(4)ibe054287(q) Voc [606081]

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GC–MS · VOCs · BTEX · Adhesive · Tobacco smoke
Abstract
A qualitative and quantitative method for measuring
volatile organic compounds by pre-concentration onactive charcoal followed by gas chromatography–massspectrometry (GC–MS) analysis was developed. Themethod was tested for the investigation of the emis-sions from different materials, adhesives, combustionsources or tobacco smoke. The MS was operated in theselective ion monitoring mode. The compounds ofinterest eluted in less than 9min. Validation of themethod adopted demonstrated the ability to identifyand to measure reliably the yields of benzene andother compounds: toluene, ethylbenzene, m- and p-
xylene, o-xylene. The method is simple and rapid,
shows good linearity, precision and accuracy for the
compounds studied.Introduction
Volatile organic compounds (VOCs) are of concern
since many are toxic and they may also be persistent inthe environment. Benzene, toluene, ethyl benzene andxylene (BTEX) are widespread pollutants of which themain source in the outside environment is from petrol,and so vehicle traffic and indoors, cigarette smoke. Theyare also present in small quantities in drinking water andfood, in paints and adhesives. All of these sources con-tribute to the pollution of indoor environments [1–13].Vehicle movement has been confirmed as the dominantinfluence on benzene and associated VOCs in the atmo-sphere [5–9,14–18,22]. The European Union in its secondAir Quality Directive, adopted the 16 November 2000,sets a limit value for benzene in ambient air of 5 /H9262g·m
/H110023
as an annual mean. While a typical maximum occupa-
tional exposure limit was set at 16 mg·m/H110023recommended
levels today are a tenth of that [19,20]. BTEX and VOCscan be found in water [11,13,21], soil [23], cigarettesmoke [24–27], adhesives [28,29], in paint and varnishshops [30,31], breath [3] (and remember petrol is a sub-stance of abuse [32,33]), or blood [4,34]. It is calculatedthat a typical smoker inhales 2 mg benzene daily, com-pared to 0.2 mg per day for a non-smoker. Thus, cigarette
Dr Monica Culea
Babes-Bolyai UniversityKogalniceanu str. No. 1, 3400 Cluj-Napoca, RomaniaTel. /H1100140-264-504300/5154. Fax /H1100140-264-595355. E-Mail [anonimizat]© 2005 Sage Publications
DOI: 10.1177/1420326X05054287Accessible online at:www.sagepublications.comEnvironmentOriginal Paper: Manchester (7)
Indoor Built Environ 2005 14:000–000 Accepted: April 29, 2004
GC–MS Measurements of
Ambient Levels of VolatileOrganic Compounds
Monica Culea Onuc Cozar Claudiu Melian Dumitru Ristoiu
Babes-Bolyai University, Cluj-Napoca, Romania14(4)IBE054287(q).pdf

