Journal of Chromatography A, 1153 (2007) 130–144

Review

Sample preparation for the analysis of volatile

organic compounds in air and
water matrices
Kristof Demeestere, Jo Dewulf ∗ , Bavo De Witte, Herman Van Langenhove
Research Group EnVOC, Department of Organic Chemistry, Faculty of Bioscience Engineering,
Ghent University, Coupure Links 653, B-9000 Ghent, Belgium1
Available online 10 January 2007

Abstract
This review summarizes literature data from the past 5 years on new developments and/or applications of sample preparation methods for
analysis of volatile organic compounds (VOC), mainly in air and water matrices. Novel trends in the optimization and application of well-
established airborne VOC enrichment techniques are discussed, like the implementation of advanced cooling systems in cryogenic trapping and
miniaturization in adsorptive enrichment techniques. Next, focus is put on current tendencies in integrated sampling–extraction–sample introduction
methods such as solid phase microextraction (SPME) and novel in-needle trapping devices. Particular attention is paid to emerging membrane
extraction techniques such as membrane inlet mass spectrometry (MIMS) and membrane extraction with a sorbent interface (MESI). For VOC
enrichment out of water, recent evolutions in direct aqueous injection (DAI) and liquid–liquid extraction (LLE) are highlighted, with main focus on
miniaturized solvent extraction methods such as single drop microextraction (SDME) and liquid phase microextraction (LPME). Next, solvent-free
sorptive enrichment receives major attention, with particular interest for innovative techniques such as stir bar sorptive extraction (SBSE) and solid
phase dynamic extraction (SPDE). Finally, recent trends in membrane extraction are reviewed. Applications in both immersion and headspace
mode are discussed.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Volatile organic compounds; Air; Water; Analysis; Sample preparation; Extraction; Preconcentration; Sorption; Trapping

Abbreviations: AES, atomic emission spectroscopy; APCI, atmospheric pressure chemical ionization; BTEX, benzene, toluene, ethylbenzene, xylene; DAI,
direct aqueous injection; DLLME, dispersive liquid–liquid microextraction; DNPH, 2,4-dinitrophenylhydrazine; DVB, divinylbenzene; ECD, electron capture
detection; FID, flame ionisation detection; FIMS, fiber introduction mass spectrometry; GC, gas chromatography; GPE, gum phase extraction; HF, hollow fibre;
HPLC, high performance liquid chromatography; HS, headspace; HSSE, high capacity headspace sorptive extraction; IC, ion chromatography; INCAT, inside
needle capillary adsorption trapping; LGLME, liquid–gas–liquid microextraction; LLE, liquid–liquid extraction; LOD(s), limit(s) of detection; LPME, liquid
phase microextraction; LVI, large volume injection; MASE, membrane assisted solvent extraction; MESI, membrane extraction with a sorbent interface; MIMS,
membrane inlet mass spectrometry; MMLLE, microporous membrane liquid–liquid extraction; MS, mass spectrometry; NMVOC, non methane volatile organic
compounds; NT, needle trap; OTT, open tubular trapping; PDMS, polydimethylsiloxane; PLE, pressurized liquid extraction; PME, polymeric membrane extraction;
PT, purge-and-trapping; PTR, proton transfer reaction; PTV, programmed temperature vaporization; RSD, relative standard deviation; RTIL, room temperature
ionic liquids; SBSE, stir bar sorptive extraction; SDE, steam distillation extraction; SDME, single drop microextraction; SEP, sample enrichment probe; SHS,
static headspace sampling; SLM, supported liquid membrane extraction; SME, solvent microextraction; SPDE, solid phase dynamic extraction; SPE, solid phase
extraction; SPME, solid phase microextraction; ST, spray-and-trapping; STP, standard temperature and pressure; SWE, supercritical water extraction; TVOC, total
volatile organic compounds; UV-DOAS, ultraviolet differential absorption spectroscopy; UV–vis, ultraviolet–visible light spectroscopy; VOC, volatile organic
compounds
∗ Corresponding author. Tel.: +32 9 264 59 49; fax: +32 9 264 62 43.

E-mail address: Jo.Dewulf@UGent.be (J. Dewulf).

1 http://www.EnVOC.UGent.be.

0021-9673/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2007.01.012
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144 131

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
2. Sample preparation methods for VOC analysis in air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
2.1. Cryogenic sample preconcentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
2.2. Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
2.3. Airborne VOC enrichment on immobilized sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
2.3.1. Active and passive sample enrichment on solid adsorption badges and packed tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
2.3.2. Solid phase microextraction based techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
2.4. Membrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
3. Sample preparation methods for VOC analysis in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
3.1. Direct aqueous injection (DAI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.2. Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.3. Aqueous VOC enrichment on immersed immobilized sorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.4. Membrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.5. Headspace techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.5.1. Static headspace techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.5.2. Dynamic headspace techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

1. Introduction To gain knowledge on the occurrence, fate and behaviour

of VOC in all fields of interest, precise and accurate analyti-
Volatile organic compounds (VOC) are an issue of major cal techniques are necessary. In view of the physical–chemical
concern for many scientists worldwide, being active in different properties of these target compounds, most common analyti-
disciplines such as (i) food, flavour and fragrances, (ii) medical, cal methods include separation by gas chromatography (GC)
pharmaceutical and forensic sciences, and particularly (iii) envi- followed by on-line mass spectrometry (MS), flame ionisation
ronmental sciences. The latter is mainly because of the growing detection (FID) or electron capture detection (ECD) [10–14].
awareness of the impact of VOC on both human health and More recently, atomic emission spectroscopy (AES) has been
global environment. Both VOC and their degradation products recognized, if applicable, as a sensitive and highly selective
may be important in the epidemiology of respiratory disorders detection system for GC [15,16]. In a limited number of cases,
and cancer [1,2]. Next, VOC contribute to major environmental high performance liquid chromatography (HPLC) or ion chro-
problems such as global warming, stratospheric ozone depletion, matography (IC) is used, particularly for the analysis of carbonyl
photochemical ozone formation and odour nuisance [3]. compounds after derivatization [17–22]. Alternatively, immedi-
In the literature, a wide range of definitions of VOC can ate detection without separation is applied, e.g. by spectroscopic
be found. Basically, two categories can be distinguished. First, techniques [23–29], and direct MS techniques such as membrane
there are effect-oriented definitions such as the one used by the inlet MS (MIMS) [30–36], atmospheric pressure chemical ioni-
US-EPA, defining VOC as organic compounds contributing to sation MS (APCI-MS) [37,38], and proton transfer reaction MS
photochemical ozone creation [4]. Other definitions make use (PTR-MS) [35,39–41].
of physical–chemical properties such as pressure in combina- However, the analytical procedure does not only imply the
tion with temperature. Kennes and Veiga [5] define VOC as analysis of the target compounds in sensu strictu, i.e. separa-
organic chemicals (vapours) containing carbon atoms and hav- tion and detection. Particularly in environmental matrices, where
ing a normal boiling temperature below 373.15 K at 101 kPa. VOC concentrations are low (mostly pg L−1 to ␮g L−1 levels),
According to test method D3960 of the American Society for appropriate sampling and preconcentration techniques are nec-
Testing and Materials, VOC are organic compounds having a essary to comply with the sensitivity of the analytical instrument
vapour pressure larger than 13.3 Pa at 25 ◦ C [6]. The EU Solvents [42]. Matrix components disturbing the instrumental analysis
Directive (1999/13/EC) defines VOC as organic compounds also have to be removed through adequate sample preparation.
having a vapour pressure of at least 10 Pa at 20 ◦ C [7]. Whatever The ultimate importance of sample preparation for VOC analy-
the definition, VOC cover a broad range of organic com- sis is well illustrated by the recommended ECA-IAQ Working
pounds including paraffinic, olefinic and aromatic hydrocarbons, Group 13 definition of total VOC (TVOC) concentration, that is
and various oxygen-, nitrogen-, sulfur-, and halogen-containing explicitely based on the analytes sorption behaviour on Tenax
molecules [8]. Methane is very often considered separately TA (Section 2.3.1), next to their chromatographic behaviour on
because of its relative nonreactivity in the troposphere and the a deactivated non-polar GC column [43]. Sample preparation is
quite different concentration range at which it occurs in the often the bottleneck and most time consuming task in the ana-
atmosphere [9]. Therefore, the acronym VOC often means ‘non lytical scheme [11]. Growing interest in the development and
methane volatile organic compounds (NMVOC)’. This review optimisation of reliable and robust extraction, trapping and/or
is dealing also with NMVOC. preconcentration techniques has resulted into intensive research
132 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144

in this field. Recent developments and applications of VOC
sample preparation and analysis in food, flavour and fragrances
are reviewed in [44–51], whereas VOC sample preparation in
medical, pharmaceutical and forensic sciences is reviewed in
[45,48,52–58].
Since the major part of literature data can be found in the
field of environmental chemistry, the scope of this review is to
highlight the state-of-the art on sample preparation methods for
VOC analysis in environmental matrices. Table 1 summarizes
review articles published since 2001 on VOC analysis in the
environment, including information on sample preparation.
Despite numerous literature data available, most articles
discuss only one or few sample preparation methods of
interest [30,36,44,46,48,58,59,61,63,66–68,70,72,74–78,81],
or focus on one particular compound or subgroup of VOC
[14,58,62,71,80]. Other reviews deal with monitoring data
[42,64,65,69,73] or focus on separation and detection tech-
niques with only limited attention to sample preparation
[10,11,14,58,72]. In this manuscript, a comprehensive overview
is given of new developments and/or applications of sample
preparation techniques, especially dedicated to VOC analysis
in air (Section 2) and water (Section 3). Focus is put on
these matrices since they represent the major field of interest,
given the physical–chemical properties of the analytes. Main
literature sources for this article consist of reviews from the
past five years (Table 1) and peer-reviewed research papers,
published between January 2003 and June 2006 and indexed
by Web of Science. The outline of our paper is shown in Fig. 1,
giving a schematic overview of all sample preparation methods
discussed in a two-dimensional grid with the sample matrix on
one axis and the extraction and/or preconcentration matrix on
the other one.

