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Atmospheric Environment 45 (2011) 1946e1959

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

A study of surface ozone variability over the Iberian Peninsula during


the last fty years
M.I. Fernndez-Fernndez, M.C. Gallego*, J.A. Garca, F.J. Acero
Departamento de Fsica, Universidad de Extremadura, Avda. de Elvas s/n, 06071 Badajoz, Spain

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 17 August 2010
Received in revised form
11 January 2011
Accepted 12 January 2011

There is good evidence for an increase in the global surface level of ozone in the past century. In this work
we present an analysis of 18 surface ozone series over the Iberian Peninsula, considering the target values
of ozone for the protection of human health and for the protection of vegetation, as well as the information
and alert thresholds established by the current European Directive on ambient air quality and cleaner air
for Europe (Directive 2008/50/EC). The results show that the stations located on the Cantabrian coast
exceeded neither the target value for the protection of human health nor the target value for the protection
of vegetation. The information threshold was exceeded in most of the stations, while the alert threshold
was only exceeded in one. The seasonal and daily evolution of ozone concentrations were as expected.
A trend analysis of three surface ozone concentration indices (monthly median and 98th percentile, and
monthly maximum of the daily maximum 8-h mean) was performed both for the whole period of each
station and for the common period from 2001 to 2007 for all the months of the year. It was noted that
generally the south of the Iberian Peninsula presented increasing trends for the three indices, especially
in the last six months of the year, and the north decreasing trends. Finally, a correlation analysis was
performed between the daily maximum 8-h mean and both daily mean temperature and daily mean
solar radiation for the whole and the common periods. For all stations, there was a signicant positive
association at a 5% signicance level between the daily maximum 8-h mean and the two meteorological
variables of up to approximately 0.5. The spatial distribution of these association values from 2001 to 2007
showed a positive northwest to southeast gradient over the Iberian Peninsula.
2011 Elsevier Ltd. All rights reserved.

Keywords:
Tropospheric ozone
Ozone variability
Ozone trends
Iberian Peninsula

1. Introduction
The global distribution of ozone is an important aspect in the
study of the atmosphere. Changes in atmospheric ozone are also
important for climate change (Intergovernmental Panel on Climate
Change (IPCC), 2007): decreases in stratospheric ozone lead to
enhanced UVB radiation in the troposphere, which in turn accelerates
certain important photolysis rates. Consequently, the formation rate
of tropospheric ozone and the oxidation capacity of the troposphere
are affected, depending on the concentrations of nitrogen oxides
(Staehelin et al., 2001). On a global scale, ozone formation depends
mainly on nitrogen oxides (NOx), whereas on a local scale volatile
organic compounds (VOCs) are more important than nitrogen oxides,
and on a regional scale both types of ozone precursors have to be
considered in the net photochemical ozone production. Tropospheric
or surface ozone is a secondary air pollutant, causing health problems
and adverse effects on living beings and the physical environment
* Corresponding author. Tel.: 34 924289300x89116; fax: 34 924289651.
E-mail address: maricruz@unex.es (M.C. Gallego).
1352-2310/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2011.01.027

(Parmet et al., 2003; Janneane et al., 2003; EPA, 1996; Finnan et al.,
1997; Agrawal et al., 2003). The background ozone has several sources, both natural and anthropogenic (Vingarzan, 2004; Castell et al.,
2008). Recently, ozone research has been attracting great interest
because, during the last century, surface ozone concentrations were
considerably raised over rural areas in Europe. Comparisons of ozone
background levels with those measured in the late 19th to early 20th
centuries indicate that current ozone levels have risen approximately
twofold (Stevenson, 2001; Bozo and Weideinger, 1995; Staehelin
et al., 1994; Cartalis and Varotsos, 1994). This rise occurred in
parallel with industrial development and motor trafc which resulted
in a strong increase of emissions of many species, including nitrogen
oxides and volatile organic compounds. However, measures have
been taken to reduce the emissions of these ozone precursors (NOx
and VOCs). Between 1990 and 2008, emissions of VOCs in Spain and
Portugal decreased by around 21% and 34% respectively. Emissions of
NOx decreased in Spain by 8%; however in Portugal they increased by
around 7% (EEA, 2010).
Some authors have found that since the 1950s in the northern
hemisphere surface ozone has increased at a mean rate of w1e2% per

