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Journal of Chromatography A, 1175 (2007) 106–111

Simultaneous determination of gasoline oxygenates and benzene,

toluene, ethylbenzene and xylene in water samples using
headspace-programmed temperature vaporization-fast
gas chromatography–mass spectrometry
José Luis Pérez Pavón ∗ , Miguel del Nogal Sánchez,
Marı́a Esther Fernández Laespada, Bernardo Moreno Cordero
Departamento de Quı́mica Analı́tica, Nutrición y Bromatologı́a, Facultad de Ciencias Quı́micas, Universidad de Salamanca, 37008 Salamanca, Spain
Received 28 May 2007; received in revised form 27 September 2007; accepted 4 October 2007
Available online 22 October 2007

Abstract
A sensitive method is presented for the fast analysis of seven fuel oxygenates (methanol, ethanol, tert-butyl alcohol (TBA), methyl tert-butyl
ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE)) and benzene, toluene, ethylbenzene
and p-xylene (BTEX) in water samples. The applicability of a headspace (HS) autosampler in combination with a GC device equipped with a
programmable temperature vaporizer (PTV) and a MS detector is explored. The proposed method achieves a clear improvement in sensitivity with
respect to conventional headspace methods due to the use of the PTV. Two different packed liners with materials of different trapping strengths
(glass wool and Tenax-TA) were compared. The benefits of using Tenax-TA instead of glass wool as packed material for the measurement of the
11 compounds emerged as better signal-to-noise ratios and hence better detection limits. The proposed method is extremely sensitive. The limits
of detection are of the order of ng/L for six of the compounds studied and of the order of ␮g/L for the rest, with the exception of the most polar
and volatile compound: methanol. Precision (measured as the relative standard deviation for a level with an S/N ratio close to 3) was equal to or
lower than 15% in all cases. The method was applied to the determination of the analytes in natural matrixes (tap, river and sea water) and the
results obtained can be considered highly satisfactory. The methodology has much lower detection limits than the concentration limits proposed in
drinking water by the US Environmental Protection Agency (EPA) and the European Union for compounds under regulation.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Headspace analysis; Programmed temperature vaporizers; Water analysis; Fuel oxygenates; BTEX

1. Introduction volume worldwide. It was incorporated in gasoline to replace

Fuel oxygenates are generally added to gasoline to increase
combustion efficiency and to reduce air pollution. Com-
monly used oxygenates in recently developed gasolines include
aliphatic alcohols and methylethers. Typical examples are
methanol, ethanol, tert-butyl alcohol (TBA), methyl tert-butyl
ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl
ether (TAME) and diisopropyl ether (DIPE) [1]. Among the
ethers, MTBE is the most commonly used octane enhancer
and one of the organic compounds with the highest production
∗ Corresponding author. Fax: +34 923 294483.
E-mail address: jlpp@usal.es (J.L. Pérez Pavón).
tetraalkyl lead and as result of increasing restrictions on aromat-
ics contents. MTBE is a persistent water contaminant due to its
high water solubility and slow rate of degradation [2,3].
The presence of these chemicals in water is related to fuel
spills, leakage from underground storage tanks, and the release
of unburned fuel directly into the atmosphere and surface water.
The BTEX content [4] in a standard gasoline blend is approx-
imately 18% (w/w). From a toxicological point of view, benzene
is the most hazardous component because it is a confirmed
human carcinogen. The US Environmental Protection Agency
[5] includes BTEX in its list of contaminants in drinking water
and limits the maximum concentration levels (MCLs) of these
compounds as follows: benzene (5 ␮g/L), toluene (1 mg/L),
ethylbenzene (0.7 mg/L) and xylenes (10 mg/L). The European