Table 1
Overview of peer-reviewed review articles, published between 2001 and mid-2006, dealing with VOC analysis in the environment, and including information on
sample preparation
Reference Matrix Target VOC Sample preparation method(s)
Air Water Other

[59] × × ×a Non-specified SPME

[14] × × Halogenated VOC Non-specified
[60] ×b Non-specified Headspace techniques
[61] × Non-specified RTIL based extraction methods
[62] × ×a Methyl tert-butyl ether DAI, SPME, headspace techniques, MIMS
[36] × Non-specified Membrane based enrichment techniques
[58] × Trichloroethylene and metabolites SPME, SPE, LLE
[42] × Non-specified Non-specified
[63] × Non-specified SPME
[64] × × ×a Non-specified Passive sampling and/or extraction techniques
[65] × Non-specified Passive sampling techniques
[66] × × ×a Non-specified SPME
[67] × × ×a Non-specified (HS)-SPME with derivatization
[48] × × ×a,c Non-specified (HS)-SPME, SBSE
[68] × × Non-specified membrane based enrichment techniques, denuders
[69] × Non-specified canisters, adsorptive enrichment, impregnated surfaces
[70] × Non-specified SBSE
[71] × Methyl tert-butyl ether, tert-butyl alcohol DAI, SPME, headspace techniques
[72] × × Non-specified Cryogenic trapping, adsorptive enrichment, SPME
[73] × Non-specified Headspace techniques, MIMS
[74] × Non-specified Cryogenic trapping, adsorptive enrichment
[75] × Non-specified LPME
[76] × Non-specified Denuders
[77] × Non-specified SPME
[46] ×a,b,c,d Moderate VOC PLE, SWE
[45] × ×a,b Non-specified Headspace techniques
[10] × × ×a,b Non-specified Non-specified
[11] × × ×a,b Non-specified Non-specified
[78] × Non-specified Adsorptive enrichment
[79] × × ×a Non-specified Adsorptive enrichment, (HS)-SPME, SBSE, OTT, GPE
[30] × × ×a Non-specified MIMS
[80] × ×b Volatile terpenoids Non-specified
[81] × × ×a Non-specified Membrane based enrichment techniques
[44] × Non-specified SDE

References are ranked chronologically. For acronyms of the sample preparation methods: see ‘Abbreviations’.
a Soil and sediment.
b Biota.
c Sludge.
d Particulate matter.
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144 133

Fig. 1. Outline of this review paper. Sample preparation methods are ordered based on the first extraction and/or preconcentration matrix to which analytes are
transferred from the sample matrix. Numbers in each cell of the scheme correspond to the section in the text discussing the sample preparation method(s) mentioned
in that particular cell. For acronyms of the sample preparation methods: see ‘Abbreviations’.

