Chemosphere 63 (2006) 502–508

www.elsevier.com/locate/chemosphere

Isomeric analysis of BTEXs in the atmosphere using

b-cyclodextrin capillary chromatography coupled
with thermal desorption and mass spectrometry
Noureddine Yassaa a,*, Enzo Brancaleoni b,
Massimiliano Frattoni b, Paolo Ciccioli b
a
Faculty of Chemistry, University of Science and Technology Houari Boumediene, USTHB, BP 32, El-Alia,
Bab-Ezzouar, 16111 Algiers, Algeria
b
Istituto di Metodologie Chimiche—C.N.R., Area della Ricerca di Roma, Via Salaria Km 29.3, C.P 10, 00016,
Monterotondo Scalo RM, Italy

Received 22 April 2005; received in revised form 25 July 2005; accepted 8 August 2005
Available online 20 December 2005

Abstract

An analytical method capable of determining trace levels of BTEX-aromatics (benzene, toluene, ethylbenzene, m-, p-
and o-xylenes) in the atmosphere with as high resolution as possible has been developed. The method is based on the
preconcentration of air samples using a multibed tube (Carbopack C, Carbograph 1) at ambient temperature, followed
by thermal desorption, and analysis of aromatic species by a b-cyclodextrin capillary chromatography coupled with
mass spectrometry. The resolution achieved was sufficient for individual separation of BTEXs as well as m- and p-xyl-
enes. The BTEX-ratios have been determined in an air tunnel and in on-road, suburban and rural forest atmosphere.
The ethylbenzene/m-xylene ratios could provide a deep insight into anthropogenic related NMHC patterns at different
locations and under different meteorological conditions and may reflect photochemical processes in the best way.
 2005 Elsevier Ltd. All rights reserved.

Keywords: VOCs; BTEXs; Air tunnel; b-cyclodextrin capillary chromatography; Graphitic carbon adsorbents; Thermal desorption;
GC/MS

1. Introduction automobiles are the dominant source of benzene, tolu-

Today aromatic hydrocarbons represent about 30%
of all non methane hydrocarbons (NMHCs) in urban
air (Becker, 1994). The major source of monocyclic aro-
matic hydrocarbons (MAHs) in these areas is anthropo-
genic production (Dearth et al., 1992). In urban regions
*
Corresponding author. Fax: +213 212 473 11.
E-mail address: nyassaa@mailcity.com (N. Yassaa).
ene, ethylbenzene and the isomers of xylene, commonly
called BTEXs (Edgerton et al., 1989). These compounds
are added to fuels to increase the octane number and are
emitted to the urban atmosphere as a component of
automobile exhaust and by gasoline evaporation and
spillage (Clark et al., 1984). Since in recent years higher
amounts of these aromatics are added to substitute for
lead, the urban atmospheric concentration of these com-
pounds has increased considerably (Perry and Gee,
1994). Additional sources of these MAHs are emission

