Analytica Chimica Acta 548 (2005) 79–85

Simultaneous determination of 22 volatile organic compounds,

methyl-tert-butyl ether, 1,4-dioxane, 2-methylisoborneol and
geosmin in water by headspace solid phase microextraction-gas
chromatography–mass spectrometry
Sadao Nakamura ∗ , Shigeki Daishima
Yokogawa Analytical Systems Inc., 9-1 Takakura-cho, Hachioji-shi, Tokyo 192-0033, Japan

Received 10 March 2005; received in revised form 27 May 2005; accepted 31 May 2005
Available online 14 July 2005

Abstract

A method for the simultaneous determination of 22 volatile organic compounds (VOCs), methyl-tert-butyl ether (MTBE), 1,4-dioxane, 2-
methylisoborneol (2-MIB) and geosmin in water by headspace solid phase microextraction (SPME)-gas chromatography–mass spectrometry
(GC–MS) is described. Three types of SPME fibers (carboxen (CAR)/polydimethylsiloxane (PDMS), divinylbenzene (DVB)/PDMS and 100-
␮m PDMS) were evaluated to achieve the method detection limits and linear range required in Japanese water regulation. A 100-␮m PDMS
was found to be the best coating to obtain a wide range of linearity for the target compounds in multiple-component system. CAR/PDMS and
DVB/PDMS of adsorbent type fibers showed a narrow linear range for 22 VOCs, MTBE and 1,4-dioxane at the ␮g/l levels due to the limited
capacity.
The detection limits of this method were 0.01–0.05 ␮g/l for 22 VOCs, 0.01 ␮g/l for MTBE, 1.2 ␮g/l for 1,4-dioxane, 0.6 ng/l for 2-
MIB and 0.3 ng/l for geosmin. The recoveries of 22 VOCs and MTBE from a river water sample spiked at 1 ␮g/l were between 93.7
and 104.0%, with R.S.D. values of between 1.7 and 9.5%. Those of 1,4-dioxane, 2-MIB and geosmin at 5 ␮g/l, 10 ng/l and 10 ng/l,
respectively, were 109.1, 95.9 and 97.4%, with R.S.D. values of 2.0, 5.6 and 1.8%. The method provided linear range from 0.1 to
100 ␮g/l for 21 VOCs and MTBE, 0.1 to 50 ␮g/l for m,p-xylene, 5 to 100 ␮g/l for 1-4dioxane and 1 to 100 ng/l for 2-MIB and
geosmin.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Water analysis; Volatile organic compounds (VOCs); Methyl-tert-butyl ether (MTBE); 1,4-Dioxane; 2-Methylisoborneol and geosmin; Solid phase
microextraction (SPME); GC–MS

1. Introduction analyzed due to their widely different standard values in

Volatile organic compounds (VOCs) and musty odor
compounds have been widely monitored in water supplies.
2-Methylisoborneol (2-MIB) and geosmin produced by Acti-
nomycetes bacteria and some species of blue-green algae
are mainly cited as the musty odor compounds. Gener-
ally VOCs and the musty odor compounds are separately
∗ Corresponding author.
E-mail address: sadao nakamura@agilent.com (S. Nakamura).
water regulation: ␮g/l levels for VOCs; ng/l levels for 2-
MIB and geosmin. Since the threshold odor concentra-
tions of 2-MIB and geosmin are 9 and 4 ng/l, respec-
tively [1], a highly sensitive method with a detection limit
below 1 ng/l is needed. Gas chromatography–mass spec-
trometry (GC–MS) with purge-and-trap [2,3] and GC–MS
using liquid–liquid extraction [4] have been applied to the
analysis of 2-MIB and geosmin in water samples. Solid
phase microextraction (SPME) [5] has recently been applied
to their analysis [6,7]. On the other hand, the analysis of

