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Ambient Air Levels of Volatile Organic Compounds (VOC) and Nitrogen

Dioxide (NO2) in a Medium Size City in Northern Spain

Article  in  Science of The Total Environment · December 2008

DOI: 10.1016/j.scitotenv.2008.10.032 · Source: PubMed

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 S CI EN CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v

Ambient air levels of volatile organic compounds (VOC)

and nitrogen dioxide (NO2) in a medium size city in
Northern Spain

M.A. Parra⁎, D. Elustondo, R. Bermejo, J.M. Santamaría

Laboratorio Integrado de Calidad Ambiental (LICA), Departamento de Química y Edafología, Facultad de Ciencias,
Universidad de Navarra. Irunlarrea 1, 31008, Pamplona, Navarra, Spain

AR TIC LE D ATA ABSTR ACT

Article history: Ambient concentrations of volatile organic compounds (VOC) and nitrogen dioxide (NO2)
Received 8 May 2008 were measured by means of passive sampling at 40 sampling points in a medium-size city in
Received in revised form Northern Spain, from June 2006 to June 2007. VOC and NO2 samplers were analysed by
10 October 2008 thermal desorption followed by gas chromatography/mass-selective detector and by visible
Accepted 14 October 2008 spectrophotometry, respectively. Mean concentrations of benzene, toluene, ethylbenzene,
xylenes, propylbenzene, trimethylbenzenes, and NO2 were 2.84, 13.26, 2.15, 6.01, 0.59, 1.32
Keywords: and 23.17 µg m− 3 respectively, and found to be highly correlated. Their spatial distribution
VOC showed high differences in small distances and pointed to traffic as the main emission
Urban atmosphere source of these compounds. The lowest levels of VOC and NO2 occurred during summer,
Spatial variation owing to the increase in solar radiation and to lower traffic densities. Mean concentrations
Traffic of benzene and NO2 exceeded the European limits at some of the monitored points.
Passive sampling © 2008 Elsevier B.V. All rights reserved.

1. Introduction
The United Nations estimate that over 600 million people
are exposed to harmful levels of traffic-generated air pollu-
tants in urban areas (Han and Naeher, 2006). Air pollution and
its impact on human health have become issues of increasing
public concern during the last decades, since the pollution pre-
vention concept emerged many years ago (Riga-Karandinos
and Saitanis, 2005).
Volatile organic compounds (VOC) are an important group
of air pollutants to study because they play an important role
in the chemistry of the troposphere: They condition the concen-
tration of the OH radical, the production of organic acids, and
the regional formation of photochemical oxidants (Atkinson,
2000; Filella and Peñuelas, 2006). Also, some of them – such
as benzene and toluene – have been shown to be harmful to
human health, ecosystems and atmosphere (WHO, 2000;
Srivastava, 2005).
Large amounts of VOC are emitted from mobile and sta-
tionary sources, mainly owing to processes of combustion,
solvent and fuel evaporation, and tank leakage (Tsai et al.,
2006). Motor vehicles can be the most important source of
VOC, especially in areas with few industrial sources, since
they can account for 35% of the total VOC emissions (Tran
et al., 2000).
Diffusive sampling has been a widely used technique to
measure the levels of aromatic compounds – benzene, toluene,
ethylbenzene, xylenes and trimethylbenzenes – in indoor,
workplace and outdoor environments because it constitutes a
simple and cost-effective method. Furthermore, it facilitates
studies with high monitoring density, necessary for examining
fluctuations of VOC within small areas (Harper, 2000).
Understanding of the spatial variations of urban air pollu-
tion is necessary not only as a basis for exposure assessment,
but also to help in identifying pollution “hot spots” and other
areas which are in need of specific intervention, as well as to

⁎ Corresponding author. Tel.: +34 948 425600x6366; fax: +34 948 425649.
E-mail address: mparravi@alumni.unav.es (M.A. Parra).

