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Analytica Chimica Acta 587 (2007) 89–96 Headspace–mass spectrometry determination of benzene, toluene and the mixture
Analytica Chimica Acta 587 (2007) 89–96 Headspace–mass spectrometry determination of benzene, toluene and the mixture

Analytica Chimica Acta 587 (2007) 89–96

Analytica Chimica Acta 587 (2007) 89–96 Headspace–mass spectrometry determination of benzene, toluene and the mixture

Headspace–mass spectrometry determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics

F.A. Esteve-Turrillas, S. Armenta, S. Garrigues, A. Pastor, M. de la Guardia

Department of Analytical Chemistry, Universitat de Val`encia, Edifici Jeroni Munoz,˜

50th Dr. Moliner, 46100 Burjassot, Val`encia, Spain

Received 5 October 2006; received in revised form 5 January 2007; accepted 15 January 2007 Available online 21 January 2007

Abstract

A simple and fast method has been developed for the determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers (BTEX) in soils. Samples were introduced in 10 mL standard glass vials of a headspace (HS) autosampler together with 150 L of 2,6,10,14- tetramethylpentadecane, heated at 90 C for 10 min and introduced in the mass spectrometer by using a transfer line heated at 250 C as interface. The volatile fraction of samples was directly introduced into the source of the mass spectrometer which was scanned from m/z 75 to 110. A partial least squares (PLS) multivariate calibration approach based on a classical 3 3 calibration model was build with mixtures of benzene, toluene and o-xylene in 2,6,10,14-tetramethylpentadecane for BTEX determination. Results obtained for BTEX analysis by HS–MS in different types of soil samples were comparables to those obtained by the reference HS–GC–MS procedure. So, the developed procedure allowed a fast identification and prediction of BTEX present in the samples without a prior chromatographic separation. © 2007 Elsevier B.V. All rights reserved.

Keywords: Benzene; Toluene; Ethylbenzene; Xylene isomers; Headspace-mass spectrometry; Chemometric analysis

1. Introduction

Volatile organic compounds (VOCs) are chemical products

based on carbon chains or rings, also containing hydrogen with

a vapour pressure greater than 0.27 kPa at 25 C excluding

methane. Measurement of VOCs in different kind of samples

has received significant attention over the past few years because of direct and indirect impacts of individual VOCs on human health and ecosystem. Many VOCs are either known or sus- pected carcinogens and some have toxic effects [1–3]. The 1990 US Environmental Protection Agency (EPA) Clean Air Act [4] includes 189 hazardous air pollutants that are mostly VOCs, and

it has been evidenced that these compounds also play a critical

role in formation of tropospheric ozone [5,6]. BTEX [benzene, toluene, ethylbenzene and the three xylene isomers (ortho, meta and para)] are a subclass of VOCs with boiling points between 80 and 150 C. Their solubility in water,

Corresponding author. Tel.: +34 963544838; fax: +34 963544838. E-mail address: miguel.delaguardia@uv.es (M. de la Guardia).

0003-2670/$ – see front matter © 2007 Elsevier B.V. All rights reserved.

doi:10.1016/j.aca.2007.01.036

together with the chronic toxicity associated with the aromatic ring present in their structure, make BTEX display a high pollution potential. These aromatic hydrocarbons are widely distributed in the environment due to natural sources; which include superior plant wax, algae and plankton, and anthro- pogenic sources of hydrocarbons; that comprise domestic and industrial wastes, biomass and wood burning, incomplete fuel oil combustion and urban runoff [7]. Analytical methods of reference for the determination of BTEX residues in environmental samples are based on gas chromatography–mass spectrometry (GC–MS), using either static [8] or dynamic [9] headspace (HS) as sample introduction modules. On the other hand, some other techniques like liquid chromatography [10] or near infrared [11] have been already employed. In recent years, several novel techniques of sample intro- duction and sample pre-treatment for GC analysis, like purge-and-trap [12], membrane extraction [13], solid-phase microextraction [14] and single-drop microextraction [15] have been developed for the determination of BTEX and other volatile compounds in different samples. On the other hand,

