Science of the Total Environment 370 (2006) 157 – 167

www.elsevier.com/locate/scitotenv

Spatial and temporal trends of volatile organic compounds

(VOC) in a rural area of northern Spain
M.A. Parra ⁎, L. González, D. Elustondo, J. Garrigó, R. Bermejo, J.M. Santamaría
Laboratorio Integrado de Calidad Ambiental (LICA), Departamento de Química y Edafología, Facultad de Ciencias, Universidad de Navarra,
Irunlarrea s/n, 31080, Pamplona, Navarra, Spain
Received 28 February 2006; received in revised form 27 June 2006; accepted 27 June 2006
Available online 8 August 2006

Abstract

Ambient concentrations of volatile organic compounds (VOCs) were measured at 40 rural sampling points in Navarre (northern
Spain). Air samples were collected by means of sorbent passive sampling and analyzed by thermal desorption (TD) and gas
chromatography/mass-selective detector (GC/MSD). A total of 140 VOCs were identified during the study, which was carried out
between May to October 2004 for a total of a 10 biweekly sampling campaigns. Concentrations of benzene, toluene, ethylbenzene, m/
p-xylenes, o-xylene (BTEX) and 1,3,5-trimethylbenzene were determined in order to investigate their temporal and spatial
distributions. Geostatistical analysis pointed to traffic as the main emission source of these compounds. Supporting this idea, BTEX
and nitrogen oxides concentrations were found to be highly significantly correlated (r = 0.495, P = 0.001), whereas a strong negative
correlation between BTEX and ozone was also observed (r = − 0.355, P = 0.025). The concentrations for the BTEX group were similar
to the values that have been previously reported for other rural areas.
© 2006 Elsevier B.V. All rights reserved.

Keywords: BTEX; Thermal desorption; Gas chromatography; Geostatistical analysis; Rural atmosphere