0048-9697/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2008.10.032
1000 S CIE N CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9
guide traffic management and other policies of development
and analysis (Lebret et al., 2000). Although air pollution in large
European cities – such as Rome or Helsinki – has been studied
(Brocco et al., 1997; Hellén et al., 2002), there is no enough
information referred to small and medium-size cities. A
striking fact considering that three-quarters of the European
urban population – which accounted for 74.6% of the total
population in 2001 – live in towns with a population of less than
250,000 (UNEP, 2002, pp. 240–270).
This paper presents and discusses data, obtained by
means of passive sampling, on the levels of VOC and NO2 in
Pamplona, a medium size city in Northern Spain. The main
aims of this study were to explore possible spatial differences
in the concentrations of the targeted pollutants and, at the
same time, try to identify emission sources in the city. Addi-
tionally, the temporal distribution of their levels and its
relation to meteorological parameters were also considered
in the discussion of the results.
2. Experimental
2.1. Study site
Pamplona (42° 49′ N and 2° 1′ W) is the capital of Navarra, an
area in Northern Spain at the western edge of the Pyrenees
(Fig. 1) and covers an extension of 23.55 km2. This area is
characterised by a sub-Mediterranean climate, a transition
Fig. 1 – Location of Pamplona in Navarra, Spain.
between oceanic temperate and continental Mediterranean
climates due to its geographical situation not far from the
Cantabric sea and in the boundary between EuroSiberian and
the Mediterranean regions. The mean annual temperature is
about 19 °C, with high differences in temperature (20 °C)
between winter and summer; the mean annual rainfall is
about 830 mm, with an average of 135 days of rain per year.
The predominant wind in this location blows NW. Pamplona
is a medium size city with about 200,000 inhabitants and a
vehicle fleet of 57 vehicle per every 100 inhabitants. Aguinaga
et al. (1999) grouped the sources of atmospheric pollutants in
Pamplona into three major categories: inter-urban traffic,
intra-urban traffic and fixed sources, including residential
heating and factories located in industrial states within the
periphery of the city. It is necessary to emphasize that there is
no heavy industry in the vicinity of the city.
2.2. Sampling strategy and analysis of VOC and
nitrogen dioxide
Sampling was carried out from June 2006 to June 2007 at 40
points selected within a 400 × 400 m sampling grid (Fig. 2).
These included locations both close emission sources, such as
those by busy roads, and others distant from local emission
sources, such as those within parks. Sampling was performed
on a 2-week basis, allowing for a total of 24 exposure periods.
Perkin Elmer stainless steel tubes (6.3 mm ED × 90 mm,
5.5 mm ID) filled with Tenax TA (200 mg) were used for VOC
 S CI EN CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9 1001

Fig. 2 – Location of the sampling points in Pamplona.

sampling (Pilidis et al., 2005; Martin et al., 2007) and Radiello®
passive samplers (Fondazione Salvatore Maugeri-IRCCS, Italy)
were used for monitoring nitrogen dioxide. The samplers were
placed at the selected sampling sites at 3 m above ground level
to reduce the possibility of undesired manipulation.
Measurements of VOC were performed using a Markes
thermal desorption unit coupled to a gas chromatograph
(Agilent 6890) and an Agilent 5973 mass selective detector
in scan mode although quantification was performed with
specific ions (Table 1). Table 1 also presents the diffusive

Table 1 – Analytical parameters and quality control of measurement methods

Quantifier ion Qualifier ions Uptake rate Precision RSD (%) Recovery (%) MQL 102 (μg m− 3)

