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Journal of Chromatography A, 1171 (2007) 1–7

Liquid–liquid extraction/headspace/gas chromatographic/mass

spectrometric determination of benzene, toluene,
ethylbenzene, (o-, m- and p-)xylene and styrene
in olive oil using surfactant-coated carbon
nanotubes as extractant
Carolina Carrillo-Carrión, Rafael Lucena,
Soledad Cárdenas, Miguel Valcárcel ∗
Department of Analytical Chemistry, Marie Curie Building (Annex), Campus de Rabanales, University of Cordoba,
E-14071 Cordoba, Spain
Received 2 May 2007; received in revised form 13 August 2007; accepted 11 September 2007
Available online 21 September 2007

Abstract
BTEX-S compounds are widely distributed in the environment and can be present in different foodstuffs, including olive oil. Taking into account
the risks of the exposure to these compounds, analytical methods for their determination in different matrices are mandatory. In this paper, the use
of surfactant-coated multiwalled carbon nanotubes as additive in liquid–liquid extraction is applied for the determination of single-ring aromatic
compounds in olive oil samples. After sample treatment, the aqueous extracts are subsequently analyzed by headspace/gas chromatography/mass
spectrometry allowing the determination of BTEX-S within ca. 15 min. Each stage of the proposed LLE/HS/GC/MS configuration involves a
selectivity enhancement avoiding the interference of other compounds of the sample matrix. Limits of detection were in the range 0.25 ng mL−1
(obtained for ethylbenzene) and 0.43 ng mL−1 (for benzene). The repeatability of the proposed method expressed as RSD varied between 1.9%
(styrene) and 3.3% (benzene) (n = 11).
© 2007 Elsevier B.V. All rights reserved.

Keywords: Carbon nanotubes; Pseudophase; Liquid–liquid extraction; Gas chromatography; BTEXS; Olive oil

1. Introduction hydrocarbons can occur by ingestion (consuming contaminated

The acronym BTEX-S defines the mixture of benzene,
toluene, ethylbenzene, the three xylenes isomers (ortho, meta
and para) and styrene; all being harmful volatile organic com-
pounds (VOCs). BTEX-S are emitted to the environment from
an extensive variety of sources including combustion products of
wood and fuels, industrial paints, adhesives, degreasing agents
and aerosols [1]. Their widespread presence in samples of envi-
ronmental concern (air, water and soil) and their lipophilic nature
leads to their accumulation in different foodstuffs, mainly edible
oils and fat [2]. Therefore the human exposure to these aromatic
∗ Corresponding author. Tel.: +34 957 218 616; fax: +34 957 218 616.
E-mail address: qa1meobj@uco.es (M. Valcárcel).
water or food), inhalation or absorption through the skin. The
effects of exposure to these substances comprise changes in the
liver and harmful effects on the kidneys, heart, lungs, and ner-
vous system [3]. In order to reduce the human intake of these
hazardous substances a chemical control (and consequently
methods of analysis) is desirable.
Gas chromatography (GC) is the main alternative of choice
for the deterination of BTEX-S in environmental samples.
Although the direct analysis of the samples’ headspace has
been traditionally employed for the determination of BTEX-S
[4,5], new extraction strategies including the so-called solvent-
less sample preparation techniques [6,7] are gaining importance,
since they improve the selectivity and sensitivity of the devel-
oped methodologies. In this sense, solid phase microextraction
(SPME) [8–10] and single drop microextraction (SDME) [11]

