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Analyst, February 199S, Vol. 120
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355
Extraction of Surfactants From Aqueous Media
by Supercritical Fluid Extraction*
M. Kane, J. R. Dean+and S. M. Hitchen
Department of Chemical and Life Sciences, University of Northumbria at
Newcastle, Ellison Building, Newcastle upon Tyne, U K N E l 8ST
C. J. Dowle
ICI plc, Wilton Research Centre, P. 0. Box 90, Wilton, Middlesbrough,
Cleieland, UK TS6 8JE
R. L. Tranter
Glaxo Manufacturing Services, Harmire Road, Barnard Castle, Co. Durham, U K
DL12 8DT
Two methods for the supercritical fluid extraction (SFE) of
analytes from aqueous media were evaluated: direct extraction
and solid-phase extraction (SPE) discs. SPE discs were used to
isolate an alcohol phenol ethoxylate (APE) non-ionic surfactant
from an aqueous matrix prior to extraction using supercritical
COz. This method was compared with the direct SFE of
surfactant from the aqueous matrix. The second method
allowed the continuousextractionof analyte from water using a
modified extraction cell. The extraction cell was designed to
maximize the exposure of the analyte to supercritical C 0 2
interactions and thereby allow the continuous extraction of the
analyte from an aqueous sample. The results suggest that there
is a difference in the effects of diffusion and equilibrium on the
extraction process for the two methods of extraction studied.
Keywords: Supercriticalfluid extraction; solid-phase extraction;
direct aqueous extraction; non-ionic surfactant; extraction
model
Introduction
In recent years the use of supercritical fluid extraction (SFE)
has become widely accepted as an alternative to more
traditional methods of extraction. 1-3 Higher diffusion rates
and selective solvent strengths are often quoted as the main
advantages of SFE over traditional methods such as liquid-
liquid and liquid-solid extraction.44
However, the published literature on analytical SFE often
considers the extraction of analytes from solid matrices with
little or no water content. In these, the supercritical fluid is
thought to interact with the analyte o n the matrix by first
dissolving the analyte. Once the analyte is dissolved, diffusion
forces control the rate at which it is transported into the bulk
supercritical fluid. Aqueous phase extraction differs from this
in that water has a very limited solubility in supercritical CO27
and under standard SFE conditions mixing is by diffusion
through the sample.
Research on the solubility of pure surfactantsx.9 in super-
critical CO? has demonstrated that non-polar non-ionic
surfactants tend to exhibit significant solubility, whereas those
of both anionic and cationic nature show very little or no
solubility. The chemical nature of surfactants, in particular
their amphilic properties, and also their tendency to exist in
' Presented by M. Kane on receipt of the Ronald Belcher Memorial
Lectureship, R & D Topics Meeting, University of Hertfordshire, July. 18-19,
1994.
+ To whom correspondence should be addressed.
micellar form above a concentration known as the critical
micellization concentration (c.m.c.) make the extraction of
surfactants using supercritical CO2 of particular interest.
SFE has the potential to reduce significantly the complexity
of the multi-step analyses currently used for the sample
preparation of aqueous-based surfactant samples.10 It has
been suggested that on a larger scale SFE may prove to be a
low energy, and hence a low cost, aIternative to distillation
and evaporation techniques currently used to isolate analy-
tes.11 These benefits would be valuable in the measurement of
surfactants in waste waters and groundwaters.
In this paper we consider two methods currently used in
SFE for the extraction of analytes from aqueous media, and
compare the results for the extraction of a non-ionic surfactant
by the two methods. The first method studied was the use
of solid-phase extraction (SPE) discs in conjunction with
SFE.12-14 The use of SPE discs allows the removal of the
aqueous part of the sample and effects preconcentration of
analyte on the disc. The analyte is removed from the disc by
conventional SFE. This method is particularly useful when
trace levels of analyte are present in the aqueous phase. The
second method, using a headspace extraction cell, allows the
direct and continuous extraction of analytes from a bulk water
sample.ls.1~Unlike flow-through cells, this type of cell
contains the aqueous sample in the cell and avoids unwanted
carryover of liquid from the extraction chamber into the
collection device.
Mechanism of Extraction From Water
A non-ionic surfactant introduced into water causes a disrup-
tion of ordered hydrogen bonded regions owing to the
presence of its hydrophobic chains. However, the hydrophilic
oxyethylene chains provide sufficient hydrogen bonding with
water molecules to compensate for the loss in energy due to
the disruption process. The removal of the hydrophobic
portions of the molecule from the aqueous phase in a
two-phase system is entropically favoured. Hence, the surfac-
tant will probably accumulate at the supercritical C02-water
interface in such an orientation that its hydrophobic part is
oriented towards the supercritical CO2 phase, whereas the
hydrophilic oxyethylene chain remains in the water (Fig. 1).
An over-all effect of this is a disruption of the order of the
water molecules at the surface resulting in a lowering of
surface tension. There is a sharp cut-off point in the lowering
of interfacial surface tension as the c.m.c. is reached. If we
relate this to the experimentally observed behaviour of a
non-ionic surfactant extracted from water using SFE, we can