Benzene 78 77, 51, 52 0.86 a 5.27 94 2.12

Toluene 91 92 1.20 a 2.42 98 15.20
Tetrachloroethene 166 164, 129, 131 2.80 a 5.22 89 0.86
Ethylbenzene 91 106 2.20 a 8.02 86 1.42
m/p-Xylene 91 106, 105, 77 1.91 a 7.34 87 2.07
o-Xylene 91 106, 105, 77 1.91 a 7.03 88 4.13
Isopropylbenzene 105 120, 77, 79 2.28 b 6.85 93 1.02
Bromobenzene 77 156, 158, 51 3.31 a 6.23 102 0.97
Propylbenzene 120 105 2.28 a 5.76 87 0.73
1,3,5-Trimethylbenzene 105 120, 119, 77 2.23 b 9.55 101 0.87
Naphthalene 128 127, 129 2.55 a 7.03 92 1.11
a
ISO/DIS 16017-2.
b
Health and Safety Executive CAR Committee.
1002 S CIE N CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9
uptake rates of the VOC measured. Further details of the
methods are described in Parra et al. (2006). The NO2 samples
were analysed as described in Parra et al. (2006) by visible
spectrophotometry (Zuzi 4418). The sampling rate value
for NO2 at 298 K and 1013 hPa is 0.141 ng ppb− 1 min− 1.
The temperature dependence of the rate value was corrected.
Ambient NO2, benzene, toluene and xylenes concentra-
tions were also continuously measured from June 2006 to June
2007 at one of the passive sampling points. A Dasibi 2108
analyser (Dasibi Environmental Corporation, Glendale, CA,
USA) was used for monitoring NO2 concentrations whereas
a Byron 301 THC analyser was used for the monitoring of
benzene, toluene and xylenes. These measurements were
averaged into hourly means. Data were retrieved from the air
quality information website (http://calidaddelaire.navarra.es),
kindly provided by the Government of Navarra. Additionally,
meteorological data (wind speed and direction, relative hu-
midity, temperature, atmospheric pressure, solar radiation
and precipitation) were registered by the automatic mete-
orological station located in the same point and managed
by the Government of Navarra (http://meteo.navarra.es).
2.3. Data analysis
Contour maps were produced using the kriging method by
means of 3DFieldPro 1.05 (http://3dfmaps.com © Vladimir
Galouchko), in order to illustrate the spatial distribution of the
different variables. On the other hand, SPSS program (v.11.0)
was used for statistical analysis.
2.4. QA/QC
Prior to sampling or calibration, all sampling tubes were
conditioned at 330 °C by passing pure nitrogen gas through the
tubes at a flow rate of 100 ml min− 1 for 40 min, then checked in
accordance with the same VOC analytical procedures to
ensure that no target pollutants were present.
Five field blank samples were transported along with each
sampler batch to the selected sites, stored in the laboratory
during the exposure period, and later used to check the possible
contamination during the collection, transportation and storage
of samples. In this study, it was found that the concentration in
each blank tube was mostly below MDL which were defined as
three times the standard deviation (S.D.) of seven blank values.
During the sampling, duplicate samples were randomly
collected on 10% of the selected sampling points in order to eval-
uate the sampling precision. Concentrations of VOC measured
in duplicate samples were in excellent agreement, with a rel-
ative standard deviation of less than 10% (Table 1). A new cal-
ibration curve was determined each time. Quantification limits
were defined as ten times the standard deviation (S.D.) of seven
blank values (Table 1). Also, four quality control tubes, spiked
onto clean adsorbent tubes were measured each time to ensure
the correct measurement of the samples.
Also, the comparison of the dataset provided by the auto-
matic station for NO2, benzene, toluene, and xylenes with that
obtained by means of the passive samplers showed an accept-
able match between these two monitoring methods: the sta-
tistical analysis of the data showed significant regressions
with determination coefficients from 0.825 to 0.955.
The identification of VOC was conducted by checking the
retention time of individual VOC and their mass spectrum.
3. Results and discussion
3.1. VOC and NO2 concentrations
Mean concentrations of BTEX, tetrachloroethene and NO2 are
presented in Table 2. Also, a statistical summary of the data on
BTEX, tetrachloroethene and NO2 levels in Pamplona from
June 2006 to June 2007 – a total of 960 sets of measurements – is
shown in Table 2.
The results clearly indicate the predominance of toluene
among all the VOC investigated, since it exhibits the highest
mean concentration with 13.26 μg m− 3. This major presence
has also been reported in other studies conducted in urban
atmospheres (Yamamoto et al., 2000; Ho and Lee, 2002; Guo
et al., 2004).
The highest levels of BTEX and NO2 were registered in
points 21, 31 and 38, which were located in a heavily trafficked
street (with more than 10,000 vehicles per day). Points 5, 14, 20,
and 26 showed the lowest concentrations, not a surprising
finding since these points were located in parks. Besides, the
highest levels of tetrachloroethene were registered in points
23, 28 and 36.
According to Directive 2000/69/EC, the annual mean
benzene concentrations in ambient air must not exceed 5 μg
m− 3. The concentration of benzene exceeded this limit value
in point 38, with a mean registered value of 5.61 μg m− 3,
whereas other points as 21 and 31 were very close to this limit
(4.98 and 4.48 μg m− 3 respectively). Furthermore, the averaged
levels of NO2 showed that the 1999/30/EC threshold for the
protection of human health (40 μg m− 3) was exceeded in three
of the selected points (points 21, 31 and 38) with mean levels of
56.64, 50.30 and 62.37 μg m− 3 respectively. Although these
locations do not register the highest traffic volumes in the city,
the traffic is not very fluid owing to numerous traffic light stops.
This fact causes that the time spent in tailback is 56% higher
than in other streets surveyed in the study. Furthermore, the
pavements are narrow and the bordering houses high, config-
uring a constricted canyon where the dispersion of pollutants is
highly impeded. Therefore, these points could be excluded
when considering the exceedances of benzene regulations
since according to the Directive, the location of the sampling
point must be taken away enough from the emission source to
be able to be representative.
Regarding toluene levels, and although they are not regu-
lated by European legislation, WHO establishes a guideline
value for the protection of human health of 260 μg m− 3 ex-
pressed as weekly average, level which indeed remains far
above the levels registered in this study.
The mean concentrations of other compounds measured
such as isopropylbenzene, bromobenzene, propylbenzene, 1,3,
5-trimethylbenzene and naphthalene were 0.74 (0.11), 7.54
(0.74), 0.59 (0.17), 1.32 (0.19) and 0.18 (0.09) µg m− 3, respectively.
The concentrations of VOC registered in this study were
in the range of those found for VOC in other European urban
areas. Northern cities show generally lower concentrations, as
those found in Helsinki and a number of British and German
 S CI EN CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9 1003

Table 2 – Mean concentrations (μg m− 3) of benzene, toluene, ethylbenzene, xylenes, tetrachloroethene and NO2 for the
40 points
Sampling point Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene Tetrachloroethene NO2

