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Headspace–mass Spectrometry Determination of Benzene, Toluene

Headspace–mass Spectrometry Determination of Benzene, Toluene

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

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Published by: api-3861299 on Oct 19, 2008
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Analytica Chimica Acta 587 (2007) 89–96
Headspace–mass spectrometry determination of benzene, tolueneand the mixture of ethylbenzene and xylene isomers insoil 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 Mu˜ noz, 50th Dr. Moliner, 46100 Burjassot, Val`encia, Spain
Received 5 October 2006; received in revised form 5 January 2007; accepted 15 January 2007Available 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 10mL standard glass vials of a headspace (HS) autosampler together with 150
L of 2,6,10,14-tetramethylpentadecane, heated at 90
C for 10min 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 partialleast 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 soilsamples were comparables to those obtained by the reference HS–GC–MS procedure. So, the developed procedure allowed a fast identificationand 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 productsbased on carbon chains or rings, also containing hydrogen witha vapour pressure greater than 0.27kPa at 25
C excludingmethane. Measurement of VOCs in different kind of sampleshasreceivedsignificantattentionoverthepastfewyearsbecauseof direct and indirect impacts of individual VOCs on humanhealth and ecosystem. Many VOCs are either known or sus-pectedcarcinogensandsomehavetoxiceffects[1–3].The1990 US Environmental Protection Agency (EPA) Clean Air Act[4]includes189hazardousairpollutantsthataremostlyVOCs,andit has been evidenced that these compounds also play a criticalrole in formation of tropospheric ozone[5,6].BTEX [benzene, toluene, ethylbenzene and the three xyleneisomers (
ortho
,
meta
and
para
)] are a subclass of VOCs withboiling 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).
together with the chronic toxicity associated with the aromaticring present in their structure, make BTEX display a highpollution potential. These aromatic hydrocarbons are widelydistributed in the environment due to natural sources; whichinclude superior plant wax, algae and plankton, and anthro-pogenic sources of hydrocarbons; that comprise domestic andindustrial wastes, biomass and wood burning, incomplete fueloil combustion and urban runoff [7].Analytical methods of reference for the determination of BTEX residues in environmental samples are based on gaschromatography–mass spectrometry (GC–MS), using eitherstatic[8]or dynamic[9]headspace (HS) as sample introduction modules. On the other hand, some other techniques like liquidchromatography[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, likepurge-and-trap[12],membrane extraction[13],solid-phase microextraction[14]and single-drop microextraction[15] have been developed for the determination of BTEX and othervolatile compounds in different samples. On the other hand,
0003-2670/$ – see front matter © 2007 Elsevier B.V. All rights reserved.doi:10.1016/j.aca.2007.01.036
 
90
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[18].The, HS–MS technique has been successfully appliedinqualitativeapplicationssuchasthedetectionofhydro-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 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.
Y
=
Tq
×
where
T
is a matrix of latent variables and
q
contains the regres-sion coefficients for the columns in
T
. The PLS factors (
T
) mustmodel most of the variation, both in the
X
- and
Y
-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[21].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. 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) andthe 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)usedtopreparethestandardsolutionsanaddedtothesamplestocompensatethebackgroundwaspurchasedfromSigma–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-tionmodelswerepreparedin2,6,10,14-tetramethylpentadecaneat a concentration of 5.0mLL
1
and stored in amber glass-stoppered bottles at 4
C. Standard solutions containing BTEXat individual concentration of 5, 25 and 50
LL
1
of benzene, toluene and xylene were also prepared in 2,6,10,14-tetramethylpentadecane by appropriate dilution of the stocones. PLS calibration standards were prepared at three differentlevels by adding 50
L of the different dilutions, that corre-spondsto0.25,1.25and2.5nLofbenzene,tolueneand
o
-xylene,inside glass headspace standard vials.Spikedsampleswerepreparedbyadding50
Lofeachstan-dard solution at 12.5, 25 and 37.5
LL
1
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. Apparatus
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
1
was used as damping gas. Data acquisition in full scan modewas carried out over a mass range of 
m
 / 
 z
75–110. The detec-tor temperature was fixed at 250
C. Ion trap tests and masscalibration were weekly performed with perfluorotributylamine(PFTBA).
 
