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Science of the Total Environment 490 (2014) 957–969

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Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

2001–2012 trends on air quality in Spain


X. Querol a,⁎, A. Alastuey a, M. Pandolfi a, C. Reche a, N. Pérez a, M.C. Minguillón a, T. Moreno a, M. Viana a,
M. Escudero b, A. Orio c, M. Pallarés c, F. Reina c
a
Institute of Environmental Assessment and Water Research, IDAEA-CSIC, C/Jordi Girona 18-26, 08034 Barcelona, Spain
b
Centro Universitario de la Defensa de Zaragoza, Academia General Militar, Ctra. Huesca s/n, 50090 Zaragoza, Spain
c
Spanish Ministry of Agriculture, Food and Environment, G.D. Environmental Quality and Evaluation, Pl. San Juan de la Cruz s/n, 28071 Madrid, Spain

H I G H L I G H T S

• We interpret the 2001–2012 trends of major air pollutants in Spain.


• Marked downward concentration trends were evidenced for PM10, PM2.5 and CO.
• The effect of major policy actions on air quality was evidenced.
• The low effect of specific actions was also shown.
• The effects of meteorological variability and financial crisis are also discussed.

a r t i c l e i n f o a b s t r a c t

Article history: This study aims at interpreting the 2001–2012 trends of major air pollutants in Spain, with a major focus on evalu-
Received 31 March 2014 ating their relationship with those of the national emission inventories (NEI) and policy actions. Marked downward
Received in revised form 15 May 2014 concentration trends were evidenced for PM10, PM2.5 and CO. Concentrations of NO2 and NOx also declined but in a
Accepted 16 May 2014
lesser proportion at rural and traffic sites. At rural sites O3 has been kept constant, whereas it clearly increased at
Available online 7 June 2014
urban and industrial sites. Comparison of the air quality trends and major inflection points with those from NEIs,
Editor: Pavlos Kassomenos the National Energy Consumption and the calendar of the implementation of major policy actions allowed us to
clearly identify major benefits of European directives on power generation and industrial sources (such as the
Keywords: Large Combustion Plants and the Integrated Pollution Prevention and Control Directives). This, together with a
PM10 sharp 2007–2008 decrease of coal consumption has probably caused the marked parallel decline of SO2, NOx and
PM2.5 for PM2.5 concentrations. Also the effect of the EURO 4 and 5 vehicle emission standards on decreasing emissions
NO2 of PM and CO from vehicles is noticeable. The smooth decline in NO2–NOx levels is mostly attributed to the low ef-
NOx ficiency of EURO 4 and 5 standards in reducing real life urban driving NO2 emissions. The low NOx decrease together
CO
with the complexity of the reactions of O3 formation is responsible for the constant O3 concentrations, or even the
O3
urban increase. The financial crisis has also contributed to the decrease of the ambient concentration of pollutants;
Time trends
Air quality policy however this caused a major reduction of the primary energy consumption from 2008 to 2009, and not from 2007 to
2008 when ambient air PM and SO2 sharply decreased. The meteorological influence was characterized by a 2008–
2012 period favorable to the dispersion of pollutants when compared to the 2001–2007.
© 2014 Published by Elsevier B.V.

1. Introduction these cases, the levels of ambition varied widely, from most Northern
and Central European countries where early measures were adopted be-
Improvement of air quality (AQ) is one of the major environmental fore the entrance in force of the 2005 limit values, up to specific Southern
objectives of developed societies. According to this objective, the and Eastern European countries where measures were much delayed and
European Union has made a large effort in the last decades by means of in most cases much less ambitious. Among the national and city scale
the elaboration and implementation of both ambient air and emission di- measures it is interesting to highlight the national German labeling (S2
rectives. Furthermore, additional measures to abate pollution have been and S4) of vehicles for the Low Emission Zones (LEZs), and the setting
applied by some member states, and regional and city governments. In up of a number of LEZs in the largest cities of Europe, such as London or
Berlin (Minguillón et al., 2013).
Out of the efficiently implemented standards in emission abatement
⁎ Corresponding author. we would like to highlight the IPPC (Integrated Prevention and Pollu-
E-mail address: xavier.querol@idaea.csic.es (X. Querol). tion Control) Directive (1996/61/EC, Industrial Emissions Directive

http://dx.doi.org/10.1016/j.scitotenv.2014.05.074
0048-9697/© 2014 Published by Elsevier B.V.
958 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

2010/75/EC), the Large Combustion Plants Directive (2001/80/EC), Exceedances of the AQ standards may be also occurring around spe-
the National Emission Ceilings (NEC) Directive (2001/81/EC), and the cific industrial hotspots, harbors and power plants. Important differ-
EURO standards on road traffic emission (1998/69/EC, 2002/80/EC, ences can be observed across the different regions of Europe according
2007/715/EC). Currently, the EC is in a process for evaluating the NEC to the regional industrial and power generation policies (EEA, 2013).
Directive and generating a new Medium Combustion Plants Directive. In spite of the above problems, there is a clear evidence for PM
Furthermore, during the last decades, several regulations have been concentrations having markedly decreased during the last decade in a
issued to control emissions from shipping (Adamo et al., 2014). IMO number of European regions (EEA, 2013; Barmpadimos et al., 2012;
(International Maritime Organization)/MARPOL and the EU have set Cusack et al., 2012), as a result of: a) the EU policy for reducing emissions;
absolute limits on sulfur content in fuel, and SOx and NOx emissions b) the national and numerous regional and local AQ plans implemented,
from ships (IMO, 2011; Directive 2005/33/EC). and c) the favorable 2008–2012 meteorology for Southern Europe as
In Spain a national AQ plan has been approved by the Council of compared with 2005–2007 (Barmpadimos et al., 2012; Cusack et al.,
Ministers of the Government of Spain, the last update being Plan Aire 2012).
(April 2013). Furthermore, 45 regional and 3 local (city scale) AQ Cusack et al. (2012) reported decreases of PM2.5 concentrations for
plans have been implemented since 2004. Thus, most of the plans are remote/rural sites within the period 2001–2010, reaching up to 30–36%
designed and approved by the Autonomous Regional Government but in a number of European regions. Barmpadimos et al. (2012) found that
the territory where these apply tends to be rather small, mostly focusing PM10 and PM2.5 concentrations decreased during 1998–2010 at a
on improving AQ at major city centers or specific industrial areas. number of urban and rural background stations in five European coun-
There is a large proportion of AQ zones across Europe meeting the AQ tries with an average decrease of the raw and meteorologically adjusted
limit values and objectives for CO, SO2, PM2.5 and metals. Conversely, data of −0.4 µg/m3/year for both PM10 and PM2.5 size fractions. How-
and in spite of the above policy efforts, an important proportion of ever, the time trend observed for coarse PM, averaged over all the con-
the European population lives in areas exceeding the AQ standards for sidered stations, was less marked and not statistically significant. EEA
the annual limit value of NO2, the daily limit value of PM10 and the (2013) reported stably high levels of O3 during the last decade, but ev-
health protection objective of O3 (EEA, 2013). For PM10 and NO2, causes idenced increases of O3 levels in a number of urban areas of Europe. EEA
of these exceedances have already been discussed by Harrison et al. (2013) also reported NO2 decreasing trends for a large number of sites
(2008) and Williams and Carslaw (2011), among others. EEA (2013) although both the relative number of sites and the quantitative decrease
shows that PM10 and NO2 limit values are exceeded mostly in urban were lower than for PM.
areas, and especially at traffic sites. In specific countries such as Spain it This study focuses on the interpretation of 2001–2012 trends for
has been reported that N90% of the NO2 exceedances are attributed to major air pollutants at a number of urban, industrial and rural sites of
road traffic emissions (Querol et al., 2012). Spain with the aim of identifying the main drivers of these trends. The
It has been evidenced that the real-life NO2 emissions of diesel data on national emissions and energy consumption are also evaluated
passenger cars in urban driving conditions are much higher than to interpret trends. Understanding past trends may be relevant for
expected and in any case much higher than the emissions produced devising new strategies for air pollution abatement. Regional back-
for the EURO test driving cycles (Williams and Carslaw, 2011). EURO ground trends are firstly evaluated on the basis of the data yielded by
standards have had a very clear benefit on PM emissions from diesel Spanish EMEP (The European Monitoring and Evaluation Programme;
passenger cars, especially since EURO 4 (2005) and EURO 5 (2009), http://www.emep.int/) monitoring sites. Concentration trends at urban
but not on abating urban ambient PM concentrations (Fuller and background and traffic sites in cities having more than 240,000 inhabi-
Green, 2006 even found evidences of an increasing trend for near road tants (to include the industrial area of A Coruña) and at industrial
PM in London), neither for reducing NO2 emissions (Carslaw and hotspots are subsequently interpreted. In order to support the under-
Rhys-Tyler, 2013). Furthermore, the proportion of diesel cars has mark- standing of the major causes of the decreasing trends found for PM, a
edly increased in many European fleets due to the support given to the similar 2002–2012 analysis was performed for a data set of PM2.5
use of diesel fuel by climate policy. Taking these two issues into account, chemical components available from the background site of Montseny,
it is easy to understand the large and widespread problem that we have in, northeast Spain.
in our cities to attain NO2 AQ standards. It becomes also evident that
non-technological measures focusing on diminishing the use of private
cars in cities are needed to attain these standards. The problem may be 2. Methodology
even more serious in specific southern European cities due to the higher
inhabitants and car density and the widespread occurrence of street 2.1. Measurement sites and techniques
canyons (Cyrys et al., 2012).
Ambient levels of PM10 and NO2 in urban areas largely exceed the Spanish monitoring stations used for AQ assessment reporting time
WHO guidelines in Europe (EEA, 2013). Concerning EC PM10 standards series of pollutants during no less than 7 years in cities having more
attainment, the problem is less generalized than for NO2, but in many than 240,000 inhabitants (to include A Coruña, an important and indus-
cases exceedances are also occurring in urban areas. Eeftens et al. trial city in NW Spain) were selected for this work, without including
(2012) showed evidences of a clear gradient of PM levels across those series interrupted by the closure of the station during the last
European cities, with an increase of both PM10 and PM2.5 from north- years (2010–2012). Furthermore data from 9 EMEP monitoring sites
ern to central and to southern and eastern regions, and that these dif- were selected. Time series for PM10, PM2.5, SO2, NOx and NO2 are avail-
ferences are more pronounced for PM10. The latter is highlighting the able for the period 2001–2012, while CO records started in 2003 and O3
large influence of road dust and anthropogenic resuspension on the records in 2004. Once selected, the stations were classified into regional
urban levels of PM10 in Southern Europe. This was already underlined background (RB; EMEP sites), urban background (UB), traffic (TR) and
by Querol et al. (2004), by comparing PM speciation data from a number industrial (IN), as reported by the respective AQ networks. The IN
of European countries, and nowadays it seems that this PM source may category contains those stations classified as industrial by the local AQ
become more relevant for attaining PM10 standards at traffic sites network, and also those classified as urban or traffic sites but located
(Harrison et al., 2008). It is evident that PM exhaust emissions have in an area with strong industrial activity. In the cities where more
clearly decreased in the last century (from 180 mg/km to 5 mg/km of than one station is available for a specific environment type, a single
EURO1 (1992) to EURO5 (2009) for diesel passenger cars according to data set was obtained as an average of those available. Table 1 and
EC standards) but non-exhaust emissions have been, and are, unaffected Fig. 1 supply information on the location, environment and parameters
by legislation during the same period. measured at the study sites selected.
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 959

