THE

ANALYST

CRITICAL REVIEW
Recent extraction techniques for solid matrices—supercritical
fluid extraction, pressurized fluid extraction and
microwave-assisted extraction: their potential and pitfalls

Valérie Camel
www.rsc.org/analyst
Institut National Agronomique Paris-Grignon, Laboratoire de Chimie Analytique, 16 rue
Claude Bernard 75231 Paris Cedex 05, France. E-mail: camel@inapg.inra.fr; Fax: +33 1 44
08 16 53; Tel: +33 1 44 08 17 25

Received 5th January 2001, Accepted 12th April 2001

First published as an Advance Article on the web 31st May 2001

1 Introduction extraction of pollutants from soils and sediments), the first step
2 Principle of the recent techniques and optimization is usually the rate-limiting step, as solute–matrix interactions
strategies are very difficult to overcome and to predict. However, for other
2.1 Supercritical fluid extraction matrices (e.g. plant materials), the rate may be limited by either
2.2 Pressurized fluid extraction the solubilization or diffusion step. As a consequence, the
2.3 Microwave-assisted extraction optimization strategy will strongly depend on the nature of the
3 Comparative performances of SFE, PFE and MAE matrix to be extracted.
3.1 Efficiency and susceptibility to matrix effects The traditional extraction techniques for solid matrices
3.2 Selectivity include the well-known Soxhlet extraction, sonication and
3.3 Level of automation blending. Even though efficient extractions may be achieved
3.4 Simplicity of the operating procedure using these simple techniques, they present major drawbacks,
4 The right technique for the right application namely long extraction times (especially for Soxhlet), high
5 Future trends solvent consumption and low temperatures, and have yet to be
6 References readily automated. In addition, the final extracts usually require
subsequent concentration and clean-up prior to the analysis
Valérie Camel obtained her Diploma of Engineering in 1991 step, as shown in Fig. 1,2,3 as well as filtration in the case of
from the Ecole Supérieure de Physique et Chimie Industrielles sonication and blending methods, which may lead to losses or
(ESPCI, Paris, France) followed by a PhD in Analytical contamination. During the last decade, new techniques have
Chemistry on ‘the development of SFE methods for the emerged that will certainly supersede the traditional techniques
determination of pollutants in soils’ from the University of Paris in the future. These include supercritical fluid extraction,
VI (France) in 1994. Since then, she has been working as a pressurized fluid extraction and microwave-assisted solvent
senior lecturer in Analytical extraction.4,5
Chemistry at the Institut Na-
tional Agronomique Paris-
Grignon (France). Current re- 2 Principle of the recent techniques and
search activities include envi- optimization strategies
ronmental chemistry, especially
determination and chemical ox- 2.1 Supercritical fluid extraction
idation of organic pollutants in In supercritical fluid extraction (SFE), the extractant is in its
water and soils. In 1999 she supercritical state, which means that both pressure and
was honoured with the award of temperature are above their critical values. Supercritical fluids
the Analytical Chemistry Divi- possess unique properties, intermediate between those of gas
sion of the French Chemical and liquids, that depend on the pressure, temperature and
Society (SFC). composition of the fluid.6 In particular, their viscosity is lower
than that of liquids, and the diffusion coefficients are higher,
allowing more efficient extractions. In addition, the density (and
therefore the solvent power of the fluid) may be adjusted by
1 Introduction varying both the pressure and the temperature, affording the
opportunity of theoretically performing highly selective extrac-
The extraction and recovery of a solute from a solid matrix can tions.7 A recent review presents the state-of-the-art of the use of
be regarded as a five-stage process:1 the desorption of the supercritical fluids in analytical chemistry.8
compound from the active sites of the matrix; diffusion into the A typical SFE system consists of a high pressure pump that
matrix itself; solubilization of the analyte in the extractant; delivers the fluid and an extraction cell containing the sample
diffusion of the compound in the extractant; collection of the and which is maintained at the correct pressure and temperature
extracted solutes. In order to obtain quantitative and reproduci- (see Fig. 2). An organic solvent (also called the modifier) may
ble recoveries, careful control and optimization of each step are be added to the fluid to enhance its solvating properties; this can
required; in particular, the collection of the extract needs to be be performed using either premixed cylinders or an additional
carefully controlled as it is often neglected when compared to pump. Due to severe drawbacks of premixed cylinders (less
the extraction step. In practical environmental applications (e.g. flexibility in the nature of the solvent used, and modifier ratio

1182 Analyst, 2001, 126, 1182–1193 DOI: 10.1039/b008243k

This journal is © The Royal Society of Chemistry 2001
changes over the lifetime of the cylinder), the use of an
additional pump is preferred despite its higher initial capital
investment.
The SFE may be carried out in either static or dynamic mode.
The pressure in the system is maintained by means of a restrictor
(either fixed or variable, the latter making the pressure
independent of the flow rate).9 At the end of the restrictor, the
fluid is depressurized and the extracted analytes are trapped in
an organic solvent or on a solid phase filled cartridge (from
which the analytes are later eluted with a small volume of
organic solvent). The trapping conditions (nature of the solvent
or the solid trap, and the temperature) are of prime importance
to ensure efficient collection of the extracted compounds, and
therefore efficient recoveries at the end. The solid trap
collection device offers both a higher selectivity (by the choice
of both the nature of the solid phase and the elution solvent) and
a higher sensitivity (a highly concentrated extract is obtained as
elution is performed with very small organic solvent volumes,
typically 2–5 mL).
Due to the numerous parameters affecting the extraction
efficiencies, SFE affords a high degree of selectivity. However,
on the other hand, this makes the optimization quite tedious and
difficult in practice. Table 1 summarizes the main factors that
influence the results of extraction. The parameters to consider
are linked to the extraction parameters inside the cell, to the
nature of the solutes or to the nature of the matrix.10–12 The
important parameters in SFE are both the pressure and
temperature inside the cell. A pressure increase leads to a higher
fluid density, thus increasing the solubility. The inverse is
observed with the temperature; however, increasing the tem-
perature may enhance the solubility of volatile analytes. In
addition, higher temperatures may be required to overcome

Fig. 1 Comparison of the operating procedures for Soxhlet and sonication

recommended by the EPA methods for extracting PCBs from soils
(according to EPA methods 3540C2 and 3550B3). Fig. 2 Principle of an SFE system and influencing parameters.

Table 1 Parameters influencing the recent techniques and optimization strategy

Technique Parameter Main effect Optimization strategy

SFE Nature of the solutes Apolar Solubilization CO2

Moderately polar to polar Solubilization CO2 + organic solvent; other fluids
Ionic Solubilization CO2 + reagent: ion pairing, complexation,
derivatization
Extraction parameters Pressure Solubilization Increase pressure
Temperature Desorption; diffusion Increase temperature
Time Extent of extraction Increase extraction time
Nature of the matrix Large particles Low extraction rate; low recoveries Grinding the matrix
Active sites Solute adsorption Addition of a modifier
Water content Water entrainment; low recoveries Drying/drying agent addition
PFE Nature of the solutes Apolar to polar Solubilization Solvent or solvent mixture
Extraction parameters Temperature Solubility; desorption; diffusion Increase temperature
Time Extent of extraction Increase extraction time
Nature of the matrix Large particles Low extraction rate; low recoveries Grinding the matrix
Water content Low recoveries Drying/drying agent addition
MAE Nature of the solutes Apolar to polar Solubilization Solvent or solvent mixture that usually
absorbs microwaves
Extraction parameters Temperature Solubility; desorption; diffusion Increase temperature
Time Extent of extraction Increase extraction time
Nature of the matrix Large particles Low extraction rate; low recoveries Grinding the matrix
Water content Overheating; low reproducibility Drying/drying agent addition