0045-6535/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2005.08.010
 N. Yassaa et al. / Chemosphere 63 (2006) 502–508
from the chemical industry, waste incinerator and com-
posting facilities (Eitzer, 1995) and household chemicals
(Sack et al., 1992).
Apart from contributing to urban pollution them-
selves by their carcinogenic and mutagenic effects on liv-
ing organisms and human health (Shepson et al., 1985;
Dumdei et al., 1988), BTEXs take part in reactions pro-
moting photochemical smog. Owing to their high reac-
tivity towards the OH-radical (Table 1) they can
contribute significantly to chemical processes leading
to ozone formation in the troposphere (Atkinson,
1989, 1990, 1994, 2000). As shown in Table 1 the reac-
tion rates of BTEX-compounds with OH cover a relative
wide range from low-reactive benzene to m-xylene that
exhibits reaction rates comparable to those of alkenes.
In or near an urban environment where several
sources of BTEX-emitters are present, the concentra-
tions of alkylated benzenes in the atmosphere do often
exceed those of benzene and do resemble the overall
emissions of the different sources (Field et al., 1992).
At rural sites the benzene concentrations are higher rela-
tive to those of toluene or other alkylated benzenes.
These findings have been explained by several authors
to be the result of an accelerated atmospheric degrada-
tion of alkylated benzenes relative to benzene (Atkinson,
1990; Clarkson et al., 1996). However, to attribute the
influence of individual emitters like the road traffic,
not only should car fleet be known, but also temporal
and spatial variation of the BTEX ratios.
The measurement of toxic organic chemicals, such as
benzene, toluene, xylenes, styrene, and 1,3-butadiene, in
ambient air is currently of great practical interest. Eval-
uation of emission control efforts, determination of
human health risks, and confirmation of required reduc-
tions in those risks, all require ambient measurements of
these and related volatile organic compounds (VOCs).
The most common method for monitoring BTEXs in
air at the low microgram per cubic meter concentration
level involves collecting samples with containers (e.g.,
plastic bags, glass or metal canisters) or solid traps (e.g.,
Table 1
Rate constants KOH for the gas-phase reactions of OH with
BTEX-compounds according to Atkinson (1990) and typical
life times si for BTEX-compounds, respectively
BTEX-compound 10 12 · KOH si (h)
(cm3 molecule 1
s 1)
Benzene 1.23 56.5
Toluene 5.96 11.7
Ethylbenzene 7.1 9.8
o-Xylene 13.0 5.1
p-Xylene 14.3 4.9
m-Xylene 23.6 2.9
Life time si was calculated using data from Simpson (1995).
According to Simpson average European summer time OH-
concentrations at noon are about 4 · 106 (molecule cm 3).
503
Tenax, XAD, silica gel, or carbon) followed by the com-
bination of gas chromatography (GC) with either a flame
ionization detector (FID) or mass spectrometry (MS).
Recently novel commercial techniques, typically the
Differential Optical Absorption Spectroscopy (DOAS)
(Platt, 1994) and on-line BTEX-measurements, have been
developed for routine BTEX-monitoring in the atmo-
sphere.
In general, the requirements of sampling and analy-
sing devices can be summarized as follows: (i) regardless
of the method employed, the sampling must be represen-
tative and quantitative, (ii) the sampling procedure
should be so simple that it can be performed by unskilled
persons and under difficult circumstances, e.g., in regions
where no electric power supply is available, (iii) no dete-
rioration or losses of the sample between the sampling
and the analysis most occur and (iv) the chromato-
graphic columns must separate as many components as
possible.
Sorbent traps are well suited for field sampling
because they are easy to handle and use simple equip-
ment and adsorbed compounds are later recovered by
solvent elution or thermal desorption. Regardless the
fact that DOAS and on-line BTEX measurements are
expensive instruments and they require electric power
supply, their utilization is not straightforward and often
involves drastic calibration conditions.
As shown in Table 1 (Atkinson, 1990), BTEXs exhi-
bit different reactivity towards the OH-radical and
ozone-forming potential in the troposphere, the deter-
mination of individual aromatic hydrocarbons is of
particular interest. Various authors have used specific
BTEX-ratios for either discriminating emission sources
or photochemical processes (Nelson and Quigley, 1983;
Rappenglück and Fabian, 1998). Since m-xylene is the
most reactive BTEX-compound, to obtain a realistic
picture of photochemical activity it is imperative to
determine its single concentration independently to that
of p-xylene.
Because they are not separated with ordinary capil-
lary columns the aerial concentrations of m- and p-xyl-
enes are given together in the most of NMHC
measurements in air and the BTEXs-ratios are often
determined considering the total amounts of the both
isomers. Although xylene isomers are now well sepa-
rated with specific stationary phases such as liquid crys-
tals or cyclodextrins, their qualitative evaluation in air
samples were attempted only recently in Algiers urban
atmosphere using charcoal sorbents followed by solvent
elution and b-cyclodextrin capillary chromatography
equipped with a flame ionization detector (Yassaa
et al., 1999). Due to their low thermal stability, charcoal
sorbents require liquid elution as a method for com-