1. Introduction
The role and importance of VOCs produced by
human activity in atmospheric chemistry was established
about fifty years ago by Haagen-Smit in his studies of
Los Angeles smog (Haagen-Smit et al., 1953). Since
then, smog has been detected in almost all major urban
and industrial centres at levels which exceed interna-
tionally agreed criteria values set to protect human health
(Derwent et al., 1995). However, elevated emissions of
VOCs from various anthropogenic sources have not only
⁎ Corresponding author. Tel.: +34 948425600x6366; fax: +34
948425649.
E-mail address: mparravi@alumni.unav.es (M.A. Parra).
0048-9697/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2006.06.022
reduced the air quality within source regions, but also
have altered the composition of the atmosphere in remote
areas due to processes of medium and long-distance
transport (Koga et al., 2001).
VOCs are released into the atmosphere as a result of
human activities, mainly from motor vehicle exhausts,
industrial activity, solvent usage, landfilled waste and
agriculture. Emissions of benzene, toluene, ethylben-
zene, xylenes and trimethylbenzene from motor vehicles
probably have the most serious effects on air quality.
Nevertheless, ambient concentrations of VOCs are also
influenced by biogenic emissions and photochemical
degradation (Yassaa et al., 2001).
VOCs constitute an important group of air pollutants to
be studied as they contribute to some of the most serious
158 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167
environmental problems. Some VOCs exert direct
adverse effects on either human health, vegetation or
both (Fernández-Martínez et al., 2001). Among these,
benzene is of particular concern since it is known to be a
genotoxic carcinogen (WHO, 2000; Hellén et al., 2002).
In addition, VOCs also play a significant role in particle
formation (Reisell et al., 2003) and, in the presence of
NOx, they react with OH radicals to form ozone
(Atkinson, 2000) thus modifying the oxidizing capacity
of the atmosphere. The potential for VOCs to have direct
effects on plants at current ambient levels is, however,
considered negligible, mainly on the basis of controlled
short-term exposure of vegetation to high concentrations
of VOCs (Cape, 2003). However, it is well known that
ozone is highly phytotoxic, causing damages to crops and
native vegetation (Krupa and Manning, 1988; Nali et al.,
2002; Gimeno et al., 2004; Paoletti, in press). Therefore,
controls on VOCs and NOx emissions have been
implemented in an attempt to decrease the concentrations
of secondary pollutants. Consequently, measurement of
VOCs in air becomes necessary: to determine the sources
of pollutants and the transport mechanics of pollution, and
to study health effects and the compliance of regulatory
limits. However, despite all this, studies in rural atmo-
spheres are not very frequent (Cooke et al., 2001; Koga
et al., 2001; Duane et al., 2002; Cerqueira et al., 2003;
Borbon et al., 2004; Guo et al., 2004; Wang et al., 2001).
The fluctuations of VOCs in air depend on time and
space (Harper, 2000). Consequently, high monitoring
density is necessary to determine spatial and temporal
distribution of these pollutants. Intensive monitoring with
passive samplers provides data on spatial variation which a
few dispersed analysers could never supply. Furthermore,
the flexibility of placement makes them an alternative for
defining exposures at locations of difficult access.
The aim of this intensive sampling was to characterise
the presence of VOCs, especially ozone precursors, in La
Ribera of Navarre, a rural area in the north of Spain of
high economic importance with 67% of its surface
devoted to agricultural exploitation of many ozone-
sensitive species. Additionally, spatial and temporal
distributions of VOCs and their relation with other
atmospheric pollutants such as ozone and nitrogen oxides
were also studied. Finally, the identification of possible
emission sources of these compounds was attempted.
2. Experimental
2.1. Study site
Research was carried out in La Ribera of Navarre,
Spain (Fig. 1), an area with an extension of 2186 km2 in
the high Ebro river basin and which is mainly made up