Analyst, 2001, 126, 1182–1193 1183

solute–matrix interactions, as observed for the extraction of
polycyclic aromatic hydrocarbons (PAHs) and polychlorinated
dibenzo-p-dioxins from environmental matrices.13
With regard to the nature of the compounds to be extracted,
polarity is the characteristic to be taken into account. Pure CO2
efficiently extracts non-polar to low polarity compounds. For
polar solutes, a modifier is added to enhance the extraction. For
very polar and ionic compounds, the modifier may be a
complexing agent, an ion-pair reagent or a derivatization
reagent.12,14,15 As an example, the addition of tetrabutyl-
ammonium enabled the extraction of anionic surfactants from
sewage sludge to be performed.16
The addition of the modifier directly to the matrix (prior to
the extraction) may help in disrupting the analyte–matrix
interactions; however, it requires that a static extraction be
performed first, to avoid sweeping the modifier out of the cell.
In cases where the analytes do not readily derivatize, the
addition of a derivatization reagent may still be useful as it can
react with the active sites of the matrix, thus enhancing the
extraction, as has already been observed during the extraction of
PAHs from urban dust.17
The users of SFE must be aware of the fact that the addition
of a modifier to CO2 presents severe drawbacks, and so it should
be avoided or minimized whenever possible. The presence of
the modifier changes the values of the critical pressure and
temperature, so that too high a modifier content may result in a
temperature lower than the critical value, resulting in a
subcritical state, with higher viscosity and lower diffusion
coefficients than the supercritical state; in this case, the
technique is commonly called enhanced-fluidity liquid extrac-
tion (EFLE).18 In addition, as the modifier enhances the
solvating power of the fluid, it reduces the extraction selectivity
as more matrix materials or non-target analytes are co-
extracted. Finally, the modifier condenses upon depressuriza-
tion, which may result in elution of the retained compounds
when a solid trap is used as the collection device, since then it
may act somewhat like a chromatographic device.
The nature of the matrix (water content, percentage of
organic carbon, humic/fulvic materials, etc.) and its physical
characteristics (such as porosity or particle size) are of prime
importance for the success of an extraction,9 as with other
extraction techniques. Grinding the matrix is recommended, to
limit the diffusion step inside the matrix and to increase the
surface area, which increases the rate of extraction when it is
limited by matrix effects. Also, the addition of a drying agent
(such as sodium sulfate) may prevent the plugging of the
restrictor by ice in the presence of humid matrices. Caution must
also be taken when filling the vessel to ensure a homogeneous
bed of material (to prevent channelling) and to take into account
possible swelling of the matrix (such as polymers) upon
introduction of supercritical CO2.19 In addition, very fine
particles may be swept out of the cell by the fluid and result in
plugging and mechanical transfer problems. Finally, a sorbent
may be added in the cell to retain matrix material and increase
the selectivity of the extraction. For instance, recent results have
shown that the addition of silica gel and Florisil favours the SFE
of organochlorinated pesticides and chloramphenicol, re-
spectively, from whole eggs.20,21
Since the early use of supercritical fluids for extraction in the
mid-1980s, numerous applications of the technique have been
reported.7,22–24 A large field has been covered: environmental
matrices, plants, foods and fats, and polymers. Similarly,
several classes of compounds have been investigated: PAHs and
polychlorobiphenyls (PCBs) (probably the most studied com-
pounds), phenols, pesticides, organometallic compounds, lip-
ids, flavour and volatile compounds, natural products, additives,
etc. In addition, SFE has been adopted by the US Environmental
Protection Agency (EPA) as a reference method for extracting
PAHs,25 PCBs26 and total recoverable petroleum hydro-
carbons27 from solid environmental matrices.
1184 Analyst, 2001, 126, 1182–1193
2.2 Pressurized fluid extraction
A new technique appeared around 5 years ago. It is called
pressurized fluid extraction (PFE), accelerated solvent extrac-
tion (ASE™, which is a Dionex trade mark), pressurized liquid
extraction (PLE), pressurized solvent extraction (PSE) or
enhanced solvent extraction (ESE) and it partly derives from
SFE. However, in the former case, the extractant is maintained
in its liquid state.28–30 In order to achieve elevated temperatures,
pressure is applied inside the extraction cell. In this way,
temperatures around 100–200 °C may be attained with classical
organic solvents. In fact, at such high temperatures and
pressures, the solvent may be considered as being in a
subcritical state, with advantageous mass transfer properties.
Indeed, this technique affords the ability to perform fast,
efficient extractions due to the use of elevated temperature, as
the decrease in solvent viscosity helps to disrupt the solute–
matrix interactions and increases the diffusion coefficients. In
addition, the high temperature favours the solubilization of the
compounds by the solvent due to a change in their distribution
coefficients. Finally, the pressure favours the penetration of the
solvent into the matrix, which again favours the extraction.
Consequently, this very recent technique is of growing interest,
and numerous commercial systems have been sold.
The scheme of a typical PFE unit is given in Fig. 3. As for
SFE, a high pressure system is used (up to 100–150 bar).
Performing an extraction requires several successive steps.
Firstly, the cell is filled with the liquid solvent before attaining
the desired temperature and pressure; then a static extraction is
performed (5–10 min is most often sufficient) and the pressure
is further released and the extract collected in glass vials. To
ensure that all the extract reaches the collection vials, the cell is
rinsed with fresh solvent; finally, to avoid any losses or memory
effects, the cell is purged with an inert gas. The typical volume
collected depends on the cell size. Volumes between 10 and 100
mL may be required, and hence evaporation steps are needed to
concentrate the final extract.
In such a system, the pressure is of minor importance, its
main effect being to maintain the solvent in its liquid state. This
reduces the number of parameters that need to be optimized to
achieve efficient extractions (see Table 1), thereby reducing the
time devoted to the development of extraction procedures. As
an example, temperatures around 100–150 °C were found to
increase the extraction recoveries of herbicides from soil
samples, while little effect of pressure was observed for dry
soils.31 However, in the case of moisturized soils, increasing the
pressure from 500 to 1500 psi was beneficial, probably due to
better dissolution of the pesticides. In addition, for wet soils,
non-polar solvents were found to give incomplete recoveries of
hydrocarbons, and a mixture of dichloromethane–acetone (1+1,
v/v) at 175 °C was found to be optimal.32,33
Fig. 3 Principle of a PFE system and influencing parameters.
 PFE has been successfully applied to the same types of
matrices and compounds as SFE.30 The development of PFE
procedures is very attractive, as the same solvent as recom-
mended in the official Soxhlet or sonication methods may be
tested, and the procedure is expected to give efficient extrac-
tions. This probably explains the great interest in this technique
today. In particular, PFE has been recognized as an official
method by the EPA,34 and the method has enabled the efficient
screening of soils to be performed for selected semivolatile
organic priority pollutants.35
However, reality is not that simple. In particular, with
polymeric matrices, it has been demonstrated that a different
solvent should be used, as that used with classical Soxhlet is a
swelling agent for the matrix, leading to partial solubilization of
the polymer under high pressure, with subsequent plugging
when the pressure drops.36
In addition, as PFE uses organic solvents as the extractants, it
offers only limited selectivity. As a consequence, it usually
requires a clean-up of the extract obtained. For instance, further
treatment with sulfuric acid and Florisil was necessary for the
determination of PAHs in smoked food samples (fish and meat
tissues) to remove co-extracted lipids;37 similarly, the determi-
nation of PCBs in fish extracts by PFE required a treatment with
sulfuric acid to destroy lipids before gas chromatographic
analysis.32
2.3 Microwave-assisted extraction
