Current Organic Chemistry, 2007, 11, 241-253 241

Solid Phase Microextraction Combined with Gas Chromatography - A

Powerful Tool for the Determination of Chemical Warfare Agents and
Related Compounds
Bogdan Zygmunt*, Agnieszka Zaborowska, Joanna wiatowska and Jacek Namienik
Department of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology, 11/12 Narutowicza St., 80-
952 Gdansk, Poland

Abstract: Solid phase microextraction (SPME) is a very versatile, convenient and simple technique of sample preparation
for chromatographic analysis. SPME finds increasingly wide acceptance in the isolation and enrichment of chemical
warfare agents (CWAs) and their degradation products in air, water and other liquid samples (e.g. urine), soil, clothing
material, etc. for their gas chromatographic (GC) determination. Until now, typical commercially available fibers have
mainly been used for the extraction of CWAs in direct immersion and headspace modes, although attempts were made to
introduce new fiber coatings, characterized by higher selectivity towards the analytes of interest. The combination of
SPME and GC enables reaching low detection limits dependent on the analyte, matrix, detection system, etc.; for example,
single ppb for benzilic acid in soil and nerve agents in aqueous samples and 200 ppb for thiodiglycol, a degradation
product of sulfur mustard.

INTRODUCTION
The first use of chemicals as weapons of mass des-
truction goes back to World War I, when on April 22, 1915
large amounts of chlorine were released by German military
forces at Ypres, Belgium [1] and bis(2-chloroethyl)sulfide
(sulfur mustard, or HD by US military designation) caused
80% of the chemical casualties in that conflict [2]. Compared
to conventional weapons, relatively small amount of modern
chemical agents may cause high number of casualties [1].
A popular method, which is used to destroy chemical
warfare agents, involves decontamination. There are special
substances to remove toxic agents from the contaminated
surfaces of equipment and territory, which reacting with the
toxic agents yield nontoxic or low-toxic products [3, 4].
In military operations chemical warfare agents (CWA)
are used to kill, seriously injure or incapacitate exposed
individuals by exerting their physiological effects [1]. Since
the first use, a large number of chemicals have been used as
warfare agents. The currently most important ones are
summarized in Table 1 [1].
The principal classification of CWAs is based on their
physiological effects on the human body [5]. Lewisite, like
the sulfur and nitrogen mustards, irritates skin and eyes and
is poisonous when inhaled; but, unlike the mustards, its
clinical effects appear within seconds of exposure. This
agent is very reactive; in aqueous media, it rapidly hydro-
lyzes to a stable, non-volatile, water soluble derivative, 2-
chlorovinylarsonous acid (CVAA), which is also toxic. The
occurrence of CVAA has never been shown except as a
hydrolysis product of lewisite [6-8]. Vesicant warfare agents
act locally on the body surface giving symptoms similar to
scorches with necrosis of tissue. They also exert a toxic
effect on the whole organism which may lead to death.
*Address correspondence to this author at the Department of Analytical
Chemistry, Chemical Faculty, Gdansk University of Technology, 11/12
Narutowicza St., 80-952 Gdansk, Poland; Tel: +48583472210; Fax:
+48583472694; E-mail: zygmuntb@chem.pg.gda.pl
Nerve agents are the most lethal of the CWAs, deriving
their toxicity from the ability to inactivate the enzyme acetyl-
cholinesterase (AChE) resulting in cholinesterase inhibition
[1, 5, 8]. The importance of atropine as an antidote was first
recognized in German laboratories [1]. All nerve agents are
organophosphate compounds and are generally subdivided
into two classes, referred to as G and V agents [5, 9]. O-
Ethyl-S-(2-diisopropylamino-ethyl)-methyl phosphonothio-
late (VX) was chosen as the most powerful agent and a full
scale production commenced in 1961 in the USA. Until now,
it has appeared to be the most effective chemical warfare
agent ever produced. The lethal dose for humans is estimated
at about 0.3 mg/person after inhalational and 5 mg/person
after dermal exposure [1]. VX belongs to a group of the most
toxic chemical warfare agents and it shows some persistence
in the environment, mainly due to its low vapor pressure
[10]. There is clear need for rapid and reliable air testing for
nerve agents during military actions and for monitoring
weapon storage bunkers and decommissioning facilities for
agent leakage [11].
The pollution of soil by CWAs or their degradation
products often results from military or terrorist operations
either in storage, production, disposal or usage. Soil analysis
is an important component of monitoring compliance with
the Chemical Weapons Convention (CWC) [12]. An
important feature of the CWC is a system for verification of
compliance, organized through the Technical Secretariat of
the Convention’s supervisory body, the Organization for the
Prohibition of Chemical Weapons (OPCW) [13]. The actual
or past presence of a chemical, which should be absent at the
inspected site according to the declarations or which has
been used for purposes prohibited under the CWC is a very
important observation in the verification process; this is the
biggest challenge for the organization [14].
Rapid and sensitive screening techniques are needed to
detect CWAs in soil to verify compliance with the CWC and
alert to any soil pollution as it relates to health issues [5].
The determination of chemical warfare agents in complex

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242 Current Organic Chemistry, 2007, Vol. 11, No. 3 Zygmunt et al.

Table 1. Classification of chemical warfare agents according to their target organs or tissues [1]

Group Chemical name Common name Symbol*)

Ethyl-N,N-dimethyl phoshoramidocyanidate Tabun GA

Isopropyl methyl phosphonofluoridate Sarin GB

Nerve agents Cyclohexyl methyl phosphonofluoridate Cyclosarin GF

Pinacolyl methyl phosphonofluoridate Soman GD
O-Ethyl-S-(2-diisopropylamino-ethyl)-methyl
- VX
phosphonothiolate
Bis(2-chloroethyl)sulfide
Sulfur mustard H,HD
(Yperite, S-Lost)
Vesicant agents
Tris(2-chloroethyl)amine Nitrogen mustard HN-3
2-Chlorovinyl dichloroarsine Lewisite L
Carbonyl chloride Phosgene CG
Lung-damaging agents
Trichloromethyl chloroformate Diphosgene DP
Hydrogen cyanide - AC
Blood agents
Cyanogen chloride - CK
Incapacitating psychochemicals 3-Quinuclidinyl benzilate - BZ
2-Chloroacetophenone - CN
Lacrimators
2-Chlorobenzalmalononitrile - CS
Diphenylchloroarsine Clark I DA
Vomiting agents Diphenylcyanoarsine Clark II DC
10-Chloro-5,10-dihydrophenarsazine Adamsite DM
* US Army symbols

