reference
material obsolete. Two more recent reviews of SFC instrumentation have been published by Greibrokk (96) and by Saito and
Yamauchi (97).
Postcolumn pressure control is now widely used in packedcolumn SFC. When the detector can be pressurized, the pressure
control device is usually postdetector as well. This downstream/
pressure control approach allows control of the outlet pressure
while the mobile-phase velocity on the column is independently
controlled by operating the pump(s) in a controlled-flow mode.
(The column inlet pressure becomes the dependent variable.) This
practice not only provides simultaneous control of both outlet
pressure and flow rate but also allows volumetric mixing of
modifier with a two-pump system. Verillon et al. described such
a system (98).
When a passive restrictor is used downstream from the column

to maintain pressure and limit mobile-phase flow, the mobile-phase
velocity on the column is not directly controlled but varies
according to the inlet pressure and the resistance provided by
the restrictor. The mobile-phase velocity can therefore change
during programming. Several efforts have been undertaken to
develop programmable restrictors to allow some adjustment of
velocity in these upstream/pressure control situations. Pyo
described a two-stage restrictor for pressure- or density-programmed SFC in which the first stage used a temperturecontrolled, 7-m-i.d. tube. It was followed by a linear restrictor.
The temperature of the first stage was programmed during the
chromatogram to keep the mobile-phase velocity constant (99).
Pyo also described a parallel flow path restrictor which was also
temperature-controllable (100). Vejrosta et al. described and
characterized a multichannel restrictor (101).
Grover et al. looked at the problem of optimizing SFC when
attempting to achieve adequate resolution with short analysis
times. A numerical model for solute adsorption was used in
conjunction with a spatial temperature profile (102). Wenclawiak
and Hees compared SFC with optimized HPLC for the separation
of 16 PAHs (103).
Smith and Briggs examined the influence of the sample solvent
choice and several instrument design features on peak shapes in
packed-column SFC. They found that memory effects caused by
adsorption of polar solutes could be eliminated with the appropriate use of a modifier (104).
Preparative SFC. Bartle et al. built a large-scale SFC system
and separated fluorene and phenanthrene and a complicated
mixture of milbemycins (105). Brunner and Upnmoor scaled up
and studied the SFC separation of tocopherols and prostaglandins.
They found that for tocopherols SFC had more capacity than a
similar LC system (106). Cretier et al. compared preparative LC
and preparative SFC for separating components in a 25:1 ratio.
They found the techniques complementarysLC was easier when
the minor component eluted first, but SFC was easier when the
minor component eluted second (107). Perrut reviewed largescale SFC, including an analysis of hydrodynamics and adsorption/desorption processes. He concluded that large-scale separations in pharmaceuticals and fine chemicals will emerge at an
increasing rate in the near future (108). Bevan and Mellish
reviewed the considerations necessary to scale-up an SFC separation, including fluid choice, safety, sample introduction, fraction
collection, and mobile-phase recovery (109). Cretier et al. studied
the competition between solutes in preparative SFC in overload
situations and the influence on solute peak shape (110). Jusforgues reviewed large-scale SFC in two reports (111, 112).
Detection. Spectroscopic detection such as mass spectrometric and infrared absorbance have long been used in SFC, but
relatively few accounts of on-line nuclear magnetic resonance
(NMR) detection, potentially one of the most informative detectors, have appeared. This may change in coming years. Albert
et al. developed a new high-pressure probe for on-line, high-field
SFC/1H NMR and applied this technique to mixtures of phthalates
(113) and acrylates (114). The advantages of HPLC/1H NMR
were described by Albert in a further review (115). The whole
proton spectral range can be observed in SFC/1H NMR with CO2
as mobile phase, without a solvent window, unlike HPLC/1H
NMR.
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A number of groups continued their work in coupling SFC with

Fourier transform infrared absorbance (FT-IR) detection. As in
previous reviews, two avenues were explored: direct deposition
(solvent elimination) and flow cell detection. Morin described
both approaches and presented a new, low-volume flow cell
intended for 50-m-i.d., open-tubular SFC columns. GramSchmidt reconstruction and spectral subtraction were used to
enhance detection despite spectral background changes due to
density programming (116). Kirschner and Taylor compared Xe
to CO2 mobile phases in packed-column SFC/flow cell FT-IR
(117). Despite xenons ability to transmit the full IR spectrum,
both mobile phases produced equivalent spectral and librarysearching results with standards. However, Xe is a poorer mobile
phase for polar analytes and is far more expensive. Jenkins et al.
explored multidetector, open-tubular SFC involving FT-IR, in
particular the influence of the flow cell size on chromatographic
resolution (118). A 500-nL flow cell was acceptable for 50-mi.d. columns, while a 980-nL cell was not. Plant extracts were
examined using open-tubular SFC/UV/FT-IR/FID. Gurka et al.
explored the differences between GC- and SFC/direct-deposition
FT-IR (119). Minimum identifiable quantities (MIQs) in the low
nanograms were achieved. The greater molecular weight range
of SFC was clear in a comparison with poly(ethylene glycol)s.
Norton and Griffiths reported subnanogram MIQs with SFC/
direct-deposition FT-IR of a strong IR absorber (600 pg of caffeine)
(120). They also described other performance characteristics
such as linearity with strong and weak absorbers.
Mass spectrometry is one of the earliest used, and arguably
the most informative, spectroscopic detection methods in SFC.
The interface/ion source configurations can generally be divided
into two groups: low flow rate (up to 15 mL/min of expanded
CO2) and high flow rate interfaces. The direct-fluid-introduction
(DFI) interface, where the effluent is admitted directly into an
electron ionization or chemical ionization ion source, is the most
common low flow rate interface. It is used for open-tubular and
packed-capillary SFC. The high flow rate interfaces are used for
microbore and standard packed SFC and are generally modified
versions of interfaces developed for LC/MS. Among those dealing
with low flow rate interfaces, Becker demonstrated a DFI interface
with improved temperature stability (121). Pinkston and Bowling
investigated the use of cryopumping to improve performance in
open-tubular SFC/MS (122). Cryopumping was shown to enhance signal by a factor of 5 in some cases. Cryopumping was
later used to assist in the identification of high molecular weight
components of olestra, a mixture of fatty acid sucrose esters (123).
Buecherl et al. built and tested an interface, incorporating a second
restriction and a stage of pumping between the SFC restrictor
and the ion source, for coupling open-tubular SFC to highresolution MS (124). The additional stage of pumping was
required to maintain a sufficient vacuum in the ion source region.
Various parameters such as restrictor position and flow rate were
examined, and an FID was used in parallel. Van Leuken et al.
also optimized a DFI interface for the characterization of polymer
additives (125).
Among those working with interfaces capable of handling
higher flow rates, Via and Taylor used a modified thermospray
interface and packed-column SFC to examine SFE extracts of
energetic materials (126). Pressure programming of the CO2
mobile phase resulted in changing background spectra with both
CH4 chemical ionization and CO2-moderated electron attachment
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ionization, but the analyte spectra did not change. The versatility
of atmospheric pressure ionization (API) has led to an increase
in its use. Thomas et al. used API for open-tubular SFC/MS of
polycyclic aromatic compounds (127), while Matsumoto used
SFC/API-MS for a more fundamental purpose, the estimation of
hydrogen ion affinities (128). Arpino and Haas reviewed progress
and future prospects (focused on API) in SFC/MS interfacing
(129). Sadoun et al. explored the utility of electrospray ionization
(a form of API) for packed-column SFC/MS (130). The combination showed great promise. However, the authors found that the
mobile-phase composition affected the response, and some less
volatile analytes were partially adsorbed near the ionization region
in the initial design. Jedrzejewski and Taylor examined the utility
of the particle beam interface for packed-column SFC/MS. They
first reported improved limits of detection for caffeine but found
that sensitivity was highly dependent on modifier concentration
(131). They later described the use of a particle-forming solvent
to improve the performance of this interface (132). Limits of
detection for caffeine were shown to be between 10 and 100 times
better than previous reports without the particle-forming solvent
(132).
Plasma emission spectrometry and plasma mass spectrometry
for detection after SFC were areas of considerable activity during
this review period. Long et al. (133) and Uden (134) reviewed
plasma-based detection. Luffer and Novotny used a surfatron
microwave-induced plasma for detection of cyclic boronate derivatives of biologically important compounds (135). Sensitivity for
boron was 25 pg/s. Wang and Carnahan (136), Arnold et al.
(137), and Ducatte and Long (138) examined the effects of various
supercritical mobile phases on helium microwave-induced plasma
emission detection. Wang and Carnahan focused on the effects
of CO2 and of CO2/methanol on plasma emission (136). They
found significant changes in molecular emission bands as the
mobile-phase composition and pressure changed, but the plasma
easily tolerated the CO2/methanol mobile phases, and the analytical capacity of the system was not compromised. Arnold et al.
found that both CO2 and N2O disturbed the helium plasma of the
plasma emission detector (137). They demonstrated improved
results with a concentric dual-flow torch. Ducatte and Long found
depression of the excitation properties of a 150-W He plasma by
the introduction of CO2 mobile phase (138). Higher energy ionic
transitions were more strongly affected, a finding consistent with
charge-transfer theory. Therefore, careful analyte line selection
is important when plasma emission detection is used in SFC.
Tomlinson et al. discussed the coupling of inductively coupled
plasma mass spectrometry with SFC and other separation methods
for the ultratrace level detection of organometallics (139). Blake
et al. described the use of open-tubular SFC/inductively coupled
plasma (ICP) mass spectrometry for the detection of organometallic species in environmental samples (140, 141). They
described a new interface for SFC/ICPMS and examined the
effects of various operating parameters on performance, such as
restrictor temperature and mobile-phase flow rate (141).
Almquist et. al. (142) and Dressman and Michael (143)
described a heretofore uncommon detector for SFC, electrochemical detection. Almquist et al. demonstrated that their miniaturized
electrochemical detector was compatible with pressure-programmed elution (142). They used CO2 containing water as
mobile phase to separate and detect ferrocene and ferrocene
derivatives. The electrochemical cell described by Dressman and
Michael was used with packed-column SFC and worked well with
unmodified, acetonitrile-containing, and methanol-containing CO2
mobile phases (143). The detector compared favorably with a
flame ionization detector for electrochemically active analytes.
Investigations using a variety of other less common detectors
were abstracted during this review period. Onuska and Terry
(144) and Zegers et al. (145) worked with the photoionization
detector (PID). Onuska and Terry found that their PID performed
well with microbore and conventional packed-column SFC but was
not suited for open-tubular SFC due to its large cell volume (144).
Zegers et al. found that the PID performed much better when
combined with packed-column SFC using modified CO2 as mobile
phase than with HPLC (145). Limits of detection ranged from
tens of picograms to low nanograms. Shirota et al. (146) and
Jew and Richter (147) used the thermionic ionization detector
(TID). The former group of authors formed the methoxime of
biologically important carbohydrates and used SFC/TID in the
nitrogen-selective mode for their characterization (146). Jew and
Richter used the TID in quite a different manner (147). They
operated it with a N2 atmosphere and obtained electron capture
detector (ECD) behavior. Halogenated compounds were detected
after SFC with LODs in the low picograms. Yarita et al.
demonstrated the use of an actual ECD after packed-column SFC
for the selective detection of chlorinated pesticides (148). Brown
et al. evaluated an electrolytic conductivity detector for the
selective detection of chlorinated compounds after open-tubular
SFC (149). LODs ranged from 0.25 to 5 ng for chlorinated
organics. Staby et al. investigated perhaps the most common
detector for open-tubular SFC, the FID, as they measured
responses to ethyl esters of sand eel fish oil (150). They
juxtaposed SFC/FID and GC/FID responses and discussed the
advantages and disadvantages which result from some of the
choices the analyst must make with these methods.
Chemiluminescent detection was investigated in three publications abstracted during this review period (151-153). Francis
et al. used nitro and nitroso chemiluminescence in the thermal
energy analyzer for the sensitive (tens of picograms) and selective
detection of these moieties in propellants and explosives (151).
Shearer and Skelton evaluated the flameless sulfur chemiluminescence detector for sulfur-containing compounds in petroleum
products (152). The detector had an LOD of 0.3 pg of S/s.
Sandmann and Grayeski used peroxyoxalate chemiluminescence
with packed-column SFC (153). The LOD for perylene was 20fold lower than by fluorescence detection and was in the attomole
range.
Lembke et al. used a radioactive flow-through detector for
packed-column SFC (154). They found that pressure or composition gradients did not seem to affect the detector. Demirbuker
et al. developed a miniaturized evaporative light-scattering detector
for the detection of polar lipids and other analytes requiring a
modifier in packed-microcolumn SFC (155). They found a region
of relatively uniform response at mobile-phase flow rates below
16 mL/min (measured after expansion at ambient temperature
and pressure). Hirata and Katoh described a means to regulate
cell pressure in the most common detector used for packedcolumn SFC, UV absorbance detection (156). This eliminated
baseline drift, even at high sensitivities, and allowed the use of
the detector as a refractive index detector. The LOD for chrysene
was 10 pg.
(ACHIRAL) SFC APPLICATIONS