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it has been done a big effort to improve the BTEX extraction by using the accelerated solvent extraction (ASE) in order to achieve an efficient removal of analytes from different matrices [16,17] prior to chromatographic analysis. However, the use of chromatography means long time of anal- ysis and, because of that, sample screening methodologies to detect BTEX residues like the combination of headspace and mass spectrometry detection have been explored providing a yes/no response in order to reduce the amount of samples to be analyzed [18]. The, HS–MS technique has been successfully applied in qualitative applications such as the detection of hydro- carbons in environmental matrices [19] and for classification of the geographical origin of olive oils [20]. Multivariate calibration is a very useful tool for extract- ing chemical information from instrumental signals. The most commonly used multivariate methods for chemical analysis are partial least squares (PLS) regression and principal component regression (PCR), where factors that relate to variation in the response measurements are regressed against the properties of interest.

Y = Tq × f

where T is a matrix of latent variables and q contains the regres- sion coefficients for the columns in T. The PLS factors (T) must model most of the variation, both in the X- and Y-variable and also attain fully adequate predictive ability. Ideally, each factor added to the model would describe variation relevant for predict- ing property values. To find the adequate number of PLS factors to retain in the calibration model there are different methods. One of the most employed is that which minimizes the predicted residual error sum of squares (PRESS) of the model [21]. In summary, the relationships between analytical signals and data to be determined are developed from the training set and then applied to the set of unknowns. For unknown samples, the concentrations of various constituents can often be predicted with a good accuracy. The aim of this study has been the development of a simple and quick method capable to identify and to quantify BTEX in soil samples using HS–MS combined with a partial least squares (PLS) treatment of spectral data obtained, without any chromatography separation.

2. Experimental

2.1. Chemicals and reagents

Toluene (99.8%, v/v), benzene (99.7%, v/v), hexane (96%, v/v), iso-octane (99.8%, v/v) and petroleum ether (multisol- vent grade) were supplied by Scharlau (Barcelona, Spain) and the isomers of xylene, ortho, meta and para (99.0%, v/v) and ethylbenzene (99%, v/v) were provided by Fluka (Buchs, Switzerland). 2,6,10,14-Tetramethylpentadecane (98%, v/v) used to prepare the standard solutions an added to the samples to compensate the background was purchased from Sigma–Aldrich (Madrid, Spain). Methyl tert-buthyl ether (MTBE) (99%, v/v), used in the evaluation of interferents, was provided by Merck (Darmstadt, Germany).

Stock standard solutions employed to build the PLS calibra- tion models were prepared in 2,6,10,14-tetramethylpentadecane at a concentration of 5.0 mL L 1 and stored in amber glass- stoppered bottles at 4 C. Standard solutions containing BTEX at individual concentration of 5, 25 and 50 L L 1 of benzene, toluene and xylene were also prepared in 2,6,10,14- tetramethylpentadecane by appropriate dilution of the stock ones. PLS calibration standards were prepared at three different levels by adding 50 L of the different dilutions, that corre- sponds to 0.25, 1.25 and 2.5 nL of benzene, toluene and o-xylene, inside glass headspace standard vials. Spiked samples were prepared by adding 50 L of each stan- dard solution at 12.5, 25 and 37.5 L L 1 level, that correspond to 0.25, 0.625 and 1.875 nL of considered compounds, to 1 g of soil. Real soil samples were taken from the vicinity of petrol pump stations in the area of Valencia and were directly heated in HS glass vials after adding 150 L of solvent.

3. Apparatus

3.1. The extraction–injection module

A static headspace autosampler Thermo Finnigan model

HS 2000 (Waltham, MA, USA) equipped with standard glass vials of an internal volume of 10 mL (23 mm × 46 mm) was employed. Once equilibrium was reached between the matrix and the gaseous phase, 1 mL vapour sample was injected into the system.