356 Analyst, February 1995, Vol. 120
suggest a mechanism of extraction based on two distinct stages
within the extraction, i . e . , an equilibration stage followed by a
kinetically controlled diffusion stage.
Initially, surfactant molecules present at the water-air
interface, in water above its c.m.c., are aligned with the
hydrophobic part towards the air and the remainder of the
molecule is randomly oriented in and between micelles. When
extraction begins the air phase is rapidly replaced with
supercritical C 0 2 . Equilibrium conditions are achieved for the
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pressure and temperature conditions used in the experiment
and the surfactant is distributed between the water and
supercritical phase. Surfactant at the interface partitions into
the supercritical phase and is replaced by surfactant from the
bulk water. This equilibrium process continues until the
concentration of surfactant reaches its c.m.c. At this point, it
is suggested that the movement of surfactant across the
supercritical CO2 boundary is exothermically feasible and that
the remaining surfactant is contained within the bulk water
phase and is unable to be extracted owing to break up of the
micelles.
Experimental
Instrumentation
For SFE, a Jasco Model 880-81 SFE/SFC back-pressure
regulator (BPR) was coupled to a modular Jasco pump
(880-PU) and oven (860-CO) system (Mettler-Toledo, Hal-
stead, Essex, UK) as shown in Fig. 2. A Rheodyne (Cotati,
CA, USA) 7010 switching valve was used to switch the
extraction chamber in-line with the fluid path. The master
pump was cooled by a refrigerated head which allows for the
pumping of liquid COZ (Air Products, Sunderland, Tyne and
O\
Aqueous / CH,
phase H2C\
/O
H,C ,
lo
H2C\
o<cH,
/ CH2
HC
\o
H,C ,
/
o<cH,
/ CH2
H2C \
0
HO’
Fig. 1 Partitioning of surfactant between the supercritical CO2 phase
and water. Alcohol phenyl ethoxylatc of hydrophobic chain length
n = 8 and oxyethylene chain length n = 8-10.
View Article Online
Wear, UK). Supercritical conditions were attained in the oven
where the flowing liquid was heated above its critical
temperature via a pulse damper and 2 m of standard 1/16 in
stainless-steel tubing. Modifier was added at an exact concen-
tration by the second pump. This arrangement is similar to a
standard gradient high-performance liquid chromatography
(HPLC) system. The extraction was monitored via a high-
pressure UV/VIS spectrophotometric detector (Jasco
UV979). The system pressure was maintained by the BPR
based on a high-speed needle valve, periodically opening and
closing the flow path.
Collection of the analytes was at the BPR exhaust where a
suitable receptacle allows trapping of the analyte and also the
escape of gaseous C02. A modified collection vial (Fig. 3)
allowed efficient separation of C 0 2 and analyte. Volatile
components were trapped on a Bond Elut cartridge (Phase
Separations, Deeside, Clwyd, UK) and back-flushed into the
vial at the end of the extraction.
Extracted analytes were quantified by UV spectropho-
tometry using a Shimadzu (Tokyo, Japan) UV-160 double-
beam instrument with 10 mm silica cells. Alcohol phenol
ethoxylate non-ionic surfactant (APE) has a wavelength of
maximum absorbance at 276 nm. The extracts were quantified
using a six-point calibration plot. The plot was linear over the
concentration range 0-400 pg ml-1 with a correlation coeffi-
cient of 0.9996.
Extraction Cell Configuration for Aqueous Samples
The cell arrangement used for the extraction of analytes from
the aqueous phase is shown in Fig. 4. The cell is made of 12.0
mm thick stainless steel, and has a total internal volume of
50.0 ml. The cell top screws on to the base with a 24.0 mm
section of threading. A Teflon coating is used on the threading
to ensure a pressure-tight seal. The seal is also maintained by a
Coolant
circulator
Pulse
damper
co2
w
cylinder Oven
UV detector Back-oressure
regulator
Slave pump
Organic
modifier
Fig. 2 Jasco system used for SFE.
Bond Elut
Restrict0r
CO, in cartridge
/
Glass co, out
vial
Solvent
Fig. 3 Collection system adopted for use with the Jasco SFE system.
 View Article Online