Mean 2.84 13.26 2.15 3.38 2.63 0.61 23.17

(S.D.) (0.87) (3.64) (0.55) (0.89) (0.75) (0.41) (11.79)

Median 2.75 12.74 2.10 3.31 2.52 0.49 20.11

N 933 932 932 929 931 933 941

1 2.70 14.48 2.92 4.34 3.03 0.41 26.54

2 2.09 12.30 2.14 3.37 2.35 0.39 15.30
3 3.29 15.44 2.37 3.98 3.16 0.35 20.15
4 1.77 8.94 1.60 2.38 1.68 0.62 15.02
5 1.78 10.28 1.79 2.90 1.77 0.34 9.63
6 2.87 13.55 1.94 3.21 2.49 0.36 12.61
7 2.23 10.78 1.62 2.56 2.09 0.35 7.34
8 2.79 14.92 2.83 4.52 3.34 0.53 18.54
9 2.07 10.69 2.13 2.74 2.15 0.50 24.34
10 3.72 16.45 2.47 4.12 3.54 0.44 28.02
11 2.88 12.82 2.07 3.31 2.56 0.34 17.54
12 3.25 15.66 2.14 3.72 2.95 0.47 33.74
13 2.56 12.29 1.75 2.99 2.41 0.48 16.61
14 1.35 5.18 0.75 1.20 0.98 0.27 13.93
15 3.04 17.07 3.57 5.01 3.72 0.42 18.16
16 2.21 11.16 2.38 3.24 2.44 0.40 19.92
17 2.22 10.61 2.48 3.03 2.26 0.86 16.17
18 3.20 15.78 2.52 4.07 3.24 0.62 26.10
19 3.97 17.02 2.28 4.25 3.50 0.36 26.56
20 1.66 7.27 1.34 1.88 1.39 0.37 11.52
21 4.98 21.69 2.85 4.90 4.10 0.49 56.64
22 2.81 12.63 1.78 2.94 2.20 0.96 15.91
23 2.69 12.59 1.87 2.86 2.24 2.12 21.17
24 3.16 15.04 2.10 3.50 2.76 0.37 34.01
25 2.39 12.65 2.42 3.87 2.72 0.53 20.24
26 1.92 9.70 1.73 2.77 1.96 0.44 15.89
27 3.19 14.29 2.11 3.76 2.91 0.51 33.95
28 3.21 14.16 2.59 3.61 2.84 1.82 16.58
29 2.05 9.07 1.56 2.29 1.75 0.63 25.61
30 3.29 13.73 2.06 3.36 2.70 0.57 28.76
31 4.48 19.12 2.53 4.64 3.82 0.61 50.34
32 2.61 12.34 1.90 2.76 2.31 0.88 12.28
33 2.42 10.73 1.53 2.44 2.04 0.42 12.21
34 2.01 9.27 1.76 2.71 1.87 0.54 19.18
35 2.65 11.32 1.64 2.94 2.26 0.51 20.07
36 3.44 16.41 2.74 4.06 3.20 1.83 23.07
37 3.00 14.01 2.03 3.45 2.68 0.67 31.69
38 5.61 24.13 3.56 5.56 4.73 0.70 62.37
39 3.23 13.74 2.13 3.31 2.75 0.36 24.41
40 2.56 11.07 2.05 2.84 2.45 0.35 24.81

cities, while large Mediterranean cities are characterised
by higher pollution levels, such as those found in Rome and
Athens (Table 3). In Toulousse (France), the levels were found
to be lower than those in Pamplona, but measurements were
performed during summer, when concentrations are gener-
ally lower (Table 3). In Spain, a study carried out in La Coruña,
a medium-size city, registered levels of BTEX higher than
those measured in Pamplona.
Fewer studies provide information on ambient levels of
other VOC such as halogenated compounds. Yamamoto et al.
(2000) found levels from 0.20 to 1.64 μg m− 3 for tetrachlor-
oethene, and Fernández-Villarenaga et al. (2004) reported
levels of 1.37 μg m− 3, levels which were higher than the ones
recorded in Pamplona in both cases.
The NO2 mean values in Pamplona are lower than those
reported by Baldasano et al. (2003) for the major Spanish cities
(50–63 μg m− 3), but higher than those reported by Fernández-
Villarenaga et al. (2004) for La Coruña, (13.4 μg m− 3).
These differences can respond to particular characteristics
of the studied cities, sampling sites, sampling periods and
main city activities as well as differences associated with vehi-
cles, such as vehicle fuel composition, etc. (Gee and Sollars,
1998).
The characteristic benzene:toluene:ethylbenzene:xylene
ratio for those points with high concentrations of these pol-
lutants was 1.78:7.67:1.00:3.35. Most of the 40 sampling points
displayed similar ratios although slightly lower (1.69:7.25:
1.00:3.22). On the other hand, those ratios observed in the
1004 S CIE N CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9