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

year, with large uctuations from year to year, mainly in relation to


meteorological variations (Feister and Warmbt, 1987; Low et al., 1992).
Coherent with this result is the small increasing trend in the
50-percentile value of ozone concentrations in the European Union
during the period 1994e1998 reported by de Leeuw (2000). According
to Oltmans et al. (2006), at mid latitudes of the SH, tropospheric ozone
has shown increases since the early 1990s. In Antarctica, surface
ozone amounts declined through the 1980s into the early 1990s with
a recovery in the most recent decade reported. However, all months
from March to August for this most recent period present smaller
amounts then the two earlier periods (1975e1984, 1985e1994).
There have been many studies on surface ozone trends in
Europe. For example, one can cite the investigations by Sicard et al.
(2009) which found for France a slight increase in annual averaged
ozone concentrations in rural areas between 1995 and 2003, but
a decrease in the upper ozone percentiles and in precursor emissions. In Switzerland in the 1990s, Brnnimann et al. (2002) also
observed slight decreases of the ozone peaks but a clear increase in
the monthly mean values, and Kuebler et al. (2001) detected a very
slight downward trend in ozone in both urban and rural sites in
spite of the reductions in ozone precursors between 1985 and 1998.
In northwest Europe, Derwent et al. (2003) observed downward
trends in episodic peak ozone during the 1990s. This decrease was
due to the reduction of ozone precursors. Ordez et al. (2005)
analysed the inuence of meteorological variables (temperature,
global radiation, wind speed, wind direction, and relative humidity)
on the daily ozone maxima in Switzerland in all seasons from 1992
to 2002. It was observed that the daily maximum ozone concentrations and temperature were strongly correlated. During the
warm seasons, the afternoon temperature and the morning global
radiation presented a positive correlation with daily ozone maxima
both in summer and in spring. Over the Iberian Peninsula (IP)
several studies related to surface ozone concentrations have been
carried out but, to the best of our knowledge, always limited to
a single location or a restricted sector of Iberia. Among others, we
can cite the following: diurnal and monthly variations in surface
ozone concentrations of ve Spanish rural stations were analysed
by Gimeno et al. (1999); Sousa et al. (2006) developed a method
for prediction of ozone concentrations in the city of Oporto by
means of statistical approaches; the behaviour of background
ozone in the northeast of the IP was studied by Milln et al. (2002)
and Ribas and Peuelas (2004); Snchez et al. (2005) investigated
the transport of ozone at a high-altitude station in the Central
Massif of Spain; and Adame et al. (2008) studied the behaviour,
distribution, and variability of surface ozone in the south of the IP.
In this work, we present a more extensive analysis of surface ozone
time series for 18 locations over the IP. As mentioned above, the
formation of tropospheric ozone depends on the concentrations of
precursors. Between 1990 and 2008, emissions of VOCs in Spain and
Portugal decreased by around 21% and 34%, respectively. Emissions
of NOx have decreased in Spain by 8%, but in Portugal they have
increased by around 7% (EEA, 2010). The objectives of this work were:
(1) to determine whether surface ozone levels in the Iberian Peninsula
in the last 20 years comply with the objectives dened by the current
European Directive (Directive 2008/50/EC of the European Parliament
and of the Council of 21 May 2008 on ambient air quality and cleaner
air for Europe); (2) to analyse the possible existence of statistically
signicant trends in the IP surface ozone time series; and (3) to study
the correlation between surface ozone concentrations and meteorological parameters such as temperature and solar radiation.
2. Data
We used hourly records of surface ozone concentrations at 18
stations distributed over the IP (see Fig. 1). Table 1 provides

1947

Fig. 1. Geographical locations of the studied stations. Red circles indicate the stations
which do not exceed the target value for the protection of vegetation (AOT40). Green
circles indicate the stations which do not exceed the information threshold
(180 mg m3). (For interpretation of the references to colour in this gure legend, the
reader is referred to the web version of this article.)

a detailed list with information about the site, geographical


coordinates, altitude, temporal period, and percentage of missing
values. The stations were grouped according to their location:
Cantabrian coast, ES08, ES16, ES05; Atlantic coast, PT04, ES17;
Mediterranean coast, ES02_ES07, ES12, ES03, ES14, ES10, ES06; and
inland (or interior of the IP), ES01_ES15, ES04, ES09, ES11, ES13. All
of these stations belong to the EMEP (European Monitoring and
Evaluation Programme) network. The EMEP programme measures
air pollution in rural areas, and relies on three main elements:
collection of emission data, measurements of air and precipitation
quality, and modelling of atmospheric transport and deposition of
air pollutants. In the EMEP directions, hourly measurements of
surface ozone, sulphur dioxide, and nitrogen monoxide are made at
each station as well as measurements of meteorological variables
such as wind direction and speed, overall solar radiation, pressure,
temperature, humidity, and precipitation. In the case we are
dealing with, the analytical method used to measure the surface
ozone concentration, expressed in mg m3, is UV photometry
(EMEP, 2001).

Table 1
Locations, coordinates, altitudes, study period, and percentage of missing values of
the selected stations.
Code Observatory

Longitude Latitude
( N)
( E)

ES01

4.34861

39.54777

917

1993e2000

6.76

3.6
0.49139
2.50305
8.92361
4.31666
3.53333
4.85027
3.14277
3.31694
6.92278
1.10194
5.86667
0.71667
4.35
7.69972
6.55
8.8

37.2
720
40.82055
44
42.45779
445
42.72805
683
39.86666
78
37.23333 1265
43.44222
134
41.28111 1360
42.31944
23
38.47583
393
39.08611
885
41.28333
985
41.4
470
39.51667 1241
43.23111
506
37.05
5
39.08333
43

1993e1995
1993e2000
1993e2001
1993e2000
2008e2009
1995e2009
1998e2009
1998e2009
1998e2009
1999e2009
1998e2009
2000e2009
2000e2009
2000e2007
2001e2009
2008e2009
1990e2007

13.16
4.66
6.30
10.11
3.35
11.00
2.52
4.86
3.84
3.00
2.93
2.38
2.19
9.84
3.76
4.54
18.17

San Pablo de
los Montes
ES02 La Cartuja
ES03 Roquetas
ES04 Logroo
ES05 Noia
ES06 Mahn
ES07 Vznar
ES08 Niembro
ES09 Campisbalos
ES10 Cabo de Creus
ES11 Barcarrota
ES12 Zarra
ES13 Peausende
ES14 Els Torms
ES15 Risco Llano
ES16 O Saviao
ES17 Doana
PT04 Monte Velho

Altitude Period
(m)

Missing
values %

1948

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

Table 2
Threshold values for ozone.
Threshold

Value

Measured as

Protection human health


Protection vegetation
Information threshold
Alert threshold

120 mg m3
18 000 mg m3h1
180 mg m3
240 mg m3

Maximum daily 8-h mean


AOT40a
Hourly average
Hourly average

AOT40 is the sum of the differences between the hourly mean surface ozone
concentration greater than 80 mg m3 and 80 mg m3 using only the 1 h values
measured between 8:00 and 20:00 from May to July.