2. Sample preparation methods for VOC analysis in air
Since air is a low density matrix (about 1.2 kg m−3 at standard
temperature and pressure, STP), i.e. about three orders lower
than liquid or solid matrices (>1000 kg m−3 at STP), and because
of the low mixing ratios of VOC (pg L−1 to ␮g L−1 ), sample
preparation for VOC in air primarily aims at preconcentration.
At present, ultraviolet differential absorption spectroscopy (UV-
DOAS) is the only technique that allows measurement of VOC
in air without sample preparation but the set of analytes is limited
[10,27,69]. Sample preconcentration can be done either simul-
taneously with sampling or in the laboratory following whole
air sampling (grab sampling) in the field.
Looking at recent literature, it is obvious that two precon-
centration methods are mostly used when dealing with lower
concentration ranges: (i) cryogenic trapping, typically used in
combination with preceding canister whole air sampling, and
(ii) adsorptive sampling either passive or active. Next to that,
solvent extraction, a number of innovative sorptive enrichment
methods, and membrane based techniques look promising.
2.1. Cryogenic sample preconcentration
Cryogenic preconcentration, passing an air flow through a
cooled tube usually filled with glass beads, remains one of the
typical VOC enrichment methods for air samples. Recent appli-
cations where this technique is combined with canister sampling
are reported for analysis of indoor environments [82], the lower
troposphere [83,84], and (sub)urban environments [85–89].
Removal or control of water vapour is essential for proper cryo-
genic preconcentration [87]. Cryogenic sample preparation is
typically done with the aid of cryogenic fluids where trapping
temperatures between −150 to −170 ◦ C are achieved. How-
ever, due to its logistic implications, there is a search for more
convenient cooling systems. As an example, Peltier type cool-
ing devices are incorporated in cryogenic preconcentration [90].
Temperatures reached with these systems are typically within the
+10 to −30 ◦ C range. In those circumstances, cryogenic precon-
centration is only possible in combination with sorbent agents
(see Section 2.3.1).
2.2. Solvent extraction
Dissolving airborne VOC in an appropriate liquid solvent for
preconcentration can be achieved using impingers and denud-
ers. Impingers are designed to distribute a gas flow through
a dispersion device yielding small bubbles rising in the sol-
vent [42]. In a denuder, a film of absorbing liquid continuously
flows down the inner wall of a cylindrical tube, while the gas
stream passes counter-currently. Design, fundamentals and prac-
tical applications of denudation techniques have been reviewed
in [68,76]. Points of attention include the limited preconcen-
tration power and the possible overlap in the chromatogram
of the extraction solvent peak with those of the analytes of
interest. On the other hand, denuder and impinger techniques
not only have the advantage that a large number of solvents
134 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
is available but also that a wide range of chemical reactions
can be carried out in the liquid phase. For example, derivatiza-
tion reagents can be added converting the analytes in reaction
products more suitable for subsequent separation and/or detec-
tion. This method is of particular use for the analysis of
carbonyl compounds in air, with 2,4-dinitrophenylhydrazine
(DNPH) the most widely used derivatization agent, forming
hydrazones which can be analysed via HPLC and UV–vis or
fluorescence detection [22,91]. Alternatively, DNPH impreg-
nated cartridges of silica gel, florisil or octadecyl silane
are widely used for collecting carbonyl compounds from air
[17,21,22,69,92]. After elution with acetonitrile, detection lim-
its (LODs) below 135 ng m−3 can be achieved by HPLC–MS
analysis [21]. Special attention should be paid towards sampling
artifacts, e.g. due to reaction with ozone [17,69]. Although the
sensitivity of these methods are mostly sufficient, they are time
consuming and not easily applicable for continuous measure-
ments. However, Motyka et al. [91] very recently described a
novel combined wet denudation–chemiluminescence method,
based on the Trautz–Schorigin reaction, allowing continuous
determination of formaldehyde in air with a LOD of 0.6 ␮g m−3 .
2.3. Airborne VOC enrichment on immobilized sorbents
2.3.1. Active and passive sample enrichment on solid
adsorption badges and packed tubes
Enrichment of VOC onto solid sorbents, either by active or
passive sampling is a well established sample preparation tech-
nique for VOC in air. Active sampling occurs by pumping air
through a bed of sorbent(s) in a tube, at a rate typically in the
10–100 mL min−1 range for a period in the order of minutes. In
passive (diffusive) sampling, sorbent material is exposed to air
for a period in the order of days. Two main sampler designs,
tube and badge type ones, are used for sorbent holding in pas-
sive sampling. The former one is characterized by a long axial
diffusion path length and a low cross sectional area. A detailed
overview of passive air samplers can be found in [64]. Recent
investigations on passive sampling, usually to evaluate exposure
of humans to outdoor and particularly indoor environments, are
reported in [18,93–101].
Mukerjee et al. [97] and McClenny et al. [100] found good
agreement in field measurements when time-averaged active
sampling was compared with 24 h diffusive sampling. However,
in case of passive sampling it is crucial that correct dose-
dependent uptake rates relations are used to calculate the VOC
concentration from the sorbed mass, as deviations of 30% easily
show up [93].
A wide range of sorbent materials is commercially avail-
able, such as carbon molecular sieves, graphitized carbon blacks
and porous organic polymers [14,42,74,78,79], albeit that new
types are still investigated. As an example, Li et al. [102] eval-
uated purified multi-walled carbon nanotubes, prepared from
catalytic decomposition of methane. Important aspects to be con-
sidered during the selection of appropriate sorbent material(s)
include: (i) target VOC, (ii) sorption equilibrium at sorption and
desorption temperature, (iii) reactivity and artifact formation
[103], (iv) water sorption interferences, particularly in the case
of polar compounds [10,104], and (v) storage stability and
blank build-up [105]. Since sorption behaviour depends on
the sorbent–VOC combination, active solid sorbent sampling
applications today mainly make use of multi-sorbent tubes
in order to achieve high breakthrough volumes for a wide
range of VOC [106]. Examples can be found for VOC analy-
sis in the lower troposphere [107,108], rural and urban areas
[21,41,109–111], and indoor environments [112–117]. Sanchez
and Sacks [118] reported multi-bed adsorption in combina-
tion with two-dimensional GC and time-of-flight MS for the
analysis of VOC in human breath. Despite the major use of
multi-bed sorbents, single-sorbent sampling mainly with Tenax,
i.e. a porous 2,6-diphenyl-p-phenylene oxide polymer, can still
be found [20,119].
VOC enriched sorbents are typically desorbed by thermal
desorption. A major disadvantage when compared to cryogenic
sample preconcentration or solid phase microextraction (SPME)
is the significant thermal resistance combined with the rather
long diffusion path. Hence, desorption is slow and refocus-
ing the analytes prior to separation is necessary to obtain high
peak resolution. Therefore, miniaturization of sorbent traps is
an important issue today. It eliminates refocusing while keep-
ing peak resolution high at the GC stage, and it allows on-line
automation. Miniaturization is only achievable with the aid of
convenient cooling and rapid heating devices. Rapid heating
should be accompanied with high rates of sample transport when
thermally non-stable VOC are analyzed in order to minimize
exposure time and contact with the hot surface of the sorbents
[104]. Ciucanu et al. [120] presented the application of a minia-
turized helical polydimethylsiloxane (PDMS) based microtrap
(Fig. 2) where trapping is performed at ambient temperature
through combination with a continuous membrane inlet (MESI),
followed by rapid desorption on-line to GC. Improved mass
transfer in the boundary layer between the gas phase and the sor-
bent was achieved due to the helical geometry of the microtrap,
enhancing turbulence and diminishing backward flow in the trap.
As an alternative to thermal desorption, Barro et al. [121]
introduced the combined use of adsorbent cartridges and SPME
for analysis of trace levels of chlorobenzenes in air. Analytes
were sampled by pumping up to 2.5 m3 of air through 25 mg
of Tenax TA. Subsequently, the adsorbent was transferred into
a glass vial placed in a water bath thermostated at 100 ◦ C,
and headspace (HS)-SPME was performed. If automated, the
adsorbent/HS-SPME method allows high-throughput analysis
of VOC at the sub ng m−3 level.
Fig. 2. Helical microtrap, consisting of a 260 mm long, 0.07 mm diameter
chromium–aluminum alloy wire with a helical inner diameter of 1.0 mm, coated
with 19.6 mm3 of PDMS (surface area of 441 mm2 , thickness of about 0.05 mm).
The helical trap is hold in a silicosteel tube and fixed inside at both ends with
two rings [120].
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
In order to keep sufficient sorption capacity while reducing
the amount of sorbent allowing on-line injection to GC, sorp-
tion can be performed at reduced temperatures. Here, Peltier
element-based equipment to establish temperatures down to
−5 to −50 ◦ C during sorption have been reported [122–126].
Not only in-house devices are developed, but the concept is
commercialized by Markes Int. Ltd. (Pontyclun, UK). Wevill
and Carpenter [127] housed an adsorbent-filled glass trap in a
programmed temperature vaporization (PTV) injector that was
cooled down to −10 ◦ C by two two-stage Peltier devices during
the sampling stage.
2.3.2. Solid phase microextraction based techniques
In order to come up with a solvent-free, fast and simple
integrated sampling–extraction–sample introduction device,
SPME was developed in the early 1990s. Since its introduction,
hundreds of manuscripts including some excellent recent review
articles [48,59,63,66,67,77] deal with both fundamentals and
applications of this attractive sample preconcentration tech-
nique. Briefly, SPME is based on the equilibrium partitioning
of target analytes between the sampled matrix and a stationary
phase, coated on a fused silica fiber. Among the liquid-like
and solid polymeric stationary phases available in a wide
variety of polarity [42], PDMS is the most widely used coating
(7–100 ␮m film thickness) so far [79,128]. Carboxen/PDMS
stationary phases have shown to be of large merit for indoor air
monitoring [129–131], but research towards optimized coating
materials is still on-going [132]. Special attention has to be
paid towards artifact formation [133], competitive (ad)sorption
effects [129], fibre storage before and after sampling [130],
and analyte quantification [134,135]. Calibration methods
required to obtain accurate and precise quantitative data are
very recently reviewed by Ouyang and Pawliszyn [59]. SPME,
in combination with GC and HPLC, has been reported for the
analysis of VOC in indoor air [129–132], gaseous industrial
effluents [136,137], and the lower troposphere [12,121,138],
with LODs typically below 1 ng L−1 .
Next to these common SPME methods, more advanced tech-
niques have been developed in recent years. Fiber introduction
