ARTICLE IN PRESS

Chemosphere xxx (2007) xxx–xxx

www.elsevier.com/locate/chemosphere

Determination of benzene, toluene, ethylbenzene, xylenes in water

at sub-ng l 1 levels by solid-phase microextraction coupled to
cryo-trap gas chromatography–mass spectrometry
a,*
Maw-Rong Lee , Chia-Min Chang a, Jianpeng Dou a,b

a
Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan, ROC
b
College of Biological and Agricultural Engineering, Jilin University, Changchun 130022, PR China

Received 26 December 2006; received in revised form 1 May 2007; accepted 3 May 2007

Abstract

A trace analytical method of benzene, toluene, ethylbenzene and xylenes (BTEX) in water has been developed by using headspace
solid-phase microextraction (HS-SPME) coupled to cryo-trap gas chromatography–mass spectrometry (GC–MS). The chromatographic
peak shape for BTEX was improved by using cryo-trap equipment. The HS-SPME experimental procedures to extract BTEX from water
were optimized with a 75 lm carboxen/polydimethylsiloxane (CAR/PDMS)-coated fiber at a sodium chloride concentration of 267 g l 1,
extraction for 15 min at 25 C and desorption at 290 C for 2 min. Good linearity was verified in a range of 0.0001–50 lg l 1 for each
analyte (r2 = 0.996–0.999). The limits of detection (LODs) of BTEX in water reached at sub-ng l 1 levels. LODs of benzene, toluene,
ethylbenzene, m/p-xylene and o-xylene were 0.04, 0.02, 0.05, 0.01 and 0.02 ng l 1, respectively. The proposed analytical method was suc-
cessfully used for the quantification of trace BTEX in ground water. The results indicate that HS-SPME coupled to cryo-trap GC–MS is
an effective tool for analysis of BTEX in water samples at the sub-ng l 1 level.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Solid-phase microextraction; Benzene; Toluene; Ethylbenzene; Xylene; Cryo-trap

1. Introduction (USEPA, 2004). The maximum contaminant level of

Benzene, toluene, ethylbenzene, m/p-xylene and o-xylene
(BTEX) are ubiquitously environmental contaminants in
air, water and soil and are widely used in industries, such
as printing, paint, synthetic resin, and synthetic rubber
(Holcomb and Seabrook, 1995; Nollet, 2001). BTEX are
also abundant in petroleum products, such as fuel oil and
gasoline. But BTEX has an effect on human health includ-
ing neurological diseases or cancer (Chiou et al., 1982). The
US Environmental Protection Agency (EPA) establishes
the maximum contaminant level (MCL) for benzene
5 lg l 1, for toluene 1000 lg l 1, for ethylbenzene 700
lg l 1 and for xylenes 10 000 lg l 1 in drinking water
*
Corresponding author. Tel.: +886 4 2285 1716.
E-mail address: mrlee@dragon.nchu.edu.tw (M.-R. Lee).
1 lg l 1 for benzene in drinking water is established by
the European Union (EU, 1998). Therefore, in order to
protect people’s health, it is necessary to establish an effec-
tive and convenient quantification method for monitoring
trace BTEX in water.
BTEX in water were analyzed by direct aqueous injec-
tion (DAI) and gas chromatography combined with flame
ionization detector (GC–FID), and limits of detection
(LOD) ranged from 0.6 lg l 1 for benzene to 1.1 lg l 1
for o-xylene (Kubinec et al., 2005). BTEX in water samples
were also analyzed by headspace solid-phase microextrac-
tion (SPME) and GC–FID (Flórez Menéndez et al.,
2000; Almeida and Boas, 2004; Ezquerro et al., 2004),
and LOD obtained with PDMS/DVB/CAR fibre ranged
from 15 ng l 1 (benzene) to 160 ng l 1 (toluene) (Almeida
and Boas, 2004). Substituted benzene was analyzed by
liquid-phase microextraction (LPME) and GC–FID, and