SAGE JOURNAL – IBE
PROOF ONLYsmoking may be the most important source of exposure
to benzene for the 50 million citizens of the United States[24,25].
GC–MS and GC with other modes of detection
following desorption from a solid adsorbent are the mostused quantitative methods for detection of VOC levels inthe indoor air [1–3,7,9,17,18,35,36].
The aim of the present work was to develop a GC–MS
method to evaluate the common aromatic ambient pollu-tants.
Experimental
Materials
Active charcoal was obtained from Merck, Germany.
All other reagents were from Comchim (Bucharest,Romania).
Sample Preparation
The air samples were adsorbed by drawing air through
active charcoal cartridges at a flow rate of 60 mL·min
/H110021
and then extracting these with dichloromethane for
2 min. After centrifugation, pyridine, used as the internalstandard, was added and 3 /H9262L aliquot samples were
injected into the GC.
Apparatus
GC–MS analyses were performed for the determina-
tion of the BTEX in air samples. A Trace DSQ Ther-moFinnigan quadrupole mass spectrometer coupled witha Trace GC was used. BTEX and the internal standardwere separated on a Rtx-5MS capillary column,15 m /H110030.25 mm, 0.25 /H9262m film thickness, using a 9 min tem-
perature programme from 30°C held for 2 min thenincreased at 10°C·min
/H110021to 70°C, then at 50°C·min/H110021to
220°C with the MS in the selected ion monitoring (SIM)mode, or in the scan mode. In the SIM mode the follow-ing important ions from the mass spectra of benzene,toluene, ethyl benzene and xylene (Figure 1) were used:m/z 78 for benzene, m/z 91 and 92 for toluene, m/z 91 and106 for ethyl benzene and the xylenes and m/z 79, 52 forthe internal standard. The method was validated in therange 0–100 /H9262g and linearity, precision, accuracy and
limit of detection parameters were studied.Results
Method Validation
Air containing aliquot samples of 20, 100, 300 and
600 ng and 20, 40, 60, 80, 100 /H9262g BTEX were drawn with
a pump at a flow rate of 60 mL·min
/H110021through 300 mg
active charcoal where they were adsorbed and the char-coal then extracted with 1 ml dichloromethane. To eachof these samples was added 20 ng (nanogram range) or1 mg (microgram range) of pyridine as internal standard.These samples were then analysed as described above.
Table 1 presents the linearity parameters obtained
over the ranges 0–100 /H9262g and 0–600 ng for BTEX, using
1 mg pyridine or 20 ng pyridine respectively as internalstandards.
A study for the precision of the analysis of the aliquot
samples of 40 and 80 /H9262g showed RSD values between
6.5–22% and between 7.5–25.8%, respectively The accu-racy RSDs calculated were between 7.6–24.4% for thesample of 40 /H9262g and between 2.5–24.9% for the sample of
80/H9262g. Table 2 presents the results obtained for precision
and accuracy. A limit of detection of 0.01 /H9262g was
obtained for the VOCs studied.
The separation chromatogram for BTEX in the SIM
mode using a 9 min temperature programme is presentedin Figure 2.
Figure 3 shows the chromatograms of BTEX (SIM
mode) found in the air samples collected in indoor envi-ronments and taken close to opened containers with avarnish and an adhesive (both products have been“sniffed” as substances of abuse) and in a public housewhere there was smoking, respectively. Some of thevolatile compounds identified in the tobacco smokeextract are shown in Figure 4. It is worth of noting thatthe peak for nicotine (19) is so insignificant. This isbecause the flow needed to adsorb sufficient of the aro-matics, BTEX, for analysis is lower (60 ml·min
/H110021) than
2 Indoor Built Environ 2005;14:000–000 Culea et al.Table 1. Linearity for BTEX in the range 0–100 /H9262g and 0–600 ng
Compound Regression curve r
Range: 0–100 /H9262g (IS: 1 mg pyridine)
By /H110050.0039x /H110010.0092 0.932
Ty /H110050.0039x /H110010.0123 0.927
Ey /H110050.0047x /H110010.0235 0.935
Xy /H110050.0038x /H110010.021 0.922
Range: 0–600 ng (IS: 20 ng pyridine)By /H110050.0002x /H110010.05 0.98
Ty /H110050.0001x /H110010.39 0.95
Ey /H110050.0001x /H110010.02 0.97
Xy /H110050.0003x /H110010.5 0.9814(4)IBE054287(q).pdf

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3 Indoor Built Environ 2005;14:000–000 GC–MS Measurements of Ambient VOCs(mainlib) Benzene102030405060708090050100
15263951
63 7478
(mainlib) Toluene2030405060708090100050100
273945516591
(mainlib) Ethylbenzene102030405060708090100110120050100
15273951 65 7791
106
(mainlib) p-Xylene102030405060708090100110120050100
273951657791
106
(mainlib) Pyridine20 30 40 50 60 70 80 90050100
27395279
N
Table 2. Precision and accuracy of the method for indoor air BTEX
Compound Concentration ( /H9262g) Comp/IS SD Precision Accuracy
n Added Measured RSD (%) RSD (%)
B 4 40 43.02 0.18 0.04 22.2 7.6
T 4 40 36.75 0.16 0.01 6.5 8.1E 4 40 30.91 0.17 0.02 11.8 22.7X 4 40 30.23 0.13 0.02 15.4 24.4B 3 80 99.9 0.40 0.03 7.5 24.9T 3 80 75.4 0.31 0.08 25.8 5.8E 3 80 82.0 0.41 0.05 12.2 2.5
X 3 80 75.2 0.31 0.05 16.1 6.0Fig. 1. Mass spectra and chemical formula of BTEX and
the internal standard (pyridine).14(4)IBE054287(q).pdf

