Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
1,
2010
Trend
s
Liquid-phase microextraction
Ali Sarafraz-Yazdi, Amirhassan Amiri
The development of faster, simpler, inexpensive and more environmentally-friendly samplepreparation techniques is an impo- rtant issue in chemical analysis.
Recent research trends involve miniaturization of the traditional liquid-liquid-extraction principle
by greatly reducing the acceptor-to-donor ratio.
The current trend is towards simplification and miniaturization of sample preparation and
decreasing the quantities of organic solvents used.
We discuss liquid-phase microextraction with the focus on extraction principles, historical development
and performance.
2009 Elsevier Ltd. All rights reserved.
Abbreviations: AAS, Atomic absorption spectrometry; BTEX, Benzene, toluene, ethylbenzene and xylenes; DI, Direct
immersion; DLLME, Dispersive liquid-liquid microextraction; DSDME, Directly-suspended droplet microextraction; CE,
Capillary electrophoresis; CFME, Continuous-flow microextraction; ECD, Electron-capture detector; EME, Electrokinetic
membrane extraction; ETAAS, Electrothermal atomic absorption spectrometry; ETV-ICP-OES/MS, Electrothermal vaporizationinductively coupled plasma optical emission spectrometry/mass spectrometry; FID, Flame-ionization detector; GC, Gas
chromatography; GF-AAS, Graphite-furnace atomic absorption spectrometry; HPLC, High-performance liquid
chromatography; HFM, Hollow-fiber membrane; HF-LPME, Hollow-fiber liquid-phase microextraction; HS, Headspace; IL, Ionic
liquid; LLE, Liquid-liquid extraction; LLLME, Liquid-liquid-liquid microextraction; LPME, Liquid-phase microextraction; MASE,
Microwave-assisted solvent extraction; MS, Mass spectrometry; PAHs, Polycyclic aromatic hydrocarbons; PCB,
Polychlorinated biphenyl; SDME, Single-drop microextraction; SPE, Solid-phase extraction; SPME, Solid-phase
microextraction; SLM, Supported liquid membrane; TD, Thermal desorption; TILDLME, Temperature-controlled ionic liquid
dispersive liquid-phase microextraction; THF, Tetrahydrofuran; VOC, Volatile organic compounds; VIS, Visible; UV, Ultraviolet
Keywords: Continuous-flow microextraction (CFME); Directly-suspended droplet microextraction (DSDME); Dispersive liquidliquid microextrac- tion (DLLME); Electrokinetic membrane extraction (EME); Extraction; Hollow-fiber liquid-phase
microextraction (HF-LPME); Liquid-phase microextraction (LPME); Miniaturization; Sample preparation; Single-drop
microextraction (SDME)
doi:10.1016/j.trac.2009.10.003
1. Introdu
n
*
Trend
s
sample-preparation
techniques
[i.e.
liquidliquid
extraction
(LLE)
and
solid-phase
extraction
rac
(SPE)]
have
involved 2010trend is towards simplification
drawbacks (e.g.,
and mini- aturization of the
complicated,
time-consuming
sample-preparation
steps
and
procedures, large amounts of
decrease in the quantities of
sample and organic sol- vents
organic solvents used.
and difficulty in automation).
In 1990, Arthur and Pawliszyn
Using harmful chemicals and
[1] introduced a new method
large
amounts
of
solvents
termed
solidphase
causes
environmental
microextraction (SPME). A polypollution, health hazards to
mer-coated fiber, on which the
laboratory personnel and extra
investigated
compound
operational costs for waste
adsorbs, is placed in the
treatment.
Ideally,
samplesample or its headspace. SPME
preparation techniques should
has
several
important
be
fast,
easy
to
use,
advantages
compared
to
the
inexpensive
and
compatible
traditional sample-preparation
with a range of analytical
tech- niques:
instruments, so the current
le
d
r
o
p
m
ic
r
o
e
x
tr
a
ct
io
n
(
S
D
M
E
)
SDME,
using
typically
13 lL
of
an
organic
solvent
at the tip of a
microsyringe, has evolved from LPME. After
extraction, the microdrop is retracted back
into the syringe and transferred for further
analysis.
In practice, two main approaches can be
used to perform SDME:
(1) direct immersion (DI)-SDME
(2) headspace (HS)-SDME
In DI-SDME, a drop of a water-immiscible
solvent is suspended directly from the tip
of a microsyringe needle immersed in the
aqueous sample.
solvent
(~1.3 lL) is suspended
in a
larger aqueous drop.