0045-6535/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2007.05.004

Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
 ARTICLE IN PRESS
2 M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx
LODs of BTEX ranged from 0.3 lg l 1 for o-xylene to
1.6 lg l 1 for toluene in a water matrix (Wang et al.,
2006). At present, gas chromatography–mass spectrometry
(GC–MS) is widely used to determine BTEX in different
water samples. Generally, sample preparation of BTEX
from real samples is an important procedure before analy-
sis. Liquid–liquid extraction, solid-phase extraction and
purge-and-trap techniques were used for determination of
BTEX in the past (Stan and Kirsch, 1995; Beketov et al.,
1996; Miermans et al., 2000; Bianchi et al., 2002; Rosell
et al., 2003). BTEX in water were analyzed by purge-and-
trap and GC–MS, and LOD ranged from 2.8 ng l 1 for
o-xylene to 22.6 ng l 1 for ethylbenzene (Bianchi et al.,
2002). However, solid-phase microextraction (SPME), as
rapid, selective and solvent-free techniques, are more and
more widely used for analysis of trace BTEX (Potter and
Pawliszyn, 1992; Elke et al., 1998; Fuoco et al., 1999; Koz-
iel et al., 2000; Li et al., 2001; Matisová et al., 2002;
Almeida and Boas, 2004; Arambarri et al., 2004). BTEX
were analyzed by SPME–GC–MS, and LODs ranged from
15 ng l 1 for benzene to 50 ng l 1 for o-xylene in a water
matrix (Potter and Pawliszyn, 1992).
The aim of this study was to develop a higher sensitivity
method for determination of trace BTEX in water samples.
In this work, BTEX were adsorbed on the fiber coating of
the SPME. A headspace (HS) SPME method was used to
extract trace BTEX in water. The cryo-trap could curtail
chromatographic peak breadth of volatile compounds
and improve chromatographic shape. Therefore, BTEX
extract was analyzed by cryo-trap-GC–MS. The conditions
for extracting BTEX from water samples are optimized.
The optimized HS-SPME–GC–MS method was used to
determine BTEX in ground water.
2. Materials and methods
2.1. Chemicals and materials
Benzene (99.99%), toluene (99.5%), ethylbenzene
(99.97%), o-xylene (99.3%), m-xylene (99.8%), and p-xylene
(99.9%) were purchased from TEDIA Company (Fairfield,
OH, USA). Sodium chloride (99.8%) was obtained from
Riedel-deHaën Company (Seelze, Germany). One standard
mixture of BTEX were prepared at individual concentra-
tion of 100 mg l 1 in acetone and diluted with water to
yield the required concentration. All solutions were stored
at 4 C in a refrigerator. All chemicals and reagents used in
Table 1
Analytical conditions of BTEX by GC–MS with SIM mode
Compound Molecular weight Retention time (min)
Benzene 78 4.95
Toluene 92 5.99
Ethylbenzene 106 7.78
m/p-Xylene 106 7.98
o-Xylene 106 8.45
Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
this work were analytical grade without further purifica-
tion. The purified water was obtained by an SG Ultra clear
water purification system (SG Water Company, Barsbüttel,
Germany). All glassware was silanized before it was used
by soaking the glassware overnight in toluene solution with
10% dichlorodimethylsilane. The glassware was rinsed with
toluene and methanol and then thoroughly dried for 4 h.
2.2. GC–MS
GC–MS and some parameters set were in accordance
with the description of a literature (Lee et al., 2000). The
GC oven temperature program was as follows: 40 C held
2 min, rate 25 C min 1 to 70 C, rate 2 C min 1 to
80 C, rate 25 C min 1 to 250 C, held for 1 min. Electron
impact ionization (EI) was used as ionization mode for
BTEX analysis. An injector temperature was maintained
at 290 C. The mass spectra were obtained at a mass-to-
charge ratio (m/z) scan range from 45 to 300 u. Cryo-trap
was produced by Scientific Instrument Services Inc. (Mode
961, Ringoes, NJ, USA). BTEX are trapped in the cryo-
trap accumulation cell, which allows all of BTEX were
quantitatively transferred from the cryo-trap cell to the
chromatographic column by the helium flow. The temper-
ature of cryo-trap was initially set at 100 C (held 2 min),
and then reached sharply to 250 C. To increase sensitivity,
the selected ion monitoring (SIM) mode of EI was also
applied in quantitative analysis.
The most abundant ion was generally monitored as well
as quantified and the specific ion was used as the confirmed
ion. The compounds of m-xylene and p-xylene were com-
bined and analyzed as sum of the corresponding peak areas
because they could not be separated during the GC analysis
and have the same fragmentation pathways. In Table 1, the
most abundant ion of benzene is m/z 78 ([M]+) ion and the
most abundant ion of the other BTEX is m/z 91 ([M H]+
or [M CH3]+) ion. Hence, the fragment ions m/z 78 and 91
were used for quantification of benzene and other BTEX,
respectively.
2.3. Sample preparation
The SPME fibers were purchased from Supelco Com-
pany (Bellefonte, PA, USA). SPME sampling was similar
to the description of a literature (Lee et al., 2007). The
ground water samples (nearby gas station, paint factory,
river and university in Taichung, Taiwan) were stored at
Quantification ions (m/z) Confirmed ions (m/z)
78 77, 52, 51
91 92, 65, 51
91 106, 77, 65
91 106, 77, 65
91 106, 77, 65
 ARTICLE IN PRESS
M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx
4 C in a refrigerator and analyzed within 48 h to avoid
storage losses. A 15 ml of sample solution was undertaken
in a 40 ml sample vials and closed with a PFTE-coated sep-
tum. A 75 lm CAR/PDMS fiber was used to extract BTEX
from water samples. Triplicate analyses were performed.
Extraction temperature was at 25 C. During extraction,
the sample solution was continuously agitated at a constant
velocity of 1000 rpm with a Teflon-coated stir bar (0.8 cm ·
2.0 cm) on a magnetic stirrer.
3. Results and discussion
3.1. Optimization of SPME conditions