of low lands with an average altitude in the range of 300
to 400 m a.s.l.
Its climatic characteristics correspond to a continental
Mediterranean climate with an annual mean temperature
of 14 °C and a summer maximum of 31 °C. Precipita-
tions are irregular and scarce, with an annual register of
400–500 mm of which 75 to 100 mm correspond to
summer time. In spite of this poor rain pattern, it is an
excellent agricultural area due to the nature of its fluvial
confluence.
2.2. Experimental design
Sampling was carried out from May to October 2004
at 40 points selected within a sampling grid composed of
100 km2 squares, which cover the whole territory
(Fig. 1). Perkin Elmer stainless steel tubes (6.3 mm
ED × 90 mm, 5.5 mm ID) filled with Tenax TA (100 mg)
were used for VOC sampling and Radiello passive
samplers were used for monitoring ozone and nitrogen
dioxide. These were placed within the selected sampling
points at well-exposed areas far away from local sources
of VOCs and NO2 (such as traffic and industries) and at
3 m above ground level. Tubes were protected from bad
weather conditions by polypropylene easily assembled
shelters.
Sampling was performed on a 2-week basis, allowing
for a total of 10 exposure periods. After each of these
periods, the tubes were retrieved and taken to the labo-
ratory in sealed glass jars inside a refrigerated chamber.
Field blanks were transported along with samplers to the
field and stored in the laboratory during the exposure
period.
2.3. Sampling and analysis of VOCs
Adsorbent tubes used to measure VOCs were con-
ditioned by passing a stream of ultra-pure nitrogen at
100 ml min− 1 at 330 °C for 30 min. The tubes were then
capped with Swagelok end-caps and stored in sealed
glass jars immediately prior to use. During the exposure
period, tubes had Perkin Elmer diffusion end caps
attached at one end and a Swagelok end cap at the other.
Singles tubes were used at each point as reproducibility
had been checked in earlier studies.
Measurements were made using a Markes thermal
desorption unit coupled to a gas chromatograph (Agilent
5890) and an Agilent 5970 mass selective detector. The
VOCs were thermally desorbed for 10 min at 300 °C
with a flow of 30 ml min− 1 of ultra-pure helium passing
through and carrying the desorbed VOCs to a pre-
 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167
Fig. 1. Map of La Ribera, Navarre, Spain and location of the sampling points.
concentration trap (− 10 °C). After the focusing step, the
analytes were desorbed from the trap by rapid heating to
250 °C into the injector of the GC. The sample was
desorbed and the cold trap cooled down to − 10 °C.
The separation of VOCs was performed on a
30 m × 0.25 mm × 0.25 μm Hewlett Packard capillary
column (HP 5MS) with ultra-pure helium as carrier gas.
After sample injection, the column oven was maintained
at 35 °C for 2 min. After the initial isothermal step, the
temperature was first increased to 70 °C at a rate of
18 °C min− 1 and then from 70 to 250 °C at a rate of
45 °C min− 1. The mass spectrometer scanned from 35 to
400 a.m.u. in the electronic impact mode.
Five-point calibration was performed using liquid
standards in methanol solutions. These liquid standards
were injected into adsorbent tubes and the tubes were
exposed to nitrogen flow for 5 min to evaporate the
solvent. Standard tubes were desorbed and analysed
159
using the same method as the samples. The MDLs
ranged from 0.01 to 0.04 ppbv for the target VOCs.
Blank values were mostly below MDLs.
Positive identification of the various components was
carried out by combining mass-spectral data with reten-
tion index information following the analytical proce-
dures described in the literature.
2.4. Sampling and analyses of ozone and nitrogen
dioxide
Radiello adsorbing cartridge for ozone is formed by a
micropore polyethylene tube filled with silica gel coated
with 4,4′-dipyridylethylene. Upon exposure, acid-cata-
lysed ozonolysis of 4,4′-dipyridylethylene leads to 4-
pyridylaldehyde. In the laboratory, 4-pyridylaldheyde is
condensed with 3-methyl-2-benzothiazolinone hydra-
zone (MBTH) to yield the corresponding azide, yellow
160 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167