At the same time, Jeannot and Cantwell
[4]
introduced
a
new
solvent
microextraction technique, where a micro
drop (8 lL) of organic solvent was left
suspended at the end of a Teflon rod
immersed in a stirred aqueous sample
solution. After extraction for a certain
time, the rod was removed from the sample
solution and,
with
the help
of
a
microsyringe, an aliquot of the organic
drop was injected into a GC instrument
for further analysis (Fig. 1).
One disadvantage of above methods is
that extraction and injection have to be
performed separately, using different
apparatus. To overcome this problem,
Jeannot and Cantwell [5] suggested an
alternative
dropbased
extraction
technique. According to this revised
protocol, microextraction was performed
simply by sus- pending a 1-lL drop
directly from the tip of a microsy- ringe
needle immersed in a stirred aqueous
solution. After extraction, the organic
phase
was
withdrawn
back
into
the
microsyringe, and then the sample was
injected
time.
But,
using
http://www.elsevier.com/locate/trac
3 11
rac
Subsequently,
Shen
and
Lee
[12]
introduced manual dynamic HS-LPME that
overcomes some limitations of the static
microdrop HS-LPME. In comparison to droplet
LPME, the dynamic LPME described provides a
larger enrichment factor within a shorter
analysis time and selection of solvent is
more
flexible.
Because
they
used
a
manually-operated extraction system, the
precision
of the method was relatively
poor [e.g., relative standard deviation
(RSD) was 5.717.7%].
In order to improve ease of the operation
and to achieve greater reproducibility in
sample extraction, Saraji [13] introduced a
semi-automatic dynamic HS- LPME system. A
variable-speed stirring motor was used to
automate the sample-extraction step.
Ouyang et al. [14] introduced a fully
automated HS- LPME technique for dynamic
methods, with a CTC CombiPal autosampler.
All the operational parameters involved in
this process could be precisely and conveniently controlled by the autosampler.
Additionally,
they
devised
a
kinetic
calibration method to correct the ma- trix
effects in applications, and demonstrated
it with the analysis of BTEX in orange
juice.
Deng et al. [15] used microwave energy
for quanti- tative analysis of paeonol (a
bioactive compound) in two traditional
Chinese medicines while using HS-SDME. The
heating mechanism of the microwave, which
can be interpreted as being mainly by
dielectric polarization and conduction, is
very different from that of conventional
heating. Microwaves are directly coupled
with the spe- cies present in the sample
matrix,
leading
to
instantaneous,
localized superheating.
Hansson and Hakkarainen [16] combined
multiple headspace extraction with SDME.
In this method, the extraction process
continued until all analytes were re-
directly
on
the
narrow
fused
silica
capillaries used for separation and because
only nL volumes of sample are injected in
traditional CE, most concentration LODs
obtained in CE
o
u
s
f
o
w
m
ic
r
o
e
x
tr
a
c
ti
o
n
(
C
F
M
E
)
Liu and Lee [26] reported a novel liquidliquid mic- roextraction technique, which
was termed CFME. In this
Figure 7. Directly suspended droplet microextraction: (a) the set up; (b) extracting; (c) sampling .
m
i
c
r
o
e
x
t
r
a
c
ti
o
n
(
D
L
L
M
E
)
Recently Assadi and co-workers [34] reported
DLLME as a new LLE technique that uses lL
volumes of extraction solvent along with a
few mL of dispersive solvents. In this
method, a cloudy solution is formed when an
appropriate
mixture
of
extraction
and
dispersive solvents is injected into an
aqueous sample containing the ana- lytes of
interest.
The
hydrophobic
solutes
are
enriched in
the
extraction
solvent,
which
is
dispersed
into
the
bulk
aqueous
solution.
After
centrifugation,
determination of the analytes in the
settled phase can be performed by
conventional analytical techniques (Fig.
8).
In DLLME, the dispersive solvent plays a
key role that helps extraction solvent
form fine droplets in aqueous samples,
representing about 9799% of the total
volume of the extraction mixture. Compared
to other methods, abundant surface contact
between fine droplets and the analyte in
DLLME
speeds
up
the
mass-transfer
processes of analytes from aquatic phase
to organic phase, which not only greatly
enhances extraction efficiency but also
overcomes the problem of the time taken.