3. Methods
As was mentioned above, the current European Directive on
ambient air quality and cleaner air for Europe is Directive 2008/50/EC.
This Directive establishes target values of ozone for the protection of
human health and for the protection of vegetation as well as information and alert thresholds (Table 2). According to this Directive, UE
Member States must inform the population of the dates and duration
of periods when the target and threshold values are exceeded and the
ozone concentrations that are reached at those times.
To analyse the possible existence of statistically signicant trends
in the IP surface ozone time series, the non-parametric ManneKendall
(MeK) test was used. This statistical test was rstly introduced by
Kendall (1976), and has been widely applied in a lot of scientic elds,
i.e.: hydrology (Kundzewicz and Robson, 2000), climatology (Gallego
et al., 2006, 2011), air quality (de Leeuw, 2000; Ruoho-Airola et al.,
2004; Sicard et al., 2009, 2011) and precipitation chemistry (Kvaalen
et al., 2002; Sicard et al., 2007). The null hypothesis Ho is that the
data (X1, X2, . Xn) are identical and independently distributed random
variables, and the alternative hypothesis H1 is that the data are

distributed according to an increasing or decreasing trend. The power


of the MeK test, the probability of rejecting the null hypothesis, is as
high as that of parametric tests. Its advantage lies in its independence
of the form of the distribution (Press et al., 1990). The statistic of the
test is Kendalls s, whose expression is the following

n1 X
n
X
i 1 j i1



sgn Xj  Xi ;

where sgn(X) is the sign function, with values equal to 1, 0, or 1


depending on whether the argument is negative, zero, or positive,
respectively. The variance of s under the null hypothesis is

vars

nn  12n 5
:
18

The exact distribution of s can be evaluated. For n > 10, the distribution
approaches a normal, especially if the following correction is made:

s0 s  sgns:
The normalised variable is evaluated from s0

s0

vars

Obviously, Z is normally distributed with mean 0 and variance 1. It


will give the values of the probability of acceptance of the null
hypothesis.
The MeK test described detects the existence of a trend, but
does not provide an estimate of its magnitude. For this purpose, we
use the algorithm proposed by Hirsch and Smith (1982), an

Fig. 2. AOT40 and the number of exceedance days related to protection of human health, information threshold, and alert threshold at the Niembro (ES08), Cabo de Creus (ES10),
Monte Velho (PT04), and La CartujaeVznar (ES02eES07) stations.

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

1949

Table 3
Summary of the analysis of the directive.
Station

Years above information threshold

e
1998,
1990,
2003,
ES02_ES07 1998,

ES08
ES10
PT04

Years above
Years above protection human health
alert threshold

e
2000, 2001, 2002, 2003, 2004, 2005, 2006. e
1996, 1997, 1999, 2001, 2002,
1997
2005, 2006
1999,2001
e

Years above protection vegetation

1999, 2000, 2003, 2004, 2005, 2006, 2007, 2009 e


1998e2009
1998e2006, 2009
1999e2006
1996
1990e1997, 1999e2006

extension of that suggested by Theil (1950a,b,c) and Sen (1968).


The statistic of this TheileSen test is related to the slope of the trend
found by the MeK test.
This test was applied to monthly series of median and
98th percentile hourly surface ozone concentrations, and of the
maximum of the daily maximum 8-h mean.

1994, 1995, 1998e2002, 2004e2008

The Kendall rank correlation method was used to study the


correlation between surface ozone concentrations and meteorological variables such as temperature and solar radiation. This is one
of the empirical measures of dependence of two random variables X
and Y based on ranking the elements of the sample (X1,Y1),.,(Xn,Yn).
The Kendall coefcient is a rank statistic dened by the formula

Fig. 3. Monthly evolution of ozone at the eighteen stations. (a) Stations with maximum concentrations in April and May. (b) Stations with maximum in June and July. Green circles
indicate the stations with the highest ozone levels. Red circles indicate the stations with the lowest ozone levels. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)

1950

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

Fig. 4. Daily evolution of ozone for the 18 stations in each season.

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

1951

Fig. 5. Example of daily evolution of (a) NO and (b) NO2 concentrations in spring.

2Sr1 ; .; rn
;
nn  1

The information threshold was exceeded at all the stations


except Logroo (ES04), Mahn (ES06), Niembro (ES08), and Doana
(ES17) (see Fig. 1). The alert threshold was only exceeded at Monte
Velho (PT04) in March. As one could expect, the rises above the
information and alert thresholds occurred in spring or summer
during the central hours of the day, the period with maximum solar
radiation and optimal conditions for the physicochemical processes
involved in ozone formation (Adame et al., 2008).
As example, Fig. 2 shows the results for four stations located at
different places over the IP. At Niembro (ES08) on the Cantabrian
coast (north of the IP), all years presented exceedances of the target
value for the protection of human health except 1998, 2001, 2002,
and 2008. Comparison against the target value for the protection of
vegetation was made in terms of AOT40. The highest AOT40 was
observed in 2005 and the lowest AOT40 in 2002. The information
and alert threshold were not exceeded on any occasion. For Cabo de
Creus (ES10), in the north of the Mediterranean coast of the IP, the
information threshold was exceeded in 1998, 2000, 2001, 2002,
2003, 2004, 2005, and 2006. The alert threshold was not exceeded
on any occasion. The target value for the protection of human
health was exceeded in all of the years. In Monte Velho (PT04) on
the Atlantic coast of the IP, all years presented exceedances of the
target value for the protection of human health except 1998 and
2007. The highest AOT40 was observed in 1996. The information
threshold was exceeded in 1990, 1996, 1997, 1999, 2001, 2002,
2003, 2005, and 2006. The alert threshold was exceeded thrice in