environmental samples is a very important but difficult task.
It is associated, among other things, with the pollution of the
marine environment by sulfur mustard (yperite) [15] and
with the resolutions of the Convention on the Prohibition of
Chemical Weapons [16]. According to this convention, there
is a need to develop a fast and sensitive method for detecting
chemical warfare agents in the environment during on-site
verification. In preparation of the mission, the Inspection
Team (IT) selects the necessary equipment approved by the
First Conference of State Parties. In regard to sampling and
analysis, the equipment currently available is: sample
collection kit, preparation kit, transport kit, analytical
instruments - GC-MS, and supporting equipment [17].
The principal analytical aim in the area of chemical war-
fare agents is to identify unknown toxic substances in the
sample and then to quantify them. GC identification is
generally based on comparing the retention of an analyte to a
standard on at least two gas chromatographic columns of
different polarity. This should be confirmed by means of
mass spectra if a coupled GC-MS system is available.
Currently the most important analytical tools used to
determine CWAs, especially in complex environmental
samples are modern separation techniques; mainly gas
chromatography and liquid chromatography [18-20]; the
former being equipped with sensitive and selective detectors
such as an atomic emission detector [21, 22], multidetection
systems [23], and increasingly often coupled with mass
spectrometry [2, 10, 21, 24-26]. Comprehensive reviews of
the application of powerful separation techniques in the
analysis of CWAs were published by Hooijschuur et al. [19]
and Witkiewicz et al. [20]. Often field methods are of special
interest – they should be rapid, safe for the analyst, reliable
even at trace levels, and assuring a high degree of certainty
regarding the analyte identity [10]. The determination of
CWAs in complex environmental samples, even with the use
of powerful chromatographic techniques, requires a sophisti-
cated sample preparation technique, which, in the majority of
cases, is the most time-consuming step of the analysis. It is
generally based on analyte isolation and enrichment,
sometimes accompanied by matrix replacement.
When the analytes of interest are very polar, thermally
labile, reactive, or insufficiently volatile for GC or if an
HPLC detection system is not sensitive enough, then the
analytes should be converted to other chemical species prior
to separation or, sometimes, prior to detection. In the GC
determination of degradation products of many important
CWAs, e.g. alkyl methylphosphonic acids (the degradation
product of nerve agents) and thiodiglycol (the degradation
product of sulfur mustard), derivatives of higher volatility
and thermal stability must be formed. Chemical conversion
of analytes is also used to reduce reactivity (the most
important example is lewisite) or reactivity and volatility
(e.g. phosgene and perfluoroisobutylene - PFIB). Derivati-
zation is often used at least to enhance selectivity and/or
sensitivity of detection (e.g. chemical conversion of lewisite
with thiol reagents considerably increases selectivity and
Solid Phase Microextraction Combined with Gas Chromatography
sensitivity when sulfur-selective flame photometric detection
(FPD) is applied). Another example is the conversion of
phosphonic acids and thiodiglycol to perfluorinated deri-
vatives for their selective detection by negative ion chemical
ionization mass spectrometry (NICI-MS). The problems of
derivatization in determination of CWAs have been compre-
hensively reviewed [13].
Sample preparation for the gas chromatographic CWA
determination is generally based on isolation and enrichment
of analytes; most often, in this process the original matrix is
exchanged for a secondary matrix which is compatible with
GC. The extraction techniques successfully used for this
purpose include solvent extraction (liquid-liquid extraction -
LLE, or solid-liquid extraction - SLE), solid phase extraction
(SPE), gas extraction (static headspace and dynamic purge
and trap), and solid phase microextraction (SPME).
SPME PRINCIPLES
Solid phase microextraction is a simple, rapid, inex-
pensive and versatile solvent-free extraction technique,
which combines sampling, extraction, and concentration into
a single step. The analytes isolated are introduced into a GC
column with the same device that is used for sampling. With
this technique, complicated sample preparation procedures,
many potential sources of error, and harmful solvents are
eliminated. It is not surprising then that SPME has found
wide acceptance in the analytical area with practical
applications ranging from environmental [27-29] to food
[30] and to biological [31] matrices, including body fluids
[32].
Solid phase microextraction was first described by
Pawliszyn in 1990 as a versatile concentration/sampling pro-
cedure [33], whose concept emerged from research on laser
desorption/fast chromatography [34]. In SPME, a fused silica
fiber is incorporated into a microsyringe in such a way that it
can be withdrawn into or pushed out of a syringe needle
[33]. This enables introducing the fiber into the GC injector
in a convenient and safe way, simply by piercing the GC
sealing septum. A typical commercially available SPME
device manufactured by Supelco is shown in Fig. (1).
In the device, a fused silica fiber coated with an
extracting medium is attached to a stainless steel plunger and
installed in a special holder, which is equipped with an
adjustable depth gauge [35]. This is important because the
fiber can be easily broken when it hits any obstacle while an
adjustable depth gauge controls in a repeatable way how far
the needle of the SMPE device penetrates a sample or in-
jector.
GC procedures for the determination of selected analytes
based on SPME sample preparation are quite simple and,
importantly, GC instrument modification is not needed. The
successive steps of analysis involving direct immersion (DI)
SPME sampling are presented in Fig. (2). Fig. (2a) shows
the extraction procedure and Fig. (2b) the desorption of