0021-9673/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2007.09.039
2 C. Carrillo-Carrión et al. / J. Chromatogr. A 1171 (2007) 1–7
have been proposed as useful alternatives to the conventional
approach.
On the other hand, only a few methods face up the determina-
tion of these compounds in olive oil due to the complex nature of
this matrix. HS has been succesfully applied on the development
of screening [12] and confirmation [13] methodologies achiev-
ing limits of detection in the range of 2–10 ␮g kg−1 . Lower
limits of detection have been achieved by means of a HS-SPME
extraction step [14], allowing the determination of volatile and
semivolatile aromatic hydrocarbons in virgin olive oil. Purge-
and-trap technique has been also proposed for the determination
of styrene in olive oil sample at the ng kg−1 level [15].
In the present paper, a new alternative for BTEX-S determi-
nation in olive oil samples is proposed. The method makes use of
the exceptional adsorption properties of multiwall carbon nan-
otubes (MWCNTs). BTEX-S are liquid–liquid extracted from
the olive oil samples using a surfactant aqueous dispersion of
MWCNTs as extracting medium, this aqueous phase being fur-
ther analyzed by HS/GC/MS. The presence of the dispersed car-
bon nanotubes in the extractant enhances not only the selectivity
but also the sensitivity of the determination achieving detection
limits at least 10 times lower than the direct HS method.
2. Experimental
2.1. Reagents and samples
All reagents were of analytical grade. The analytes: benzene,
toluene, ethylbenzene, m-, p- and o-xylene, and styrene were
purchased from Sigma–Aldrich (Madrid, Spain). Stock standard
solutions of each analyte were prepared in methanol, purchased
from Panreac (Barcelona, Spain), at a concentration of 1 g L−1
and stored in glass-stoppered bottles in the dark at 4 ◦ C. Work-
ing solutions were prepared by dilution of the stocks in the
appropriate solvent.
MWCNTs, purity of 95%, were obtained from
Sigma–Aldrich. The diameters and lengths are in the range of
20–50 nm and 5–20 ␮m, respectively. The solubilization, by
dispersion, of MWCNTs in an aqueous medium were achieved
following a previously optimized procedure [16]: an accurately
weighted amount of 5.0 mg of the nanotube was mixed with
130 mg of solid sodium dodecyl sulphate (SDS). The solid
mixture was placed in a 50 mL volumetric flask, filled with
distilled water and sonicated in an ultrasonic bath (50 W,
60 Hz) during 20 min. The final dispersion contained SDS
and MWCNTs at concentrations of 9 mM and 0.1 mg mL−1 ,
respectively.
Olive oil samples were purchased at a local supermarket. In
order to increase the samples variability, olive oil from different
years and storing conditions were employed. Once in the lab,
they were stored in amber glass bottles without headspace at
room temperature until the analysis.
A blank refined olive oil sample, previously analyzed by
HS/GC/MS, was employed for calibration and comparison stud-
ies. The blank sample was also subjected to a stirring process in
an opened glass bottle during 5 h, in order to guarantee the total
absence of the target analytes.
Fig. 1. Schematic diagram of the headspace/gas chromatography/mass spec-
trometry system employed for the determination of BTEX-S. LLE, liquid–liquid
extraction; MWCNTs, multiwall carbon nanotubes; HS, headspace module, GC,
gas chromatograph and MS, mass spectrometer.
2.2. Apparatus
The instrumental set-up used, depicted in Fig. 1, consists
of three modules: a MPS2 32-space headspace autosampler
(Gerstel, Mülhein an der Ruhr, Germany) including a robotic
arm and an oven for sample heating/headspace generation, a
Hewlett-Packard HP6890 gas chromatograph (Palo Alto, CA,
USA) equipped with a HP-5MS fused silica capillary col-
umn (30 m × 0.32 mm i.d., and 0.25 ␮m of thickness) and a
HP5973 mass spectrometer based on a quadrupole analyser and