0003-2670/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2005.05.077
80 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85
VOCs requires a method with detection at the sub-␮g/l
levels. Headspace GC–MS, purge and trap GC–MS and
SPME GC–MS have been applied to their analysis [8,9].
Recently methyl-tert-butyl ether (MTBE) and 1,4-dioxane
in water supplies have received attention. MTBE is an addi-
tive used in reformulated gasoline. MTBE has been iden-
tified as a ground water contaminant. Common methods
for the determination of MTBE are purge-and-trap GC–MS
and headspace GC–MS. SPME is also applied to its anal-
ysis [10,11]. 1,4-Dioxane is a manmade compound pri-
marily used as an industrial solvent or solvent stabilizer.
1,4-Dioxane is also present in ordinary household prod-
ucts like shampoos, soap, lotion, bath foam and other cos-
metic products. The U.S. Environmental Protection Agency
(EPA) has listed 1,4-dioxane as a probable human carcino-
gen. Japan has established a drinking water standard at
50 ␮g/l for 1,4-dioxane. Purge and trap GC–MS has been
applied to the determination of 1,4-dioxane in water. Solid-
phase extraction (SPE) GC–MS has also been applied to
its analysis [12,13]. Although, currently, VOCs, MTBE,
1,4-dioxane and the odor compounds are separately ana-
lyzed by adequate methods, the simultaneous determina-
tion of VOCs, MTBE, 1,4-dioxane, 2-MIB and geosmin is
strongly required for high efficiency. It increases produc-
tivity and saves time. However, no method for its analysis
has been reported. There are difficulties in detecting 2-MIB
and geosmin at the 1 ng/l level with retaining a wide lin-
ear range of VOCs in the ␮g/l levels in multiple-component
system.
On the other hand, SPME has been widely used for the
extraction of volatile and semi-volatile organic compounds
from environmental, biological and food samples [14–18].
SPME is a simple, effective sample preparation technique.
The analytes of interest are extracted by the exposure of the
fiber to the sample or the headspace above the sample. The
type of polymer coating on the needle is chosen to match the
characteristics of the analytes of interest.
In this study, SPME was applied to the simultaneous
determination of 22 VOCs, MTBE, 1,4-dioxane, 2-MIB
and geosmin in aqueous samples. Three types of polymer
coatings (carboxen (CAR)/polydimethylsiloxane (PDMS),
divinylbenzene (DVB)/PDMS and 100-␮m PDMS) were
evaluated to select the appropriate coating for the extraction
of the target compounds considering the sensitivity and
linear range required in Japanese water regulation.
2. Experimental
2.1. Chemicals
Twenty-two VOCs (1 mg/ml in methanol) were obtained
from Kanto Chemical (Tokyo, Japan). 2-MIB and geosmin
(100 ␮g/ml in methanol), MTBE and 1,4-dioxane were
obtained from Wako (Osaka, Japan). Geosmin-d3 and 1,4-
dioxane-d8, used as surrogate, were obtained from Hayashi
Pure Chemicals (Osaka, Japan). Methanol, pesticide grade,
was purchased from Wako. Sodium chloride, reagent grade,
was obtained from Wako and baked at 350 ◦ C for several
hours before use.
2.2. Extraction procedure
Tap water was taken at Hachioji, Tokyo, and river water
was collected from the Tama River at Hachioji, Tokyo. The
water samples were added to 500 ml bottle without empty
space and stored at 4 ◦ C before analysis. A 100-␮m PDMS
fiber (Supelco, Bellefonte, PA, USA) was used for extraction.
The fiber was thermally conditioned at 250 ◦ C for 30 min. The
automatic SPME device (MPS2) was commercially available
from Gerstel GmbH (Mülheim a/d Ruhr, Germany). Three
grams of sodium chloride was added to a 20 ml glass vial.
A 10 ml of water sample was transferred into the vial. The
geosmin-d3 (0.1 ng) used as surrogate for 22 VOCs, 2-MIB
and geosmin and the 1,4-dioxane-d8 (500 ng) used as sur-
rogate for MTBE and 1,4-dioxane were then added to the
sample. A PTFE-faced septum cap was immediately crimped
on the vial. After sodium chloride was dissolved, the fiber was
exposed in the headspace of the sample for 30 min at 60 ◦ C.
Finally, the fiber was removed from the vial and immediately
inserted into a GC injection port for thermal desorption of
the extracted analytes for 1 min.
2.3. Instrumentation
GC–MS was carried out with an Agilent 6890/5973 (Agi-
lent Technologies, Palo Alto, CA, USA) equipped with an
MPS2 (Gerstel GmbH). The injection port was equipped
with a SPME insert and was kept at 270 ◦ C. Pulsed splitless
injection was used with a pulse pressure of 40 psi (1.0 min)
and a purge time delay of 1.0 min. A DB-1 capillary column
(Agilent Technologies, Palo Alto, CA, USA; 60 m × 0.25 mm
i.d. × 1.0 ␮m film thickness) was used. The column tempera-
ture was held at 35 ◦ C for 5 min, then programmed to increase
at 10 ◦ C/min to 280 ◦ C, which was held for 3 min. Helium was
used as the carrier gas with a column flow rate of 1.3 ml/min
in constant flow mode. The MS transfer line temperature was
kept at 280 ◦ C. The solvent delay time was set at 6 min. The
ion source was kept at 230 ◦ C. The MS was operated in the EI
mode. Monitoring ions in the selected ion-monitoring (SIM)
mode are listed in Table 1: one being the target ion (quanti-
tation) and another the qualifier ion.
3. Results and discussion
3.1. Selection of SPME fiber with the object of
sensitivity and linearity
Three types of SPME fibers (CAR/PDMS, DVB/PDMS
and 100-␮m PDMS) were evaluated to select the appropriate
 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85 81