Microwave energy is a non-ionizing radiation (frequency,
300–300 000 MHz) that causes molecular motion by migration
of ions and rotation of dipoles. Dipole rotation refers to the
alignment, due to the electric field, of molecules that have either
permanent or induced dipole moments in both the solvent and
samples. As the field intensity decreases, thermal disorder is
restored which results in thermal energy being released. At 2450
MHz (the frequency used in commercial systems), the align-
ment of the molecules followed by return to disorder occurs 4.9
3 109 times per second, resulting in rapid heating. However, the
absorption of microwave energy and its release as heat are
strongly dependent on the relative permittivity and the dipolar
moment of the medium. The greater the relative permittivity,
the more thermal energy released, and the more rapid the
heating for a given frequency.
Even though microwaves have been used for several years in
analytical laboratories to mineralize samples,38,39 their use to
enhance extraction is very recent. Preliminary studies per-
formed in the late 1980s using domestic ovens showed the great
potential of microwaves for extraction.40,41 However, their
extended use in laboratories began around 5 years ago, with the
commercialization of several instruments dedicated to extrac-
tions.
Microwave-assisted extraction (MAE) uses microwave ra-
diation as the source of heating of the solvent–sample
mixture.42–44 Due to the particular effects of microwaves on
matter (namely dipole rotation and ionic conductance), heating
with microwaves is instantaneous and occurs in the heart of the
sample, leading to very fast extractions. Most of the time, the
extraction solvent is chosen to absorb microwaves. Alter-
natively (for thermolabile compounds), the microwaves may be
absorbed only by the matrix, resulting in heating of the sample
and release of the solutes into the cold solvent.
The results obtained so far have concluded that microwave
radiation causes no degradation of the extracted compounds,
unless too high a temperature arises in the vessel.45,46
At the same time, a specific effect of microwaves on plant
material has been found.42 They interact selectively with the
free water molecules present in the gland and vascular systems,
leading to rapid heating and temperature increase, followed by
rupture of the walls and release of the essential oils into the
solvent. Similar mechanisms are suspected in soils and
sediments, where strong, localized heating should lead to an
increase in pressure and subsequent destruction of the matrix
macrostructure.47,48
The application of microwave energy to the samples may be
performed using two technologies: either closed vessels (under
controlled pressure and temperature), or open vessels (at
atmospheric pressure).49,50 These two technologies are com-
monly named pressurized MAE (PMAE) or focused MAE
(FMAE), respectively. Both systems are shown in Fig. 4.
Whereas in open vessels the temperature is limited by the
boiling point of the solvent at atmospheric pressure, in closed
vessels the temperature may be elevated by simply applying the
correct pressure.51 The latter system seems most suitable in the
case of volatile compounds. However, with closed vessels, after
extraction one needs to wait for the temperature to decrease
before opening the vessel, increasing the overall extraction time
(by around 20 min). With regard to the extraction efficiencies,
both systems were shown to have similar performances for the
extraction of PAHs from soils.52,53
The closed vessel technology is quite similar to the PFE
technology, as the solvent is heated and pressurized in both
systems. The main difference is in the means of heating, either
microwave energy or conventional oven heating. Consequently,
as for PFE, the number of influential parameters is reduced, thus
making the application of this technique quite simple in practice
(see Table 1).49,50
The nature of the solvent is obviously of prime importance in
MAE. As with other techniques, the solvent (or solvent mixture)
should efficiently solubilize the analytes of interest without
significantly extracting matrix material (i.e. the extraction
should be as selective as possible to avoid further clean-up). In
addition, it should be able to displace the solute molecules
adsorbed onto matrix active sites in order to ensure efficient
extractions. Finally, the microwave-absorbing properties of the
solvent are of great importance as sufficient heating is required
(to allow efficient desorption and solubilization, thus efficient
extraction). Most of the time, the chosen solvent should absorb
the microwaves without leading to strong heating so as to avoid
degradation of the compounds. Thus, it is common practice to
use a binary mixture (e.g. hexane–acetone, 1+1), with only one
solvent absorbing microwaves.54–56 However, in some cases,
polar solvents (such as water or alcohols) may give efficient
extractions.57–59 Alternatively, apolar solvents may be used if
Fig. 4 Principle of MAE systems.
Analyst, 2001, 126, 1182–1193 1185
the matrix absorbs microwaves or if an additional microwave-
absorbing material (such as Weflon®) is added.60,61
Other important parameters are the applied power, the
temperature and the extraction time (the latter being dependent
on the number of simultaneous extractions performed56).
Sufficient heating is usually required to enable efficient
extractions to be performed, as shown for triazines and
phenols.62,63 However, too high a temperature may lead to
solute degradation as has been observed previously.46,52,64
As with other techniques, the nature of the matrix is also an
important factor for the success of the extraction. In particular,
the water content needs to be carefully controlled to avoid
excessive heating and to allow reproducible results. As an
example, 30% water was found to be the optimum for extracting
PAHs from soils and sediments.65 Therefore, drying the matrix
before the extraction or adding a drying agent, with subsequent
addition of the required water content, may be advisable. Also,
the strength of the analyte–matrix interactions may induce
matrix effects and require a change in the extraction conditions
from one matrix to another, as has been observed for pollutants
from soil.66
MAE, especially using closed vessels, has been successfully
used for several applications, most of them environ-
mental.43,49,52 An official EPA method for PMAE is currently
under standardization.67
3 Comparative performances of SFE, PFE and
MAE
Very few studies have compared the recent techniques with the
classical Soxhlet or sonication extraction methods for particular
applications. Based on the reported results and on the
specifications of each technique, the comparative performances
of the three recent techniques are discussed with regard to
extraction efficiency and susceptibility to matrix effects,
selectivity, level of automation and simplicity of the operating
procedure.
stronger solute–matrix interactions.69 Therefore, in this case,
more extreme extraction conditions should be used to overcome
such interactions and achieve efficient extractions with this
soil.
As already discussed, matrix effects due to strong adsorption
of the solutes onto the matrix are particularly crucial for
environmental matrices. As an example, the extraction of PAHs
from fly ash samples was highly dependent on the matrix,
whatever the technique (Soxhlet, SFE or PFE). As shown in Fig.
5, satisfactory recoveries were observed from a lignite coal fly
ash (with a low carbon content), while under the same extraction
conditions insufficient recoveries were obtained from a bitumi-
nous coal fly ash (with a high carbon content and a much larger
surface area) due to the stronger solute–matrix interactions that
require more stringent extraction conditions, as well as the
possible decomposition of the PAHs onto fly ash.70,71 The ash
samples had been initially spiked with a mixture containing the
PAHs, and left to equilibrate during 2 weeks. It was suspected
that, during this time, losses of the volatile PAHs (such as
naphthalene) occurred due to volatilization.
In addition to the organic content, the particle size of the
matrix has been shown to influence the extraction efficiency (as
observed during the PFE of PCBs from a harbour sediment72),
and grinding of the sample before the extraction is highly
recommended.
Finally, the water content of the matrix may be crucial for the
success of the extraction, especially with SFE and MAE. With
the former, a high content may prevent the extraction of non-
polar compounds and also result in plugging of the restrictor.10
With the latter, water will cause strong heating of the matrix,
with possible degradation of the compounds. Therefore, the