Fats, Oils, and Other Lipids. The advantages of SFC for
the characterization of lipids are clear, and the number of
publications in this area has grown during this review period.
Bartle and Clifford (157, 158), Matsumoto and Taguchi (159),
and Hoving (160) have reviewed the SFC separation of various
classes of lipids.
Blomberg et al. (161) and Blomberg and Demibuker (66) used
argentation SFC for the quantitation of triacylglycerols. This
technique, in combination with a miniaturized ELSD, was a
powerful tool for studying saturated vs unsaturated lipids (161).
Hansen et al. used open-tubular SFC to determine the level of
unaltered triolein remaining during a deep fat frying time study
(162). Kaplan et al. studied normal cheeses and cheeses high
in unsaturated triglycerides using open-tubular SFC with on-line
FT-IR and FID detection (163). Manninen et al. found opentubular SFC with a very polar, siloxane-based stationary phase
(25% cyanopropyl, 50% phenyl) separated natural oils by carbon
number and degree of unsaturation (164). They also found that
it was difficult to determine fat-soluble vitamins in these oils using
convention open-tubular SFC because of overloading of the
triglyceride components. Manninen et al. also used this stationary
phase to separate - and R-linolenic acid-containing triglycerides
(165). Combining two 50-m-i.d., 10-m-long columns enhanced
the separation of one critical pair by 23%. The SFC/MS characterization of olestra, a noncaloric fat replacement, was described
by Pinkston and Bowling (123). Both CI and EI spectra of major
and minor components were obtained using a modified direct fluid
introduction interface.
Borch-Jensen et al. (166), Staby and Mollerup (167), Staby et
al. (168, 169), and Baiocchi et al. (170) focused on the SFC
analysis of fish oils and lipids of marine origin. Staby et al. found
open-tubular SFC superior to GC or HPLC for the characterization
of fish oil (168). Shen et al. used a packed capillary column with
FID detection to study a variety of oils, including several traditional
Chinese medicines (171).
The separation of fatty acids, both free and as alkyl esters,
was studied by a number of groups. The work of Sakaki (172)
fits well with the results of Smith and Cocks (173). Sakaki found
that selectivity of the separation of fatty acid methyl esters
(FAMEs) on an aminopropyl-bonded silica according to carbon
chain length increased with the degree of aminopropyl bonding,
while selectivity according to degree of unsaturation decreased
(172). Smith and Cocks separated FAMEs on bare silica
columns with ELSD detection (173). They found the separation
independent of chain length but strongly dependent on degree
of unsaturation. Nakajima and Yamamoto patented a means of
removing free fatty acids from seed oils using packed-column SFC
on silica gel (174). Conversely, Nomura et al. studied fatty acid
compositions with a C18-bonded column (175). A very inert
column was required since the authors eluted free fatty acids with
unmodified CO2. Staby et al. used both open-tubular SFC/FID
and GC/FID to study a fatty acid ethyl ester mixture from sand
eel oil (150). They found good agreement within methods and
fair agreement between methods.
Pfander et al. (176) and Sakaki et al. (177) discussed the
separation of carotenoids. Pfander et al. reviewed both LC and
SFC methods (176), while Sakaki et al. studied retention behavior
on nonpolar and polar packed columns (177). They concluded
retention on nonpolar packings most closely resembled reversedAnalytical Chemistry, Vol. 68, No. 12, June 15, 1996
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phase HPLC behavior, while that on more polar columns resembled normal-phase behavior. Hui et al. studied spectral shifts
of carotenoids under SFC conditions with respect to their spectra
in hexane (178). Changes in pressure and temperature had
greater effects on the spectral shift of some carotenoids than
others. Yarita et al. investigated the SFC separation of tocopherols
in vegetable oils (179). They found that the addition of a small
amount of methanol modifier provided a good separation of the
tocopherols, including - and -tocopherols.
Miscellaneous Food-Related Samples. Calvey et al. (180)
and Block and Calvey (181) explored the utility of SFC and SFE
in the study of thermally labile compounds derived from members
of the Allium genus. Low oven and restrictor tip temperatures
(50 and 115 C, respectively) were required to prevent thermal
degradation of allicin, the main thiosulfinate in freshly cut garlic
(180). Calvey et al. also characterized compounds extracted from
microwave susceptor packaging using SFC/MS and SFC/FT-IR
(182). These compounds, which could potentially migrate to
microwaved foods, were primarily aliphatic ketones and alcohols.
Chester and Innis used in situ derivatization/extraction followed
by SFC/FID to determine maltodextrin in psyllium-based bulk
laxatives (183). This determination would not have been possible
without the in situ derivatization to render the maltodextrin
extractable. Yarita et al. combined packed-column SFC on-line
with GC/FID to fractionate and study citrus essential oils (184).
The preliminary fractionation on the silica gel SFC column was
based primarily on polarity.
Natural Products and Related Samples. The mild elution
temperatures possible with SFC and the wide range of analyte
molecular weights that may be eluted in SFC make it particularly
valuable for the characterization of natural product extracts. The
components of these extracts often cover a wide molecular weight
range and are thermally labile. Taylor et al. used SFE to extract
and a variety of other techniques to characterize Dalea spinosa
(185). They performed on-line SFE/SFC of portions of a dissected
seed to determine the distribution of odoriferous compounds.
Raynor et al. used SFC to characterize limonoids in bark and seed
extracts (186). Morin described the separation of geometric
isomers of sesquiterpene and diterpene alcohols by packed-column
SFC (187). The separation was performed on a bare silica
packing with methanol-modified CO2. Sewram et al. used the
molecular shape selectivity of a liquid crystal-modified polysiloxane, open-tubular SFC column to separate triterpene acids,
including geometric isomers, from Dysoxylum pettigrewianum
(188). The separations were not successful on a biphenylmodified polysiloxane or a poly(ethylene glycol)-coated column.
Coupled SFC/MS and SFC/FT-IR, as well as judiciously
chosen derivatization, are powerful tools for structure elucidation
of natural product extracts. Scandola et al. used SFC/MS and
SFC/MS/MS to study alkaloids in extracts from the roots of
Securidaca longipedunculata Fres. (189). The mass spectrometric
data indicated the presence of the ergoline skeleton in some of
the alkaloids. Johannsen and Brunner used SFC in their study
of the solubilities of the xanthines caffeine, theophylline, and
theobromine in supercritical CO2 (13). The solubilities of the
three differ greatly though their structures are quite similar. HadjMahammed et al. used SFC/FT-IR to study substituted flavones
(35). They were separated on a 100% methyl polysiloxane opentubular column with unmodified CO2. Shim et al. used the unique
derivatization results offered by boronic esters to characterize
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ecdysteroids sharing a 20,22-diol structure (190). The bidentate

derivative moved the elution time of the products away from those
of the reactants and of other components. SFC/MS was used by
Young and Games to determine Fusarium mycotoxins in F. roseum
culture extracts (191).
Agrochemicals. The determination of agrochemicals is often
a challenging endeavor. Most of the publications abstracted
during this review period take advantage of the rapid analysis
capabilities of packed-column SFC or the reduced sample handling
and trace analysis capabilities associated with on-line SFE/SFC
for the determination of agrochemicals. Mulcahey et al. included
agrochemicals in their review of the use of SFC for environmental
applications (192). Berger demonstrated the propensity of
packed-column SFC for rapid analysis with the separation of up
to 10 phenylurea herbicides in less than 7 min (193). Berger et
al. also used packed-column SFC to separate a variety of carbamate
pesticides in 9 min (194). They used in-line UV and NPD
detection and achieved detection limits as low as 110 ppt.
Benfenati et al. used packed-column SFC/UV for the rapid
determination of a herbicide, bromofenoxim (195). They found
that the LOD (15 pg) and the linear dynamic range of the method
were better than those achievable with HPLC/UV. The NPD was
used by Zegers et al. to selectively detect 19 organophosphorus
pesticides in vegetable extracts (196). These authors evaluated
seven stationary phases for packed-capillary columns with modified CO2 as mobile phase. Yarita et al. used packed-column SFC
with unmodified CO2 and electron capture detection to determine
chlorinated pesticides in extracts from carrots (148).
Murugaverl and Voorhees combined the trace analysis capabilities of on-line SFE/SFC with on-line solid-phase extraction
cleanup to determine pesticides in fats and oils (197). This
arrangement greatly reduced sample handling. Nam and King
also described a multihyphenated technique for the characterization of pesticides in fats and lard (198). They used SFE,
followed by on-line packed-column SFC to extract and separate
the pesticide fraction from the coextracted lipids. On-line, opentubular GC was then used to separate the pesticide fraction. They
found the method to be faster and less laborious than conventional
methods, while still accurate and reproducible. The selectivity
and sensitivity of SFC/MS for agrochemical analysis has also been
described during this review period. Jablonska et al. investigated
a variety of ionization methods for the determination of chlorinated
pesticides by SFC/double-focusing MS (199). Detection limits
in the low-nanogram range were reported regardless of the
ionization method used. This is somewhat surprising since lower
limits of detection should be achievable with electron attachment
negative ionization using the mobile phase as moderating gas.
Nelieu et al. compared thermospray LC/MS with electrospray
SFC/MS for the determination of atrazine metabolites (200). They
found SFC/MS to be more sensitive for the less polar chlorotriazine compounds. Massey and Tandy reviewed the separation
and analysis of chiral agrochemicals, including the promise offered
by chiral packed-column SFC (201).
Fossil Fuels, Polycyclic Aromatic Compounds, and Synthetic Lubricants. Substantial progress has been made in the
application of SFC to the characterization of fossil fuels. Three
reviews describing this progress in SFC and in other techniques
appeared in one issue of The Journal of High Resolution Chromatography. Lundanes and Greibrokk described the separation of
petroleum and petroleum products into compound classes using
a variety of techniques, including SFC, in their review (202).

Peaden (203) reviewed simulated distillation while Levy (204)
presented a variety of applications of SFC and SFE in fossil fuel
research.
Packed-column SFC has been shown to be quite useful in rapid
group-type separations of petroleum products. Schubert patented
a method to separate and collect fractions of petroleum-based oils
using packed-column SFC (205). Li et al. described the use of
long (1 m) packed capillary columns for rapid (10 min) hydrocarbon group-type separations (206). They examined the effects
of packing material pore size and surface area, as well as of column
temperature and pressure. The method appears promising for
quality control of diesel fuels. Lynch and Heyward coupled
packed-column SFC with GC for the analysis of petroleum
fractions (207). After detection by FID and UV, effluent from the
UV detector could be cut to the injection port of the GC. The
system was shown to be quantitative and reproducible for the
automotive fuel range. A similar system was described by Chen
et al. (208). The SFC is useful for rapid group-type analysis, and
selected regions can be directed to the GC for quantitative
determination of individual hydrocarbons.
The use of SFC for simulated distillation is an active area of
research. Raynie et al. extended the boiling range of simulated
distillation to over 800 C using open-tubular SFC (209). They
found an n-octylpolysiloxane-coated column minimized the aliphatic vs aromatic boiling point discrepancy common to chromatographic methods. Shariff and Bartle evaluated the use of
packed capillary columns in SFC for simulated distillation (210).
They evaluated a variety of columns and minimized the aforementioned discrepancy by using three columns. Bartle et al. used
simulated-distillation SFC in their investigation of progress in the
co-refining of coal and petroleum (211). Campbell et al. also used
SFC (with MS detection), along with a variety of other techniques,
in the characterization of nondistillable coal liquefaction process
streams (212).
The greater molecular weight range of SFC with respect to
GC makes it better suited for determining a wide range of PAHs.
Gadzala and Buszewski included SFC in their review of methods
used for PAH determination (213). Mulcahey et al. included
PAHs in their review of the uses of SFC in the environmental
field (192). Jinno et al. compared the PAH molecular shape
recognition properties of liquid crystal-bonded phases in packedcolumn SFC and in HPLC (214). They found that selectivity was
enhanced in SFC. Heaton et al. also compared packed-column
SFC to HPLC for the determination of PAHs (215). They achieved
a separation of 16 PAHs in 6 min by SFC. Kot et al. developed a
similar, 7-min, packed-column SFC separation of the 16 priority
PAHs (42). Lee reported the results of an interlaboratory roundrobin evaluation of SFC for the determination of aromatics
according to ring number (216). The study concluded that SFC
possessed distinct advantages over GC/MS and NMR including
cost, speed, and wide applicability. Hoener et al. used packedcolumn SFC with fluorescence detection to determine PAHs in
waste gases of a fuel oil boiler (217). The PAHs were extracted
from foam plugs by off-line SFE. Yao et al. also used SFE followed
by SFC to determine PAHs in air particulates from air near a coke
oven and a traffic island (218). The SFE and SFC steps were
combined on-line, however. Recovery of 16 PAHs was 90% and
RSDs ranged from 1.9 to 6%. Jinno et al. discussed the potential
of on-line SFE/SFC to isolate, purify, and collect fullerenes from
carbon soot (219). Liu et al. also described the separation of

fullerenes (220). They compared the separation of C60 and C70
fullerenes by SFC and HPLC on acceptor bonded phases.
Synthetic Polymers and Oligomers. Supercritical fluid
chromatography may be most widely known for its ability to
provide information about relatively low molecular weight polymers and oligomers. Polymers that are too low in volatility for
GC, and which are difficult to characterize by size exclusion
chromatography, are often amenable to SFC. Anton et al. provided
a wide-ranging review of the potential of packed-column SFC for
analysis, primarily focusing of applications involving polymers and
polymer additives (221). They found the analysis times to be
shorter than with HPLC, and the method development to be
simpler.
Perhaps the best example of oligomer characterization by SFC
is the characterization of oligomeric surfactants, most commonly
ethoxylated alcohols, using open-tubular SFC with flame ionization
detection. Wang and Fingas (222), Holzbauer and Just (223),
and Ye et al. (224) studied various aspects of this separation. Wang
and Fingas (222) and Ye et al. (224) verified the distributions
using HPLC. While Ye et al. advocated the routine use of SFC in
this area, they observed a polar oligomeric series by HPLC that
was not eluted in SFC (224). They did not use derivatization to
make the polar species more soluble in CO2. Just et al. compared
the abilities of SFC and matrix-assisted laser desorption/ionization
mass spectrometry (MALDI-MS) for ethoxylated oligomer characterization (225). In their hands, SFC worked best for oligomers
with molecular weights up to 1000 while MALDI-MS was more
useful for the higher molecular weight oligomers. Kane et al.
demonstrated the use of SFC in the trace analysis of oligomeric
surfactants in water (226). Other groups used packed-column
SFC to separate ethylene oxide oligomers. Hagen et al. used a
poly(divinylbenzene) packed column and evaporative light-scattering detection to achieve baseline resolution of oligomers with
up to 44 oligomeric units (227). An open-tubular column with a
50% phenyl polysiloxane phase did not perform as well in their
hands. (The reviewers note that well-resolved separations of
silylated PEGs with molecular weights exceeding 2000 have been
obtained using a 30% biphenyl polysiloxane-coated open-tubular
columns and an integral restrictor (228).) Guerrero and Rocca
studied the separation of ethoxylated alcohols on cyanodecylbonded silica packings (229). They used preparatory-scale HPLC
and mass spectrometry to explain the coelution of some compounds.
The success of SFC extends to other surfactants and emulsifiers. Artz and Myers described the separation of a number of
emulsifiers by open-tubular SFC/FID (230). Carey and Sutton
also used open-tubular SFC/FID to characterize polyol ester fluids
used as synthetic refrigeration lubricants (231). They could
deduce the starting carboxylic acids, base polyol structure,
reaction scheme, degree of reaction completeness, and additives
from the chromatographic data. Wang and Fingas described the
SFC separation of sorbitan ester surfactants (232). Open-tubular
SFC provided better separations of the higher molecular weight
polyesters than did a previous HPLC method. Macka et al.
separated silylated polyglycerols with a degree of polymerization
up to 10 (233). Higher oligoglycerols were eluted but not cleanly
resolved in their method. Ye et al. developed an open-tubular
SFC method for the separation of ethoxylated sorbitan esters
(234). While the method was superior to GC or gel permeation
495R
chromatography for these emulsifiers, the authors later found that