pound extractions. However, large air volumes (ca.
100 l) are required to meet the sensitivity of the detection
system and hence the sampling times are too long (8 h)
504 N. Yassaa et al. / Chemosphere 63 (2006) 502–508
to give useful information in situation in which the
concentration of a chemical changes rapidly due to the
variation of emission strength or atmospheric photo-
chemical activity. These limitations have provided us
the impetus for developing simple, inexpensive, not
time-consuming and sensitive method based on b-cyclo-
dextrin capillary chromatography/mass spectrometry
combined with a preconcentration device using carbon
traps and a thermal desorption apparatus. This method
has been successfully applied in the evaluation of enan-
tiomeric monoterpenes discrimination in terrestrial plant
emission and in the atmosphere (Yassaa et al., 2001).
In this study, a quantitative evaluation of BTEX-aro-
matics was accomplished in tunnel air and in ambient
atmosphere of urban, suburban, and rural forest areas
by combined use of carbon traps with multi-layer beds
for air samples collection and thermal desorption system
installed on GC–MS equipped with a b-cyclodextrin
capillary column. The BTEX-ratios were evaluated to
assess the relative reactivity of individual species in the
atmosphere characterized by different typology.
2. Experimental
2.1. Site description
Air samples were collected in: (1) the biggest tunnel
of Rome located in the heart of the city, (2) on-road
at Viale di Liegi characterized by rush traffic and located
in the Rome city center, (3) a big green park at Vila-Ada
situated at about 15 km far from Rome city center and
(4) Montelibretti located at about 30 km from Rome
and characterized by very weak traffic.
2.2. Air sample collection and analysis
Air samples were enriched on glass tubes (15 cm ·
0.3 cm I.D.) filled with a bed of Carbopack C (0.034 g)
and Carbograph 1 (0.17 g), set in series. The graphitic
materials from 20 to 40 mesh particle size were supplied
by Supelco (Bellefonte, PA, USA) and LARA s.r.l.
(Rome, Italy), respectively. The features of these new
materials and their efficiency were discussed elsewhere
(Brancaleoni et al., 1999). Before sample collection, car-
tridges were cleaned at 300 C under a flow-rate of
helium (100 ml min 1). After 10 min purging, the traps
were closed with tight connectors and stored in large
(10 l) sealed glass containers till ambient air sampling
was performed. Air was drawn through the adsorption
traps by using battery operated samplers (Alpha 1 type)
supplied by Ametek (Mansfield & Green Division,
Largo, FA, USA). Flow rates ranging from 200 to
330 ml min 1 were used for sample collection. After
sample collection, traps were wrapped in aluminium foil
and stored at room temperature until they were sub-
jected to chemical determinations. After removing oxy-
gen and the excess of water from the adsorbents by a
back-flushing step, traps were thermally desorbed at
250 C and VOCs cryofocused in an empty liner kept
at 120 C. Injection into the capillary column was
achieved by fast heating the liner from 150 to
+150 C in 10 s.
The separation of desorbed VOCs was performed on
a b-cylodextrin capillary column (CYCLODEX-B,
30 m-long, 0.256 mm ID, 0.25 lm film thickness) sup-
plied by J&W Scientific (California, USA). It was con-
nected to a HP 5890 gas chromatograph coupled with
a HP 5970B mass selective detector (MSD) (Hewlett
Packard instruments, Palo Alto, CA, USA). Thermal
desorption of sampled tubes was performed by connect-
ing a Chrompack (Middleburg, The Netherlands) TCT/
PT1 CP4001 desorption unit to the gas chromatograph.
The MSD was operated in electron impact mode with
the following conditions: potential ionization 70 eV;
source temperature 230 C; transfer line temperature
280 C and scan range from 20 to 250 m/z. A scan fre-
quency of 3 scans s 1 was used for generating the mass
chromatogram. Selective detection of arene compounds
was achieved by plotting the current profiles generated
by the most specific fragments generated by electron
impacts. Positive identification was obtained by combin-
ing the mass spectral information with the elution
sequence obtained through the analysis of pure com-
pounds.
3. Results and discussion
Since both the initial temperature and the tempera-
ture program are quite critical for the separation of iso-
mers on cyclodextrin coated columns, several tests were
performed to achieve the best resolution not only for
geometric isomers but also for optic isomers (Yassaa
et al., 2001). Tests carried out by changing the initial
temperature of the column from 30 C to 60 C and tem-
perature gradient from 1 to 3 C min 1 showed that the
best compromise between analysis time, the resolution
of the aromatic species present in the standard mixture
and their separation from all other VOCs was achieved
by keeping the column at 40 C for 5 min and by
increasing the temperature of the oven up to 200 C at
a rate of 1.5 C min 1.
To simulate the adsorption and desorption processes
to which air samples were subjected, liquid standard
mixtures containing toluene, m-, p- and o-xylenes and
ethylbenzene were injected into the capillary column
using the thermal desorption system. Small aliquots
(usually 1–2 ll) of the standard mixture were injected
into the adsorption traps under a flow of helium of
100 ml min 1. The sample was ready for the analysis
after the bulk of methanol was removed by the trap
 N. Yassaa et al. / Chemosphere 63 (2006) 502–508 505