0021-9673/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2007.10.044
 J.L. Pérez Pavón et al. / J. Chromatogr. A 1175 (2007) 106–111
Union has also included benzene in its list of 33 priority pollu-
tants in waters [6] and has established a limit MCL of 1 ␮g/L
for benzene in drinking water [7].
Gas chromatography is one of the techniques most widely
employed to quantify mixtures of organic compounds. In the
analysis of fuel oxygenates and BTEX in water, gas chro-
matography is generally combined with mass spectrometry (MS)
[8–14] or flame ionization detection (FID) [15–19]. Prior to
analysis, extraction and preconcentration of compounds from
the aqueous samples are generally required. Analytical methods
include purge and trap (P&T) [8–10,], headspace solid-phase
dynamic extraction (HS-SPDE) [11], headspace solid-phase
microextraction (HS-SPME) [12,15,17,18], headspace solvent
microextraction (HS-ME) [16], headspace (HS) [14,20] or direct
aqueous injection (DAI) [13,19].
Recently, a new alternative to improve sensitivity, main-
taining the simple headspace (HS) instrumentation, has been
proposed. It consists of the use of a programmed temperature
vaporizer inlet (PTV) to inject the samples into the chromato-
graphic column [21–23]. The conditions are chosen such that the
components are retained in the liner by cold trapping, while the
solvent is eliminated through the split line. This has the advan-
tage that it is possible to inject large volume coming from the
HS. The PTV injector is equipped with an efficient heating and
cooling system, in which cooling is carried out by means of
air, liquid nitrogen, carbon dioxide, or by electrical systems. By
using liners [24] packed with different materials, the range of
components that can be trapped in the liner can be significantly
extended. This setup, not very used up to date, offers benefits in
terms of simplicity and automation possibilities together with a
very good sensitivity.
In the present work, we propose the determination of seven
fuel oxygenates and BTEX in water samples with a highly sen-
sitive method, using a programmed temperature vaporizer inlet
followed by fast capillary gas chromatography coupled to mass
spectrometry in the selected ion-monitoring mode acquisition
(PTV-fast GC/MS(SIM)). Previously, two packed liners with
materials of different trapping strengths were compared.
2. Experimental
2.1. Chemicals
The solvents used were purchased from the following
sources: methanol was from Merck (Darmstadt, Germany);
ethanol from Scharlau (Barcelona, Spain); tert-butyl alcohol
and diisopropyl ether from Fluka (Buchs, Switzerland); methyl
tert-butyl ether, toluene, ethylbenzene and p-xylene from Acros
Organics (Geel, Belgium); ethyl tert-butyl ether and ben-
zene from Sigma–Aldrich (Steinheim, Germany) and tert-amyl
methyl ether from Supelco (Bellefonte, PA, USA).
2.2. Standard solutions and samples
Solutions of the 11 analytes indicated in Section 2.1 were
prepared in ultra-pure water. They were employed to obtain the
calibration curves and detection and quantification limits.
107
To perform the measurements, 5 mL of sample was placed in
10 mL vials sealed with silicone septum caps. Each sample was
analyzed in triplicate.
The calibration curves obtained in ultrapure water were used
to predict the concentrations of these compounds in a sample
of tap water. The determination was also performed with sea
water and river water using the standard additions method. The
tap water sample was taken from the public water system of
Salamanca (Spain); that of sea water from Salou (Spain) and
that of river water from the River Tormes in its passage through
Salamanca. Each sample was analyzed in triplicate.
2.3. HS-PTV-fast GC–MS measurements
A schematic diagram of the apparatus used is shown in Fig. 1.
2.3.1. Headspace sampling
HS sampling was performed with a model 7694 headspace
sampler from Agilent Technologies. This sampler is equipped
with a tray for 44 consecutive samples and an oven with positions
for six sample vials. The oven temperature was kept at 90 ◦ C for
30 min. The sampling system consisted of a stainless steel nee-
dle, a 316-SS six-port valve with a 3 mL nickel loop (heated to
95 ◦ C), and two solenoid valves (for pressurization and venting).
The headspace sampler was coupled to a PTV injector through a
thermostatted transfer line heated to 100 ◦ C (Fig. 1). The carrier
gas was helium N50 (99.995% pure; Air Liquide).
2.3.2. Programmed-temperature vaporization
All experiments were carried out in a PTV inlet (CIS-4;
Gerstel, Baltimore, MD, USA). Two different packed liners
(deactivated glass wool and Tenax-TA) were compared. The
solvent vent injection mode was used in all cases. Cooling was
carried out by means of CO2 .
The injector starting temperature was 5 ◦ C. The vent flow
was adjusted to 50.0 mL/min and the vent pressure to 5.00 psi.
After 1.70 min, the split valve was closed and the liner was flash-
heated at 12 ◦ C/s to 250 ◦ C. The analytes were transferred from