Table 1 Table 1 (continued)

VOCs identified in La Ribera
Classes of compounds identified
Classes of compounds identified
Free acids Cycloalkanes and Esters
Alkanes Monocyclic arenes Aldehydes cycloalkenes
n-C5 Benzene Butanal Acetic acid Cyclohexane Acetic acid, methyl ester
Butane, 2, Toluene Pentanal Propanoic acid Cyclohexene Acetic acid,
2-dimethyl- isopropylester
Pentane, Ethylbenzene Hexanal Butanoic acid Methylcyclohexane Acetic acid, butyl ester
2-methyl- Pentanoic acid 1,3,5-Cycloheptatriene Nitrogen containing
Pentane, m,p-Xylene Heptanal compounds
3-methyl Hexanoic acid Cyclooctane Nitromethane
n-C6 Styrene Benzaldehyde Heptanoic acid Byciclic arenes Nitrobenzene
Pentane, 2, o-Xylene Octanal Hexanoic acid, Indene Terpenes
5-dimethyl- 2-ethyl-
Hexane, Isopropylbenzene Benzaldehyde, Octanoid acid Indane α-Pinene
2-methyl- 4-methyl- Benzoic acid Naphthalene Camphene
Hexane, n-Propylbenzene Nonanal Nonanoic acid Naphthalene, 1-methyl- 1,8-Cineol
3-methyl- Decanoic acid Naphthalene, 2-methyl- Limonene
n-C7 Benzene, 1-methyl- Decanal Dodecanoic acid Naphthalene, 2-ethenyl- Camphor
3-ethyl- Tetradecanoic Furans
Hexane, 2, Benzene, 1-methyl- Undecanal acid
3-dimethyl- 4-ethyl-
Heptane, Benzene, 1,3,5-trimethyl Dodecanal Phenols Furan
2-methyl- Phenol Furan, 2-methyl-
Heptane, Benzene, 2-propenyl- Tridecanal Phenol, 4H-Pyran-4-one,
3-methyl- 2-methyl- tetrahydro
Heptane, Benzene, 1-methyl- Pentadecanal Phenol, 2-(3H)-Furanone,
4-methyl- 2-ethyl- 3-methyl dihydro, 5-buthyl-
Heptane, Benzene, 2-propenyl- Octadecanal 2-(3H)-Furanone,
3-ethyl- dihydro, 5-hexyl-
n-C8 Benzene, 1-propenyl- Ketones
Heptane, 2, Benzene, 1,2-diethyl- 2-Heptanone
4-dimethyl-
Octane, Alkenes 3-Heptanone coloured and determined by visible spectrophotometry at
2-methyl- 480 nm (Hewlett Packard 8452A Diode Array
Octane, 1-Hexene 2-Octanone Spectrophotometer).
4-methyl-
Octane, 1-Heptene 2-Nonanone
For NO2 monitoring, the cartridge is made of
3-methyl- microporous polyethylene coated with triethanolamine
n-C9 1-Octene 2-Decanone (TEA). NO2 is chemiadsorbed onto TEA as nitrite ion
Nonane, 1-Nonene 3-Buten-2-one, 4- and extracted from the cartridge with water. After the
2-methyl- phenyl- addition of sulphanilamide, nitrite forms a diazonium
Nonane, Halogen containing Ethanone, 1-phenyl-
compound which on coupling with N-(1-napthyl)ethy-
4-methyl- compounds
Nonane, Dichloromethane Methanone, diphenyl- lenediamine dihydrochloride (NEDA) forms purple
3-methyl- azodye. Nitrite is quantified by visible spectrophotom-
n-C10 Chloroform Alcohols and oxy- etry (Hewlett Packard 8452A Diode Array Spectropho-
alcohols tometer) measuring the absorbance at 537 nm (Varshney
n-C11 Tetrachloromethane 1-Butanol
and Singh, 2003).
n-C12 Trichlorotrifluoroethane 1-Pentanol
n-C13 Trichloroethene 1-Hexanol
n-C14 Tetrachloroethene 1-Heptanol 2.5. Meteorological data
n-C15 Benzene, 1,4-dichloro- Benzyl alcohol
n-C16 Benzene, 1,3-dichloro- 1-Hexanol, 2-ethyl- Meteorological data during the sampling period were
n-C17 Benzene, 1,2-dichloro- 1-Octanol
obtained from the meteorological stations located in
n-C18 Benzene, 1,2, 1-Undecanol
3-trichloro- the area that belong to the Government of Navarre, the
n-C19 Benzene, 1,2, 1-Dodecanol Ministry of Agriculture, Fishing and Food, Riegos of
4-trichloro- Navarre S.A. and the National Meteorological Institute
n-C20 Octane, 1-bromo- 1-Tetradecanol (INM). In the study area, there are 30 automatic stations
that continuously register the following parameters: wind
 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167 161

Fig. 2. Benzene, toluene, ethylbenzene, m/p-xylene and o-xylene during sampling periods.

speed and direction, relative humidity, temperature,
atmospheric pressure, solar radiation and precipitation,
and 16 manual stations that register temperature and
precipitation.
2.6. Data analysis
Contour maps were developed to illustrate the spatial
distribution of the different variables, using the Kriging
method. All calculations were done in the geostatistical
modelling program IDRISI, v. 14.1 (Kilimanjaro).
Differences in VOC concentrations between the sites
and between the sampling periods were determined with
one-way analysis of the variance by using SPSS 11.0.
Correlations between VOCs were also calculated.
3. Results and discussion
A total of 140 VOCs were identified in La Ribera of
Navarre. These compounds can be classified into two groups:
anthropogenic compounds emitted from traffic and industries,
and biogenic compounds emitted from vegetation (Table 1).
Anthropogenic compounds were identified all over the area
whereas biogenic compounds were identified at points 1, 3
and 13, where large extensions of cereals were predominant,
and at points 12, 21 and 36, where nearby dense forest
formations were present (Pinus halepensis and Populus alba).
Among the identified compounds, benzene, toluene,
ethylbenzene, xylenes and 1,3,5-trimethylbenzene were
the majority and recognised as ozone precursors. Their
diffusive uptake rates are well known (ISO/DIS 16017-2,
1999; Health and Safety Executive CAR Committee,
2001), which allows the quantification of their mean
level during each exposure period. Also, these com-
pounds are quantitatively retained in Tenax TA, a fact
which not attributable to other compounds identified.
For these reasons, these compounds were chosen to be
quantified in this study.
The BTEX mean concentration (sum of the concentra-
tions of benzene, toluene, ethylbenzene, m/p-xylene and