analytes in the GC injector. For analyte extraction, an SPME
fiber coated with a thin sorbent film is exposed to a sample
for a pre-determined period of time, during which the
analytes partition into the coating on the fiber pushed out of
the needle. After the sorption, the fiber is withdrawn into the
syringe needle and introduced into the injector of the gas
chromatograph, then pushed out of the needle and exposed
Current Organic Chemistry, 2007, Vol. 11, No. 3 243
Fig. (1). Manual holder for solid phase microextraction:
1. Plunger; 2. Barrel; 3. Plunger retaining screw; 4. Z-slot; 5. Hub-
Viewing window; 6. Adjustable depth gauge; 7. Septum piercing
needle; 8. Fiber attachment tubing; 9. Coated fused silica fiber. The
drawing is based on the commercial SPME device made by
Supelco.
for a given period of time; the analytes are thermally
desorbed and transferred by a stream of carrier gas into a GC
column for separation. In SPME-HPLC, analytes are
liberated from the fiber by solvent desorption in a special
interface [36].
SPME with the extracting medium (fiber coating, station-
nary phase) coated on the fiber is used most often, but it is
not the sole mode of SPME. In a different mode, called in-
tube SPME, the sorption material is coated onto the internal
surface of a capillary tube [36]. This mode enables auto-
mation of SPME-HPLC hyphenated systems and consider-
ably extends the application range of SPME [37, 38]. Until
now, many SPME devices have been designed and con-
structed to cope with different analytical problems, e.g.
SPME devices for breath analysis, and for field applications,
or a gas-tight device whereby SPME sampling of analytes
from the headspace (HS) is combined with the sampling of
HS itself [36, 39]. Some SPME sampling designs allow
passive sampling to determine time-weighted average
concentrations [36, 40].
THEORETICAL CONSIDERATIONS
The most frequently used SPME approach is the one
where the fiber is kept in the medium investigated until
equilibrium is reached [41]. In this case, the amount
extracted can be directly related to the initial concentration
of an analyte in a sample (the value looked for) on the basis
of the thermodynamics of the process; this was described in
numerous publications [36, 40, 42, 43].
In the direct immersion mode, the amount of the analyte
extracted into the coating (number of moles) is expressed by
Eq. 1.
244 Current Organic Chemistry, 2007, Vol. 11, No. 3
Fig. (2). Direct immersion solid phase microextraction from liquid sample:
a) Procedure for extraction of analytes: 1. Piercing septum; 2. Fiber exposure (extraction); 3. Fiber retraction and needle removal.
b) Desorption in GC injector: 1. Needle introduction into GC injector; 2. Fiber pushing out of needle (desorption of analytes); 3. Fiber
retraction and needle pushing out of injector.
K fs V f C0Vs
n= (Eq. 1)
K fs V f + Vs
In Eq. 1, Kfs is the stationary phase/sample matrix
distribution constant, Vf is the stationary phase (coating)
volume, Vs is the sample volume, and C0 is the initial analyte
concentration in the sample. This equation is valid for a
homogeneous liquid coating when no headspace is present in
the system. As follows from Eq. 1, in calibration experi-
ments standard solutions of the same volume should be used
to obtain a linear relation between the amount extracted and
the initial concentration C0. If the sample volume is very
large (Vs>> Kfs Vf), the amount extracted does not depend on
the sample volume and Eq. 1 can be simplified to Eq. 2.
n = K fs V f C0 (Eq. 2)
Eq. 2 reveals that analytes can be sampled directly from a
water body or from the atmosphere in the field and the
calibration performed using a different volume of a standard
solution provided that the volume is also much larger than
the product Kfs Vf.
When analytes are sampled from the headspace above a
liquid sample into a liquid coating, a three-phase system
must be considered. The amount of the analyte extracted can
be related to the initial concentration C0 (quantity looked for)
according to Eq. 3:
K fs V f C0Vs
n= (Eq. 3)
K fs V f + K hs Vh + Vs
Khs and Vh are the headspace/sample distribution constant
for an analyte of interest and the headspace volume,
respectively. The relation is valid irrespective of location of
the fiber in the system (headspace or liquid sample).
Zygmunt et al.
The extraction kinetics depends on many parameters,
such as coating type and thickness, analyte, composition and
volume of a sample, temperature as well as the manner and
rate of agitation; this problem has been described in detail in
a number of publications [36, 42, 44, 45]. For perfect
agitation, when the stationary layer of the solution extracted
on the fiber coating can be neglected, the equilibration time
te, defined as the time (t95%) required to extract 95% of the
equilibrium amount, can be calculated from the fiber
dimensions (fused silica fiber radius and thickness of the
coating) and the diffusion coefficient of the analyte in the
fiber coating.
Under practical agitation conditions, a stationary layer
with the thickness dependent on the manner of agitation is
formed on the fiber. The thickness of this layer and the
analyte diffusion coefficient in the sample matrix must be
taken into account [36, 42, 46, 47].
SELECTION OF SPME OPERATING PARAMETERS
The effectiveness of analyte transfer from the medium
studied to the GC column for the separation and detection
using SPME depends on a number of parameters, including:
the mode of extraction, type and size of fiber coating, sample
volume, agitation, temperature and time of extraction, salting
out, pH, manner of desorption of the analytes from the fiber
and the derivatization process if applied [48].
Fiber
The amount of the analyte extracted, and hence the
sensitivity of SPME, depends primarily on the value of the
distribution constant of the analyte partitioned between the
sample and the stationary phase coated on the fiber [Kfs] and
the amount of stationary phase (Vf) or its film thickness. A
thicker coating results in a higher sensitivity, but also in a
longer equilibration time, so that the fiber selection is often a
Solid Phase Microextraction Combined with Gas Chromatography Current Organic Chemistry, 2007, Vol. 11, No. 3 245