a separation by gradient elution reversed-phase HPLC was
comparable to the SFC separation (235). However, isocratic
elution, and a correspondingly poorer separation, was necessary
for quantitation by HPLC (235).
Supercritical fluid chromatography has been used to characterize a variety of other low-molecular weight, nonpolar polymers
and polymer additives. Low-molecular weight (up to 25 000)
polysiloxanes are perhaps best addressed by SFC. Just et al.
described the use of SFC/FID and SFC/MS for the determination
of cyclic siloxanes in silicone oils (236) and for the characterization
of methyl and hydroxyl end-capped siloxanes (237). They found
that matrix-assisted laser desorption MS was a useful complementary technique for higher molecular weight polysiloxanes
(237). Takeuchi and Sugihara used packed-column SFC to
separate various functionalized polysiloxanes based upon the
organic functional end group (238). The fractions were further
characterized by NMR and GC/MS.
MacKay and Smith used SFC/MS to study additives to
polyurethanes (239, 240). They demonstrated the potential of
on-line SFE/SFC/MS for this application. Pasch et al. used SFC
in one dimension of a two-dimensional approach to characterize
complex polymer mixtures (241). Critical chromatography
(chromatography at the critical point of adsorption, at the border
of adsorption and exclusion modes of liquid chromatography
where separation is governed by the type and number of functional
groups alone) was used to separate various methacrylate block
copolymers according to functional group in the first dimension,
while SFC was used to separate primarily according to molecular
weight in the second dimension (241). Raynor and Bartle
reviewed the use of SFC for the characterization of surface-coating
polymers (242). They described the use of open-tubular SFC with
CO2 to separate reactive oligomeric mixtures. More polar oligomeric mixtures were separated by packed-column SFC using
modified CO2. Just and Gross conducted a study of vulcanization
using SFC to separate and identify the reaction products (243).
They employed squalene as a model compound and conducted a
variety of reactions, simulating various vulcanization processes.
Preparative-scale SFC is useful in fractionating and studying
polymers. Ute et al. used preparative-scale SFC with CO2/ethanol
on silica gel to prepare highly isotactic and highly syndiotactic
fractions of poly(methyl methacrylate) with degrees of polymerization of 25 and 50 (244). They then used these fractions to
explain some peculiarities in the separation of these materials by
gel permeation chromatography. Ute and Hatada later reviewed
the preparative-scale separations of a variety of nonpolar and
moderately polar polymers (245).
Other publications described the use of SFC to study species
that could potentially migrate from packaging polymers. Additives
in packaging polymers were separated by Buecherl et al. using
SFC with FID and MS detection (246, 247). They used on-line
SFE to extract the additives from the polymers and found the
combined methods offered considerable time savings. Berg et
al. used a novel large-volume-injection technique and open-tubular
SFC to achieve detection of additives at concentrations as low as
10 ppb (248). They extracted polymers in aqueous acetic acid
and isooctane to simulate foods and concentrated the extracts
before injection. Calvey et al. studied potential migrants from
microwave susceptor packaging (182). They found aromatic
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compounds as well as aliphatic alcohols and ketones in solvent

extracts of the susceptor packaging.
(Achiral) Pharmaceutical Agents and Biologically Important Mixtures. Supercritical fluid chromatography is being used
for the characterization of pharmaceutical agents and biologically
important compounds with increasing frequency. Recent applications in this area were reviewed by Wilson et al. (249) and by
Giron (250). The move toward SFC is in part due to the
increasing reliance on packed-column SFC for chiral separations.
These applications are reviewed in a separate section on chiral
SFC. Many pharmaceutical agents and biologically important
compounds are relatively polar. These polar analytes can be
separated by packed-column SFC with modified CO2 as mobile
phase, with all the advantages this technique brings over HPLC
(see above). Fat-soluble vitamins are a natural for SFC. Wyss
published a comprehensive review of the chromatographic and
electrophoretic methods for the determination of retinoids (251).
On the basis of the publications he reviewed, he judged SFC/
FID insufficiently sensitive when compared to HPLC with UV
detection. However, he did not consider packed-column SFC/
FID or packed-column SFC/UV, which should be at least as
sensitive as HPLC/UV. Ibanez et al. described their use of a
rotatable central composite experimental design method to
optimize the SFC separation of fat-soluble vitamins using a single
micropacked column (252) and two coupled columns (253).
Hanson studied the retention behavior of steroids in packedcolumn SFC (254). Retention was influenced not only by polar
functional groups but also by intramolecular interactions, shielding, and shape. He also demonstrated that commercial packedcolumn SFC equipment could be used for small-scale preparative
chromatography of a steroid hormone, cyproterone acetate (255).
Preparative-scale SFC was economically viable and environmentally friendly. Open-tubular SFC/FID was used by Kim et al. to
study cholesterol and cholesteryl esters in human serum (256).
They achieved an RSD of 2.6% and found that SFC/FID had
advantages over GC, HPLC, and enzymatic methods. They
reported a limit of detection of 4-6 pg, which must be in error,
since detection limits for the FID are typically in the low-nanogram
range or, at best, in the hundreds of picograms.
Ramsey et al. used the propensity of packed-column SFC for
eluting polar analytes, and the selectivity and sensitivity of tandem
mass spectrometry, to demonstrate a sensitive assay for ionophore
antibiotics in animal feeds (257). A number of the ionophores
were, surprisingly, sodium salts. The mass spectrometric data
indicate that these species were eluted as salts, in spite of the
fact that the mobile phase was unmodified CO2. Pyo et al.
described the use of water-modified CO2 for the SFC separation
of polar antibacterial agents (258). Arimoto and Adachi patented
the use of a surface ionization detector for SFC detection of
macrolide antibiotics (259).
Berger and Wilson published a series of demonstrations of
the power of packed-column SFC for the rapid separation of
psychoactive agents (260-262). They clearly demonstrated the
large number of degrees of freedom in packed-column SFC by
evaluating mobile-phase, pressure, and temperature gradients. The
first paper in the series dealt with the separation of phenothiazine
antipsychotics (260). They used a tertiary mixture of CO2,
methanol, and isopropylamine to separate 10 components in 11
min. Isopropylamine was essential for elution of the analytes. Ten
antidepressant drugs were separated in less than 6 min (261).
Stimulants exhibited a wider range of retention behavior than did

the antipsychotic or antidepressant agents (262). Takaichi et al.
demonstrated the separation of benzodiazepine tranquilizers by
SFC/UV (263).
Simmons et al. described their evaluation of packed-column
SFC/UV for the determination of the antiinflammatory agent
phenylbutazone and its major metabolite in human serum and in
a commercial tablet (264). The limit of detection of the method
was 100 ng/mL. Smith et al. determined ranitidine, an antiulcer
agent, and its polar metabolites in extracts from biological fluids
using packed-column SFC (265). The separation was performed
in under 10 min using a mobile phase of CO2 modified with
methanol/methylamine/water. Bailey et al. evaluated the separation of 10 -blocker drugs on a variety of packed SFC columns
(266). They found that addition of triethylamine to the methanolmodified CO2 mobile phase and the aminopropyl-bonded phase
provided the best separation. The speed and advantages of
packed-column SFC for the determination of pharmaceutical
agents were also demonstrated by Strobe et al. in their work with
felodipine, an antihypertensive agent, and a potential degradation
product (267). The authors used methanol-modified mobile phase
with simultaneous electron capture and UV detection. The
separation was completed in less than 6 min, which allowed a
sample throughput 60% greater than that achieved with HPLC,
with a 90% decrease in solvent waste. Mount et al. also used
packed-column SFC with electron capture detection for the
determination of artemisinin in whole blood (268). They documented a limit of detection of 20 ng in 1 mL of blood.
Lembke and Engelhardt capitalized on the lower viscosity of
the SFC mobile phase in their determination of the ethyl ester of
phytanic acid extracted from human blood serum (269). They
coupled three different columns in series (silica, aminopropylbonded silica, and C8-bonded silica) to improve the separation, a
move they called selectivity tuning. Evans and Smith compared
the performance of GC, HPLC, and SFC for the separation of
hydroxylated dialkyldithiocarbamates with up to three hydroxyl
groups, models for drug metabolites (270). SFC compared
favorably with the other two techniques. Heaton et al. used SFC
to monitor extracts of taxicin, which may be used to prepare
anticancer drugs, from the English yew tree (271). They
compared open-tubular SFC with a carbowax phase to packedcolumn SFC with a cyano column. The cyano packed column
provided better resolution of taxicins I and II, shorter analysis
times (<10 min), and greater accuracy.
Pinkston et al. evaluated the potential of open-tubular SFC/
MS for trace analysis of mebeverine, an antispasmodic agent
(272). The drug was determined after extraction from spiked dog
plasma. Accuracy and precision were judged acceptable in withinday and between-day comparisons for samples spiked at 6 and 60
ng/mL of plasma. Wong et al. encountered one of the obstacles
of commercial open-tubular SFC equipment in their evaluation of
open-tubular SFC/FID for the determination of new immunosuppressants extracted from whole blood (273). They used splitting
injection with a small effective injection volume, coupled with the
nonselective FID. This resulted in unacceptable selectivity/
sensitivity for their assay. A simple, larger volume injection
technique, as described earlier (85), would have improved the
performance of the SFC instrument. On the other hand, Walther
and Netscher demonstrated one of the strengths of open-tubular
SFC/FID, as compared to GCsthe analysis of reactive and
thermolabile compounds (274). They characterized 63 reactive

or thermally labile intermediates which are useful in the synthesis
of natural products. The lower analysis temperatures and low
surface areas of open-tubular SFC made it the method of choice
for these compounds.
Organometallic Species and Miscellaneous Applications.
A number of groups described the SFC separation of a variety of
nonpolar organometallic species. Lin et al. reviewed SFC of
chelated metal ions and of organometallic compounds (275).
Fluorinated ligands are very effective for metal ions, since the
fluorinated metal chelates are very soluble in CO2. Laintz et al.
demonstrated the separation of geometric isomers of Cr and Rh
chelates using packed-column SFC (276). Phenyl-bonded phases
and (trifluoroacetyl)acetone chelates yielded the best separations.
Both Blake et al. (277) and Bayona and Cai (278) worked with
organotin compounds. Blake et al. evaluated a new interface for
SFC/ICPMS using organotin compounds (277). Bayona and Cai
reviewed extraction, separation, and detection of organotins (278).
They described the use of SFC with both nonselective (FID) and
selective (atomic emission, flame photometric, mass spectrometric) detectors. Wenclawiak and Krahs goal was to determine
organic and inorganic arsenic species extracted from solid
matrices (279). They compared open-tubular SFC to GC of the
thioglycolic acid methyl ester derivatives. They found that, unlike
GC, SFC produced no thermal degradation of the inorganic arsenic
derivatives.
Hanson et al. used packed-column SFC to study the reaction
products from the addition of trimethylaluminum to R,-unsaturated aldehydes (280). They found that the FID was necessary
for the detection of species with no chromophore. Aqueous formic
acid, which is compatible with the FID, was used as mobile-phase
modifier to elute the more polar species. Carey et al. compared
FID to inductively coupled plasma MS detection for the SFC of
chromium chelates and of a thermally labile chromium dimer
(281). They found that the limit of detection for the ICPMS couple
system was 1-2 orders of magnitude better than that of the SFC/
FID system for stable analytes, but that the thermally labile
organometallic was not detected with the ICPMS system. Laintz
et al. conducted a study of the packed-column SFC of lanthanide
-diketonates using unmodified and alcohol-modified CO2 (282).
They compared six ligands and found advantages with some. One,
thenoyltrifluoroacetone, showed thermal degradation during SFC
at elevated temperature.
De Geus et al. used packed-capillary SFC to determine trialkyl
and triaryl phosphates extracted from harbor sediment (283).
They used thermionic detection and found detection limits in the
0.1-0.2 mg/kg of sediment range.
CHIRAL SFC
There has been great progress in the development and
application of chiral SFC and related techniques. Numerous
reports of superior separations, easier and faster method development, and adoption by industry have been published. Many more
successes are being reported, formally and informally, at meetings.
The fundamental reasons for these advantages seem to stem from
higher ordering of the stationary phases under some SFC and
SubFC conditions (particularly when compared to GC conditions
with the same stationary phases), solute solvation effects different
from that with conventional liquid mobile phases, and of course
the typical advantages of faster diffusion, faster optimum velocities,
497R
and much faster column recovery to initial conditions following