Fig. 3. 1,3,5-Trimethylbenzene during sampling periods.

162 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167

o-xylene) registered in La Ribera during the study period
(May–October) was 2.98 ± 1.04 ppbv. The mean concen-
trations of benzene, toluene, ethylbenzene, m/p-xylene
and o-xylene were 0.75 ± 0.29, 1.38 ± 0.50, 0.27 ± 0.11,
0.55 ± 0.25 and 0.30 ± 0.14 ppbv, respectively. The mean
concentration registered for 1,3,5-trimethylbenzene was
2.44 ± 1.07 ppbv.
Among BTEX, toluene was the most abundant
compound at all points surveyed, followed by benzene,
as observed in other studies (Guo et al., 2004). Ambient
concentrations of BTEX and 1,3,5-trimethylbenzene
measured in this study were found to be similar and
comparable to those described for rural areas elsewhere
(Guo et al., 2004; Yassaa et al., 2001).
According to Directive 2000/69/EC, the annual
benzene mean concentrations in air may not exceed
5 μg m− 3 (1.4 ppbv). Mean values obtained in this study
were always below this limit. However, it should be
mentioned that these measurements were conducted in
summer, when concentrations are generally lower so the
limits could have been exceeded when considering the
annual mean. On the other hand, although toluene levels
are not regulated by European legislation, WHO estab-
lishes a guideline value of 260 μg m− 3 (63.3 ppbv) as a