the liner to the capillary column (0.60 min). The split valve was
then opened and the liner temperature was held at 250 ◦ C for
9.00 min. The experimental conditions are shown schematically
in Fig. 2.
Fig. 1. Schematic diagram of the apparatus used.
108 J.L. Pérez Pavón et al. / J. Chromatogr. A 1175 (2007) 106–111
Fig. 2. Sequence of events for solvent vent injection.
2.3.3. Gas chromatography
To perform the gas chromatographic measurements, an Agi-
lent 6890 GC device equipped with a DB-VRX capillary column
(20 m × 0.18 mm × 1 ␮m) was used. The column oven tem-
perature program involved an initial temperature of 35 ◦ C for
4.50 min; this was increased at a rate of 20 ◦ C/min to 70 ◦ C,
then increased at 70 ◦ C/min to 190 ◦ C, and held for 1.0 min.
The latter temperature ramp is the maximum one permitted by
the instrumental configuration employed. The total chromato-
graphic run time was 8.96 min. The experimental conditions are
schematized in Fig. 2.
2.3.4. Mass spectrometry
The detector was a quadrupole mass spectrometer (HP
5973 N). It was operated in the electron impact mode using
a 70 eV ionization voltage. The ion source temperature was
230 ◦ C and the quadrupole was set to 150 ◦ C. The analyses were
performed in the scan and SIM modes.
2.3.4.1. Scan detection mode. Initially, this detection mode was
only used for the identification of the compounds in the samples.
The m/z range was 25–120 amu, and the abundance threshold
value was set to 0. The different compounds were identified
by comparison of the experimental spectra with those of the
NIST’98 database (NIST/EPA/NIH Mass Spectral Library, ver-
sion 1.6).
2.3.4.2. SIM detection mode. Six SIM groups were used. The
first contained the most abundant ions of methanol and ethanol
(29, 31, 32, and 45). The second was formed by the characteristic
ions of tert-butyl alcohol and methyl tert-butyl ether (41, 43, 59
and 73). The third contained five m/z variables (43, 45, 57, 59
and 87) characteristic of diisopropyl ether and ethyl tert-butyl
ether. The next group was formed by six m/z variables (43, 51,
55, 73, 77 and 78) characteristic of benzene and tert-amyl methyl
ether. The next group was formed by the characteristic ions of
toluene (65, 91 and 92). The last group contained the typical
ions of ethylbenzene and p-xylene (77, 91, 105 and 106). The
ions were acquired with a dwell time of 50 ms for groups 1 and
2, 30 ms for groups 3 and 4 and 20 ms for groups 5 and 6.
2.4. Data analysis
Data collection was performed with Enhanced ChemStation,
G1701CA Ver. C 00.00 software [25] from Agilent Technolo-
gies.
3. Results and discussion
3.1. Study of HS-PTV-fast GC–MS data
3.1.1. Solvent injection parameters
The sequence of steps involved when solvent injection was
used is shown in Fig. 2. Initially, the sample from the headspace
through the transfer line (100 ◦ C) was injected in the cooled PTV
inlet (5 ◦ C). The split valve was opened to allow the solvent to be
removed, whilst the analytes would remain trapped in the liner
packing material. The next step involved the PTV transfer time;
i.e., the time during which the split valve remained closed and
the PTV injector was heated at 12 ◦ C/s up to 250 ◦ C. With this,
analyte desorption and transfer to the chromatographic column
were achieved.
Finally, the split valve was opened again, a stream of helium
cleaning the liner and hence leaving it ready for the next injec-
tion. Then chromatographic separation was begun, with the
temperature program also shown in Fig. 2.
3.1.2. Comparison of the different packed liners
A comparative study of the signals obtained when using two
different packed liners was carried out. The packing materials
were glass wool, an inert support, and Tenax-TA, a porous poly-
mer designed to trap organics without retaining water. Fig. 3
shows the chromatogram obtained upon injecting a solution of
the analytes in ultrapure water using a liner packed with Tenax-
TA. The concentrations of the analytes in the solution were 68.4,
3.15 and 0.700 mg/L for methanol, ethanol and TBA, respec-
tively and 123, 8.75, 14.0, 35.0, 35.0, 14.0, 14.0, 14.0 ␮g/L for
MTBE, DIPE, ETBE, benzene, TAME, toluene, ethylbenzene
and p-xylene, respectively. When glass wool was used as the
packing, the chromatogram corresponding to the same solution
of compounds had shorter retention times for the analytes that
eluted in the first part of the chromatogram. This can be attributed
to the volatility of these compounds, which are less strongly
retained in the liner when an inert packing is used.
The signals obtained with the glass wool packing were con-
siderably less intense for most of the analytes. The reason is that
these compounds were to a large extent removed through the split
valve, while they were retained by the Tenax-TA during the sol-
vent removal step. The retention times and signal-to-noise ratios
(for the concentrations given in the previous paragraph) corre-
 J.L. Pérez Pavón et al. / J. Chromatogr. A 1175 (2007) 106–111 109