mass spectrometry (FIMS), i.e. direct introduction of a SPME
fiber into a (portable) mass spectrometer, is demonstrated to
allow trace level detection of VOC in air (LODs in the low
ng L−1 range) with short preconcentration times (3–5 min) [34].
Next, derivatization techniques on the SPME fiber, in the sam-
ple matrix, or in the injector port are investigated to increase the
extraction efficiency and LOD [67]. This is of particular impor-
tance in case of thermally unstable, polar, highly reactive and/or
volatile compounds. Attention should be paid to the repeatability
of the extraction method: through optimization, relative stan-
dard deviations (RSD) of about 10–15% can be obtained [67]. A
novel SPME concept was developed by Mangani et al. [138] for
determination of volatile halocarbons in air after sampling with
stainless steel canisters. The outlet of the canister was connected
to a common GC inlet for packed columns, refrigerated down
to −40 ◦ C. During the enrichment step, the SPME fiber was
inserted in this cooled GC inlet and the air sample was passed at
a flow-rate of 5 mL min−1 . Sample volumes down to 75 mL were
135
sufficient to detect (GC–MS) halocarbons at 63–2748 ng m−3
with good reproducibility (RSD = 2.4–17%). A Nafion dryer
containing Carbograph 3 was used to retain relatively less
volatile compounds and to reduce air relative humidity.
Despite the wide application potential of SPME and its
numerous advantages over more conventional preconcentration
techniques, it suffers some main limitations [139,140]. First,
the small volume of sorbent coated on a SPME fiber (usually
less than 1 ␮L) results in a rather limited sorption capacity.
Second, the fragility of the fused-silica rod necessitates a careful
handling during the extraction and desorption steps, and limits
the lifetime of the fibre. Third, bleeding of the SPME coating
into a GC injector and sample carry-over are sometimes difficult
to be avoided. In order to overcome these limitations, extraction
techniques such as gum phase extraction (GPE), in which a trap-
ping material is used in a packed-bed configuration, and in-tube
SPME, evolved from open tubular trapping (OTT), have been
developed [79].
More recently, innovative in-needle extraction devices have
been introduced. Berezkin et al. [139] constructed a tubular
cylindrical microconcentrator, consisting of an in-needle Tenax
sorbent layer (diameter 2 mm; length 100–150 mm), surrounded
by a tubular furnace for thermal desorption of the analytes. Wang
et al. [141] investigated the extraction and desorption properties
of two different needle trap (NT) devices for analysis of BTEX
and n-alkanes in gaseous samples (Fig. 3). A first NT (NT-1) was
characterized by a sealed tip and contained a multilayer sor-
bent bed consisting of PDMS (3 mm), divinylbenzene (DVB,
2 mm) and Carboxen (2 mm) particles. A second NT (NT-2),
having a blunt tip, contained only Carboxen as a sorbent. Larger
breakthrough volumes (72–1000 mL) and better reproducibility
(RSD = 1–9%) were obtained with NT-2. By adjusting the GC
injector temperature and desorption time at 300 ◦ C and 1.5 min,
respectively, desorption efficiencies (expressed as the ratio of
the mass of analytes quantified after the first desorption over
that after two desorptions) up to 100% were achieved. LODs for
BTEX compounds ranged between 0.23 and 2.10 ng L−1 (FID).
Saito et al. [140] synthesized a copolymer of methacrylic acid
and ethylene glycol dimethacrylate and packed it as a sorbent
(∼6 ␮L) into an in-needle extraction device. Desorption effi-
ciencies higher than 99.9% were obtained at 180 ◦ C, whereas
copolymer decomposition was observed at temperatures higher
than 220 ◦ C. Overall extraction-desorption recoveries between
100 and 109% were measured for organic solvents such as hex-
ane, acetone and toluene. In conclusion, it appears that in-needle
extraction devices may combine the advantages of SPME with
an easier handling during extraction and desorption. This may
offer large potential for automation and on-line coupling to GC
instruments [140].
2.4. Membrane extraction
Main advantages of membrane techniques for VOC sam-
pling and/or preconcentration are the improved selectivity and
enrichment power, the minimized solvent use and the automa-
tion potential [36,81]. Typically, analytes are transferred from a
donor to an acceptor phase through a single or multi-membrane
136 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
Fig. 3. (A) Needle trap device NT-1 with a sealed tip and containing a multilayer
sorbens bed consisting of PDMS, DVB and Carboxen particles. Quartz wool is
packed between the tip of the needle and the side port, for efficient injection
of desorbed analytes. (B1) NT-2, having a blunt tip, and filled with Carboxen
1000 particles. During sampling, the side hole is sealed with a septum. Analytes
enter the needle through the blunt tip and are retained on the sorbent. (B2)
For desorption of NT-2, the hub of the needle is sealed in a narrow-neck glass
GC liner (i.d. 0.8 mm), and the septum is removed to open the side hole. The
carrier gas (1.8 mL min−1 ), entering the needle through the side hole, desorbs
the analytes (T = 300 ◦ C; desorption time = 1.5 min) and transfers them to the
GC column [141].
device, where distinction can be made between non-porous and
(solvent impregnated) porous membranes. Excellent reviews
dealing with membrane extraction techniques for analytical pur-
poses can be found in [30,36,68,81].
Important membrane techniques for VOC sampling out of
air are membrane inlet mass spectrometry (MIMS) and mem-
brane extraction with a sorbent interface (MESI), mostly making
use of silicone membranes [31,32,36,120,142]. They allow
selective transport of volatile non-polar compounds while keep-
ing water vapour from entering the analytical instrument. In
MIMS, analytes permeate selectively through the membrane
into the ion source of a mass spectrometer. Environmental
applications of MIMS, with particular interest towards VOC
analysis, have been reviewed by Ketola et al. [30]. Multi-
membrane inlet devices aiming at higher enrichment factors
belong to the most recent optimizations of MIMS. For exam-
ple, Viktorova et al. [31] reported an inlet system consisting
of three sequential membranes with a dynamic non-steady-
state mode of sample introduction. VOC enrichment factors up
to 105 were achieved compared to direct sample introduction.
Because of the integrated sample introduction and enrichment,
and the relative short analysis time (∼few minutes), MIMS
allows a high sample throughput and enables real-time VOC
sampling and monitoring. Therefore, current research focuses
on system miniaturization. An important step herein may be
the use of micro ion trap mass analysers with submillimeter
dimensions [32]. Although LODs, ranging between 1.1 (xylene)
and 32.8 ␮g L−1 (acetone), were somewhat higher than those
obtained with more common instruments, the use of MS/MS
could improve sensitivity by reducing background noise.
In MESI, gaseous analytes are usually extracted into a mem-
brane module of silicone rubber. A stream of inert gas flowing
inside the module transports the extracted compounds to a cryo-
genic or sorption trap. After thermal desorption, analytes are
separated by GC [36]. Optimization focuses on fastened and/or
enhanced analyte enrichment and desorption, e.g. by using a
helical sorbent trap [120] (see also Section 2.3.1), or through
the development of a temperature controlled membrane interface
instead of a sorbent trap [142]. In the latter case, the temperature
of the membrane can be controlled in a range between −70 and
250 ◦ C, using an electric heater and a flow of cooled nitrogen or
helium gas. After preconcentration in the membrane, rapid heat-
ing transfers trapped analytes as a sharp peak into a (GC–)MS
device. LODs below 0.5 ng L−1 are reported for toluene and
benzene, being a 20-fold increase in sensitivity compared to
conventional MIMS.
Membrane extraction techniques are suitable for passive sam-
pling over extended periods, e.g. for monitoring indoor air
quality. An obstacle, however, is the necessity to calibrate each
compound individually. Zabiegala et al. [143,144] countered this
problem, finding correlations between calibration constants of
permeation passive samplers equipped with PDMS membranes
on the one hand, and physical–chemical properties and linear
temperature programmed retention indexes of several groups of
organic compounds, on the other hand. Due to these correlations,
calibration constants for analytes with unknown experimental
calibration constants may be estimated, so that permeation pas-
sive samplers might be used as efficiently as e.g. sorption tubes,
while preserving all the advantages of passive sampling.
3. Sample preparation methods for VOC analysis in
water
VOC concentration levels found in drinking and natural
water samples are typically in the order of ppt (ng L−1 ) to ppb
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
(␮g L−1 ) [145–147]. Unless large volume injection (LVI) is
applied, the injection volume into a capillary GC column is lim-
ited to microliter(s) [73]. Taking into account the sensitivity of
most detectors, high preconcentration factors are usually nec-
essary during sample preparation for trace analysis of VOC in
water. Solvent extraction has long been the method of choice,
but current challenges within the scope of ‘green’ analytical
chemistry favour the development of ‘solvent-minimized’ and
‘solvent-free’ sample preparation methods. The latter include
VOC extraction in immobilized sorbent phases and membrane
materials, either directly from the aqueous phase (immersion
methods) or by transfer through the headspace.
3.1. Direct aqueous injection (DAI)
Direct injection of an aqueous sample into a chromatographic
column eliminates sample pre-treatment and preconcentra-
tion, minimizing losses of volatile analytes as well as sample
contamination. Main disadvantages, however, are (i) possible
interferences due to matrix effects, and (ii) the non-compatibility
of water with most capillary column stationary phases and with
the widely used FID. As a consequence, the upper limit for DAI
combined with capillary GC is about 10 ␮L [148], limiting its
use to the analysis of a rather small number of VOC that are
present at relatively high concentrations and/or that can be mea-
sured with a selective highly sensitive detector. For example,
for volatile organohalogen compounds, LODs between 1 and
50 ng L−1 are measured by 2–5 ␮L DAI (cold on column injec-
tor) in a GC-ECD [19,149]. Other applications of DAI can be
found in [62,71,150–153].
A novel analytical device allowing DAI of aqueous volumes
up to 250 ␮L (LVI) has been developed by Kubinec et al. [148].
Chromosorb P NAW (210 mg) is placed as a sorbent inside the
liner of a GC injection port. The aqueous sample is introduced
into the GC injector at splitless mode, low injection port tem-
perature (70 ◦ C) and low oven temperature (20 ◦ C). Whereas
the analytes pass through the sorbent material and are focused
onto the column forehead (5 ␮m thick stationary phase), water
is retained on the Chromosorb surface. After 3 min, adsorbed
water is purged using split flow and the GC oven temperature
programme starts for analyte separation. LODs ranged between
0.6 and 1.1 ␮g L−1 for BTEX analysis with FID.
Pettersson and Roeraade [154] reported a new method for
analysis of polar volatile trace compounds in aqueous sam-
ples by DAI and GC-FID. To avoid introducing water into
the GC capillary column, 0.8 g of Chromosorb W 60/80 mesh