Table 2
Mean concentrations of BTEX and 1,3,5-trimethylbenzene for the 40 points
Sampling point Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene BTEX 1,3,5-Trimethylbenzene
a,b a,b
1 0.63 1.00 0.13 0.78 0.15 1.95 2.87b
2 1.96a 1.74a,b 0.23 0.45 0.24 3.43 2.22b
3 1.52a,b 1.45a,b 0.23 0.43 0.26 3.02 2.67b
4 0.49b 0.82a,b 0.10 0.17 0.08 1.27 1.49b
5 1.32a,b 1.32a,b 0.29 0.53 0.57 3.29 3.15b
6 0.89a,b 1.21a,b 0.31 0.70 0.36 3.30 2.75b
7 0.96a,b 2.66a 0.48 0.97 0.48 5.55 2.08b
8 0.88a,b 1.83a,b 0.28 0.52 0.27 3.40 3.11b
9 0.87a,b 1.64a,b 0.42 1.08 0.42 4.17 2.36b
10 0.46b 0.72b 0.18 0.41 0.31 1.91 1.22b
11 0.75a,b 1.23a,b 0.28 0.61 0.36 2.78 2.19b
12 0.88a,b 1.69a,b 0.33 0.67 0.42 3.58 2.49b
13 0.76a,b 0.94a,b 0.20 0.33 0.17 2.31 2.52b
14 0.83a,b 2.27a,b 0.47 1.00 0.52 5.10 2.77b
15 0.98a,b 2.41a,b 0.45 0.97 0.64 4.84 8.05a
16 0.74a,b 1.83a,b 0.31 0.68 0.32 3.39 2.94b
17 0.80a,b 1.36a,b 0.40 0.85 0.37 3.27 3.41b
18 0.64a,b 1.39a,b 0.27 0.61 0.30 3.14 2.22b
19 0.74a,b 1.17a,b 0.28 0.61 0.36 3.15 2.36b
20 0.53b 1.21a,b 0.13 0.24 0.29 2.31 2.03b
21 0.64a,b 2.18a,b 0.44 0.71 0.38 3.94 1.11b
22 0.44b 1.07a,b 0.20 0.42 0.21 2.21 2.27b
23 0.50b 0.81a,b 0.13 0.26 0.13 1.33 1.56b
24 0.48b 0.65b 0.17 0.33 0.24 1.64 2.02b
25 0.62b 0.75b 0.20 0.39 0.16 2.02 2.48b
26 0.80b 1.90a,b 0.41 0.75 0.41 4.26 1.84b
27 0.65a,b 1.46a,b 0.30 0.51 0.29 3.18 2.33b
28 0.59b 0.89a,b 0.25 0.50 0.25 2.47 2.50b
29 0.57b 0.91a,b 0.24 0.48 0.34 2.46 2.91b
30 0.46b 0.86a,b 0.13 0.24 0.10 1.58 1.33b
31 0.73a,b 1.93a,b 0.39 0.80 0.48 4.33 2.49b
32 0.77b 2.23a,b 0.45 0.85 0.46 4.63 2.14b
33 0.55b 1.01a,b 0.21 0.32 0.18 1.99 2.82b
34 0.75a,b 1.00a,b 0.14 0.21 0.13 2.08 2.89b
35 0.57b 1.14a,b 0.18 0.33 0.13 2.02 1.84b
36 0.61a,b 1.58a,b 0.21 0.31 0.22 2.80 2.03b
37 0.78a,b 1.38a,b 0.28 0.49 0.24 3.11 2.33b
38 0.57b 1.18a,b 0.23 0.38 0.18 2.46 1.59b
39 0.56b 1.16a,b 0.15 0.24 0.10 2.15 1.40b
40 0.77a,b 1.42a,b 0.44 0.96 0.48 3.45 2.83b
Different letters indicate significant differences between sampling sites for the respective variables (P b 0.05).
 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167
weekly average for the protection of human health, level
which indeed remains much above the measured levels
in this study.
3.1. Temporal distributions of BTEX and 1,3,5-
trimethylbenzene
Fig. 2 shows the evolution of BTEX mean concen-
trations of the 40 monitored points over the sampling
campaigns. The results showed significant differences
between sampling periods for all these compounds. The
lowest BTEX levels corresponded to the second fort-
night of July with a mean concentration of 1.34 ppbv. On
the contrary, the highest levels of these pollutants were
registered in the second fortnight in June and the first in
October, with concentrations of 8.57 and 3.89 ppbv,
respectively. This finding may be attributable to the
increase in agrarian activities and the associated traffic
due to cereal and grape harvesting (second fortnight of
June and first fortnight of October, respectively).
Besides, the high total level of BTEX detected during
the second fortnight of June can be related to the
particular meteorological conditions registered in that
moment, when a persistent thermal inversion avoided the
dispersion of pollutants which probably caused the
accumulation of these compounds.
This temporal pattern was also observed for each
BTEX alone (Fig. 2). The lowest levels were recorded in
July and August, when temperatures were higher, so that
a major loss of these compounds by photochemical
degradation was to be expected. This process might
have been intensified in the case of ethylbenzene and
xylenes since their higher reactivity causes their early
degradation (Hellén et al., 2002).
Data statistical analysis (one-way ANOVA) indicated
significant differences between the different sampling
periods for 1,3,5-trimethylbenzene. We found that the
sampling corresponding to the first fortnight of June had
the highest levels of 1,3,5-trimethylbenzene (5.24 ppbv),
while the second fortnight of July had the lowest value
(1.21 ppbv, Fig. 3). In this case, the previously men-
tioned meteorological conditions could also have had an
important role in the high concentrations of the second
fortnight of June campaign, preventing pollutant
dispersion.
3.2. Spatial distributions of BTEX and 1,3,5-trimethyl-
benzene
Mean concentrations of BTEX and 1,3,5-trimethyl-
benzene for the distinct sampling points are presented in
Table 2. Attending to spatial distribution (Fig. 4), the
163
Fig. 4. Distribution map of BTEX concentrations (ppbv) in La Ribera.
highest levels of BTEX were registered in points: 7, 9, 14
and 31, close to roads with high density traffic; 15, next
to an industrial zone; 32, in the vicinity of a densely
populated town; and 26, near two power stations. Points
4, 23, 24, 25, 30, 33, 34 and 35 showed an opposite
behaviour, a predictable fact as these points were located
far from sources of pollution such as roads and
industries. BTEX concentrations showed a similar
pattern to the main road layout in the studied area,
pointing to traffic as the main emission source of VOCs
in the study area.
Toluene, ethylbenzene and xylenes also revealed a
similar distribution to the road map, whereas benzene
and 1,3,5-trimethylbenzene differed (Fig. 5). Toluene
also showed significant differences between points
(Table 2), with the highest concentration corresponding
to a spot with high density traffic.
Significant differences were also observed for
benzene at point 2 (Table 2), where concentrations of
other pollutants were not so high. This result is consistent
with the different origins of these pollutants. Whereas
toluene, ethylbenzene and xylenes are indicative of
traffic emissions, benzene can be emitted into the
atmosphere from different sources such as wood
combustion and landfills (Fernández-Martínez et al.,
2001; Hedberg et al., 2002; Hellén et al., 2006).
Furthermore, benzene can show a different distribution
as its lower reactivity with OH radicals allows it to be
transported long distances without degradation (Hellén
et al., 2002).
1,3,5-Trimethylbenzene had a significant maximum
peak at point 15 (Table 2). These results suggest that
industries play an important role as sources of this
pollutant, exceeding traffic emissions due to the
164 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167