Table 1
Details of the industrial, urban background and traffic monitoring sites from cities having N240,000 inhabitants and with a data availability N75% for 2001–2012, and EMEP monitoring
sites whose data is evaluated in the present study. Lack of data availability for pollutants does not necessary mean that the site is not or were not measuring a given pollutant, but the
data coverage is not meeting the requirements of 75%. RB, regional background, UB, urban background, TR, traffic, IND, industrial.

City Station Location Pollutants measured

Name Code Type Lat Long Height SO2 O3 NO2 CO PM10 PM2.5

Urban background, traffic & industrial sites (dgr) (dgr) m.a.s.l.

ALGECIRAS E4:RINCONCILLO ES1637A IND 36.162 −5.443 1 x


ALGECIRAS ALGECIRAS EPS ES1664A IND 36.136 −5.453 24 x
ALICANTE/ALACANT ESTACIÓN RENFE ES1178A TR 38.342 −0.493 55 x x
ALICANTE/ALACANT ALACANT-EL PLÁ ES1635A TR 38.359 −0.472 45 x x x x
AVILÉS PLAZA DE LA GUITARRA ES1424A IND 43.559 −5.928 20 x x x x x
BARCELONA IJ-BARCELONA (GRACIA-S. GERVASI) ES1480A TR 41.399 2.153 57 x x x x x
BARCELONA PLAÇA UNIVERSITAT ES0559A TR 41.387 2.165 24 x
BARCELONA ID-BARCELONA ES1396A TR 41.379 2.133 35 x
BARCELONA IL-CIUTADELLA ES1679A UB 41.386 2.187 7 x x x
BARCELONA ZONA UNIVERSITARIA ES0567A UB 41.385 2.120 24 x
BARCELONA IN-BARCELONA(VALL. D'HEBRON) ES1856A UB 41.426 2.148 136 x
BARCELONA L.SOLÉ SABARIS-P.REIAL ES1782A UB 41.385 2.119 55 x X
BILBAO PARQUE EUROPA ES1713A UB 43.255 −2.902 76 x x x x x
BILBAO MAZARREDO ES1244A TR 43.268 −2.918 33 x x x x
CÓRDOBA ASOMADILLA ES1800A UB 37.903 −4.780 152 x x x
CORUÑA (A) CORLAB 1 ES1138A IND 43.368 −8.419 35 x x x
GIJÓN AVENIDA DE CASTILLA ES1358A IND 43.542 −5.650 7 x x x x x
GRANADA GRANADA — NORTE ES1560A TR 37.196 −3.613 689 x x x x x
HOSPITALET DE LL. (L') I3-L'HOSPITALET DE LLOBREGAT ES0692A TR 41.371 2.115 29 x x x
MADRID CASA DE CAMPO ES1193A UB 40.420 −3.749 645 x x x x x x
MADRID ARTURO SORIA ES0124A UB 40.440 −3.639 698 x
MADRID FAROLILLO ES0126A UB 40.395 −3.732 625 x x x
MADRID PLAZA DEL CARMEN ES1422A UB 40.419 −3.703 657 x
MADRID PUENTE DE VALLECAS ES1532A UB 40.388 −3.651 677 x x
MADRID MORATALAZ ES1426A TR 40.408 −3.645 685 x x x x
MADRID ESCUELAS AGUIRRE ES0118A TR 40.422 −3.682 672 x
MADRID BARRIO DEL PILAR ES1521A TR 40.478 −3.711 673 x x x
MÁLAGA EL ATABAL ES1751A UB 36.730 −4.466 86 x
MÁLAGA CARRANQUE ES1750A UB 36.720 −4.448 36 x
MURCIA SAN BASILIO ES1633A TR 37.994 −1.145 40 x x x x
OVIEDO PURIFICACIÓN TOMÁS ES1572A IND 43.373 −5.873 286 x x x x x
PALMA DE MALLORCA CASTILLO DE BELLVER ES1604A UB 39.563 2.621 117 x x x x x
PALMA DE MALLORCA FONERS ES1610A TR 39.570 2.656 23 x x x x x
PALMAS DE GRAN CANARIA (LAS) MERCADO CENTRAL ES1573A TR 28.134 −15.433 11 x x x x x x
PALMAS DE GRAN CANARIA (LAS) JINÁMAR III FASE ES0873A IND 28.035 −15.416 53 x x
PALMAS DE GRAN CANARIA (LAS) NÉSTOR ÁLAMO ES1451A IND 28.015 −15.243 33 x x x x
PAMPLONA/IRUÑA ITURRAMA ES1472A UB 42.807 −1.651 449 x x x x x
PAMPLONA/IRUÑA ROTXAPEA ES1747A UB 42.827 −1.649 418 x
PAMPLONA/IRUÑA PLAZA DE LA CRUZ ES1740A TR 42.812 −1.640 455 x x x
SANTA CRUZ DE TENERIFE TOME CANO ES1131A IND 28.462 −16.262 67 x x x x x
SANTA CRUZ DE TENERIFE LOS GLADIOLOS ES1132A IND 28.459 −16.268 95 x x x x x
SANTA CRUZ DE TENERIFE MERCA TENERIFE ES1757A IND 28.444 −16.277 130 x x
SANTA CRUZ DE TENERIFE CASA CUNA ES1759A IND 28.451 −16.278 183 x
SEVILLA PRINCIPES ES1425A UB 37.375 −6.006 9 x x
SEVILLA SANTA CLARA ES1450A UB 37.398 −5.952 29 x x x x
SEVILLA BERMEJALES ES1638A UB 37.347 −5.980 26 x x x x
SEVILLA CENTRO ES1644A UB 37.388 −5.991 19 x
SEVILLA LA RANILLA ES0817A TR 37.384 −5.960 29 x x x
SEVILLA TORNEO ES0890A TR 37.395 −6.003 17 x
SEVILLA SAN JERÓNIMO ES1519A IND 37.430 −5.980 21
VALENCIA VALÈNCIA-VIVERS ES1619A UB 39.478 −0.368 11 x x x x x x
VALENCIA VALÈNCIA-PISTA DE SILLA ES1239A TR 39.456 −0.376 11 x x x
VALLADOLID LA RUBIA ES1016A TR 41.632 −4.740 689 x x
VALLADOLID ARCO DE LADRILLO II ES1631A TR 41.646 −4.730 700 x x
VALLADOLID VEGA SICILIA ES1632A TR 41.621 −4.747 690 x
VALLADOLID PUENTE REGUERAL ES1636A IND 41.656 −4.734 691 x
VALLADOLID ENERGYWORKS-VA 1 ES1596A IND 41.666 −4.715 694 x x
VALLADOLID ENERGYWORKS-VA 2 ES1597A IND 41.683 −4.741 753 x
VIGO ARENAL ES1137A TR 42.219 −8.742 53 x x x
VIGO ESTACION 2 (OESTE) ES1439A IND 42.203 −8.747 26 x x
ZARAGOZA RENOVALES ES1641A UB 41.635 −0.894 220 x x x x x
ZARAGOZA ROGER DE FLOR ES1047A TR 41.651 −0.916 212 x x x x x
ZARAGOZA EL PICARRAL ES1044A TR 41.670 −0.871 195 x x x x