3.1 Efficiency and susceptibility to matrix effects

In terms of extraction efficiencies, once correctly optimized for
a given solute–matrix couple, all techniques are comparable, as
recently discussed for PAHs, PCBs and pesticides from soils
and sediments.68
For the same class of compounds, different results may be
obtained when several matrices have to be extracted. In
particular, SFE has been claimed to be highly matrix dependent,
and the extraction conditions should most of the time be
optimized for each new matrix. A possible explanation for this
apparent strong matrix dependence may lie in the use of SFE
conditions that are as selective as possible (in order to limit the
co-extraction of matrix material). This implies the minimization
of modifier content as well as a mild extraction temperature. As
a consequence, when matrices with stronger adsorption of the
analytes have to be extracted, the SFE conditions have to be re-
optimized, with increased modifier content and/or temperature.
Therefore, as already noted by Smith,8 established SFE methods
must have an excess of extraction capability (by using a stronger
extractant or a longer time than required for an ideal sample) to
ensure robustness.
The other extraction techniques (Soxhlet, sonication, PFE
and MAE) do not seem to be as matrix dependent as SFE as they
initially use less selective conditions (due to the use of organic
solvents), thereby overcoming part of the matrix effects. Yet,
the nature of the matrix may still strongly influence the
Fig. 5 Comparison of the performances for extracting PAHs from fly ash
extraction efficiency. For example, the extraction of a fungicide samples:70,71 (a) lignite coal fly ash (surface area, 0.453 m2 g21; carbon
(hexaconazole) from two different aged (52 weeks) soils content, 0.02 wt.%); (b) bituminous coal fly ash (surface area, 2.859 m2 g21;
showed that PMAE under the same conditions leads to lower carbon content, 15.42 wt.%). N, Naphthalene; F, fluorene; Ph, phenan-
recoveries for the soil with the highest carbon content due to threne; Py, pyrene; BP, benzo(a)pyrene; IP, indeno(1,2,3-cd)pyrene.

1186 Analyst, 2001, 126, 1182–1193

water content of the matrix must be carefully controlled. In
some cases, it may also be advisable to add a drying agent to the
matrix. PFE affords the advantage of being much less prone to
water influence. However, a recent study showed that better
recoveries of chloroacetanilide and heterocyclic herbicides
were obtained from moisturized soils as compared to dry soils
using PFE with acetone.31
In order to take into account the matrix effects, a general
strategy for optimizing the extraction conditions, whatever the
technique, is given in Fig. 6. First, extracting spiked samples is
recommended to determine the minimum conditions to ensure
efficient extraction, as well as to check that the extracted solutes
are quantitatively collected (as losses may occur in SFE upon
depressurization, or in MAE during the filtration step). Then,
certified matrices should be extracted as they may require more
drastic conditions (especially higher temperatures) to overcome
solute–matrix interactions. Finally, the optimized conditions
may be used to extract real samples.
3.2 Selectivity
SFE appears undoubtedly to be the most potentially selective
extraction technique.9 This is particularly true when using pure
CO2 as the extractant. The more modifier added to the CO2, the
lower the selectivity of the extraction. To illustrate the higher
selectivity of SFE as compared to PFE (as well as MAE and
traditional techniques as they also use liquid organic solvents
similar to PFE), the values of the limits of detection for selected
pesticides in tomatoes are presented in Table 2.73 The higher
values obtained by PFE are due to the greater matrix
interference that hinders pesticide determination by gas chro-
matography. In addition, despite further clean-up after PFE, the
final extract may not be as clean as that obtained after SFE as
observed for PCBs from several environmental matrices.72
Another recent study reported that pure CO2 removed only 8%
of a bulk organic PAH-contaminated soil, while the use of
solvents in Soxhlet and PFE led to 20–30% matrix material
being extracted.74
Fig. 6 General strategy for optimizing extraction conditions for SFE, PFE and MAE.
In addition, SFE offers the potential of performing selective
extractions by correctly adjusting the solvent power by varying
the pressure, temperature and modifier content, as recently
demonstrated for the fractionation of the phenolic content of
grape seeds.75 However, a compromise must be found between
selectivity and susceptibility to matrix effects (i.e. robustness)
of SFE methods as already discussed.
As MAE and PFE use organic solvents, they offer a lower
selectivity than SFE. To minimize the extraction of matrix
material, the nature of the solvent should be correctly chosen
and moderate temperatures are recommended. However, for
strongly adsorbed compounds, elevated temperatures are re-
quired to achieve efficient extraction of the analytes.
3.3 Level of automation
With the present commercial systems, SFE and PFE systems are
more automated than MAE, as the latter requires manual
operations (such as loading the solvent into the cell, and
especially filtration or centrifugation to separate the extract
from the matrix). On the other hand, PMAE systems offer the
opportunity to perform as many as 14 (or 50 for a given system)
extractions simultaneously, while SFE and PFE systems
commercially available today allow only one or two extractions
at a time. However, to avoid overpressure in the cells, the
samples to be simultaneously extracted should have similar
characteristics (to ensure that the temperature and pressure
recorded in one cell are similar to those in the others), such as
the matrix nature (i.e. carbon or water content) and the
extraction solvent. In addition, in the case of FMAE, operating
under atmospheric pressure offers the possibility to add reagents
(such as sulfuric acid) to the medium after extraction in order to
perform microwave-assisted purification in the same vessel.76
3.4 Simplicity of the operating procedure
To illustrate the different steps that are involved when
performing SFE, PFE or MAE, the extraction of PCBs from
Analyst, 2001, 126, 1182–1193 1187
soils has been chosen, as EPA methods have been reported for beginning of the extraction; (iv) whereas SFE uses supercritical
all three techniques for this application. All the steps, from the carbon dioxide as an extractant, PFE and MAE use a mixture of
pretreatment of the matrix to the generation of the final extract, hexane–acetone as solvent, which is the same solvent mixture as
are indicated in Fig. 7. From this practical application of the recommended in the EPA methods of classical extraction
recent techniques, several comments can be made: (i) pretreat- techniques (namely Soxhlet and sonication) as shown in Fig. 1;
ment of the matrix (especially grinding and removal of water) is (v) MAE requires a filtration step before collecting the final
crucial for the success of extractions, whatever technique is extract, which may lead to losses or contamination; (vi) with
considered; (ii) the sample mass that can be extracted varies regard to the final volume of the extract, SFE offers the lowest
from a few grams in the case of SFE up to 20 or 30 g for MAE values as already noted;77 however, if the ratio of the extract
and PFE, respectively; (iii) MAE is the sole technique requiring volume (mL) to the sample mass that has been extracted (g) is
the manual addition of the solvent in the cell prior to the considered, which can be regarded as a dilution factor, then we
obtain the approximate ranges: 0.64–3.2 for SFE, 1.5–5 for PFE
Table 2 Limits of detection (LODs/ng g21) of pesticides from tomatoes73 and 2–40 for PMAE; thus, the extent of dilution of the extract
obtained for SFEa and PFEb obtained by PFE and MAE depends on the sample size, and
under some conditions it may be close to that obtained by SFE;
Pesticide SFE PFE Pesticide SFE PFE
(vii) in PFE and MAE, the extracted PCBs are collected in the
Trifluralin 0.3 0.5 Carbofuran 3 4 extraction solvent, which is hexane–acetone, while in SFE they
Pendimethalin 0.4 0.7 Phosalone 5 8 are eluted from the Florisil trap by n-heptane; the nature of the
Diazinon 1 1 Chlorpyrifos 1 9 solvent is important for further steps, such as concentration or
Ethion 0.6 2 Atrazine 2 13 gas chromatographic analysis; (viii) the time devoted to the
Malathion 4 2 Iprodione 6 28 whole SFE procedure is nearly 1 h, against around 30–45 min
Parathion 1 3 Carbaryl 3 35
Methoxychlor 2 3 Lindane 32 82
for PFE and MAE.
Hexachlorobenzene 1 3 Azinphos-methyl 29 130 So, from this particular application, it can be shown that PFE
Parathion-methyl 1 3 and MAE offer the advantages of using liquid organic solvents
a SFE conditions: 2 g tomato + 2 g fibrous cellulose powder; CO , 50 °C,
2
(mostly the same as Soxhlet and sonication) and of a reduced
350 bar; 2 min equilibration time; 20.3 min dynamic time (2 mL min21); time devoted to the overall procedure. In contrast, SFE uses a
C18 silica trapping, elution with 1.2 mL acetone. b PFE conditions: 2 g specific extractant, and the procedure is somewhat longer. At
tomato + 2 g fibrous cellulose powder; acetonitrile, 60 °C, 2000 psi; 5 min the same time, it must be pointed out that, once the extract has
preheating; 2 min static + 100% flush volume + 1 min N2 purge; addition of been collected after PFE or MAE, it frequently contains
NaCl to the collected extract; collection of the supernatant; addition of
Na2SO4; concentration.
interferents that have been co-extracted, so that further clean-up
is required, which increases the overall sample preparation time

Fig. 7 Comparison of the operating procedures for SFE, PFE and MAE recommended by the EPA methods for extracting PCBs from soils (according to
EPA methods 3562,26 3545A34 and 354667).