Table 2. Basic SPME fibers commercially available from Supelco (Based on papers 28,30,31,42)

Max. Conditioning
Stationary phase
Target analyte working Polarity
(fiber coating)
temperature Temp. [˚C] Time [h]

Polydimethylsiloxane PDMS Volatile

100
m/non-bonded Nonpolar semivolatile 280 250 1
Nonpolar
30
m/non-bonded Moderately polar to nonpolar 280 250 1
7
m/bonded semivolatiles 340 320 2-4
Polyacrylate
Polar semivolatiles 320 Polar 300 2
PA
Polydimethylsiloxane/
Divinylbenzene Polar volatiles 270 Semipolar 260 0,5
PDMS/DVB
Polydimethylsiloxane/ Carboxen
Polar semivolatiles 320 Semipolar 280 0,5
PDMS/CAR
Carbowax/
Divinylbenzene Polar 265 Semipolar 250 0,5
CW/DVB
Carbowax/Templated Resin Surfactans
- - - -
CW/TPR (for HPLC only)
Polydimethylsiloxane/
Divinylbenzene/ Carboxen Polar 270 Polar 270 4
PDMS/DVB/CAR

compromise between sensitivity and extraction time. There-
fore, it is important to select an appropriate fiber (type of
coating and its thickness) for a given analytical task. For a
given analyte, sample matrix and temperature, the parameter
Kfs is determined by the sorbent coated on the fiber. Con-
ventional sorbents for SPME include two types of extraction
media: homogeneous polymers and composite extraction
media composed of porous solid particles of some substance
dispersed in a cross-linked liquid polymer of some other
substance [49]. A range of SPME fibers coated with both
types of sorbents are commercially available (Table 2). Poly-
dimethylsiloxane (PDMS) and polyacrylate (PA) are homo-
geneous polymeric SPME coatings. PDMS is most widely
used in SPME: 7 μm thick coating is cross-linked while 30
and 100 μm are not, and due to this, they are characterized
by a lower maximum working temperature and lower solvent
stability, but higher extraction efficiency. Thin cross-linked
PDMS coatings are used for higher boiling analytes,
characterized by larger Kfs values, since equilibration will be
faster and thermal desorption in the GC injector more
efficient (reduced carryover) because higher temperatures
can be applied. Volatile analytes have higher diffusion
coefficients and thicker coatings can be selected to increase
the extraction efficiency. PDMS is nonpolar and therefore
best suited to extract nonpolar analytes. It is also quite often
used for moderately polar analytes. The commercially
available PA fiber is partially cross-linked and characterized
by maximum working temperature which is intermediate
between those for thick and thin PDMS fibers.
PA is highly polar and finds use in the extraction of polar
analytes. This is in agreement with the general rule that “like
dissolves like”, which suggests that polar fibers should be
selected for the extraction of polar compounds, while
nonpolar coatings should be used for nonpolar analytes. To
fill the gap between polarity of PDMS and PA, ethoxypoly-
dimethylsiloxane was proposed as a fiber coating [50], which
is also presumably homogeneous. It was used successfully to
isolate volatile monoaromatic hydrocarbons. Some other
experimental coatings proposed include polyethylene glycol
(PEG)-based coatings (Carbowax 20 M) for polar molecules
[51-54] or Nafion to isolate polar molecules from nonpolar
matrices [55].
Composite coatings consist of two different materials: a
liquid polymer (PDMS, CW) and a solid polymer (DVB,
CAR, TPR) and can be applied to more volatile analytes due
to addition of adsorption process to solution in liquid
polymer; their selectivity can be adjusted to some extent.
However, they are characterized by lower mechanical sta-
bility, longer extraction times and narrower linear range.
Typical composite coating fibers commercially available are
listed in Table 2.
To extend applicability of SPME, new polymeric
materials of improved selectivity, sensitivity, thermal resis-
tance and solvent stability were prepared and investigated
[56]. Molecularly imprinted polymers are characterized by
high selectivity or even specificity. Introduction of poly-
pyrrole-based coatings by Pawliszyn and co-workers [57-61]
greatly extends the use of SPME, especially in the areas of
polar and ionic analytes and in coupling of SPME to liquid
phase separation techniques. Though held by physical forces,
they have quite good stability due to poor solubility. They
246 Current Organic Chemistry, 2007, Vol. 11, No. 3
are characterized by high stability in a wide range of pH
(1.5-10), low affinity to nonpolar solvents and increased
resistance to organic solvents and can also be used to extract
polar analytes from nonpolar matrices (methanol, ethanol, 2-
propanol from hexane) [59].
Sol-gel polymeric media [62-66] are surface-bonded
organic-inorganic hybrid coatings characterized by high
thermal (PDMS: 340-360oC) and solvent stability and hence
longer life-times. Consequently, more complete desorption
and improved precision can also be obtained for higher
boiling analytes. Attempts were also made to prepare
coatings using carbon-based materials [67, 68] or reverse
phase HPLC particles [69-70].
Until now, a limited number of SPME coating types have
been used in CWAs determination by gas chromatography
but with the progress in new coating technologies perhaps
attempts will be undertaken to produce individual CWA-
dedicated coatings.
SPME-GC was used for the field determination of an
important CWA, O-ethyl-S-(2-diisopropylaminoethyl)
methylphosphonothiolate (VX) [71]. A number of com-
mercial fibers were studied and those coated with PDMS
(100 μm), PA (85 μm), CW (Carbowax)/DVB (65 μm) and
PDMS/DVB (65 μm) were found to give statistically the
same response while PDMS/CAR (65 μm) provided statis-
tically lower sensitivity. PDMS was selected since, apart
from relatively high sensitivity, it showed good durability.
SPME extraction was performed at 50oC from the HS of
polluted clothing material.
Experiments were performed with the same coatings to
isolate and enrich a VX degradation product, bis(diiso-
propylaminoethyl)disulfide [10]. In the case of PDMS/CAR,
the response was about 3 times lower which, in our opinion,
was caused by poor desorption rather than low extraction
efficiency. Although PDMS, PA and CW/DWB provided the
highest sensitivity and statistically indistinguishable peak
areas, the authors selected the PDMS fiber because it gave
good sensitivity and was shown to be optimal for field
sampling and analysis of intact VX [71].
A PDMS fiber (100 μm) was used in the determination of
non-volatile 2-chlorovinylarsonous acid (CVAA), which is
formed upon rapid hydrolysis of lewisite, in humane urine
after derivatization with 1,3-propanedithiol (PDT) [6]. Again
ruggedness and reliability of PDMS, compared with other
fibers, were important features considered in the selection. In
fact, the authors based their choice on earlier works [7, 72]
where a PDMS fiber was used for the extraction of CVAA
[72] and CVAO (syn.2-chlorovinyl arsenious oxide) deri-
vatives obtained in the reaction of CVAA or CVAO analytes
with PDT or with EDT (1,2-ethanedithiol). Three fibers were
examined: PDMS (100 μm), PA, and CW/DVB [72]. With
PDMS, the response was 10% higher and 40% lower than
with CW/DVB and PA, respectively; PDMS was selected
because of ruggedness and reliability. Similar observations
were made for PDT derivatives of dimethylarsenic acid
(DMA) and phenylarsonic acid (PhAs). Reliable extractions
were obtained with individual PDMS fibers for at least 250
cycles of extraction and desorption for PDT derivatives of
CVAO and phenylarsine oxide (PhAsO) [7]. Though lower
sensitivity was obtained with a 7 μm PDMS fiber, its use
was advised at higher concentrations of derivatized CVAO.
Zygmunt et al.
Applicability of five commercial SPME fibers, i.e.
PDMS (100 μm), PA, CW/DVB, PDMS/DVB and