EMEP sites
BARCARROTA BARCARROTA ES0011R EMEP 38.473 −6.924 393 x x x x x
CADAQUÉS CABO DE CREUS ES0010R EMEP 42.319 3.316 23 x x x x x
VÍZNAR VÍZNAR ES0007R EMEP 37.237 −3.534 1230 x x x x
CAMPISÁBALOS CAMPISÁBALOS ES0009R EMEP 41.274 −3.143 1360 x x x x x

(continued on next page)


960 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

Table 1 (continued)
City Station Location Pollutants measured

Name Code Type Lat Long Height SO2 O3 NO2 CO PM10 PM2.5

Urban background, traffic & industrial sites (dgr) (dgr) m.a.s.l.

EMEP sites
TORMS (ELS) ELS TORMS ES0014R EMEP 41.394 0.735 470 x x x x x
SAVIÑAO (O) O SAVIÑAO ES0016R EMEP 42.635 −7.705 506 x x x x x
LLANES NIEMBRO ES0008R EMEP 43.439 −4.850 134 x x x x x
ZARRA ZARRA ES0012R EMEP 39.083 −1.101 885 x x x x x
PEÑAUSENDE PEÑAUSENDE ES0013R EMEP 41.239 −5.898 985 x x x x x

PM2.5 speciation x
MONTSENY MONTSENY ES1778A RB 41.779 2.358 693 x

2.1.1. Regional background, urban, traffic and industrial sites was done individually for around 35 major and trace PM components.
The 2001–2012 daily and annual average concentrations of SO2, NOx, PM2.5 samples were collected on quartz fiber filters for 24-h periods
NO2, O3, PM10 and PM2.5 from 9 EMEP Spanish regional background roughly once a week until 2007, and uninterruptedly every four days
(currently 13 sites are available, but only 9 have long records) and up from 2008, with high volume samplers (30 m3 h− 1) DIGITEL-DH80
to 11 urban background, 16 traffic and 9 industrial monitoring sites and MCV-CAV, equipped with a PM2.5 cut off inlet. Filters were ana-
were compiled from the data set of the Spanish Ministry of Agriculture, lyzed using different instrumental techniques to determine concentra-
Food and Environment (SMAFE) (Fig. 1). The number of sites varies tions of a range of elements and components, as described by Querol
depending on the pollutant (Table 1). At all Spanish EMEP sites the et al. (2008). Briefly, 1/2 of each filter was acid digested (HF:HNO3:
same measurement instruments are used to determine the ambient HClO4) for the determination of major and trace elements. Major
concentrations of the above pollutants. Also the measurement protocols components (Al, Ca, Na, Mg, Fe, K) concentrations were determined
followed at the selected stations meet the requirements of the European by Inductively Coupled Plasma Atomic Emission Spectroscopy, ICP-
AQ directives and therefore the data can be considered as comparable. AES. Trace element concentrations (Pb, Cu, Zn, Cr, Mn, Cd, As and P
The monitoring methods used for the measurements of air pollutants among others) were determined by means of Inductively Coupled Plas-
in this study are summarized in Tables S1 and S2. ma Mass Spectroscopy, ICP-MS. Water leachates from 1/4 of the filter
were used to analyze SO− 2 −
4 , NO3 and Cl

by Ion Chromatography
2.1.2. 2002–2012 PM speciation data from Montseny HPLC (High Performance Liquid Chromatography), and NH+ 4 by an ion
In the case of the 2002–2012 PM2.5 chemical composition data set specific electrode. The remaining 1/4 of each filter was used for the
from the Montseny regional background station, the analysis of trends elemental analysis of organic and elemental carbon (OC and EC) by a

Regional Background Urban Background Traffic Industrial


Regional Background PM2.5 speciation

A Coruña Gijón
Niembro
Avilés Pamplona
Cabo de
Oviedo Bilbao
Vigo Creus
O Saviñao
Zaragoza Montseny
Campisábalos Barcelona
El Torms
Peñausende Valladolid
Madrid L’Hospitalet

P. Mallorca
Valencia

Barcarrota Zarra

Córdoba Alicante
Murcia
Sevilla
Granada Víznar
Santa Cruz
Las Palmas

Fig. 1. Location of the monitoring sites considered in this work: EMEP stations (circles), urban background (white rectangles), traffic (black rectangles), industrial (white triangles), and
Montseny regional background station for chemical data (white cross).
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 961