a photomultiplier detector. For individual analyte identification
and quantification, the program temperature was as follows:
3 min at 40 ◦ C, raised up to 80 ◦ C at 5 ◦ C min−1 , ramped at
50 ◦ C min−1 up to 200 ◦ C and kept finally at 200 ◦ C for 3 min.
An automated injector fitted with a 2.5 mL gastight HS-syringe
was used for the introduction of 2.5 mL of the homogenized
headspace from the vial into the gas chromatograph. Helium
(5.0 grade purity, Air Liquide, Seville, Spain), regulated by a
digital pressure and flow controller, was used as carried gas
(1.4 mL min−1 ) for driving the analytes to the detector. The
mass spectrometer detector was operated in full scan mode,
by scanning a mass range from m/z 40 to 180 at a rate of
1.36 scan s−1 ; electron impact ionization (70 eV) was used for
analyte fragmentation. The MS source and quadrupole temper-
atures were maintained at 230 and 150 ◦ C, respectively. Total
ion current chromatograms were acquired and processed using
G1701BA Standalone Data Analysis software. The peak areas
calculated from the total ion current chromatogram were used
for quantification of benzene, toluene, ethylbenzene and (m-,
p-)xylene. Taking into account that o-xylene and styrene over-
lapped, quantification and identification of both compounds
were achieved by extracting a specific m/z fragment (91 for
o-xylene and 104 for styrene). The resulting chromatograms
 C. Carrillo-Carrión et al. / J. Chromatogr. A 1171 (2007) 1–7
were integrated, the peak areas being used for quantification
purposes.
System control was achieved with an HP1701CA MS Chem-
Station (Agilent Technologies) on a Pentium 4 computer which
also controlled the whole system.
2.3. Reference method
The reference method, described elsewhere [13], consists of
the direct analysis of the samples’ headspace by GC/MS. For this
purpose, 10 mL of sample were placed in a 20 mL headspace
glass vial. The vial was sealed with PTFE/silicone septa and
600 ␮L of ethyl acetate was added, by means of an appropriate
syringe, as chemical modifier. The vial was heated in the oven at
95 ◦ C during 30 min with mechanical stirring, to ensure the equi-
libration of the BTEXS residues between the gaseous phase and
the liquid sample. Finally, 2.5 mL of the resulting headspace was
injected in the chromatograph. The chromatographic conditions
were identical than those described for the proposed method.
2.4. Analytical procedure
Before the analysis, real olive oil samples were liquid–liquid
extracted using the surfactant-coated aqueous dispersion of
MWCNTs as extractant. In a 20 mL vial, 9 mL of sample and
9 mL of the extractant were placed, and 100 ␮L of methanol
was added for extraction enhancing. After mixing, the vial was
closed and manually shaken during 30 s in order to facilitate the
close contact between phases. Finally, the phases were separated
and 6 mL of the aqueous extracts were placed into 10 mL glass
vials, hermetically sealed with PTFE/silicone septa and placed
in the autosampler. The robotic arm took each vial from the
tray and placed it into the oven where extracts were heated at
80 ◦ C for 15 min under mechanical stirring to ensure the equili-
bration of the BTEX-S between the two phases (the headspace
and the aqueous dispersion of MWCNTs). Then, 2.5 mL of the
gaseous phase was sampled by inserting the needle of the gas-
tight syringe (heated at 80 ◦ C) through the septum cap and driven
to the column where the separation took place. The BTEX-S
were identified by comparison of the retention times and mass
spectra of the chromatographic peaks with those obtained for
standards under the same chromatographic and mass spectro-
metric conditions. A representative chromatogram is shown in
Fig. 2. In order to quantify o-xylene and styrene, which present
a similar retention time, specific m/z ratios (91 and 104, respec-