Table 3 – Comparison of levels of VOC (μg m− 3) found in different European cities

City of reference Benzene Toluene Ethylbenzene m,p-Xylene o-Xylene

Pamplona 2.84 13.26 2.15 3.38 2.63

La Coruña (Fernández-Villarenaga et al., 2004) 3.43 23.6 3.34 5.08 2.74
Germany (Schneider et al., 2001) 1.13–1.62 4.46–4.98 – 1.20–1.76 –
Athens (Chatzis et al., 2005) 13.3–26.0 – – – –
Toulousse (Simon et al., 2004) 2.0 6.6 – 1.2 3.7
United Kingdom (Derwent et al., 2000) 1.23–6.23 2.30–13.8 0.71–3.84 1.68–11.8 0.88–5.73
Helsinki (Hellén et al., 2002) 2.1 6.6 1.3 4.1 1.6
Roma (Brocco et al., 1997) 35.5 99.7 17.6 54.1 25.1

‘background points’, where the lowest levels of these pol-
lutants were registered, were also the lowest as well (1.48:6.
62:1.00:2.94). This suggests that BTEX had a common main
origin in motor vehicles; the non-background ratios registered
in this study presented some resemblance with those reported
in roadside studies (Mohamed et al., 2002). These ratios were
also similar to those reported in La Coruña by Fernández-
Martínez et al. (2001). However, a different behaviour is expected
in the background points.
3.2. VOC and NO2 correlations
The results of correlation analyses are presented in Table 4.
Strong correlations were found among the BTEX group, and
also between them and other aromatic hydrocarbons known
to be emitted by road traffic, such as propylbenzene and 1,3,
5-trimethylbenzene. In order to confirm vehicle emissions as
the main source of these compounds in the studied area, the
dependence of their levels to road distance was explored. As
expected, significant negative correlations were found for all
of them. Also, an evaluation of toluene/benzene concentration
ratio is useful for characterising the distance of vehicular emis-
sion sources (Brocco et al., 1997; Derwent et al., 2000), since
toluene/benzene ratios decreases as the distance from the
source increases (Simon et al., 2004). The concentration ratios
found in this work ranged from 2.8 to 5.9 and a negative and
significant correlation was found between toluene/benzene
concentration ratio and distance to road (r = 0.680; p = 0.037).
On the other hand, the levels of tetrachloroethene showed
no relationship with either the levels of other compounds or
road distance. However, a significant correlation was found
between tetrachloroethene concentration and the distance
from each sampling point to the closest dry-cleaning store (r =
−0.685; p b 0.01). This was related to the facts that tetrachlor-
oethene is a known dry-cleaning solvent and that its presence
in air samples is usually attributed to small commercial activ-
ities, such as dry-cleaning, that emit this compound to the
atmosphere (Doherty, 2000).
Although the correlation coefficients between VOC and NO2
are significantly smaller than those found between the various
VOC, the correlations are still highly significant and consistent
with vehicular emissions, the primary local source of emis-
sions of both pollutants. However, correlations are higher dur-
ing summer months (r = 0.77; p b 0.01) than during winter (r = 0.53;
p b 0.05), which could be related to the existence of sources other
than traffic during this time of the year, such as emissions of
NO2 from house heating.
3.3. Spatial distributions of VOC and NO2
A cluster k-means analysis was applied in order to group sim-
ilar sampling points. The analysis, carried out with benzene,
toluene, ethylbenzene, xylenes, tetrachloroethene, and NO2
discriminated the data into six groups, which were found to
be statistically different. Table 5 shows mean values defining
clusters from 1 to 6. We have only considered three of them.

Table 4 – Pearson correlation coefficients between VOC, NO2, distance to road and meteorology
Compound 1 2 3 4 5 6 7 8 9