thermal–optical transmission technique using a Sunset Laboratory patterns, a short evaluation of the NECo statistical data for Spain is pre-
OCEC Analyzer using the EUSAAR-2 protocol (Cavalli et al., 2010). sented here (MINETUR, 2013) as well as of the time trends evidenced
for the NEIs (MAGRAMA, 2013).
2.2. Data analysis The primary energy consumption increased by +15% from 2001 to
2007, slightly decreased from 2007 to 2008 (− 3%), and markedly
The time trends of the selected AQ parameters were evaluated using decreased in 2009 (− 12% with respect to 2007) (Fig. 2). Since 2009,
the Theil–Sen statistical estimator (Theil, 1950; Sen, 1968), available in the energy consumption indicator seems to remain constantly low.
the OpenAir software (Carslaw, 2012; Carslaw and Ropkins, 2012). This Thus the marked 2007–2008 decrease detected in many trends of air
estimator allows the calculation of the regression parameters of the data pollution described above does not seem to be related with a trend of
trends, including slope, uncertainty in the slope and p value. The applied emission patterns from energy consumption. Oil consumption was
method yields accurate confidence intervals even with non-normal data more constant, with only an increase of + 8% during 2001–2007, but
and it is less sensitive to outliers and missing values (Hollander and an important (− 24%) decrease during 2007–2012, without major
Wolfe, 1999). Regarding the single data set on chemical composition, changes from 2007 to 2008 (− 3%). This trend is probably governed
monthly averages of each of the PM2.5 major and trace component by the fuel consumption for traffic road. Natural gas consumption in-
concentrations were used for the statistical analysis, which required a creased by 119% from 2001 to 2008, and since then diminished by 20%
prior seasonal adjustment. Annual data averages were used for the until 2012. Coal consumption remained constantly high from 2001 to
rest of considered pollutants. Bootstrap resampling was used to esti- 2007 whereas, as for ambient air levels of PM and SO2, a sharp decrease
mate the resulting regression parameters. The symbols shown in the occurred from 2007 to 2008 (− 30%), continuing until 2010 (− 65%
figures for each trend estimate relate to how statistically significant 2007–2010 decrease). However, in the last 2 years there was an impor-
the trend estimate is: p b 0.001 = ***, p b 0.01 = **, p b 0.05 = * and tant increase, leading to a consumption only slightly lower than in 2001.
p b 0.1 = +; no symbol stands for no significant trend (p N 0.1). Nuclear energy consumption remained relatively constant along the
Official data on the annual National Energy Consumption (NECo) study period, whereas the hydroelectric generation had three maxima
from different energy sources (MINETUR, 2013) and from the National in 2001, 2003 and 2010, the latter coinciding with the fall of coal con-
Emission Inventories (NEIs, MAGRAMA, 2013) were also evaluated in sumption. Renewable energy consumption increased by 207% from
order to interpret trends of air pollution. 2001 to 2012, with a gradual growth in the NECo. The 2010 increase
of hydroelectrical consumption (125% over the minimum value of the
3. Results study period, 2005) is very remarkable and due to the high rainfall
rate of this year. Thus, 2010 was a favorable year for atmospheric disper-
Before the trend analysis for air pollutants, and in order to analyze sion and washout of pollution in Spain (Cusack et al., 2012), but air qual-
the possible relationship of the ambient air pollution with the emission ity also improved by lower atmospheric emissions due to the decrease
Million tons equivalent oil

150

145

140
Primary energy
135

130

125
Million tons equivalent oil

75
180
70 160
Arbitrary units

65 Oil 140
60 120
100
55 80 Primary energy + (iNAO*10)
50 60
45 40
20
40
0

25
Million tons equivalent oil

40
Arbitrary units

Natural gas 20
35
30 15
25
10
20 Coal
Coal + (iNAO*2)
15 5
10
5 0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
0
Million tons equivalent oil

18 Nuclear
16
14
12
10 Renewables
8
6 Hydroelectric
4
2
0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Fig. 2. Annual (2001–2012) energy consumption for Spain (in million tones equivalent oil). Data from the Spanish Ministry of Industry (MINETUR, 2013) The two right graphs illustrate
specific energy consumption data multiplied by 10× and 5× North Atlantic Oscillation Index (iNAO) to modulate energy consumption by meteorological factors.
962 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

of coal consumption in favor of a hydroelectrical growth. To adjust ener- rate of agricultural and farming emissions (87% of NH3 emissions,
gy consumption by the meteorological patterns of the specific years, we −0–6%/year, *).
added to Fig. 2 two graphs where the energy consumption is multiplied
by a factor depending on the winter North Atlantic Oscillation Index 3.1. Time trends of major air pollutants
(iNAO, defined as the pressure difference between the Azores High
and the Icelandic depression) obtained from Osborn (2013). These A marked 2001–2012 decrease was recorded for SO2 concentrations
data will be discussed together with air pollution data in the subsequent across Spain (Fig. 3). Concerning the RB EMEP sites, 2 types of trends are
sections. clearly evidenced. The northern sites, close to important coal power
The evaluation of the NEIs for Spain for the studied pollutants evi- generation plants (O Saviñao, Niembro and Peñausende; Sav, Nie,
denced the following patterns of temporal trends (Table S3): Peñ), show relatively high and constant 2001–2007 concentrations, a
sharp decrease in 2008–2009, and relatively low and constant levels
• A clear and high statistically significant decrease of the total SO2 emis- since 2009. This sharp decrease is parallel to the decrease of SO2 emis-
sion was evidenced (−6.1%/year, ***) driven by the trend from power sions from the power generation sector as shown by the NEIs (Fig. 3,
generation (accounting in 2001 70% of the national emissions) MAGRAMA, 2013); see later possible causes. The other EMEP sites,
(−7.2%/year, ***). spread across Spain (Barcarrota, Cabo de Creus, Viznar, Campisábalos,
• A less pronounced decrease was followed by total NOx emissions, with Els Torms and Zarra; Bar, CdC, Viz, Cam, Tor, Zar), also show a marked
a moderate statistical significance (*) and a much lower decreasing decrease in 2008–2009, although concentrations at the beginning of
rate (−2.5%/year). This trend is probably the combination of a statis- the study period were much lower and the trend is much more gradual.
tically significant smooth decreasing trend for road traffic (38% of The time trend analysis (Table S4) shows a statistically significant de-
NOx emissions, − 3.1%/year, ***) and those of power generation, crease (*** to *) of − 3.6 to − 7.7%/year, with the exception of Víznar
non-road transport and industrial processes with low or no statistical (in some cases very close to the trend found for national emissions
significance (15% of NOx emissions, − 0.4 to − 4.5%/year, no signifi- Table S3). Concerning the UB, TR and IN sites, relatively higher average
cance to +). SO2 concentrations (4, 5 and 8 μg/m3 as averages for the whole study
• A highly significant decreasing trend was obtained for primary period, respectively for UB, TR and IN, respectively) were observed com-
PM10 national emissions (− 2.5%/year, ***) mostly driven by the pared with EMEP stations. Statistically significant decreasing trends
decrease of three major emission sources (road transport, power were found in around 50% of the cases (Table S5.). Thus, mean decreas-
generation and non-industrial combustion, 60% of the primary ing rates of −3.6, −4.6 and −4.3%/year at UB, TR and IN sites, respec-
PM10 emissions, −0.4 to −6.9%/year, ***). A similar trend was evi- tively, were obtained when all sites were computed together, from 35
denced for PM2.5 (− 2.2%/year, ***), but in this case mostly driven to 50% lower than the decrease found for national emissions.
by the decrease of only two major emission sources (road transport The NO2 concentrations at RB sites decreased during the study
and non-industrial combustion, 52% of the primary PM2.5 emissions, period, with the sharpest decrease occurring in 2007-2008 (Fig. 3).
−0.4 to −3.5%/year, ***). This sharp decrease is again coincident with the decrease of NOx
• A significant decreasing trend was obtained for CO emissions emissions from the power generation shown by the NEIs (Fig. 3,
(− 3.1%/year, **) driven by the trend from road transport (39% of MAGRAMA, 2013). Here it is again interesting to distinguish between
the CO emissions, − 9.0%/year, ***). two groups of EMEP sites, but different from those described for SO2.
• Finally also a less significant and much lower decreasing trend was On the one hand, Cabo de Creus, Víznar, Els Torms, O Saviñao and
obtained for NH3 emissions (−0.5%/year, *) due to the low decreasing Niembro (CdC, Viz, Tor, Sav, Nie), show high concentrations from

20 60 120
18 SO2 NO2 NOx
50 100
16
14 40 80
12
µg/m3

µg/m3

µg/m3

10 30 60
8
6 20 40
4 10 20
2 Traffic Urban backgraound Industrial Traffic Urban backgraound Industrial Traffic Urban backgraound Industrial
0 0 0