3.2. The transfer line

The transfer line ensures coupling of the extraction–injection module to the mass spectrometer. This line must be designed to maintain a high-quality vacuum in the spectrometer source while allowing rapid transfer of the extracted molecules between the two modules. A Scharlab fused silica tube of 30 m length with an internal diameter of 0.32 mm was employed. The temperature of this tube was held at 250 C to prevent condensation of the considered compounds.

A Hewlett Packard HP5MS column (Palo Alto, CA, USA)

(30 m × 0.32 mm i.d., 0.25 m film thickness) was used to obtain the reference data by chromatography.

3.3. The mass spectrometer

A Thermo Finnigan Trace gas chromatograph, equipped

with a Thermo Finnigan ion trap mass spectrometer detector Polaris Q was used. Ionization of the molecules introduced into the source of the mass detector was carried out by elec- tron ionization at 70 eV and an helium flow of 0.3 mL min 1

was used as damping gas. Data acquisition in full scan mode was carried out over a mass range of m/z 75–110. The detec- tor temperature was fixed at 250 C. Ion trap tests and mass calibration were weekly performed with perfluorotributylamine (PFTBA).

F.A. Esteve-Turrillas et al. / Analytica Chimica Acta 587 (2007) 89–96

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3.4. HS–GC–MS reference procedure

One gram of soil sample was accurately weighted inside

a 10 mL standard glass vial and 150 L of 2,6,10,14-

tetramethylpentadecane were added. After that, the vial was capped hermetically and heated in the headspace autosampler

at 90 C for 10 min with shaking. The syringe temperature was

selected at 100 C and 1 mL injection volume was introduced into the system in split mode (1:10), employing a constant flow of 1 mL min 1 helium as carrier. The oven temperature program started from 40 C, held for 10 min, increased at a

rate of 20 C min 1 up to 200 C and finally held for 2 min. The transfer line and source temperature were fixed at 300 and

employing their characteristic ions. However, ethylbenzene and xylenes cannot be differentiated from each other because they present the same characteristic ions and only could be quantified after an appropriate separation. Additionally, in Fig. 1, it can be seen the mass spectra of 2,6,10,14-tetramethylpentadecane. The specific ions generated by this molecule at m/z 83–85 and 97–99 do not overlap with the characteristic ions of the analytes and, thus this compound could be used as internal reference for the determination of BTEX compounds. On the other hand, it is clear from Fig. 1 that ethylbenzene and xylenes could be determined by MS without any interference of benzene nor toluene.

250

C, respectively.

 

4.2.

HS–GC–MS recording of a BTEX mixture

3.5.

Headspace–mass spectrometry procedure (HS–MS)

Preparation of sample and headspace conditions were kept as

for the reference procedure. In order to measure the patterns of

volatile compounds in soil samples without any chromatography

separation (HS–MS methodology), the column was replaced by

a silica tube transfer line and the oven temperature was pro- grammed to keep a constant temperature of 250 C.

3.6. Chemometric analysis

For instrumental, measurement control and data acquisition

it was employed the Xcalibur from Thermo Finnigan (Waltham,

A conventional chromatographic separation of a mixture of

1 nL of each one of BTEX compounds, using an HP-5 (5%- phenyl)-methylpolysiloxane column and full scan acquisition mode with selected ions at m/z 77, 78, 91, 92 and 106, is shown in Fig. 2. As it can be seen in the figure, BTEX compounds are well separated in a run time of 11 min, except meta- and para-xylene that coelute. Thus, five peaks were obtained at 2.4, 4.1, 7.8, 8.4 and 10.0 min, corresponding to benzene, toluene, ethylbenzene, (m,p)-xylenes and o-xylene, respectively.