where ri is rank of Y belonging to the pair (X,Y) for which the rank of
X is equal to i, and S 2N  n(n  1)/2, with N being the number of
elements of the sample for which j > i and rj > ri simultaneously.
The inequality 1  sc  1 always holds. The Kendall coefcient of
rank correlation has been extensively used (see Kendall, 1970) as
an empirical measure of dependence. In particular, the test was
applied to determine the possible correlations between the daily
maximum 8-h mean of surface ozone concentration and daily
means of temperature and solar radiation, respectively.
4. Results
4.1. Analysis of the directive
Surface ozone concentrations at each station were analysed
in accordance with the current Directive. The results for the 18
stations showed the target value for the protection of human health
to be exceeded at all the stations except O Saviao (ES16) and
Niembro (ES08), both located on the Cantabrian coast. The target
value for the protection of vegetation was surpassed in all the
stations with the exception of Roquetas (ES03) in the Ebro valley,
and Niembro (ES08), Noia (ES05), O Saviao (ES16), and Monte
Velho (PT04) on the north and west coasts of the IP (see Fig. 1).

Table 4
Magnitude of the trend and p-value of the median for the whole period at each station.
INDIC

January
B

ES01eES15
ES05
ES08
ES10
ES11
ES13
ES14
PT04
INDIC

ES01eES15
ES02eES07
ES08
ES09
ES10
ES13
a

12.65
28.25
3.25
L22.27
11.52
27.03
4.27
4.56

February
p-value
0.03
0.09
0.38
0.001
0.19
0.09
0.46
0.23

July

March

April

May

June

p-value

p-value

p-value

p-value

p-value

9.36
36.58
8.06
L23.9
17.78
1.49
26.32
5.73

0.07
0.02
0.12
0.0006
0.11
0.5
0.01
0.12

5.1
31.02
12.74
25.31
4.18
5.72
18.76
4.5

0.31
0.03
0.01
0.0004
0.38
0.38
0.09
0.27

8.34
28.25
13.83
L21.86
9.05
18.39
16.65
8.18

0.12
0.19
0.02
0.0004
0.11
0.17
0.23
0.04

7.24
25.96
8.31
L18.77
20.46
4.84
28.08
6.76

0.08
0.13
0.11
L0.01
0.02
0.46
0.04
0.07

11.24
23.9
2.44
10.25
1.28
L31.85
14.28
5.99

0.1
0.05
0.38
0.06
0.38
L0.004
0.23
0.1

August

September

October

November

December

p-value

p-value

p-value

p-value

p-value

p-value

12.74
3.84
4.27
8.89
L16.52
L22.13

0.03
0.37
0.38
0.19
L0.04
L0.04

6.02
11.95
8.89
13.25
L18.11
10.09

0.23
0.02
0.27
0.10
L0.001
0.08

8.18
10.63
24.49
6.19
L18.88
4.77

0.25
0.04
0.01
0.23
L0.01
0.24

1.36
11.06
6.27
L16.95
L27.72
10.08

0.50
0.005
0.37
L0.01
L0.003
0.06

3.57
11.58
7.86
L13.19
L23.65
6.47

0.31
0.01
0.06
L0.01
L0.01
0.24

11.97
1.95
11.37
4.73
15.61
3.17

0.11
0.38
0.12
0.29
0.10
0.36

Percentage of variation per 100 years. P-value is dimensionless.

1952

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

Table 5
Magnitude of the trend and p-value of the 98th percentile for the whole period at each station.
INDIC

ES01eES15
ES04
ES05
ES08
ES10
ES11
ES13
ES14
PT04
INDIC

ES01eES15
ES02eES07
ES09
ES10
ES11
ES12
ES13
PT04
a

January

February

March

April

May

June

Ba

p-valuea

p-value

p-value

p-value

p-value

p-value

11.85
17.47
28.31
10.57
20.39
4.71
18.76
21.94
8.39

0.01
0.09
0.05
0.06
0.02
0.30
0.23
0.04
0.02

6.80
19.14
33.50
13.74
18.44
5.67
9.48
19.81
4.57

0.20
0.03
0.03
0.03
0.002
0.36
0.13
0.02
0.18

1.29
6.70
25.97
8.80
7.74
4.77
14.80
19.12
2.48

0.38
0.19
0.05
0.18
0.04
0.18
0.17
0.13
0.26

0.52
7.45
14.46
14.77
8.04
22.90
27.00
8.11
6.59

0.36
0.27
0.27
0.03
0.23
0.01
0.06
0.42
0.02

7.48
8.42
24.17
2.93
20.71
9.68
10.03
19.96
7.40

0.08
0.36
0.09
0.32
0.01
0.18
0.30
0.15
0.08

8.64
2.48
8.56
2.29
17.00
1.03
31.40
3.31
12.07

0.14
0.45
0.45
0.32
0.04
0.44
0.01
0.38
0.01

July

August

September

October

November

December

p-value

p-value

p-value

p-value

p-value

p-value

20.28
4.59
9.23
13.33
2365.00
5.46
17.07
12.09

0.004
0.29
0.23
0.12
0.41
0.14
0.06
0.01

14.31
6.50
14.10
20.76
0.35
9.56
8.41
9.32

0.008
0.007
0.08
0.02
0.50
0.19
0.36
0.08

15.96
3.30
11.25
19.54
9.02
10.85
12.61
6.76

0.03
0.20
0.02
0.04
0.32
0.04
0.11
0.04

10.29
11.89
6.32
20.16
3.72
1.85
10.23
4.31

0.03
0.02
0.19
0.03
0.50
0.50
0.24
0.24

5.32
8.95
10.08
14.91
0.96
3.04
7.17
4.87

0.31
0.04
0.04
0.06
0.50
0.42
0.04
0.14

8.69
2.48
6.23
9.26
15.09
13.72
1.86
10.45

0.16
0.42
0.27
0.18
0.01
0.10
0.50
0.09

Percentage of variation per 100 years. P-value is dimensionless.