3,5 7,0 8,0

3,0 7,0 NOx


Regional Background 6,0 Regional Background
(EMEP) (EMEP) 6,0
2,5 5,0
5,0
µg/m3

µg/m3
µg/m3

2,0 4,0
4,0
1,5 3,0
3,0
1,0 2,0 2,0
0,5 1,0 1,0
Mean Sav, Nie, Peñ Bar, CdC, Viz, Cam, Tor, Zar Media CdC, Viz,Tor, Sav, Nie Bar, Cam, Zar, Peñ Media CdC, Viz,Tor, Sav, Nie Bar, Cam, Zar, Peñ
0,0 0,0 0,0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

1.2E+6 6E+5
SO2NationalEmissions NOx National Emissions
1.0E+6 5E+5

8.0E+5 4E+5
Industrial processes with combustion
Mg
Mg

6.0E+5 Power generation and transformation 3E+5


Other transport and mobile machinery
4.0E+5 2E+5
Industrial processes with combustion
2.0E+5 1E+5 Power generation and transformation
Other transport and mobile machinery
Road transport
0.0E+0 0E+0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Fig. 3. Time trends of annual mean concentrations of SO2, NO2 and NOx at traffic, urban background and industrial (top) and regional background (middle) sites. Spanish national emission
of SO2 and NOX from different sectors (in Mg, bottom).
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 963

2001 to 2007, a sharp 2007-2008 decrease, and constant lower levels significant trends (** to +), with a slight decrease in two cases
since 2008; on the other hand, Barcarrota, Campisábalos, Zarra and (− 1.9%/year) and a slight increase in the other case (+ 0.4%/year)
Peñausende (Bar, Cam, Zar, Peñ) show little trend but with relatively (Table S4). As expected, in the case of the UB, TR and IN sites, relatively
lower concentrations. These decreasing trends were statistically signifi- lower levels of O3 were measured (40–62, 35–59 and 35–52 μg/m3 on
cant (* to +, see Table S4) only for the first set of EMEP sites (closer to average for UB, TR and IN, respectively), and statistically significant in-
urban and industrial anthropogenic emissions compared with the creasing trends were also found in around 38% of the cases (Table S8.).
others). Mean decreasing rates from −2.8 to −3.7%/year, much lower Thus, mean increasing rates of + 1.7, + 3.0 and + 1.2%/year for UB,
than those for SO2, were obtained for the stations with statistically sig- TR and IN, respectively, were obtained when all sites were computed
nificant decreasing rates. In the case of NOx the trend obtained is very together. The trends are constantly characterized by a progressive
similar to the one of NO2 (Fig. 3) but this decreasing trend is slightly increase until 2009 and a slight decrease during 2009–2012 (Fig. 4).
higher −2.3 to −4.2%/year, and the statistical significance is also mark- CO concentrations were only available for UB, TR and IN sites. Rela-
edly higher (*** to +, Table S7). This reflects probably the higher de- tively low levels were recorded (0.2–0.6, 0.1–0.6 and 0.2–0.4 mg/m3
creasing rate of NO vs NO2, even at these remote/rural sites. As far as on average for UB, TR and IN, respectively), and statistically significant
the UB, TR and IN sites are concerned, relatively high levels of NO2 decreasing trends were found in around 82% of the cases (Table S9.).
(10–42, 25–61 and 11–38 μg/m3 on average for the whole period and This decrease is parallel to the decrease of national CO emissions from
sites for UB, TR and IN, respectively) were recorded, and statistically sig- road transport (Fig. 4, MAGRAMA, 2013). Mean decreasing rates of
nificant decreasing trends were also found in around 60% of the cases − 3.8%, − 6.4% and − 5.1%/year for UB, TR and IN sites, respectively,
(Table S6.). Mean decreasing rates of − 1.1, − 1.8 and −2.0%/year for were obtained when all sites were computed together. This decreasing
UB, TR and IN, respectively, were obtained when all sites were comput- trend was progressive during 2003–2009, whereas from 2009 to 2012
ed together. These trends are lower than the ones obtained for NOx in slight changes were observed (Fig. 4). In absolute values the decrease
the emission inventory (Table S3). Overall, the decrease of ambient is intermediate between those found for the total (national) and road
NO2 levels is progressive since 2001, with the 2007-2008 minimum traffic CO emissions (Table S3).
being much less evident than for RB sites (Fig. 3). In a few cases (Vigo- Fig. 5 and Tables S10 and S11 show the 2001–2012 trends for PM2.5
industrial site and the traffic sites of Murcia and Pamplona) there was and PM10 concentrations. Although with a parallel trend two groups of
a clear increasing statistically significant trend (Table S6). In the case RB sites were identified based on the PM2.5 concentrations. On the one
of NOx (TS7, Fig. 3) the trends are similar to NO2 in the case of UB hand, the southern and northeastern sites (Barcarrota, Cabo de Creus,
sites (where NO contribution to NOx is expected to be low with Víznar and Els Torms), with relatively higher concentrations, and on
respect to NO2), but much marked in the case of IN and specially TR the other hand, the central, northern and eastern sites (Campisábalos,
sites (closer to emission sources and where higher NO/NO2 ratios are O Saviñao, Niembro, Zarra and Peñausende), with lower PM2.5 concen-
expected to occur). Thus, not only the statistical significance is higher trations. Regarding PM10 concentrations, the distinguished groups are
(for NOx compared to NO2) in a large proportion of sites, but also the de- similar, but the eastern site (Zarra) and one northern site are included
creasing trends are much more marked −0.8 to −4.4%/year, ***to * for in the group with higher PM10 levels. The decreasing trends of PM2.5
TR, and −3.8 to −4.9, *** to *, with the exception of the above tree in- concentrations are statistically significant (*** to +) in all sites, but
creasing sites. This shows very clearly the higher decreasing trend of NO with a higher level (*** to **) reported for Els Torms, Campisábalos,
vs NO2 recorded close to the emission sources. Cabo de Creus and Peñausende, and a lower level (+) for the southern
The concentration of O3 has been high at the RB sites in the last de- and eastern sites (Zarra, Niembro and Viznar) (Table S4). The de-
cade without significant trends (Fig. 4). In this case, the RB sites were creasing rate of ambient PM10 concentrations varies from − 3.9 to
also grouped into two sets: 1) Cabo de Creus, Víznar, Campisábalos, − 5.1%/year, and from − 1.7 to − 3.0%/year for the first and second
Zarra and Peñausende, with higher concentrations and spread across group respectively. In the case of PM10 the decreasing trends are char-
the Iberian peninsula, but far from anthropogenic emissions; and acterized by a high statistical significance level (*** to **) in most sites
2) Barcarrota, Els Torms, O Saviñao and Niembro, closer to emission (Table S4). However, the decrease rate is less pronounced than for
sources. Only in 3 of the 9 RB sites annual O3 levels follow statistically PM2.5 concentrations (− 2.5 to − 3.4%/year, and −1.7 to −2.4%/year

60 100

O3 90 O3
50
80
70
40
60
µg/m3
µg/m3

30 50
Regional Background
40 (EMEP)
20
30
20
10
10
Traffic Urban Background Industrial Media CdC, Viz, Cam, Zar, Peñ Bar, Tor, Sav, Nie
0 0

0,7 1.2E+6
Industrial processes with combustion
CO Agriculture and farming CO
0,6 1.0E+6 Industrial processes without combustion
Road transport
0,5 Non industrial combustion
8.0E+5
mg/m3

0,4
Mg

6.0E+5
0,3
4.0E+5
0,2

0,1 2.0E+5
Traffic Urban background Industrial National Emissions
0,0 0.0E+0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Fig. 4. Time trends of annual mean concentrations of CO and O3 at traffic, urban background and industrial and regional background sites. Spanish national emission of CO from different
sectors (in Mg, bottom right).
964 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

Fig. 5. Time trends of annual PM2.5 concentrations at EMEP sites across Spain.