Table 1
SIM ions and linear range of the target compounds by using CAR/PDMS, DVB/PDMS and 100-␮m PDMS fibers; compounds listed in elution order
Pk# Compounds Target ion Qualifier ion Linear range (␮g/l)
CAR/PDMS DVB/PDMS 100-␮m PDMS
1 1,1-Dichloroethylene 61 96 0.1–1 0.1–5 0.1–100
2 Dichloromethane 84 86 0.1–1 0.1–5 0.1–100
3 Trans-1,2-dichloroethylene 61 96 0.1–5 0.1–10 0.1–100
4 Methyl-t-butylether (MTBE) 73 57 0.1–1 0.1–5 0.1–100
5 Cis-1,2-dichloroethylene 61 96 0.1–5 0.1–10 0.1–100
6 Chloroform 83 85 0.1–1 0.1–5 0.1–100
7 1,2-Dichloroethane 62 64 0.1–5 0.1–5 0.1–100
8 1,1,1-Trichloroethane 97 99 0.1–1 0.1–5 0.1–100
9 Benzene 78 77 0.1–10 0.1–10 0.1–100
10 Carbon tetrachloride 117 119 0.1–1 0.1–10 0.1–100
11 1,2-Dichloropropane 63 62 0.1–5 0.1–5 0.1–100
12 Bromodichloromethane 83 85 0.1–10 0.1–10 0.1–100
13 1,4-Dioxane 88 58 0.1–1 0.5–5 5–100
14 Trichloroethylene 130 132 0.1–10 0.1–10 0.1–100
15 Cis-1,3-dichloropropene 75 110 0.1–50 0.1–10 0.1–100
16 Trans-1,3-dichloropropene 75 110 0.1–100 0.1–10 0.1–100
17 1,1,2-Trichloroethane 97 99 0.1–10 0.1–5 0.1–100
18 Toluene 91 92 0.1–10 0.1–10 0.1–100
19 Dibromochloromethane 129 127 0.1–50 0.1–10 0.1–100
20 Tetrachloroethylene 166 129 0.1–10 0.1–10 0.1–100
21 m,p-Xylene 91 106 0.1–10 0.1–10 0.1–50
22 Bromoform 173 171 0.1–50 0.1–10 0.1–100
23 o-Xylene 91 106 0.1–10 0.1–10 0.1–100
24 p-Dichlorobenzene 146 148 0.1–10 0.1–10 0.1–100
25 2-MIB 95 108, 107 1–100 ng/l 1–100 ng/l 1–100 ng/l
26 Geosmin 112 111, 126 1–100 ng/l 1–100 ng/l 1–100 ng/l
The fibers were evaluated at the concentration above 0.1 ␮g/l considering the regulation for VOCs, MTBE and 1,4-dioxane.