1188 Analyst, 2001, 126, 1182–1193

before analysis. When using SFE, especially with CO2 as the
sole extractant, the collected extract is often ready for analysis.
As a consequence, in terms of the time required for sample
preparation, it can be considered that, whatever recent technique
is used, approximately 1 h is sufficient to obtain a final extract
that can be directly analysed.
To better illustrate the extraction performance of each
technique in terms of extraction conditions, time and further
treatment required, comparisons are given for several applica-
tions in Tables 3–7. From these results, it can be observed that
extraction efficiencies are on the whole similar, and that
reduced time and solvent consumption are achieved with the
recent techniques. In addition, PFE and MAE offer the
advantage of using solvents similar to those used with the
traditional methods, with the major drawback of usually
requiring further filtration, clean-up and concentration steps.
4 The right technique for the right application
Choosing the right technique for the right application requires a
consideration of the features of the matrix and of the analytes.
SFE is very suitable for extracting thermolabile compounds
as it allows the possibility to perform fast extractions at
moderate temperatures (around 40 °C). In addition, when pure
CO2 is used as the extractant, this technique remains the most
selective for most applications, except for the extraction of low
polarity compounds from samples that contain a high lipid
content. In this case, further clean-up will be required due to the
simultaneous extraction of lipids and solutes, unless an
appropriate solid phase is added to the sample (for example,
alumina allowed the retention of lipids during the SFE of drug
residues in poultry feed, eggs and muscle tissue84). However, in
such an application, the other techniques will also require a
clean-up step due to the co-extraction of lipids, as observed for
PFE of PCBs from fish tissues.32
The main drawbacks of SFE are the difficulties in extracting
polar compounds (this requires the addition of an appropriate
modifier to the fluid) and the different operating conditions that
may be required between spiked and real samples as already
discussed.77 This may lead to a tedious optimization of SFE
methods, as several parameters need to be considered with this
technique. Consequently, the current use of SFE in laboratories
will require the promulgation of official methods (at the present
time, only a few have been published by the US EPA for
environmental applications25–27).
As they require less parameters to be optimized, and as they
use liquid organic solvents as the extractant, PFE and MAE are
more easily optimized than SFE and, for the same reasons,
experimental conditions developed for spiked samples are more

Table 3 Comparison of technique performances for the extraction of PAHs

Further treatment
Application Technique Solvent Conditions Time after extraction Extraction resultsa Reference

PAHs/certified Soxhlet (EPA Hexane–acetone, 10 g sediment; 18 h Concentration 50.3–161% 64

marine method) 1+1 300 mL solvent
sediment
(NIST 1941a)
Sonication (EPA CH2Cl2–acetone, 30 g sediment; 3 3 3 3 min Concentration 20.6–213%
method) 1+1 3 100 mL
solvent
SFE CO2 + 10% 5 g sediment; 60 min dynamic None 31.7–171%
CH3OH copper filings;
450 bar, 120
°C; 1–1.5 mL
min21
collection:
CH2Cl2
PMAE Hexane–acetone, 10 g sediment; 30 10 min + 20 min Supernatant 26–97.5%
1+1 mL solvent; 115 cooling collected;
°C, 72 psi concentration;
centrifugation;
concentration
PAHs/native Soxhlet CH2Cl2 10 g soil + 10 g 24 h Concentration Total: 1623 mg kg21 53
contaminated Na2SO4; 150
soil mL solvent
SFE CO2 + 20% 1 g soil; 250 kg 5 min static + 30 Concentration Total: 1544 mg kg21
CH3OH cm22; 70 °C; 2 min dynamic
mL min21
collection:
CH2Cl2
PFE CH2Cl2–acetone, 7 g soil; 100 °C; 5 min preheating + Concentration Total: 1537 mg kg21
1+1 2000 psi 5 min static
PMAE Acetone 2 g soil; 40 mL 20 min + cooling Filtration; Total: 1578 mg kg21
solvent; 120 °C concentration
FMAE CH2Cl2 2 g soil; 70 mL 20 min Filtration; Total: 1492 mg kg21
solvent concentration
PAHs/ Soxhlet CH2Cl2 10 g soil + 30 g 6 h + cooling None Total: 297.4 mg kg21 78,79
contaminated Na2SO4; 100
soil mL solvent
SFE CO2 + 20% 1 g soil; 250 kg 5 min static + 60 None Total: 458.0 mg kg21
CH3OH cm22; 70 °C; 1 min dynamic
mL min21
collection:
CH2Cl2
PMAE Acetone 2 g soil; 40 mL 20 min + cooling Filtration Total: 422.9 mg kg21
solvent; 120 °C
a Concentration values obtained (mg kg21) or recoveries versus certified values (%).

Analyst, 2001, 126, 1182–1193 1189

rapidly adapted to real samples (e.g. by simply increasing the
temperature or the extraction time). The nature of the extractant
needs to be chosen to match the polarity of the solutes and to
limit the co-extraction of matrix material, while the extraction
temperature should allow a high and selective solubilization and
desorption of the analytes, along with rapid mass transfer.
Therefore, PFE and MAE can be successfully applied to all
types of solutes and solid matrices, with the limitation that
experimental conditions are chosen to avoid possible thermal
degradation of the analytes.
Of prime interest is the very recent use of PFE with
subcritical water as the extractant.85 This fluid has been
successfully used for several applications and is a promising
alternative to the well-known supercritical carbon dioxide. By
simply increasing the temperature at constant pressure, the
relative permittivity of water may be reduced, so that analytes
with a wide range of polarities may be extracted. Thus, at high
temperatures (around 200–300 °C), water acts as a low polarity
solvent, allowing the selective extraction of non-polar analytes,
such as PCBs, from soils and sediments.86–88 In addition, class-
selective extractions may be achieved by simply raising the
temperature.89 However, even though subcritical water shows
great potential as a ‘clean’ solvent, it leads to dilution of the
analytes in the liquid extract (thus requiring concentration steps
for some applications), and more matrix material is extracted as
compared to pure CO2 extraction.74 In addition, at such high
temperatures, degradation of the solutes may occur.90
5 Future trends
As legislation will tend to restrict or even ban the use of many
common solvents, recent extraction techniques will in the future
undoubtedly supersede the traditional methods, as the former
considerably reduce the solvent volumes required, along with a
reduction in the time devoted to the extraction step (see Table
8).
Yet, future trends will depend on the commercially available
apparatus. Table 9 summarizes the characteristics of the
systems available today for the recent techniques. Indeed, when
we look back over the past 10 years, numerous changes have
occurred in the commercial systems available for the recent
techniques devoted to solid sample extraction. About 10 years
ago, when SFE appeared promising and a viable alternative to
Soxhlet extraction, several manufacturers proposed their own
apparatus, the most famous being Hewlett-Packard (Agilent),
Dionex, Isco and Suprex. Then, due to the emergence of MAE
and PFE, as well as problems inherent in SFE as previously
discussed, the number of types of apparatus commercially
available was reduced as indicated in Table 9. This reflects the