1 Benzene 1
2 Toluene 0.96 ⁎⁎ 1
3 Ethylbenzene 0.68 ⁎⁎ 0.83 ⁎⁎ 1
4 m/p-Xylene 0.83 ⁎⁎ 0.94 ⁎⁎ 0.93 ⁎⁎ 1
5 o-Xylene 0.92 ⁎⁎ 0.98 ⁎⁎ 0.88 ⁎⁎ 0.97 ⁎⁎ 1
6 Propylbenzene 0.66 ⁎⁎ 0.67 ⁎⁎ 0.56 ⁎⁎ 0.66 ⁎⁎ 0.69 ⁎⁎ 1
7 1.3.5-Trimethylbenzene 0.61 ⁎⁎ 0.61 ⁎⁎ 0.60 ⁎⁎ 0.59 ⁎⁎ 0.65 ⁎⁎ 0.43 ⁎⁎ 1
8 Tetrachloroethene 0.13 0.13 0.16 0.06 0.07 − 0.06 − 0.10 1
9 NO2 0.59 ⁎⁎ 0.57 ⁎⁎ 0.56 ⁎ 0.66 ⁎⁎ 0.64 ⁎⁎ 0.25 ⁎ − 0.27 0.02 1
11 Distance to road − 0.52 ⁎⁎ − 0.54 ⁎⁎ − 0.49 ⁎⁎ − 0.50 ⁎⁎ − 0.55 ⁎⁎ − 0.35 ⁎⁎ − 0.33 ⁎⁎ −0.03 −0.36 ⁎⁎
12 Temperature − 0.83 ⁎⁎ − 0.66 ⁎⁎ − 0.64 ⁎⁎ − 0.59 ⁎⁎ − 0.59 ⁎⁎ − 0.55 ⁎⁎ 0.23 −0.16 −0.43 ⁎⁎
13 Relative humidity 0.64 ⁎⁎ 0.58 ⁎⁎ 0.59 ⁎⁎ 0.43 ⁎⁎ 0.46 ⁎⁎ 0.54 ⁎⁎ − 0.12 −0.01 0.32
14 Solar radiation − 0.82 ⁎⁎ − 0.77 ⁎⁎ − 0.72 ⁎⁎ − 0.72 ⁎⁎ − 0.78 ⁎⁎ − 0.50 ⁎⁎ 0.21 0.17 −0.56 ⁎⁎
15 Wind speed − 0.37 ⁎⁎ − 0.34 ⁎⁎ − 0.43 ⁎⁎ − 0.30 ⁎⁎ − 0.39 ⁎⁎ − 0.35 ⁎⁎ − 0.31 ⁎⁎ −0.15 −0.42 ⁎⁎

⁎ Correlation is significant at the 0.05 level.

⁎⁎ Correlation is significant at the 0.01 level.
 S CI EN CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9 1005

Table 5 – Mean chemical composition (µg m− 3) of VOC and NO2 of each cluster of samples
Compound 1 2 3 4 5 6

Benzene 3.15 (0.46) 2.65 (0.54) 1.64 (0.20) 5.02 (0.56) 3.11 (0.38) 2.49 (0.37)
Toluene 15.45 (1.31) 12.10 (2.31) 7.91 (2.20) 21.64 (2.50) 14.39 (1.92) 11.64 (1.13)
Ethylbenzene 2.56 (0.44) 1.88 (0.23) 1.37 (0.45) 2.98 (0.53) 2.40 (0.47) 1.97 (0.28)
m/p-Xylene 4.13 (0.43) 3.04 (0.53) 2.09 (0.72) 5.03 (0.47) 3.51 (0.60) 2.97 (0.28)
o-Xylene 3.19 (0.34) 2.36 (0.46) 1.45 (0.36) 4.21 (0.46) 2.75 (0.48) 2.31 (0.20)
Tetrachloroethene 0.45 (0.09) 0.49 (0.13) 0.40 (0.15) 0.60 (0.10) 1.92 (0.17) 0.55 (0.21)
NO2 25.20 (5.84) 22.11 (9.71) 12.52 (2.42) 56.45 (6.01) 20.27 (3.33) 18.44 (4.96)

Cluster 3 comprises four sampling points with low contents
of VOC and NO2 owing to their location in parks, far away from
emission sources of pollutants. Cluster 4 was characterised
by high levels of VOC and NO2. The three sampling points
included in this group are situated in high density traffic
roads. Those sampling points with high levels of tetrachlor-
oethene and close to dry-cleaning stores form cluster 5. The
other clusters are formed by sampling points that present
concentrations of pollutants between these categories.
Contour maps were drawn to show the spatial distribution
of ambient BTEX and NO2 in urban air of Pamplona and to pro-
vide a better insight on this subject. The maps show large spa-
tial variations of the pollutants within the city (Fig. 3).
In order to study the spatial variations over small distances
within the urban area, differences in concentrations between
a point located in a heavily-trafficked road (point 19; 18,077
vehicles per day) and another located at 155 m in an adjacent
urban park (point 20) were estimated. These points were sep-
arated by a high wall and dense deciduous vegetation. De-
pending on time of the year, the benzene concentrations were
2.5 to 10 times higher in the trafficked road. These results are
comparable to those obtained in a number of European cities,
where levels of benzene at hot spots were 3 to 5 times higher
than the urban background levels (Hansen and Palmgren,
1996). The concentrations within the park were 27% lower
than those registered in the adjacent street in January. This
difference increased up to 72% in June, a fact also observed
for other compounds emitted from traffic such as toluene (42%
in January, 74% in July), ethylbenzene (32% in January, 77% in
July), m/p-xylene (36% in January, 81% in July) and o-xylene
(35% in January, 78% in July). This could be related to a shield-
ing effect of the vegetation and walls along roads, leading to
lower concentrations, and that BTEX concentrations decrease
rapidly in relation to the distance to the source, as also report-
ed in Thorsson and Eliasson (2006). As for the seasonal varia-
tion, in January the deciduous trees have no foliage whereas in
June trees displayed fully foliage, hence they would act more
efficiently as a pollution barrier. Also, photochemical reactions
in summer could decrease the concentrations of some of the
traffic-emitted VOC contributing to the urban background pol-
lution, but significant decreases in benzene and toluene con-
centrations based on their reaction rates should not be expected
due to the short distance between the compared points (Upmanis
et al., 2001). Nevertheless, that could be expected for ethylben-
zene and xylenes, since their reaction rates are higher. In the case
of NO2, these differences were lower (8% in January, 56% in July),
which could be related to the lower chemical reactivity of this
compound.
As mentioned before, the highest levels of tetrachloroe-
thene were registered in those sampling points situated close
to dry-cleaning-stores, as observed in other studies (Fernández-
Martínez et al., 2001; Mohamed et al., 2002; Parra et al., 2008b).
3.4. Seasonal variations of VOC and NO2
Table 6 illustrates the seasonal variations of the mean concen-
trations of VOC and NO2 in the 40 monitored points. As shown
in it, there was a large and statistically significant variation in
VOC levels. One-way ANOVA results (Table 6) show that the
concentrations of all VOC and NO2 significantly differ among
sampling periods.
Generally, VOC and NO2 concentrations were higher in win-
ter and autumn than in spring and summer, as found in many
other cities (Batterman et al., 2002; Kourtidis et al., 2002; Pankow