The extraction efficiency of the SPME experiment could
be affected by type of fiber, desorption temperature,
desorption time, absorption time, sample matrix and vari-
ous other factors (Lagalante and Felter, 2004). Different
types of coatings provide different absorption properties
for different kinds of analytes. The choice of an appropriate
coating is crucial for the SPME method. Various coatings
were tested under the conditions: standard solution con-
centration of BTEX, 40 lg l 1; extraction temperature,
25 C; extraction time, 15 min. Triplicate analyses were
performed, relative standard deviations of all fibers were
less than 10%. The result in Fig. 1 reveals that the 75 lm
CAR/PDMS fiber is the best for simultaneous extraction
of BTEX. CAR/PDMS coating (Elke et al., 1998; Koziel
et al., 2000; Li et al., 2001; Arambarri et al., 2004) was suit-
able for analysis of small molecular and nonpolar com-
pounds. Although Cho et al. proposed that CAR/PDMS
should be carefully used for determination of BTEX in
groundwater samples, there is hardly interference among
BTEX components when the concentration of the analyte
is at a low level (Cho et al., 2003). Therefore, 75 lm
CAR/PDMS was used for the analysis of low-concentra-
tion BTEX in this study.
The principle of SPME is based on partition equilibrium
between the concentration of analytes in a sample and that
1
Fig. 1. Extraction efficiencies of 40 lg l BTEX in water with various fiber coatings adsorption for 15 min at 25 C (n = 3).
Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
3
in the solid-phase fiber coating (Arthur and Pawliszyn,
1990). Although a stir bar could accelerate the mass trans-
fer of analytes through the aqueous matrix, the time of
extraction, the temperature and headspace of sample vial
have an effect on the partition equilibrium. Extractions
were performed from 5 to 30 min to determine the effect
of extraction time (Fig. 2). Fresh samples were used for
each extraction time studied. BTEX have all reached parti-
tion equilibrium in 15 min. The extraction temperature
determines the mass transfer rate of BTEX from water into
fiber. Extraction temperatures from 25 to 75 C were inves-
tigated. The maximum amount extracted was at 25 C, and
then decreased gradually as the temperature increased fur-
ther. The reason probably is the partition coefficient of
BTEX on fiber coating decreased as the temperature
increased. The more BTEX volatilized from water matrix
to gas phase as extraction temperature rose, the more ana-
lytes were adsorbed on the fiber, but at the same time the
much more analytes were desorbed from fiber for higher
extraction temperature, therefore the total abundance of
BTEX gradually decreased as the extraction temperature
increased. The headspace of vial would also affect extrac-
tion efficiencies for sample by SPME. The absolute amount
of BTEX on headspace of sample vial was relevant to head-
space and solution volume of vial. A solution of 1, 2, 5, 10,
15 and 20 ml was added in 40 ml of vial, respectively. The
results in Fig. 3 show the peak areas of BTEX increased
with the volume of solution to a maximum at 15 ml except
o-xylene. Therefore, 15 ml of BTEX water solution in 40 ml
vial are extracted for 15 min by HS-SPME at 25 C.
The desorption temperature and desorption time deter-
mine the amount of analytes desorbed from the fiber coat-
ing, as determined by the SPME method. The desorption
temperature was investigated with a range of 260–300 C.
The results indicate that the peak areas of BTEX increased
with the desorption temperature, reaching a maximum
desorption amount at 290 C. Desorption time was investi-
gated within a range of 0.5–4 min, by leaving the fiber in
the injector for an increasing period of time and maintain-
 ARTICLE IN PRESS
4 M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx
Fig. 2. Effect of extraction time on peak areas of 40 lg l
Fig. 3. Effect of solution volume in 40 ml vial on peak areas of 40 lg l
ing the temperature of the injector at 290 C. The amount
of BTEX desorption increased with desorption time and
reached a maximum after 2 min. Therefore, a 290 C
desorption temperature and 2 min desorption time were
used in the experiment. The SPME fiber can be continu-
ously used during the experiment without any carry over
after desorbed 290 C for 2 min.
Changes in the sample matrix had a significant effect on
the signal intensities of analytes obtained by SPME (Lee
et al., 2000, 2007). The analyte of neutral molecular form
is extracted easily by SPME. In order to investigate the
effect of salting out on the signal intensities of analytes,
sodium chloride was added to the water samples to yield
final concentrations of sodium chloride of 0.067, 0.133,
0.200, 0.267 and 0.333 g ml 1. A blank solution (40 lg l 1
of BTEX standard solution) with no added sodium chlo-
ride was also tested. Sodium chloride is able to increase
Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
1
BTEX in water produced by HS-SPME at 25 C.
1
BTEX in water produced by HS-SPME for 15 min at 25 C.
the ionic strength and improve the amount of analytes
extracted by the SPME fiber. The results indicate that the
peak areas of BTEX increase with the amount of NaCl
to a maximum at 0.267 g ml 1. Therefore, the extraction
is pursued at additional sodium chloride concentration of
0.267 g ml 1.
3.2. Method validation
The linearity, limits of detection and precision were cal-
culated when the optimum conditions for the HS-SPME–
cryo-trap-GC–MS procedure were established. The linear-
ity of the HS-SPME method was examined by extracting
standard solutions spiked 0.0001, 0.001, 0.01, 1, 10 and
50 lg l 1 BTEX, respectively. Triplicate injections were
performed. The r2 were above 0.996. Lack-of-fit and Man-
del’s fitting test were performed to check the goodness of fit
 ARTICLE IN PRESS