4.3. HS–MS determination of benzene, toluene and

o-xylene

MA, USA). Data were exported in excel format and the PLS cali- bration models were developed by means of TurboQuant Analyst 6.0 software developed by Thermo Nicolet Corp. (Madison, WI, USA). The proposed PLS model was built using 27 standards for calibration (using a classical 3 3 design) and it was validated

The main objective of this study was to establish a fast screen- ing procedure based on the decrease of the run time and the increase of the sample throughput for BTEX determination in soils. So, the chromatography column was changed by a silica empty tube as transfer line, in order to obtain one unresolved

by

means of a set of 10 spiked samples with known amounts

peak and to use the mass spectra of this peak for BTEX quan-

of

BTEX. As it has been aforementioned, the calibration stan-

tification.

dards correspond to different mixtures of benzene, toluene and o-xylene at three different concentration levels (3 3 ). High level

was fixed at 2.5 nL, medium value was evaluated at 1.25 nL and low concentration level was fixed at 0.25 nL. Concentration of

the aforementioned components in spiked samples was predicted

employing the PLS calibration using the information of the mass

spectra between m/z 75 and 110. To build and select PLS models, the optimum number of fac- tors was chosen to minimize the PRESS, based on the criterion of Haaland and Thomas [22].

4. Results and discussion

4.1. MS spectra of BTEX compounds

One nanoliter benzene, toluene, ethylbenzene and each xylene isomer standards were measured by HS–GC–MS, in

order to obtain the retention time and mass spectra of each com- pound. Mass spectra are shown in Fig. 1 in which it can be seen

the specific ions generated at m/z 77 and 78 for benzene, m/z 91

and 92 for toluene and finally m/z 91 and 106 for ethylbenzene

and the three xylenes. Benzene and toluene can be determined

In a first attempt, a silica tube of 5 m length and 0.32 mm

i.d. was assayed, but the vacuum of the mass spectrometer was not acceptable, so a longer column of 30 m length and 0.32 mm i.d. was used as transfer line and the vacuum problems were avoided. Using the aforementioned interface, a standard mixture of 1 nL of benzene, toluene and o-xylene was measured by HS–MS in full scan mode in a mass range of m/z 75–110. Fig. 3 shows the obtained MS time recording for selected ions of m/z 77, 78, 91, 92 and 106. Inset of Fig. 3 shows the corresponding mass spec- trum of this wide peak from 1 to 4 min. Mass spectra obtained as described for mixtures of benzene, toluene and o-xylene were used for multivariate calibration based on partial least squares (PLS) to predict the concentration of these compounds in soil samples.

4.4. PLS models for HS–MS determination of benzene,

toluene and o-xylene

A classical design of 3 3 standards for the three analytes con-

sidered (benzene, toluene and o-xylene), at three concentration

levels was used. Table 1 shows the analytical features of the

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et al. / Analytica Chimica Acta 587 (2007) 89–96 Fig. 1. Mass spectra of benzene, toluene,

Fig. 1. Mass spectra of benzene, toluene, ethylbenzene, xylene and 2,6,10,14-tetramethylpentadecane obtained in the full scan mode for an individual amount of 1 nL of each one.

PLS model developed for the different compounds under study. It has been indicated the number of factors required for predic- tion of each analyte concentration with the minimum predicted residual error sum of squares (PRESS), the coefficient of deter- mination, R 2 of the calibration model, the root mean square error of calibration (RMSEC) and the mean absolute validation errors, established for ten spiked soil samples previously analyzed by the reference procedure and not included in the calibration set.

As it can be seen, in the best conditions, using all the infor- mation of the spectral range, without any baseline correction nor spectra pre-treatment, RMSEC of 12.1, 24.2 and 34.6 and mean relative validation errors of 4.0, 5.4 and 5.9% were obtained for benzene, toluene and xylene, respectively. The principal component spectra (PCS) were obtained in order to explain the contribution of factors on the analysis of each volatile organic compound (see Fig. 4). On comparing

F.A. Esteve-Turrillas et al. / Analytica Chimica Acta 587 (2007) 89–96

93

et al. / Analytica Chimica Acta 587 (2007) 89–96 93 Fig. 2. Typical HS–GC–MS chromatogram obtained

Fig. 2. Typical HS–GC–MS chromatogram obtained for a BTEX mixture of 1 nL of each compound measured in full scan mode at m/z 77, 78, 91, 92 and 106 selected ions.

scan mode at m / z 77, 78, 91, 92 and 106 selected ions. Fig. 3.