coating for the extraction of 22 VOCs, MTBE, 1,4-dioxane,
2-MIB and geosmin considering the sensitivity and lin-
ear range required in Japanese water regulation. The small
pores in carboxen particles make this carbon molecular
sieve particularly effective for extracting small molecules.
Divinylbenzene polymer increases the available surface area
and thus improves the extraction of small polar molecules.
DVB/PDMS is considered to be effective for 1,4-dioxane,
2-MIB and geosmin. CAR/PDMS is suitable for 22 VOCs
and MTBE. A thick fiber coating will extract more of a given
analyte than will a thin coating. Consequently, a fiber with
a thicker coating (100 ␮m) is used to retain volatile com-
pounds, but a thin coating (7 ␮m) is used to ensure fast
diffusion and release of higher boiling compounds during
thermal desorption. Fig. 1 shows a comparison of chro-
matograms of 22 VOCs, MTBE and 1,4-dioxane at 0.1 ␮g/l
obtained by using CAR/PDMS, DVB/PDMS and 100-␮m
PDMS. Split injection with the ratio of 20:1 was carried
out when using CAR/PDMS that was particularly effec-
tive for extracting small molecules. Splitless injection was
performed when using DVB/PDMS and 100-␮m PDMS.
CAR/PDMS provided the highest sensitivity to all the tar-
get compounds and was particularly effective for peaks of
numbers 1–14. Aromatic compounds such as toluene, xylene
and p-dichlorobenzene strongly adsorbed to DVB/PDMS
and showed high sensitivity by using this fiber. A 100-␮m
PDMS provided the lowest sensitivity for all the target com-
pounds. However, CAR/PDMS and DVB/PDMS that were
adsorbent type fibers had limited capacity. Table 1 shows the
linear range of the target compounds by using CAR/PDMS,
DVB/PDMS and 100-␮m PDMS. The linear range of each
analyte was determined in multiple-component system: all 26
components for DVB/PDMS and 100-␮m PDMS; 24 compo-
nents for CAR/PDMS in 22 VOCs, MTBE and 1,4-dioxane;
2 components for CAR/PDMS in 2-MIB and geosmin.
Although CAR/PDMS provided the method detection lim-
its below 0.1 ␮g/l for 22 VOCs and MTBE even in the split
mode (20:1), this work was evaluated at the concentration
above 0.1 ␮g/l considering the water regulation in Japan.
CAR/PDMS and DVB/PDMS provided a narrow range of
linearity for 22 VOCs, MTBE and 1,4-dioxane. Fang et al.
reported the capacity of adsorbent-type fibers and the linear
range of MTBE were more complex when analytes additional
to MTBE (multi-component) were extracted simultaneously
[11]. The number of sites or pores is limited for the adsorbent-
type fibers. Analytes may compete for the same site. As
the concentration of a mixture of analytes is increased,
the sites will eventually become occupied. The total con-
centration of analytes can affect the competitive extrac-
tion of analytes by the adsorbent type fibers (CAR/PDMS
or DVB/PDMS). However, 100-␮m PDMS (absorbent-type
fiber) provided a wide range of linearity. The linear range of
100-␮m PDMS was 0.1–100 ␮g/l for 21 VOCs and MTBE,
0.1–50 ␮g/l for m,p-xylene and 5–100 ␮g/l for 1-4dioxane.
82 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85

Fig. 2. Effect of salt addition on the responses of representative compounds.