Fig. 3 – Distribution maps of the concentrations (µg m− 3) of (A) BTEX, and (B) NO2 in Pamplona.
1006 S CIE N CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9

Table 6 – Seasonal variations of VOC and NO2 concentrations this fact cannot immediately affect the emissions, it might
(μg m− 3) and meteorological parameters be responsible for the decrease of ethylbenzene in background
Summer Autumn Winter Spring areas, as the higher distance from the emission point allows
(μg m− 3) (μg m− 3) (μg m− 3) (μg m− 3) a major reaction of this compound and, consequently, the
increases of both B/E and T/E in these areas. With respect to
T (°C) 25.80 18.89 11.95 18.75
HR (%) 76.52 83.94 86.51 80.91 X/E ratio, it followed a similar pattern for both groups of sam-
Rad 169.86 70.88 69.31 133.12 pling points, since the atmospheric reactivity of xylenes is
Precip. (l m− 2) 222.74 226.67 196.74 373.36 also high.
Wind speed 0.74 0.80 0.75 0.75 A considerable and significant negative correlation (Table 4)
(m s− 1) was found between either temperature or solar radiation and
Benzene 1.33 1.58 1.82 2.17
the concentration of hydrocarbons. Because the total daily
(0.38) (0.80) (1.59) (0.71)
Toluene 8.74 9.76 10.79 12.02
emissions from motor vehicles do not vary significantly, other
(3.20) (3.41) (6.68) (2.73) factors beside traffic emissions contributed to the observed
Tetrachloroethene 0.43 0.81 0.72 0.45
(0.21) (0.20) (0.23) (0.16)
Ethylbenzene 1.30 2.56 3.12 1.69
(0.44) (0.88) (1.49) (0.50)
m/p-Xylene 2.47 4.23 4.88 2.65
(0.95) (1.26) (1.70) (0.64)
o-Xylene 1.71 3.78 3.53 1.52
(0.60) (1.55) (1.61) (0.29)
Isopropylbenzene 0.19 0.62 1.05 1.01
(0.05) (0.59) (0.83) (0.93)
Bromobenzene 10.96 9.22 7.87 1.91
(2.68) (2.39) (5.51) (2.15)
Propylbenzene 0.23 0.60 0.75 0.73
(0.07) (0.66) (0.46) (0.35)
1.3.5- 1.67 1.18 1.36 1.04
Trimethylbenzene (0.25) (0.16) (0.47) (0.54)
Naphthalene 0.18 0.22 0.23 0.11
(0.15) (0.12) (0.09) (0.02)
NO2 19.54 25.23 27.19 20.60
(5.34) (4.85) (2.49) (3.08)

ANOVA indicated significant differences between all sampling

periods and all compounds.