Table 4 Comparison of technique performances for the extraction of PCBs

Application Technique Solvent Conditions Time Further treatment Extraction resultsa Reference
after extraction

PCBs/certified Soxhlet Hexane–acetone, 0.2 g soil + 2 g 24 h + cooling Concentration; 81–100 80

industrial soil 25+75 Na2SO4; 200 centrifugation;
(CRM 481) mL solvent florisil clean-up;
elution with
hexane;
concentration
PFE Hexane–acetone, 0.2 g soil + 2 g 10 min Concentration; 89.2–133
25+75 Na2SO4; 100 florisil clean-up;
°C; 1800 psi elution with
hexane;
concentration
PMAE Hexane–acetone, 0.2 g soil + 2 g 40 min Filtration; 94.2–111
26+74 Na2SO4; 15 mL concentration;
solvent; 21 psi florisil clean-up;
elution with
hexane;
concentration
PCBs/certified Soxhlet n-Hexane 5–20 g soil; 75 12 h AgNO3 and silica 97 61
soil CRM mL solvent gel clean-up;
910-050 concentration
PFE n-Heptane 2 g soil; 120 °C; 10 min Concentration 98
120 MPa
PMAE n-Heptane 2 g soil + 2 g 15 min + cooling Centrifugation; 111
Na2SO4; concentration
Weflon® disc;
15 mL solvent;
150 °C
PCBs/certified SFE (EPA CO2 1 g sediment + 7 g 10 min static + 40 None 79–141 72
harbour method) Na2SO4 + 2 g min dynamic
sediment Cu powder; 80
CRM 536 °C, 305 bar 1
mL min21;
florisil trapping
PFE (EPA Hexane–acetone, 1.5 g sediment + 5 min preheating + Concentration; 109–211
method) 1+1 1.5 g Na2SO4; 5 min static sulfuric acid;
100 °C impregnated
silica clean-up;
elution with
hexane;
concentration;
Cu powder
addition
a Recoveries versus certified values (%).

1190 Analyst, 2001, 126, 1182–1193

disinterest of several laboratories towards this technique, and it
will in the future additionally hinder the routine development of
this technique.
In the case of PFE, there is so far only one commercial system
available devoted to this technique, from Dionex. However, it
should be noted that the new SFE extractor commercialized by
Isco is presented as a dual mode system, operating in either SFE
or PFE modes. This shows the growing interest of analysts
towards PFE for the extraction of solid matrices.
For MAE, the open systems initially commercialized by
Prolabo (Soxwave 100 and 3.6) were sold at the end of 1999 to
CEM Corporation, but they have not been commercially
Table 5 Comparison of technique performances for the extraction of pesticides
available since (only cells or pieces for repair can be obtained
from CEM). As a consequence, the interest in FMAE should
decrease in the future, unless other systems become available.
Thus, today, there are only two PMAE systems commercially
available: Mars-X from CEM and Ethos SEL from Milestone.
Both systems offer possible stirring of the samples during
extraction (which was not the case with previous systems), as
well as the use of additives to allow heating when using apolar
solvents.
However, due to the high investment cost of these techniques
(especially SFE and PFE as shown in Table 8), economic
considerations will in practice also influence the choice of the

Application Technique Solvent Conditions Time Further treatment Extraction resultsa Reference
after extraction

Hexaconazole/ Soxhlet CH3CN–H2O, 1+1 40 g soil; 80 mL 6h Partitioning: Fresh soil 1: 0.140; 69

weathered solvent CH2Cl2; aged soil 1: 0.070;
soils (fresh + reduced to fresh soil 2: 0.140;
52 week dryness; dilution aged soil 2: 0.080
aged). Soil 1: 1 mL CH2Cl2;
sandy loam silica clean-up;
soil; soil 2: dryness; dilution
sandy clay in hexane–
soil acetone, 1+4
SFE CO2 + 20% 4 g soil; 245 bar, 5 min static + 20 Cyano-bonded Fresh soil 1: 0.074;
CH3OH 55 °C; 2 mL min dynamic silica clean-up; aged soil 1: 0.034;
min21 elution with fresh soil 2: 0.119;
collection: 5 mL CH3OH; aged soil 2: 0.072
CH3OH C18silica clean-
up; elution with
CH3OH;
concentration
PFE Acetone 5 g soil + sand; 5 min Concentration Fresh soil 1: 0.124;
2000 psi, 100 equilibration + aged soil 1: 0.093;
°C 10 min fresh soil 2: 0.136;
aged soil 2: 0.070
PMAE Acetone 5 g soil; 30 mL 15 min + 30 min Filtration; C18 Fresh soil 1: 0.08;
solvent; 115 °C cooling silica clean-up; aged soil 1: 0.035;
elution with fresh soil 2: 0.134;
CH3OH; aged soil 2: 0.073
concentration
HCH isomers/ Soxhlet Hexane–acetone, 0.2 g soil + 2 g 8–24 h + cooling Concentration; a-HCH: 370; b-HCH: 81
polluted 75+25 Na2SO4; 200 centrifugation; 820
landfill soil mL solvent Florisil clean-
up; elution with
hexane;
concentration
PFE Hexane–acetone, 0.2 g soil + 2 g 16 min Concentration; a-HCH: 340; b-HCH:
1+1 Na2SO4; 120 Florisil clean- 800
°C; 1700 psi up; elution with
hexane;
concentration
PMAE Hexane–acetone, 0.2 g soil + 2 g 10 min Filtration; a-HCH: 370; b-HCH:
25+75 Na2SO4; 10 mL concentration; 829
solvent; 21 psi Florisil clean-
up; elution with
hexane;
concentration
a Concentration values obtained (mg kg21).

Table 6 Comparison of technique performances for the extraction of phenols

Further
treatment
after Extraction
Application Technique Solvent Conditions Time extraction resultsa Reference

Phenols/cokery Sonication (EPA CH2Cl2 2.5 g soil; 3 3 10 mL 3 3 3 min None 1.7–8.3 82

soil method) solvent
SFE CO2 1 g soil + Celite + 0.1 mL 10 min static + 15 None 2.1–15.1
CH3OH; 90 °C; C18 min dynamic
silica trapping
PMAE Hexane–acetone, 1 g soil; 130 °C 5 min equilibration + None 3.7–16.8
20+80 10 min + cooling
a Concentration values obtained (mg kg21).

Analyst, 2001, 126, 1182–1193 1191

Table 7 Comparison of technique performances for the extraction of additives from polymers

Further treatment Extraction

Application Technique Solvent Conditions Time after extraction resultsa Reference

Irganox 1010/ Soxhlet CHCl3 1 g polymer; 50 mL solvent 2h Dryness; dilution in NDb 83

polypropylene CH3OH
Sonication CHCl3 0.2 g polymer; 10 mL 2h Dryness; dilution in ND
solvent; 40 °C CH3OH
Reflux CHCl3 0.3 g polymer; 30 mL 1h Dryness; dilution in 0.1395%
solvent; 63 °C CH3OH
PFE Propan-2-ol 0.2 g polymer + sand; 3 min preheating + Filtration; dryness; 0.1396%
150 °C; 2000 psi 10 min dilution in CH3OH
PMAE Propan-2-ol 0.3 g polymer; 30 mL 5 min + 20 min Filtration; dryness; 0.1368%
solvent; 150 °C cooling dilution in CH3OH
a Irganox 1010 content values obtained (w/w). b ND, not determined.