Analyst, February 1995, Vol. 120 357

PEEK O-ring placed between the cell top and base. The 1/16
in inlet tubing is extended to the base of the chamber where it
is coiled to allow a swirling motion of the flowing C 0 2 . The
headspace configuration of the extraction cell allows the
supercritical fluid to flow through the sample prior to exiting.
The outlet is covered by a frit which allows only dissolved
analytes to flow from the extraction chamber into the
collection vessel.
A second extraction cell configuration designed to improve
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were then treated according to the following extraction
method. For extraction using SPE discs the solution was
filtered through the discs and then extracted by SFE. With
continuous extraction from water the 45 ml sample was placed
in the extraction cell and then extracted by SFE.
SFE Conditions
The pressure was kept constant at 220 kg cm-2 and the oven

the mixing of the C02 and the area of contact between the
fluid and the bulk water was also used. The modified cell
configuration is shown in Fig. 5. The inlet tubing was replaced
with a standard solvent filter normally used for helium
sparging in HPLC. The porous 10 pm frit outlet enabled the
fluid to escape through a larger surface area into the aqueous
sample as a continuous stream of supercritical fluid.
Preconcentration Onto SPE Discs
Empore CI8bonded silica SPE discs (Jones Chromatography,
Hengoed, Clwyd, UK) were used for the preconcentration of
the non-ionic surfactant (APE 8-10). The aqueous sample was
passed through SPE discs at flow rates of about 10 ml min-1. A
standard filtration apparatus was used in preconcentrating
aqueous samples. Methanol (5 ml) and distilled water (10 ml)
were used to activate the extraction disc immediately prior to
filtering the sample through the preconcentration apparatus.
A 45 ml aqueous sample took approximately 20 min to pass
through the disc. The disc was partially dried by pulling air for
5 min through the filter and then drying it in an oven at 45 "C
for 30 min. The discs were then ready for extraction by SFE.
Standard Sample Preparation
A 1ml aliquot of a 1%m/v stock solution containing 10 mg of
the alcohol phenyl ethoxylate (APE 8-10) (ICI, Wilton,
Cleveland, UK) was diluted to 45 ml with distilled water giving
an initial concentration of 222 pg ml-1 of APE. Samples were
prepared by this method to ensure that the initial concentra-
tion of sample was consistent. The 45 ml of sample solution
Inlet C
O
,
-
, Outlet CO,
Supercritical
phase -
Bulk water
Diffusing
supercritical
CO,
temperature was set at 45 "C, resulting in a supercritical fluid
density of 0.84 g ml-1. The fluid was pumped at 1 ml min-1.
The BPR outlet, held at a temperature of 40 "C, was placed in
the collection vial containing 5 ml of HiPerSolv grade
methanol (Merck, Poole, Dorset, UK). SPE discs were
extracted with both unmodified supercritical C 0 2 and super-
critical C02 modified with 10 v01.-% methanol. Modified C02
was not used when extracting from water.
Results and Discussion
Effect of Modifier on Extraction
Initial extractions from SPE discs demonstrated that the
solvent strength of pure C02 was insufficient to extract more
than 2.0 mg of the 10 mg of APE preconcentrated on the disc.
Table 1 shows the results of a 30 min extraction from three
separate SPE discs using first C 0 2 only followed by 10 v01.-%
methanol-modified C02. It is apparent that most of the 10 mg
of APE is extracted only with the presence of modifier.
Re-use of SPE Discs
An experiment to investigate the possible re-use of SPE media
was undertaken. Three discs were preconcentrated, extracted
and then cleaned four times to assess the feasibility of
Table 1 Extraction of non-ionic surfactant from SPE discs. Effect of
C 0 2 and methanol-modified C 0 2 on extraction efficiency
Recovery of Recovery of APE using
APE using 10vol.-% methanol- Total extracted
Sample CO2 only/mg modified C02/mg (%>
Disc1 1.6 7.1 87
Disc2 1.9 6.9 89
Disc3 2.2 7.3 95
Average = 90 k 4.3% (n = 3)
Table 2 Effect on extraction recovery from SPE discs of repeated
supercritical C02 extraction of 10 mg of APE