Fig. 3. HS–MS time recording of a benzene, toluene and o-xylene mixture of 1 nL of each compound. Inset: Mass spectrum obtained for the recording between 1 and 4 min.

these signals with spectra in Fig. 1 it can be seen that the most discriminant original variables correspond to the m/z ratios 85, 77, 78, 91, 92 and 106, which are the major mass fragments for the 2,6,10,14-tetramethylpentadecane, used as internal ref- erence, and BTEX compounds, and that the signals are well modelized with the PCS from 1 to 5 being all other variables characteristics of the background noise. On the other hand, the general occurrence of positive and negative peaks in PLS PC plots is due to the sign of corre- lation between the component to be determined and the PLS factor. The negative correlation between a PLS factor and an analyte will provide a negative peak at its specific m/z. The load- ings cannot be interpreted as spectra. Due to the orthogonality forces, some loadings could have negative values that cannot

Table 1 Statistics for the PLS-MS calibration and prediction

exist in spectra [21]. Fig. 5 shows the evolution of both, the percentage of explained variance and that of the percentage of cumulative variance for benzene determination as a function of the number of PCs, that four components are enough for a good modelization. Calibration models obtained in different sessions provided different detector responses in the whole m/z range used and thus, in the following studies the calibration model was established from measurements made in the same session than samples. There are several circumstances that can introduce variations in the new spectra that had not been included in the calibra- tion step. The presence of these unmodeled variations in the new data can lead to strongly biased predictions from multivari- ate calibration models. The situation arises from changes in the

Region

Baseline

Spectra pre-treatment

Analyte

Factors a

R 2b

RMSEC c

Mean accuracy error d (nL)

109-76

None

None

Benzene

4

0.9994

12.1

0.04

 

Toluene

4

0.998

24.2

0.05

Xylene

5

0.996

34.6

0.06

a The number of factors were chosen in order to obtain the minimum predicted residual error sum of squares.

b R 2 is the coefficient of determination of the regression line between predicted and actual values of analyte concentration in the calibration set.

c Root mean square calibration error for a cross-validation.

d Mean accuracy error (%) found from the comparison of data obtained for the validation set of samples with results obtained by HS–GC–MS.

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et al. / Analytica Chimica Acta 587 (2007) 89–96 Fig. 4. Principal component spectra diagnostic applied

Fig. 4. Principal component spectra diagnostic applied to verify the effect of the number of factors on the signals of benzene, toluene and o-xylene. Vertical lines represent the characteristic m/z for each BTEX compound. Note: Benzene (B), toluene (T), ethylbenzene (E) and xylene (X).

instrumental response function. These changes can occur when the data to be predicted are collected on an instrument differ- ent from that used to build the model or simply in the same instrument but in different measurement sessions. Although the spectra may have the same basic shape or profile, the measured intensity values from two instruments will generally be differ-

values from two instruments will generally be differ- Fig. 5. Effect of the number of PCs

Fig. 5. Effect of the number of PCs used in the PLS model on the explained variance and cumulative variance for benzene determination.

Table 2 Effect of the use of o-xylene in the calibration set for PLS HS–MS determination of ethylbenzene, different xylene isomers and a mixture of all of them in the presence of benzene and toluene

Compound

Amount added (nL)

%Recovery

o-Xylene

1

101 ± 6 102 ± 9 101 ± 11 93 ± 8 99 ± 12

m-Xylene

1

p-Xylene

1

Ethylbenzene

1

Mix a

1

Results are the average of three independent measurements ± the corresponding standard deviation.

a Mix: 0.25 nL of o-xylene, m-xylene, p-xylene and ethylbenzene.

ent, also, in the case of two different sessions, due to changes in the environment of the instrument or in its response. A solution to the calibration transfer problem is to apply chemometric techniques to correct for instrumental and envi- ronmental differences, thereby making the model transferable and avoiding full recalibration. Various methods for calibration transfer exist in the literature, and most have been discussed in recent reviews [23,24].