for the above groups). As a whole, PM2.5 trends are characterized by a PM, and not only primary PM as it occurs in the NEIs. This also support-
gradual decrease, with a marked fall from 2007 to 2008 (as described ed by the fact that the sharp decrease observed in ambient air PM2.5
for SO2 and NO2), followed by a slight decrease or even nearly stable levels coincides also with the above described sharp decrease of
average levels since 2008. For PM10 concentrations, the decreasing the national SO2 and NOx emissions from power generation (Fig. 3,
trend is very similar, with also a less pronounced decline since 2008; MAGRAMA, 2013).
nevertheless, the sharp decrease from 2007 to 2008 is not observed so The decreasing PM10 and PM2.5 trends reported for UB and TR sites
clearly (Fig. 5). are parallel to that described for the RB sites. However, in the case of the
As regard to the UB, TR and IN sites, the recorded PM10 concentra- IN sites, the decrease is sharper until 2006 and from this year trends are
tions are relatively high (means of 18–35, 20–39 and 18–30 μg/m3 for similar to ones from the UB, TR and RB sites.
UB, TR and IN, respectively) with statistically significant decreasing
trends being reported for around 55% of the cases (Table S10.). Thereby,
mean decreasing rates of −1.9, −3.3, and −4.7%/year for UB, TR and IN, 3.2. Time trends of PM2.5 components
respectively, were obtained when all sites were computed at once. At
the UB and TR sites, high and constant PM10 concentrations were In order to support interpretations of major causes for the PM de-
recorded during 2001–2007, undergoing a progressive decrease since creasing time trends found, a similar trend analysis was performed
2008 (Fig. 6). Conversely, PM10 levels at the IN sites are characterized for the chemical components of PM2.5, making use of the longest
by a drastic 2001–2008 decrease, remaining then almost constant dur- available regional background data record. This data record has
ing 2009–2012 (Fig. 6). Focusing on PM2.5 levels, only 5 cities recorded been obtained at the Montseny regional background site (40 km
long time series (2003–2012), one traffic site and 4 urban background NNE of Barcelona, NE Spain). The Montseny rural background site
sites. Mean concentrations range between 7 and 19 μg/m3. Statistically is relatively remote from urban and industrial areas, but given the
significant decreasing trends were detected in all the sites (*** to +), high population density and industrial development of the region,
with a mean decreasing rate of −2.7%/year (Table S11). This decreasing the site can be affected by anthropogenic emissions under specific
trend was progressive along the study period (Fig. 6). meteorological conditions. The 2002–2010 PM2.5 trends at this
The NEIs evidenced a marked decreasing trend for both primary site are documented by Cusack et al. (2012). The re-analysis of the
PM10 and PM2.5, but lower in absolute values (−2.2 and −2.5%/year, 2002–2012 trends using the methodology of the current paper is
Table S3), but closer to the decrease of emissions from the road traffic shown in Table S12 and Figs. 7 and 8. The results show a statistically
sector (− 2.9- and − 3.9%/year, TS3 and Fig. 6). This is due to the fact significant (* to ***) decreasing trend for all PM2.5 components with
that secondary PM is also contributing to this decrease of ambient air the exception of EC and sea salt.
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 965

70 30

60 PM10 PM2.5
25

50
20
40

µg/m3
µg/m3
15
30
10
20

10 5
Traffic Urban background Industrial
Mean
0 0

25 14

12
20
10
15

µg/m3
µg/m3

6
10
Regional Background
Regional Background 4
(EMEP)
5 (EMEP)
2
Media Bar, CdC,Viz, Tor Cam, Sav, Nie, Zar, Peñ
Media Bar, CdC, Viz,Tor, Zar, Nie Cam, Sav, Peñ
0 0

3.5E+4 3.0E+4
PM10 National Emissions PM2.5 National Emissions
3.0E+4 2.5E+4

2.5E+4
2.0E+4
2.0E+4

Mg
Mg

1.5E+4
1.5E+4
Industrial processes with combustion 1.0E+4
1.0E+4 Agriculture and farming Industrial processes with combustion
Other transport and mobile machinery Other transport and mobile machinery
5.0E+3 5.0E+3 Road transport
Road transport
Non industrial combustion Non industrial combustion
0.0E+0 0.0E+0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Fig. 6. Time trends of annual mean concentrations of PM10 and PM2.5 at traffic, urban background and industrial (top) and regional background (middle) sites. Spanish national emission
of PM10 and PM2.5 from different sectors (in Mg, bottom).

5
4
Crustal Sea salt SO42-
1.0 4
3
[ng/m3]

[ng/m3]

[ng/m3]

3
2
0.5
2
1

1
0 0.0

8 6

NO3- OC 0.6 EC
5
6
0.5
4
[ng/m3]

[ng/m3]

[ng/m3]

0.4
4
3
0.3

2 2
0.2

1 0.1
0
2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
year year year

Fig. 7. Time trends of concentrations of major PM2.5 components measured at Montseny site.
966 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

8 Pb 6
Cu
6
[ng/m3]

[ng/m3]
4

2
2

0
2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2004 2005 2006 2007 2008 2009 2010 2011 2012

0.6
1.0

0.8
Cd 0.5 As
[ng/m3]

[ng/m3]
0.4
0.6
0.3
0.4
0.2
0.2
0.1
0.0
2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

60
6
Mn 50 Zn
40
4
[ng/m3]

[ng/m3]

30

2 20

10

0 0
2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

1.2

3 Ni 1.0
Sb
0.8
[ng/m3]

[ng/m3]

2
0.6

0.4
1
0.2

0.0
2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2004 2005 2006 2007 2008 2009 2010 2011 2012
year year

Fig. 8. Time trends of annual mean concentrations of trace elements in PM2.5 measured at Montseny site.

OC concentrations show a statistically significant decreasing rate concentrations were statistically significant in all cases (*** for SO24 −

of − 5.2%/year (− 0.1 μg/m3/year). EC concentrations were relatively and NH+ 4 and * for NO3 ) with rates of − 5.5, − 7.0 and − 5.3%/year
low and trends are difficult to identify due to the noise of the analyt- (− 0.1, − 0.1, − 0.05, μg/m3/year), respectively.
ical error, therefore the results do not show a statistically significant Crustal (mineral) matter (SiO2 + Al2O3 + Fe + Ca−+ Mg + CO23 +
trend. However, downward trends of secondary inorganic pollutants Mn + Ti + K) concentrations decreased by around − 6.5%/year
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 967