M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx 5

and linearity (Bianchi et al., 2002; Přikryl et al., 2006).
Lack-of-fit tests demonstrated that the linear models were
adequate because the whole p values were more than 0.05
at significance level of 95%. Mandel’s fitting tests were also
performed for the mathematical verification of linearity. F
values calculated lower than the tabulated F-value at the
confidence level of 95% indicating that a quadratic regres-
sion would not provide a significantly better fit than a lin-
ear one (Table 2). The linear range experiments provided
the necessary information to estimate LODs, based on
the lowest detectable peak with a signal-to-noise ratio of
three. LODs of SPME used to determine BTEX in water
relies on the amount of analytes adsorbed by coating on
the fiber and the sensitivity of the GC–MS. Under the
experimental conditions, LODs were 0.01–0.05 ng l 1 in
water. The precision of the HS-SPME method was evalu-
ated by analyzing BTEX at two concentration levels for
each analyte. The results in Table 2 showed that the RSDs

Table 2
Linear range, limit of detection (LOD) and precision of BTEX in water by SPME–cryo-trap-GC–MS
Compound Linear range (lg l 1) r2 LOD (ng l 1) Lack-of-fit, pa Mandel’s fitting test, Fa RSD (%, n = 9)
1 1
0.1 lg l 40 lg l
Benzene 0.0001–50 0.998 0.04 1.000 0.01 11.2 5.2
Toluene 0.0001–50 0.998 0.02 0.862 2.27 8.9 4.5
Ethylbenzene 0.0001–50 0.996 0.05 0.999 0.18 11.6 6.8
m/p-Xyleneb 0.0001–50 0.999 0.01 0.606 4.16 8.4 3.1
o-Xylene 0.0001–50 0.998 0.02 0.661 4.17 7.8 4.8
a
Confidence interval, 95%.
b
The value of m/p-xylene expressed the sum of m-xylene and p-xylene.

Table 3
Concentration (lg l 1) of BTEX in water samples by SPME–cryo-trap-GC–MS
Real water sample Benzene Toluene Ethylbenzene m/p-Xylenea o-Xylene
b
S1 5.9 ± 0.5 6.2 ± 0.8 0.62 ± 0.05 0.85 ± 0.04 0.35 ± 0.05
S2 0.72 ± 0.08 0.95 ± 0.04 0.15 ± 0.02 0.10 ± 0.03 0.12 ± 0.02
S3 <c < < < <
S4 0.18 ± 0.05 36 ± 4.20 ND 1.60 ± 0.05 0.56 ± 0.04
S5 < 24.2 ± 2.2 0.28 ± 0.06 0.52 ± 0.02 0.98 ± 0.05
S6 15.2 ± 2.5 35.2 ± 6.0 7.4 ± 0.9 12.1 ± 0.4 4.0 ± 0.4
S7 < 1.21 ± 0.09 < < <
a
The value of m/p-xylene expressed the sum of m-xylene and p-xylene.
b
S1–S3: ground water nearby different gas station in Taichung; S4–S5: ground water nearby different paint factory in Taichung; S6: ground water nearby
some university in Taichung; S7: river water in Taichung.
c
< : <LOQ value.

Fig. 4. Mass ion chromatogram of ground water S6 analyzed by HS-SPME–cryo-trap-GC–MS.

Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
 ARTICLE IN PRESS
6 M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx
were lower than 12% in aqueous matrix. Therefore, BTEX
in sorption on a CAR/PDMS-coated fiber in HS-SPME
were deemed acceptable for determining at sub-ng l 1 lev-
els in water solution.
3.3. HS-SPME–cryo-trap-GC–MS of real samples
The proposed method was used to quantify BTEX in
ground water. The HS-SPME was operated under the opti-
mum conditions. Triplicate analyses were performed. The
results in Table 3 shows that BTEX was present in ground
water. Fig. 4 shows the mass ion chromatogram of S6,
which the contents of BTEX were 4.0 lg l 1 (o-xylene) to
35.2 lg l 1 (toluene). Recoveries in the range 102–106%
were obtained for all samples. The results indicate the suit-
ability of the HS-SPME–cryo-trap-GC–MS method for
analyzing trace BTEX in water.
4. Conclusions
Results from this study indicate that SPME coupled to
GC–MS is a precise method for reproducibly analyzing
trace BTEX in water. Better sensitivity were obtained by
headspace SPME combined with GC–MS, and the chro-
matographic shape is improved further by cryo-trap.
Detection limits of BTEX in water at sub-ng l 1 concentra-
tion levels were achieved and linear ranges were over five
orders of magnitude for all the analytes. Earlier studies
on determination of BTEX were at from lg l 1 to ng l 1
level and linear ranges were less than four orders of magni-
tude. BTEX were indeed present in ground water samples
probably contaminated by gasoline, paint and thinners,
and chemical solvents.
Acknowledgements
The authors thank the National Science Council of the
Republic of China for financially supporting this research
under contract No. NSC92-2113-M-005-024.
References
Almeida, C.M.M., Boas, L.V., 2004. Analysis of BTEX and other
substituted benzenes in water using headspace SPME-GC–FID:
method validation. J. Environ. Monitor. 6, 80–88.
Arambarri, I., Lasa, M., Garcia, R., Millán, E., 2004. Determination of
fuel dialkyl ethers and BTEX in water using headspace solid-phase
microextraction and gas chromatography–flame ionization detection.
J. Chromatogr. A 1033, 193–203.
Arthur, C.L., Pawliszyn, J., 1990. Solid phase microextraction with
thermal desorption using fused silica optical fibers. Anal. Chem. 62,
2145–2148.
Beketov, V.I., Parchinski, V.Z., Zorov, N.B., 1996. Effects of high-
frequency electromagnetic treatment on the solid-phase extraction of
aqueous benzene, naphthalene and phenol. J. Chromatogr. A 731, 65–
73.
Bianchi, F., Careri, M., Marengo, E., Musci, M., 2002. Use of
experimental design for the purge-and-trap-gas chromatography–mass
spectrometry determination of methyl tert.-butyl ether, tert.-butyl
Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004
alcohol and BTEX in groundwater at trace level. J. Chromatogr. A
975, 113–121.
Chiou, C.T., Schmedding, D.W., Manes, M., 1982. Partition of organic
compounds in octanol–water systems. Environ. Sci. Technol. 16, 4–10.
Cho, H.-J., Baek, K., Lee, H.-H., Lee, S.-H., Yang, J.-W., 2003.
Competitive extraction of multi-component contaminants in water
by carboxen–polydimethylsiloxane fiber during solid-phase micro-
extraction. J. Chromatogr. A 988, 177–184.
Elke, K., Jermann, E., Begerow, J., Dunemann, L., 1998. Determination
of benzene, toluene, ethylbenzene and xylenes in indoor air at