PDMS/CAR, for the isolation of bis(2-chloroethyl) sulfide
(sulfur mustard) was studied [2]. With the use of polar PA
and composite CW/DVB fibers, SPME-GC responses were
not different from each other at a statistically significant
level and were higher than with the other fibers studied when
sampling from gas standard mixtures of sulfur mustard.
However, when the analyte was extracted from the
headspace of wet soil, the corresponding peak area with
CW/DVB was only 48% of that with PA. The authors
concluded that the decrease in sensitivity was caused by a
negative effect of water on the extraction to CW/DVB.
Consequently, polar PA polymeric coating was selected for
the analysis of agricultural soil spiked with sulfur mustard.
In the determination of airborne sarin, a composite
PDMS/DVB fiber coating proved appropriate for SPME
sampling and injection into GC [25]. When a portable GC-
MS system was used for the determination of sarin extracted
to the PDMS/DVB coating with the use of a rapid portable
dynamic air sampler (PDMS)-SPME system, a sarin peak
with a 3:1 noise ratio was obtained at a concentration of 0.10
mg m-3, which is half the value immediately dangerous to
life and health.
A PDMS/DVB coating was also applied for sampling
sarin from air and water with the use of an SPME field
sampler [73]. Sarin degrades rapidly in water so it is very
important to sample it from this matrix on site. The method
based on SPME field sampling is best suited as a semi-
quantitative screening method in response to potential emer-
gencies in which quick positive identification is required.
Four different types of SPME fibers were evaluated for
the isolation of nerve agents (sarin, soman, tabun, VX) from
natural waters [8]. CW/DVB was discarded at an early stage
since it showed extremely low uptake of nerve agents. Of the
remaining three, i.e. PDMS (100 μm), PA, and PDMS/DVB,
the greatest responses for all the agents studied were
obtained for PDMS/DVB for an extraction time of 50 min.
A method was developed for the determination of degra-
dation products of CWAs in water, based on SPME of
volatile tert.-butyldimethylsilyl derivatives formed in-situ
[74]. The compounds studied were ethyl-2-hydroxyethyl
sulfide (EHES) and thiodiglycol (TDG), which represent
sulfur mustard degradation products; and ethyl methyl-
phosphonic acid (EMPA), methylphosphonic acid (MPA), n-
propylphosphonic acid nPPA), being degradation products of
nerve agents and also benzylic acid (BA), a degradation
product of 3-quinuclidinyl benzilate (BZ). The fibers used in
the study were coated with PDMS (100 μm), PA,
PDMS/DVB and PDMS/CAR. The PDMS/CAR fibers were
found to be most efficient for all the compounds except for
TDG, which was better extracted with PDMS/DVB. The
PDMS/CAR fiber was found to be more rugged and with-
standing more extraction/injection cycles.
The PDMS/CAR fiber was found to be appropriate for
passive sampling of HCN gas from the atmosphere after high
temperature dispersion of CS riot control agent [75].
When a given analyte is to be determined at a low
concentration in a sample of very complex matrix, which is
often the case for nerve agents, then selective fiber coatings
can be necessary for SPME sampling. A novel stationary
Solid Phase Microextraction Combined with Gas Chromatography
Fig. (3). Three basic modes of SPME extraction: 1) Direct immersion; 2) Extraction from headspace; 3) Protective membrane SPME.
phase, BSP3, for the SPME sampling of airborne sarin was
evaluated [11]. The polymer BSP3 consists of acidic
hexafluorobisphenol groups, alternating with oligo(dimethyl-
siloxane) segments. Determination of selectivity was based
on the retention factors (k) determined by gas chromato-
graphy using these coatings as stationary phases (two
batches of phenol-based polymers, BSP3 and BSP3 (b) and
PDMS (OV-1)). It was found that BSP3 and BSP3(b) have
20-fold higher affinity towards sarin than PDMS and at least
twice lower affinity toward n-tridecane and n-tetradecane,
thus ensuring much higher selectivity. However, a BSP3
coated fiber has relatively low thermal stability. According
to the authors, application of this fiber in combination with
fast GC can provide a good tool for an almost real-time
determination of sarin.
Extraction Mode
Two basic extraction modes are: direct sampling from a
gas or liquid medium and sampling from the headspace (HS)
of a liquid or solid sample. Mode selection depends on the
nature of sample matrix, analyte volatility and its affinity to
the matrix. For clean liquid matrices, the analytes can be
sampled by both direct immersion of the fiber in a sample or
exposing it to HS if the analytes are sufficiently volatile. In
fact, the HS mode is preferred for the analytes with large Khs
values since a large fraction of the analytes is in the gas
phase, where the analyte diffusion coefficients are much
greater than in liquids and equilibration is faster. Diffusion
coefficients can be increased by raising the temperature;
however, this can result in lower sensitivity. For dirty liquid
samples, especially those with a high content of solids, high
molecular organics, surfactants, etc., and for solid matrices,
HS sampling should be used, provided that analytes are
relatively volatile. HS sampling has an additional advantage
that restrictions on matrix modification are smaller, which
can help lower the analyte solubility in water and, in this
way, improve sensitivity. For analytes of low volatility
present in dirty samples, semi-permeable membrane pro-
Current Organic Chemistry, 2007, Vol. 11, No. 3 247
tected sampling is recommended. The three modes of oper-
ation mentioned above are shown schematically in Fig. (3)
[76].
Extraction Temperature
Temperature affects the extraction efficiency in a number
of ways. In DI sampling, an increase in temperature lowers
the distribution constant, Kfs and hence decreases the sen-
sitivity. However, at the same time extraction rate can
increase and equilibration can be faster. If sensitivity is not
the limiting factor, then an increased temperature is recom-
mended provided that it does not lead to analyte loss. In
sampling from HS, an increase in temperature raises the
fraction of analyte in the HS (higher Khs), but decreases the
Kfs values and therefore each system should be optimized
individually. This is very critical when solid samples, whose
matrix has a high affinity to the analytes, are to be analyzed.
An ingenious solution to this problem was proposed [77]. It
was based on heating the sample and cooling the fiber, but it
has not found wide application, possibly due to technical
problems. When in-fiber derivatization is applied, then an
additional parameter, i.e. derivatization yield, determining
temperature selection, is introduced. Quite often room
temperature is used, especially in the case of DI, such as in
the extraction of nerve agents (sarin, soman, tabun, VX) [8].
EDT and PDT derivatives of CVAA, DMA, and PhAs were
sampled directly from aqueous solutions, where derivati-
zation proceeded at room temperature [7, 72]. Sarin from
water was sampled at 19 oC immediately after its addition,
since it degrades rapidly in water. A HS-SPME sampling
temperature of 70 o C was found to be optimal for the PDT
derivatives of CVAA and PhAs in urine [6]. The peak areas
of (DES)2, when sampling it from soil spiked with VX and
treated with a decontamination solution at 50, 75 and 100 oC,
were found not to be statistically different, and a temperature
of 100 oC was selected for sampling [10]. The temperature of
VX sampling from the HS above contaminated clothing
material was optimized by measuring peak areas at 25, 50,
248 Current Organic Chemistry, 2007, Vol. 11, No. 3 Zygmunt et al.