March 1997, with this being the only station of the set studied at
which this threshold was surpassed. At La CartujaeVznar
(ES02eES07), in the southeast interior of the IP, all years presented
exceedances of the target value for the protection of human health
except 1993. The highest AOT40 was reached in 1998 and 1999. The
alert threshold was not exceeded on any occasion. The information
threshold was exceeded in 1998, 1999, and 2001. The results for
these four stations shown as examples are summarised in Table 3.
This type of analysis of the Directive has also been carried out in
other European countries. de Leeuw (2000), for instance, analysed
the ground level ozone concentrations in the European Union
for the period between 1994 and 1998. For the majority of
stations, exceedances of the threshold for health protection,
vegetation protection, and population information were found.
However, those stations showed downward trends in the number
of exceedance days.

4.2. Seasonal evolution of the ozone concentrations


Using hourly surface ozone concentrations, monthly ozone averages were obtained for the study period of each station, giving
a monthly typical year. Fig. 3 shows the monthly average evolution of
ozone concentrations for the study period of each station. This gure
is in two parts for clarity. Ozone monthly concentrations show
a clear cycle with minima in December and January and maxima in
AprileMay (Fig. 3a) and JuneeJuly (Fig. 3b). Maxima of surface ozone
concentrations in April and May are probably due to enhanced
photochemistry after a winter accumulation of air pollutants
(Penkett and Brice, 1986), or, depending on the geographical location,
although they may also be partly of natural origin due to stratospheric intrusions which may be favoured by the variation of stratosphericetropospheric exchange (Atlas et al., 2003). The presence of
a main maximum in JuneeJuly seems to be due to temperature as

Table 6
Magnitude of the trend and p-value of the monthly maximum of the daily maximum 8-h mean for the whole period at each station.
INDIC

ES01eES15
ES04
ES05
ES08
ES10
ES13
ES14
PT04
INDIC

ES01eES15
ES02eES07
ES04
ES08
ES09
ES10
ES13
PT04
a

January

February

March

April

May

June

Ba

p-valuea

p-value

p-value

p-value

p-value

p-value

13.79
18.19
25.61
8.15
21.19
13.21
18.65
10.07

0.004
0.04
0.03
0.27
0.08
0.03
0.09
0.03

6.95
14.13
34.25
20.60
20.15
4.14
10.23
3.59

0.14
0.09
0.03
0.02
0.08
0.30
0.04
0.19

3.39
11.10
21.87
7.54
11.36
0.08
16.50
1.64

0.21
0.27
0.27
0.38
0.04
0.50
0.17
0.24

4.21
23.32
14.54
15.57
2.94
9.48
24.90
5.75

0.21
0.19
0.27
0.02
0.32
0.38
0.06
0.10

9.92
4.47
28.58
1.96
20.62
5.28
7.98
3.72

0.05
0.45
0.13
0.38
0.01
0.38
0.38
0.09

11.81
19.09
5.40
3.84
12.78
39.50
1.44
9.13

0.06
0.09
0.50
0.38
0.19
0.002
0.50
0.03

July

August

September

October

November

December

p-value

p-value

p-value

p-value

p-value

p-value

12.75
6.14
27.35
5.88
5.94
12.81
14.24
12.17

0.04
0.19
0.01
0.22
0.19
0.15
0.02
0.01

15.56
7.84
34.58
1.96
15.65
19.60
7.01
9.15

0.062
0.10
0.13
0.38
0.007
0.003
0.24
0.10

15.21
12.40
20.87
7.74
12.66
8.20
9.94
5.81

0.01
0.02
0.09
0.27
0.03
0.27
0.05
0.22

8.70
10.08
16.19
6.10
11.42
7.15
5.30
7.64

0.08
0.02
0.13
0.37
0.19
0.10
0.43
0.15

3.99
11.40
12.76
11.04
13.63
16.10
9.47
1.88

0.33
0.01
0.19
0.12
0.08
0.02
0.11
0.33

14.42
4.54
6.85
10.85
4.04
11.66
7.45
5.21

0.06
0.22
0.27
0.01
0.47
0.19
0.36
0.19

Percentage of variation per 100 years. P-value is dimensionless.

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

a controlling factor (Garca et al., 2005). One observes in Fig. 3a that


all the stations located on the coast e Cantabrian coast (ES08, ES05
and ES16), Atlantic Ocean (PT04 and ES17), and Mediterranean coast
(ES06 and ES10) e present maxima in spring. The lowest monthly
mean concentrations correspond to the observatories located on the
Cantabrian coast (Niembro (ES08), O Saviao (ES16)), and the Atlantic
coast (Doana (ES17) and Monte Velho (PT04)). The highest monthly
mean concentrations were in Mahn (ES06) on the Mediterranean

1953

island of the same name, and Cabo de Creus (ES10) on the Mediterranean coast, both stations inuenced by the Mediterranean Sea
which is a more polluted region than those bordering the Atlantic.
In Fig. 3b, the stations located in the interior of the IP show maxima in
summer. The lowest monthly mean concentrations were observed
in Roquetas (ES03) in the Ebro valley. The highest monthly mean
concentrations were observed in San Pablo de los MonteseRisco
Llano (ES01eES15) almost in the centre of the IP. Nevertheless, this

Fig. 6. ManneKendall test for monthly median series of surface ozone concentration for the period from 2001 to 2007 (from left to right and from top to bottom): January, February,
March, April, May, June, July, August, September, October, November, and December. Upward triangles represent increasing trends and downward triangles decreasing trends.
The size of each triangle is proportional to the magnitude of the normalised trend (normalised to the standard deviation). Solid black triangles represent trends signicant at the 5%
level, solid grey triangles indicate trends signicant at the 10% level, and triangles and transparent triangles indicate non-signicant trends at the 5% and 10% levels. Isolines
correspond to interpolated values of the normalised trend (percentages).