SPME fiber: 100-␮m PDMS.

the effect of salt addition on the responses of representative

Fig. 1. Comparison of chromatograms of 22 VOCs, MTBE and 1,4-dioxane
at 0.1 ␮g/l obtained by using CAR/PDMS, DVB/PDMS and 100-␮m PDMS.
The numbers labeling the peaks correspond to those in the Pk# column
of Table 1. Experimental conditions: CAR/PDMS split 20:1, DVB/PDMS
splitless, 100-␮m PDMS splitless; headspace-SPME extracted at 60 ◦ C for
30 min in 30% NaCl.
For 2-MIB and geosmin, CAR/PDMS, DVB/PDMS and
100-␮m PDMS provided good linearity in the range from
1 to 100 ng/l all in the splitless mode. The method detec-
tion limits (MDLs) of 2-MIB and geosmin were 0.3 and
0.1 ng/l for CAR/PDMS, 0.3 and 0.2 ng/l for DVB/PDMS
and 0.6 and 0.3 ng/l for 100-␮m PDMS. All the fibers achieve
the detection limits below 1 ng/l. The linear range of 22
VOCs and MTBE is required from 0.1 to 50 or 100 ␮g/l
considering the Japanese water regulation. In addition, the
method detection limits of 0.1 ␮g/l meet the needs of the
regulation for 22 VOCs and MTBE. Consequently, to deter-
mine 22 VOCs, MTBE, 1,4-dioxane, 2-MIB and geosmin
simultaneously, 100-␮m PDMS was chosen for further
study.
compounds. The responses of all compounds were increased
with increasing the percentage of NaCl. The responses of
most VOCs with 30% NaCl addition were two to three times
higher than those without salt addition. The responses of
MTBE, 1,4-dioxane, 2-MIB and geosmin with 30% NaCl
addition were 2.9, 2.6, 5.1 and 3.6 times higher, respectively,
than those without salt addition. Responses were also esti-
mated at 60, 70 and 80 ◦ C of extraction temperature (NaCl
addition: 30%, extraction time: 30 min). Fig. 3 shows the
effect of extraction temperature on the responses of the rep-
resentative compounds. The responses of all compounds were
decreased with increasing the temperature. The responses of
most compounds at 70 ◦ C were 0.7–0.9 times lower than those
at 60 ◦ C. The responses of most compounds at 80 ◦ C were
0.4–0.7 times lower than those at 60 ◦ C. Consequently, NaCl
addition and extraction temperature were chosen as 30% and
60 ◦ C, respectively, for further study. Responses were also
estimated for 10, 20 30, 40 and 50 min of extraction time