Fig. 5. Distribution maps of the concentrations (ppbv) of (A) benzene, (B) toluene, (C) ethylbenzene, (D) m/p-xylene, (E) o-xylene and (F) 1,3,5-
trimetilbenzene in La Ribera.
 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167 165

Table 3
Correlation coefficients for the studied compounds and meteorology
Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene BTEX 1,3,5-Trimethylbenzene
Benzene 1.000
Toluene 0.700 a 1.000
Ethylbencene 0.694 a 0.819 a 1.000
m/p-Xylene 0.644 a 0.705 a 0.881 a 1.000
o-Xylene 0.622 a 0.707 a 0.897 a 0.850 a 1.000
BTEX 0.779 a 0.925 a 0.939 a 0.857 a 0.857 a 1.000
1,3,5-Trimethylbenzene 0.542 a 0.202 0.347 b 0.415 a 0.344 b 0.321 b 1.000
Ozone −0.285 −0.376 b − 0.338 b − 0.422 a − 0.313 b − 0.355 b 0.083
NO2 0.192 0.547 a 0.477 a 0.443 a 0.360 b 0.495 a − 0.077
Temperature −0.566 a −0.375 b − 0.196 − 0.313 b − 0.218 − 0.238 b − 0.239
Relative humidity 0.450 a 0.317 a 0.282 0.358 b 0.335 b 0.356 b 0.161
a
Significant with a probability over 99%.
b
Significant with a probability over 95%.

proximity of an industrial area in this sampling point.
The lowest values correspond to points 10, 21 and 30, all
situated in areas far from local emission sources.
3.3. BTEX ratios and correlations
Correlation coefficients between the compounds
studied are presented in Table 3. There were strong
correlations among TEX (toluene, ethylbenzene and
xylenes), suggesting a common source for these
compounds. Although the correlation coefficients be-
tween TEX and benzene were significantly lower than
those between the various TEX, the correlations were
still highly significant and were consistent with vehicular
emissions, although this lower correlation could also
suggest another possible origin for benzene in the study
area, as mentioned above. However, 1,3,5-trimethylben-
zene exhibited low correlations with the totality of
studied compounds, a result which is consistent with the
industrial origin suggested for this compound.
More evidence can be found by calculating the ratio
toluene/benzene in the different sampling points of La
Ribera. Yassaa et al. (2001) determined that this value, in
Algiers, is close to 2.3 when emissions are recent and
basically from road traffic. These emissions in Algiers,
and also in Spain, are mainly from diesel engines as it is
used in most vehicles. In this study, similar values have
been found at points 15, 22, 26, 27 and 32, points located
near emission focuses, such as industrial areas or road
traffic.
3.4. VOCs vs. ozone and nitrogen oxides
BTEX exhibited similar behaviour to NO2 (Fig. 6).
The significant correlation (Table 3) between them
confirms traffic as the main source of these compounds,