(− 0.06 μg/m3/year, ***), a component that at Montseny is primarily facilities in 2007–2008 in Spain. Furthermore, the increase of energy
associated with Saharan intrusion episodes and regional soil resuspen- produced from renewable sources and de decreease of coal consump-
sion processes. This trend is mainly driven by the declines experienced tion contributed to lower the emissions. The 2009–2012 increase of
in the Ca and Fe concentrations (− 8%/year), especially in 2009 and coal consumption described above (Fig. 2) did not result in an increase
2010. Regarding Fe concentrations, there is a notable increase in 2011, of the SO2 ambient air levels and it might reflect the fact that FGD sys-
indicating that the former decrease is linked to meteorological factors tems were operative in this period.
that reduced re-suspension of PM, since 2010 was characterized by Mean levels of NO2 at IN and UB sites did not show clear trends,
the most negative iNAO (North Atlantic Oscillation Index) from the last whereas a slight decreasing trend can be observed in the TR sites. At the
150 years and this favored rainfall and dispersive conditions (Cusack RB sites, NO2 concentrations did not decrease as sharply as SO2 concentra-
et al., 2012). tions with a decline being only recorded in a limited number of EMEP sta-
SO2−4 concentrations at Montseny are characterized by a marked de- tions. The decreasing trends NOx are much more marked and statistically
crease from 2007 to 2008 and a small increase in the last 2 years (Fig. 7). significant, especially at TR and IN sites, although in 3 specific sites in-
This trend is similar to the one described for SO2 levels and for the coal creasing statistically significant trends were evidenced. This suggests a
consumption adjusted for meteorology by using an equation in which more marked decrease of NO levels compared to NO2, probably to the in-
iNAO is included (Figs. 2 and 3) and for PM2.5 measured at EMEP sites crease of the NO2/NO ratios of diesel exhaust emissions. As shown by the
in regions where large coal fired power plants operate (Fig. 7). In this MINETUR (2013) data presented above (Fig. 2), the oil consumption
northeastern Spanish region the use of heavy oils and petroleum coke trends did not show also a sharp variation as reported for other energy
for power generation is forbidden since 2007 and this may also contrib- consumption data, this being probably due to the lower impact of the fi-
uted to the ambient decrease of SO2− 4 concentrations and, as explained nancial crisis, and meteorological features of a given year, on fuel con-
above, consequently PM2.5 concentrations. sumption by urban traffic. The sharp 2007–2008 decrease of ambient
Regarding trace elements (Table S11 and Fig. 8), there is also a clear NO2 and NOx concentrations is again coincident with the decrease of
downward trend with high statistical significance (*** for Pb, Cu, Zn, Mn, NOx emissions from the power generation shown by the NEI (Fig. 3,
Cd, As, Ti, Sr, Sn, Sb, and V; and also for Ni and Cr, ** and P *). The source MAGRAMA, 2013). As for many EU member states, there is an inconsis-
of trace elements at the Montseny environment is difficult to discern tency with the clear downward emission trends of NOx reported by the
due to the mixing and dilution of PM during transport. After the high Spanish NEI (Fig. 3, MAGRAMA, 2013) and the much less marked trend
levels recorded between 2003 and 2004, trace elements related to observed for ambient NO2 concentrations recorded at UB, TR and IN
industrial production (smelters) at regional scale around Barcelona sites. This is probably due to the higher real-life urban driving emissions
(Cu, Sb, Mn, Pb, Zn, Cr, Cd, according to Cusack et al., 2012; Amato of EURO4 (2005–2008) and EURO5 (since 2009) diesel passenger cars
et al., 2009) decreased significantly until the end of the study period. Be- compared to the emission factors applied in the European emission in-
sides the industrial source, Cu, Sb, Sn and Zn have been also partially at- ventories (Williams and Carslaw, 2011). This demonstrated also the low
tributed to non-exhaust road dust emissions in the study area (Amato impact of the national, regional and local actions on the vehicle related
et al., 2009). The reduction of levels of these industrial-traffic markers NO2 emissions. Furthermore, industrial NOx emissions in Spain have de-
ranges between −4.3 (Cr) and −10.0 (Sb)%/year. The implementation clined much less than those of other pollutants such as SO2 and PM. In
of the IPPC Directive in the study area is the most probable cause of this Spain there are still very few De-NOx industrial plants. Also, in spite of
downward trend, which was evident already before the financial crisis. the reported reduction of NOx (NO + NO2) emissions, the decrease in am-
Typical tracers of fuel–oil combustion, V and Ni, experienced a signif- bient concentrations has been much more marked for NO than for NO2.
icant gradual reduction since 2004, with a slope close to −5%/year, but O3 concentrations remained relatively constant at RB sites, with
on the contrary concentrations appear to remain constant since 2010. significant decreasing trends at only 2 sites, and non-significant trends
The 2007 ban on the use of heavy oils and petroleum coke for power at the rest of the stations. However, at UB, TR and IN sites a statistically
generation may also account for the drastic decrease of Ni and V since significant slight increase was detected for 38% of the sites. These re-
that year. verse patterns are attributed probably to a decrease of NOx emissions,
For the mineral-related trace elements (Ti, Mn, Sr), the decline is particularly NO. Under lower NO concentrations in an urban environ-
very evident since 2006, however, no pattern can be distinguished ment, less O3 is consumed to oxidize this pollutant into NO2. Further-
since 2010. The lowest slope (−2.5%/year) among the mineral-related more, an increased urban formation of O3 can be due to a possible
species and statistically significant degree (*) was found for P concen- VOCs/NOx disequilibrium induced by decreased NOx concentrations
trations, probably due to its partial biogenic origin. (Jeffries and Crouse, 1990, Seinfeld and Pandis, 1998). Hopefully, if
actions are taken to drastically reduce VOCs and NO2 levels in the near
4. Discussion future, O3 levels will also be reduced, both at urban and regional scales.
Concerning CO concentrations, a decreasing trend was gradual
The data analysis shows that AQ in Spain has markedly improved during 2003–2009, whereas from 2009 to 2012 slight changes were ob-
during the last 12 years. This improvement is evident at most RB, UB, served (Fig. 4). This decrease coincides with the one of the national CO
TR and IN sites. Levels of PM2.5, PM10, CO and SO2 decreased more emissions from road transport (Fig. 4, MAGRAMA, 2013). The decrease
markedly than those of NO2. Indeed, these decreases reached total is most likely related with the abatement of CO emissions induced by
values for the last 12 years of −28 to −43% for PM2.5, −18 to −48% the implementation of the EURO 4 and 5 emission standards, but also
for PM10, − 42 to − 51% for CO (last 9 years in this case), − 38 to by the progressive dieselization of the fleet, since diesel engines emit
−72% for SO2 and −18 to −27% for NO2. As regards O3, levels remained much less CO than gasoline vehicles. The higher CO decreasing rate
constant across the last 9 years in 70% of the RB sites and increased by at the TR sites compared to the UB sites (68% higher) points also to a
around 15% at most UB, TR and IN sites. major road traffic origin.
Time series of SO2 levels are characterized by a continuous 2001– The higher PM levels in the Southern and Eastern regions (Barcarrota,
2012 decrease. Nonetheless, in the northern regions, where most of Víznar and Zarra) are probably the result of the higher influence of
the coal power generation facilities are based, an abrupt 2007–2008 de- African dust outbreaks; whereas in the north and northeastern regions
crease is evident (Fig. 3). This sharp decrease is parallel to the decrease (Cabo de Creus, Niembro and Els Torms) this is probably due to a higher
of SO2 emissions from the power generation sector as shown by the NEI anthropogenic influence given their proximity to urban and industrial
(Fig. 3, MAGRAMA, 2013) and coincident with the implementation of areas. The decrease rate obtained for PM2.5 concentrations is by 70%
the EC Directive on Large Combustion Plants, which resulted in the ap- higher than that obtained for PM10 concentrations at those RB sites
plication of flue gas desulfurization (FGD) systems in a number of large with time trends reaching the highest statistical significance levels. This
968 X. Querol et al. / Science of the Total Environment 490 (2014) 957–969