Table 8 Comparison of the recent techniques with the traditional Soxhlet extractor and sonication

Technique Time Solvent volume Sample size Cellsa Filtration required Investment

Soxhlet 6–24 h 100–500 mL 1–50 g 1 No Very low

Sonication 5–45 min 50–200 mL 1–30 g Multiple Yes Very low
2–5 mL (solid trap); 15–60
SFE 10–45 min mL (liquid trap) 1–5 g 1–2 No High
PFE 10–30 min 10–100 mL 1–30 g 1 No High
PMAE 10–30 min 10–50 mL 1–20 g 6–50 Yes Moderate
FMAE 10–30 min 30–70 mL 1–10 g 1–3 Yes Low
a Number of cells that can be simultaneously extracted using the same apparatus.

Table 9 Commercial systems available for the recent extraction techniques

Technique Model Manufacturer Specifications

SFE SFX 220 Isco Inc. Maximum extraction temperature: 150 °C; maximum pressure: 10000 psi; cell
volume: 10 mL; two samples extracted simultaneously; modifier addition (an
option); syringe pump
SFE SFX 3560 Isco Inc. Maximum extraction temperature: 150 °C; maximum pressure: 7500 or 10000 psi;
24 sample carousel + 1 blank; 24 collection vial carousel + 2 wash + 2 blanks;
collection vials: 20 mL; modifier addition: 0–100%; syringe pump capacity: 103
or 266 mL
SFE + PFE SFX 3560DM (dual Isco Inc. Same characteristics as SFX 3560, with a mode dedicated to PFE
mode)
PFE ASE 200 Dionex Corp. Maximum temperature: 200 °C; maximum pressure: 3000 psi; cell volume: 1, 5,
11, 22 or 33 mL; collection vials’ capacity: 40 or 60 mL; 24 sample carousel;
26 collection vial carousel + 4 rinse vials
PFE ASE 300 Dionex Corp. Maximum temperature: 200 °C; maximum pressure: 1500 psi; cell volumes: 34,
66 or 100 mL; collection vials’ capacity: 250 mL; 12 sample carousel; 12
collection vial carousel + 1 rinse vial
PMAE Mars-X CEM Corp. Maximum temperature: 200 °C; maximum pressure: 140 to 200 psi; cell volumes:
100 or 120 mL; 12 or 14 sample carousel; available magnetic stirring bars;
Carboflon® inserts to allow the use of non-polar solvents
PMAE Ethos SEL Milestone Inc. Maximum temperature: 290 °C; maximum pressure: 150 to 500 psi; cell volumes:
100 or 270 mL; 6, 12 or 50 sample carousel; 10 sample carousel; magnetic
stirring of solvent/sample; Weflon™ encapsulated magnetic stir bars to allow
the use of non-polar solvents

extraction technique. This explains in large part the continued
use of sonication, Soxhlet and blending extractions (despite
high operating costs related to solvent consumption and
disposal), along with the fact that these methods are still the
reference methods for numerous applications. Therefore, there
is a crucial need for the approval of reference methods that use
the recent techniques (not only for environmental samples but
also for foods or polymers) in order to favour their development
and reduce both solvent consumption in laboratories and the
time devoted to sample preparation.
Taking into account these considerations, future trends may
be proposed. Hence, it appears that the peculiarity of SFE lies in
its high potential selectivity. However, to maintain this
selectivity, mild conditions should be used, which limits the
robustness of the method as already discussed. Consequently,
SFE should be used for particular applications and/or when a
very limited range of matrix types are to be extracted. For
example, it could be used for the routine control of processes.
Whenever less selectivity is required and/or several matrices
have to be extracted, PFE or MAE should be preferred, as the
use of organic solvents and elevated temperatures partly
overcomes the solute–matrix interactions. They afford a
reduction in influent parameters as compared to SFE, which
allows faster optimization steps. On the one hand, PFE seems to
be more attractive than MAE as it is more convenient to use,
because of a higher degree of automation and the absence of
further filtration. On the other hand, MAE systems offer the
advantages of enabling multiple simultaneous extractions to be
performed under moderate pressures. Consequently, both
techniques should experience increasing development in labo-
ratories in the future.
6 References
1 J. Pawliszyn, J. Chromatogr. Sci., 1993, 31, 31.
2 EPA Method 3540C, Soxhlet Extraction, Test Methods for Evaluat-
ing Solid Waste, EPA, Washington DC, December 1996.