programming when supercritical or subcritical fluids are used
instead of conventional liquids. Schurig and co-workers have been
doing chiral SFC for many years. They published two reviews
recently (284, 285) dealing with their developments of enantiomer
separations using immobilized cyclodextrin stationary phases.
Petersson and Markides also reviewed chiral SFC noting its speed,
efficiency, low-temperature capability, and wide selection of
detection options (286).
Much work continues in the development and application of
new chiral stationary phases for SFC. Cyclodextrin derivatives
are receiving considerable atention. Yi et al. prepared and
evaluated seven permethyl-substituted -cyclodextrins (bound to
poly(dimethylsiloxane)) for use in SFC and GC, reporting excellent separations (287). Yi et al. also prepared four large-rimtethered permethyl- (or per(methyl/acetyl)-) substituted -cyclodextrin stationary phases and again reported excellent separations
of a variety of enantiomers (288). Petersson et al. investigated
the chromatographic performance of copolymeric and side armsubstituted -cyclodextrin/polysiloxane stationary phases. They
varied the amount of cyclodextrin present, the way it was attached
to a silicone backbone, and the effect of chemical substitution on
the cyclodextrin (289). Additional developments of cyclodextrin/
polysiloxane stationary phases were disclosed by Bradshaw et al.
(290, 291).
Schmalzing et al., using immobilized permethyl--cyclodextrin,
studied the effects of temperature and pressure on chiral retention
and selectivity for four racemic mixtures (292). Schurig et al.
separated hexobarbital by SFC, and other chromatography
techniques using Chirasil-DEX (293, 294). This phase contains
an octamethylenepermethyl--cyclodextrin linked to poly(dimethylsiloxane). Doennecke et al. anchored -cyclodextrin to a
polysiloxane. They reported that very polar compounds could be
eluted at low temperatures using SFC, achieving higher separation
factors than when GC was used (295). Francotte et al. prepared
stationary phases of polysiloxane or poly(ethylene glycol) polymers containing substituted benzoylcellulose derivatives and
demonstrated separations using GC and SFC (296). Petersson
et al. prepared polymeric stationary phases with alternating blocks
of chiral (1R)-trans-N,N-1,2-cyclohexylenebisbenzamide and achiral
blocks of siloxane. They then used these phases to separate a
number of chiral diols by both GC and SFC. SFC produced
superior resolution most likely from its lower operating temperature and stronger solute/stationary-phase interactions (297).
Schleimer and Schurig and Schleimer et al. evaluated Chirasilnickel, a polysiloxane containing an immobilized Ni(II) chiral
complex, in open-tubular SFC. They used this phase to separate
coordinating solutes by both GC and SFC. Once again, they found
the low temperatures afforded by SFC provide higher selectivity
for separating enantiomers (298, 299).
Bargmann-Leyder et al. evaluated chiral stationary phases
based on tyrosine demonstrating separations of enantiomers of
warfarin and a pharmaceutical substance, ICI 176334 (300).
Bargmann-Leyder et al. separated -blockers on ChyRoSine-A,
noting that SFC separations are achieved in little time but that
the same solutes were poorly resolved using normal-phase liquid
chromatography. They then showed using NMR that CO2 acts
as a complexing agent for the solutes, changing their chiral
discrimination (301). Bargman-Leyder et al. separated -blockers
in under 2 min using short columns packed with ChyRoSine-A
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(302). Bargmann-Leyder et al. later used molecular modeling to

develop an explanation of how the solvating effect of CO2 induces
conformational changes in propranolol analogs that enhance chiral
discrinimation (303). Bargmann-Leyder et al. also studied the
effects of spacer length and steric hindrance near the stereogenic
center of several chiral stationary phases and proposed a new
stationary phase which should allow a broad range of applications
(304). Wilkins et al. adsorbed an anthrylamine derivative to
porous graphitic carbon and used this to separate two antiinflammatory agents and a series of racemates (305). Lohmann and
Dappen made chiral stationary phases from -lactones and report
that SFC applications are possible (306).
Numerous additional applications have been reported. These
represent both promising possibilities and, more importantly,
reports of real-world success stories. Themes running through
these reports echo superior selectivity, shorter analysis times, fast
method development, economic operation, etc. Siret et al.
separated four optical isomers of a calcium channel blocker by
LC and SFC. The LC separation required two stationary phases
used together, but under SFC conditions, a single stationary phase
(one of those used in the LC experiment) was sufficient (307).
Kot et al. performed chiral separations of -blockers, benzodiazepines, nonsteroidal antiinflammatory agents, and -agonists
by both SubFC and SFC. They reported short analysis times in
every case, and often sufficient resolution to allow solute mass
approaching column overload and semipreparative collections of
enantiomers (308). Sandra et al. also reported benefits of coupling
different chiral columns in series to broaden the scope of possible
applications (309). Peytavin et al. separated enantiomers of seven
antimalarial agents (310). Almquist et al. used SFC to separate
10 benzodiazepine racemates and temazepam derivatives (311).
Petersson et al. determined the enantiomeric purity of (S)carboranylalanine using open-tubular SFC with a stationary phase
of permethyl--cyclodextrin methyloctylsiloxane (312). Biermanns et al. separated enantiomers of propranolol, atenolol, and
metoprolol by packed-column SFC with sub-part-per-million detection of propranolol (313). Wilson separated enantiomers of
ibuprofen in under 7 min, and flurbiprofen in under 4 min using
packed-column SFC (314). Juvancz et al. used open-tubular
columns coated with Chirasil-Dex to separate racemates of several
amines, amino acids, amino alcohols, carboxylic acids, coumarines,
diols, and imides (315). Whatley preparatively separated racemic
glibenclamide analogs by SFC on chiral stationary phases and
noted advantages of SFC over HPLC (316).
Lynam and Nicolas compared Chiracel OD columns from the
same lot in an LC instrument (using hexane plus modifiers) and
an SFC instrument (using CO2 and similar modifiers) for the
separation of repeated injections of trans-stilbene oxide and
(carbobenzyloxy)phenylalaninol. They reported that, for similar
analysis times, the Chiralcel OD column gave superior resolution
when used with the SFC system, plus had the added benefit of
faster equilibration following solvent changes (317). Blum et al.
used a Whelk-O 1 column to separate a variety of enantiomeric
pairs, noting superior results in SubFC compared to LC. They
successfully performed preparative separations on a 1-in.-diameter
column of the same stationary phase (318). Stringham et al.
reported advantages of speed and ease of methods development
for SFC and SubFC compared to LC. They developed methods
for four intermediates from a synthetic process of an antiviral drug
candidate. They were not able to develop HPLC methods for two
of the compounds, and a third was marginal (319).
Walther et al. used (S)-trolox methyl ether to derivatize chiral
alcohols and then separated the derivatives by GC and SFC with
achiral columns (320).
Chiral SFC examples and procedures are included, along with
HPLC and GC data, in a database described by Koppenhoefer et
al. (321-323).
Unwarranted generalities proclaiming success are just as
dangerous to a new technique as unwarranted generalities
proclaiming failure. Although we have seen many reports of
different chiral recognition mechanisms and superior chiral
separations using SFC, this is not always so for every application.
Anton et al. showed two cases where subcritical fluid chromatography gave poorer resolution than HPLC. In the first, CO2
was shown to interact with phenylalaninol, reducing resolution.
In the second, a secondary amine was shown by NMR not to
interact with CO2 but still was resolved more poorly with SubFC
than with HPLC (324). Smith et al. showed examples where a
temperature reduction improved chiral resolution for enantiomers
of a Chromakalim analog in both SFC and HPLC separations on
Chiracel-OD, while another analog had opposite temperature
dependency with both separation techniques (325). However, at
comparable resolution the SFC conditions eluted the solutes in
less than half the time required for the HPLC separations. Instead
of sweeping generalities, it is perhaps more important at this stage
in the development of chiral SFC to fully realize that CO2 often
interacts differently with solutes than conventional liquids. Chiral
selectivity is almost always different and frequently, but not always,
better in SFC than in HPLC. A borderline or failed separation in
HPLC has a real chance for success in SFC, and vice versa. One
generality that will always be true, however, is that when chiral
selectivity is roughly equal with the two techniques, SFC techniques will always be much faster than HPLC on comparable
columns.
SUPERCRITICAL FLUID EXTRACTION
More emphasis has been placed on analytical sample preparation over the past few years, partly due to the advancements in
SFE. Though process-scale SFE, physical-chemical studies, and
analytical uses of supercritical fluids cannot be completely
divorced, this portion of our review is focused on analytical SFE.
References to these ancillary uses of the technology are included
only when they are directly applicable to analytical sample
preparation. However, a bibliographic guide to SFE covering
physical and thermodynamic data, phase equilibria, and SFE
processes and applications from 1980 through 1993 may be of
strong interest (326). Because SFE does not generally provide
additional information about a sample compared with other
extraction procedures, the advantages of speed, efficiency, organic
solvent minimization, and cost per extraction must be significant
before general analysts will move away from their tried-and-true
extraction methods. While SFE is rapidly gaining acceptance in
the analytical community, factors such as regulatory approval,
standardization of commercial instrumentation configurations, and
a more general understanding of the extraction process are
necessary for a more complete acceptance of SFE, or other newer
extraction technologies, in general analytical laboratories. For
example, carbon dioxide either alone at high pressure or combined with modifier at moderate pressure may work for a given
applicationsuntil there is some consensus regarding which is

preferred, SFE will be viewed as confusing to those contemplating
entering this exciting and promising field.
While there has been a wealth of information uncovered about
the fundamentals of SFE, the most rapid area of growth is the
application of the technique to analytical problems. The novelty
of the on-line combination of SFE with other analytical methodologies is also losing favor to the exploration of the applicability of
SFE. The balance of this review will reflect this trend.
SFE Theory and Fundamental Measurements. Because
solvating power, as well as physical properties like viscosity and
diffusivity, can be easily varied in a supercritical fluid, SFE is
unique in its ability to be useful to study the extraction process
in general. King and Catchpole reviewed physicochemical data,
including phase equilibria and mass-transfer parameters, used in
the design of SFE (327). Solute solubility in the extracting fluid
is an obvious prerequisite to SFE that can be modeled in
predicting SFE processes. A neural network approach to predicting solubility providing data based on analyte molecular structure
was reported (328, 329). Another method for predicting solute
solubility is based on determining the solubility parameter and
hydrophobic interactions from easily obtained constants (330).
Veress developed a mathematical model for dynamic SFE using
the diffusion layer theory (331). The model predicted the time
required to extract a predetermined amount of analyte, in this
case cannabinoids from marijuana and hashish.
SFE Instrumentation, Techniques, and Performance.
Methodologies for the performance of SFE are still being defined
as more information is uncovered regarding the factors that
influence the technique. Because supercritical fluid solvent
strength can be varied simply by changing temperature and/or
pressure, these factors, and their influences on extraction, lead
to variety of approaches to SFE. A collaborative study, using blind
replicate design with balanced replicates, was performed for the
SFE/IR determination of petroleum hydrocarbons (332). The
study showed that a carefully documented procedure can provide
quality results. Bayona reviewed state-of-the-art SFE, including
common approaches to method development (333). Gere and
Derrico presented an approach to method development in SFE
(334). Taylor reviewed strategies for performing SFE (335). He
discussed occasions where extraction of the matrix, while leaving
the analyte of interest behind (i.e., inverse SFE), may be preferred.
Study of the influence of flow rate can be used to characterize
the extraction behavior (336). Extractions limited by solute
solubility show a flow rate dependence, while those limited by
analyte desorption from the matrix and/or diffusion through the
matrix are not. Clifford et al. modeled the kinetics of dynamic
SFE by evaluating the effect of the matrix on retarding rapid
extraction of analyte material (337). Wet matrices are generally
dried prior to SFE, and Burford et al. surveyed a number of drying
agents (338). They found that magnesium sulfate, molecular
sieves, and Hydromatrix diatomaceous earth successfully bound
excess moisture in most cases. Fang and Chau noted the
possibility of contaminating the laboratory atmosphere during
dynamic SFE and advocated venting the expanded fluid into a
fumehood or through an adsorbent (339). Via and Taylor
reviewed the use of SFE to address processing problems like the
fractionation of polymers and soil remediation (340).
New commercial instrumentation for SFE was developed and
patented during this reporting period (341-344). These instruAnalytical Chemistry, Vol. 68, No. 12, June 15, 1996
499R
ments feature on-line addition of solvent modifiers and some