Extraction Mean amount

Headspace extraction cell (50 ml). Disc number number Extraction (%) extracted (YO) (n = 3)
Fig. 4
1 78
2 92
Inlet ,
-
O
C Outlet CO, 3 90
87 k 7.6
1 2 100
2 2 103
3 2 91
Supe rcrit ical 98 k 6.2
phase 1 3 88
Bulk water
2 3 76
Diffusing 3 3 70
supercritical 78 k 9.2
Solvent CO, 1 4 70
inlet filtei 4 45
2
3 4 65
60 & 13.2
Fig. 5 Modified 50 ml headspace extraction cell with 10 pm frit.
 View Article Online

358 Analyst, February 1995, Vol. 120

repeated use. The discs were cleaned by filtering extracted
discs with 10 ml of methanol and allowing to dry for 1 h in an
oven at 45°C. Subsequent extraction of the cleaned discs
showed no residual APE on the discs. The results ( n = 3)
demonstrate how the percentage recovery of APE decreased
*
from 87 +_ 7.56 to 60 13.2% with re-use. This suggests that
the effectiveness of the extraction discs deteriorates with
repeated use and is consistent with the experimental observa-
tions of foaming (owing to analyte breakthrough) occurring in
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supercritical C 0 2 was methanol-modified (10 v01.-%
methanol) with all other conditions the same as described
previously. The repeatability of extraction was 100 k 3.4% ( n
= 6) which was better than the previous reproducibility study
with dynamic extraction alone, shown in Table 2, of 92 k
8.8% (n = 6). Therefore, it is clear that a period of static
extraction prior to dynamic extraction allows excellent
recovery of the APE. Also, the results demonstrate that
non-ionic surfactants can be effectively preconcentrated from

the filtration apparatus with re-used discs. It was also observed aqueous samples using a combined SPE-SFE method and
that re-used discs become deformed. methanol-modified C02.