et al., 2003). Several factors can affect the concentrations of

VOC. Thus, NO2 and VOC concentrations reach a maximum in
the winter due to higher atmospheric stability, and a minimum
in summer, when atmospheric dispersion is more important.
Moreover, chemical removal of VOC by OH radicals is faster in
summer than in winter since more sunlight and higher tem-
peratures produce higher chemical removal reaction rates (Ho
et al., 2004). The NO2 levels depend mainly on chemical reac-
tions and not on direct emissions, since this pollutant proceeds
from the oxidation of traffic-emitted NO chiefly, although it is
also directly emitted by traffic in a minor proportion (Mayer,
1999; Zabalza et al., 2007).
Besides, the seasonal distribution of BTEX ratios corres-
ponding to those points situated inside the canyon street was
compared to those obtained for background points (parks).
The comparison is represented in Fig. 4. It can be seen that
the ratios generally followed a similar pattern, with higher
values during winter as observed elsewhere (Ho et al., 2004).
At the same time, the ratios were generally lower in the
background points, with the exception of B/E and T/E ratios
in summer. This finding could be related to the higher re-
activity of ethylbenzene compared to that of benzene and Fig. 4 – Temporal distribution patterns of BTEX ratios across
toluene, which allows a major loss of this pollutant in this the whole study period. SC and B denote street canyon and
season, and therefore higher B/E and T/E ratios. Although background measurements respectively.
 S CI EN CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9
Fig. 5 – Average weekly and diurnal cycles of benzene, toluene, xylenes and NO2 at the urban air quality station for the period
June 2006–June 2007.
seasonal changes in urban air pollution. These results are
consistent with the effects of photochemical reactions ex-
plained above. Furthermore, these seasonal trends can also
be related to emissions from house heating sources, which
are higher in winter months and contribute to the increase
in hydrocarbons levels. Likewise, a significant positive cor-
relation (Table 4) was found between relative humidity and
BTEX concentrations, since winter periods are associated
with higher humidity values in the area. Moreover, a negative
and significant correlation between wind velocity and pol-
lutant levels was observed, a fact associated to the higher dis-
persion of pollutants promoted by faster winds, which mainly
occurred in winter periods.
On the other hand, halogenated compounds appear to be
relatively unaffected by temperature and season.
3.5. Daily and weekly evolution
Fig. 5 shows the daily and weekly profiles for NO2, benzene,
toluene and xylenes obtained from the automatic air quality
station. Pollutant levels followed every week day a similar
pattern that changed during the weekend. The daily variation
was determined by traffic since the time series plots followed
a typical pattern characterised by maximums registered during
peak hours (Parra et al., 2008a). The variations of the daily
BTX and NO2 levels were characterised by a maximum in the
morning, between 8 and 10 am, and a second and slightly lower
peak in their concentrations in the evening between 8 and
10 pm. The highest levels were reached in the morning due
to the intense traffic. Furthermore, the differences between
the morning and evening peaks were more pronounced in
the case of BTX because of the absence of photochemical reac-
tions during the night and the lower sunlight intensity during
morning hours.
The main cause for the detected decrease of concentra-
tions during the weekend was believed to be the reduction of
traffic during those days. Statistical differences were found
between the concentrations of week days and weekend days
for benzene, toluene, xylenes and NO2, using a t-Student test.
At the same time, the distribution of the detected peaks dif-
1007
fered from the ones observed in weekdays, since the maximum
peak was that registered during the evening and not the
morning one, again directly related to road traffic densities.
4. Conclusions
The data presented in this study show that the VOC and
NO2 levels measured in Pamplona exceeded both benzene and
NO2 European air quality guidelines in some of the sampling
points, thus identifying areas where an effective strategy for
the control of pollution should be applied.
Emissions from motor vehicles are the dominant source
of VOC and NO2 in the urban area, although other sources
such as dry-cleaning stores, responsible for the emissions
of tetrachloroethene, were also identified.
The results show temporal variations between summer
and winter values. The concentrations were lower in summer,
corresponding to periods with high temperatures and low rel-
ative humidity, conditions that favour the depletion of VOC
by photochemical degradation. The daily variation was deter-
mined by traffic and followed a typical pattern characterised
by maximums in peak hours and decreases of concentrations
during the weekends.
Also, large spatial variations of urban VOC and NO2 con-
centrations were detected between the different sampling
points. The data obtained showed that street level concen-
trations were up to 10 times higher than those found in an
adjacent park. Furthermore, there was a high variation in
VOC and NO2 concentrations within highly trafficked streets
due to topographic characteristics that caused different wind
dispersion. These results demonstrate that unique sampling
point measurements can sometimes not be adequate for the
representation of larger urban areas or for exposure assess-
ment. Therefore, careful consideration must be given to how
representative these single measurements are in large areas,
when estimating urban air pollution. Also, more intensive
studies are necessary to study the distribution of pollutants
inside cities and the influence that buildings have on the dis-
persion of pollutants within the city.
1008 S CIE N CE OF T H E TOT AL E N V I RO N M EN T 4 0 7 ( 2 0 09 ) 99 9–1 00 9
Acknowledgements
This research work was made possible by the kind permission of
the Pamplona City Council. The authors are also grateful to ‘Aso-
ciación de Amigos de la Universidad de Navarra’ for the conces-
sion of a research grant. Government of Navarra and Pamplona
City Police are greatly acknowledged for providing valuable data
on air quality, and on meteorology and traffic, respectively.
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