degree of automation. Jarvis et al. used robotics to modify
commercial instrumentation to achieve the automation necessary
for around-the-clock SFE determination of pesticides in environmental samples (345). Brewer and Kraus described the development of an SFE apparatus for the direct extraction of organics
from water (346). They presented results for the extraction of
pentachlorophenol at concentrations as low as 0.1 ppm.
Restrictors to maintain operating pressure while allowing
dynamic flow have often caused problems in SFE. One report
described the construction of a robust stainless-steel-clad fusedsilica restrictor (347). Meanwhile, another restrictor nozzle was
evaluated for use in the SFE of rubber additives, fullerenes, and
soil constituents (348). Yang et al. developed a mathematical
equation to calculate the fluid flow rate through linear restrictors
(349).
Solute Collection. Collecting or trapping the extracted
analyte following SFE remains an important area for improvement.
Factors such as collection temperature, fluid flow rate, analyte
volatility, and extraction time all play important roles in efficient
analyte collection. Collection methods can generally be classified
into two schemes: collection into liquid solution (i.e., solvent
trapping) and collection onto a solid surface, such as a beaker or
test tube, chromatographic interface, or sorbent media (i.e., solid
trapping). Since each vendor of commercial SFE instrumentation
uses different variations of these collection methods some level
of confusion will exist for novice users and those outside the field,
until analyte collection is thoroughly understood. Bowadt and coworkers compared the two trapping methods for the SFE of
chlorinated materials, using 2,2,4-trimethylpentane as the collecting solvent and silica, Florisil, and octadecyl-coated silica as the
sorbent traps (350). For nonvolatile polychlorinated biphenyls
(PCBs), they saw little difference between the two collection
methods. When more volatile chlorobenzenes were extracted,
the solid-phase methods provided better results under the conditions studied, due to the purging of analytes from the collecting
solvent.
Analyte collection directly into organic solvents is the most
straightforward collection method. For subsequent analysis that
requires solvent dilution, this method eliminates at least one step
from the total SFE process. Thompson et al. surveyed nine
different collection solvents and four mixed solvents for the
collection efficiency of a polarity test mixture (351). They found
that quantitative analyte recovery was not always possible with
single-solvent systems, but recoveries improved with mixedsolvent systems. Subsequently, Thompson and Taylor investigated the effects of solvent-trapping collection when mixed fluids
(i.e., carbon dioxide entrained with organic cosolvents) were used
for extraction (352). The mixed collection solvent that provided
the highest recovery when pure carbon dioxide was used gave
the lowest results when modified carbon dioxide was employed.
Under the conditions studied, a single collection solvent, hexane,
gave the best results with mixed extracting fluids. Wenclawiak
and co-workers determined that changes in the extracting pressure, fluid flow rate, solvent selection and temperature, and
configuration of the collection device all played important roles
in the efficient recovery of volatile chlorobenzene and hexachlorocyclohexane isomers (353).
When sorbent-trapping methods are used, it is generally easier
to allow collection at subambient temperatures than with solvent500R
based collection. This leads to two significant, general advantages: restrictors can be heated to minimize the possibility of
plugging, and volatile analytes can be more efficiently trapped.
Huesers and Kleiboehmer evaluated silica-based traps for the
collection of PAHs (354). They found that high flow rates and
organic modifiers in the carbon dioxide extracting fluid did not
significantly impact their collection efficiency and claimed that
the necessity for subsequent sample cleanup is minimized.
Postextraction sample cleanup is also minimized using a solidphase extraction (SPE) cartridge as the collection device (355).
The influence of alcohol modifiers and different concentrations
and temperatures on the collection efficiency of PCB congeners
was studied using stainless-steel beads, octadecyl-modified silica,
Florisil, or silica gel for trapping (356). Levy and Houck
demonstrated the cryogenic collection advantage of sorbent
trapping for volatile analytes (357). Ezzell introduced a two-step
collection procedure where a octadecylsilica-embedded glass fiber
membrane was placed in-line prior to solvent trapping (358).
Moore and Taylor found that high modifier amounts can lead to
collection losses with solid-phase trapping and advocated a tandem
trapping procedure (359). Trap temperature and fluid flow rates
are also especially important when modifiers are used with solidphase traps.
Finally, Vejrosta and co-workers developed a novel collection
device that combines attractive features of both solvent and
sorbent trapping (360-362). In this device, the restrictor capillary
is placed into a cryogenic trapping capillary. The extraction
effluent sprays into a flow of condensed modifier solvent (i.e., a
moving liquid layer) for collection.
Extracting Fluids. Carbon dioxide and carbon dioxide-based
fluids are the predominantly used fluids in SFE. In addition to
its favorable physical properties, carbon dioxide is inexpensive,
safe, and abundant. The purity issues that previously limited the
use of carbon dioxide for trace analysis have been resolved for
most applications. Bernal et al. compared three different grades
of carbon dioxide to show that, when large amounts of extractants
are used, ECD-sensitive compounds can contaminate the extract
(363). SFE pumping efficiency is dramatically improved when
liquid carbon dioxide is delivered to the pump. Rather than
cooling the pumps to liquefy the carbon dioxide, most commercial
instruments request that carbon dioxide with a helium head
pressure be used. While helium is generally considered an inert
gas, extraction kinetics can be slowed when helium-entrained
carbon dioxide is used (364). While the first report of this effect
dealt with the extraction rate of cholesterol from dried egg yolk,
King et al. showed that the solubility of soybean oil dramatically
decreased when helium and carbon dioxide mixtures are used
(365). When carbon dioxide is not feasible, alternative extracting
fluids become necessary. Howard et al. demonstrated the use of
Freons as extracting fluids for environmental samples (366).
Results matched those obtained for Soxhlet when chlorodifluoromethane extracted three- and four-ring PAHs from montmorillonite clay. Hillmann and Baechmann observed a 15% increase
in the extraction efficiency of pesticides when they used trifluoromethane, rather than carbon dioxide, as the extracting fluid
(367). They did not observe any selectivity differences between
the two fluids.
While carbon dioxide is the preferred fluid in SFE, it possesses
several polarity limitations. Solvent polarity is important when
extracting polar solutes and when strong analyte/matrix interac-
tions are present. Organic cosolvents are frequently added to the

carbon dioxide extracting fluid to alleviate the polarity limitations
of the fluid. Langenfeld et al. compared nine different carbon
dioxide modifiers for the removal of PCBs from river sediment
and PAHs from air particulate matter (368). They determined
that acidic/basic modifiers enhanced the extraction of PCBs, while
modifiers capable of dipole-induced dipole and - interactions
enhanced the extraction of PAHs. Tena et al. also studied the
nature of the cosolvent, as well as the volume and contact time,
on the SFE of PAHs in soil (369).
Another modifier-based approach for the SFE of polar compounds is to use a derivatizing agent and allow for the derivatization reaction to occur prior to dynamic extraction. Hillmann
and Bachmann demonstrated this approach for the on-line SFEGC determination of phenoxycarboxylic acids (370). The method
allowed quantitative analysis down to low parts-per-billion levels.
Chatfield et al. allowed acidic acids to bind onto an anionic
exchange resins prior to methylation with methyl iodide (371).
SFE-COUPLED TECHNIQUES
During the rapid initial development of SFE, the direct
combination of the technique to subsequent analysis (i.e., on-line
SFE) was promoted. Growth of such approaches has appeared
to slow as researchers use the simpler, off-line approaches to
understand the fundamentals of SFE and instrument manufacturers work to establish simple SFE methodology for general
laboratory use. However, one significant advantage of the online approach is that the entire extract can be readily analyzed
without intervening sample handling and contamination, significantly improving method detection limits. Successful development
of on-line methods will also provide the complete level of
automation necessary to gain total acceptance in some situations.
Generally, SFE is coupled with chromatographic methods, though
specific spectroscopic techniques are also being developed.
SFE/Chromatography. The key to combining SFE with
chromatographic methods is the interface between the techniques.
Francis et al. used a thermally modulated interface approach for
the SFE-GC determination of explosives with detection with a
thermal energy analyzer (372). Detection in SFE-GC systems was
also evaluated by Farnsworth et al. who used a two-channel optical
device to enhance the selectivity of sulfur detection with a radiofrequency plasma detector (373). Sandra et al. discussed a
number of applications of the SFE-GC approach (374).
Daimon and Hirata studied trapping efficiency and solute
focusing in coupling SFE with open-tubular SFC (86). Their
approach used a linear SFE restrictor and a capillary collection
tube containing a stationary phase. Subsequently, they expanded
their system for use with modified extraction fluids (375). Ullsten
and Markides placed a solid-phase adsorption device in front of
their SFE/SFC system for the automated analysis of polar solutes
from liquids (88). A dual-trapping system was needed to eliminate
the modifier solvent. Greibrokk reviewed applications of SFE
coupled with chromatography (376).
Other SFE-Coupled Techniques. SFE combined with IR
is becoming an accepted method for the determination of total
petroleum hydrocarbons (332). The technique was collaboratively
evaluated in a number of laboratories. Heglund et al. used a
chalcogenide fiber optic to construct a simple SFE/IR system
(377). For petroleum hydrocarbon determination, the linear
dynamic range of this approach covered 3 orders of magnitude.
Taylor and Jordan (378) reviewed SFE/IR, including applications

to the evaluation of textile fiber finishes. Wang and Marshall
evaluated SFE coupled with atomic absorption spectrometry for
the determination of metals in the subnanogram to low-picogram
range (379). During extraction, in situ complexation of the metal
species occurred. Tena et al. achieved continuous derivatization
and monitoring of extracted analytes with a continuous-flow
manifold that included a flow-through sensor connect in-line with
the SFE collector (380). Braumann et al. monitored the SFE
process in an on-line fashion using proton nuclear magnetic
resonance spectroscopy (381). These researchers also obtained
two-dimensional NMR spectra during the extraction process.
SFE APPLICATIONS
The largest area of growth in the development of SFE has been
the rapid expansion of applications. Environmental and food
analysis led the way. Because many of the applications of SFE
are interrelated (e.g., pesticides and environmental samples or
pesticides, foods, and natural products), the reader should peruse
all related applications to gain a more comprehensive understanding of the application of SFE to their field of interest.
Fossils Fuels and Environmental Samples. The largest
application for SFE continues to be in the field of environmental
analysis. A number of reviews have been written during this
reporting period which can give the reader a broad overview (204,
382-389). Hawthorne et al. described the factors that influence
quantitative SFE from environmental samples (390). They
proposed increasing extraction rates through the use of alternative
fluids like chlorodifluoromethane, organic modifiers, or elevated
temperatures.
Hydrocarbons. Furton et al. compared SFE at temperatures
up to 350 C to Soxhlet extraction for the determination of
biomarkers in geological samples (391). Higher recoveries with
improved precision were obtained with the supercritical method.
Hawthorne et al. also found that SFE gave higher extraction yields
than Soxhlet extraction (392). They extracted heavy petroleum
hydrocarbons from soil and needed static modifier addition and
temperatures to 150 C to get the best results. Lighter hydrocarbons, in the gasoline and diesel range, required lower temperatures for SFE-GC (393). The optimized SFE-GC system used
split injection with high SFE flows, thick-film columns, and
cryogenic trapping (394). In extracting petroleum hydrocarbons
from soil, Yang et al. compared sorbent- and solvent-based
collection methods and found that both methods give comparable
results, higher than by Soxhlet procedures (395). Water content
had no effect on the Soxhlet extraction of soil-bound petroleum
hydrocarbons but did affect the extraction efficiency of SFE (396).
Camel et al. found that, as soils age, aromatic compounds become
more difficult to extract than phosphonates and phosphates (397).
Oostdyk et al. found that aliphatic amines on soils extracted
favorably with supercritical fluids, compared with sonication (398).
Factors that influenced amine recovery included the percent clay
content, the soil surface area, and the cation exchange capacity
of the soil. Meanwhile, two studies investigated the parameters
that influence the recovery of petroleum hydrocarbons from
contaminated soils (399, 400).
Interest in nonsoil matrices was also strong. Bowyer and Pleil
used SFE to clean and desorb common air sampling sorbents
(401). Hansen et al. developed a sorbent trap to collect atmospheric aerosols which were then extracted and analyzed with
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SFE-GC/MS (402). Nguyen et al. employed an in situ trimethysilylation procedure in the on-line SFE-GC/MS determination of
sterols in sewage sludge (403). A research group at the U.S. EPA
combined SFE with the disk approach to solid-phase extraction
prior to the GC/MS characterization of phenols and other trace
organic pollutants in water (404, 405). Daneshfar et al. looked
at the effects of pressure, temperature, and modifiers on the
extraction efficiency of phenoxy acids from water (406).
Polycyclic Aromatic Hydrocarbons. The extraction of PAHs from
soils, sediments, and other environmental matrices remains a
difficult proposition that is being addressed by a variety of
approaches. Three independent laboratories participated in a
mini-round-robin study of the SFE of these samples (407). The
method, using carbon dioxide with methylene chloride as the
extracting fluid, appears rugged, though interlaboratory method
precisions appeared to be concentration-dependent. Dean et al.
compared SFE with Soxhlet and microwave extraction for PAHcontaminated soil (408). They reported that the SFE and
microwave approaches yield higher levels of PAHs than Soxhlet
extraction. Lee et al. notes that, although nitrous oxide and
Freon-22 are stronger supercritical solvents than carbon dioxide,
the efficacy of carbon dioxide for the extraction of PAHs is
improved with a mixed modifier of water, methanol, and methylene chloride (409). As in the previous report, Meyer and
Kleiboehmer reported SFE as more efficient than Soxhlet procedures (410). They also found nitrous oxide or carbon dioxide
modifiers (toluene, in this case) improved SFE efficiency.
(Note: Despite these reports of the use of nitrous oxide for SFE,
as we warned in our previous review (1), we do not condone the
use of nitrous oxide in most SFC or SFE applications.) Haeufel
et al. reported methanol as their preferred modifier (411). In
evaluating the experimental design for SFE of soil-bound PAHs,
Barnabas et al. studied extraction pressure, temperature, time,
and percent methanol addition and noted a high level of imprecision due to the elemental sulfur content of the soils studied (412).
Tena et al. also investigated the parameters to optimize PAH
extraction (413). They especially noted the influence of PAH
molecular weight on the extraction efficiency. Reimer and Suarez
compared SFE with Soxhlet using methylene chloride modifier
addition in two different modes (414). They reported that 85% of
the variance of the SFE method was due to the sample matrix, a
phenomenon that seems to be prevalent in this type of analysis.
Rather than using modifiers, Hawthorne and Miller demonstrated that greatly elevated temperatures, 200 C and higher,
proved effective for the extraction of PAHs, chlorinated phenols,
and other environmental samples (415). Thermal considerations,
i.e., thermal desorption, did not account for the increased
extractability of these materials at these temperatures. Yang et
al. found that toluene and diethylamine both provided even greater
efficiency at these elevated temperatures, while methanol was
similar to pure carbon dioxide (416). Using pure carbon dioxide,
Champagne and Bienkowski modeled the SFE of anthracene and
pyrene from white quartz sand and soil (417). They determined
the equilibrium partition coefficients and Freundlich isotherm
constants and examined the effect of additional water in the soil
phase.
Straightforward uses of SFE showed the seasonal and areal
variations of PAH concentration in street dust (418). Lewis et al.
used SFE and a multidimensional LC/GC/MS approach to
determine oxygenated, nitrated, and alkylated PAHs adsorbed
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onto urban air particulates (419, 420). They subsequently