4.5. Effect of the use of different xylene isomers in the calibration set

Ethylbenzene and the three xylene isomers present exactly the same mass spectra in the m/z range monitored (see Fig. 1). So, it seems impossible to do an individual determination of all of them by HS–MS without any chromatography separation. Due to this, the effect of the use of o-xylene in the calibration set to determine the aforementioned compounds as total xylene has been evaluated. One nanoliter of ethylbenzene and the different xylene iso- mers and a mixture of 0.25 nL of each one of the aforementioned compounds were measured in the presence of 1 nL of both, ben- zene and toluene. Table 2 shows the mean recovery data found for the considered compounds in the assayed solutions expressed as o-xylene. As it can be seen, the recovery of the different

Table 3 Effect of increasing amounts from 0.25 to 25 nL of different interferents on the recovery of benzene, toluene and xylene at 1.25 nL level by PLS HS–MS

Interferent

Compound

%Recovery

Petroleum ether

Benzene

105 ± 19 104 ± 24 107 ± 18

Toluene

Xylene

n-Hexane

Benzene

91 ± 14 98 ± 19 106 ± 21

Toluene

Xylene

iso-Octane

Benzene

104 ± 16 105 ± 9 96 ± 14

Toluene

Xylene

MTBE a

Benzene

94 ± 13 94 ± 14 100 ± 9

Toluene

Xylene

a MTBE: methyl tert-buthyl ether.

 

F.A. Esteve-Turrillas et al. / Analytica Chimica Acta 587 (2007) 89–96

 

95

Table 4 BTEX concentration in soil samples obtained by both, reference HS–GC–MS and HS–MS developed procedures

 

Sample

Soil concentration (nL g 1 ± s, n = 3)

 

HS–GC–MS

HS–MS

Benzene

Toluene

E. Benzene

(m,p)-Xylene

o-Xylene

E. Benzene + Xylenes

Benzene

Toluene

E. Benzene + Xylenes

1

0.20 ± 0.10

1.5 ± 0.2

1.10 ± 0.08

1.68 ± 0.11 – – – a 0.50 ± 0.03 2.1 ± 0.10 1.81 ± 0.10 – a 1.52 ± 0.09 – a

a

a

1.31 ± 0.10 – – – a 0.53 ± 0.02 1.16 ± 0.12 0.62 ± 0.03 – a 2.2 ± 0.2 – a

a

a

4.09

a

1.5 ± 0.2 2.4 ± 0.3 3.0 ± 0.4 1.5 ± 0.3 3.4 ± 0.2 0.5 ± 0.2 – a 4.8 ± 0.3 – – a

a

4.2 ± 0.3 1.4 ± 0.2 – – a 1.4 ± 0.2 4.8 ± 0.2 2.90 ± 0.10 – a 3.4 ± 0.4 7.0 ± 0.2

a

2

3

a

a

2.50 ± 0.15

3.1 ± 0.2

0.91 ± 0.07

a

0.91

a

a

a

4

a

1.72 ± 0.11

a

a

a

5

a

3.3 ± 0.2

0.20 ± 0.01

1.23

a

6

a

0.86 ± 0.10

1.4 ± 0.2

4.66

a

7

a

a

0.71 ± 0.08

3.14

a

8

a

4.2 ± 0.3

a

a

a

9

a

a

a

3.72

 

a

10

a

a

6.8 ± 0.4

6.80

a

a Less than LOD (estimated in 0.1 nL g 1 ).

xylenes is around 100%. So, being acceptable, the use of o- xylene in the calibration set for the prediction of ethylbenzene, m- and p-xylenes.