and aromatic hydrocarbons distributed through the Table 2

adsorbing beds. This was obtained by passing 4 l of Elution order of some VOCs separated with CP-SIL 8 CB and
helium through the cartridge. Fig. 1 displays an example CYCLODEX-B capillary columns
of extracted ion chromatogram at m/z 91 that was Elution order in CP-SIL 8 CB Elution order
obtained by submitting to GC/MS analysis of this stan- in CYCLODEX-B
dard mixture. Benzene n-Heptane
The xylene isomers as well as m- and p-xylenes were n-Heptane Benzene
resolved at baseline and each compound was eluted far Toluene n-Octane
from the other. The typical BTEX elution sequence n-Octane Toluene
commonly observed in ordinary stationary phases like Ethylbenzene n-Nonane
CP SIL 8 CB was somewhat reversed for certain p/m-Xylenes p-Xylene
compounds using cyclodextrins as phases (Table 2). In m-Xylene
o-Xylene Ethylbenzene
particular, ethylbenzene eluted after p-xylene and m-
n-Nonane o-Xylene
xylene and before o-xylene. As these compounds present n-Propylbenzene 1-Ethyl-3-methylbenzene
substituents at isomeric positions, this can be attributed 1-Ethyl-3-methylbenzenes n-Propylbenzene
to the conic structures of b-cyclodextrin which leads to
the formation of inclusion complexes.
The first experiments were aimed at assessing that the
trapping materials and the thermal desorption process of these components in air samples free from ozone
were not a source of artifacts in the analysis of aromatic (Larsen et al., 1997). The results obtained during these
compounds. These tests were performed by comparing experiments are reported in Table 3. They show that
the theoretical values of, p-xylene/m-xylene and ethyl- the combination of carbon adsorbents and Tenax TA
benzene/m-xylene ratios present in a standard mixture provided consistent results that only slightly deviated
with those obtained by submitting the mixture to GC– from theoretical values. Direct injection of pure com-
MS analysis after adsorption of the BTEX mixture on pounds into the columns showed that these small
solid sorbents and its transfer into the chiral column discrepancies were not originated by the thermal treat-
by thermal desorption. To check for possible decompo- ment of the sample but by changes in composition of
sition effects arising from the chemical nature of the the liquids stored in the bottles. Pure aromatic compo-
solid sorbents, experiments were performed with traps nents showed a lower purity than that declared by the
filled with graphitic carbons and Tenax TA. The latter company, probably due to contamination or partial deg-
adsorbent was selected as reference material in our radation. This was possible because liquids were stored
experiments because it is the most widely used for the for long time in the laboratory (ca. 2 years) and often
quantification of monoterpenes in plant emissions and used for the preparation of standard mixtures of
it is sufficiently inert to prevent the thermal degradation different aromatics.

Abundance
1
35000

30000

25000
4
20000

15000 3

10000 2 5
5000

7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00
Time-->

Fig. 1. Extracted ion chromatogram at m/z 91 of standard mixture of toluene (1), p-xylene (2), m-xylene (3), ethylbenzene (4) and
o-xylene (5).
506 N. Yassaa et al. / Chemosphere 63 (2006) 502–508