reported that the temporal variations of the PAH correlate closely
with the atmospheric nitrogen oxides and carbon monoxide (421).
Stalling et al. patented an SFE and adsorption chromatography
method for the separation of fullerenes from carbon soot (422).
A device to sample indoor PAH and extract them with SFE was
constructed and evaluated (423). Miao et al. also extracted
airborne organic contaminants and found that Florisil was the best
sampling adsorbent (424). Yao et al. determined the PAHs in
air particulates near a coke oven with SFE-SFC (218), while
Hoener et al. monitored the crude gas of boiler plants with offline SFE-SFC and fluorescence detection (217). Messer and
Taylor extracted aqueous PAHs at the low parts-per-billion level
using a combination of SPE disks and SFE (425).
Polychlorinated Biphenyls, Dibenzofurans, and Dioxins. Removal
of PCBs and other chlorinated compounds from sediments
represents a significant analytical challenge due to the complexity
of both the sample and the analyte. Akgerman measured the
adsorption isotherms of hexachlorobenzene and pentachlorophenol on soil and carbon (426). The method subsequently
developed predicted desorption profiles to better understand the
SFE process. Langenfeld et al. developed a kinetic model for the
extraction of PCDD from soils and sediments after examining SFE
at temperatures ranging from 40 to 200 C (427). Miao et al.
used supercritical fluid extraction and cleanup with neat carbon
dioxide, selective sorbents, and extraction temperatures up to 250
C as a sample preparation method for the determination of
PCDDs and PCBs (428). Larsen and Facchetti reviewed the use
of SFE for the analysis of PCDD and PCDF (429). They reported
that fluids stronger than carbon dioxide, such as nitrous oxide
and methanol- or benzene-modified carbon dioxide, are often
needed. Sweetman and Watts reported the need for methanolmodified carbon dioxide in developing an SFE method for the
removal of PCBs and chlorobenzenes from soils and sludgeamended soils (430). Tong and Imagawa reported methylene
chloride as the optimal modifier for the extraction of PCBs from
sediments (431). The resulting extracts required subsequent
cleanup with Florisil and graphitized carbon black. Lee and Peart
did not need carbon dioxide modifiers for the extraction of PCBs
from sediments, but the method required postextraction sample
cleanup and sulfur removal with mercury (432). Bowadt and
Johansson extracted PCB congeners from sulfur-containing sediment (433). They evaluated three different trapping adsorbents
and compared their final data to the Soxhlet method. Carbon traps
permitted efficient trapping of a variety of chlorinated compounds,
though some dependency on analyte aromaticity and polarity was
noted (434). Three laboratories performed SFE in an interlaboratory comparison of congener-specific PCB analysis (435). The
data showed that SFE is a very competitive analysis method in
terms of accuracy and precision. Stachel et al. also found that
SFE compared favorably with Soxhlet extraction for the determination of organochlorine compounds in sediment (436). Johansen
et al. developed a method for the determination of planar PCBs
in milk and tissue samples, using on-line SFE-LC (437). An
alumina sorbent placed in the extraction vessel removed the bulk
of the coextracted lipids in the SFE of chlorinated pesticide and
PCBs from adipose breast tissue (438). SFE was also used for
the determination of PCBs in lyophilized fish tissue (439). Identity
and quantitative determination was accomplished with GC with
ECD and MS. Lopez-Avila and co-workers directly determined
PCBs in soil with an off-line SFE-ELISA approach (440). Reactivemodifier systems, such as the addition of BSTFA to the sample
prior to SFE, expedited the extraction of halogenated compounds
(441). Kvernheim et al. used different extraction methods
(including SFE for nonpolar compounds), purification, and derivatization in combination with chlorine-specific GC detection for
the characterization of organohalogen matter in sediments near
a bleach plant (442).
Metals and Organometallics. While SFE is generally thought
of as being applicable to nonpolar organics, there has been a great
deal of recent research in the application of the technique to metalcontaining samples. Lin and co-workers reviewed the application
of SFE to metal chelates and organometallic compounds (275),
while Lin and Wai determined a synergistic effect between
fluorinated -diketones and tributyl phosphate for the SFE of
lanthanides (443). Meanwhile Laintz and Tachikawa employed
tributyl phosphate and thenoyltrifluoroacetone for the SFE of
lanthanides in acidic solution (444). Wai investigated a number
of chelating agents and crown ethers for the SFE of trace metals
from solid and liquid materials (445). Wang and Marshall
established the effect of the alkyl chain length on the tetraalkylammonium chelating agent on the SFE of metals from aqueous
media (446).
Bayona and Cai discussed strategies for the determination of
organotin in aqueous and solid matrices using in situ derivatization
or acid-modified carbon dioxide SFE (278). Alzaga and Bayona
applied these methods to the SFE of tributyltin and its degradation
products from seawater (447). In the latter study, they employed
solid-phase extraction disks, followed by in situ Grignard ethylation and SFE of the derivatized disks. Cai and Bayona also
developed a method for the simultaneous speciation of butyl-,
phenyl-, and cyclohexyltin compounds (448). Bayona reviewed
this and other work on the determination of organotin compounds
in aquatic sediments (449). A comparison of SFE with an
improved tropolone solvent extraction procedure for the determination of butyltin species was made by Chau et al. (450). A
complexation procedure with SFE was investigated for the
extraction of 13 organotin compounds in soils or sediment samples
(451). Cai et al. needed only mild SFE conditions, 40 C and 350
atm, to extract butyl- and phenyltin compounds in sediment
samples after derivatization with hexylmagnesium bromide (452).
A more detailed study of the SFE of tributyltin in sediment
required the use of methanol-modified carbon dioxide (453). Ionic
alkyllead species in sediment and urban dust required methanol
modifier for SFE and postextraction derivatization (454). Li and
Li used supercritical Freon extraction and MECC for the determination of alkylead and alkyltin compounds in soil and poly(vinyl
chloride) plastic (455).
Wai et al. used carbon dioxide with a chelating agent as
modifier for the SFE of organic and inorganic mercury from solid
materials (456). Wenclawiak and Krah reacted thioglycolic acid
methyl ester with organic and inorganic arsenic compounds prior
to SFE and SFC determination (279). Furton et al. used in situ
chelation from the SFE of uranium from solid matrices (457).
Subsequent characterization was by UV absorption spectroscopy.
Following the chelation SFE of metals in solid samples, Liu et al.
characterized the extracts using GC with atomic emission detection (458).
Miscellaneous Environmental Applications. Kane et al. developed an SFE and SFC method for the analysis of aqueous nonionic
surfactants (226, 459), while Poiger et al. used SFE in the LC

determination of detergent-derived fluorescent whitening agents
in sewage sludges (460). Louie et al. developed sulfur removal
methods using analytical-scale SFE under pyrolysis conditions on
coal samples (461). Preliminary evidence demonstated that SFE
recoveries for explosives can equal those for an 18-hour acetonitrile sonication (462).
Pesticides and Herbicides. The extraction of pesticides
and/or herbicides can be a challenging situation due to the typical
sample matrices. Extraction from soils encounters the matrix
problems observed in environmental analysis, and extraction from
animal tissues may result in a large amount of coextracted lipid
matter. Additionally, many of these agrochemicals or their
analytes are polar. Brooks and Uden extracted the insecticide
abamectin from both sample matrices (463). Soil samples needed
2-methoxyethanol modifier, but clean extracts were obtained from
animal tissues. Argauer et al. dealt with the problem of high lipid
levels in meat samples by extracting carbamates with acetonitrile
while leaving the lipid matter behind (464). The acetonitrile
extract was mixed with diatomaceous earth and extracted by SFE
to eliminate coextracted compounds. A mixed-adsorbent system
eliminated fatty acids and sterols from the SFE of carbamates from
tissues such as chicken muscle (465). Snyder et al. also
investigated SFE to remove lipophilic pesticides from chicken
tissues (466). To extract strychnine from oat grain bait, Kelly
and Johnston used two sequential modifiers (467). Methanolmodified carbon dioxide was used during a static extraction step
followed by dynamic extraction using chloroform modifier.
Lehotay and Ibrahim extracted pentachloronitrobenzene analogs from vegetables using carbon dioxide at 40 C and 200 atm
(468). They used an alumina collection to remove chlorophyll
and other matrix interferences from the sample. In another study,
investigating the presence of 46 different pesticides in fruits and
vegetables, Lehotay and Eller used octadecyl-coated silica for
trapping and extract cleanup (469). The same research group
added Hydromatrix to control the amount of water in the solid,
moist vegetable samples (470). Dry ice kept the samples frozen
and reduced the degradation or volatilization of several pesticides.
Valverde-Garcia et al. added anhydrous magnesium sulfate to the
vegetable material prior to the SFE of a very polar pesticide,
methamidophos (471). Parks and Maxwell placed a neutral
alumina trap in-line during the SFE of pesticides in chicken tissue
and did not require subsequent cleanup of the extract (472).
Rather than mixing the plant material or extract with an adsorbent,
Jimenez et al. lyophilized lettuce leaves prior to the SFE determination of carbendazim (473). On-line SFE-SFC/GC provided
accurate and precise determination of organochlorine pesticides
(OCPs) and organophosphorus pesticides (OPPs) from fatty food
samples like chicken fat, ground beef, and lard (198). Following
extraction, they used packed-column SFC to fractionate the
pesticides prior to GC.
Papilloud and Haerdi noted that extracts of atrazine metabolites
from soils, sediments, and plants were cleaner with SFE than when
liquid solvents were used, allowing for a more reproducible
analysis (474, 475). Van der Velde et al. used a multiple linear
regression technique to study the effects of parameters on the
SFE of triazines from soils (476). Camel et al. evaluated the effect
of soil surface area and methanol addition to the SFE of OPP from
soils (477). They also noted potential difficulties with effective
analyte collection. Acid/base interactions are important to the
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binding of pirimicarb to soil, as noted by Alzaga et al. (478). They

evaluated carbon dioxide, nitrous oxide, chlorodifluoromethane,
and a number of carbon dioxide modifiers, with the best results
coming with pyridine and triethylamine modifiers. Lancas et al.
determined norflurazon residues in cotton seeds with an SFE
method that was improved over existing methods (479). Khan
showed that carbon dioxide with methanol modifier was preferable
to either pure carbon dioxide or pure methanol for the extraction
of radiolabeled pesticides in soil, plants, and wheat (480). Skopec
et al. also found that methanol-modified carbon dioxide was
necessary for the SFE of OPP from rice (481). Also using
methanol modifier for the SFE of OCP and OPP, Snyder et al.
reported that SFE and sonication methods compare equally for
the recovery of these compounds from four different soils (482).
Van der Velde et al. also explored the optimization of extracting
OCP from soils (483). High organic content (50%) leads to poor
recovery of sulfonylurea herbicides from soils (484). Water and
methanol were added to the soil for this extraction. Reddy and
Locke also needed to add water to air-dried soil samples prior to
SFE (485). Two studies reported the utility of SFE for degradation
studies. One report studied the breakdown of oxadixyl residues
in food crops (486), while the degradation of s-triazine herbicides
from granular activated carbon was investigated by Robertson and
Lester (487). Additionally, Robertson and Lester extended their
SFE development to include soil matrices and phenylurea herbicides (488). They found that the phenylurea herbicides were less
susceptible to thermal degradation by the SFE technique than
by Soxhlet extraction.
Koskinen et al. used carbon dioxide, methanol, and methanolmodified carbon dioxide to study the binding of atrazine to soils
(489), and Cassada et al. determined atrazines in sediments with
SFE followed by isotope dilution GC/MS (490). Nam and King
developed a tool for the rapid screening of pesticides in meat tissue
using SFE and enzyme immunoassay (491). The system featured
pumpless SFE based on the phase change of dry ice as it is
warmed. Lopez-Avila also explored the use of enzyme immunoassays following SFE of pesticides from soil (492). Del Valle
and Nelson compared SFE with a number of liquid extraction
methods for removing atrazine from soil and found that, while
the methods gave equal efficiencies, SFE was more variable (493).
Steinheimer et al. thoroughly explored the SFE of triazines from
soils (494). They used principal component analysis to correlate
each component in a matrix of dependent variables that included
extraction efficiency. They also noted that the modifiers and
conditions used did not promote conversion of chlorotriazines to
the hydroxy or methoxy analogs. Sundaram and Nott constructed
an inexpensive, homemade SFE and applied the system to the
determination of pesticide residues from forest soil and conifer
foliage (495). Tena et al. found that the formation of tetramethylammonium ion pair was needed for the efficient extraction of
sulfonamides from solid supports (496). Lopez-Avila et al. also
used ion pair formation and derivatization, using tetrabutylammonium hydroxide and methyl iodide during the SFE of
chlorophenoxy acid herbicides from soils (497). Tilio et al. used
SFE to selectively remove interferences from elemental sulfur in
the SFE of chlorinated pesticides from sediment (498). In a rather
unique application of SFE, Paquet and Khan confirmed that
organophosphates and their metabolites covalently bound to
serine residues in protein chains could be released by SFE without
altering the protein (499).
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Extracting pesticides from water using SFE requires considerations different from that of the solid matrices discussed above.
Barnabas et al. used the solid-phase extraction disk approach prior
to SFE for the determination of OCP and OPP from water (500,
501). They were able to extract the OCP with pure carbon dioxide
but needed a methanol-modifier for the OPP. They also studied
the effect on OCP recovery of increasing the ionic strength of
the aqueous sample (502). Wolfe et al. employed this same
approach and were able to maintain biological activity for
subsequent bioassay of water collected from rice fields (503). Ho
and Budde also used the combined SPE disk-SFE approach to
monitor rotenone levels in natural river waters (504). The low
pH necessary for the SPE of some pesticide/sorbent combinations
may degrade some sensitive pesticides (505). The use of bulk
sorbents and SFE alleviated the acidification problem. Alzaga et
al. studied the stability of freeze-dried water for use as a reference
material and compared liquid/liquid extraction with SFE (506).
Foods and Fragrances. Continued interest in the applications of SFE within the food industry is strong. While other
potential application areas for SFE have been slow to develop,
the application of SFE for food applications is strong for a variety
of reasons, including the use of SFE for food processing. Because
carbon dioxide will not leave behind any residues, supercritical
processing is finding its role in the food industry and this interest
and knowledge base are being directly reapplied in the analytical
laboratory. Of course, the other advantages of SFE are also
applicable to foods analysis. While workers in other applications
areas, such as environmental solids analysis, often elaborate on
the difficulty of their analyzes (e.g., matrix interactions), food
analysis is also less than straightforward due to factors such as
sample type (e.g., meats vs vegetables), the presence of interfering
moisture or lipid content, and even the definition of the analyte
(e.g., does fat content include bound vs unbound lipids, phospholipids, etc.).
The primary food applications of SFE include essential oils
(including flavor and fragrance compounds) and fats and oils.
However, SFE is finding utility in other applications as well. A
number of applications dealt with food processing issues. Pensabene et al. explored the occurrence of N-nitrosamines in hams
processed with elastic rubber netting (507). The SFE method is
more sensitive, more precise, and faster than the alternative SPE
procedure. Lembke et al. used SFE and GC to simultaneously
determine the hydrocarbon patterns and the presence of irradiation markers (i.e., alkylcyclobutanones) in irradiated fatty foods
(508). Thiebaud et al. studied the fumes generated during the
high-temperature frying of beef (509). Following SFE of the
sample collection filters, they determined chemical composition
by GC/MS and mutagenic activity with a modified Ames Salmonella assay. DOdorico et al. also used SFE to isolate carcinogens
and anticarcinogens from dietary and fecal samples (510).
Concentrated products, like spray-dried milk, may accumulate
contaminants. Malik et al. determined residues of the animal drug
sulfamethazine spiked into spray-dried milk (511). Holak treated
seafood samples and mixed the sample with cellulose powder
containing stearic acid prior to the SFE of methylmercury (512).
Calvey et al. noted higher recoveries of the thiosulfinate allicin
from fresh garlic and onion when they used sorbent trapping
rather that solvent collection (513). Extractions at greater than
36 C led to thermal decomposition. An on-line SFE-GC/FT-IR
procedure for the analysis of basil reduced the total analysis time
from more than 1 day to 90 min compared with the previous