is probably due to the fact that the African mineral dust influences more the bulk decrease. If we take into account that this component is mostly
heavily the PM10 concentrations (especially in the southern and eastern present as ammonium sulfate, this accounts for 47% of the −0.41 μg/m3
regions) compared to PM2.5 concentrations, that are highly influenced total annual mean decrease. The OC decrease explains another 26% of
by the regional anthropogenic emissions. This is also supported by the the bulk decrease, the ammonium nitrate 14% and the crustal matter
finding that, with the exception of Niembro (with very strong industrial the remaining 12%.
development in the region), the PM2.5 decreasing rates are much more
pronounced and with higher statistical significance levels in the northern 5. Conclusions
sector of the Iberian peninsula (Els Torms, Peñausende, O Saviñao, Cabo
de Creus, Campisábalos) than in the southern one. In the southern sector Taking into account all the above discussion on time trends of the
a more constantly high influence of African dust hinders the decreasing levels of atmospheric pollutants, the NEI and NECo indicators, on the
patterns probably arising from a progressive lowering of anthropogenic major policy actions on atmospheric emissions and on the meteorolog-
emissions. In the case of the UB, TR and IN sites, the difference between ical scenarios, the observed decreasing trends of pollutants can be
the decreasing rate of PM2.5 and PM10 concentrations is not as high as explained based on the following factors:
at the RB sites, probably due to the PM2.5-10 fraction being mostly
anthropogenic in these environments (Amato et al., 2009). As stated 1. The implementation of European directives affecting industrial and
above the decreasing PM10 and PM2.5 trends reported for UB and TR power generation emissions (such as the Large Combustion Plants
sites are parallel to that described for the RB sites. However, in the case and the IPPC Directives), and sulfur content in fuels (whether used
of the IN sites, the decrease is sharper until 2006 and from this year the on ships and road traffic), as well as the increase of the proportion
trend is parallel to those from the UB, TR and RB sites. This evidences of energy produced from renewable sources, among others, pro-
the effect of possible actions taken specifically at industrial sites, such duced a significant reduction of SO2, and, in a lesser extent, NOx emis-
as the implementation of IPPC directive and other effects from environ- sions. Even though NH3 national emissions were only slightly
mental policies. reduced in absolute values (−0.5%) in the same proportion accord-
The abatement of ambient PM in the last 12 years is very evident. ing to NEI, an associated reduction of secondary PM (mainly ammo-
In 2005, around 35 AQ zones of Spain exceeded both the annual and nium sulfate and nitrate) is evidenced. This, together with the sharp
the daily PM10 limit values, whereas in 2012 only one zone exceeded 2007–2008 decrease on coal-based NECo would have likely been the
the annual limit and nine exceeded the daily one (MAGRAMA, 2013), cause of the sharp decline observed for SO2, NOx and for PM2.5 con-
although the 2007–2008 sharp decrease is very evident in most sites. centrations (and emission inventories in the case of the two gaseous
This decrease has been in general gradual, even before the 2008- pollutants) during 2007–2008 (47% of the PM2.5 decrease being at-
starting financial crisis, and especially evident in the industrial areas tributed to ammonium sulfate in the Montseny RB site). Although
where the IPPC implementation had a very positive effect. the coal energy production increased in the last 3 years, the imple-
When considering the spatial variation of PM2.5 concentration mentation of FGD systems accounted for the maintenance of SO2 at
trends at EMEP RB sites across Spain, we observe a gradual decrease in low concentrations, even in the coal production regions (northwest-
the central region, where industrial clusters are scarce. All the other re- ern sector: Sav, Nie, Peñ EMEP sites in Fig. 3).
gions show the stated sharp 2007–2008 decrease (Fig. 5) observed also 2. Also the effect of the EURO 4 and 5 standards on decreasing emis-
for the trend of annual coal consumption adjusted by iNAO (Fig. 2). sions of PM and CO from vehicles is noticeable, since filter traps are
PM2.5 concentrations at the northeastern and southern regions show required for new diesel cars since 2005. This is supported by the
a clear 2002–2008 decreasing trend, remaining constant since then, progressive downward trends and the similarity of decreasing rates
whereas in the northwestern sites a marked fall from 2008 to 2010 is observed for the road transport sector in the NEIs for PM10, PM2.5
observed (parallel to the decrease on coal consumption and SO2 levels, and CO. In central Spain, where industrial emissions are reduced,
Figs. 2 and 3). Here PM levels increased from 2010 to 2012 (Fig. 5) as the progressive downward trends of ambient PM2.5 (Fig. 5) con-
also observed for the coal consumption adjusted by iNAO (Fig. 2). At centrations recorded at the EMEP sites follow the same pattern
the eastern regions, 2 periods are clearly differentiated, with high levels than those of the emissions from the road traffic sector in the NEI
during 2001–2007, and low levels for 2008–2012 but a progressive (Fig. 6). In the other regions of Spain the downward RB trends
decrease was not observed (Fig. 5). of PM2.5 (Fig. 5) evidence the influence of both the road traffic
In summary a clear and gradual decline of SO2, CO, PM10 and PM2.5 (progressive downward trend) and industrial (sharp changes in
concentrations during the study period can be concluded. The trend 2007–2008) emission reduction of both primary PM10 and PM2.5
shows a sharp decline from 2007 to 2008, which is followed by slow or and gaseous precursors of secondary PM.
even absent decreasing trends from 2009 to 2012. The NEI evidenced a 3. One national (Plan Aire from the Government of Spain), 45 regional
marked decreasing trend for both primary PM10 and PM2.5 emissions and 3 local action plans implemented to improve AQ applied in
only from the road traffic sector (Fig. 6, MAGRAMA, 2013), but the most regions and cities since 2004 might also account for a local/
sharp decrease observed in ambient air PM2.5 levels coincides also with regional decrease of SO2, SO24 − and PM2.5 concentrations. An
the above described sharp decrease of the national SO2 and NOx emissions example is the 2007 ban around Barcelona on the use of heavy oil
from power generation (Fig. 3, MAGRAMA, 2013) probably caused by the and petroleum coke for power generation, or the 2008–2012 imple-
2008 implementation of the EC Directive on Large Combustion Plants. The mentation of SCRT (continuously regenerating PM traps with a selec-
reduction of the industrial (power generation) emissions of these gaseous tive catalytic reduction for NO2), hybridization and shift to natural
precursors may account for a decrease of ambient levels of secondary PM gas engines of the bus fleet of this city.
species, such as ammonium sulfate and nitrate. Also the clear decrease on 4. The financial crisis, whose impact on industrial production and use
ambient concentrations of PM10 recorded for in industrial areas from of fuels is evident since October 2008. As shown by Fig. 2, the main
2003 to 2006 (Fig. 6) may be related with the progressive implementa- decrease of primary energy consumption was evidenced from 2008
tion of the IPPC Directive, and this is not fully accounted by the NEI. to 2009, and not from 2007 to 2008 when a sharp decrease of ambi-
The downward trend of PM2.5 concentrations at Montseny is char- ent air PM and SO2 was evidenced.
acterized by a slope of −2.7%/year (***, −0.39 μg/m3/year). In absolute 5. The meteorological cycles, which were characterized by a 2008–
concentration values, this decrease is very similar to the total decrease 2012 period that eas very favorable to the dispersion of pollutants
aggregately suffered by the mass concentrations of crustal matter, OC, when compared to the 2001–2007 weather conditions. This was

SO2− +
4 , NO3 and NH4 , accounting for a decrease of − 0.41 μg/m /year.
3
described by Cusack et al. (2012), evidencing a high iNAO during
This total decrease is dominated by SO2− 4 , which accounted for 34% of 2001–2007, while in 2010 the iNAO was the most negative of the
X. Querol et al. / Science of the Total Environment 490 (2014) 957–969 969

last 150 years. When the iNAO is negative (less pressure difference Carslaw DC, Rhys-Tyler G. New insights from comprehensive on-road measurements
of NOx, NO2 and NH3 from vehicle emission remote sensing in London, UK. Atmos
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6. The smooth decline in ambient NO2 levels (more marked for NOx), over the last nine years (2002–2010). Atmos Chem Phys 2012;12:8341–57. http://dx.
mostly due to the low effectiveness of EURO 4 and 5 standards in doi.org/10.5194/acp-12-8341-2012. [www.atmos-chem-phys.net/12/8341/2012/].
reducing real life urban driving NO2 emissions. The dieselization of Cyrys JM, Eeftens J, Heinrich C, Ampe A, Armengaud R, Beelen T, et al. Variation of NO2
and NO concentrations between and within 38 European study areas: results from
the fleet has also probably contributed to increase NO2 emissions
the ESCPAE study. Atmos Environ 2012;62:374–90.
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MAGRAMA. Inventario Nacional de Emisiones de Contaminantes a la Atmósfera.
Ministerio de Agricultura, Alimentación y Medio Ambiente del Gobierno de España.
Acknowledgments http://www.magrama.gob.es/ca/calidad-y-evaluacion-ambiental/temas/sistema-
espanol-de-inventario-sei-/, 2013.
MINETUR. Ministerio de Industria, Energía y Turismo. Gobierno de España: energy statis-
The research leading to these results has received funding from the
tics and balances. http://www.minetur.gob.es/energia/balances/Balances/Paginas/
European LIFE + AIRUSE Project (LIFE11 ENV/ES/584) and the Spanish CoyunturaTrimestral.aspx, 2013.
Ministry of Agriculture, Food and the Environment (UCA2009020083). Minguillón MC, Viana M, Querol X, editors. Particulate matter: environmental monitoring
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6547–55.
Querol X, Alastuey A, Moreno T, Viana MM, Castillo S, Pey J, et al. Spatial and temporal
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