be attributed to trace level pollution of the air and water of the

laboratory, which could not be removed, as seen upon inserting
vials containing only air.
For the set of 11 compounds, repeatability (n = 10) was evalu-
ated at a level corresponding to an S/N ratio of approximately 3.
The repeatability was satisfactory (Table 3) with an RSD equal
to or less than 15% both when the glass wool liner and when the
Tenax-TA liner was used. In many cases, the RSD was lower than
8%. Likewise, repeatability was studied for higher concentra-
tions: 24.4, 1.13 and 0.25 mg/L for methanol, ethanol and TBA,
respectively, and 43.8, 3.13, 5.00, 12.5, 12.5, 5.00, 5.00 and
5.00 ␮g/L for MTBE, DIPE, ETBE, benzene, TAME, toluene,
ethylbenzene and p-xylene, respectively. The RSD (Table 3)
improved since it was less than or equal to 12% when the glass
wool liner was used and less than or equal to 6% in the case of
Fig. 3. Extracted ion chromatograms for m/z 31, 45, 59, 73, 78 and 91 for a
laboratory-prepared solution containing the 11 compounds studied in ultrapure
the Tenax-TA liner.
water. The concentrations were: 68.4, 3.15 and 0.700 mg/L for methanol, ethanol The detection limits (DLs) were estimated using the follow-
and TBA, respectively and 123, 8.75, 14.0, 35.0, 35.0, 14.0, 14.0, 14.0 ␮g/L for ing equation:
MTBE, DIPE, ETBE, benzene, TAME, toluene, ethylbenzene and p-xylene,
3.3σ
respectively. A Tenax-TA liner was used. DL =
S
sponding to the two materials compared in the liner are shown where σ is the standard deviation of peak response for 10 repli-
in Table 1, together with the boiling points of the analytes. cates (n = 10) corresponding to an S/N ratio of approximately
After the initial study, two calibration curves were built, one 3, S is the slope of the calibration curve and 3.3 is the student
for each type of liner, preparing standards in ultrapure water with t-factor (n-1, 0.99). The detection limits obtained were always
seven uniformly distributed concentration levels. The concentra- lower when Tenax-TA was used as the filler of the liner (Table 3).
tion ranges are shown in Table 2. Each standard was analyzed For the most polar compounds, with shorter retention times
in triplicate and the linearity of the method was evaluated. (methanol, ethanol, tert-butyl alcohol) the improvement in the
The variables used in the calibrations were the area under detection limit ranged between 3- and 11-fold. For the remaining
the curve of methanol, ethanol, tert-butyl alcohol (TBA), compounds, a more significant increase was observed. The limit
methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), decreased 80-, 333-, 500-, 100-, 40-, 200- and 35-fold for MTBE,
tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE)) DIPE, ETBE, benzene, TAME, toluene, and ethylbenzene. In