Table 3. Characteristics of agitation methods applied in SPME extraction [42]

Method Advantages Disadvantages

limited to volatile analytes and headspace

Static (no agitation) simple, performs well for gaseous samples
SPME
Magnetic stirring common equipment, good performance requires stirring bar in the vial
Intrusive stirring very good performance sealing the sample vial difficult

good performance, no need for stirring bar in

Vortex/moving vial stress on needle and fiber
vial
good performance, no need for stirring bar in stress on needle and fiber, limited to small
Fibre movement
vial sample volumes
potential for cross contamination, requires
Flow through good agitation at rapid flows
constant flow
Sonication very short extraction times noise, heating of sample

75, and 100 oC [71]. The highest sensitivity was obtained at
50 oC and 75 o C; 50 oC was selected for sampling.
Extraction Time and Agitation
The extraction of analytes into the fiber coating is not
instantaneous and some time is needed for the analytes to
reach the fiber and to disperse within the fiber coating. The
amount extracted increases until equilibrium is reached and
then remains constant, if there are no processes leading to
analyte loss. This is the best approach to SPME analysis for
two reasons: it assures the highest sensitivity and the changes
of extraction conditions (agitation, time, etc.) have the lowest
effect on the amount extracted. The time required to extract
the analyte amount equal, within an experimental error, to
the amount present in the coating at equilibrium, is defined
as the equilibration time. In sampling from the gaseous
phase, equilibration is quite fast. In HS sampling two pro-
cesses should be considered: transport of analytes from the
HS to the fiber and from the condensed phase (liquid, solid)
to the HS. If the capacity of HS (KhsVh) is about 20 times
larger than the capacity of the fiber (KfsVf), i.e. 95% of the
equilibrium amount assumed, then the extraction is very
rapid, since a decrease in the analyte concentration in the
system is negligible during extraction [42]. This is true if the
equilibrium between the HS and the sample was reached
prior to SPME sampling.
The equilibration rate can be increased by temperature
increase and by fast agitation to raise the rate of transport of
the analytes to the condensed phase-gas phase interface (HS
case) or to the surface of the fiber coating in the liquid.
Different agitation methods can be applied in SPME
sampling; they were discussed in detail in a number of
papers [36, 42, 44]. They are listed and characterized in
Table 3 [42].
For some systems, equilibration takes a long time (small
diffusion coefficients, presence of some analyte binding
components in the sample matrix, poor agitation, etc.); this
lengthens the analysis time and increases the opportunity to
lose analytes via adsorption, evaporation, microbial degra-
dation, etc. If this is the case and, at the same time,
sensitivity (the amount of the analyte extracted to the fiber)
is not a limiting factor for a given analytical task, then
extraction can be interrupted before equilibrium is reached.
This approach can yield reliable data provided that the
extraction conditions are closely controlled (agitation, extra-
ction time, temperature, etc.) during analysis and calibration
[45].
The extraction time for a given system is usually
determined experimentally by plotting the amount extracted
(system response) vs. extraction time. An example of the
extraction - time profiles for aliphatic amines from the air is
given in Fig. (4). For the extraction times corresponding to
the plateau, it could be assumed that the equilibrium was
reached.
In the CWAs analysis making use of SPME, sampling
under both equilibrium and non-equilibrium conditions was
applied. It is often a compromise between time of analysis
and sensitivity and reproducibility of the results produced. If
several analytes are to be determined at the same time, which
is often the case, an extraction time can be selected which
corresponds to equilibration time for some analytes and to
non-equilibrium conditions for the others. When determining
CWAs degradation products in water after conversion to
volatile derivatives, much lower reproducibility was ob-
served for those analytes which were sampled under non-
equilibrium conditions (30 min extraction time). For BA,
which was sampled under equilibrium conditions, a standard
deviation was 10-11% at 1-20 ppm concentration, while for
the remaining five sampled under non-equilibrium con-
ditions, it ranged from 12 to 35%, depending on the
steepness of the curve at the extraction time selected [74].
For nerve agent precursors or degradation products of
dimethyl methylphosphonate, diisopropyl methylphos-
phonate, and diethyl methylphosphonate in sandy loam clean
soil sampled from the HS on a PDMS (100
m) fiber,
equilibrium was reached in 10 min [5, 6].
However, it was demonstrated that, for the PDT deri-
vative of CVAO, equilibration was reached within approxi-
mately 20 min, while for the same derivative of PhAs,
equilibrium was not achieved even after 40 min [7]. As a
result, the sampling time had to be carefully monitored to
ensure reproducible results. A steady state signal was
Solid Phase Microextraction Combined with Gas Chromatography
Fig. (4). Extraction – time profiles for selected volatile amines on PDMS/DVB fiber:
- trimethylamine.
achieved after 10 min for the EDT derivative of CVAA
sampled from the HS of acidic aqueous solution on the same
fiber [72]. A degradation product of VX, (DES)2, has rather
low volatility and even when sampled on the 100 μm PDMS
fiber at 100oC, requires a 20 min equilibration time [10]. It
was shown that for a 10 min extraction time, the peak areas
were much lower.
For VX sampled from the HS over clothing material on a
100 μm PDMS fiber at 50oC, equilibrium was not reached
even after 60 min [71]. This is probably due to an extended
time needed to liberate the analytes from the clothing
material to the HS.
For sampling CWA, bis(2-chloroethyl) sulfide from the
HS over wet soil on a PA fiber at room temperature, 20 min
time was sufficient for reaching equilibrium [11]. The
studies on the kinetics of HS sampling of sarin on a BSP3
fiber in glassy polymer composition showed that even after
120 min time equilibrium was not reached. The same was
observed for n-tetradecane. This is probably caused by small
diffusion coefficients of analytes in the coating of glassy
nature.
In the case of sampling of volatile analytes, such as
HCN, from the air matrix on a PDMS/CAR fiber, 2 min
extraction was used [78]. Sampling sarin from air on a
PDMS/DVB fiber, the plateau on the plot of the amount of
sarin detected vs. the collection time was observed after 10
min, and only 60% of the equilibrium amount was extracted
within 2 min; this confirms that not only the matrix but also
the analyte (the higher the molecular mass the lower the
diffusion coefficient) can have a noticeable effect on the
equilibration time [73].
Matrix Modification
Matrix composition can have a considerable influence on
the analyte amount extracted to the fiber in DI and HS
Current Organic Chemistry, 2007, Vol. 11, No. 3 249
dimethylamine - triethylamine
sampling due to possible interaction of matrix components
with analytes of interest (forming complexes with some
components, e.g. humic matter in water, adsorption on
colloidal solid particles, etc.) and changing the form of
analytes (ionic or non-ionic form). The matrix can also
change to some extent the characteristics of fiber coating.
Extraction efficiency can be improved by matrix modi-
fication. A common approach is adjusting pH to convert
acids or bases to their neutral forms and salting out to
decrease the solubility of neutral forms of substances. In DI
sampling, care should be taken to select matrix modifiers
which do not have negative effects on fiber coatings.
By acidifying and saturating a solution with NaCl, a great
improvement in the extraction yield was observed for CWA
degradation products, such as MPA, MPPA, BA, EMPA,
nPPA, and TGA [74]. The addition of NaCl and lowering the
pH from neutral to 1.5 resulted in the amount extracted being
increased by about 3.8 to 7.6 times for MPA, MPPA, BA
and EMPA.
The distribution constants, Kfs for CVAA-EDT were
found to increase by a factor of two by the addition of
inorganic salts [72]. By saturation of solutions, the enrich-
ment factors for a PDMS/DVB fiber for sarin, soman, tabun
and VX were greatly increased: from 53 to 163, 522 to
>2000, 60 to 600, and >3 to >260, respectively [8].
The above data demonstarte that by appropriate matrix
modification, the extraction efficiency and hence sensitivity
of many CWA analytes in water samples or aqueous extracts
can be greatly improved and this must be considered when
developing an analytical procedure.
Sample Volume
For a given extraction system (fiber type and size,
temperature, matrix, etc.), the amount of analyte extracted is
the largest if an initial analyte concentration and its
250 Current Organic Chemistry, 2007, Vol. 11, No. 3 Zygmunt et al.