method (514). In addition to the pesticide applications previously
discussed, SFE is used for specific investigations of fungicides,
insecticides, and other related compounds in foods. Atienza et
al. used SFE followed by reversed-phase LC for the determination
of fluvalinate in honey from beehives treated for the prevention
of varroatosis (515). Aharonson et al. tested potato, banana, and
apple samples for benzimidazole fungicides (516). SFE compared
favorably to liquid extraction procedures for the determination of
aflatoxins in airborne grain dust samples (517). Heikes presented
the identification of chlorinated fatty acid adducts from the
bleaching of flour (518). Supercritical carbon dioxide extracted
the bleaching adducts, which were subsequently purified via acid
hydrolysis/methylation and characterized with GC and electrolytic
conductivity detection.
Essential Oils. The miscibility of essential oils with carbon
dioxide leads to a number of applications of the SFE of essential
oils, and other flavor and fragrance components, in the food
industry and elsewhere. Walker et al. modeled the kinetics of
the SFE of organic flavor and fragrance compounds from dried
lavender flowers and rosemary leaves (519). Reverchon et al.
compared the SFE of lavender essential oil with steam distillation
(520). The major differences between the two methods was
significantly higher levels of linalyl acetate in the SFE extract,
attributed to hydrolysis during the steam distillation procedure.
In a continuing series of reports, Kollmannsberger and Nitz are
investigating the flavor composition of supercritical extracts of
spices and report the results for allspice and clove (521, 522).
Comparison of the SFE with simultaneous distillation/extraction
(SDE) shows less thermal degradation products in the SFE profile.
Bartley and Foley also noted that the mild SFE conditions do not
concentrate degradation products when they characterized the
flavor volatiles of ginger (523).
Vilegas et al. found that oxygenated sesquiterpenes comprise
the main components of essential oils from the laurel family,
regardless of whether the extraction method was SDE or SFE
(524). This same type of analysis, using the on-line SFE-GC
approach, was performed by Kallio et al. who optimized their
analysis for the determination of carvone and limonene in caraway
fruits (525). Saffrole and other allylbenzenes, such as eugenol,
make up the SFE extract of unbrewed sassafras tea determined
by Heikes (526). To extract aroma volatiles from an extruded
oat ready-to-eat cereal, the sample was exposed to high-pressure
carbon dioxide and then depressurized prior to extraction (527).
This method improved recoveries and reduced coextracted lipid
interferences. Following extraction, a two-stage fractionation
separation removed undesired compounds from the essential oil
of chamomile (528). Goto et al. developed a mathematical model
for the extraction of the essential oil from peppermint leaves, based
on the local adsorption equilibrium of the oil on lipid in the leaves
(529). The adsorption equilibrium constant determined with
experimental data increased with temperature and decreased with
pressure. Blanch et al. developed an off-line SFE-GC method for
essential oil analysis where they collected the extracted analytes
in the quartz liner of a programmed temperature vaporizer (PTV)
injector that they placed in their commercial SFE system (530).
These researchers subsequently compared the method to conventional off-line and on-line SFE-GC for the characterization of
wine aroma (531). Mau et al. reviewed the aroma and flavor
components of cultivated mushrooms and noted SDE, SFE,
headspace techniques, and solvent extractions as the isolation

methodologies currently used (532). The volatiles and semivolatiles in oilseed could be determined without interferences with
a method developed by Snyder and King (533). The extract was
not contaminated with compounds resulting from lipid degradation, due to the mild SFE conditions.
Yao et al. determined the flavonoid in Gingko biloba leaves with
SFE and LC (534), while Verotta and Peterlongo determined the
toxic phenolic components of G. biloba with SFE and GC/MS
(535). Poiana et al. desired an essential oil extract from bergamot
that was free of bergapten, a phototoxic compound (536). SFE
produced an oil 6 times lower in bergapten than the conventional
cold-pressed oil. Dugo et al. deterpenated sweet orange and
lemon oils by SFE (537). Anklam and Mueller extracted vanillin
and ethyl vanillin from flavored sugars and compared the results
to the values declared on the sample package (538). A sesquiterpene-rich volatile fraction was obtained in the SFE of guava
(539). Smith and Burford extended the SFE of essential oils to
medicinal herbs, such as feverfew, tansy, and chamomile (540).
Sagrero-Nieves et al. determined aromadendrene as the major
constituent of the SFE extract of tamarind (541). Not all analyses
of aromas in the food industry dealt with the foods themselves.
Nielsen and Jaegerstad found that they could measure the aroma
compounds sorbed by plastic packaging materials (542). The
method was then applied to the determination of the partition
coefficients between apple aroma and common packaging material
and to the study of limonene sorption in refillable poly(ethylene
terephthalate) bottles.
Fats and Oils. Bartle and Clifford published two extensive
reviews on the advantages of using SFE and SFC for lipid analysis
(157, 158). In a more specific review, Staby and Mollerup
discussed solubility data, SFE, and SFC of fish oil (167), Mishra
et al. presented SFE and SFC as methods for the direct extraction
of oils rich in -3 fatty acids and the concentration of the esterified
forms of these acids (543), and Paschke reviewed the SFE of fats
and oils in food, mineral oils in wastes, and metalworking oils on
steel (544). To study the SFE of lipids in a multiple number of
food products simultaneous, King et al. developed an extractor
capable of extracting six samples simultaneously (545). They
balanced fluid flow between the extraction vessels and also
explored the extraction of pesticides from adipose tissue. Subsequently, this extractor was used to determine the fat content of
foods in a total diet study (546). They found reproducible results
for a variety of food types including meats, snack chips, cheese,
and peanut butter. Levy and co-workers developed manual and
automated SFE methods for the gravimetric determination of fats
in snack foods and animal feeds (547).
Thermal oxidation of oils, such as canola, can be studied with
SFE, as presented by Hansen and Artz (548). Walker et al.
investigated the oil content of ground and dried canola and needed
a moisture adsorbent during the extraction (549). By using a
sorbent trap, Snyder and King characterized the volatile and
semivolatile constituents of SFE processed soybean oil (550). The
method can be used to monitor the extraction and the quality of
the resulting oil. Snyder used this approach for the characterization of the volatiles in oxidized canola, corn, soybean, and
sunflower oils (551). Peroxide values correlated well with the
increasing concentration of several volatiles in the oxidized oils.
Another SFE method for the determination of volatiles in lipid
extracts is the method of King et al. for the study of raw beef
505R
(552). During SFE, they collected noncondensible volatiles on

Tenax for further characterization and examined the volatiles in
the lipid fraction by direct headspace sampling. Li et al. used a
multivariate optimization scheme to develop SFE for the extraction
of vitamin E in corn oil (553). Maness et al. determined that SFE
and organic solvents produce extracts with the same composition
(554). Carboxylic and fatty acids were determined in mushrooms
and compared to those reported earlier with other methods (555).
The SFE method extracted several acids that had not been
previously reported from these sources. Suzuki et al. characterized the polyunsaturated fatty acids in fish oil by mixing the oil
with aqueous silver nitrate prior to SFE (556). For the characterization of fat and cholesterol in beef patties, King et al. examined
the effect of freeze-drying before and after cooking (557). Freezedrying enhanced the extraction of both fat and cholesterol. The
lipid and cholesterol contents of meat and beef tallow can be
reduced with SFE using carbon dioxide (558).
Carotenoids are also of interest and were determined in sweet
potatoes by Spanos et al. (559). The SFE extract contained up
to 94% -carotene with an isomer composition of approximately
14% 13-cis and 11% 9-cis. Birtigh et al. evaluated SFE as a method
to determine whether palm oil extracts were enriched in carotene
or tocopherol for downstream processing (560). They also
determined solubility data for R-tocopherol in carbon dioxide.
Phospholipids are generally not soluble in carbon dioxide and
cannot be extracted without the use of modifiers. Dunford and
Temelli studied ethanol as a carbon dioxide modifier for the
extraction of phospholipids in canola (561). Lancas et al.
optimized the use of supercritical pentane for the extraction of
soybean oil (562).
SFE is also applicable to the study of fat substitute compounds
and other fat-related materials. One of these materials is SALATRIM. Huang et al. characterized these interesterified triacylglycerols in foods with SFE and LC and compared with standard
fat determination methods (563, 564). LC detection was performed by MS and by evaporative light-scattering detection. Artz
and Myers characterized selected emulsifiers using SFC and SFE
(230). The emulsifiers studied included acetylated monoglycerides, lactylated monoglycerides, hexaglycerol distearate, triglycerol mono-/dioleate, and decaglycerol decaoleate. Boutte and
Swanson used SFC and SFE to characterize fat substitutes of the
methyl glucose polyester and sucrose polyester type (565).
Polymers. The inherent diffusivity and adjustable solvent
strength advantages of supercritical fluids make them favorable
for the extraction of materials from polymers. The increased
solvent properties of these fluids can be exploited to extract
polymers. Clifford and co-workers compared theoretical models
to experimental results for the extraction of additives and other
materials from polymers (566). They discussed diffusion and
solvation limitations. Diffusivity issues were also important for
the extraction of binders in ceramics (567). Franz et al. used
SFE-SFC to study the migration and release of materials in
recycled plastics for possible use as food packaging materials
(568). This coupled approach, SFE-SFC, often combined with MS,
found great utility in the evaluation of polymer homologs and
additives. One group demonstrated the approach for both
structural research work and routine polymer analysis (246).
Meanwhile, McKay and Smith developed SFE-SFC/MS for the
study of organophosphate flame retardants in polyurethane foams
(239) and other polyurethane additives (240). Brominated flame
506R
retardants in low-density polyethylene were determined with

carbon dioxide after studying the influences of temperature,
pressure, and methanol addition (569). Janda et al. used SFE
with SFC to characterize aromatic amines in rubber and other
materials (570). Quantitative recovery was obtained from inert
materials, but acidic matrices yielded poor results. In studying
high- and low-density polyethylenes, Juo et al. found that SFE
produced results similar to toluene extraction (571). Werthmann
et al. also found that results for extracting additives from rubber
was similar for SFE and conventional solvent extractions (572).
The amounts of antioxidants in the SFE extracts were determined
with LC. De Crosta and Jagnandan patented an SFE method for
the removal of residual additives from elastomers (573). In one
claim, they removed phthalates and PAHs from rubber articles.
Gawdzik and Matynia investigated the efficiency of porous
polymer purification with SFE-GC/MS (574). Venema et al.
looked at SFE for the removal of caprolactam and oligomers from
nylon-6 (575).
One industry where supercritical fluid techniques can find
particular utility is the textile industry. Raynor and Bartle
reviewed the application of SFC and SFE to the study of surface
coatings (242), while Drews et al. reviewed specific textile and
fiber applications (576). Drews et al. compared a number of
commercial SFE systems for the characterization of extractables
on fibers, yarns, and textiles (577). These researchers established
the temperature and pressure effects of the extraction efficiency
and composition. Kirschner et al. developed an on-line SFE-IR
method for the analysis of fiber finishes, ranging from poly(dimethylsiloxane) oil to multicomponent finishes containing
surfactants, soaps, antioxidants, and oils (578). Jordan et al. used
this on-line SFE-IR procedure for the determination of polyesterfiber finishes, such as the percent finish on yarn (579). Sikorski
filed a patent for using SFE to extract pure polymeric components
from textile wastes, such as carpets and disposable diapers (580).
Natural Products and Drugs. A variety of natural products,
especially high-value-added products, are processed with supercritical fluids. Since many of these have pharmacological activity,
a natural extention of this application is to the field of drug
analysis. A French review discussed the SFE of compounds of
plant origin (581). Sargenti and Lancas constructed an SFE
system for the semipreparative SFE of natural products (582),
while Queckenberg and Frahm built a unit for analytical SFE of
threatened Amaryllidaceae species (583). Taylor et al. employed
on-line SFE-SFC for the study of single seeds of a desert botanical
(185). Their results indicated that the resin sac may be particularly enriched in odoriferous compounds. Henning et al. were
also concerned with the large sample amounts needed for
conventional extraction methods and used SFE to study specific
morphological regions from individual plants (584). They applied
SFE to study volatiles associated with alfalfa germplasm tissue.
These researchers applied the approach to the study of the effect
of stem and leave volatiles on resistance to weevils (585).
Simoes et al. developed a countercurrent column for the
separation of terpenes for the purification of eucalyptus oil (586).
Bicchi and co-workers compared SFE with hydrodistillation and
solvent extraction of triterpenes in iris rhizomes (587). Rhizomes
of Zingiber zerumbet were extracted by Ahmad et al. (588). They
placed a silica column in-line to obtain an extraction of nonpolar
components. Terauchi et al. found that the compositions of
supercritical extracts of conifer woods were similar to the essential
oils obtained by steam distillation (589). The SFE extracts also