tively) were extracted from the total ion chromatogram and the
resulting peaks were integrated.
2.5. Carbon nanotubes recovery
Dispersed MWCNTs were mixed with methanol and water
under continuous magnetic stirring. Under these conditions the
dispersion breaks, liberating the solid nanotubes which are col-
lected by filtration and sequentially washed with fresh portions
of n-hexane, pure water and methanol. Finally, MWCNTs are
dried in an oven at 50 ◦ C.
3
Fig. 2. Chromatogram obtained for a blank refined olive oil sample spiked with
20 ng mL−1 of each analyte. The chromatographic peaks of interest are indicated.
Chromatographic peaks of interest: (1) benzene, (2) toluene, (3) ethylbenzene,
(4) m-xylene, (5) p-xylene, (6) o-xylene and (7) styrene. SD, solvent delay.
3. Results and discussion
Carbon nanotubes (CNTs) have strong adsorption affinity to
a wide variety of organic compounds and are also characterized
by their high sorption surface. These interesting properties have
been exploited in some analytical methodologies. In this way,
CNTs have been used as sorbent material in solid phase extrac-
tion (SPE) [17–19], as fibre material coating in SPME [20],
as stationary phase in gas chromatography [21–23] and also as
pseudostationary phase in capillary electrophoresis [24].
The main limitation when CNTs are used as sorbent material
is their aggregation tendency, which reduces the active surface
area of this material and therefore their effectiveness. Differ-
ent methodologies have been proposed in order to overcome
this problem, the most used being chemical derivatization and
dispersion in a surfactant medium. In the second approach,
the apolar hydrocarbon chain of the surfactant interacts with
the nanotubes allowing their homogeneous distribution in the
aqueous medium. Surfactant-coated MWCNTs aqueous solu-
tion enhances the adsorption properties of MWCNTs, reducing
the aggregation, and can be used as pseudophase or additive in
liquid–liquid extraction [16].
3.1. Optimization/selection of variables
Liquid–liquid extraction is a key step of the whole analytical
process as it is the source for sensitivity and also selectivity
enhancement. The effectiveness of MWCNTs dispersed in a
surfactant medium as analyte extractant has been proven in a
recent publication [16]. The referenced study demonstrated that
MWCNTs act as the real “driving force” in the extraction, with
negligible effect of the surfactant medium.
In the present paper, different factors that can affect the effi-
ciency of the extraction, namely: phases’ ratio, the addition of
chemical modifiers and extraction time, were studied. Aqueous
carbon nanotubes dispersion, containing SDS and MWCNTs at
final concentrations of 9 mM and 0.1 mg mL−1 , was employed
as extracting medium. A real olive oil sample, spiked with
BTEX-S at individual concentrations of 50 ng mL−1 , was used
in the variables’ selection process. The ratio between sample
and extractant volumes was studied within the interval 7:1 to
1:3, obtaining the best results when a 1:1 ratio is used. Finally,
4 C. Carrillo-Carrión et al. / J. Chromatogr. A 1171 (2007) 1–7
Fig. 3. Influence of the headspace temperature (A) and equilibration time (B) on the toluene’ peak area.
the addition of chemical modifiers (organic solvents) was stud-
ied, resulting in 100 ␮l of methanol being found to be the best
alternative. This small amount of methanol facilitates the extrac-
tion of the analytes and does not affect the pseudophase stability.
The extraction time was studied within the interval 0.5–10 min.
Despite the concentration of extracted analyte slightly increas-
ing with the extraction time, 0.5 min was selected in order to
increase the sample throughput of the method. In the same way,
the possible losses of target analytes in the transference of the
extracts from the extraction vial to the headspace vial were taken