Table 3 Table 4
Comparison between the theoretical values of some BTEX- Individual and total concentrations (lg m 3) of BTEXs
ratios in the standard mixture and those experimentally recorded in air tunnel and in ambient air at Viale di Liegi (V.
measured by using adsorption traps filled with graphitic di Liegi), Vila Ada (V. Ada) and at Montelibretti (MTL)
carbons and Tenax TA
Compounds Tunnel V. di Liegi V. Ada MTL
Compounds Theoretical Graphitic Tenax TA
Benzene 68 35 2.7 0.5
carbon
Toluene 367 156 11.8 0.9
p-Xylene/ 1.20 ± 0.05 1.27 ± 0.03 1.15 ± 0.03 p-Xylene 79 33 2.1 0.1
m-xylene m-Xylene 183 71 4.6 0.2
Ethylbenzene/ 1.35 ± 0.05 1.42 ± 0.03 1.35 ± 0.03 Ethylbenzene 78 33 1.9 0.1
m-xylene o-Xylene 106 42 2.4 0.1
Total 881 370 25.5 1.9
Benzene/toluene 0.19 0.22 0.23 0.55
The repeatability of the sampling and analytical
p-Xylene/m-xylene 0.43 0.46 0.46 0.50
method is here expressed as the relative standard devia- Ethylbenzene/m-xylene 0.43 0.46 0.41 0.50
tion (RSD) determined in the basis of peak areas
recorded for more that triplicate samples. The RSD Benzene/toluene, p-xylene/m-xylene and ethylbenzene/m-xylene
ratios are also reported.
was in general within an acceptable level and ranged
from 3% to 10%.
Automobile sources are relatively difficult to estimate
from laboratory experiments because of differences in Table 5
vehicle types, fuel, and vehicle operating modes under BTEXs to benzene ratios obtained in air tunnel and in ambient
on-road driving conditions. A tunnel atmosphere pro- air at at Viale di Liegi, Vila Ada and at Montelibretti
vides appropriate conditions for the in situ measurement Sites Tunnel V. di V. Ada MTL
of the average composition of vehicular emissions, Liegi
because the measured concentrations of exhaust emis-
Toluene 5.38 4.44 4.43 1.94
sions are significantly higher than levels in ambient air.
p-Xylene 1.15 0.93 0.78 0.19
Tunnels also offer the advantage of providing an accu- m-Xylene 2.69 2.03 1.72 0.39
rate appraisal of the traffic composition and the volume Ethylbenzene 1.15 0.94 0.71 0.27
into which these emissions are released (Touaty and o-Xylene 1.56 1.20 0.89 0.29
Bonsang, 2000). For these reasons, the air tunnel was Styrene 0.06 0.05 0.03 0.01
selected in this study as representative of direct auto- Isopropylbenzene 0.08 0.06 0.05 0.01
vehicular emissions. 1,3,5-Trimethylbenzene 0.47 0.32 0.26 0.05
Individual and total concentrations of BTEX-aro- (1)-Methylethylbenzene 0.51 0.34 0.30 0.07
matics recorded in air tunnel and in ambient air at Viale (2+3)-Methylethylbenzene 1.08 0.76 0.69 0.16
di Liegi, Vila Ada and at Montelibretti are summarized n-Propylbenzene 0.33 0.23 0.22 0.08
1,2,4-Trimethylbenzene 1.81 1.20 1.01 0.25
in Table 4. At each investigated site and during the same
1,2,3-Trimethylbenzene 0.29 0.20 0.21 0.04
journey, three samples were collected at around 10 A.M.
in the morning. In order to determine the impact of pho-
tochemical processes on BTEX-compounds it is prere-
quisite to consider specific BTEX-ratios. The benzene/ (air tunnel) to rural forest site (Montelibretti). In fact,
toluene, the p-xylene/m-xylene, the ethylbenzene/m- benzene is of relatively low importance in terms of pho-
xylene ratios were selected here and are reported in tochemical activity. Though found in considerable
Table 4. amounts in ambient urban air its low reaction rates
Regarding the content of BTEX-species in air tunnel makes it a BTEX species of almost marginal importance
and on-road (Via di Liegi) toluene is the predominant in urban air at least as far as its photochemical relevance
aromatic followed by m-xylene. It is worth noting that is concerned. However, benzene remains a hazardous
the concentration of m-xylene that is supposed to be compound due to its well-documented carcinogenicity.
the most reactive xylene isomer (Table 1) is almost dou- Table 5 also demonstrates the importance of the atmo-
ble the corresponding value of p-xylene. spheric photochemical reactivity of aromatic com-
In Table 5, BTEXs were used to form ratios with pounds. Their high reactivity was mirrored by the
benzene, a compound emitted anthropogenically, pre- lowest values of BTEXs/benzene ratios recorded at
dominantly through exhaust processes. Photochemi- Montelibretti. Owing to its fast build up, m-xylene
cal influences seemed to lead to a more rapid decay exhibited the strongest spatial variation with respect to
for the faster reacting BTEXs resulting in decreasing the others. In particular, the value of m-xylene/benzene
BTEXs/benzene ratios going from emission sources ratio in Montelibretti during is 6 times lower than that
 N. Yassaa et al. / Chemosphere 63 (2006) 502–508
in air tunnel. Whilst the combustion processes favour
the formation of benzene through cracking high aro-