1954

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

last station is one of the highest altitude stations of our set, and these
commonly show only slight seasonal variation possibly because they
sample more tropospheric air. With respect to the season when the
maximum concentrations were registered, all the features described
are consistent with the ndings of Castell et al. (2008) who note that
stations located on the coast present maxima in spring. This spring
maximum may be explained by the smaller spatial development of
the breeze cell during these months, i.e., the levels stay conned
relatively close to the production areas. However, at the stations
located within the Peninsula, the spring maximum was secondary,
while the main maximum was recorded during the summer months
reecting the typical smog maxima.

4.3. Daily ozone cycle


In order to analyse the daily evolution of the surface ozone
concentrations, hourly ozone averages were obtained for each
season at each station, giving a typical day for each season. Fig. 4
shows the daily evolution of surface ozone concentrations for
the eighteen stations in each season. This gure has been divided
into two graphs to improve the visualisation. The seasons
were dened as follows: spring (MarcheAprileMay), summer
(JuneeJulyeAugust), autumn (SeptembereOctobereNovember),
and winter (DecembereJanuaryeFebruary). As was expected, the
highest ozone concentrations were obtained in spring and summer,

Fig. 7. ManneKendall test for monthly 98th percentile series of surface ozone concentration for the period from 2001 to 2007 from January to December. Symbols as in Fig. 6.

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

and the lowest in autumn and winter. Niembro (ES08) on the


Cantabrian coast was the station which presented the lowest ozone
concentrations in winter. This could be due to the low radiation
levels in this season. In all seasons, the ozone concentrations
showed a clear cycle with minima in early morning and maxima in
the central hours of the day. The early morning minimum may be
because the residual ozone from the previous night is transformed
into NO2 by reaction with NO. This is illustrated in Fig. 5 which,
taking only spring by way of example, includes the analysis of the
diurnal cycle of NO and NO2 for the simultaneous measurements.
In this gure, one observes that early morning minima in O3

1955

concentrations here correspond to maxima in NOx. The phenomenon can be explained as follows. The NO from trafc emissions is
produced in the early morning when human activities begin. Once
the minimum ozone levels are reached, the elimination of further
ozone by NO is not very effective; the NO2 concentration is greater
than the NO concentration, thus enhancing ozone formation
(Adame et al., 2008). Another process which can decrease surface
O3 concentrations during the night is dry deposition, and this is not
effective in the residual layer whose air is mixed downwards in the
late morning by vertical mixing when the surface inversion layer
breaks up.

Fig. 8. ManneKendall test for monthly maximum of daily maximum 8-h mean of surface ozone concentration for the period from 2001 to 2007 from January to December. Symbols
as in Fig. 6.

1956

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

4.4. Trend analysis


From the hourly ozone concentrations, we constructed monthly
series of median and 98th percentile, and monthly maximum of
the daily maximum 8-h mean. These index series were used for
a twofold study: an analysis of the complete period of each station
(in order not to lose any information, using the entire record), and
an analysis of a selected common period.
Tables 4e6 present the statistically signicant results of the
trend analysis for these three indices, respectively, for the whole
period of each station, listing the magnitude of the trend estimated
by the TheileSen test (B) and the signicance level (p-value)
provided by the MeK test. The trends signicant at a 5% level
appear in bold type.
It is interesting to note that at Cabo de Creus (ES10) in the north
of the Mediterranean coast of the IP, the median decreases signicantly at the 5% level in all months except December and June, when
the decrease is signicant at the 10% level. The decrease in the 98th
percentile is signicant at the 5% level in January, February, March,
May, June, August, and September. Finally, the monthly maximum of
the daily maximum 8-h mean decreases signicantly at the 5% level
in March, May, August, and November. At La CartujaeVznar
(ES02eES07) in the southeast interior of the IP, the median increases
signicantly at the 5% level in August, September, October, and
November. The 98th percentile increases signicantly at the 5%
level in August, October, and November. At San Pablo de los
MonteseRisco Llano (ES01eES15) in the interior of the IP (Central
Plateau), a decreasing trend signicant at 5% is observed for the two
indices related to the highest ozone concentrations: the 98th
percentile and the monthly maximum of the daily maximum 8-h
mean in July, August, September, and October. Lastly, at Noia (ES05)
in the north of the Atlantic region of the IP, an increasing trend
signicant at the 5% level is observed in February for both extreme
ozone concentration indices. This behaviour also extends to the
monthly maximum of the daily maximum 8-h mean in January.
In order to study the spatial distribution of ozone trends over
the Iberian Peninsula, we selected a period common to the greatest
number of stations and that covers the greatest number of years.
This period is from 2001 to 2007, and is common to the following
stations: Vznar (ES07), Niembro (ES08), Campisbalos (ES09), Cabo
de Creus (ES10), Barcarrota (ES11), Zarra (ES12), Peausende (ES13)
Els Torms (ES14), O Saviao (ES16), and Monte Velho (PT04). For
these stations, a new trend analysis was performed in the common
period for the aforementioned three indices: one related to normal
values of ozone concentration (monthly median), and two related
to extreme ozone concentrations (monthly 98th percentile, and
monthly maximum of the daily maximum 8-h mean).
The spatial distributions of the trend found for the three indices
for the period from 2001 to 2007 are shown in Figs. 6e8. The results
for the median are shown in Fig. 6. All months except June present
the same pattern of increasing trends in the south of the IP. In
January and December, there is a slight increase in the median in
the southeast and a decrease in the southwest of the IP. The north of
the IP is characterised by a general decrease in the median during
all months except June, August, and December when this index
shows a positive trend. All months except August and December
present a decrease in the northwest of the IP. The northeast of
the Peninsula shows negative trends in all months, although
in February, March, April, May, June, July, and November slight
increases also exist. In the centre of the IP during all the year except
February, there is a decrease in the median over the 2001e2007
period. With respect to the behaviour of each of the stations, it is
noticeable that at Cabo de Creus (ES10) in the northeast of the IP
there are generalised negative trends throughout the year. These
decreasing trends are signicant at the 5% level in January,