and benzene, toluene, ethylbenzene and p-xylene (BTEX) in the case of p-xylene, a compound that showed an ordinate at the
the extracted ion chromatogram for the quantitation ions shown origin in its calibration line the limit decreased six-fold.
in Table 2: m/z 31, 31, 59, 73, 45, 59, 78, 73, 91, 91 and 91, The higher peak response of measurements with Tenax-TA
respectively. All the calibrations showed good linear behavior, resulted in higher signal-to-noise ratios and hence lower detec-
with coefficient of determination (R2 ) values above 0.99. tion limits.
The intercept included zero in all cases, except for p-xylene, The quantitation limits (QLs) were estimated using the fol-
indicating the presence of this in the ultrapure water. This could lowing equation:
10σ
Table 1 QL =
Retention times, signal-to-noise ratios, boiling points and log Kow for the 11 S
compounds studied
where σ is the standard deviation of peak response for 10 repli-
Compound tR (min) S/N Boiling pointa (◦ C) cates (n = 10) corresponding to an S/N ratio of approximately
1 2 1 2 3, and S is the slope of the calibration curve. The results for
precision, and detection and quantitation limits in both cases are
Methanol 2.17 2.20 3366 7050 65
Ethanol 2.43 3.11 162 2820 78
summarized in Table 3.
TBA 2.98 3.66 354 2252 82 In light of the results obtained, we decided to use Tenax-TA
MTBE 3.65 4.46 185 10098 55 as material for the PTV inlet liner.
DIPE 4.29 5.03 16 3660 69
ETBE 4.76 5.35 23 8099 73
Benzene 5.73 6.13 174 18169 80
3.2. Determination of the 11 compounds in different
TAME 5.97 6.30 124 4258 86 aqueous matrices
Toluene 7.12 7.21 143 29157 111
Ethylbenzene 7.68 7.71 596 22343 136 To check the predictive capacity of the calibration curves,
p-Xylene 7.74 7.76 493 12089 139 different aqueous matrices were employed: tap, sea and river
(1) Glass wool liner was used; (2) Tenax-TA liner was used. water. Initially, we studied the possible presence of these com-
a Reference [2].
pounds in the samples from the chromatograms corresponding
110 J.L. Pérez Pavón et al. / J. Chromatogr. A 1175 (2007) 106–111

Table 2
Concentrations and m/z ratios selected for the 11 compounds studied
Compound Concentration range m/z

Quantitation ion Qualifier ion Qualifier ion

Methanol 0–83.1 (mg/L) 31 29 32

Ethanol 0–3.15 (mg/L) 31 45 29
TBA 0–0.700 (mg/L) 59 41 43
MTBE 0–96.3 (␮g/L) 73 41 43
DIPE 0–10.6 (␮g/L) 45 43 87
ETBE 0–17.0 (␮g/L) 59 87 57
Benzene 0–35.0 (␮g/L) 78 77 51
TAME 0–42.5 (␮g/L) 73 43 55
Toluene 0–17.0 (␮g/L) 91 92 65
Ethylbenzene 0–17.0 (␮g/L) 91 106 77
p-Xylene 0–17.0 (␮g/L) 91 106 105

Table 3
Relative standard deviation and detection and quantitation limits (␮g/L) for the methods compared
HS-PTV-GC–MS (1) HS-PTV-GC–MS (2)