3.2. Effect of salting out, extraction temperature and

extraction time on responses

To increase responses, salt addition, extraction tempera-

ture and extraction time were examined at 1 ␮g/l for 22 VOCs
and MTBE, at 5 ␮g/l for 1,4-dioxane and at 10 ng/l for 2-MIB
and geosmin. Responses were estimated upon the addition of
0, 5, 10, 20 and 30% sodium chloride (NaCl) (extraction Fig. 3. Effect of extraction temperature on the responses of representative
temperature: 60 ◦ C, extraction time: 30 min). Fig. 2 shows compounds. SPME fiber: 100-␮m PDMS.
 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85
Fig. 4. Effect of extraction time on the responses of representative com-
pounds. SPME fiber: 100-␮m PDMS.
(NaCl addition: 30%, extraction temperature: 60 ◦ C). Fig. 4
shows the effect of extraction time on the responses of the rep-
resentative compounds. The responses of most compounds
were increased with increasing extraction time, especially for
2-MIB, geosmin and bromine-contained methane. Although
equilibration was not reached in 50 min, extraction time was
chosen as 30 min considering high sample throughput, and
the responses in 30 min were increased by half the increasing
rate of 50 min of extraction time.
3.3. Simultaneous determination of 22 VOCs, MTBE,
1,4-dioxane, 2-MIB and geosmin in SIM mode
Fig. 5 shows reconstructed ion chromatogram of 22
VOCs, MTBE, 1,4-dioxane, 2-MIB and geosmin at 0.1 ␮g/l,
0.1 ␮g/l, 5 ␮g/l, 2 ng/l and 2 ng/l, respectively. Benzene,
toluene, m,p-xylene, o-xylene, p-dichlorobenzene were
detected at 0.01, 0.03, 0.02, 0.04 and 0.02 ␮g/l, respectively,
Fig. 5. Reconstructed ion chromatogram of 22 VOCs, MTBE, 1,4-dioxane, 2-MIB and geosmin at 0.1 ␮g/l, 0.1 ␮g/l, 5 ␮g/l, 2 ng/l and 2 ng/l, respectively.
The numbers labeling the peaks correspond to those in the Pk# column of Table 1. Experimental conditions: SPME fiber, 100-␮m PDMS; headspace-SPME
extracted at 60 ◦ C for 30 min in 30% NaCl.
83
as experimental blank. All the target compounds were simul-
taneously analyzed by SPME-GC–MS with a DB-1 column
(60 m, 0.25 mm i.d., 1.0 ␮m). This column allows the sepa-
ration of 1,1-dichloroethylene from water due to the 1.0 ␮m
thick film and 60 m long. For higher sensitivity the thermal
desorption of the analytes in the GC inlet was performed in
the splitless mode. Generally the PDMS phase is not effec-
tive for extracting small molecules. Therefore, the peak areas
of VOCs (small molecules) at 100 ng/l (0.1 ␮g/l) except aro-
matic compounds were approximately the same level as those
of 2-MIB and geosmin at 2 ng/l. Considering the standard val-
ues of 22 VOCs and the musty odor compounds (2-MIB and
geosmin) in water regulation described in the introduction
section, the differences are two to three orders of magnitude
in the two groups. Consequently, the PDMS phase has a sig-
nificant advantage for the simultaneous determination of 22
VOCs and the musty odor compounds with linearity in the
regulated concentration range.
Table 2 shows correlation coefficient of calibration curve,
repeatability and MDL obtained by this method using 100-
␮m PDMS fiber. The linearity was evaluated at seven levels
of concentration ranging from 0.1 to 100 ␮g/l [0.1, 0.5, 1, 5,
10, 50 and 100 ␮g/l] for VOCs and MTBE with correlation
coefficient between 0.9964 and 0.9999, at four levels of con-
centration ranging from 5 to 100 ␮g/l [5, 10, 50 and 100 ␮g/l]
for 1,4-dioxane with correlation coefficient of 0.9991, and at
six levels of concentration ranging from 1 to 100 ng/l [1, 2, 5,
10, 50 and 100 ng/l] for 2-MIB and geosmin with correlation
coefficient of 0.9976 and 0.9988, respectively. The repeata-
bilities of the method were tested at 0.1 ␮g/l for 22 VOCs and
MTBE, at 5 ␮g/l for 1,4-dioxane, and at 2 ng/l for 2-MIB and
geosmin. The repeatabilities, expressed as a R.S.D. (n = 6),
for peak areas of 22 VOCs, MTBE, 1,4-dioxane, 2-MIB and
geosmin were between 1.5 and 9.2%. The MDLs of 22 VOCs
and MTBE ranged from 0.01 to 0.05 ␮g/l. The MDLs of
1,4-dioxane, 2-MIB and geosmin were 1.2 ␮g/l, 0.6 ng/l and
84 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85