F.A. Esteve-Turrillas et al. / Analytica Chimica Acta 587 (2007) 89–96 
91
3.4. HS–GC–MS reference procedure
One gram of soil sample was accurately weighted insidea 10mL standard glass vial and 150
L of 2,6,10,14-tetramethylpentadecane were added. After that, the vial wascapped hermetically and heated in the headspace autosamplerat 90
C for 10min with shaking. The syringe temperature wasselected at 100
C and 1mL injection volume was introducedinto the system in split mode (1:10), employing a constantflow of 1mLmin
1
helium as carrier. The oven temperatureprogram started from 40
C, held for 10min, increased at arate of 20
Cmin
1
up to 200
C and finally held for 2min.The transfer line and source temperature were fixed at 300 and250
C, respectively.
3.5. Headspace–mass spectrometry procedure (HS–MS)
Preparationofsampleandheadspaceconditionswerekeptasfor the reference procedure. In order to measure the patterns of volatilecompoundsinsoilsampleswithoutanychromatographyseparation (HS–MS methodology), the column was replaced bya 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 acquisitionit was employed the Xcalibur from Thermo Finnigan (Waltham,MA,USA).DatawereexportedinexcelformatandthePLScali-brationmodelsweredevelopedbymeansofTurboQuantAnalyst6.0softwaredevelopedbyThermoNicoletCorp.(Madison,WI,USA).The proposed PLS model was built using 27 standards forcalibration (using a classical 3
3
design) and it was validatedby means of a set of 10 spiked samples with known amountsof BTEX. As it has been aforementioned, the calibration stan-dards correspond to different mixtures of benzene, toluene and
o
-xylene at three different concentration levels (3
3
). High levelwas fixed at 2.5nL, medium value was evaluated at 1.25nL andlow concentration level was fixed at 0.25nL. Concentration of theaforementionedcomponentsinspikedsampleswaspredictedemployingthePLScalibrationusingtheinformationofthemassspectra 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 criterionof Haaland and Thomas[22].
4. Results and discussion
4.1. MS spectra of BTEX compounds
One nanoliter benzene, toluene, ethylbenzene and eachxylene isomer standards were measured by HS–GC–MS, inorder to obtain the retention time and mass spectra of each com-pound. Mass spectra are shown inFig. 1in which it can be seen the specific ions generated at
m
 / 
 z
77 and 78 for benzene,
m
 / 
 z
91and 92 for toluene and finally
m
 / 
 z
91 and 106 for ethylbenzeneand the three xylenes. Benzene and toluene can be determinedemploying their characteristic ions. However, ethylbenzene andxylenes cannot be differentiated from each other because theypresentthesamecharacteristicionsandonlycouldbequantifiedafter an appropriate separation.Additionally, inFig. 1,it can be seen the mass spectra of  2,6,10,14-tetramethylpentadecane. The specific ions generatedbythismoleculeat
m
 / 
 z
83–85and97–99donotoverlapwiththecharacteristicionsoftheanalytesand,thusthiscompoundcouldbe used as internal reference for the determination of BTEXcompounds.Ontheotherhand,itisclearfromFig.1thatethylbenzeneand xylenes could be determined by MS without any interference of benzene nor toluene.
4.2. HS–GC–MS recording of a BTEX mixture
A conventional chromatographic separation of a mixture of 1nL of each one of BTEX compounds, using an HP-5 (5%-phenyl)-methylpolysiloxane column and full scan acquisitionmode with selected ions at
m
 / 
 z
77, 78, 91, 92 and 106, is showninFig. 2.As it can be seen in the figure, BTEX compounds are well separated in a run time of 11min, except
meta
- and
 para
-xylene that coelute. Thus, five peaks were obtained at 2.4,4.1, 7.8, 8.4 and 10.0min, corresponding to benzene, toluene,ethylbenzene, (
m
,
 p
)-xylenes and
o
-xylene, respectively.
4.3. HS–MS determination of benzene, toluene and o-xylene
Themainobjectiveofthisstudywastoestablishafastscreen-ing procedure based on the decrease of the run time and theincrease of the sample throughput for BTEX determination insoils. So, the chromatography column was changed by a silicaempty tube as transfer line, in order to obtain one unresolvedpeak and to use the mass spectra of this peak for BTEX quan-tification.In a first attempt, a silica tube of 5m length and 0.32mmi.d. was assayed, but the vacuum of the mass spectrometer wasnot acceptable, so a longer column of 30m length and 0.32mmi.d. was used as transfer line and the vacuum problems wereavoided.Using the aforementioned interface, a standard mixture of 1nLofbenzene,tolueneand
o
-xylenewasmeasuredbyHS–MSinfullscanmodeinamassrangeof 
m
 / 
 z
75–110
.
Fig.3showstheobtained MS time recording for selected ions of 
m
 / 
 z
77, 78, 91,92 and 106. Inset of Fig. 3shows the corresponding mass spec- trumofthiswidepeakfrom1to4min.Massspectraobtainedasdescribed for mixtures of benzene, toluene and
o
-xylene wereused for multivariate calibration based on partial least squares(PLS) to predict the concentration of these compounds in soilsamples.
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 concentrationlevels was used.Table 1shows the analytical features of the

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