RSDa RSDb LD LQ RSDa RSDb LD LQ

Methanol 3.4 5.3 1199 3630 5.6 3.2 387 1171

Ethanol 5.6 2.7 53 160 14 3.6 5 17
TBA 3.4 4.7 2 6 4.1 4.1 0.5 1
MTBE 15 6.6 4 11 7.7 6.1 0.05 0.2
DIPE 5.4 6.8 2 6 6.3 4.4 0.006 0.02
ETBE 9.6 0.2 4 12 8.9 4.6 0.008 0.02
Benzene 5.6 5.5 2 5 5.9 4.7 0.02 0.06
TAME 11 2.9 4 11 15 3.5 0.1 0.3
Toluene 7.3 12 2 5 5.7 3.6 0.01 0.03
Ethylbenzene 7.7 12 0.7 2 2.1 2.5 0.02 0.06
p-Xylene 7.0 6.9 0.6 2 3.9 3.3 0.1 0.4

(1) Glass wool liner was used; (2) Tenax-TA liner was used.
a RSD at a level corresponding to the detection limit.
b RSD at the following concentrations: 24.4, 1.13 and 0.25 mg/L for methanol, ethanol and TBA, respectively, and 43.8, 3.13, 5.00, 12.5, 12.5, 5.00, 5.00 and

5.00 ␮g/L for MTBE, DIPE, ETBE, benzene, TAME, toluene, ethylbenzene and p-xylene, respectively.

to them and from the mass spectra of the compounds for which In light of the above results, quantification of the tap water
retention times equal to those of the analytes were obtained. samples was performed with an external standard. The added
The tap water did not contain any of the compounds stud- and predicted concentrations are shown in Table 4. It may be
ied; in sea water, only p-xylene was found, while in the river seen that the calibration curves in ultrapure water are suitable
water sample, methanol, MTBE, benzene and p-xylene were for predicting the content of the compounds in tap water.
detected. A study was conducted to explore the possibility of In the case of analyte quantification in sea and river water,
carrying out analyte quantification using an external standard, the standard additions method was used to overcome matrix
with the calibration curves generated in ultrapure water, in order
to predict the concentration of the compounds in the different Table 4
aqueous samples (tap, river, sea). To accomplish this, the sam- Added and predicted concentrations and confidence intervals (95% probability)
in tap water when the ultrapure water model was used.
ples were spiked at the laboratory with the 11 compounds studied
at the same concentrations as those used to obtain the calibration Compound Added concentration Predicted concentration
lines of ultrapure water, employing regression lines. The signals Methanol 39.1 (mg/L) 36 ± 3 (mg/L)
obtained for the tap, river and sea water matrices, respectively, Ethanol 1.80 (mg/L) 1.5 ± 0.1 (mg/L)
were plotted on the OY axis of these lines, while the values found TBA 0.400 (mg/L) 0.32 ± 0.02 (mg/L)
in ultrapure water were plotted on the OX axis. Thus, each point MTBE 70.0 (␮g/L) 53 ± 5 (␮g/L)
DIPE 5.00 (␮g/L) 4.1 ± 0.6 (␮g/L)
of the lines represented the values of the peak areas of a com- ETBE 8.00 (␮g/L) 6 ± 1 (␮g/L)
pound in two different matrices (tap-ultrapure, river-ultrapure Benzene 20.0 (␮g/L) 19 ± 2 (␮g/L)
and sea-ultrapure). Whereas the analytes studied in river and TAME 20.0 (␮g/L) 14 ± 2 (␮g/L)
sea water had slopes departing from unity in comparison with Toluene 8.00 (␮g/L) 7.6 ± 0.8 (␮g/L)
the ultrapure water, in most cases the tap water sample afforded Ethylbenzene 8.00 (␮g/L) 7.7 ± 0.9 (␮g/L)
p-Xylene 8.00 (␮g/L) 7.4 ± 0.9 (␮g/L)
slopes very close to unity.
 J.L. Pérez Pavón et al. / J. Chromatogr. A 1175 (2007) 106–111 111