environmental levels using diffusive samplers in combination with
headspace solid-phase microextraction and high-resolution gas chro-
matography–flame ionization detection. J. Chromatogr. A 826, 191–
200.
EU, 1998. Council Directive 98/83/EC of 3 November 1998 on quality of
water intended for human consumption, Official Journal of the
European Communities, L 330, 5/12/1998, 0032–0054.
Ezquerro, Ó., Ortiz, G., Pons, B., Tena, M.T., 2004. Determination of
benzene, toluene, ethylbenzene and xylenes in soils by multiple
headspace solid-phase microextraction. J. Chromatogr. A 1035, 17–22.
Flórez Menéndez, J.C., Fernández Sánchez, M.L., Sánchez Urı́a, J.E.,
Fernández Martı́nez, E., Sanz-Medel, A., 2000. Static headspace,
solid-phase microextraction and headspace solid-phase microextrac-
tion for BTEX determination in aqueous samples by gas chromato-
graphy. Anal. Chim. Acta 415, 9–20.
Fuoco, R., Ceccarini, A., Onor, M., Marrara, L., 1999. Analysis of
priority pollutants in environmental samples by on-line supercritical
fluid chromatography cleanup–cryo-trap-gas chromatography–mass
spectrometry. J. Chromatogr. A 846, 387–393.
Holcomb, L.C., Seabrook, B.S., 1995. Indoor concentrations of volatile
organic compounds: implications for comfort, health and regulation.
Indoor Environ. 4, 7–26.
Koziel, J., Jia, M.Y., Pawliszyn, J., 2000. Air sampling with porous solid-
phase microextraction fibers. Anal. Chem. 72, 5178–5186.
Kubinec, R., Adamuščin, J., Jurdáková, H., Foltin, M., Ostrovský, I.,
Kraus, A., Soják, L., 2005. Gas chromatographic determination of
benzene, toluene, ethylbenzene and xylenes using flame ionization
detector in water samples with direct aqueous injection up to 250 ll. J.
Chromatogr. A 1084, 90–94.
Lagalante, A.F., Felter, M.A., 2004. Silylation of acrylamide for analysis
by solid-phase microextraction/gas chromatography/ion-trap mass
spectrometry. J. Agric. Food Chem. 52, 3744–3748.
Lee, M.R., Song, Y.S., Hwang, B.H., Chou, C.C., 2000. Determination of
amphetamine and methamphetamine in serum via headspace deriva-
tization solid-phase microextraction–gas chromatography–mass spec-
trometry. J. Chromatogr. A 896, 265–273.
Lee, M.R., Chang, L.Y., Dou, J., 2007. Determination of acrylamide in
food by solid-phase microextraction coupled to gas chromatography–
positive chemical ionization tandem mass spectrometry. Anal. Chim.
Acta 582, 19–23.
Li, K., Santilli, A., Goldthorp, M., Whiticar, S., Lambert, P., Fingas, M.,
2001. Solvent vapour monitoring in work space by solid phase micro
extraction. J. Hazard. Mater. 83, 83–91.
Matisová, E., Medved’ová, M., Vraniaková, J., Šimon, P., 2002. Optimi-
sation of solid-phase microextraction of volatiles. J. Chromatogr. A
960, 159–164.
Miermans, C.J.H., van der Velde, L.E., Frintrop, P.C.M., 2000. Analysis
of volatile organic compounds, using the purge and trap injector
coupled to a gas chromatograph/ion-trap mass spectrometer: review of
the results in Dutch surface water of the Rhine, Meuse, Northern
Delta Area and Westerscheldt, over the period 1992–1997. Chemo-
sphere 40, 39–48.
Nollet, L.M.L. (Ed.), 2001. Handbook of Water Analysis. Marcel Dekker,
New York (Chapter 33).
Potter, D.W., Pawliszyn, J., 1992. Detection of substituted benzenes in
water at the pg/ml level using solid-phase microextraction and gas
chromatography–ion trap mass spectrometry. J. Chromatogr. A 625,
247–255.
 ARTICLE IN PRESS