Effect of Static Equilibration Time on the Extraction of APE Continuous Extraction of APE From Water
From SPE Discs
The practical problems of containing a liquid sample were
It has been reported that the inclusion of a static extraction overcome by using a headspace extraction cell of the type
step, where the fluid is allowed to equilibrate and permeate shown in Fig. 4. The extraction cell was modified to include a
the sample matrix, can enhance sample extraction.17 The solvent filter on the inlet tube of the cell (Fig. 5 ) . The two
repeatability of static extraction was compared with that of a sample inlet configurations were compared in order to
dynamic extraction. A period of static extraction (5 min) evaluate their effectiveness in continuously extracting 10 mg
followed by a 25 min dynamic extraction was performed. The of the APE sample.
Initial experiments indicated that there were practical
difficulties in implementing a continuous system for the direct
extraction from water. The headspace extraction cell design
Table 3 Continuous extraction of APE from aqueous sample using
meant that water carryover into the collection device was not a
modified cell problem, although trace amounts of water observed in the
collector were probably associated with the small, but finite
Extract Time of Amount solubility of water in C02.7 However, the main problem was
number extractiodmin extracted (%) that even at relatively long extraction times (2 h), the amount
1 5 10 of APE recovered was below 100% (Table 3). As discussed
2 10 12 earlier, these poor extraction recoveries from water may be
3 15 12 attributable to the hydrogen bonding that exists between the
4 20 15 water and non-ionic surfactant.
5 25 15
6 30
It is also thought that the surface area of the extracting fluid
29
7 60 34 in contact with the sample may affect the diffusion controlled
8 90 40 part of the extraction. A larger surface area was created by the
9 120 41 addition of a solvent filter to the inlet tube of the extraction
cell (Fig. 5). The results in Table 4 show clearly that there is an
improvement in extraction efficiency with the addition of the
solvent filter.
Table 4 Continuous extraction of APE from aqueous sample using The total amount of APE extracted is related to the amount
modified extraction cell with 10 ym solvent filter of C 0 2 used in the extraction and it can be expressed as the
Extract Time of Amount
mole fraction, x ,
number extractiodmin extracted (%) x = moles of APE/(moles of APE + moles of COz used)
5 15 Data for the extraction were plotted using this function (Fig.
10 20
15 22 6). The plot is characteristic of extractionhime profiles
20 25 predicted for the extraction of an analyte from a matrix.18 The
25 27 first part of the extraction is equilibrium-controlled and results
30 32 in rapid extraction with respect to the C02 used. The latter
60 40 part of the graph is not as steep and is a result of kinetic
90 47 diffusion-controlled extraction of the surfactant.
120 60
Conclusions
I A I Two different approaches to the extraction of surfactants from
D
2 0.020
a water sample have been investigated. Both methods are
simple in design and require little sample preparation.
Continuous extraction directly from the water matrix was
.-S
c.
0.010 c improved by the addition of a 10 pm frit to the inlet tube of the
extraction cell. However, the process seems to be kinetically
limited as the amount of surfactant extracted with respect to
the amount of C 0 2consumed is small at long extraction times.
The advantage of extraction directly from water is that no
I I I I I I sample preparation is required as the aqueous sample can be
0 20 40 60 80 100 120 placed directly into the extraction chamber. The method has
Time/min potential for use as a sample clean-up procedure for non-ionic,
Fig. 6 Relationship between mole fraction of APE extracted and anionic and cationic surfactants. The possibility for selective
time of extraction. H, Unmodified cell; A , modified cell. extraction from an aqueous sample has been identified as a
 View Article Online

Analyst, February 1995, Vol. 120 359

major benefit of these methods owing to the potential
insolubility of both anionic and cationic surfactants8 in
supercritical CO?.
SPE discs have proved to be efficient in the trapping of
surfactant molecules. The use of SFE with SPE discs has been
shown to be quantitative and reproducible provided that the
supercritical CO2 is modified with methanol.
The speed of sample analysis is a major advantage of these
methods. The sample throughput for one sample with the
Published on 01 January 1995. Downloaded by University of Western Ontario on 26/10/2014 01:20:49.
7 Chemical Engineering at Supercritical Fluid Conditions, eds.
Paulitis, J . M., Gray, R. D., and Davidson, K . P., Ann Arbor
Science Publishers, Ann Arbor, MI, 1983, p. 101.
8 Consani. K. A., and Smith, R. D., J. Supercrit. Fluids, 1990,3,
51.
9 Sandra, P., and David, F . , J. High Resolut. Chromatogr., 1990,
13, 415.
10 Nonionic Surfactants Chemical Analysis, ed. Cross, J . , Marcel
Dekker, New York, 1987.
11 Knez, Z . . Posse]. F., Goblob, J., and Bauman, D., Vestn. Slov.

direct method is approximately 1-2 h including the time of Kern. Drus., 1989, 36, 155.
extraction. The time is slightly longer with SPE discs, but 12 Tang, P. H . , Ho, J. S . . and Eichelbcrgwer, J . W., J. Assoc. Off.
shorter extraction times with better extraction efficiencies are Anal. Chem., 1993, 76, 72.
possible. In comparison, current methods19 of determining 13 Barnabas, I. J., Dean, J . R . , Hitchen, S. M., and Owen, S. P.,
Anal. Chim. Acta, 1994, 291, 261.
non-ionic surfactants in environmental samples involve eight 14 Barnabas, I . J., Dean, J. R., Hitchcn, S. M., and Owen, S. P.,
separate stages prior to chromatographic analysis which can J. Chromatogr., 1994, 665,307.
take up to 24 h per analysis. 1s Hedrick, J., and Taylor, L. T., Anal. Chem., 1989, 61, 1986.
16 Hedrick, J . , and Taylor, L. T., J . High Resolut. Chromatogr.,
1990, 13, 312.
17 Applications of Supercritical Fluids in Industrial Analysis, ed.
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