Table 7
Kendall rank correlation between daily maximum 8-h mean and daily mean
temperature.
Code

Period

Association (Kendalls s)

ES01eES15
ES02eES07
ES04
ES06
ES08
ES09
ES10
ES11
ES12
ES13
ES14
ES16
ES17
PT04

1993e2007
1993e2009
1993e2001
2008e2009
1998e2009
1998e2009
1998e2009
1999e2009
1998e2009
2000e2009
2000e2009
2001e2009
2008e2009
1990e2007

0.48
0.41
0.46
0.2
0.08
0.45
0.32
0.43
0.48
0.46
0.55
0.22
0.27
0.07

February, August, and October, and signicant at the 10% level in


March, April, and September. Other stations with noteworthy
patterns of behaviour, both of them in the northern sub-plateau,
are Campisbalos (ES09) with decreasing trends signicant at 5% in
January, August, and November, and Peausende (ES13) with
decreasing trends signicant at the 5% level in January and June.
Vznar (ES07) in the southeast interior of the IP shows positive
trends signicant at the 5% level in October and November, and
positive trends signicant at the 10% level in September.
The two extreme ozone concentration indices, the monthly
98th percentile (Fig. 7) and the monthly maximum of the daily
maximum 8-h mean (Fig. 8), show similar behaviour. Generally, the
rst six months of the year present a decreasing trend over
the entire IP, except for April which presents increasing trends. For
the 98th percentile, the rst seven months show negative trends
in the northwest of the IP. The south of the IP is characterised by an
increase of the 98th percentile except in May and June, when
decreasing trends are depicted over the entire IP. In the case of the
monthly maximum of the daily maximum 8-h mean, the rst eight
months show decreasing trends in the northwest of the IP, except
April. This decrease in the rst eight months is also observed in the
northeast of the IP except in March, April, and May. On the contrary,
the south of the IP is characterised by an increase of this index in all
months except February, May, and June. With respect to particular
stations, for the median, Cabo de Creus (ES10) in the northeast of
the IP presents decreasing trends in all months in these extreme
indices: for the 98th percentile, the decreasing trends are
signicant at the 5% level in February and May; for the monthly
maximum of the daily maximum 8-h mean the decreasing trends
are signicant at the 5% level in May and signicant at the 10% level

Table 8
Kendall rank correlation between daily maximum 8-h mean and daily mean solar
radiation.
Code

Period

Association (Kendalls s)

ES01eES15
ES02eES07
ES04
ES06
ES08
ES09
ES10
ES11
ES12
ES13
ES14
ES16
ES17

1993e2007
1993e2009
1993e2001
2008e2009
1998e2009
1998e2009
1998e2009
1999e2009
1998e2009
2000e2009
2000e2009
2001e2009
2008e2009

0.45
0.52
0.59
0.35
0.26
0.48
0.41
0.50
0.53
0.50
0.54
0.34
0.39

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

1957

Fig. 11. Association values between daily maximum 8-h mean and daily mean solar
radiation.
Fig. 9. Red circles indicate the stations which present the highest association values
between daily maximum 8-h mean and daily mean temperature. Green circles indicate
the stations that present the highest association values between daily maximum 8-h
mean and daily mean solar radiation. (For interpretation of the references to colour in
this gure legend, the reader is referred to the web version of this article.)

in August and November. Vznar (ES07) and Barcarrota (ES11), both


in the south of the IP, show signicant positive trends in August,
September, and October. This could be due to the farming activities
carried out during these months in these rural locations, for
example, the use of nitrogen fertilisers to prepare the land for
sowing. Finally, it is interesting to note that Niembro (ES08) on the
Cantabrian coast presents increases of the three ozone concentration indices in all months except January and May. A common
behaviour of the three indices is an almost generalised decrease of
the surface ozone concentrations over the IP in May and June at all
the stations except Els Torms (ES14) in the Ebro Valley, but already
near the Mediterranean coast. This result may cause a drop in the
AOT40 values calculated from May to July, but the search for its
causes and consequences needs further requires further study
because, according to EMEP (EEA, 2009), no signicant changes in
anthropogenic ozone precursors seem to have taken place (at least
at over the IP) during the period of the measurements. With respect
to the results of numerical simulations, the EEA (2009) report gives
the EMEP Eulerian photochemistry model as indicating little

Fig. 10. Association values between daily maximum 8-h mean and daily mean
temperature.