into account. No evidence of volatile losses was found using a
pipette as transference tool between vials and working at room
temperature.
Headspace is the extraction technique used in the proposed
method. Different variables, including chemical and instru-
mental ones, were considered with the aim of enhancing the
sensitivity of the determination. For this purpose, a control olive
oil sample was spiked with 50 ng mL−1 of toluene, which was
selected as model analyte, and analyzed using the proposed
method. The samples were liquid–liquid extracted following the
above-mentioned procedure and the extracts were analyzed by
the HS/GC/MS method. First, the influence of the volume of
the extract (viz. surfactant-coated carbon nanotubes containing
the BTEX-S) on the analyte transfer to the headspace phase was
studied within the interval 3.0–7.0 mL using 10 mL glass vials.
A volume of 6.0 mL was fixed as optimum because this ratio of
extract/headspace volumes provided the highest MS response.
Then, different organic solvents, namely: methanol, isopropanol
and ethyl acetate, were assayed as chemical modifiers. It is well
known that the release of volatiles from the sample matrix is
favored by the presence of these modifiers; however, in this
case negligible effect on the analytical signal was observed and
therefore no chemical modifier was added to the samples.
The instrumental variables that markedly affected the
headspace enrichment were also optimized. Oven temperature
was studied in the range 40–90 ◦ C and equilibration time was
Table 1
Figures of merit of the proposed method
Linear range (ng mL−1 ) LOD (ng mL−1 )
Benzene 1.5–200 0.43
Toluene 1.5–200 0.42
Ethylbenzene 1–200 0.25
(m + p)-Xylenea 1–200 0.26
o-Xylene 1–200 0.32
Styrene 1–200 0.38
a The linear range corresponds to the mixture of both isomers.
optimized in the interval 5–30 min. Fig. 3 shows the variation
of the chromatographic peak areas with the temperature (A) and
time (B) for toluene. As can be seen, the highest signals were
obtained for 80 ◦ C and 15 min, so these values were fixed as
optimal.
3.2. Analytical features of the LLE/HS/GC/MS system
Analytical curves were obtained using a completely blank
refined olive oil spiked with the analytes at different con-
centrations (between 1 and 200 ng mL−1 ). Calibration models
were constructed by plotting the peak area against the ana-
lyte concentration for each BTEX-S. By using the proposed
chromatographic conditions, the peaks for o-xylene and styrene
overlapped (this problem can be overcome using a 45 m length
column). In this case, individual quantification and identification
were achieved by extracting the m/z fragment 91 for o-xylene
and 104 for styrene and the chromatographic peaks obtained
were integrated. Taking into account the fragmentation pattern
of the analytes and the relative intensity of the fragment ions
selected, negligible influence on the sensitivity was observed in
comparison with that obtained for the rest of analytes. The fig-
ures of merit of the calibration graphs are summarized in Table 1.
The detection limits were calculated as the concentration provid-
ing an analytical signal three times higher than the background
noise. The precision of the method expressed as relative stan-
dard deviation was estimated at two concentration levels (20 and
50 ng mL−1 ) by analyzing 11 independent aliquots of refined
olive oil spiked with the seven analytes studied. The values are
also listed in Table 1.
3.3. Analysis of samples
The proposed method was used for the determination of
BTEX-S in commercial olive oil samples. Ten real sam-
ples, coming from different places and packed under different
R2 RSD (%) (at 20 ng mL−1 ) RSD (%) (at 50 ng mL−1 )
0.998 4.0 3.3
0.997 3.6 2.8
0.998 2.4 1.8
0.998 2.2 1.5
0.999 2.5 1.8
0.999 2.6 1.9
 C. Carrillo-Carrión et al. / J. Chromatogr. A 1171 (2007) 1–7 5