AW impregnated with lithium chloride (weight ratio 1:1) was
packed into a 20 cm long precolumn. Following injection of
up to 120 ␮L, water is strongly retained on the hygroscopic
LiCl salt, whereas polar as well as non-polar VOC show very
low retention and are eluted ahead from the water. After trans-
fer of the analytes to the capillary column, water is removed
from the salt by backflushing the precolumn at elevated tem-
peratures (160 ◦ C). Recoveries between 90 and 107% were
obtained, except for acetone showing a recovery of 175%,
due to coelution with a background peak. LODs were about
1 ␮g L−1 .
137
3.2. Solvent extraction
Liquid–liquid extraction (LLE) and steam distillation extrac-
tion (SDE), the latter sometimes called gas-phase LLE under
reflux conditions, are among the oldest and most estab-
lished preconcentration techniques in analytical chemistry
[12,58,146,155]. However, traditional LLE copes with several
main disadvantages. First, the occurrence of the solvent in the
chromatogram can limit the range of VOC that can be measured.
Second, sample loss may occur due to the high volatility of the
compounds to be extracted. Third, the limited amount of solvent
that can be injected often results in moderate LODs. Finally, LLE
is a time consuming preconcentration technique that needs rel-
ative large amounts of often-toxic solvents, making that it does
not fit well with the idea of ‘green’ analytical chemistry.
A modified solvent extraction device allowing single extrac-
tion of large water volumes (10 L) with 10 mL of n-hexane
was used by Zoccolillo et al. [156]. In a flat-bottomed flask, a
modified stopper with a shovel-shaped end was used, preventing
the formation of a whirlpool during stirring while ensuring
that extraction was running in a closed system. With a normal
stopper, the organic phase tended to locate itself inside the
whirlpool, reducing the effective contact surface area between
the aqueous and the organic phases. Recently, Pandey [61]
discussed the potential use of room temperature ionic liquids
(RTIL) as extraction solvents.
In order to overcome limitations of conventional LLE
methods, innovative solvent microextraction (SME) techniques
gain large interest [75]. Two major SME methodologies can be
distinguished: (i) single drop microextraction (SDME), based
on the distribution of the analytes between an aqueous solution
and a microdrop of a water immiscible organic solvent at the
tip of a microsyringe needle; (ii) liquid phase microextraction
(LPME) using immiscible liquid films in two- or three-phase
systems. Main advantages of these techniques include the large
reduction (by a factor of 1000) of solvent use, and the integration
of extraction, preconcentration and sample introduction in one
step [157–159]. Tor and co-workers reported SDME for the
enrichment of trihalomethanes [159] and chlorobenzenes [160]
from aqueous matrices. Important parameters such as the type
of solvent, solvent drop volume, extraction time, sample ionic
strength and stirring rate have been optimized, resulting into
LODs between 0.23 and 0.45 ␮g L−1 for trihalomethanes, and
between 4 and 8 ng L−1 for chlorobenzenes (ECD).
Next to SDME and LPME, a novel third SME technique,
called dispersive liquid–liquid microextraction (DLLME), is
very recently developed by Rezaee et al. [161]. An appropriate
mixture of extraction solvent (8.0 ␮L of C2 Cl4 ) and disperser
solvent (1.0 mL of acetone) is rapidly injected into an aqueous
sample (5.0 mL). As a result, a ‘cloudy’ solution is formed con-
sisting of fine droplets of extraction solvent dispersed into the
aqueous phase. Through centrifugation, the extraction solvent
is collected at the bottom of the conical sample vial, with-
drawn with a microsyringe and injected into a GC. Although the
DLLME method was optimised for GC-FID analysis of poly-
cyclic aromatic hydrocarbons, its ability to extract VOC such
as BTEX from water is also demonstrated. Compared to other
138 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
SME techniques and SPME, DLLME is characterized by very
short extraction times (few seconds), mainly because of the large
surface area between the solvent and the aqueous phase. A more
time consuming step is centrifugation, taking about 2 min. Other
advantages are simplicity of operation, low cost, and high recov-
ery (82–111% at a spiking level of 5 ␮g L−1 ) and enrichment
factors (603–1113), offering potential for ultra-trace analysis
(LODs between 0.007 and 0.030 ␮g L−1 , with RSD below 10%
at 2 ␮g L−1 ).
3.3. Aqueous VOC enrichment on immersed immobilized
sorbents
Solid phase extraction (SPE) offers a well-known alternative
to LLE that needs less solvent use. However, SPE is of major
use for analysis of semi-volatile organic compounds [11,19,58].
Only few SPE applications have been reported for VOC pre-
concentration, mainly because of the risk of losses due to the
volatility of the compounds [58]. An optimized SPE procedure
to enrich BTEX compounds next to cumene from river water has
been described by Mottaleb et al. [162]. Similar as in air matri-
ces (Section 2.3.2), SPME is a prominent enrichment technique
for VOC in aqueous samples [48,58,59,62,64,66,67,71,79],
with applications reported recently for volatile halocarbons
[12,23,163,164], monocyclic and substituted aromatic com-
pounds [164,165], carbonyl compounds [165] and other VOC
emitted by particular industrial processes [137]. As an alterna-
tive to common fiber coating materials such as PDMS, polyacry-
late, Carboxen, and DVB, a new mechanically more stable and
low cost SPME fiber, based on high-temperature silicone glue
coated on a stainless steel wire, has recently been investigated
for extraction of BTEX compounds in water [166]. Combined
with GC-FID, LODs ranged from 0.07 to 0.24 ␮g L−1 . Single
fiber repeatability less than 7% was obtained, but fiber-to-fiber
reproducibility amounted up to 22%. While most applications of
SPME aim at maximizing the extraction efficiency, negligible
depletion SPME (nd-SPME) represents a specific application
for passive sampling, with as main advantage the negligible
disturbances of existing equilibria within the sampled matrix.
However, because of the small amount of analytes extracted,
quantification problems may occur [65,167].
Since SPME lacks sensitivity for sub-trace analysis
(<ng L−1 ), stir-bar sorptive extraction (SBSE) has been intro-
duced as a more powerful extraction technique at the end of the
nineties [70,79]. Stir bars, in the meantime marketed by Gerstel
(Mülheim, Germany) under the name ‘Twisters’, are coated
with 50–250 times larger PDMS volumes and used to stir
aqueous samples. Hereby, solutes are extracted and enriched
into the PDMS layer, allowing LODs in the sub ng L−1 range
[79]. Fundamentals and applications of SBSE, including VOC
related ones, are reviewed in [70]. Loughrin [168] quantified
10 malodorous compounds in wastewater by both SPME and
SBSE and observed for most compounds higher sensitivity (up
to a factor of 9) with the latter technique. Next to that, the repro-
ducibility was better with SBSE. For aromatic hydrocarbons,
RSD obtained with SBSE were less than 2.5%, whereas RSD up
to 8.1% were measured with SPME. Volatile fatty acids could
only be determined semi-quantitatively: RSD amounted up to
34% and 81% with SBSE and SPME, respectively. One of the
limits of SBSE is that PDMS is the only coating material in use
so far, making it difficult to recover polar analytes from com-
plex matrices and those with very volatile compounds (C1 –C4
analytes). Therefore, new generation Twisters exploiting both
absorption and adsorption has been developed: a short PDMS
tube is closed at both ends with two magnets, creating an inner
cavity that can be packed with different adsorbents [169].
Unlike SPME and SBSE, other techniques such as inside
needle capillary adsorption trapping (INCAT), open tubular trap-
ping (OTT) and in-tube SPME utilize sorbent material packed
or coated within flow-through devices [79,170,171]. A new ana-
lytical method based on in-tube SPME, thermal desorption and
GC–MS has recently been described for trace analysis of 55
volatile and semi-volatile organic compounds in drinking water
[147]. Aqueous samples up to 50 mL are pumped (1 mL min−1 )
through a 8 cm × 0.32 mm i.d. PLOT capillary column contain-
ing a 10 ␮m thick styrene–DVB stationary phase. After drying
the trap by flushing with air, it was inserted into a modified
heated GC injector to desorb the analytes. The main advantage
of this system is the relative large sample volume that can be
extracted in one run, enhancing sensitivity.
A quite novel commercialized technique based on the same
principle is solid-phase dynamic extraction (SPDE) [172]. SPDE
utilizes a 2.5 mL headspace syringe attached to a stainless steel
needle that is coated on its inner side with an immobilized
extraction phase. For the extraction, the needle can be immersed
directly into the aqueous sample or in the headspace above
it (Section 3.5). The syringe plunger is moved up and down
several times for extraction, and the analytes are sorbed in the
internal coating. After several extraction cycles (aspirating and
dispensing), the analytes are thermally desorbed from the coat-
ing in a GC injector (Fig. 4). Compared with a 100 ␮m SPME
fiber, SPDE needle coatings (length: 5.6–8.0 cm, film thickness:
7–50 ␮m) possess up to six times larger extraction phase vol-
umes [173]. Other advantages include the reduced fragility of
the needle part, and the higher extraction speed. Using a SPDE
needle coated with a 7 ␮m thick PDMS film, a five times shorter
extraction time was needed to obtain similar LODs than with a
PDMS coated SPME fiber having a film thickness of 100 ␮m
[172]. Important parameters related to SPDE include extraction
temperature, ionic strength, and number of extraction cycles.
Very recently, Ridgway et al. [174] evaluated SPDE for the
extraction of furan, benzene and toluene from aqueous solu-
tions in both headspace and liquid injection modes. LODs ranged
from 0.2 to 1.5 ␮g L−1 (GC–MS), with immersion SPDE giving
higher responses than HS-SPDE.
3.4. Membrane extraction
Several membrane extraction techniques can be used for
the enrichment of VOC out of water: supported liquid mem-
brane extraction (SLM), microporous membrane liquid–liquid
extraction (MMLLE), polymeric membrane extraction (PME),
membrane assisted solvent extraction (MASE), MESI and
MIMS. A detailed description of these techniques is given in
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
Fig. 4. Schematic overview of the various steps in a SPDE procedure [173]. (A) Conditioning of the needle in the flush station before first use and after each analysis.
(B) HS extraction. (C) Aspiration of a 1 mL desorption volume from a N2 gas station, followed by thermal desorption in the injector.
[30,36,68,81]. Membrane assisted passive sampling techniques
for monitoring pollutants in water are reviewed in [65].
A quite recent evolution involves the integration of porous
hydrophobic hollow fibre (HF) membranes, impregnated with
an organic phase, in solvent microextraction (SME, Section
3.2) techniques. The HF adds a protective feature to micro-
drop systems and/or aids the formation of immiscible liquid
films. Other advantages include the increased sensitivity and,
because of the disposable nature of the HF, the elimination of
carry-over between successive analyses [75]. Two main sys-
tems can be distinguished. First, two-phase HF-LPME, based
on the principles of MMLLE, extracts analytes from an aqueous