reduction in AOT40 and SOMO351 in Spain from 1995 to 2005,


presumably reecting the smaller emission changes over the
area of this country. This result is consistent with the reduction
in extreme ozone concentrations (98th percentile and daily
maximum 8-h mean) found for the most of the IP in May and June.
The Europe-wide modelled trends predict a reduction in extreme
ozone concentrations (MTDM2) from April to September that is
only in agreement with measurements over the IP for the Cantabrian coastal region.
4.5. Correlation analysis
As was mentioned above, a Kendall rank correlation analysis
was made of the daily maximum 8-h mean with both the daily
mean temperature and the daily mean solar radiation for the
whole period and the common 2001e2007 period. There were no
temperature data for Roquetas (ES03) or Noia (ES05), and no solar
radiation data for Monte Velho (PT04), Roquetas (ES03), or Noia
(ES05). Tables 7 and 8 present the respective association values
obtained for the whole period. They were all signicant at the 5%
level. The greatest association values, of around 0.5, were observed
at the stations located in the northeast quadrant of the IP
(see Fig. 9). Figs. 10 and 11 show the respective spatial distributions
of the association values for the years 2001e2007. The patterns are
similar to those obtained for the whole period. All the association
values were signicant at the 5% level. In Fig. 10 (showing the
association values between surface ozone concentrations and
temperature), the greatest association values correspond to the
stations located in the eastern half of the IP. Monte Velho (PT04), O
Saviao (ES06), and Niembro (ES08) on the north and west coasts of
the IP presented the lowest association values. In Fig. 11 (showing
the association values between surface ozone concentrations and
solar radiation), the greatest association values correspond to
the stations located in the southeast of the IP, precisely where the
highest temperatures over the IP are observed. According to
Solberg et al. (2008) and Vautard et al. (2003), high temperatures
lead to stabilisation and subsidence due to dryness of the soil

1
SOMO35 Accumulated ozone concentrations in excess of 70 mg m3 (or 35 ppb).
SOMO35 is the sum of the amounts by which maximum daily 8-h concentrations
(in mg m3) exceed 70 mg m3 on each day in a calendar year (WHO, 2001).
2
MTDM mean of the 10 highest daily maximum ozone concentrations (based on
hourly mean data) during AprileSeptember, corresponding approximately to the
mean of the data  95th percentile.

1958

M.I. Fernndez-Fernndez et al. / Atmospheric Environment 45 (2011) 1946e1959

leading to low humidity in the lower troposphere. The stagnation of


the air mass over elevated emissions in continental areas raise the
ozone concentrations. O Saviao (ES06) and Niembro (ES08) on the
Cantabrian coast presented the lowest association values. In both
gures, there appears a northwest to southeast positive gradient
for the correlation between the surface ozone concentrations and
the two meteorological variables.
5. Conclusions
There have been many studies of surface ozone levels for
different regions around the world, especially in the northern
hemisphere. We have here described the results of an analysis of
surface ozone series over the IP. The result of the Directive analysis
for our set of 18 stations showed the target value for the protection
of human health to be exceeded at all the stations except O Saviao
(ES16) and Niembro (ES08), both located on the Cantabrian coast.
The target value for the protection of vegetation was exceeded at all
the stations except Roquetas (ES03) in the Ebro valley, and Niembro
(ES08), Noia (ES05), O Saviao (ES16), and Monte Velho (PT04) on
the north and west coasts of the IP. The information threshold was
exceeded at all the stations except Logroo (ES04), Mahn (ES06),
Niembro (ES08), and Doana (ES17). The alert threshold was only
exceeded at Monte Velho (PT04) in March, noting that this station is
one of those presenting a spring maximum.
The monthly evolution in ozone concentrations was characterised by maximum concentrations during spring and summer.
The lowest concentrations were observed in winter. With respect to
the daily evolution of the ozone concentrations, as expected, the
highest levels were reached in the central hours of the day and the
lowest in the early morning.
A trends analysis showed that in general, for the common period
from 2001 to 2007, the median, 98th percentile, and monthly
maximum of the daily maximum 8-hour mean presented decreasing
trends in the north of the IP. This could be due to the reduction of
ozone precursors in the IP for the period from 1990 to 2008, as was
reported by Derwent et al. (2003) for northwest Europe. However,
the south of the IP presented increasing trends, especially in the last
six months of the year. This probably reects the high temperatures
during the summer. At Cabo de Creus (ES10), the three surface ozone
indices increased in all months. Signicant positive trends were also
observed for the extreme ozone concentration indices at Vznar
(ES07) and Barcarrota (ES11), both in the south of the IP. For the
whole period, worthy of note was the case of Cabo de Creus (ES10)
where the median decreased signicantly at the 5% level in all
months except in December and June decrease was signicant at the
10% level. In the case of the extreme indices, this decrease was only
present in some months of the year.
Finally, for all the stations there was a positive association of
approximately 0.5 in value, signicant at the 5% level, between the
daily maximum 8-h mean and the two meteorological variables
daily mean temperature and daily mean solar radiation. This was
also observed by Ordez et al. (2005) in Switzerland for the period
from 1992 to 2002. The spatial distribution of these association
values for the years from 2001 to 2007 showed a northwest to
southeast positive gradient over the IP. This seems reasonable given
that the northwest of the IP, characterised by continuous rain
during most of the winter, is the wettest region and the southeast of
the IP is the driest.
Acknowledgements
The authors thank J.M. Vaquero for his helpful comments. They
also express their gratitude to the Ministry of Environment and
Marine and Rural Affairs of the Spanish Government and the EMEP

Programme for providing series of surface ozone concentrations,


temperature, and solar radiation over the IP. Authors received support
from the Junta de Extremadura-FEDER Funds (IB10077) and from the
Ministerio de Educacin y Ciencia (CGL2007-65891-C05-05).
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