Table 2
Correlation coefficient of calibration curve, repeatability and method detection limit (MDL) obtained by the method using 100-␮m PDMS fiber
Pk# Compounds RT m/z Correlation R.S.D.b at 0.1 ␮g/l (%) Method detection
coefficincya limits (␮g/l)
1 1,1-Dichloroethylene 6.91 61 0.9999 4.4 0.03
2 Dichloromethane 7.04 84 0.9981 4.5 0.05
3 Trans-1,2-dichloroethylene 8.17 61 0.9998 2.5 0.03
4 Methyl-t-butylether (MTBE) 8.46 73 0.9997 6.5 0.01
5 Cis-1,2-dichloroethylene 9.31 61 0.9999 5.8 0.02
6 Chloroform 9.63 83 0.9999 3.2 0.01
7 1,2-Dichloroethane 10.40 62 0.9997 1.5 0.02
8 1,1,1-Trichloroethane 10.69 97 0.9999 2.6 0.01
9 Benzene 11.16 78 0.9999 2.3 0.01
10 Carbon tetrachloride 11.32 117 0.9999 1.9 0.01
11 1,2-Dichloropropane 11.97 63 0.9998 2.4 0.02
12 Bromodichloromethane 12.15 83 0.9999 4.5 0.02
13 1,4-Dioxane 12.15 88 0.9991 9.2b 1.17
14 Trichloroethylene 12.20 130 0.9999 2.1 <0.01
15 Cis-1,3-dichloropropene 13.03 75 0.9999 2.5 0.01
16 Trans-1,3-dichloropropene 13.53 75 0.9999 8.4 0.02
17 1,1,2-Trichloroethane 13.73 97 0.9998 4.3 0.02
18 Toluene 14.03 91 0.9998 2.4 <0.01
19 Dibromochloromethane 14.46 129 0.9995 4.4 0.02
20 Tetrachloroethylene 15.19 166 0.9994 2.1 <0.01
21 m,p-Xylene 16.46 91 0.9986 4.0 <0.01
22 Bromoform 16.56 173 0.9991 4.1 0.01
23 o-Xylene 16.97 91 0.9980 2.3 <0.01
24 p-Dichlorobenzene 19.31 146 0.9964 2.1 <0.01
25 2-MIB 22.59 95 0.9976 6.9b 0.6 ng/l
26 Geosmin 26.06 112 0.9988 3.9b 0.3 ng/l
a Concentration range: 0.1–100 ␮g/l; 1,4-dioxane: 5–100 ␮g/l; m,p-xylene: 0.1–50 ␮g/l, 2-MIB and geosmin: 1–100 ng/l.
b 1,4-Dioxane: 5 ␮g/l; 2-MIB and geosmin: 2 ng/l.

0.3 ng/l, respectively. The MDLs were calculated at signal-

Table 3 to-noise ratio of 3. The recoveries of the method were tested
Recoveries of the analytes from river water and precision (n = 6) by replicate analysis (n = 6) of a spiked river sample and the
Pk# Compounds Recoverya (%) R.S.D.a (%) results are listed in Table 3. Each recovery was calculated
1 1,1-Dichloroethylene 99.4 4.3 using a calibration curve. Good recoveries were obtained for
2 Dichloromethane 95.1 9.5 22 VOCs and MTBE (between 93.7 and 104.0%, with R.S.D.
3 Trans-1,2-dichloroethylene 97.4 5.9 values of between 1.7 and 9.5%) at 1 ␮g/l. Good recover-
4 Methyl-t-butylether (MTBE) 96.9 5.5 ies were also obtained for 1,4-dioxane, 2-MIB and geosmin
5 Cis-1,2-dichloroethylene 100.6 2.9
(109.1, 95.9 and 97.4%, with R.S.D. values of 2.0, 5.6 and
6 Chloroform 95.1 2.9
7 1,2-Dichloroethane 104.0 4.0 1.8%, respectively) at 5 ␮g/l, 10 ng/l and 10 ng/l, respectively.
8 1,1,1-Trichloroethane 101.1 2.3
9 Benzene 97.4 2.4
10 Carbon tetrachloride 101.7 1.7
11 1,2-Dichloropropane 96.6 2.8
12 Bromodichloromethane 100.2 4.8
13 1,4-Dioxane 109.1a 2.0a
14 Trichloroethylene 98.7 3.8
15 Cis-1,3-dichloropropene 99.2 4.4
16 Trans-1,3-dichloropropene 102.0 4.6
17 1,1,2-Trichloroethane 96.4 2.6
18 Toluene 93.7 3.2
19 Dibromochloromethane 100.2 4.7
20 Tetrachloroethylene 98.8 3.8
21 m,p-Xylene 96.8 4.5
22 Bromoform 98.1 4.0
23 o-Xylene 95.4 4.2
24 p-Dichlorobenzene 96.6 5.7
Fig. 6. SIM chromatograms of chloroform, 1,1,1-trichloroethane,
25 2-MIB 95.9a 5.6a
trichloroethylene, tetrachloroethylene and 2-MIB extracted from the river
26 Geosmin 97.4a 1.8a
water. Experimental conditions: SPME fiber, 100-␮m PDMS; headspace-
a 1,4-Dioxane: 5 ␮g/l; 2-MIB and geosmin: 10 ng/l. SPME extracted at 60 ◦ C for 30 min in 30% NaCl.
 S. Nakamura, S. Daishima / Analytica Chimica Acta 548 (2005) 79–85 85