Fig. 6. Distribution maps of the concentrations of NO2 (μg m− 3) and ozone (μg m− 3) in La Ribera.
166 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167
Fig. 7. Relative humidity and temperature distributions in La Ribera.
as road traffic constitutes the major source of these
pollutants. The fact that these coefficients are not as high
as the ones between VOCs could be linked to the
different chemical nature that can cause a different
dynamic reaction, despite their similar origin.
No relationships between benzene and 1,3,5-tri-
methylbenzene with NO2 were found. These results
seem to indicate that additional sources of benzene and
1,3,5-trimethylbenzene other than traffic could exist at
local levels.
In the same way, the relationship between VOCs and
ozone levels was studied (Table 3). In this case, there was
a significant negative correlation between them. Al-
though BTEX are known to be ozone precursors and,
therefore, increases in their concentrations should imply
intensification of the ozone formation, this behaviour
was not observed in this case. This finding may be
attributable to the association of VOC emissions with
those of NO, a compound emitted into the atmosphere
from road traffic which disappears by reaction with
ozone. Therefore, NO concentrations are high enough to
reduce ozone concentration, as is observed in our study.
Consequently, traffic is once again confirmed as the main
source for BTEX.
Regarding ozone distribution (Fig. 6), it can be
observed that zones with higher concentrations corre-
sponded to those far away from precursor's sources of
emission. So this seems to confirm that in areas of
emissions of VOCs, NO reacts destroying it.
3.5. VOCs vs. meteorology
VOCS and NO2 atmospheric chemistry are not
strongly affected by temperature. There is a temperature
effect on reaction rates, but it is less important than for
emissions. However, a significant negative correlation
(Table 3) between temperature and BTEX concentration
has been determined. This seems to be because,
normally, increases in temperature correspond to higher
radiation, conditions that favour the loss of VOCs by
photochemical degradation and, consequently, a de-
crease in their concentration (Sillman, 1999).
Likewise, a significant positive correlation (Table 3)
has been found between relative humidity and BTEX
concentrations. Generally and for this area, the higher
solar radiation (hence the temperature), the lower the
relative humidity. So relative humidity decreases are
indirectly related with a higher photochemical activity
and a descent in VOC concentrations.
Relative humidity and temperature distributions are
represented in Fig. 7.
4. Conclusions
VOC levels registered in La Ribera during summer
2004 by the use of passive samplers were low and similar
to others registered in rural atmospheres. Geostatistical
analysis of BTEX indicated an increment in levels
corresponding to the areas situated close to principal
roads, pointing to traffic as the main source of these
pollutants. However, an industrial origin was considered
for 1,3,5-trimethylbenzene.
BTEX levels were found to be related to NO2 and O3
levels. BTEX concentrations were higher at those points
with major levels of NO2 and lower levels of O3, indi-
cating the joint emission of BTEX and NO, leading to
ozone depletion. At the same time, BTEX concentrations
were higher in periods with high temperatures and low
relative humidity, conditions that favour the depletion of
VOCs by photochemical degradation. On the other hand,
 M.A. Parra et al. / Science of the Total Environment 370 (2006) 157–167
the highest levels were registered in the period with
persistent thermal inversion and very low wind velocity.
Acknowledgements
This research work was made possible by the
financial support of Departamento de Medio Ambiente
of Gobierno de Navarra. Also we would like to thank
Asociación de Amigos of the Universidad de Navarra for
the concession of a research grant.
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