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4 Indoor Built Environ 2005;14:000–000 Culea et al.RT:0.00 -7.99
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
Time (min)05101520253035404550556065707580859095100 Relative abundanceIS
E
TB
oX(m+p)X2.19
1.36
4.06
2.524.19
1.111.06 4.61 1.53 3.04 7.527.08 4.77 6.89 3.40 6.343.62 5.185.435.82 1.88NL:
5.22E7
TIC MS
2BTEX40 µga
Fig. 2. Chromatographic separation of BTEX and IS (9 min temperature program: 30°C (2 min), 10°C·min to 70°C then 50°C·min to
220°C, SIM mode).
that necessary for the highly volatile compounds such as
nicotine (ca 400 ml·min/H110021). Table 3 shows the BTEX
levels measured in the air contaminated with vapoursfrom varnish or adhesive, as well as other indoor pollu-tants found in a shoemaker’s workshop. In the lastcolumn, the ppm levels for an outdoor air sample wereobtained after a short sampling time, 1 L air, in a smallparking area, 10 m close to a truck with engine running atrest. Table 4 compares some indoor air values for BTEXmeasured in the mainstream smoke from a cigarette(Winston), in the side-stream smoke of a Kent cigarettein a laboratory room (40 m
3) at different distances and in
a public house, respectively. The laboratory room wasnot ventilated during the experiment and the publichouse was very poorly ventilated.Discussion
The GC–MS method developed for BTEX determina-
tions in indoor air is simple and rapid. Validation of themethod gave good values for precision with an RSD of6.5–25% and accuracy with RSD between 2.5–24.9%.The limit of detection for BTEX was 10 ppb.
The method when tested for some applications
showed indoor values in ppm or values of /H9262g per ciga-
rette for tobacco smoke (Table 3 and 4). The precision ofthe repeated measurements gave RSD below 10%. Theresults demonstrate that statistical work is needed topresent accurate results and for comparison with othervalues for indoor air pollutants.14(4)IBE054287(q).pdf

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5 Indoor Built Environ 2005;14:000–000 GC–MS Measurements of Ambient VOCsTable 3. BTEX (ppm) determination in some indoor and
outdoor air measurements (n /H110052)
Compound Varnish Adhesive Shoemaker Outdoor air
B 38.81 60.15 21.43 0.024
T 41.31 157.86 95.85 0.001E 0.55 – 1.5
X 1.79 2.56 0.7Table 4. BTEX determination in tobacco smoke extracts (n /H110052)
Compound Winston Kent/labaKent/labbPub
/H9262g/cigarette ppm ppm ppm
B 14.86 44.6 21.26 5.97
T 229.04 76.36 15.3 37.38E 0.5 4.88 5.06 0.21
X 37.69 3.99 2.55 –
aClose to the source.
bDistant from the source.RT:0.98-5.71
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
Time (min)020406080020406080Relative abundance020406080
XETIS
B2.13
2.46 1.30
1.06 4.034.19 2.98 4.74 4.58 2.87 3.59 5.32 3.153.48 5.43 1.61 1.88 5.15 3.94
2.16
2.46
1.30
1.084.194.05 2.98 1.58 2.05 4.60 4.74 3.593.453.28 1.83 4.44 5.295.15 3.70 5.40
2.16
2.46
1.30
1.061.582.98 1.83 4.224.06 4.61 3.31 3.45 3.75 4.74 4.99 5.16 5.295.65NL:
4.11E7
TIC MS
Auro1l
NL:
4.06E7
TIC MS
pren1l
NL:
4.67E6
TIC MS
bar21l
Fig. 3. Separation chromatograms for varnish, adhesive and tobacco smoke indoor air extracts (SIM mode).14(4)IBE054287(q).pdf

SAGE JOURNAL – IBE
PROOF ONLYReferences
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7 Indoor Built Environ 2005;14:000–000 GC–MS Measurements of Ambient VOCs14(4)IBE054287(q).pdf

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