matic compounds and since xylene isomers could have
additional sources other than auto-exhaust emission,
the best way could be obtained only by considering com-
pounds having the same origin. According to Nelson
et al. (1983), besides traffic emissions primary sources
for ethylbenzene and the xylene isomers are releases of
solvents. They are often co-emitted and have source fin-
gerprints that do not differ a lot (Nelson and Quigley,
1983). It appears therefore that only p-xylene/m-xylene
and ethylbenzene/m-xylene ratios may reflect photo-
chemical processes in the systematic way. It appears also
from Table 4 that these ratios provide a good tool for
estimating the ageing of hydrocarbons. During daytime
the ethylbenzene/m-xylene and p-xylene/m-xylene ratios
were higher due to photochemical processes. Moreover,
the both ratios exhibited the similar trends and overall
similar values. Since m-xylene reacts significantly faster
with OH-radical than p-xylene, the ethylbenzene/m-
xylene ratio alone should be even more sensible with
respect to photochemical processes.
On the other hand, since m- and p-xylenes do not
have biogenic sources thus differences between urban,
suburban and rural sites should be significant. Though
m- and p-xylenes median values appear to be an ade-
quate quantity for site discrimination, this approach is
difficult to assess when the fast build up of m-xylene is
considered. At rural sites m-xylene is often depleted dur-
ing daytime making it impossible to calculate mean diur-
nal variation based on a minimum data set. The diurnal
patterns reflect not only chemical removal but also emis-
sions, transport and dilution. Chemical removal of
BTEXs will only occur through reaction with the OH-
radical during daytime and the important contribution
to the enhancement of ozone production by the oxida-
tion of m-xylene may not be ruled out. The photochem-
ical impact of the other BTEX-aromatics are estimated
to be between the potentials of m-xylene and benzene.
Indeed, the emission of anthropogenic compounds
will mostly follow traffic patterns, while transport and
dilution are influenced by the synoptic weather circula-
tion, and the spatial and temporal variation of the
mixing height. Usually urban areas are marked by
VOC-limitation of ozone formation due to relative high
emissions of NOx. Ozone formation in rural areas, how-
ever, is determined by NOx-limitation. Previous investi-
gations carried out in Montelibretti which is situated
inside the Tiber Valley have shown that transport of
anthropogenically polluted air masses from the urban
area of Rome is the main source of VOCs in that site
(Ciccioli et al., 1999) and that local sources are not
strong enough to explain the content of BTEXs in air.
This implies that the urban/rural transition zones are
subject to VOC-limitation, at least as long as the urban
plume stretches over these areas.
507
This is in good agreement with theoretical assump-
tion made by Bowman and Seinfeld (1994). According
to their investigations aromatic compounds, especially
xylene isomers and toluene are most effective in terms
of photochemistry in areas where VOC-limitation pre-
vails. As a matter of fact, xylene isomers were very
low at Montelibretti and one could not expect significant
difference in ethylbenzene/m-xylene ratios between emis-
sion sources, on road and rural site.
The benzene/toluene ratio, a specific ratio often asso-
ciated with traffic related processes and used as a tool for
characterizing the distance from vehicular emission
sources (Gelencsér et al., 1997), lies in very low range
in tunnel (ca. 0.19) and in the similar values in on-road
at Viale Liegi, and at Vila Ada and Montelibretti during
nighttime (0.22–0.23). Typical values for benzene/tolu-
ene ratios for exhaust processes are 0.3 for gasoline
(QUARG, 1992). The highest value of this ratio was
reached at Montelibretti during daytime again indicat-
ing the effective photochemical activity during day
hours.
4. Conclusions
The combined use of adsorption traps, thermal
desorption and GC–MS on b-cyclodextrin capillary col-
umns has made possible the positive identification and
quantitative determination of monoaromatic hydrocar-
bons as well as xylene isomers in the atmosphere. Aro-
matic hydrocarbon ratios were found to be a useful
tool to investigate photochemical processes. In particu-
lar, the BTEX-compounds seem to take part effectively
in photochemcial processes even in areas that are more
distant to primary emittents.
Within the BTEX-compounds m-xylene could be
selected as a key compound in discriminating different
location. Ethylbenzene/m-xylene ratio was found to be
a good indicative of the impact of anthropogenically
related hydrocarbon atmospheric chemistry.
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