M.-R. Lee et al. / Chemosphere xxx (2007) xxx–xxx 7

Přikryl, P., Kubinec, R., Jurdáková, H., Ševčı́ky, J., Ostrovsk, I., Soják,
L., Berezkin, V., 2006. Comparison of needle concentrator with SPME
for GC determination of benzene, toluene, ethylbenzene, and xylenes
in aqueous samples. Chromatographia 64, 65–70.
Rosell, M., Lacorte, S., Ginebreda, A., Barceló, D., 2003. Simultaneous
determination of methyl tert.-butyl ether and its degradation products,
other gasoline oxygenates and benzene, toluene, ethylbenzene and
xylenes in Catalonian groundwater by purge-and-trap-gas chromato-
graphy–mass spectrometry. J. Chromatogr. A 995, 171–184.
Stan, H.J., Kirsch, N.H., 1995. GC–FID determination of chloroben-.
zene isomers in methanogenic batch-cultures from river sediments. Int.
J. Environ. Anal. Chem. 60, 33–40.
USEPA, 2004. List of Contaminants & their Maximum Contaminant
Level (MCLs) in drinking water. http://www.epa.gov/safewater/
mcl.html#organic.
Wang, J.-X., Jiang, D.-Q., Yan, X.-P., 2006. Determination of substituted
benzenes in water samples by fiber-in-tube liquid phase microextrac-
tion coupled with gas chromatography. Talanta 68, 945–950.

Please cite this article in press as: Lee, M.-R. et al., Determination of benzene, toluene, ethylbenzene, xylenes in water ..., Chemo-
sphere (2007), doi:10.1016/j.chemosphere.2007.05.004