Table 2
Analysis of real olive oil samples using the proposed method

Typeb Packagec Concentration (ng mL−1 ) ± SDa

Benzene Toluene Ethylbenzene (m + p)-Xylene o-Xylene Styrene

Sample 1 EVOO G 173.7 ± 5.0 115.5 ± 3.5 n.dd n.d n.d n.d
Sample 2 EVOO G 20.2 ± 0.6 28.4 ± 0.7 n.d n.d n.d 2.29 + 0.1
Sample 3 EVOO P(2004) 75.1 ± 2.8 50.9 ± 0.9 n.d n.d n.d 102.8 ± 1.0
Sample 4 VOO G 23.2 ± 0.7 235.6 ± 3.8 17.6 ± 0.3 17.0 ± 0.1 16.1 ± 0.2 8.8 ± 0.1
Sample 5 VOO P(2004) 16.5 ± 0.6 15.7 ± 0.5 14.8 ± 0.3 14.5 ± 0.1 14.0 ± 0.2 101.9 ± 2.5
Sample 6 OO P(2006) 6.6 ± 0.2 8.9 ± 0.3 8.3 ± 0.1 8.4 ± 0.1 8.0 ± 0.2 7.8 ± 0.2
Sample 7 OO P(2005) 36.0 ± 0.9 31.5 ± 1.2 34.3 ± 0.4 25.0 ± 0.1 19.8 ± 0.2 32.2 ± 0.1
Sample 8 ROO G 44.2 ± 1.4 64.1 ± 2.1 4.8 ± 0.1 4.5 ± 0.1 4.6 ± 0.1 4.7 ± 0.1
Sample 9 ROO M de 4.0 ± 0.1 3.1 ± 0.1 2.9 ± 0.1 2.8 ± 0.1 3.5 ± 0.1
Sample 10 ROO P(2006) 46.5 ± 1.3 80.2 ± 2.5 5.6 ± 0.1 5.3 ± 0.1 5.3 ± 0.1 5.1 ± 0.1
a SD; standard deviation.
b EVOO, extra virgin olive oil; VOO, virgin olive oil; OO, olive oil and ROO, refined olive oil.
c G, glass bottle; P, plastic bottle and M, metal can. For plastic bottles, the year of packing is indicated into brackets.
d n.d, non detected. Concentration below the detection limit.
e d, detected at a concentration lower than the quantification limit.

conditions, were analyzed in triplicate. The results are presented

in Table 2. In this table the type and package conditions of the
analyzed samples are also indicated.
Some conclusions can be inferred from these results. In
the majority of samples analyzed, the total concentration of
BTEX-S is lower than the maximum recommended value of
2000 ng mL−1 . The overall BTEX-S concentration resulted to
be significantly higher in extra virgin olive oil (EVOO) and vir-
gin olive oil (VOO) than in refined olive oil (ROO) because a
main part of the volatile fraction is lost during the refining pro-
cess. In addition, refined olive oil (labelled as samples 8, 9 and
10) presented a low concentration of xylenes, which are unde-
tectable in extra virgin olive oil samples (samples 1, 2 and 3).
Moreover, while benzene and toluene were detected in all sam- Fig. 4. Chromatograms obtained by the analysis of real samples. (A) Refined
ples, the presence of styrene is directly related to the packaging olive oil sample, (B) mixture of refined and virgin olive oils and (C) virgin olive
oil sample. The retention time of each analyte is also indicated.
material, the concentration of styrene being higher when the
samples are stored in plastic bottles.
Finally, a relationship between styrene concentration and the
ity of the determination. In order to confirm the usefulness of
storage time was also observed. Samples bottled in 2006 (sam-
this proposal a direct comparison of the new methodology with
ples 6 and 10) contained a lower concentration of styrene that
a reference method was performed.
those with a longer packing time (samples 3, 5 and 7).
For this purpose, two series of blanks refined olive oil sam-
The typical chromatograms obtained for real samples are
ples were spiked with the BTEX-S at five concentrations levels
depicted in Fig. 4.
(25, 40, 50, 80 and 100 ng mL−1 ). The first set of samples was
analyzed using the reference method, while the second set was
3.4. LLE/HS versus HS direct analysis