4.6. Study of interferences

The main contamination sources of BTEX in soils include the massive use of petroleum and its derivatives, and that of solvents. So, it was evaluated the interference of hydrocarbons like petroleum ether, n-hexane or iso-octane together with that

of methyl tert-buthyl ether, a common used additive of gasoline.

In order to assure the accuracy of the developed procedure,

it was evaluated the interference of increasing amounts of the considered compounds from 0.25 to 25 nL for a fixed amount of benzene, toluene and xylene of 1.25 nL of each one. We can notice that whatever the interferent studied and the concentration of that, the mean recovery values stay around 100%, as it can be seen in Table 3. So, the presence of these com- pounds does not interfere on BTEX determination by HS–MS, for interferent/analyte ratios from 0.2 to 20.

4.7. Real sample analysis

In a first attempt, 1 g of soil samples taken near petrol sta-

tions in the area of Valencia were introduced inside headspace vials and measured by HS–MS, being the obtained results for benzene, toluene and xylene unacceptables. The main difference between soil samples and standards was the presence of the solvent and, taking into consideration the effect of the solvent in the PLS model which is well explained by the PC1 (see Fig. 4), it was decided to add 2,6,10,14- tetramethylpentadecane to the solid samples.

A 150 L of solvent added to the soil samples avoided the

mentioned problem and results found for the PLS HS–MS deter- mination of toluene and ethylbenzene plus xylenes shown in Table 4 indicate the excellent comparability with data found by HS–GC–MS. Benzene was detected only in a single sample by GC–MS at a level of 0.2 ± 0.1 nL g 1 .

The regression between concentrations found by the recom- mended procedure and those obtained by HS–GC–MS provide equations C HSMS = (0.15 ± 0.15) + (1.08 ± 0.09)C HSGCMS with a coefficient of determination R 2 = 0.98 (n = 10) and C HSMS = (0.06 ± 0.11) + (1.00 ± 0.03)C HSGCMS with a coef- ficient of determination R 2 = 0.991 (n = 10) for toluene and xylenes, respectively. In those equations, the intercept and slope values were statistically comparables to 0 and 1, respectively, for a probability level of 95% (being t exp lower in all cases than t theoretical = 1.734 (n = 18)) thus indicating that the devel- oped procedure provides an accuracy comparable with that of the chromatography method. The developed procedure allowed the individual identi- fication and quantification of benzene and toluene and the determination of the sum of ethylbenzene and xylenes. As it can be seen, benzene was undetected in actual samples, proba- bly as a result of the easy evaporation of this compound, as well as its low concentration in petroleum derivatives (less than 5%, v/v). Toluene and xylenes were found in the major part of soil samples analyzed, at concentrations higher than those of other analytes. These results are consistent with the high concentration of these compounds in petroleum derivatives (mainly gasoline).

5. Conclusions

The present work describes the development of an HS–MS method for the determination of aromatic hydrocarbons (BTEX) in soil matrices by using a PLS multivariate calibration approach. Considering the results, the HS–MS methodology could be applied for the differentiation and classification of samples, and also for the quantitative determination of BTEX in soil samples. In fact, benzene, toluene and the mixture of ethylbenzene and xylenes could be determined with an excellent accuracy. The dis- advantage of the need of a multivariate calibration technique for data treatment is compensated by the time saving (no chromatog- raphy separation step is required). Results are comparables with those obtained by HS–GC–MS and the sampling throughput is considerably improved, from 5 samples per hour by HS–GC–MS to 12 samples per hour by the developed procedure.

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Acknowledgements

The authors acknowledge the financial support of the Ministe- rio de Educacion´ y Ciencia (Project CTQ2005-05604, FEDER) and Direccio´ General d’Investigacio´ i Transferencia` Tecnologica` de la Generalitat Valenciana (Project 017609). F.A. Esteve- Turrillas and S. Armenta also acknowledge the V segles (Universitat de Valencia)` and FPU grant (Ministerio de Edu- cacion´ y Ciencia (Ref. AP2002-1874)), respectively.

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