F.A. Esteve-Turrillas et al. / Analytica Chimica Acta 587 (2007) 89–96
it has been done a big effort to improve the BTEX extractionby using the accelerated solvent extraction (ASE) in order toachieve an efﬁcient removal of analytes from different matrices[16,17]prior to chromatographic analysis.However,theuseofchromatographymeanslongtimeofanal-ysis and, because of that, sample screening methodologies todetect BTEX residues like the combination of headspace andmass spectrometry detection have been explored providing ayes/no response in order to reduce the amount of samples tobe analyzed.The, HS–MS technique has been successfully
appliedinqualitativeapplicationssuchasthedetectionofhydro-carbons in environmental matricesand for classiﬁcation of
the geographical origin of olive oils.Multivariate calibration is a very useful tool for extract-ing chemical information from instrumental signals. The mostcommonly used multivariate methods for chemical analysis arepartial least squares (PLS) regression and principal componentregression (PCR), where factors that relate to variation in theresponse measurements are regressed against the properties of interest.
is a matrix of latent variables and
contains the regres-sion coefﬁcients for the columns in
. The PLS factors (
) mustmodel most of the variation, both in the
-variable andalso attain fully adequate predictive ability. Ideally, each factoraddedtothemodelwoulddescribevariationrelevantforpredict-ing property values. To ﬁnd the adequate number of PLS factorsto retain in the calibration model there are different methods.Oneofthemostemployedisthatwhichminimizesthepredictedresidual error sum of squares (PRESS) of the model.In summary, the relationships between analytical signals anddata to be determined are developed from the training set andthen applied to the set of unknowns. For unknown samples, theconcentrations of various constituents can often be predictedwith a good accuracy.The aim of this study has been the development of a simpleand quick method capable to identify and to quantify BTEXin soil samples using HS–MS combined with a partial leastsquares (PLS) treatment of spectral data obtained, without anychromatography separation.
2.1. Chemicals and reagents
Toluene (99.8%, v/v), benzene (99.7%, v/v), hexane (96%,v/v),
-octane (99.8%, v/v) and petroleum ether (multisol-vent grade) were supplied by Scharlau (Barcelona, Spain) andthe isomers of xylene,
(99.0%, v/v)and ethylbenzene (99%, v/v) were provided by Fluka (Buchs,Switzerland). 2,6,10,14-Tetramethylpentadecane (98%, v/v)usedtopreparethestandardsolutionsanaddedtothesamplestocompensatethebackgroundwaspurchasedfromSigma–Aldrich(Madrid, Spain). Methyl
-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-tionmodelswerepreparedin2,6,10,14-tetramethylpentadecaneat a concentration of 5.0mLL
and stored in amber glass-stoppered bottles at 4
C. Standard solutions containing BTEXat individual concentration of 5, 25 and 50
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 differentlevels by adding 50
L of the different dilutions, that corre-spondsto0.25,1.25and2.5nLofbenzene,tolueneand
-xylene,inside glass headspace standard vials.Spikedsampleswerepreparedbyadding50
Lofeachstan-dard solution at 12.5, 25 and 37.5
level, that correspondto 0.25, 0.625 and 1.875nL of considered compounds, to 1g of soil.Realsoilsamplesweretakenfromthevicinityofpetrolpumpstations in the area of Valencia and were directly heated in HSglass vials after adding 150
L of solvent.
3.1. The extraction–injection module
A static headspace autosampler Thermo Finnigan modelHS 2000 (Waltham, MA, USA) equipped with standard glassvials of an internal volume of 10mL (23mm
46mm) wasemployed. Once equilibrium was reached between the matrixand the gaseous phase, 1mL vapour sample was injected intothe system.
3.2. The transfer line
Thetransferlineensurescouplingoftheextraction–injectionmodule to the mass spectrometer. This line must be designed tomaintainahigh-qualityvacuuminthespectrometersourcewhileallowing rapid transfer of the extracted molecules between thetwo modules. A Scharlab fused silica tube of 30m length withaninternaldiameterof0.32mmwasemployed.Thetemperatureof this tube was held at 250
C to prevent condensation of theconsidered compounds.A Hewlett Packard HP5MS column (Palo Alto, CA, USA)(30m
0.32mm i.d., 0.25
m ﬁlm thickness) was used toobtain the reference data by chromatography.
3.3. The mass spectrometer
A Thermo Finnigan Trace gas chromatograph, equippedwith a Thermo Finnigan ion trap mass spectrometer detectorPolaris Q was used. Ionization of the molecules introducedinto the source of the mass detector was carried out by elec-tron ionization at 70eV and an helium ﬂow of 0.3mLmin
was used as damping gas. Data acquisition in full scan modewas carried out over a mass range of
75–110. The detec-tor temperature was ﬁxed at 250
C. Ion trap tests and masscalibration were weekly performed with perﬂuorotributylamine(PFTBA).