sample matrix into an organic acceptor phase contained inside
the channel of the HF and immobilized inside its wall pores.
After extraction, the acceptor phase is directly introduced into
a GC or HPLC. Second, three-phase HF-LPME is based on
SLM principles: analytes are first extracted from an aqueous
matrix into a thin organic layer inside the HF wall pores and
then extracted again by an aqueous based acceptor phase that
can be further analysed by HPLC or capillary electrophoresis
[75,175]. Recent applications of HF-LPME are reported for the
enrichment of trihalomethanes in drinking and tap water [176]
and of hydroxycarbonyl compounds in rainwater [177]. In the
latter case, HF-LPME was combined with a two-step derivatiza-
tion enabling GC–MS analysis. LODs ranged between 0.01 and
0.2 ␮g L−1 for the trihalomethanes (GC-ECD) [176], and from
0.023 to 4.75 ␮g L−1 for the hydroxycarbonyl compounds [177].
Despite the large merit of porous HF-LPME, non-porous
membranes have the advantage that very complex matrices can
be handled with minimized degree of clean-up. A typical MASE
device, as introduced by Popp and co-workers [178–182] and
commercialized by Gerstel (Mülheim, Germany), utilizes a non-
139
porous polypropylene membrane bag containing 800 ␮L of an
organic solvent for analyte extraction from a 15 mL aqueous
sample. After extraction, large volume injection (LVI) into a GC
is performed. However, for VOC, this LVI approach is not suit-
able because of losses during solvent removal through the open
split valve. Therefore, Schellin and Popp [183] developed a new
MASE module with miniaturized bags (100 ␮L), from which
1 ␮L of solvent is injected into a conventional split/splitless
injector of a GC-ECD for analysis of chlorinated VOC. LODs
between 5 ng L−1 (tetrachloroethylene) and 50 ng L−1 (chloro-
form) were obtained, with RSD below 10%. The same research
group also developed a membrane extraction cell consisting of
four flat membranes, including silicone and supported liquid
membranes, enabling simultaneous extraction of VOC and more
polar compounds like phenols from contaminated waters [184].
Whereas HF-LPME and MASE make use of organic solvents
to transfer and/or extract VOC from the aqueous matrix, MIMS
(see also Section 2.4) is an emerging solvent-free technique for
VOC analysis in natural waters [12,30,62,73]. Its applicability to
follow-up the efficiency and kinetics of aqueous VOC abatement
techniques such as adsorption on activated carbon also has been
demonstrated [33]. The rather low sensitivity and poor speci-
ficity are the main limitations, but optimizations are extensively
investigated [34,73,142]. Recently, coupling MIMS with pro-
ton transfer reaction MS (MI-PTRMS) has been demonstrated
to be a rather sensitive technique (LODs down to 100 ng L−1 )
for on-line and on-site VOC monitoring in fresh and seawater
[35]. Another approach for VOC analysis in water is the use of a
membrane inlet coupled to an infrared detector. The membrane
reduces contamination and instability of the sensing element
immersed in the water phase. Both porous Teflon [29] and micro-
porous propylene [28] membranes have been used for analyte
140 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
extraction, in different configurations. Through optimization of
process parameters such as sampling and purging flow rates,
LODs between 0.2 and 2.9 mg L−1 can be obtained, depending
on the analyte’s volatility and type of membrane material.
A novel membrane based solvent-free microextraction
technique, called liquid–gas–liquid microextraction (LGLME)
is very recently reported by Zhang et al. [175]. A small amount
(6 ␮L) of an alkaline aqueous acceptor solution is introduced
into the channel of a 2.65 cm hydrophobic microporous
polypropylene HF, the pores of which are filled with air.
When the HF is subsequently immersed in an aqueous sample,
analytes pass through the HF by gas diffusion and are trapped
by the aqueous acceptor solution. After extraction, the acceptor
solution is withdrawn into a microsyringe and injected into the
analytical device. So far, the system was only applied for analysis
of phenols, using capillary electrophoresis. LODs between 0.5
and 10 ␮g L−1 were achieved, with RSD less than 8%.
3.5. Headspace techniques
The HS approach has been widely used for VOC extraction
from aqueous matrices [45,48,62,67,71,73,79], mainly because
(i) the extraction phase (air or an inert gas) is compatible with
most analytical instruments and is suitable for field opera-
tions [185], and (ii) matrix effects and clean-up are minimized
[12]. Parameters affecting analyte partitioning between aqueous
phase and HS (e.g. temperature, ionic strength), next to sam-
ple and HS volumes (phase ratio) have to be controlled [174].
Basically, two modes of HS techniques can be distinguished.
A first category involves static HS techniques, where (non-
exhaustive) extraction proceeds until equilibrium partitioning
is reached between the aqueous phase, the HS, and – if present
– the enrichment matrix (solvent or immobilized sorbent). Sec-
ondly, there are dynamic HS methods, where all analytes present
in the aqueous matrix can (exhaustively) be extracted by purge-
and-trapping (PT).
3.5.1. Static headspace techniques
In static headspace sampling (SHS), an aliquot of vapour
phase being in thermodynamic equilibrium with a condensed
phase is analysed [12]. The simpliest way involves sampling
with a common headspace syringe without any preconcentration
[155,186]. Recently, an enhanced SHS device with a built-in
trap for VOC preconcentration and focusing prior to injection
has been commercialized by Perkin-Elmer [187].
The majority of recent international literature on SHS focuses
on the application and optimization of miniaturized enrichment
techniques such as HS-SME (both HS-SDME and HS-LPME),
HS-SPME, HS-SBSE (more often called HSSE), and HS-SPDE.
In HS-SDME, HS-SPME and HSSE, analytes are transferred
through the HS mainly by molecular diffusion processes. Among
these techniques, HS-SPME is by far the most established
method [23,34,165,166,188–192]. Compared to immersion
SPME, faster mass transfer in the HS results in shorter extrac-
tion times [174,191], albeit that Alonso et al. [165] observed the
opposite during extraction of polar VOC such as acetone, ethyl
acetate and methyl tert-butyl ether (extraction times in the order
of 15 min). High capacity headspace sorptive extraction (HSSE)
has been reported for the first time in 2000 [193,194]. An
in-depth study on the effect of the analytes physical–chemical
properties (e.g. vapour pressure, water solubility, Kow ) and the
sampling conditions (e.g. PDMS and HS volumes, extraction
time and temperature) on HSSE of 6 high-to-medium volatile
analytes is recently performed by Bicchi et al. [195]. The same
authors also evaluated the potential of the new generation dual-
phase Twisters (Section 3.3) for HSSE [169]. As an alternative
to HSSE, Burger et al. [196] developed a high capacity sample
enrichment probe (SEP) consisting of a thin rod (1.4 mm outer
diameter) of an inert material embedded at one end with a 1.5 cm
(28.2 mg) PDMS rubber sleeve. After extraction, the SEP can be
directly introduced into a slightly modified heated GC injector,
without need for cryotrapping and/or additional thermal desorp-
tion devices. For a wide range of (semi-)volatile compounds,
SEP gave results comparable with those obtained by HSSE.
Whereas HS-SPME and HSSE preconcentrate analytes on an
immobilized sorbent, a microdrop of organic solvent is the
enrichment matrix in HS-SDME (Fig. 5A). Recent applications
of this technique are reported for trihalomethanes [157,197],
2-butoxyethanol [198], n-alkanes [199], and methyl tert-butyl
ether [200], with LODs in the ng L−1 to ␮g L−1 range for methyl
tert-butyl ether (FID), n-alkanes (FID) and trihalomethanes
(ECD), and in order of mg L−1 for 2-butoxyethanol. HS-SDME
with in-drop derivatization for GC–MS analysis of acetone in
blood is reported by Dong et al. [158].
Quite novel HS enrichment techniques, such as dynamic
HS-LPME and HS-SPDE, are bridging static and dynamic HS
techniques. Whereas based on the same principle of common
static HS preconcentration techniques, the extraction time
is reduced by aspirating and dispensing the HS along an
enrichment matrix positioned inside a syringe needle. Addi-
tional parameters to control are the syringe withdrawal rate,
dwelling time between plunger pulling and pushing steps, and
number of extraction cycles. In dynamic HS-LPME (Fig. 5B), a
microsyringe barrel is filled with 0.8–2.0 ␮L of organic solvent,
and serves as both separatory funnel for extraction and syringe
for injection into GC. When the syringe plunger is withdrawn, a
thin organic solvent film is generated on the inner syringe wall,
and mass transfer of the analytes occurs between the HS and
the solvent film. Compared to HS-SDME, dynamic HS-LPME
provides larger enrichment factors within shorter analysis time
(5–10 min), and it eliminates the problem of drop dislodging
[201]. Recent applications for VOC include dynamic HS-LPME
of alcohols [201] and BTEX compounds [185] in a (semi-)
automated device. LODs ranged between 0.2 and 0.4 ␮g L−1
for BTEX (GC-FID) and between 1 and 97 ␮g L−1 for alcohols
(GC–MS). RSD were less than 12%. HS-SPDE is based on the
same principle but an immobilized sorbent is coated on the inner
wall of the syringe needle. Ridgway et al. [174] investigated
HS-SPDE for analysis of non-polar VOC using PDMS as a sor-
bent. HS-SPDE of 3 ethers and 12 alcohols has been performed
by Jochmann et al. [173]. The lowest LODs (0.02–3.5 ␮g L−1 )
were obtained using a polar polyethylene glycol WAX phase.
Very recently, Tölgyessy and Hrivnák [202] reported a new
enrichment technique in which 20 out of 250 mL of HS is aspi-
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
Fig. 5. Schematic representation of a (A) HS-SDME [198] and (B) automated
HS-LPME device [185].
rated (40 mL min−1 ) through a microcolumn filled with 30 mg
of Tenax TA. The loaded microcolumn is then transferred into
a Twister desorption unit assembled to a cooled PTV injector
and a GC–MS device. The method showed to be applicable for
qualitative VOC screening at the ␮g L−1 to sub ␮g L−1 level
and for the quantitative determination at the ng L−1 level (SIM
mode).
3.5.2. Dynamic headspace techniques
In dynamic HS sampling, VOC extracted by purging an
aqueous sample with an inert clean gas stream, have to be
141
trapped and refocused prior to further analysis. In most cases,
trapping occurs in a cryogenic or sorbent device [185]. If
sorbent trapping is applied, an additional cryogenic refocusing
is necessary prior to injection [203], unless microtraps are used
[19]. Whereas purging is usually performed by bubbling the
gas stream through the water matrix [16,164,204–207], in some
cases [208] only the headspace is purged to minimize water
vapour interferences. As an alternative, hygroscopic membranes
(Nafion), desiccants, cryogenic or sorbent traps, or dry purging
stages are used to remove water vapour [73,204–207,209,210].
LODs obtained with PT techniques (typically in the ng L−1
to low ␮g L−1 range [211]) are often more than 10 times
lower than those achieved with static HS techniques [186].
Main drawbacks of PT, however, are (i) the quite complex
instrumentation that is required especially for on-line and
real-time monitoring [212,213], (ii) possible water vapour
interferences, (iii) cross contamination, and (iv) foaming [185].
Next to that, it is rather time consuming: typical extraction
times are in the 10–30 min range [157,159,199,214].