Table 5 was possible to carry out quantitative analysis for methanol

Concentration range for the standard additions and predicted concentration and at mg/L level; ethanol, TBA, TAME and p-xylene at ␮g/L
confidence intervals (95% probability) for the compounds in the sea and river
water
level, and MTBE, DIPE, ETBE and benzene, toluene and
ethylbenzene at ng/L level. It should be emphasized that the
Sea water method showed good precision and accuracy.
Compound Standard additions Added Predicted The proposed method, with headspace sampling, does not
Methanol 0–31.3 (mg/L) 9.77 (mg/L) 9 ± 1 (mg/L) require prior sample treatment, which reduces the errors asso-
Ethanol 0–1.44 (mg/L) 0.450 (mg/L) 0.41 ± 0.04 (mg/L) ciated with this step of the analysis and at the same time high
TBA 0–0.320 (mg/L) 0.100 (mg/L) 0.11 ± 0.01 (mg/L) sensitivity is obtained owing to the injection mode used. The
MTBE 0–56.0 (␮g/L) 17.5 (␮g/L) 18.8 ± 0.6 (␮g/L) method also has the advantage of simplicity over other precon-
DIPE 0–4.00 (␮g/L) 1.25 (␮g/L) 1.4 ± 0.2 (␮g/L)
ETBE 0–6.40 (␮g/L) 2.00 (␮g/L) 2.3 ± 0.3 (␮g/L)
centration modes, such as purge and trap.
Benzene 0–12.0 (␮g/L) 5.00 (␮g/L) 5.1 ± 0.3 (␮g/L)
TAME 0–16.0 (␮g/L) 5.00 (␮g/L) 5.5 ± 0.7 (␮g/L) Acknowledgments
Toluene 0–4.80 (␮g/L) 2.00 (␮g/L) 1.95 ± 0.07 (␮g/L)
Ethylbenzene 0–4.80 (␮g/L) 2.00 (␮g/L) 2.2 ± 0.3 (␮g/L) The authors acknowledge the financial support of the DGI
p-Xylene 0–6.80 (␮g/L) – 2.6 ± 0.4 (␮g/L)
(Project CTQ2004-01379/BQU) and the Consejerı́a de Edu-
River water cación y Cultura of the Junta de Castilla y León (Project
Compound Standard additions Added Predicted SA057A05) for this research.
Methanol 0–68.4 (mg/L) – 5 ± 1 (mg/L)
Ethanol 0–2.03 (mg/L) 0.450 (mg/L) 0.47 ± 0.09 (mg/L)
References
TBA 0–0.450 (mg/L) 0.100 (mg/L) 0.09 ± 0.01 (mg/L)
MTBE 0–43.8 (␮g/L) – 4 ± 1 (␮g/L) [1] F. Ancillotti, V. Fattore, Fuel Process. Technol. 57 (1998) 163.
DIPE 0–7.50 (␮g/L) 1.25 (␮g/L) 1.3 ± 0.2 (␮g/L) [2] M. Rosell, S. Lacorte, D. Barceló, Trends Anal. Chem. 25 (2006) 1016.
ETBE 0–9.00 (␮g/L) 2.00 (␮g/L) 2.4 ± 0.3 (␮g/L) [3] T.C. Schmidt, Trends Anal. Chem. 22 (2003) 776.
Benzene 0–12.5 (␮g/L) – 2.4 ± 0.4 (␮g/L) [4] A. Serrano, M. Gallego, J. Chromatogr. A 1045 (2004) 181.
TAME 0–30.0 (␮g/L) 5.00 (␮g/L) 5.8 ± 0.8 (␮g/L) [5] http://www.epa.gov/safewater/contaminants. National primary drinking
Toluene 0–12.0 (␮g/L) 2.00 (␮g/L) 2.3 ± 0.3 (␮g/L) water regulations, EPA 816-F-03-016, Washington DC, United States, June
Ethylbenzene 0–12.0 (␮g/L) 2.00 (␮g/L) 2.2 ± 0.3 (␮g/L) 2003.
p-Xylene 0–14.0 (␮g/L) – 2.3 ± 0.5 (␮g/L) [6] Decision 2455/2001/EC of the European Parliament and of the Council of
20 November 2001, Off. J. Eur. Commun. 331, 15 December 2001.
[7] Directive 98/83/EC of the Council of 3 November 1998, Off. J. Eur. Com-
effects. The concentration range for the set of standard additions mun. 330, 5 December 1998.
in both aqueous matrices is shown in Table 5. All samples were [8] A. Tanabe, Y. Tsuchida, T. Ibaraki, K. Kawata, A. Yasuhara, T. Shibamoto,