1192 Analyst, 2001, 126, 1182–1193

 3 EPA Method 3550B, Ultrasonic Extraction, Test Methods for 49 V. Camel, Trends Anal. Chem., 2000, 19, 229.
Evaluating Solid Waste, EPA, Washington DC, December 1996. 50 M. Letellier and H. Budzinski, Analusis, 1999, 27, 259.
4 C. F. Poole and S. K. Poole, Anal. Commun., 1996, 33, 11H. 51 B. W. Renoe, Am. Lab., 1994, 34.
5 R. E. Majors, LC-GC Int., 1996, 9, 638. 52 V. Lopez-Avila and J. Benedicto, Trends Anal. Chem., 1996, 15,
6 M.-L. Riekkola and P. Manninen, Trends Anal. Chem., 1993, 12, 334.
108. 53 N. Saim, J. R. Dean, M. d. P. Abdullah and Z. Zakaria, J.
7 S. B. Hawthorne, Anal. Chem., 1990, 62, 633A. Chromatogr., A, 1997, 791, 361.
8 R. M. Smith, J. Chromatogr., A, 1999, 856, 83. 54 V. Lopez-Avila, R. Young, R. Kim and W. F. Beckert, J.
9 J. M. Levy, LC-GC Eur., 2000, 13, 174. Chromatogr. Sci., 1995, 33, 481.
10 M. E. P. McNally, Anal. Chem., 1995, 67, 308A. 55 K. K. Chee, M. K. Wong and H. K. Lee, J. Chromatogr., A, 1996,
11 M. E. P. McNally, J. AOAC Int., 1996, 79, 380. 723, 259.
12 L. T. Taylor, Anal. Chem., 1995, 67, 364A. 56 E. V. Blanco, P. L. Mahia, S. M. Lorenzo, D. P. Rodriguez and E. F.
13 J. J. Langenfeld, S. B. Hawthorne, D. J. Miller and J. Pawliszyn, Anal. Fernandez, Fresenius’ J. Anal. Chem., 2000, 366, 283.
Chem., 1995, 67, 1727. 57 S. J. Stout, A. R. daCunha, G. L. Picard and M. M. Safarpour, J.
14 M. D. Luque de Castro and M. T. Tena, Trends Anal. Chem., 1996, Agric. Food Chem., 1996, 44, 3548.
15, 32. 58 S. J. Stout, A. R. daCunha and D. G. Allardice, Anal. Chem., 1996, 68,
15 P. R. Eckard, G. L. Long, L. T. Taylor and G. C. Slack, J. 653.
Chromatogr. Sci., 1998, 36, 547. 59 G. Xiong, B. Tang, X. He, M. Zao, Z. Zhang and Z. Zhang, Talanta,
16 J. A. Field, D. J. Miller, T. M. Field, S. B. Hawthorne and W. Giger, 1999, 48, 333.
Anal. Chem., 1992, 64, 3161. 60 K. Hummert, W. Vetter and B. Luckas, Chromatographia, 1996, 42,
17 J. W. Hills and H. H. Hill, J. Chromatogr. Sci., 1993, 31, 6. 300.
18 T. S. Reighard and S. V. Olesik, Anal. Chem., 1996, 68, 3612. 61 R.-A. Düring and St. Gäth, Fresenius’ J. Anal. Chem., 2000, 368,
19 H. J. Vandenburg, A. A. Clifford, K. D. Bartle, J. Carroll, I. Newton, 684.
L. M. Garden, J. R. Dean and C. T. Costley, Analyst, 1997, 122, 62 R. Hoogerbrugge, C. Molins and R. A. Baumann, Anal. Chim. Acta,
101R. 1997, 348, 247.
20 W. Fiddler, J. W. Pensabene, R. A. Gates and D. J. Donoghue, J. 63 M. P. Llompart, R. A. Lorenzo, R. Cela and J. R. J. Paré, Analyst,
Agric. Food Chem., 1999, 47, 206. 1997, 122, 133.
21 J. W. Pensabene, W. Fiddler and D. J. Donoghue, J. AOAC Int., 1999, 64 V. Lopez-Avila, R. Young and N. Teplitsky, J. AOAC Int., 1996, 79,
82, 1334. 142.
22 V. Camel, A. Tambuté and M. Caude, J. Chromatogr., 1993, 642, 65 H. Budzinski, M. Letellier, P. Garrigues and K. Le Menach, J.
263. Chromatogr., A, 1999, 837, 187.
23 V. Camel, Trends Anal. Chem., 1997, 16, 351.
66 V. Lopez-Avila, R. Young and W. F. Beckert, Anal. Chem., 1994, 66,
24 R. M. Smith, LC-GC Int., 1996, 9, 8.
1097.
25 EPA Method 3561, Supercritical Fluid Extraction of Polynuclear
67 EPA Method 3546, Microwave Extraction, Test Methods for
Aromatic Hydrocarbons, Test Methods for Evaluating Solid Waste,
Evaluating Solid Waste, pre-release version, EPA, Washington DC,
EPA, Washington DC, December 1996.
September 1999.
26 EPA Method 3562, Supercritical Fluid Extraction of Polychlorinated
68 J. R. Dean and G. Xiong, Trends Anal. Chem., 2000, 19, 553.
Biphenyls (PCBs) and Organochlorinated Pesticides, Test Methods
69 S. P. Frost, J. R. Dean, K. P. Evans, K. Harradine, C. Cary and M. H.
for Evaluating Solid Waste, EPA, Washington DC, January 1998.
I. Comber, Analyst, 1997, 122, 895.
27 EPA Method 3560, Supercritical Fluid Extraction of Total Recover-
able Petroleum Hydrocarbons, Test Methods for Evaluating Solid 70 D. V. Kenny and S. V. Olesik, J. Chromatogr. Sci., 1998, 36, 59.
Waste, EPA, Washington DC, December 1996. 71 D. V. Kenny and S. V. Olesik, J. Chromatogr. Sci., 1998, 36, 66.
28 B. E. Richter, J. L. Ezzell, D. Felix, K. A. Roberts and D. W. Later, 72 E. Björklund, S. Bowadt, T. Nilsson and L. Mathiasson, J.
Am. Lab., 1995, 27, 24. Chromatogr., A, 1999, 836, 285.
29 B. E. Richter, B. A. Jones, J. L. Ezzell, N. L. Porter, N. Avdalovic and 73 S. J. Lehotay and C.-H. Lee, J. Chromatogr., A, 1997, 785, 313.
C. Pohl, Anal. Chem., 1996, 68, 1033. 74 S. B. Hawthorne, C. B. Grabanski, E. Martin and D. J. Miller, J.
30 R. C. Richter, LC-GC, 1999, 17, S22. Chromatogr., A, 2000, 892, 421.
31 Y. Zhu, K. Yanagihara, F. Guo and Q. X. Li, J. Agric. Food Chem., 75 R. Murga, R. Ruiz, S. Beltran and J. L. Cabezas, J. Agric. Food
2000, 48, 4097. Chem., 2000, 48, 3408.
32 R. C. Richter and L. Covino, LC-GC, 2000, 18, 1068. 76 H. Budzinski, M. Letellier, S. Thompson, K. LeMenach and P.
33 R. C. Richter and L. Covino, J. Chromatogr., A, 2000, 874, 217. Garrigues, Fresenius’ J. Anal. Chem., 2000, 367, 165.
34 EPA Method 3545A, Pressurized Fluid Extraction, Test Methods for 77 M. D. Luque de Castro and M. M. Jimenez-Carmona, Trends Anal.
Evaluating Solid Waste, EPA, Washington DC, January 1998. Chem., 2000, 19, 223.
35 J. A. Fisher, M. J. Scarlett and A. D. Stott, Environ. Sci. Technol., 78 I. J. Barnabas, J. R. Dean, W. R. Tomlinson and S. P. Owen, Anal.
1997, 31, 1120. Chem., 1995, 67, 2064.
36 X. Lou, H.-G. Janssen and C. A. Cramers, Anal. Chem., 1997, 69, 79 I. J. Barnabas, J. R. Dean, I. A. Fowlis and S. P. Owen, Analyst, 1995,
1598. 120, 1897.
37 G. Wang, A. S. Lee, M. Lewis, B. Kamath and R. K. Archer, J. Agric. 80 O. Zuloaga, N. Etxebarria, L. A. Fernandez and J. M. Madariaga,
Food Chem., 1999, 47, 1062. Trends Anal. Chem., 1998, 17, 642.
38 F. E. Smith and E. A. Arsenault, Talanta, 1996, 43, 1207. 81 O. Zuloaga, N. Etxebarria, L. A. Fernandez and J. M. Madariaga,
39 R. C. Richter, D. Link and H. M. Kingston, Anal. Chem., 2001, 73, Fresenius’ J. Anal. Chem., 2000, 367, 733.
30A. 82 M. P. Llompart, R. A. Lorenzo, R. Cela, K. Li, J. M. R. Bélanger and
40 K. Ganzler, A. Salgo and K. Valko, J. Chromatogr., 1986, 371, J. R. J. Paré, J. Chromatogr., A, 1997, 774, 243.
299. 83 H. J. Vandenburg, A. A. Clifford, K. D. Bartle, J. Carroll and I. D.
41 K. Ganzler and A. Salgo, Z. Lebensm.-Unters.-Forsch, 1987, 184, Newton, Analyst, 1999, 124, 397.
274. 84 D. K. Matabudul, N. T. Crosby and S. Sumar, Analyst, 1999, 124,
42 J. R. J. Paré, J. M. R. Bélanger and S. S. Stafford, Trends Anal. Chem., 499.
1994, 13, 176. 85 M. D. Luque de Castro and M. M. Jimenez-Carmona, Trends Anal.
43 C. S. Eskilsson and E. Björklund, J. Chromatogr., A, 2000, 902, Chem., 1998, 17, 441.
227. 86 K. Hartonen, K. Inkala, M. Kangas and M.-L. Riekkola, J.
44 R. E. Majors, LC-GC Int., 1995, 8, 128. Chromatogr., A, 1997, 786, 219.
45 V. Lopez-Avila, R. Young and W. F. Beckert, J. AOAC Int., 1998, 81, 87 Y. Yang, S. Bowadt, S. B. Hawthorne and D. J. Miller, Anal. Chem.,
462. 1995, 67, 4571.
46 V. Lopez-Avila, J. Benedicto and K. M. Bauer, J. AOAC Int., 1998, 88 S. B. Hawthorne, C. B. Grabanski, K. J. Hageman and D. J. Miller, J.
81, 1224. Chromatogr., A, 1998, 814, 151.
47 O. F. X. Donard, B. Lalere, F. Martin and R. Lobinski, Anal. Chem., 89 S. B. Hawthorne, Y. Yang and D. J. Miller, Anal. Chem., 1994, 66,
1995, 67, 4250. 2912.
48 J. Szpunar, V. O. Schmitt, O. F. X. Donard and R. Lobinski, Trends 90 K. J. Hageman, L. Mazeas, C. B. Grabanski, D. J. Miller and S. B.
Anal. Chem., 1996, 15, 181. Hawthorne, Anal. Chem., 1996, 68, 2892.

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