In order to overcome these limitations, mainly two quite
new approaches have been reported. A first strategy involves
the utilization of more recently developed trapping devices.
For example, Silva et al. [215] built a lab-made extraction
device allowing the use of a SPME fiber as the sorptive trap for
purged analytes. Alternatively, purge-and-membrane extraction
techniques have been developed [12], but recent applications
are scarce. HS-MESI is demonstrated to be a useful tool for
field HS monitoring of VOC in water [216,217]. Applications
of HS-MIMS can be found in [218–220]. A second strategy
focuses on reduction of the extraction time and enhancement
of the sample throughput. Therefore, Yang et al. [214] used
an automated spray-and-trap (ST) system. A spray nozzle
generates small sample droplets within an extraction chamber.
Because a small volume of water contacts a large volume of
extracting gas, the partitioning process is accelerated. ST was
evaluated for extraction of BTEX compounds and halogenated
VOC from aqueous matrices. Whereas recovery (51–109%),
precision (RSD = 0.7–7.3%) and linearity (R2 > 0.990, n = 7, at
10–54 ␮g L−1 ) were inferior to PT, ST showed a fast response,
making it suitable for on-site surface or groundwater monitoring.
4. Conclusions
Within the entire analytical scheme, sample preparation is
often the most time consuming and challenging step, particularly
for VOC present at trace concentration levels (pg L−1 to ng L−1 )
in air and water matrices. Main tasks to be fulfilled during sample
preparation are (i) analyte preconcentration allowing low LODs,
(ii) elimination of interferences, (iii) if needed, analyte conver-
sion making it more suitable for separation and detection, and
(iv) providing a robust and reproducible method not sensitive
for matrix effects.
For VOC enrichment out of air, cryogenic trapping and
adsorptive enrichment are well-established methods. Recent
research focuses on the development of new sorbent materials
such as purified multi-walled carbon nanotubes. Miniaturization
eliminates refocusing while keeping high resolution and allow-
142 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
ing on-line automation. SPME has become an attractive and
widely used integrated sampling–extraction–sample introduc-
tion technique, despite its relative recent character. Most recent
tendencies include FIMS and cold-SPME. Next, novel in-needle
trap devices have been developed combining the advantages of
SPME with a larger robustness. Membrane extraction techniques
such as MIMS and MESI are emerging. Due to their automation
potential and high sample throughput, they have large merit for
passive sampling.
For VOC analysis in water, high preconcentration factors
are needed for trace analysis, making DAI applicability limited.
Since traditional LLE does not fit with current challenges of
green analytical chemistry, there is a big tendency towards
solvent microextraction, with SDME, (HF)-LPME, DLLME
and miniaturized MASE being new interesting developments.
Alternatively, solvent-free sorptive enrichment can be used,
with SPME and SBSE being the most mature techniques.
Membrane extraction and novelties such as SPDE offer fast
and high capacity alternatives.
Overall, it may be concluded that the state-of-the-art in
sample preparation and analytical methods allows reliable trace
analysis of VOC in both air and water matrices. Continued
research effort is desired towards reduction of artifact effects,
e.g. due to water and ozone, and towards the development
of more robust and highly sensitive automated enrichment
techniques allowing on-site and real-time ultra-trace monitoring
(<ng L−1 ) of VOC in the environment.
References
[1] R.B. Larson, E.J. Weber, Reaction Mechanisms in Environmental Organic
Chemistry, Lewiss Publishers, Boca Raton, 1994.
[2] L. Forst, L.M. Conroy, in: H.J. Rafson (Ed.), Odor and VOC Control
Handbook, McGraw-Hill, New York, 1998, p. 3.1.
[3] J.G. Calvert, Chemistry for the 21st Century. The Chemistry of the Atmo-
sphere: Its Impact on Global Change, Blackwell Scientific Publications,
Oxford, 1994.
[4] http://www.epa.gov/epahome/lawregs.htm (30/08/2006). Code of Fed-
eral Regulations. Title 40: Protection of Environment. Chapter I:
Environmental Protection Agency. Subchapter C: Air Programs. Part 51,
Subpart F, Section 51.100.
[5] C. Kennes, M.C. Veiga, in: C. Kennes, M.C. Veiga (Eds.), Bioreactors
for Waste Gas Treatment, Kluwer Academic Publishers, Dordrecht,
2001, p. 3.
[6] The ASTM standard practice for determining volatile organic compounds
(VOC) contents of paints and related coating (D3960), American Society
for Testing and Materials, Philadelphia, 1989.
[7] http://www.europa.eu.int/(30/08/2006). Council Directive 1999/13/EC
of 11 March 1999 on the limitation of emissions of volatile organic
compounds due to the use of organic solvents in certain activities and
installations.
[8] P. Hunter, S.T. Oyama, Control of Volatile Organic Compound Emissions:
Conventional and Emerging Technologies, John Wiley & Sons, Inc., New
York, 2000.
[9] E. Wauters, K. Van den Berghe, J. Brouwers, In: M., Van Steertegem,
(Ed.), MIRA-S 2000. Milieu-en Natuurrapport Vlaanderen: Senario’s,
Garant, Leuven, 2000, p. 231.
[10] J. Dewulf, H. Van Langenhove, G. Wittmann, Trends Anal. Chem. 21
(2002) 637.
[11] F.J. Santos, M.T. Galceran, Trends Anal. Chem. 21 (2002) 672.
[12] F. Mangani, M. Maione, P. Palma, Adv. Chromatogr. 42 (2003) 139.
[13] G.A. Eiceman, J. Gardea-Torresdey, E. Overton, K. Carney, F. Dorman,
Anal. Chem. 76 (2004) 3387.
[14] J. Dewulf, T. Huybrechts, H. Van Langenhove, Trends Anal. Chem. 25
(2006) 300.
[15] L.L.P. van Stee, U.A.Th. Brinkman, H. Bagheri, Trends Anal. Chem. 21
(2002) 618.
[16] N. Campillo, P. Vinas, I. Lopez-Garcia, N. Aguinaga, M. Hernandez-
Cordoba, J. Chromatogr. A 1035 (2004) 1.
[17] E.M. Fujita, G. Harshfield, L. Sheetz, Atmos. Environ. 37 (2003) S135.
[18] D.G. Shendell, A.M. Winer, T.H. Stock, L. Zhang, J. Zhang, S. Maberti,
S.D. Colome, J. Expo. Anal. Env. Epid. 14 (2004) 44.
[19] A. Kot-Wasik, J. Debska, J. Namiesnik, Mar. Pollut. Bull. 49 (2004) 264.
[20] A.-S. Claeson, A.-L. Sunesson, Indoor Air 15 (2005) 41.
[21] H. Hellén, H. Hakola, L. Pirjola, T. Laurila, K.-H. Pystynen, Environ. Sci.
Technol. 40 (2006) 103.
[22] S. Uchiyama, E. Matsushima, H. Tokunaga, Y. Otsubo, M. Ando, J.
Chromatogr. A 1116 (2006) 165.
[23] S.I. Semb, S. Pedersen-Bjergaard, E.M. Brevik, Chemosphere 49 (2002)
1349.
[24] P.A. Mosier-Boss, S.H. Lieberman, Anal. Chim. Acta 488 (2003) 15.
[25] Z. Bacsik, J. Mink, G. Keresztury, Appl. Spectrosc. Rev. 39 (2004) 295.
[26] A.M. Parkes, R.E. Lindley, A.J. Orr-Ewing, Anal. Chem. 76 (2004) 7329.
[27] T.-Y. Lin, U. Sree, S.-H. Tseng, K.H. Chiu, C.-H. Wu, J.-G. Lo, Atmos.
Environ. 38 (2004) 4111.
[28] Y.K. Wei, J. Yang, Anal. Sci. 21 (2005) 1195.
[29] J. Jang, A. Ramesh, Analyst 130 (2005) 397.
[30] R.A. Ketola, T. Kotiaho, M.E. Cisper, T.M. Allen, J. Mass Spectrom. 37
(2002) 457.
[31] O.S. Viktorova, V.T. Kogan, S.A. Manninen, J. Anal. Chem. 58 (2003)
942.
[32] J. Moxom, P.T.A. Reilly, W.B. Whitten, J.M. Ramsey, Anal. Chem. 75
(2003) 3739.
[33] R.M. Lago, A.C.B. Silva, A.C.M. Teixeira, R. Augusti, Analyst 128
(2003) 884.
[34] L.S. Ritter, E.C. Meurer, I. Cotte-Rodriguez, M.N. Eberlin, R.G. Cooks,
Analyst 128 (2003) 1119.
[35] E. Boscaini, M.L. Alexander, P. Prazeller, T.D. Märk, Int. J. Mass Spec-
trom. 239 (2004) 171.
[36] N. Jakubowska, Z. Polkowska, J. Namiesnik, A. Przyjazny, Crit. Rev.
Anal. Chem. 35 (2005) 217.
[37] M. Aznar, M. Tsachaki, R.S.T. Linforth, V. Ferreira, A.J. Taylor, Int. J.
Mass Spectrom. 239 (2004) 17.
[38] M. Tsachaki, R.S.T. Linforth, A.J. Taylor, J. Agric. Food Chem. 53 (2005)
8328.
[39] C.N. Hewitt, S. Hayward, A. Tani, J. Environ. Monit. 5 (2003) 1.
[40] R.S. Blake, C. Whyte, C.O. Hughes, A.M. Ellis, P.S. Monks, Anal. Chem.
76 (2004) 3841.
[41] W.C. Kuster, B.T. Jobson, T. Karl, D. Riemer, E. Apel, P.D. Goldan, F.C.
Fehsenfeld, Environ. Sci. Technol. 38 (2004) 221.
[42] M. Michulec, W. Wardencki, M. Partyka, J. Namiesnik, Crit. Rev. Anal.
Chem. 35 (2005) 117.
[43] ECA-IAQ, Total Volatile Organic Compounds (TVOC) in Indoor Air
Quality Investigations, Report No. 19, EUR 17675 EN, Office for Official
Publications of the European Community, Luxembourg, 1997.
[44] A. Chaintreau, Flavour Fragr. J. 16 (2001) 136.
[45] N.H. Snow, G.C. Slack, Trends Anal. Chem. 21 (2002) 608.
[46] L. Ramos, E.M. Kristenson, U.A.Th. Brinkman, J. Chromatogr. A 975
(2002) 3.
[47] F. Augusto, A.L.E. Lopes, C.A. Zini, Trends Anal. Chem. 22 (2003) 160.
[48] G. Vas, K. Vekey, J. Mass Spectrom. 39 (2004) 233–254.
[49] W. Wardencki, M. Michulec, J. Curylo, Int. J. Food Sci. Tech. 39 (2004)
703–717.
[50] C.F. Ross, D.M. Smith, Compr. Rev. Food Sci. Food Safety 5 (2006) 18.
[51] R.S. Garcia, A.S. Silva, I. Cooper, R. Franz, P.P. Losada, Trends Food
Sci.Technol. 17 (2006) 354.
[52] A.B. Lindstrom, J.D. Pleil, Biomarkers 7 (2002) 189.
[53] C. B’Hymer, Pharm. Res. 20 (2003) 337.
[54] P. Drasar, J. Moravcova, J. Chromatogr. B 812 (2004) 3.
 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
[55] S. Nyiredy, J. Chromatogr. B 812 (2004) 35.
[56] W. Miekisch, J.K. Schubert, G.F.E. Noeldge-Schomburg, Clin. Chim.
Acta 347 (2004) 25.
[57] H. Kataoka, Curr. Pharm. Anal. 1 (2005) 65.
[58] A.D. Delinsky, J.V. Bruckner, M.G. Bartlett, Biomed. Chromatogr. 19
(2005) 617.
[59] G. Ouyang, J. Pawliszyn, Trends Anal. Chem. 25 (2006) 692.
[60] D. Tholl, W. Boland, A. Hansel, F. Loreto, U.S.R. Röse, J.-P. Schnitzler,
Plant J. 45 (2006) 540.
[61] S. Pandey, Anal. Chim. Acta 556 (2006) 38.
[62] J. Atienza, P. Aragon, M. Asunción Herrero, R. Puchades, Á. Maquieira,
Crit. Rev. Anal. Chem. 35 (2005) 317.
[63] F.V. Parreira, Z. de Lourdes Cardeal, Quim. Nova 28 (2005) 646.
[64] J. Namiesnik, B. Zabiegala, A. Kot-Wasik, M. Partyka, A. Wasik, Anal.
Bioanal. Chem. 381 (2005) 279.
[65] B. Vrana, G.A. Mills, I.J. Allan, E. Dominiak, K. Svensson, J. Knutsson,
G. Morrison, R. Greenwood, Trends Anal. Chem. 24 (2005) 845.
[66] W. Liming, L. Jubai, O. Qingyu, L. Bing, Chin. J. Anal. Chem. 32 (2004)
1667.
[67] E.E. Stashenko, J.R. Martı́nez, Trends Anal. Chem. 23 (2004) 553.
[68] L.N. Moskvin, T.G. Nikitina, J. Anal. Chem. 59 (2004) 2.
[69] K.C. Clemitshaw, Crit. Rev. Environ. Sci. Techol. 34 (2004) 1.
[70] F. David, B. Tienpont, P. Sandra, LC–GC North Am. 21 (2003) 108.
[71] T.C. Schmidt, Trends Anal. Chem. 22 (2003) 776.
[72] E. Matisová, M. Dömötörová, J. Chromatogr. A 1000 (2003) 199.
[73] T. Huybrechts, J. Dewulf, H. Van Langenhove, J. Chromatogr. A 1000
(2003) 283.
[74] K. Dettmer, W. Engewald, Chromatographia 57 (2003) S339.
[75] E. Psillakis, N. Kalogerakis, Trends Anal. Chem. 22 (2003) 565.
[76] A. Kloskowski, M. Pilarczyk, J. Namiesnik, Crit. Rev. Anal. Chem. 32
(2002) 301.
[77] J.A. Koziel, I. Novak, Trends Anal. Chem. 21 (2002) 840.
[78] K. Dettmer, W. Engewald, Anal. Bioanal. Chem. 373 (2002) 490.
[79] E. Baltussen, C.A. Cramers, P.J.F Sandra, Anal. Bioanal. Chem. 373
(2002) 3.
[80] G.B. Lockwood, J. Chromatogr. A 936 (2001) 23.
[81] J.A. Jönsson, L. Mathiasson, J. Sep. Sci. 24 (2001) 495.
[82] L.-L. Hsieh, C.-C. Chang, U. Sree, J.-G. Lo, Water Air Soil Pollut. 170
(2006) 107.
[83] M. Gautrois, T. Brauers, R. Koppmann, F. Rohrer, O. Stein, J. Rudolph,
J. Geophys. Res. 108 (2003) 4393, doi:10.1029/2002JD002765.
[84] M. Das, V.P. Aneja, J. Environ. Eng. ASCE 129 (2003) 1085.
[85] M. Colón, J.D. Pleil, T.A. Hartlage, M.L. Guardan, M.H. Martins, Atmos.
Environ. 35 (2001) 4017.
[86] A. Juszkiewicz, B. Kijak, Pol. J. Environ. Stud. 12 (2003) 49.