concentration after equilibration are the same, i.e. the sample
is infinitely large. In practice, it means that the difference
between the amount which can be actually extracted and the
amount for the infinite sample is lower than the experimental
error. For a two-phase system, the minimal sample volume
(Vs) assuring maximum efficiency of extraction, can be
calculated from the following formula [36, 42]:
100K fs V f
Vs =
E low-volume liner to assure high linear velocity of the carrier
E is a relative error (often assumed to be 5%), Kfs is the
analyte distribution constant between the fiber and the
sample and Vf is the coating volume (100 μm PDMS film –
0.65 μL, 30 μm – 0.14 μL, 7 μm – 0.028 μL). For 5% error,
the minimal volume Vs should be equal to Vs = 20 KfsVf.
Thus, the effect of sample volume on the amount extracted
increases with the distribution constant. For a three-phase
system (HS included), the combination of Kfs and Khs
determines the magnitude of sample volume effect on the
amount extracted to the fiber [42].
If the limit of detection (LOD) is not the limiting factor
or it can be lowered by other means, then the sample volume
does not have to be optimized from the sensitivity point of
view, but care must be taken to apply the same sample
volume at calibration and analysis steps. In the papers des-
cribing the determination of CWAs, their precursors and
degradation products by means of SPME-GC, the issue of
sample volume was not discussed.
Table 4. Published application of SPME-GC in determination of CWAs
Analyte Desorption from SPME Fibers
Liberation of analytes from a SPME fiber and their
introduction into GC is carried out by thermal desorption in
the GC injector, which can be heated to a temperature
depending on the analyte, up to a maximum operating
temperature of the fiber coating. A split/splitless injector in
the splitless mode is used most often, but programmed tem-
perature vaporization and a septum-equipped programmable
injector can also be employed. The first injector requires a
(Eq. 4.)
gas to carry the desorbed analytes into a chromatographic
column. The desorption temperature should be high enough
to minimize carryover, but at the same time only as high as
necessary to minimize bleeding and maximize the fiber
lifetime. The bands of desorbed analytes are generally too
wide and refocusing is recommended with the use of a thick
film column, cryofocusing or at least starting the separation
program at a low temperature. Quite recently, the sample
transfer efficiency for SPME fiber injection has been shown
to be affected by the cross-sectional area of the space
between the column and the liner, the carrier gas flow rate,
and the column inside the liner [79].
Among CWAs and their degradation products which are
to be determined are compounds of both low and high
volatility, and the derivatives formed, if necessary, can be of
different volatility, too. Thus, various desorption tem-
peratures were used in their determination. The desorption
conditions for specific groups of CWAs, their degradation
products and derivatives, if produced, are compiled in Table
4.

Fibre coating Extraction and Final analysis,

Matrix Target analyte Ref.
Derivatizing agent desorption conditions*) LOD **)

PA 85
m, Te=25 ˚C, te=30 min GC-MS

Soil Sulfur mustard H, HD 2
CW/DVB 65
m Td=250 ˚C, td=2 min 237 ng g -1

Te=100 ˚C, te=30 min GC–MS

Soil PDMS 100
m, 10
(DES)2 Td=250 ˚C , td=2 min 1
g -1

GC-FPD
Td=250 °C from 0.14 to 0.30
g
PDMS 100
m
Soil Degradation products of lewisite: CVAO g -1
7
CVAA, CVAO
PDT GC-MS
Td=225˚C, te=20 min
0.066
g CVAO g -1

GC-MS
Hydrolysis degradation products of
1
g dm-3 for BA
sulfur mustard: EHES, TDG;
Water PDMS/CAR 75
m 10
g dm-3 for MPA and
Degradation products of nerve Te = 25˚C, te = 15 min,
nPPA 74
agents - EMPA, MPA, nPPA; Td=250˚C
MTBSTFA and 1% TBDMSCl 100
g dm-3 for EMPA
Precursor and a degradation product
and EHES,
of BZ- benzilic acid BA.
and 200
g dm-3 for TDG

te=5 min, Te=19˚C GC-MS

Air
Td=250˚C 100
g m-3
Sarin GB PDMS/DVB 65
m 73
te=5 min, Te= ambient GC-MS
Water
temp., Td=250˚C 12 mg dm-3
Solid Phase Microextraction Combined with Gas Chromatography Current Organic Chemistry, 2007, Vol. 11, No. 3 251

Table 4. Contd….