For low tox- icity and low cost, acetone,
methanol, ethanol and ace- tonitrile have
generally
been
used
as
dispersive
solvents. However, they could apply some
extraction solvents to form a constant,
large volume of sediment when the dosage
of extraction solvent is low. Though more
p
h
a
s
e
m
i
c
r
o
e
x
t
r
a
c
ti
o
n
(
H
F
L
P
M
E
)
Pedersen-Bjergaard
and
Rasmussen
[43]
introduced HF- LPME. They used the basic
principle of supported liquid membrane
(SLM), for the first time, in simple,
inexpen- sive, disposable extraction units
for
the
liquid-liquid-liquid
microextraction
(LLLME)
utilizing
polypropylene HFs as the membrane. Fig. 9
illustrates the basic prin- ciple of HFLPME.
The sample vial is filled with the
aqueous sample. A short piece of a porous
HF may be either a rod with a closed
bottom or a u-shape where both ends are
con- nected to guiding tubes. Prior to
extraction, the HF is first dipped in the
organic solvent for a few times to
immobilize solvent in the pores, and
excess solvent is removed. The solvent is
immiscible with water to ensure that it
remains within the pores during the
extraction with no leakage to the aqueous
sample. The organic solvent forms a thin
layer within the wall of the HF. The
extraction solvent must be compatible
with the HF so that the pores in the wall
of the HF can be filled com- pletely.
The acceptor solution then fills the
lumen of the HF. This acceptor solution can
be an organic solvent (the same as that
used for the organic solvent in HF pores),
resulting
in a
two-phase
extraction
system, or the acceptor solution may be
an acidic or alkaline aqueous solution,
resulting in a three-phase extraction
system.
In the two-phase LPME system, the target
analytes are extracted from the aqueous
sample and into the organic solvent
(acceptor solution) present both in the
porous wall and inside the lumen of the HF.
This process may be described by the
following equation:
Asample
Aorg
$
1
where A represents the target analyte. As
discussed in more detail later, two-phase
LPME may be applied to most analytes with
solubility
in
an
organic
solvent
immiscible
with
water
substantially
higher than in an aqueous medium. The
acceptor
solution
may
be
directly
analyzed with capillary GC, or may be
evaporated
and
reconstituted
in
an
aqueous medium for injection into HPLC or
CE.
The extraction solvent must be compatible
with the HF so that the pores in the wall
of the HF can be filled completely. Also,
the extraction solvent must have good
affinity
for
target
compounds,
be
immiscible
with
water
and
have
low
volatility. Finally, the organic solvent
should
have
excellent
GC
behavior.
Successful two-phase LPME requires large
distribution ratios for target ana- lytes.
Such Korg/s (distribution ratio Korg/s is
defined as the ratio of the concentrations
of analyte A in the acceptor and sample
phase at equilibrium conditions) values
correspond
to
moderately
or
highly
hydrophobic compounds containing acidic or
basic groups, or neutral compounds of
similar hydrophobicity.
In three-phase LPME, the analytes are
extracted
from
the
aqueous
sample,
through the organic solvent in HF pores,
and further into the aqueous acceptor
solution present inside the lumen of the
HF.
This process may be described by the
following equa- tion:
Asample
Aorg
Aacceptor
2
This extraction mode is limited to basic
or
acidic
analytes
with
ionizable
functionalities. For extraction of basic
compounds, pH in the sample has to be
adjusted into the alkaline region to
suppress analyte solubility, whereas pH in
the acceptor solution should be low in
order to promote analyte solubility. In
this manner, the basic compounds may be
easily extracted into the or- ganic phase
and further into the acceptor phase without
into
the
acceptor
solution,
whereas
counter-ions present in a very high
concentration in the acceptor solution ionpair with the carrier in the contact area,
and the new ion-pair com- plex are backextracted into the sample.
The deionized analytes in an aqueous
solution are extracted from the sample
solution,
entering
into
the
organic
solvent included in the pores of the HF,
and further into the inside of the HF,
which holds a small volume of an acceptor
solution.
LPME-based methods were found to provide
excellent
sample clean up by excluding macromolecules
from the acceptor phase.
The first report on HF-LPME utilized
three-phase extraction with methamphetamine
as a model drug [43]. King et al. [44] used
two-phase HF-LPME for extracting PAHs from
soil.
HF-LPME is carried out in two modes:
static and dy- namic. In the static mode,
extraction speed is enhanced by extensive
vibration or stirring of the sample and by
careful design of the set-up to minimize
diffusion dis- tances of the analytes.
In
dynamic
mode,
a
conventional
microsyringe with the HF attached to its
needle is connected to a syringe pump to
perform the extraction. The microsyringe
is used as both the microextraction
device
and
the
e
x
t
r
a
c
ti
o
n
(
E
M
E
)
SLMs have been used in analytical chemistry
for extraction and preconcentration of
chemical substances before HPLC, GC and CE.