Table 4
Quantitative results of tap water and river water
Pk# Compounds Tap water (␮g/l) R.S.D. (%) River water (␮g/l) R.S.D. (%)
1 1,1-Dichloroethylene n.d. n.d.
2 Dichloromethane n.d. n.d.
3 Trans-1,2-dichloroethylene n.d. n.d.
4 Methyl-t-butylether (MTBE) n.d. n.d.
5 Cis-1,2-dichloroethylene n.d. n.d.
6 Chloroform 13.4 4.7 0.11 8.1
7 1,2-Dichloroethane n.d. n.d.
8 1,1,1-Trichloroethane n.d. 0.02 12.9
9 Benzene n.d. n.d.
10 Carbon tetrachloride n.d. n.d.
11 1,2-Dichloropropane n.d. n.d.
12 Bromodichloromethane 5.5 4.5 n.d.
13 1,4-Dioxane n.d. n.d.
14 Trichloroethylene n.d. 0.26 4.4
15 Cis-1,3-dichloropropene n.d. n.d.
16 Trans-1,3-dichloropropene n.d. n.d.
17 1,1,2-Trichloroethane n.d. n.d.
18 Toluene 0.49 3.7 n.d.
19 Dibromochloromethane 2.5 5.2 n.d.
20 Tetrachloroethylene n.d. 0.08 4.8
21 m,p-Xylene n.d. n.d.
22 Bromoform 1.4 10.1 n.d.
23 o-Xylene n.d. n.d.
24 p-Dichlorobenzene n.d. n.d.
25 2-MIB n.d. 3.7 ng/l 6.0
26 Geosmin 1.7 ng/l 3.0 n.d.
n.d.: not detected.

The quantitative results of tap water and river water are listed
in Table 4. Fig. 6 shows SIM chromatograms of chloroform,
1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene
and 2-MIB extracted from the river water. These target com-
pounds could be determined without interference from the
river matrix.
4. Conclusion
A rapid and sensitive SPME-GC/MS method for the
simultaneous determination of 22 VOCs, MTBE, 1,4-
dioxane, 2-MIB and geosmin in water was developed. A
100-␮m PDMS fiber was the appropriate coating for the tar-
get compounds considering the linear range and sensitivity
required in Japanese water regulation. The method provides
linear range from 0.1 to 100 ␮g/l for 21 VOCs and MTBE, 0.1
to 50 ␮g/l for m,p-xylene and 5 to 100 ␮g/l for 1,4-dioxane
and 1 to 100 ng/l for 2-MIB and geosmin. The method allows
the detection of levels of 22 VOCs and MTBE in the range
0.01–0.05 ␮g/l, and also allows the detection of 1.2 ␮g/l,
0.6 ng/l and 0.3 ng/l of 1,4-dioxane, 2-MIB and geosmin,
respectively.
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