Fibre coating Extraction and Final analysis,

Matrix Target analyte Ref.
Derivatizing agent desorption conditions*) LOD **)

GC-MS
0.5
g dm-3 for VX
Sarin GB te=30min, 0.05
g dm-3 for GB, GD,
Water: PA 85
m
Soman GD Te= room temperature GA
sea, river, tap, PDMS 100
m 8
Tabun GA td=1 min GC-NPD
sewage. PDMS/DVB 65
m
VX Td=200˚C 1
g dm-3 for VX
0.05
g dm-3 for GB, GD,
GA

BSP3 – hydrogen bonding

acidic hexafluoro-bisphenol Te–room temp., te=20 min,
Sarin GB GC-FID
Hexane extract groups, alternating with td=4 min, Td=250˚C 11
oligo(dimethylsiloxane) not determined
segments; 12-13
m

PDAS-SPME (portable
dynamic air sampler)
Static SPME: 60 s3,
GC-MS
Air Sarin GB PDMS/DVB 65
m Dynamic SPME: 30 s2, 25
0.10 mg m-3
Average flow rate: 2,16
dm3/min
Td=175˚C
Td=200˚C GC-MS
te=2 min identification
Air Hydrogen cyanide CAR/PDMS 85
m 75
Td= 225˚C GC-NPD
te=2 min about 5 mg m-3
te=1h
Water, GC-MS
PDMS 100
m Te=room temperature
soil, CVAA 2
g dm-3 in aqueous 72
EDT td=5min
sediment. solution
Td=250˚C
PDMS 100
m te=10min, Te=70˚C, GC-MS
Human urine CVAA 6
PDT td=14 min, Td=270˚C 7.4 ng dm-3
te=5min, Te=50˚C GC-MS
Clothing material VX PDMS 100
m 71
td=2 min, Td=250˚C mg/sample
*) Te - extraction temperature, te – fibre exposition time, Td – desorption temperature, td – desorption time
**) LOD – limit of detection

CHARACTERISTICS OF SPME-GC PROCEDURES
OF CWA DETERMINATION
Table 4 presents the published applications of SPME
combined with GC. The table reveals that SPME was used in
numerous cases to collect samples of air [25, 73], water [6,
8, 72, 74] and soil [2, 5, 6, 7, 10, 72] and some other
materials, such as, e.g. clothing material [71] for gas
chromatographic determination of CWAs, their precursors
and degradation products. The analytes were sampled from
air or aqueous matrices and from the headspace above liquid
or solid matrices. In many cases, the analytes of interest had
to be derivatized to render them amenable to GC analysis;
the derivatives were extracted to a fiber or they were formed
directly in the fiber coating with a derivatizing agent added
to the fiber before or after the analyte extraction.
SUMMARY
Gas chromatography is a method of choice for the
determination of chemical warfare agents, and their degra-
dation products in a variety of gas, liquid and solid matrices.
Some analytes can be determined in their free form, but
others are insufficiently volatile and thermally stable and
have to be converted to derivatives amenable to gas chro-
matography. Excluding very few cases, samples need pre-
paration before they can be introduced into a gas chromato-
graph for separation and detection. Solid phase micro-
extraction finds increasingly wide use in sample preparation
for GC; about 3000 papers have already been published
documenting its applicability in many areas of chemical
analysis. The advantages of SPME approach over traditional
sampling include: combining sampling, isolation and
enrichment into a single step; extraction device is used for
sample injection into GC with no need for chromatograph
modification; complete elimination of expensive and toxic
solvents; simplification of sampling procedure; reduction in
analysis time and cost; near real-time analysis; regeneration
of the fiber for immediate reuse; possibility of analyzing
semi-polar and nonpolar compounds in a variety of gas,
252 Current Organic Chemistry, 2007, Vol. 11, No. 3 Zygmunt et al.

liquid or solid samples; only small samples are required; HPLC = High performance liquid chromato-
amenability to automation; sampling in situ is possible; graphy
sample handling and preparation procedures are minimized; HS = Headspace
interfering solvent peaks are eliminated. The disadvantages Kfs = Stationary phase/sample matrix distri-
of SPME technique are relatively low recovery of analytes bution constant
and relatively low precision of determination; “one-shot”
Khs = Headspace/sample distribution constant
nature of analysis so collecting duplicate samples is recom-
for an analyte of interest
mended.
The technique has been increasingly often used to LLE = Liquid-liquid extraction
sample, enrich and inject CWAs into GC. Free analytes and MPA = Methylphosphonic acid
derivatives of some analytes were sampled directly form gas MS = Mass spectrometry
and aqueous samples and also from the headspace above MTBSTFA = N-Methyl-N-(tert.-butyldimethylsilyl)
liquid and solid samples. Attempts to perform derivatization trifluoroacetamide
directly in the fiber coating were also successful. Typical nPPA = n-Propylphosphonic acid
commercially available fibers proved applicable to the
NICI-MS = Negative ion chemical ionization mass
determination of CWAs. PDMS fibers of different film
spectrometry
thickness were used most often due to their durability and
stability. Development of new dedicated coating could OPCW = Organization for the Prohibition of
improve selectivity, which is very important when CWAs at Chemical Weapons
very low concentrations in complex matrices are to be PA = Polyacrylate
determined. For the analysis proper, GC coupled with MS PDMS = Polydimethylsiloxane
was most common, because MS gives an additional PDT = 1,3-Propanedithiol
dimension of qualitative information. Reliable identification PEG = Polyethylene glycol
is crucial since false negatives could lead to dangerous health
effects and false positives to useless spending money and PFIB = Perfluoroisobutylene
some legal problems. Moreover, MS can be used in selected PhAs = Phenylarsonic acid
ion monitoring mode, which can make MS selective with PhAsO = Phenylarsine oxide
respect to chosen substances. P&T = Purge and trap
In the applications published until now, whereby SPME SLE = Solid-liquid extraction
sample preparation was combined with GC separation and SPE = Solid phase extraction
selective detection, the limits of detection ranging from
SPME = Solid phase microextraction
single ppb to hundreds of ppb were achieved, depending on
the analyte, matrix and detection system. The number of t95% = Time required to extract 95% of the
applications is expected to noticeably increase. equilibrium amount
TBDMSCl = Tert-butyldimethylsilyl chloride
ABBREVIATIONS TDG = Thiodiglycol
AChE = Acetylcholinesterase TPR = Templated resin
BA = Benzylic acid Vh = Headspace volume
C0 = Initial concentration Vf = Stationary phase (fiber coating) volume
CAR = Carboxen Vs = Sample volume
CVAA = 2-Chlorovinylarsonous acid
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