contained higher levels of high molecular mass compounds and
terpenes. Mendes et al. studied the SFE of hydrocarbons from a
microalga (590). The extraction behavior led the researchers to
believe they were extracting the hydrocarbons outside of the cell
wall. They subsequently refined their approach for studying other
microalgae and plant tissue (591). Needles and seeds of Taxus
cuspidata contained taxol, as determined by Chun et al. (592).
Heaton et al. combined SFE with SFC and NMR to evaluate the
taxanes in yew needles (271). Miki et al. compared SFE with
Soxhlet extraction for the extraction of mangrove and determined
the antitermite activity of the extracts (593). Acid hydrolysis prior
to SFE led to the extraction of diosgenin from a plant tuber (594).
Prokopczyk et al. developed SFE as an integral step in the analysis
of tobacco-specific N-nitrosamines (595). Terpenoids extracted
with SFE were similar to those obtained by Soxhlet procedures
for Moraceae species, providing a method for rapid phytochemical
examination (596). Moria et al. investigated the SFE of oxygencontaining sesquiterpenes (597). Cocks et al. compared the use
of SFE for the extraction of biologically active compounds from
the biomass of microbial fermentations with methanol and
methylene chloride extractions (598).
The extraction of drugs and other materials of medicinal value
is necessary. The specific samples may be the natural products
from which they originate, the drug formulation, or the biological
systems where they interact. Drug formulations are designed to
bind the materials they carry until the drug enters the appropriate
biological system. One formulation type is tablets. Scalia et al.
showed that SFE can minimize the number of sample-handling
steps in the characterization of vitamin tablets (599). The mild
extraction conditions allowed extraction of labile materials and
were suitable for quality control applications. They also used SFE
for the extraction of these same vitamins from cosmetic creams
and lotions (600). The degree of sample dispersion influenced
the SFE efficiency. Another group extracted water-soluble vitamins with a reversed micellar solution (601). They needed SFE
with ethanol-modified carbon dioxide to remove the residual
surfactant from the isolated vitamins. Takaichi et al. employed
both SFE and SFC for the evaluation of benzodiazepine transquilizer tablets (263). They reported recoveries that varied
according to analyte polarity, with the lowest recoveries occurring
with the most polar materials. Lawrence et al. also used SFE to
isolate benzodiazepines from solid dosage forms (602). These
latter researchers claimed that extracts of suitable purity and
quantity for MS analysis were obtained, even with low concentration dosage forms.
Dean and Lowdon compared SFE with a USP monograph
method for the analysis of megestrol acetate from tablet formulations (603). The researchers observed different recoveries with
two different commercial SFE systems, presumably due to solute
collection considerations. Howard et al. needed sequential static
and dynamic steps for the effective extraction of felodipine from
sustained-release tablets (604). Messer et al. demonstrated the
importance of trapping considerations for the SFE of a pharmaceutical in animal feeds (605). In many instances the solute of
interest is too polar to be effectively extracted by SFE. In this
case, SFE can successfully be applied to the removal of the
formulation matrix to isolate the drug material. Moore and Taylor
demonstrated this approach for low concentrations of polar
pharmaceuticals in semisolid Neosporin ointments and creams
(606). Messer and Taylor used this inverse SFE approach to

investigate Zovirax ointment (607).
Extracting drugs and metabolites from tissues, fluids, and other
biological matrices represents another challenge. Walker et al.
reviewed a number of newer extraction methodologies, including
SFE, for the analysis of drugs and environmental pollutants in
aquatic species (608). Edder et al. employed polar modifiers with
carbon dioxide to extract morphinic alkaloids (609, 610). The
opiates in urine and other liquids required adsorption onto a solid
support (609), while hair samples could be extracted directly and
these small samples could be easily accommodated by SFE (610).
Liu and Wehmeyer extracted drugs directly from plasma without
immobilization onto a solid support; however, the samples were
treated with an antifoaming agent to minimize restrictor plugging
(611). Karlsson et al. extracted a corticosteroid from plasma,
using a low-density initial extraction to remove interfering water
(612). Muellner et al. obtained a German patent for the SFE of
a number of organic compound classes from complex matrices
such as tissue, feces, urine, and serum (613). Metals and
organometallics in biological studies could be determined with
SFE and ICPMS (614, 615). Organotins were characterized in
tuna fish (614), and arsenic compounds in a certified dogfish
muscle were determined (615). Wang and Marshall investigated
SFE to characterize cadmium, zinc, and copper bound to metallothionein isolated from rabbit liver (616).
Polychlorinated biphenyls (PCBs) incurred in biological samples
can be extracted with considerations for extracting PCBs from
environmental samples, as previously discussed, and biological
samples. Alley and Lu separated PCBs from fish tissue and
chicken egg containing high levels of fat (617). Florisil cleanup
facilitated separation of PCBs from the lipid material. Lee et al.
used alumina in-line during their SFE of PCBs in fish, in addition
to Florisil cleanup (618). Hale and Gaylor also extracted PCBs
in fish tissue using the in-line alumina approach without subsequent Florisil cleanup (619). Quantitative extraction of PCBs from
human adipose tissue was achieved by van Bavel et al. (620).
Klink et al. compared SFE with carbon dioxide and chlorodifluoromethane for the removal of free carboxylic acids and sterols
from a plant tissue and a sediment sample (621). Mgrd and coworkers extracted androstenone from boar fat samples. They
improved selectivity by mixing alumina with the sample (622).
Acosta et al. adjusted SFE conditions to selectively extract fat from
phospholipid biomembranes structures (623). Modified fatty
acids, acetogenins, were extracted from seed oil as a potential
source of these bioactive materials (624). An unrefined wool
grease extract resembled high-grade commercial lanolin in terms
of color and odor (625). Selective fractionation could yield
products enriched in cholesterol. The effect of organic modifiers
on the SFE of fungal lipids was determined and the costs of
developing SFE processing were estimated (626).
Miscellaneous Applications. As SFE develops, applications
that do not fit into the categories defined above are being
developed. Lin et al. extended their previous work on the SFE
of metal compounds to the SFE of uranium- and thoriumcontaining materials from nitric acid solutions with organophosphorus reagents (627). Wang et al. extracted mercury with
ionizable crown ethers (628). Purtell et al. cleaned precision metal
parts with SFE and characterized the extracted hydrocarbons,
silicones, and fluorocarbons with SFC (629). Dahmen et al.
extracted hydrocarbon oils from grinding and metal working waste
507R
with carbon dioxide (630). Lim and co-workers described the

influences of fluid properties, phase flow rates, column dimensions,
and phase dispersion on both mass-transfer efficiency and
hydraulic characteristics of spray and packed-extraction columns
(631). Esser and Klockow coupled SFE with thin-layer chromatography to detect hydroperoxides in combustion aerosols (632).
Taylor reported the monitoring of propellant stability with SFE
by studying the aging of single-base propellants (633). A patent
described the used of SFE for the remediation of pentachlorophenol-containing wood (634).
OTHER SUPERCRITICAL FLUID MEASUREMENTS

AND RELATED TECHNIQUES
Other applications of supercritical fluids may be of interest to
the analytical chemist. Huang et al. used an SFE method to clean
silica aerogel particles intended for use as a cosmic dust capture
medium (635). A patent was issued for monitoring contaminant
levels in supercritical fluid streams using a quartz crystal microbalance (636). An aerosol solvent extraction system was
described for the production of microparticles (637).
Microwave extraction systems have been commercialized.
Meanwhile, another, similar analytical extraction technique, accelerated solvent extraction, was introduced by Dionex (638642). Both of these extraction methods are fundamentally similar
to SFE in that the extraction is conducted at elevated pressure so
that temperatures greater than the atmospheric boiling point of
the extracting fluid can be used. At these temperatures, properties
influencing analytical extraction, such as diffusion, viscosity, and
solubility, become more favorable. While initially developed for
the environmental field, the application of these new techniques
to other areas will proceed rapidly. In another related method,
Huettenhain et al. modified an LC system for extraction (643).
Soil, denatured with an inert salt, acted as a stationary phase for
the elution of organic compounds.
Thomas L. Chester received his B.S. in chemistry from the Florida
State University in 1971, spent a year at the Baychem Corp. in Charleston,
SC, and then began graduate studies at the University of Florida under
the direction of J. D. Winefordner. He received the Ph.D. degree in 1976
and joined Procter & Gamble where he is currently Head of the
Separations and Optical Spectroscopy Section, Corporate Research
Division, at the Miami Valley Laboratories. He has been active in SFC
research and application since 1982. His research interests also include
other microcolumn techniques, SFE, and chromatography detectors.
J. David Pinkston came to Procter & Gamble in 1985 after receiving
his Ph.D. from Michigan State University. Before beginning his graduate
studies in 1980, he spent a year working with G. Spiteller at the University
of Bayreuth in West Germany as a DAAD Fellow. He received his B.S.
in chemistry and math in 1979 from Ouachita Baptist University in
Arkadelphia, AR. He is currently a member of Procter & Gambles
Corporate Research Division at the Miami Valley Laboratories. His
research interests include the development and application of SFC and
SFE and the coupling of microcolumn separation methods with MS.
Douglas E. Raynie is a Senior Scientist in the Corporate Research
Division of Procter & Gamble. He received his Ph.D. in analytical
chemistry in 1990 from Brigham Young University. He has an M.S. in
analytical chemistry from South Dakota State University and a B.A. in
biology and chemistry from Augustana (SD) College. He is on the
Editorial Advisory Board of the Journal of Microcolumn Separations,
responsible for Microcolumn Abstracts, and is President of the Tri-State
Supercritical Fluids Discussion Group. His research interests include
analytical uses of supercritical fluids, high-resolution chromatographic
methods, and chromatographic and separations theory.
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Supercritical Fluid Chromatography and Extraction 1996

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Anal. Chem.

1996, 68, 487R-514R

Supercritical Fluid Chromatography and Extraction

We are happy to report continued growth in both research

1996 American Chemical Society

prices. The apparent marketing strategy among the more

The critical point (or mixture critical point) of a fluid is very

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

the sections on stationary phases, applications, etc. We will begin

interactions between the solutes and the stationary-phase surface

in the retention factor, but velocity and diffusion coefficient

work requiring accurate (or precise) fluid compositions may

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

SFC INSTRUMENTATION, TECHNIQUES, AND

column inlet. This technique accommodates injection volumes

When a passive restrictor is used downstream from the column

A number of groups continued their work in coupling SFC with

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(ACHIRAL) SFC APPLICATIONS

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

ecdysteroids sharing a 20,22-diol structure (190). The bidentate

a variety of techniques, including SFC, in their review (202).

carbon soot (219). Liu et al. also described the separation of

chromatography for these emulsifiers, the authors later found that

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

compounds as well as aliphatic alcohols and ketones in solvent

Stimulants exhibited a wider range of retention behavior than did

thermolabile compounds (274). They characterized 63 reactive

and much faster column recovery to initial conditions following

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(302). Bargmann-Leyder et al. later used molecular modeling to

applicationsuntil there is some consensus regarding which is

ments feature on-line addition of solvent modifiers and some

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

tions are present. Organic cosolvents are frequently added to the

Taylor and Jordan (378) reviewed SFE/IR, including applications

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

onto urban air particulates (419, 420). They subsequently

surfactants (226, 459), while Poiger et al. used SFE in the LC

binding of pirimicarb to soil, as noted by Alzaga et al. (478). They

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

from more than 1 day to 90 min compared with the previous

headspace techniques, and solvent extractions as the isolation

(552). During SFE, they collected noncondensible volatiles on

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

retardants in low-density polyethylene were determined with

oils obtained by steam distillation (589). The SFE extracts also

(606). Messer and Taylor used this inverse SFE approach to

with carbon dioxide (630). Lim and co-workers described the

OTHER SUPERCRITICAL FLUID MEASUREMENTS

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(3) Kordikowski, A.; Schneider, G. M. Fluid Phase Equilib. 1995,

(53) Koehler, U.; Biermanns, P.; Klesper, E. J. Chromatogr. Sci. 1994,

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(210) Shariff, S. M.; Bartle, K. D. J. Chromatogr. Sci. 1994, 32, 541546.

(305) Wilkins, S. M.; Taylor, D. R.; Smith, R. J. J. Chromatogr. 1995,

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(406) Daneshfar, A.; Barzegar, M.; Ashraf-Khorassani, M. J. High

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(562) Lancas, F. M.; Queiroz, M. E. C.; Silva, I. C. E. Chromatographia

Analytical Chemistry, Vol. 68, No. 12, June 15, 1996

(603) Dean, J. R.; Lowdon, J. Analyst (Cambridge, U.K.) 1993, 118,