Headspace generation can be considered as a simple sam- Table 3

pling technique which allows the determination of volatile Comparison of the results obtained with the proposed method and those obtained
compounds, at the same time reducing the effect of potential by direct HS analysis
interferences presented in the sample matrix as long as these are SEFa SSEF b R2
less volatile than the analyte. HS analysis has been frequently
used for the direct analysis of olive oil, not only for the individ- Benzene 20.2 0.5 0.9990
Toluene 39.3 0.8 0.9998
ual quantification of a broad variety of compounds but also for Ethylbenzene 45.1 0.6 0.9997
sample characterization and qualitative analysis. However, in (m + p)-Xylene 44.3 0.3 0.9998
the proposed method a new approach is presented, using a prior o-Xylene 45.4 0.9 0.9992
liquid–liquid extraction of the samples using a surfactant aque- Styrene 39.0 1.1 0.9976
ous dispersion of MWCNTs as extracting medium. This LLE a Sensitivity enhancement factor.
b
step was envisaged to enhance both the sensitivity and selectiv- Standard error of SEF.
6 C. Carrillo-Carrión et al. / J. Chromatogr. A 1171 (2007) 1–7
Table 4
Effect of the pseudophase’ recovery on the analytical signal
Peak area (fresh pseudophase) Peak area (recovered pseudophase)
Benzene 4,592,807 4,385,476
Toluene 5,147,460 4,934,847
Ethylbenzene 3,991,271 3,882,121
(m + p)-Xylene 6,806,315 6,642,351
o-Xylene 965,474 939,290
Styrene 840,757 819,928
a Relative standard deviation of the method at the same concentration level (see Table 1).
liquid–liquid extracted before the analysis. Finally, the results
were expressed for each analyte in the form:
Sp = KSc + b
where Sp and Sc are the signals provided by the proposed and the
reference method, respectively. K, the slope of the linear regres-
sion models, can be considered as the sensitivity enhancement
factor (SEF) obtained with the new method for the correspond-
ing analyte. Table 3 summarizes the SEF values as well as the
standard error associated obtained for each analyte. The linear
fittings obtained were acceptable in all instances (R2 > 0.997)
and the intercept (b) of the models (data not given) were neg-
ligible compared with the slopes (in the range 0.01–0.5%). As
can be seen, a clear sensitivity enhancement is obtained in all
cases, the lower value being for benzene (20) and the highest for
o-xylene (45.4). With the prior liquid–liquid extraction step an
enhancement of sensitivity is obtained despite the distribution
coefficient of BTEX-S between a hydrophobic organic phase and
the dispersed MWCNTs phase being lower than 1. This detail
can be explained taking into account two facts: (a) Headspace
generation depends directly on the donor liquid phase nature
(aqueous or organic) and for BTEX-S, the release to the gas
phase is favored if an aqueous phase, instead of an organic one, is
employed; (b) At 80 ◦ C, the headspace temperature used for this
application, the MWCNTs dispersion becomes unstable which
favors the transfer of the analytes to the gaseous phase.
The average of the mentioned factors establishes the enhance-
ment sensitivity factor for each analyte.
3.5. Pseudophase regeneration
The question of recovery of MWCNTs after use is interesting
to reduce the cost of the methodology. In order to evaluate the
potential reusing of MWCNTs a simple study was developed. A
blank refined olive oil sample spiked with 20 ng mL−1 of all the
analytes was analyzed following the proposed method. Aliquots
of the spiked sample were extracted using fresh and regener-
ated MWCNTs pseudophase and the chromatograms obtained
were compared in terms of peak area (see Table 4). As can be
seen, negligible differences were observed between the results
(if these differences are compared with the RSD of the method)
and the variability can be attributed to the inherent imprecision
of the method.
Variation (%) RSDa (%)
4.5 4.0
4.1 3.6
2.7 2.4
2.4 2.2
2.7 2.5
2.4 2.6
4. Conclusions
In the present work, the potential of the use of multiwall car-
bon nanotubes as additives in liquid–liquid extraction has been
demonstrated. The extraction step enhances the sensitivity of the
determination reducing the limit of detection at least 10 times
in comparison with the direct headspace analysis method. The
extraction process reduces the amount of matrix components
that must be injected into the chromatographic system, which
clearly improves the selectivity of the determination. It also
increases the lifetime of the column and other chromatographic
components.
Compared with the HS-SPME approach, the proposed
method is a valid alternative in terms of sensitivity, precision and
time of analysis. Although the LLE-procedure is more manual
and requires higher sample’ volume, it is cheaper taking into
account the price of the SPME fibres and their stability. Carry-
over problems, which sometimes appear in SPME applications,
are here avoided since every sample is extracted with a fresh
pseudophase.
Acknowledgement
Financial support from the Spanish DGICyT (Grant
CTQ2004-01220) is gratefully acknowledged.
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