[87] N. Ochiai, S. Daishima, D.B. Cardin, J. Environ. Monit. 5 (2003) 997.
[88] C. Warneke, J.A. De Gouw, W.C. Kuster, P.D. Goldan, R. Fall, Environ.
Sci. Technol. 37 (2003) 2494.
[89] C.-C. Chang, U. Sree, Y.-S. Lin, J.-G. Lo, Atmos. Environ. 39 (2005)
867.
[90] M. Navazo, N. Durana, L. Alonso, J.A. Garcı́a, J.L. Ilardia, M.C. Gómez,
G. Gangoiti, Int. J. Environ. Anal. Chem. 83 (2003) 199.
[91] K. Motyka, P. Mikuska, Z. Vecera, Anal. Chim. Acta 562 (2006) 236.
[92] H. Hellén, H. Kakola, A. Reissell, T.M. Ruuskanen, Atmos. Chem. Phys.
4 (2004) 1771.
[93] U. Wideqvist, V. Vesely, C. Johansson, A. Potter, E. Brorström-Lundén,
K. Sjöberg, T. Jonsson, Atmos. Environ. 37 (2003) 1963.
[94] E. Yamada, Y. Hosokawa, Y. Furuya, K. Matsushita, Y. Fuse, Anal. Sci.
20 (2004) 107.
[95] K. Sexton, J.L. Adgate, S.J. Mongin, G.C. Pratt, G. Ramachandran, T.H.
Stock, M.T. Morandi, Environ. Sci. Technol. 38 (2004) 2593.
[96] K. Sakai, D. Norbäck, Y. Mi, E. Shibata, M. Kamijima, T. Yamada, Y.
Takeuchi, Environ. Res. 94 (2004) 75.
[97] S. Mukerjee, L.A. Smith, G.A. Norris, M.T. Morando, M. Gonzales, C.A.
Noble, L.M. Neas, A.H. Özkaynak, J. Air. Waste Manage. Assoc. 54
(2004) 307.
[98] B. Strandberg, A.-L. Sunesson, K. Olsson, J.-O. Levin, G. Ljunqvist, M.
Sundgren, G. Sällsten, L. Barregard, Atmos. Environ. 39 (2005) 4101.
143
[99] W.A. McClenny, K.D. Oliver, H.H. Jacumin Jr., E.H. Daughtrey Jr., D.A.
Whitaker, J. Environ. Monit. 7 (2005) 248.
[100] W.A. McClenny, H.H. Jacumin Jr., K.D. Oliver, E.H. Daughtrey Jr., D.A.
Whitaker, J. Environ. Monit. 8 (2006) 263.
[101] C. Thammakhet, V. Muneesawang, P. Thavarungkul, P. Kanatharana,
Atmos. Environ. 40 (2006) 4589.
[102] Q.-L. Li, D.-X. Yuan, Q.-M. Lin, J. Chromatogr. A 1026 (2004) 283.
[103] W. Kornacki, P. Fastyn, T. Gierczak, J. Gawlowski, J. Niedzielski, Chro-
matographia 63 (2006) 67.
[104] J.M. Sanchez, R.D. Sacks, J. Sep. Sci. 28 (2005) 22.
[105] J. Volden, Y. Thomassen, T. Greibrokk, S. Thorud, P. Molander, Anal.
Chim. Acta 530 (2005) 263.
[106] J.D. Donaldson, S.M. Grimes, L. Mehta, A.J. Jafari, J. AOAC Int. 86
(2003) 39.
[107] C.M. Karbiwnyk, C.S. Mills, D. Helmig, J.W. Birks, Environ. Sci. Tech-
nol. 37 (2003) 1002.
[108] X. Xu, L.L.P. van Stee, J. Williams, J. Beens, M. Adahchour, R.J.J. Vreuls,
U.A.Th. Brinkman, J. Lelieveld, Atmos. Chem. Phys. 3 (2003) 665.
[109] J.F. Pankow, W. Luo, D.A. Bender, L.M. Isabelle, J.S. Hollingsworth, C.
Chen, W.E. Asher, J.S. Zogorski, Atmos. Environ. 37 (2003) 5023.
[110] V. Fernández-Villarrenaga, P. López-Mahia, S. Muniategui-Lorenzo, D.
Prada-Rodrı́guez, E. Fernández-Fernández, X. Tomàs, Sci. Total Environ.
334–335 (2004) 167.
[111] K.-H. Kim, S.-I. Oh, Y.-J. Choi, Talanta 64 (2004) 518.
[112] C.-H. Wu, M.-N. Lin, C.-T. Feng, K.-L. Yang, Y.-S. Lo, J.-G. Lo, J.
Chromatogr. A 996 (2003) 225.
[113] T. Seko, K. Usukura, N. Onda, Bunseki Kagaki 52 (2003) 1215.
[114] C.-H. Wu, C.-T. Feng, Y.-S. Lo, T.-Y. Lin, J.-G. Lo, Chemosphere 56
(2004) 71.
[115] M.S. Zuraimi, K.W. Tham, S.C. Sekhar, Build. Environ. 39 (2004) 165.
[116] J. Zhu, R. Newhook, L. Marro, C.C. Chan, Environ. Sci. Technol. 39
(2005) 3964.
[117] O.O. Kuntasal, D. Karman, D. Wang, S.G. Tuncel, G. Tuncel, J. Chro-
matogr. A 1099 (2005) 43.
[118] J.M. Sanchez, R.D. Sacks, Anal. Chem. 78 (2006) 3046.
[119] M. Hippelein, J. Environ. Monit. 6 (2004) 745.
[120] I. Ciucanu, A. Caprita, A. Chiriac, R. Barna, Anal. Chem. 75 (2003) 736.
[121] R. Barro, S. Ares, C. Garcia-Jares, M. Llompart, R. Cela, J. Chromatogr.
A 1045 (2004) 189.
[122] J.-L. Wang, C.-H. Wu, Anal. Chim. Acta 461 (2002) 85.
[123] A.C. Rivett, D. Martin, G. Nickless, P.G. Simmonds, S.J. O’Doherty, D.J.
Gray, D.E. Shalcross, Atmos. Environ. 37 (2003) 2221.
[124] M. Maione, J. Arduini, G. Mangani, A. Geniali, Int. J. Environ. Anal.
Chem. 84 (2004) 241.
[125] K.-H. Kim, Environ. Sci. Technol. 39 (2005) 6765.
[126] D. Tanner, D. Helmig, J. Hueber, P. Goldan, J. Chromatogr. A 1111 (2006)
76.
[127] D.J. Wevill, L.J. Carpenter, Analyst 129 (2004) 634.
[128] A. Kloskowski, W. Chrzanowski, M. Pilarczyk, J. Namiesnik, J. Chem.
Thermodynam. 37 (2005) 21.
[129] V. Larroque, V. Desauziers, P. Mocho, J. Environ. Monit. 8 (2006) 106.
[130] V. Larroque, V. Desauziers, P. Mocho, J. Chromatogr. A 1124 (2006) 106.
[131] M. Hippelein, Chemosphere 65 (2006) 271.
[132] L. Wei, Q. Ou, J. Li, B. Liang, Chromatographia 59 (2004) 601.
[133] F. Lestremau, F.A.T. Andersson, V. Desauziers, Chromatographia 59
(2004) 607.
[134] L. Tuduri, V. Desauziers, J.L. Fanlo, Analyst 128 (2003) 1018.
[135] J.A. Koziel, P.A. Martos, J. Pawliszyn, J. Chromatogr. A 1025 (2004) 3.
[136] F.V. Parreira, C.R. de Carvalho, Z. de Lourdes Cardeal, Bull. Environ.
Contam. Toxicol. 70 (2003) 957.
[137] C. Domeño, F. Martı́nez-Garcı́a, L. Campo, C. Nerı́n, Anal. Chim. Acta
524 (2004) 51.
[138] G. Mangani, A. Berloni, M. Maione, J. Chromatogr. A 988 (2003) 167.
[139] V.G. Berezkin, E.D. Marakov, B.V. Stolyarov, J. Chromatogr. A 985
(2003) 63.
[140] Y. Saito, I. Ueta, K. Gotera, M. Ogawa, H. Wada, K. Gino, J. Chromatogr.
A 1106 (2006) 190.
[141] A. Wang, F. Fang, J. Pawliszyn, J. Chromatogr. A 1072 (2005) 127.
144 K. Demeestere et al. / J. Chromatogr. A 1153 (2007) 130–144
[142] C.S. Creaser, D. Gómez Lamarca, L.M. Freitas dos Santos, FA.P. New,
P.A. James, Analyst 128 (2003) 1150.
[143] B. Zabiegala, T. Górecki, J. Namiesnik, Anal. Chem. 75 (2003) 3182.
[144] B. Zabiegala, M. Partyka, T. Górecki, J. Namiesnik, J. Chromatogr. A
1117 (2006) 19.
[145] H.-W. Kuo, T.-F. Chiang, I.-I. Lo, J.-S. Lai, C.-C. Chan, J.-D. Wang, Sci.
Total Environ. 208 (1997) 41.
[146] J. Dewulf, H. Van Langenhove, J. Chromatogr. A 843 (1999) 163.
[147] S.M. Pyle, G.W. Sovocool, L.A. Riddick, Talanta 69 (2006) 494.
[148] R. Kubinec, J. Adamuscin, H. Jurdáková, M. Foltin, I. Ostrovský, A.
Kraus, L. Soják, J. Chromatogr. A 1084 (2005) 90.
[149] Z. Polkowska, Chemosphere 57 (2004) 1265.
[150] K. Kozlowska, Z. Polkowska, A. Przyjazny, J. Namiesnik, Trends Anal.
Chem. 25 (2006) 609.
[151] Z. Polkowska, K. Kozlowska, Z. Mazerska, T. Górecki, J. Namiesnik,
Chemosphere 53 (2003) 899.
[152] A. Monod, N. Bonnefoy, P. Kaluzny, I. Denis, P. Foster, P. Carlier, Chemo-
sphere 52 (2003) 1307.
[153] M. Wortberg, W. Ziemer, M. Kugel, H. Muller, H.J. Neu, Anal. Bioanal.
Chem. 384 (2006) 1113.
[154] J. Pettersson, J. Roeraade, Anal. Chem. 77 (2005) 3365.
[155] M.V. Russo, L. Campanella, P. Avino, J. Sep. Sci. 26 (2003) 376.
[156] L. Zoccolillo, C. Abete, L. Amendola, R. Ruocco, A. Sbrilli, M. Termine,
Int. J. Environ. Anal. Chem. 84 (2004) 513.
[157] R. Zhao, W. Lao, X. Xu, Talanta 62 (2004) 751.
[158] L. Dong, X. Shen, C. Deng, Anal. Chim. Acta 569 (2006) 91.
[159] A. Tor, M.E. Aydin, Anal. Chim. Acta 575 (2006) 138.
[160] A. Tor, J. Chromatogr. A 1125 (2006) 129.
[161] M. Rezaee, Y. Assadi, M.-R. Milani Hosseini, E. Aghaee, F. Ahmadi, S.
Berijani, J. Chromatogr. A 1116 (2006) 1.
[162] M.A. Mottaleb, M.Z. Abedin, M.S. Islam, J. Environ. Sci. 16 (2004)
497.
[163] K. Luks-Betlej, D. Bodzek, Pol. J. Environ. Stud. 11 (2002) 255.
[164] L. Zwank, M. Berg, T.C. Schmidt, S.B. Haderlein, Anal. Chem. 75 (2003)
5575.
[165] A. Alonso, M.A. Fernández-Torroba, M.T. Tena, B. Pons, Chro-
matographia 57 (2003) 369.
[166] D. Panavaité, A. Padarauskas, V. Vickackaité, Anal. Chim. Acta 571
(2006) 45.
[167] M.B. Heringa, J.L.M. Hermens, Trends Anal. Chem. 22 (2003) 575.
[168] J.H. Loughrin, J. Agric. Food Chem. 54 (2006) 3237.
[169] C. Bicchi, C. Cordero, E. Liberto, P. Rubiolo, B. Sgorbini, F. David, P.
Sandra, J. Chromatogr. A 1094 (2005) 9.
[170] H. Wang, W. Liu, Y. Guan, LC–GC North Am. 22 (2004) 16.
[171] R. Kubinec, V.G. Berezkin, R. Górová, G. Addová, H. Mracnová, L.
Soják, J. Chromatogr. B 800 (2004) 295.
[172] J. Lipinski, Fresenius J. Anal. Chem. 369 (2001) 57.
[173] M.A. Jochmann, M.P. Kmiecik, T.C. Schmidt, J. Chromatogr. A 1115
(2006) 208.
[174] K. Ridgway, S.P.D. Lalljie, R.M. Smith, J. Chromatogr. A 1124 (2006)
181.
[175] J. Zhang, T. Su, H.K. Lee, J. Chromatogr. A 1121 (2006) 10.
[176] N. Vora-adisak, P. Varanusupakul, J. Chromatogr. A 1121 (2006) 236.
[177] P.-S. Chen, S.-D. Huang, J. Chromatogr. A 1118 (2006) 161.
[178] B. Hauser, P. Popp, E. Kleine-Benne, J. Chromatogr. A 963 (2002) 27.
[179] M. Schellin, P. Popp, J. Chromatogr. A 1020 (2003) 153.
[180] M. Schellin, B. Hauser, P. Popp, J. Chromatogr. A 1040 (2004) 251.
[181] B. Hauser, M. Schellin, P. Popp, Anal. Chem. 76 (2004) 6029.
[182] M. Schellin, P. Popp, J. Chromatogr. A 1072 (2005) 37.
[183] M. Schellin, P. Popp, J. Chromatogr. A 1103 (2006) 211.
[184] G. Köller, P. Popp, K. Weingart, B. Hauser, W. Herrmann, Chro-
matographia 57 (2003) S-229.
[185] A. Mohammadi, N. Alizadeh, J. Chromatogr. A 1107 (2006) 19.
[186] V.I. Safarova, S.V. Sapelnikova, E.V. Djazhenko, G.I. Teplova, G.F. Sha-
jdulina, F.Kh. Kudasheva, J. Chromatogr. B 800 (2004) 325.
[187] H. Grecsek, LC–GC 23 (Suppl. S) (2005) 42.
[188] J. Wypych, T. Manko, Chem. Anal. (Warsaw) 47 (2002) 507.
[189] I. Ciucanu, Anal. Chem. 74 (2002) 5501.
[190] A. Novotná-Rychtecká, J. Lenicek, Chem. Listy 97 (2003) 1074.
[191] I. Arambarri, M. Lasa, R. Garcia, E. Millán, J. Chromatogr. A 1033 (2004)
193.
[192] S. Nakamura, S. Daishima, Anal. Chim. Acta 548 (2005) 79.
[193] B. Tienpont, F. David, C. Bicchi, P. Sandra, J. Microcolumn. Sep. 12
(2000) 577.
[194] C. Bicchi, C. Cordero, C. Iori, P. Rubiolo, P. Sandra, J. High Resolut.
Chromatogr. 23 (2000) 539.
[195] C. Bicchi, C. Cordero, E. Liberto, P. Rubiolo, B. Sgorbini, P. Sandra, J.
Chromatogr. A 1071 (2005) 111.
[196] B.V. Burger, B. Marx, M. le Roux, W.J.G. Burger, J. Chromatogr. A 1121
(2006) 259.
[197] Y. Yamini, M.H. Hosseini, M. Hojaty, J. Arab, J. Chromatogr. Sci. 42
(2004) 32.
[198] Y. Yamini, M. Hojjati, M. Haji-Hosseini, M. Shamsipur, Talanta 62 (2004)
265.
[199] M. Khalili Zanjani, Y. Yamini, S. Shariati, J. Hazard. Mater. B136 (2006)
714.
[200] N. Bahramifar, Y. Yamini, S. Shariati-Feizabadi, M. Shamsipur, J. Chro-
matogr. A 1042 (2004) 211.
[201] M. Saraji, J. Chromatogr. A 1062 (2005) 15.
[202] P. Tölgyessy, J. Hrivnák, J. Chromatogr. A 1127 (2006) 295.
[203] E. Martinez, I. Llobet, S. Lacorte, P. Viana, D. Barceló, J. Environ. Monit.
4 (2002) 253.
[204] T. Huybrechts, J. Dewulf, H. Van Langenhove, Water Res. 38 (2004)
3241.
[205] T. Huybrechts, J. Dewulf, H. Van Langenhove, Environ. Pollut. 133 (2005)
255.
[206] L. Zoccolillo, L. Amendola, C. Cafaro, S. Insogna, J. Chromatogr. A 1077
(2005) 181.
[207] V. Fernández-Villarrenaga, P. López-Mahia, S. Muniategui-Lorenzo, D.
Prada-Rodriguez, Chem. Anal. (Warsaw) 51 (2006) 89.
[208] P.L. Morrill, G. Lacrampe-Coulome, B.S. Lollar, Rapid Commun. Mass
Spectrom. 18 (2004) 595.
[209] H. Okochi, M. Kataniwa, D. Sugimoto, M. Igawa, Atmos. Environ. 39
(2005) 6027.
[210] O. Christof, R. Seifert, W. Michaelis, Biogeochemistry 59 (2002) 143.
[211] I. Lavagnini, G. Favaro, F. Magno, Rapid. Commun. Mass Spectrom. 18
(2004) 1383.
[212] M. Krigbaum, LC–GC Suppl. S (2004) 39.
[213] E. Martinez, S. Lacorte, I. Llobet, P. Viana, D. Barceló, J. Chromatogr. A
959 (2002) 181.
[214] K.-L. Yang, C.-H. Lai, J.-L. Wang, J. Chromatogr. A 1027 (2004) 41.
[215] R.C. Silva, P.M.S. Aguiar, F. Augusto, Chromatographia 60 (2004) 687.
[216] Y.Z. Luo, J. Pawliszyn, Anal. Chem. 72 (2000) 1058.
[217] A. Segal, T. Górecki, P. Mussche, J. Lips, J. Pawliszyn, J. Chromatogr. A
873 (2000) 13.
[218] M. Ojala, I. Mattila, T. Särme, R.A. Ketola, T. Kotiaho, Analyst 124
(1999) 1421.
[219] M.A. Mendes, R. Sparrapan, M.N. Eberlin, Anal. Chem. 72 (2000) 2166.
[220] M. Ojala, I. Mattila, V. Tarkiainen, T. Särme, R.A. Ketola, A. Määttänen,
R. Kostiainen, T. Kotiaho, Anal. Chem. 73 (2001) 3624.