J. Chromatogr. A 1066 (2005) 159.
measured in triplicate. The concentration obtained and its con- [9] M. Rosell, S. Lacorte, A. Ginebreda, D. Barceló, J. Chromatogr. A 995
fidence interval (95% probability) for p-xylene in sea water was (2003) 171.
(2.6 ± 0.4) ␮g/L (Table 5). The concentrations and confidence [10] A.K. Vickers, C. George, Analysis of low concentration oxygenates in
intervals (95% of probability) for methanol, MTBE, benzene environmental water samples using purge and trap concentration and gas
and p-xylene in river water were (5 ± 1) mg/L, (4 ± 1) ␮g/L, chromatography/mass spectrometry, Agilent technologies 2003, Folsom,
CA, USA.
(2.4 ± 0.4) ␮g/L and (2.3 ± 0.5) ␮g/L, respectively (Table 5). [11] M.A. Jochmann, M.P. Kmiecik, T.C. Schmidt, J. Chromatogr. A 1115
With a view to checking the possibilities of the proposed (2006) 208.
methodology for the analytes not detected initially in the sam- [12] S. Nakamura, S. Daishima, Anal. Chim. Acta 548 (2005) 79.
ples, they were spiked with these compounds. Thus, the sea [13] L. Zwank, T.C. Schmidt, S.B. Haderlein, M. Berg, Environ. Sci. Technol.
water was spiked with all the analytes except p-xylene, and 36 (2002) 2054.
[14] Z. Lin, J.T. Wilson, D.D. Fine, Environ. Sci. Technol. 37 (2003) 4994.
the river water was spiked with ethanol, TBA, DIPE, ETBE, [15] J. Ji, C. Deng, W. Shen, X. Zhang, Talanta 69 (2006) 894.
TAME, toluene and ethylbenzene. The added concentrations and [16] N. Bahramifar, Y. Yamini, S. Shariati-Feizabadi, M. Shamsipur, J. Chro-
those predicted with the standard additions method are shown matogr. A 1042 (2004) 211.
in Table 5. These results reveal the applicability of the proposed [17] I. Arambarri, M. Lasa, R. Garcı́a, E. Millan, J. Chromatogr. A 1033 (2004)
methodology for the quantification of these compounds in water 193.
[18] J. Dron, R. Garcı́a, E. Millán, J. Chromatogr. A 963 (2002) 259.
matrixes. [19] R. Kubinec, J. Adamuscin, H. Jurdákova, M. Foltin, I. Ostrovský, A. Kraus,
L. Soják, J. Chromatogr. A 1084 (2005) 90.
4. Conclusions [20] J.L. Pérez Pavón, M. del Nogal Sánchez, C. Garcı́a Pinto, M.E. Fernández
Laespada, B. Moreno Cordero, Anal. Chem. 78 (2006) 4901.
The proposed methodology has been successfully applied [21] J. Efer, S. Müller, W. Engewald, T. Knobloch, K. Levsen, Chromatographia
in different types of water samples. The advantage of this 37 (1993) 361.
approach over previously described methods [20] is that in [22] M.V. Russo, Chromatographia 39 (1994) 645.
[23] J.L. Pérez Pavón, M. del Nogal Sánchez, M.E. Fernández Laespada, C.
the present case a PTV inlet was used. Important benefits of Garcı́a Pinto, B. Moreno Cordero, J. Chromatogr. A 1141 (2007) 123.
using Tenax-TA as packed material in the PTV instead of an [24] B. Kolahgar, E. Pfannkock, Tecnical Note 36, Gerstel, 2002 Mülheim/Ruhr.
inert support, such as better signal-to-noise ratios, and better [25] Enhanced ChemStation, G1701CA, Version C00.00, Agilent Technolo-
detection limits, were found. Using solvent vent injection, it gies1999, CA, United States.